Documente Academic
Documente Profesional
Documente Cultură
BY
W.^H. PERKIN,
F.
AND
STANLEY KIPPING,
Edinburgh
R. Chambers, Limited.
:
Printed by
W. &
PREFACE.
OUR
original
on
useful
to
classes
in the
as a
attending
subject,
handy book
the
of reference.
advanced
elementary or
to
teachers
soon became
it
a course of
the
this
useful
extent,
to
so
as
at
the
general students as
first
quently employed
of organic compounds,
weight.
methods most
fre-
and analysis
properties
of
typical
com-
PREFACE.
and in the
on structure
at
an
use of constitutional formula?, accompanied by a clear conception of their meaning, is one of the greatest helps, even to
a beginner, in committing the facts to memory.
tar
its
treatment.
an account of
coal-
the
student
is
thus
and
is
from
the
fatty,
principal
compounds,
described, but in a
is
of
systematic
Part
of the
summaries given in
I.
most
PREFACE.
The concluding chapters on dyes, alkaloids, and stereoisomerism will doubtless offer the greatest difficulties, but,
considering the importance of the matters with which they
their omission or curtailment
deal,
The account
on dyes deals
with a variety of substances of even greater practical value,
and indicates the methods employed in one of the most im-
The chapter on
now
attained, a text-book
on
it is
is
more advanced
and should be
left
out of
mastered,
or, at
any
rate, studied.
at
The
consideration of the
is
of a beginner.
One
been to treat
the subject from a practical point of view (as far as this could
be done in a text-book on theoretical chemistry), because, unless
theoretical,
no
really satisfactory
PREFACE.
VI
involved in
the
many
purification
become
practically acquainted
Such
sulphonation,
&c.,
and
the
Cliemie.
Handbuch, and of
We
are also
much
Ost's
indebted to
and
Richter, of
Dr
A. Harden for
been added
index.
We
for
whom
THE
favourable
accorded
reception
to
our
Text-book on
I.
and
II.
Although, in doing
so,
in the
account
into
of
of
the
considerable
new
facts
general plan of
to
the work,
importance
order
to
take
progress of
of
size
;
of the book
we
prove useful
whom
trust,
to
has not
therefore,
that
Theoretical and
Author of Mackay's Euclid.'
ARITHMETIC,
Practical.
By
J.
S.
'
4/6.
B.Sc., Registrar,
University of the Cape of Good Hope, formerly Assistant-Professor of Mathematics and Mathematical Examiner, University of Edinburgh. 576 pages.
Cloth, 4/6.
2/6.
J. S.
the most important Tables required in Trigonometry, Mensuration, LandSurveying, Navigation, Nautical Astronomy, &c. The tables of Logarithms
to 108000), Logarithmic Sines, &c., are carried to seven decimal places.
496 pages. 4/6.
(1
CONTENTS.
PAGE
'
3
4
4
12
14
18
18
23
27
CHAPTER
II.
WEIGHT
30
METHANE
SERIES
Methane, or Marsh-gas
Ethane
48
53
53
58
Propane
Butanes
60
Pentanes
63
61
Isomerism
Homologous
64
Series
General Formulae
66
66
67
CONTENTS.
PAGE
71
Ethylene
71
Propylene
78
Hydrocarbons
79
Acetylene Series
80
81
Acetylene
87
Crotonylene
and Extension
Allylene
Summary
CHAPTER VI.
89
89
Methyl Alcohol
89
94
Ethyl Alcohol
Production of Wines and Beers; Alcoholic Fermentation... 97
103
Homologues of Ethyl Alcohol
Propyl Alcohol
Butyl Alcohols
Isopropyl Alcohol
Alcohols
Amyl
105
106
107
Ill
Methyl Ether
Ill
Ethyl Ether
Ill
115
Radicles
116
CHAPTER
VIII.
118
Formaldehyde
118
Polymerisation
121
122
--pA.cetaldehyde
Polymerisation of Acetaldehyde
Acetal Chloral
Homologues
of
Acetaldehyde
Ketones
127
129
130
Acetone
130
Condensation of Acetone
133
CHAPTER
126
IX.
34
136
145
Formic Acid
145
Acetic Acid
149
CONTENTS.
XI
PACK
Homologues
of Acetic
Acid
156
Propionic Acid
158
Iso valeric
Acid
58
59
160
160
Acid Chlorides
161
Anhydrides
162
Acetic Anhydride
1 63
164
./Amides
Acetamide
165
Chlor-, Dichlor-,
64
166
167
169
169
Soaps
171
Butter
173
CHAPTER X.
Methyl Chloride
Methylene Dichloride
Carbon Tetrachloride
lodoform
Chloroform
72
174
of the
174
175
....177
Ethyl Chloride
178
Ethyl Bromide
179
Ethyl Iodide
180
Ethyl Nitrate
Ethereal Salts of Nitrous Acid Ethyl Nitrite
182
Nitro-paraffins
184
183
185
185
1
Ethyl Sulphide
Ethereal Salts of Organic Acids
86
187
Ethyl Mercaptan
188
Ethyl Acetate
188
190
CONTENTS.
Xll
PAGE
MALONATE
193
Ethyl Acetoacetate
Ketonic Acids
200
Ethyl Malonate
201
193
CHAPTER
XII.
PHORUS,
ARSENIC,
204
Ethylamine
205
Diethylamine
208
Triethylainine
209
Tetretliylammonium Hydroxide
Preparation and Identification of Amines
210
Phosphines
214
215
Arsines
Trie thy larsine
Tetrethylarsonium Iodide
Dimethylarsine Oxide
Tetramethyl
Silicon Tetrethyl
CHAPTER
XIII.
216
217
211
218
219
220
220
222
DUCTS
Ethy lene Glycol
Oxidation Products of the Glycols Glyoxal
Hydroxycarboxylic Acids Glycollic Acid
Lactic Ac^d
223
224
229
229
231
Hydracrylic Acid
Dicarboxylic Acids
233
Oxalic Acid
235
Oxamide
239
234
Malonic Acid
239
SuccinicAcid
240
Succinic Anhydride
241
CONTENTS.
Xlll
PAGE
Malic Acid
245
247
Citric
Acid
251
CHAPTER XIV.
253
254
Glycerol
Chlorohydrins
257
Nitro-glycerin
258
Allyl Sulphide
Acrylic Acid
Polyhydric Alcohols
Monoses
Acrole'in
262
263
THE CARBOHYDRATES
264
266
Glucose
Mannose
260
261
Allyl Iodide
CHAPTER XV.
260
267
Galactose
269
Fructose
270
272
274
Maltose
276
Lactose
277
Polyoses
Starch
Gluten
278
Dextrin
280
Cellulose
281
Gun-cotton
Cordite
Collodion
282
CYANOGEN COMPOUNDS
283
:
285
285
Cyanogen
Hydrogen Cyanide
287
Potassium Ferrocyanide
Potassium Ferricyanide
293
292
Nitriles
293
Cyanic Acid
Thiocyanic Acid
295
296
Allyl Isothiocyanate
298
CONTENTS.
XIV
PAGE
CHAPTER XVII.
AMIDO- ACIDS
GLYCINE
299
^^rea,
301
Uric Acid
303
CHAPTER XVIII.
PERTIES OF BENZENE
305
CHAPTER XIX.
OF BENZENE DERIVATIVES
313
GENERAL PROPERTIES
CHAPTER XX.
POUNDS
.OF
AROMATIC COM331
Classification of Organic
331
Compounds
334
Diphenyl methane
350
Triphenylmethane
benzene
Bromobenzene
lodoxybenzene
lodobenzene
lodoso-
Chlorotoluene
Benzyl
Chloride
357-361
CHAPTER XXIII.
Nitrobenzene
CHAPTER XXIV.
Aniline and
352
its
NITRO-COMPOUNDS
Meta-dinitrobenzene
362
Nitrotoluenes
367
Derivatives
CHAPTER XXV.
365-367
373
376, 377
379
380
TIVES
381
386
Phenylhydrazine
Azo- and Azoxy-compounds
388
CHAPTER XXVI.
TIVES...,
390
XV
CONTENTS.
PAGE
PHENOLS
CHAPTER XXVII.
Monohydric Phenols
398
Phenol
Picric
Acid
404-409
Cresols
5 Aldehydes
~>Ketones
ALDEHYDES,
414
414, 415
Benzyl Alcohol
417, 418
Benzaldehyde
Hydroxy-aldehydes
^
ALCOHOLS,
421, 422
Salicy lahlehyde
423
Acetophenone
425
Qninone
Quinones
CHAPTER XXIX.
CARBOXYLIC ACIDS
Benzoic Acid
Benzoyl Chloride
Benzonitrile
B.enzamide
428
Benzoic Anhydride
430-433
434
Tolnic Acids
435
Dicarboxylic Acids
Cinnamic Acid
Salicylic
Anisic Acid
Acid
Acid
443
'.
CHAPTER XXX.
Tannin
446
Protocateclmic Acid
Gallic
Mandelic Acid
NAPHTHALENE AND
CHAPTER XXXI.
ACIDS
450-453
ITS
DERIVATIVES
454
455
Naphthalene
Naphthalene Tetrachloride
Nitro-derivatives
Amido-
Sulphonic Acids
a-Naph-
derivati ves
Naphthols
thaquinone
/3-Naphthaquinone
463-469
CHAPTER XXXII.
470
Anthracene
470
Anthraquinone
quinone
Piperidine
Phenanthrene
Diphenic Acid
CHAPTER XXXIII.
Pyridine and
Alizarin
its
Phenanthra475-484
484
485
489
XVI
CONTENTS.
PAGE
Homologues
of Pyridine
Pyridinecarboxylic Acids
491
493
Quinoliiie
496
Isoquinoline
CHAPTER XXXIV.
ALKALOIDS
497
Caffeine,
501
504
&c
&c
508
510
Antipy line
511
513
CHAPTER XXXV.
514
The Phthaleins
Azo-dyes
Benzopurpurins
Various Colouring Matters
Blue, Indigo
CHAPTER XXXVI.
APPENDIX.
OPTICAL-
533-538
Martius' Yellow, Methylene
538-540
AND STEREO-ISOMERISM
Haemoglobins
Prote'ids
541
ANIMALS... 561
Terpenes.. 563-586
Amido-acids
587-615
INDEX
617
INDEX TO APPENDIX...
633
ORGANIC CHEMISTRY.
PART
I.
CHAPTER
COMPOSITION, PURIFICATION,
I.
COMPOUNDS.
Origin and Present
'Organic.'
wine, sugar, fats, and many other substances obtained directly or indirectly from animals or plants
have been known from the earliest times, their investiga-
Although
spirit
of
tion made but little progress until towards the close of the
eighteenth century, when the composition of many of these
natural products was established by the French chemist
Lavoisier (1743-94).
Lavoisier
it
was who
first
showed
that,
different
artificially or synthetically in
the laboratory.
it
this synthesis
'
stance urea.
many
'
'
'
all
The supposed difference between the two classes of compounds having thus been recognised as purely an imaginary
one, the terms
'
'
organic
and
'
'
inorganic
lost,
of course, their
made use of in
original meaning ; they are, nevertheless,
the classification of chemical compounds for the following
still
reasons
(2)
differ
they form, in
fact,
a special group
OF ORGANIC COMPOUNDS.
constituent of
chemistry,
all
pounds.
Some
of the simpler
compounds
which are
works on
so
are
known
are
chemical action
these
new
so
numerous
is
as
great
nine, for
Those occurring
contain nitrogen as well.
contain
nitrogen as well as
kingdom generally
example
in the animal
and oxygen urea and uric acid, for incomposed of these four elements ; a few vegetable
and animal substances also contain sulphur and phosphorus.
carbon, hydrogen,
stance, are
COMPOSITION, PURIFICATION,
AND ANALYSIS
element.
Some
benzene, for
so
which form
salts
There
first
to qualitative
and
For these reasons organic analysis usually consists of several proFirstly, the substance is submitted to a preliminary qualitative examination, the object of which is to find out how many
distinct compounds are present, and to separate and purify each of
them. The nature of each constituent is then determined ; this
may sometimes be done by proving it to be identical with some
known compound by methods to be described later. If this be
impossible, a further qualitative examination is made to ascertain
cesses
Separation
The separation
of
any kind
is
usually necessary to
is
employ
it
OP ORGANIC COMPOUNDS.
mixtures.
Although, therefore,
it
is
impossible to give a
more
of
important processes used in the separation and purification
organic substances may be briefly indicated.
In the case of any substance of unknown nature, a small
is first ignited on platinum foil ; if it leave a noncombustible residue, it is probably a salt of some organic acid,
or it contains inorganic compounds as impurity.
The separation of an organic from an inorganic substance
portion
can usually be accomplished by shaking or warming the substance with some solvent, such as alcohol, ether, benzene,
or dilute acids
pose,
since
may
many
substances
many
in
insoluble,
organic
these
liquids.
sugar,
acid,
acid,
and benzoic
last-named
being
ether,
then
separated
from
the
sugar
organic
subFig. 1.
stances
in
solvent,
aqueous solution, or
suspended in water in a fine state of division, may often
be isolated by agitating the solution or mixture with some
COMPOSITION, PURIFICATION,
AND ANALYSIS
running
off that
which
is
The
of
rest of
the material
portion,
if
any,
The
is tried.
filter
or
if necessary.
If only one constituent of a mixture be dissolved
by the
liquid employed,
state of purity without
*
difficulty,
because
the
others are
is
necessary
OP ORGANIC COMPOUNDS.
easily got rid of
by
filtration;
usually be effected
process, advantage
the substances.
On
In
by fractional crystallisation.
is
this
fig.
2)
which
is
connected
a rapid
is
way according
to circumstances.
In
this simple
compound when
manner
all
other
COMPOSITION, PURIFICATION,
AND ANALYSIS
ordinary
volatile
in steam,
boiling-
points
Fig.
2.
When
placed just below the opening of the side-tube (B), and a few
scraps of unglazed porcelain, or platinum, are put in the dis-
In
prevent bumping or sudden ebullition.
the case of liquids which boil at temperatures above 130 or so,
tilling flask, to
'
OF ORGANIC COMPOUNDS.
instead of
a long glass tube (C) without a water-jacket is used
the
If
compound
a Liebig's condenser, which is apt to crack.
of non-volatile
to be purified contain only a small quantity
rises very rapidly as soon as the
impurities, the thermometer
remains practically stationary
then
but
to
boil,
liquid begins
Towards the end of the
almost the whole has distilled.
until
Fig.
3.
operation, however,
redistilled,
definite
boiling-point (b.p.),
As
which
is
dependent on the
pressure.
pressure diminishes, the boiling-point is
lowered, so that, by carrying out the process under reduced
the
See foot-note,
p. 14.
10
COMPOSITION, PURIFICATION,
AND ANALYSIS
it is
often possible to distil a substance which
would undergo decomposition under ordinary atmospheric
pressure, because in the latter case it would have to be
heated more strongly.
pressure,
point
if
order to
make
sure that
it
tilling a substance, it
it
may
contain
them
sium carbonate, potash, or other dehydrating agent, according
to circumstances, and then decanting or filtering.
When a mixture of two (or more) volatile substances is
distilled in the
boil at
its
constituents.
As
distillation
at last registers
is due to a
change in the composition of the
the
mixture;
alcohol, being more volatile, passes off more
It is possible, therefore, to partially
quickly than the water.
OP ORGANIC COMPOUNDS.
ll
By redistilling each
fraction separately a further separation is effected, and, after
a sufficient number of operations, the constituents of the
being termed fractional distillation.
than
in
this,
many
cases,
As an
The
87-100
33 c.c.
100-110
(1)
(2)
16
c.c.
110-120
8-5
120-130
c.c.
(3)
8 c.c.
130-140
33 c.c.
(4)
(5)
and last are larger than the others, bedause the temperatures at which they are collected are near the boiling-points
of the constituents.
the fractions 1 and 5 be sepaIf, now,
first
The
is greatly facilitated by
a
flask
with
a
or
employing
by causing the mixed
long neck,
to
tube before they
a
vertical
vapours
pass through
long
enter
the
condenser.
By
this
of
the
liquid
of
out
under
A simple
is
12
COMPOSITION, PURIFICATION,
AND ANALYSIS
easily
made by
The
tillation is carried
interrupted
when
is
being changed,
TO VACUUM PUMP AN
PRESSURE GAUGE
Fig. 4.
Tests
of Purity.
composition
established.
of
It
Before
an organic substance,
would be useless to
test for
chlorine, for
OF ORGANIC COMPOUNDS.
determination of
of its behaviour
its boiling-point,
on
when
the microscope,
or rather an examination
distillation, will
A solid substance,
or not.
13
however,
is
its
may
often be
is
melting-point
always
made.
Pure substances which melt or liquefy without decomposing do so at a definite temperature, which
melting-point of
the-
is
called the
compound ;
when,
is
but
lowered,
usually
melting-point
it is
and
not
melting
completely
the
of
therefore,
purity,
melting-point
a valuable
and
means of
affords,
serves
also
identifying
of
test
as
com-
pound.
The apparatus
for
ployed
generally emthe
determining
beaker
c.c.
(a,
fig.
capacity,
centrated
5)
50
of about
con-
containing
sulphuric
and
acid,
fitted
substance
which
small
it
by
being
is
is
india-rubber
capillary
constantly
ring,
or
simply
attraction.
stirred,
and
The
the
caused
acid
is
to
adhere
slowly
temperature
at
to
heated,
which
14
COMPOSITION, PURIFICATION,
the
substance
*
(m.p.)
is
liquefies
that
to
is
AND ANALYSIS
say,
its
melting-point
noted.
it is
often possible,
is composed.
In order, in the first place, to make sure that the substance
that is to say, that it really is an organic
contains carbon
a
small
If
quantity is heated on platinum foil.
compound
is
in all probability
organic.
when
The
Sodium
of
is
analysis.
acetate,
acetate,
silver.
the
If a
halogen,
it
inorganic
sulphur,
the metal.
The behaviour
of a substance
concentrated
OF ORGANIC COMPOUNDS.
15
carbon,
is
oxide,
hard glass sealed at one end, the escaping gases being led into
lime-water; under these conditions all organic substances*
decomposed, yielding carbon dioxide, the formation of
are
which
is
is
of
The presence
quently indicated
is
proved.
about the
size of a pea,
Except the stable carbonates and cyanides of the alkalies and alkaline
earths.
is prepared by intimately mixing slaked lime and caustic
and strongly heating the mixture until it is quite dry.
f Soda-lime
soda,
16
chars
The mixture
it.
broken by
is
finally
and
at a red heat,
The
a few
alkaline solution
drops of
mixture warmed
chloric acid,
and
is
produced.
This test depends on the fact that the nitrogen and some of
compound combine with the sodium
Fe(OH) 2 = Na4Fe(CN) G +
adding
is
2;NT aOH,
so
that
on
afterwards
produced.
The presence of
compounds cannot,
when pure
it
A
wire,
Bunsen flame
until
it
should
be
done
in
such
is
that
the
eyes
are
not
endangered.
OF ORGANIC COMPOUNDS.
the wire in the flame, when,
colouration
if
17
is
it
ceous
The
alkaline
the
matter,
solution
filtrate
is
acidified
filtered
from carbona-
with pure
nitric
acid,
a precipitate be
;
of
the
of
formed,
halogen (or
nitrogen, see below)
presence
in the original substance is proved, and its nature may be
silver nitrate
if
precipitate, to the
on the fact that
when any
iodine
or
organic
is
substance containing
with sodium, the
heated
chlorine, bromine,
halogen combines with the metal to form chloride, bromide,
or iodide of sodium, which can then be tested for in the
usual manner.
mixture
it
chloride.
When
lected, dried,
the cyanide
silver salt is
dilute
nitric
is
acid
presence of halogen
Org.
if
is.
it
established.
the,
18
COMPOSITION, PURIFICATION,
AND ANALYSIS
The residue
phuric acid, the phosphorus to phosphoric acid.
dissolved in water, and the solution of potassium salts
tested for the above-mentioned acids in the usual way.
is
When
is,
pounds
f are
dioxide, the
weight
products
of
and
substance,
of
combustion,
collecting
the
The apparatus
gener-
19
OF ORGANIC COMPOUNDS.
used for this purpose
ally
is
shown
in the
accompanying
figures.
tube
(a),
Fig. 6.
chloride, serving
Fig.
7.
to retain the
of
latter
representing
the
amount
of
carbon
dioxide
formed.
The combustion
is
bustion tube
and open
tube
is
at
by
bottle (g\
*
both ends
a current of
ture
air,
*
(h, j)
containing
20
COMPOSITION, PURIFICATION,
AND ANALYSIS
matter
organic
removed
be
then
is
(I)
into the
fitted
traces
may
empty section
the
being
order
having
end (b)
and
out
in
weighed
accurately
a narrow
porcelain
order
in
to
prevent
as
far
backward
as
any
possible
of the products of
diffusion
When
combustion.
volatile
liquid
analysed,
the
is
a
to
very
be
substance
is
fully freed
now
the
is
OP ORGANIC COMPOUNDS.
taps (beginning at
c).
As soon
as the
21
and
to
may
=
U-
0-0987 x 100 co
= 62-40
IKQQ
LDoZ
,
parts
01
carbon.
and 100 must represent the quantity of oxygen; the percentage composition of the substance
*
is
therefore,
N=14
are used
22
COMPOSITION, PURIFICATION,
AND ANALYSIS
4-31
33-29
The percentage
,.
(by difference).
The following
oxygen
is
with the
bright copper gauze, about four inches long, into the front
part (&) of the tube in the place of some of the copper
oxide ; this is kept red hot during the combustion, and
serves to decompose any oxides of nitrogen* produced
When
the sub-
gauze must be
its
action being
equation,
10 0.
Any sulphur dioxide, phosphorus pentoxide, or halogen produced during the combustion is completely retained by the
lead, as PbS0 4 PbCl 2 &c., and thus its passage into the
,
absorption apparatus
is
prevented.
* In
order to render the roll of gauze as efficient as possible, it is
heated in a blowpipe flame until thoroughly oxidised, and, while red
hot, dropped into a little (1 c.c.) pure methyl alcohol contained in a
test tube ; the methyl alcohol reduces the copper oxide, giving a very
OF ORGANIC COMPOUNDS.
23
or
by Kjeldahl's,
method.
1.
Dumas' Method.
This process
is
when
ignited with copper oxide, nitrogenous organic substances are entirely decomposed into carbon dioxide, water,
If the gaseous products of com(or its oxides).
bustion be passed over heated copper to decompose the oxides
of nitrogen and then collected over potash, the carbon dioxide
and nitrogen
and hydrogen
(fig. 8),
in a boat,
finely
The stream
of gas
is
now
As soon
*
The gas
as the
is
more conveniently
eudiometer con-
in the apparatus
shown
to a dull-
magnesite.
it is
impossible to drive
carbon dioxide
is
is
thumb
water,
and
moved
may
the
re-
fall
After
about
time,
the tube
held ver-
is
such
in
water.
half-an-hour'a
position
that the levels of the water
tically
inside
is,
The
apparatus
shown
nitrometer)
(Schiffs
in fig. 9,
Fig 9
tube
stop-cock (a) and a reservoir
tube
may
be
filled
with potash
(d),
(ac\
graduated
provided with a
(sp. gr.
serves for
passed
time,
through
the tube
lowered.
If
the
the
combustion
tube
for
considerable'
(b)
is
combustion
is
OF ORGANIC COMPOUNDS.
25
ceeded
(d) is
being noted.
The weight
when
readily ascertained
is
its
volume
where
w = the
cury*
at the
tension
of
aqueous vapour in
temperature
mm. would be
v x
t, the
B-W
-- x
volume
mm.
of mer-
and 760
at
273
1
now,
As,
c.c.
of
gen measured at
16; B =
753-5 mm.,
0=13-5 mm.
40
is
7-1 x
273
x
89
The
0-001251
3-59.
Some
following
of the values of
t=
w=
When
10
12
14
16
18"
20
9-14
10-43
11-88
13-51
15-33
17-36
mm.
fig.
is
26
COMPOSITION, PURIFICATION,
that
way
ammonia;
AND ANALYSIS
the
known weight
decomposition of a
The apparatus
of
piece
of
end
(a),
to & is filled
the part b
Fig. 10.
to c contains
and
finely
(e)
acid,
The amount
air
known volume
of standard hydro-
may
get choked
up and a
OP ORGANIC COMPOUNDS.
27
and
by the ammonia
is
estimated volu-
This decomposition
acid,
ammonium
their nitrogen
is
hot,
concentrated
of
sulphate.
is placed in a round-bottomed
and covered with about 20 c.c. of concenThe flask is then heated directly over
trated sulphuric acid.
an Argand burner, very gently at first, afterwards sufficiently
flask of
hard
glass,
to boil the acid, the process being continued until the liquid
(which is usually very dark in colour owing to the separation
operation
is
produced
the boiling-point.
is
frequent use.
with
nitric acid at a
employed where
this
method
high
is
in
28
COMPOSITION, PURIFICATION,
AND ANALYSIS
the substance
is
is
glass tube,
which
silver nitrate.
Fig. 11.
having been added, the open end is drawn out and sealed, as
shown at 5. The tube is then placed in an iron case, and
heated in a specially constructed apparatus (fig. 11) at a
temperature necessary to ensure complete decomposition,
usually at about 180, for four hours; in the case of very
stable substances, a much higher temperature and prolonged
heating are required, and fuming nitric acid must be used.
When quite cold the tube is opened,* the contents are
*
Very great care must always be taken in working with sealed tubes, as
they frequently explode, and very serious accidents may occur. The tube
should not be removed from its iron case, but should be cautiously pulled or
tipped forward until the capillary just projects, using a cloth to protect the
OP ORGANIC COMPOUNDS.
transferred to a beaker with the aid of distilled water,
after
boiling
29
and
way.
is
substance
is
proceeded with.
When
sulphur
is
methods of analysis.
Another method for determining sulphur and phosphorus,
and also halogens (applicable only in the case of organic
acids and some non-volatile neutral compounds), consists in
heating the substance with a mixture of potassium carbonate
and nitre in a platinum crucible, until the product is colourless.
Here, again, the substance is completely oxidised, and the sulphate or phosphate produced may be estimated in the residue.
hand
a Bunsen flame
up by any
is
solid particles.
30
DEDUCTION OF A FORMULA.
CHAPTER
II.
which
In the
is
unknown.
quite
first case,
what
is
Example.
of
composition
is
= 40-56,
= 5-12,
gave the following results:
54-32 (by difference) per cent. Since the percentage
analysis,
is
believed to be.
it is
aifords
arrived
succinic
H = 5-08,
40-68,
strong
acid,
calculated
from
its
formula,
= 54-24
confirmation
of
at.
In the second
entirely
unknown,
case,
it
is
numbers
Example.
found to be
substance,
this
DEDUCTION OF A FORMULA.
31
Example.
= 39-95,
H = 6-69,
= 53-36; deduce
dividing
39-95
now
formula.
number
of atoms is
= 6-66,
11
6-69
:
= o-by,
U=
53-36
_>,
o-oo
for experimental
= 1:2:1;
is
Pro-
L>
of a substance
its
way
is
therefore
CH 2 0.
In order, then, to calculate a formula from the percentage
composition, the quantity of each element is divided by the
atomic weight of that element, and the ratio is then expressed
in whole
smallest, or
= 1.657-1. 649 =
=1
H=
6 88
'
=6-880-1.649 =
14
The formula,
= l-649-
therefore, is
CH4N
1-649
=1
DEDUCTION OF A FORMULA.
32
The formula
and
and
lactic
acid,
may
is
is
the
termed
not,
show
CH
formaldehyde,
C 3H6
C2H4
acetic acid,
for example,
CH
0.
example,
it
can
be
CH
has
empirical formula
2
molecular formula must be C 2
total
60),
CH
and not
or
(C 2 = 24,
C 3 H6
that
is
4,
= 32;
to say,
the
The determination
is
and
adopted whenever
known by which
are
no
chemical
methods
purely
possible
the molecular weight can be established with certainty,
methods,
physical
described
later,
are
may
will
acids,
the
position ensues,
and a residue
DEDUCTION OP A FORMULA.
Example.
H = 6-69,
= 39-95,
is
therefore
CH
0.
= 53-36;
its
33
an organic acid
empirical formula is
of
= 54-73.
is
rToTT^Ti
U-
Now,
'
o4-7o
acid
is
number
CH
C 3 H5
=
3 Ag (
196-7).
based on the assumption that one molecule of the silver salt contains only one atom of silver
that
This conclusion
is
C 6 H 12
displaceable hydrogen
that
salt
C 6 H 10
silver,
and
6,
is
to say,
were dibasic
the silver
Ag2 would
would point
Org.
C 6 H 12
If this were
DEDUCTION OF A FORMULA.
34
that the
to form
form double salts with
chloride.
These double salts
platinic chloride and with auric
usually have the composition B 2 ,H 2 PtCl 6 and B',HAuCl 4
where B' represents one molecule of a monacid base, such as
salts
which, like
ammonium
chloride,
/
methylamine,
CH
N, ethylamine,
&c.
C^^N,
When
these
crucible,
molecule of the
salt contains
salt
(platinicliloride)
of
195
weight
.,
is
of
the base
the
tr*
195 parts of
the
(C 3
= 527
^=-^
salt,
H N)
-r-r
-.-TV
is
.,
therefore
ft
9fl
or
527 - 409-2
~2~
~^~
'
As
B",H 2 PtCl 6
tjtie
DEDUCTION OP A FORMULA.
35
ing
has
the
percentage
yields
= 45-86,
of
H = 3-18,
Br = 50-96 per
C =
cent.
The empirical
is,
^p =
3-82
-0.637 =
3.18
4-0-637
o-io
hydrocarbon
is
C 6 H6
it
cannot be
less
than
this,
but
it
may
be greater.
hydrocarbon C 12 12 for example, might give
a bromo-derivative C 12 10 Br2 and these compounds would
C6H 6 and C6 H5 Br
respectively.
tolerable certainty
substance.
When,
with con-
it is
which, on analysis, is
C 3 4 The fact that this hydrocarbon boils at 163
very strong evidence that the molecular formula is not
C 6H 8
but probably
C 9 H 12
affords
C 3 H4
or
DEDUCTION OF A FORMULA.
36
at temperatures
increase in molecular
a rise in boiling-point.
is
weight
generally accompanied by
One of the most important physical
Physical Methods.
methods by which the molecular weight can be ascertained is
density.
This method
is
based on
be
number
is
= 2),
hydrogen
gr.
compared with
air is
so that, in order
DEDUCTION OP A FORMULA.
37
of
a substance
is
ascertained experi-
known weight
substance at
the
of
known
by that
of the
hydrogen
is
An
Example.
C 4 H 10
The volume
and
c.c.
at
of
720
x
273
x
5Q
=18-57
c.c.
therefore 18-57
0-062 _
The weight of the vapour
~ 371 _ y-p
~
The weight of the hydrogen 0-00167
The molecular weight = V.D. x 2 or 37-1 x 2 = 74-2.
Since the molecular weight of a compound of the empirical
C 4 10 is calculated to be 74, the determination of
formula
tical
experimental errors;
since all that
is
is
only possible
DEDUCTION OP A FORMULA.
38
when
a substance
compound, or a com-
non-volatile
can
substance
parent
be
ascertained.
The following
are some
methods employed
of the
Gay-Lussac's
mann's Method.
ated barometer
fig.
12),
or
Hof-
gradu-
tube
(ab,
known
liquid boiling at a
(c) is
connected with a
in rapid ebullition.
The liquids most
are water (b.p. 100), xylene
(b.p.
made
of
Fig. 12.
(b.p.
213).
(/),
sequent use.
As soon as the barometer tube
is
and
is
kept
commonly employed
140),
aniline
(b.p.
The condensed
is
liquid
collected for sub-
at a constant temperature,
DEDUCTION OF A FORMULA.
39
a weighed quantity (about 0-05 gram) of the substance, contained in a small stoppered vessel (d\ which it fills completely,
The vessel immediately
is placed under the open end (b).
rises to
tube
of
the
to
0.*
taken.
The
affords a
stances under
greatly reduced
much below
temperatures very
so that it can often be employed with
success in the case of substances which
are
13),
globe-shaped
fairly
being noted.
large quantity of the substance (about
8-10 grams) is now introduced by
pressure
(B')
By
Flg 13 *
The
at
least
air in
20
above
the apparatus
DEDUCTION OF A FORMULA.
40
is
quickly expelled by the rapid vaporisation of the suband the vessel is filled with the vapour of the liquid.
stance,
As soon
which
as the
is
known by
the
fact
the
oil-bath
(t)
the
height
of
barometer
and
the
being
(B)
The globe is
allowed to cool, and is
then
dried,
cleaned,
noted.
and weighed.
The point
is
of the tube
water
fills
mercury),
(or
which
rushes
the
pletely,
minute
in
liquid produced
condensation
vapour
and
com-
globe
in
by the
of
the
the
globe;
the
is
globe
again
weighed, and its capacity
or volume
(v) obtained
Fig. 14.
water contained in
directly
it.
by transferring the
graduated vessel.
When the globe
W,
is
v,
of
vapour
less
the weight
DEDUCTION OP A FORMULA.
of the volume,
v,
of air.*
The weight
41
by reducing the volume, v, at t' and B' to N.T.P., and multiplying by 0-001293, the weight of 1 c.c. of air at N.T.P.
this
weight added to
?;,
of
B is
vapour at t and B.
then reduced to N.T.P., the weight of an equal volume of
hydrogen at N.T.P. calculated, and divided into the weight
of the vapour.
rapidity with
when bubbles
or bulb (d,
the air out of the apparatus into the graduated vessel (g).
When air ceases to issue (from d), the stopper (a) is at once
vapour
is
e)
ascertained
by measuring the
*
Changes in the temperature of the air, height of the barometer, and
volume of the globe occurring during the experiment may be neglected.
t See page 38 in determining the vapour density of substances of high
boiling-point, diphenylamine (b.p. 310) or sulphur (b.p. 448) may be used,
or the bulb tube (ab) may be heated at a constant temperature in a metal
;
bath.
placed in
6.
little
DEDUCTION OP A FORMULA.
42
273
273
*
t
E-iv
760
w ^ ein g
,,
obtained.
owing to the
c.c.
at 250
if
of air at 230
230,
the 24-04
c.c.
>
When
sugar
is
Compare
p. 24.
DEDUCTION OF A FORMULA.
43
the
same (approximately) in
From
all
which should be
If 1
gram
K x ^ because K is the
weight in grams
100
be
would
D,
that
to say,
by
grams
44
DEDUCTION OF A FORMULA.
p
D = K x ^,
pression,
=r
M = KxP
molecular weight
and
hence the
being known,
if
T;r
;
Jl
the de-
pression
M, can be calculated.
This method of determining
the molecular weight of organic
compounds was
Raoult, and
as
The
with
observation
the
aid
apparatus devised by
in
the
(fig.
15),
manner
applied by
usually known
the cryoscopic
or
Raoult's
method.
made
first
is
large
of
is
the
Beckmann
following
tube
(A),
with
closed
cork
(C),
to
weighed quantity
T^j-.
(about 25 grams) of the solvent
is placed in the tube, which is
then
Fig. 15.
fitted
into
a wider tube
apparatus
is
now
introduced
DEDUCTION OF A FORMULA.
is
about 5
The
45
solvent
is
A)
(in
thermometer rapidly
now
falls,
arid
thermometer now
the
through
freezing-points
is
the substance
is
formula.
Example.
solved
in
quantity
in
for water is
sugar
is
found
to
19x5-139
be
001
= ool,
the
true
value
being 342.
As in the determination of molecular weight from the
vapour density, the experimental and theoretical values
frequently differ by several units, but this is of little importance for the reasons already stated.
The constants, K, for the solvents most frequently used
are: acetic acid,
are
dissolved
in
a fixed
and
sufficiently large
DEDUCTION OF A FORMULA.
46
may
"be
deduced.
is
(approximately) a constant,
known weight
M=
being employed.
(Compare
p. 44.)
means
jacket,
is
of a cork into a larger one (c) which serves as an airand the outlet (d) of which is connected with an
DEDUCTION OP A FORMULA.
47
the time of the second reading has now to be found, and the
molecular weight of the substance can then be calculated.
m
Fig. 16.
may be
DEDUCTION OF A FORMULA.
48
Example.
K,
for
carbon disulphide
weight, therefore,
128.
The constants
acid,
25-3;
23-7
/T
is
acetic
is
for
benzene, 26-7;
water, 5-2;
ether,
21-1;
The
all substances
molecules
of
the
dissolved
substance
are
associated,
or
form
CHAPTEE
III.
it
is
composed, there
49
(differently united.
There
is
nothing at
all
in
;the case of
NH
(Only difference
between them
(.combination.
It is just the
is
all
Methyl
on by sodium,
CH 3 NaO, which is
formed by the displacement of one hydrogen atom (a) by one
atom of the metal the other three hydrogen atoms in methyl
CH 4 0,
alcohol,
CH4 + HC1 = CH
When
into
this
compound
is
C1
+ H 2 0.
it is
transformed
50
the change
C 3H 8 0,
as ethyl alcohol,
C 2 H 6 0,
propyl
&c.,
in a similar state of
combination.
It
is
thus possible to
or of all the
many
may be
expressed.
substance.
graphic formulae,
Before
it
giving
examples of
the
use
of
51
For this
formulae of some of the simpler organic compounds.
be
directed
in
the
first
to comattention
place
may
purpose
pounds such as
COC1 2 ; and
(c)
(a)
(d)
carbon
(&)
is
and
(c)
monad atom
these
all
of
combined with
2 dyad atoms,
triad
that
is
to say,
(d) 1
atoms
and
this fact
less
is
carbon, therefore,
equivalent;
be expressed by writing
may
=C=
or
its
or
tetravalent,
symbol,
drawn simply
to express
be represented by
trivalent nitrogen
by
0=
N= or
N"
and
so on, the
number
CH CH3 C1,
,
monad
H
H
C
I
H
H
Cl
Cl
Cl
Cl
C0 2 COC1 2 COS,
,
to be a tetrad in
CO.
each
52
o=c=o
Similarly,
HCN may be
H C=N.
that
compounds
is
to
the
say,
state of
lines
the
as
represented
by that symbol
is
known
The
combine.
to"
C^
by
elements
bonds
is
or linkings
C=N", the
is
said to be
as a
CH
H
which
signifies the
same
as
CH3 -OH
and
H.
All
53
GHAPTEE
IV.
SATURATED HYDROCARBONS.
of
It
places
matter
pond
in
of
marsh-gas,
carbon
dioxide,
80-90 per
with
cent, of
Methane
*
is
direct union
The words formed, obtained, and produced are used when the method
theoretical importance, and not suitable for the wind preparation of
is of
the compound.
54
SERIES.
of carbon
when
is
(Berthelot),
CS 2 + 2H 2 S + 8Cu = CH 4 + 4Cu 2 S
CS 2 + 2H 2 + 6Cu = CH 4 + 2Cu 2 S + 2CuO
and when carbon tetrachloride
amalgam and water (p. 55),
Methane
is
also
is
reduced with
(p.
sodium
222)
is
de-
composed by water,
C 2H3
The
Na + NaOH - CH 4 + Na 2 C0 3
way
hydrogen, ethylene (p. 71), and other impurities; if, however, barium oxide be used instead of soda-lime the gas is
Pure methane
is
a zinc-copper couple, f
The methyl
iodide
is
reduced by the
*
Compounds, such as zinc methyl, are often unavoidably introduced
long before their properties are described; in such cases references are
The groups of atoms,
9-, are termed
given.
5 -, C 3 H7-, and C 4
3 -, C 2
methyl, ethyl, propyl, and butyl respectively (p. 117).
CH
55
SERIES.
the gas
is
(p.
tjie
heat,
zinc-copper
is
ammonia,
Tin
is
acid,
Sn + 2HCl=SnCl 2 +2H.
Stannous Chloride
is
Hydrogen Iodide,
may
sulphur and
HYDROCARBONS OP
56
Methane
is
11
liquid at
T,HB
METHANE
SERIES:
CH4 +
2 vols.
20 2
4 vols.
= C0 2 + 2H 2
= 2 vols. 4 vols.
-t-
alcohol.
potash, nitric
acid,,
when
more
soluble in
mangana^e,
an,d solution of
or changed;
in,
any way.
When
in the
is-
deposited,.
CH 4 + C1
= CH 3 C1 + HCL
CH4 + 2C1
Methyl Chloride.
- CH 2 C1 2 + 2HCL
Methylene Chloride.
Chloroform.
Carbon Tetrachloride.
or
take place.
of
methyl
hydrogen,
form
of
is
Now,
chloride,
it
may
CH
3 C1,
ammonium
sulphide.
it is
SO 2 + 2H 2 O = H 2 SO 4 + 2H.
re--
is
57
SERIES.
drawn away from the carbon by the superior attracand that one atom of chlorine takes up
change
may then be
Cl
CH
C1 2
it
may be
assumed that in
all
above
the
examples
the
action
of
is
is
methane and
products of
of one another
are
substitution
methyl chloride,
'CH 3 C1, is a mono-substitution product, methylene chloride,
'CH 2 C1 2 a di-substitution product of marsh-gas, and so on;
:
chloroform,
CHC1 3
is
a di-substitution product of
58
SERIES.
must be displaced
if
any other
Compounds such
as
these, in
occurs
petroleum
or
methyl iodide
like
methane,
earth
in
the
districts.
solution,
is
is
affords a
into
Zn(C 2 H 6 ) 2 + 2H 2
when ethylene
(p.
71)
is
- 2C 2 H 6 + Zn(OH) 2
decom-
C 2 H4 + 2H = C 2 H6
and when methyl iodide
is
is
prepared by reducing ethyl iodide with the zinccopper couple, exactly as described in the preparation of pure
Ethane
is
methane,
or
by the
CH 3 -C0 2H =
when potassium
positions occur
acetate
is
59
SERIES.
and
so that the
insoluble
in
water,
soluble
slightly
in
It
alcohol.
is
in-
2C 2 H 6 +
4 vols.
It is very stable,
sulphuric
acid,
70 2 - 4C0 2 + 6H 2
+ 14 vols. = 8 vols. + 12 vols.
and
is
bromine,
or
oxidising
When mixed
temperatures.
agents
at
ordinary
C 2 H 6 + 2C12 = C 2 H 4 C1 2 + 2HC1.
C 2H 6 + C1 2 = C 2 H 5 C1 + HC1.
Ethyl Chloride.
Ethylene Bichloride.
Perchlorethane.
The
constitution of ethane
manner
the following
may be deduced
theoretically in
united with
three
atoms of
as
hydrogen
represented
in
H H
the
following graphic
formula,
H.
This
view,
H H
based entirely
on considerations of valency,
is
confirmed
60
SERIES.
by a study
ethane.
When
H
this
tetravalent,
group
like the
atom
of
hydrogen
H
H-, cannot
exist alone,
CH -CH
or dimethyl, which
similar group forming ethane,
3
3
is a saturated compound, because all the carbon atoms in the
maximum
valency or combining
capacity.
It
also obtained
iodides with
C 2 H 5 T + CH 3 I + 2Na = C 3 H 8 + 2NaI,
and by treating zinc ethyl with methyl
Zn(C 2 H 5 ) 2 +
Propane
is
a gas,
and
in chemical properties.
iodide,
closely resembles
chloride
in diffused sunlight,
it
or
yields propyl
more hydro-
is
that propane
61
SERIES.
iodide, it is concluded
H
C
H C C
formula
and
H H
its
constitution
H H H
H-C C C
H H H
H, or
is
therefore represented
CH3 .CH
.CH 3 and
,
it
by the
may be
CH3
group
hydrogen.
Butanes,
formula C 4
C4 H 10
Two
are
known.
2C 2 H 5 I + 2Na = C 4 H 10 + 2NaI.
The
tertiary
butyl
iodide
(p.
181)
is
reduced
formed when
with
nascent
hydrogen,
at about
In
The production
same
of butane
62
SERIES.
by the formula,
H H H H
H-C-C-C-C-H,
or
C 2H5 -C 2H5
.CH 2 .CH 3
of formation of
its relation to
propane.
regarded as propane in which one
of hydrogen has been displaced by the monovalent
When, however, the graphic formula of progroup.
Butane, in
CH3-
CH3 .CH
to
atom
or
' ,
may be
fact,
it
all
H H H
H-i-C-i-H,
i A i
or
CH 3 -CH 2 -CH
9,
CH (CH3
or
(a)
)2
(a)
(a)
atom which
is itself
combined with
H
H-C
H
C-H,
--
or
CH3 -CH-CH
3,
or
CH(CH3 )3
CH8
Isobntane.
(n.)
whereas,
if
63
SERIES.
all
of the
different.
next important to note that the above two are the only
which can be constructed with four atoms of carbon
and ten atoms of hydrogen, if it be assumed that carbon is
All formulae such as
tetravalent and hydrogen monovalent.
It is
formulae
H
TT
H
TT/
H/
will,
-y
H
or
H//
i.
represents the constitution of butane, that of isobutane or trimethylmethane is expressed by formula u.
This
conclusion is confirmed by a study of the methods of forma-
formula
tion
Pentanes.
by the
formulae,
Except when otherwise stated, all the boiling-points given in this book
refer to ordinary atmospheric pressure.
64
HHHHH
H
SERIES.
HHH
H H
HHHHH
H H
x
I
-n
H-C-H
A
Pentane.
Isopentane.
Tetraniethylmethane..
all be regarded as derived from the butanes (pentane and isopentane from normal butane,* tetramethylmethane
- group for one
from isobutane) by the substitution of a
3
They may
CH
atom
of hydrogen.
C 4 H 10 and
,
When
C 5 H 12 and
,
three isomerides only are known; more could not be represented by graphic formulae, assuming always that carbon is
tetravalent.
and observed
character of carbon.
Compare
p. 65.
hydrocarbons, 'C 6
65
isomerides
molecular
less
than
C? H
16>
the
number
of carbon
becomes
rapidly
formuk
As
C 8 H 18 and no
18 of the formula
C 13 H 28
02 of the formula
could, theoretically, be
The
by the terms
A normal or
which no carbon atom is directly
normal or primary,
.CH3
as, for
example,
CHs-CH^CHyCHo-CH^CHs.
Normal Hexane.
Normal Butane.
CH
CH3
Isobutane (or Trimethylmethane).
atom
Di-isopropyl.
CH
CH3
CH
CH3 - C - CH
C - CH3
CH3
CH3
CH3
Tertiary Pentane
(or Tetranietliylinetliane).
Tertiary
Hexane
(or Triinethylethylniethane).
name which
Drg.
66
SERIES.
only
The
class, or generic,
name
'
'
was
paraffin
parum
was given
to it for this
reason.
Butane,
Pentane,
CH^
C 2H6 j
{
C3H8 {
C4 H 10
C5 H 12 f
many homologous
series of organic
compounds.
General Formulae.
members
of a
formula.
is
C w H2M+2 which
)
=
=
hydrogen ; in propane, C 3 H 8 for example, n 3 2w + 2 8.
That this is so can be readily seen by writing the graphic
formulae of some of the paraffins in the following manner
,
HH
C-C
HH
H
H
H H
67
SERIES.
HHH
C-C-C
HHH
H H
when
are
is
member
chemical
the
of
a detailed account
properties,
may be omitted
series
if
be
of each
compound
increases.
The following
is
summary
Series.
Saturated hydrocarbons of
Methane (1), CH 4
Ethane (1), C 2 H 6
Propane (1), C 3 H 8
Butane (2), C 4 H 10
Pentane (3), C 5 H12
Hexane (5), C 6 H 14
Heptane (9), C 7 H 16
Octane
Nonane
Decane
(18),
(35),
(75),
C 8 H 18
CgH^
C 10 H 22
Occurrence.
The paraffins are found in nature in enormous
quantities as petroleum or mineral naphtha, in smaller quantities
as natural gas, and as earth -wax, or ozokerite.
68
Methods of Preparation.
salt of a fatty acid (p. 145)
SERIES.
(2)
By
compounds,
(3)
By
CHC1 + 2H = C
pounds (Wtirtz),
2C 2 H 5 I + 2Na = C 2 H 5 -C 2 H 5 + 2NaI
2CH 3 I + 2Na = CH 3 .CH 3 + 2NaI.
(4)
By decomposing
(Frankland),
(p.
(5)
By
alkyl derivatives,
(p. 142),
first
four
members
Physical Properties.
colourless gases under ordinary conditions, but they are liquefied
fairly easily and the more readily the greater the number of carbon
The meaning
of the
word alkyl
is
given on
p. 117.
69
SERIES.
members
solids,
They
are,
The
directly
series.
70
SERIES.
number
collected in fractions.
in this
way,
Petroleum ether
(b.p.
and
When
this tar is fractionally distilled, it yields several liquid products similar to those obtained from petroleum such as photogene
and
*
All petroleum products of low boiling-point are highly infiai
and form explosive mixtures with air (use in gas-engines)
they should
be handled with extreme caution.
;
CHAPTER
71
SERIES.
V.
UNSATUBATED HYDROCARBONS.
THE OLEFINES, OR HYDROCARBONS OF THE ETHYLENE
When
paraffins,
SERIES.
CH4
Ethane,
Ethylene,
CH 2
carbon
C 2 H6
C2 H4
of
(methylene),
;
;
Propane,
Propylene,
the series
is
C3 Hg
C3 H 6
Butane,
Butylene,
CjH^
C4 Hg.
which would
correspond
with
The word
'
making
'olefine'
gas, a
name
is
is incapable of existing.
derived from 'olefiant' or
'oil-
on account
of its property of
forming an oily liquid (ethylene dichloride
or Dutch liquid) with chlorine ; the term ' olefine ' is now
applied as a generic or class name to all the hydrocarbons of
the series.
72
is
SERIES.
to a great extent
due to
ethylene.
is
a sealed tube,
Ethylene
succinate
is
is
also
240)
(p.
is
by
obtained
Ethylene is prepared by heating ethyl alcohol with concentrated sulphuric acid or with phosphoric acid ; the reaction
may
but in reality
it is
not so simple
(p. 186).
sulphuric acid
placed in a capacious flask (fig. 17) and heated to about
165, the gas thus produced being passed first through water and
then through a solution of potash, to free it from sulphur dioxide
and carbon dioxide, and finally collected over water; when the
evolution of gas slackens, a further supply may be obtained by
dropping a mixture of 1 part of alcohol and 2 parts by weight
(150 g.)
is
of sulphuric acid
constant.
owing
The
73
SERIES.
C 2 H 5 Br + KOH = C 2 H 4 + KBr + H 2 0.
The
condenser
(p.
190),
Fig. 17.
Ethylene
unpleasant
60 atmospheres
readily in
flame,
and forms
is
it
alcohol
and
a
highly explosive
mixture with
oxygen,
C 2H4 + 30 2 = 2C0 2 + 2H 2
+ 6 vols. = 4 vols. + 4 vols.
2 vols.
air
or
74
SERIES.
temperatures (in
of
presence
C 2 H4 + H 2 = C 2 H 6
it is not acted on
by hydrochloric acid, it combines directly with concentrated hydrobromic and hydriodic
acids at 100, forming ethyl bromide and ethyl iodide
Although
respectively,
C 2 H 4 + HBr = C 2 H 5 Br
It
C 2 H 4 + HI = C 2 H 5 L
C 2 H4 + X 2 = C 2 H4 X 2
It
is
absorbed
sulphuric acid,
(X =
Cl,Br,I).
hydrogen sulphate
C H4 + H
2
(p.
\85),
so 4 = C.HS-HSO,.
Constitution of Ethylene.
Ethylene is formed when ethyl
bromide, a mono-substitution product of ethane, is heated with
alcoholic potash, which simply takes away one atom of hydrogen
H 4 + HBr)
of bromine (C 2 5 Br
C2
the
constitution
of
bromide
fore,
ethyl
is
since, there-
represented by the
formula,
H H
\
(&)
()
C H,
that
of
ethylene
would
be
H H
II
H-C-C
H
(i.),
Br
(a)
H H
H
C C
(H.) if
one of the
(b)
removed.
But
ethylene
C 2 H 4 Br 2
75
SERIES.
H H
H
of the paraffins,
it is
Br
known
Br, because,
CH3-
H H
represented by the only alternative formula,
H C
H.
Br Br
This being the case, the constitution of ethylene might
But such a formula does
be expressed by formula (H.).
not indicate that carbon
is
H H
H C C H
I
to
are tetravalent
still
group.
monad atom
or
H H
H-C=C-H
CH
CH
=
or
orCH 2 :CH 2
ethylene by the formula
2
2
the two carbon atoms being joined by two lines, bonds, or
linkings this formula is not quite the same as that just given,
,
indicates that the particular portion of the combining power of each of the carbon atoms, which before was
represented as doing nothing, or free, is in some way exerted
because
in
'
it
satisfying,' or
There are at
least
76
SERIES.
bonds;
H
prepare hydrocarbons such as
H
C
or
H, a fact
it
is
CH2 - C0 H+
=| - +
CO 2 HCH2 .COOH CH2
CH -COOH
2
CH
+2C0 2 +
=||
CH
again,
CH2
:
CH2
+ 2CU 2 I 2
||
combination
ethylene
with
77
SERIES.
for
bromine,
is
example,
expressed graphically,
and
its
paraffins,
H H
H H
C = C + Br Br = Br
Br,
except by substitution.
The substances formed by the direct union of unsaturated
compounds with atoms or groups of atoms are called additive
products, in contradistinction to substitution products.
saturated compounds always combine with 2, 4, 6,
Un&c.,
Ethylene dichloride,
C 2 H 4 C1 2
or
CH
131;
2-21 at 0.
It is isomeric
and
boils at
with ethylidene
CH
vinyl
CH
a halogen, because
way.
They
additive
are the
first
CH
(p.
82),
Vinyl chloride
is
78
SERIES.
propyl alcohol
105),
(p.
It is
prepared by
with alcoholic potash,
Propyl bromide,
Isopropyl bromide,
it
liquefies
CH
.CH 2 .CH:CH2
Normal or
CH 3 .CH:CH.CH3
The isomerism
Iso- or y-butylene.
/3-Butylene.
-butylene.
of the first
two compounds
is
due
to a differ-
^>C:CH-CH
and
boils at
32.
it
is
a colourless liquid,
79
Olefine or
of the general
Ethylene
Series.
C n H 2n
formula
Unsaturated hydrocarbons
series,
Ethylene (1),
Propylene (1),
Butylene (3),
C2 H 4
C3 H 6
C 4 H8
Amylene
(5),
Hexylene
(13),
C 5 H 10
C 6 H 12
such as
+ H 2 O.
By
(p. 174),
By
their
potassium
2 O.
better, of
salts,
CH .COOH CH
2
+2C0 2 + H 2
=11
!
CH -COOH CH
2
all
The
nascent hydrogen,
CraH 2 n + 2H = CnH^n-f 2-
CH .CH:CH
3
+ C1 2 = CH 3 .CHC1.CH 2 C1.
80
SERIES.
rule,
CH
iodide,*
3,
and
so on.
Fuming
CH2 :CH
Hypochlorous
acid, in
chlorohydrins
(p. 228).
CH
same number
of
(p.
224)
butylene,
CH CH
=
this group, on oxidation, is in the first
place converted into the group
The compounds thus
CH(OH)-CH(OH)
formed readily undergo further oxidation in such a
way that the
,
Propylene,
and formic
acids,
The
relation
Compare
SERIES.
of
the acetylene
between
members
foot-note p. 265,
the series
is
Paraffins,
C n H2n _ 2
CMH2n+2
81
SERIES.
Olefines^
C n H2
,t
Acetylenes,
C w H 2n _ 2
Methane,
CH4
Ethane,
C 2H6
Ethylene,
C 2 H4
Acetylene,
Propane,
C 3H8
Propylene,
Allylene,
C 4 H 10
C2H2
C 3 H4
Butane,
C 3 H6
C4 H8
Crotonylene,
C 4 H6
Acetylene,
C 2H 2
Butylene,
,
the simplest
member
when hydrogen
arc is passing
electric
number
alcohol,
compounds, starting
salt of
p. 72),
may be
(compare
p. 73),
F^
82
In the
first
place,
SERIES.
(C 2
is to burn
with
a
of
insufficient
for
coal-gas
supply
oxygen
complete
combustion.
when
When
calcium carbide
left
is
exposed to the
air it
quickly
absorbs
being evolved,
= C 2 H 2 + Ca(OH) 2
CaC 2 + 2H 2
This reaction
is
made use
the gas.
a colourless gas,
is
which
SERIES.
83
liquefies at 1
under a
When burnt in an
great violence when ignited.
or
from
an
flat-flame
burner, acetylene
ordinary
open gas jar
gives a very smoky flame, this behaviour being shown, but
to a less extent, by all hydrocarbons which contain a very
explodes
ivitJi
the flame
is
almost dazzling in
its
brilliancy
specially
con-
prevented and
and very
rich
Copper acetylide,
C 2 Cu 2
is
a brownish-red
amorphous com-
pound which
is
as
a delicate
84
Silver acetylide,
pure acetylene.
SERIES.
When
acetylene
is
hydrogen
formed,
is
2C 2 H 2 + 2Na = 2C 2 HNa + H2
'
'
C 2 H 2 + 2H = C 2 H4
It
C 2 H 2 + 4H = C 2 H 6
light,
H C1
2
forming
with hydrochloric
passes over,
Acetaldehyde
a
is
warm aqueous
also
acid.
is
frequently
85
SERIES.
employed as a method
investigations.
When
is
acetylene
it is
converted
3C 2 H 2 = C 6 H6
Constitution of Acetylene.
ethylene dibromide
may be
The formation
of acetylene from
expressed by the equation,
H H
H-C-C-H = C H + 2HBr,
2
Br Br
so that the constitution of the
H H
C
H-C-C,
H H
-C-C-
H
or
H-C-C-.
II
II
ii.
i.
Since,
gen,
is
in
H H
c=c
But
and
it is
written,
CH;CH.
at the
actively
or
satisfying
is
86
by the formula
which
recalls
two
compounds.
is
The formation
or
the
of acetylene
by the
CH COOH
constitution
of acetylene
its
CH COOH
of
capable
This view of
CHiCH,
it
monad groups
of
pairs
SERIES.
CH
C0 2
+
CH
CO 2
H
H
CH
=111
CH
+2CO 2 + H 2
Fumaric Acid.
When
the hydrocarbon
CH CH + 2H = CH 2 :CH 2
CH CH + Br
1
= CHBr:CHBr.
compounds,
CH 2 :CH 2 + 2H = CH 3 -CH3
CHBr:CHBr + Br2 = CHBr2 .CHBr2
H H
CH
+
I
;H
Two
known
V
o
CH3
I
H c=o
CH
.C!CH
and
Allyleue or Methylacetyleue.
CH2 :C:CH2
Alleue.
C 3 H4
are
87
SERIES.
CH
:C:CH 2
the latter,
occur even
when
the carbon
'
skeleton
'
or
framework
is
the
may be
ticular
carbon atom
is
C M H 2n _ 2
CH
CH .CHBr.CH
3
Br + 2KOH = CH 3 -C
CH + 2KBr + 2H
O.
is
potash,
a liquid boiling at 27-28 ; it does not form copper or silver derivatives with ammoniacal solutions of cuprous chloride or silver
is
nitrate,
Diallyl,
olefine
CH :CH.CH
2
series,
.CH 2 .CH:CH2
which allene
of
(see
is
above)
Diallyl
(p.
by warming
allyl
iodide
Br + 4KOHCHoBr.CHBr.CHo-CH
"
2 .CHBi-.CH 2
CH C.CH2 .CH2 -C CH + 4KBr + 4H2 O.
;
88
SERIES.
is
and
silver derivatives.
CH
.C;C.CH 3
Methods of Preparation.
By
By
tlie electrolysis of
0.
CH-COOH
CH
Je. COOH
CH
+ 2C0 2 + H 2
Physical
series
up
odour.
alcohol,
to
the group
,
89
SERIES.
at 325,
In the case of
in such a
all
way
CH -CH 2 .CHO.
3
CH
C H + 4H = C H 6
C H 2 + 2H = C.,H
CH -C CH + Br = CH3 -CBr:CHBr
2
Like the defines, they are readily oxidised and finally converted
into compounds containing a smaller number of carbon atoms in
the molecule.
CHAPTEE
VI.
The monohydric
general formula
C nH 2n+1 -OH,
as
regarded
of the monovalent hydroxyl-group
HO-
for
one atom of
hydrogen.
Methyl
alcohol,
Ethyl
Propyl
CH8 -OH,
C 2 H 5 -OH,
C 3 H r OH,
,.
ethane,
propane,
CH 3 -H
C 2 H 5 -H
C 3 H r H,
&c.
CH
occurs in
Methyl alcohol, 'wood-spirit, or carbinol,
3 -OH,
nature in several substances, amongst others in combination
as
methyl
salicylate,
When
in oil of winter-
this oil
is
distilled
90
with dilute
alcohol
an
potash,
collects
in
the
aqueous solution of
pure
methyl
receiver.
into
vessels,
KOH = CH
-OH + KC1.
Methyl alcohol
the receiver
is
and wood-coke
or charcoal remains.
2CH3 .OH + C 2
this crystalline
substance
is
= C2
(CH3 ) 2 + 2H 2
drained on a
filter
pump,
de-
is
a colourless,
91
mobile liquid of
sp.
gr.
20;
boils at
it
oxygen,
varnishes,
and
for
the
of
preparation
methylated
spirit
101).
(p.
with
which
is
Sodium
by sodium.
but can be obtained in a solid condition by evaporating the solution in a stream of hydrogen \ it is a colourless,
alcohol,
crystalline,
CH 3 .ONa + H
= CH 3 -OH + NaOH.
it
92
CH 3 -OH + H 2 S0 4 = CH 3 -HS0 4 + H 2
2CH3 -OH + H 2 S0 4 = (CH 3 2 S0 4 + 2H 2 0.
)
When
manner.
Methyl alcohol
is
* These reactions
only take place to a small extent ; the principal products
are eaters of phosphorous or phosphoric acid,
dioxide
Cl2+H 2 O=2HCl + 0.
Nitric acid gives up some of its oxygen and is reduced to an oxide of
nitrogen, the nature of which depends on that of the substance undergoing
oxidation, and on the conditions of the experiment,
2HNO3 = H2O + N2
Chromic acid
2HNO 3 = H2 O + 2NO 2 + O,
+ 2O
&c.
and
a chromic salt,
or
A mixture
K Cr
2
is
decomposed, yielding a
five instead
CH3 .OH +
= CH 2 + H 2
93
acid,
CH
= CH 2
is
Formic Acid,
Formaldehyde.
CH4 0,
is
displaceable
is
formed by
th*- three
known
to
be
by metals.
It is
evident, therefore,
H
H-C-0
H
H, which
is
usually
written
CH 3 -OH.
When
as, for
,
PBr5
example,
&c.
is
when
recalled
sodium.
Methyl
alcohol, in fact, is
with acids
(p.
174),
forms
salts
94
it
contains dis-
placeable hydrogen,
Zn(OH) 2 +
It
may
of the paraffin,
because
2KOH = Zn(OK) + 2H 2 0.
it
methane
it is
C 2 H 5 -OH,
contained in all fermented liquors it occurs in plants in combination with organic acids.
It may be obtained from ethane by converting the hydrocarbon into ethyl chloride and heating the latter with dilute
;
alkalies
under pressure,
C 2 H4 + H 2 S0 4 = C 2 H5 -HS0 4
C 2 H 5 -HS0 4 + H 2 - C 2 H 5 -OH + H 2 S0 4
also
by
amalgam and water,
with sodium
warm
froth
After
being evolved by passing the gas into lime-water.
about twenty-four hours' time the yeast is filtered off, and
is
95
The
distillate
It is poured
an aqueous solution of slightly impure alcohol.
into a retort or flask connected with a condenser, and a con-
lumps
distilled
this prosufficient
is
less
Wines, beers, and spirits contain alcohol, and its preparafrom these liquids is very simple. The liquid is distilled,
tion
and the alcohol, thus freed from colouring matter and other
solid substances, is then dehydrated by distillation with
caustic lime
Alcohol
it
at
78,
use in
is
its
C 2 H 5 .OH + 30 2 = 2C0 2 + 3H 2 0.
mixes with water in
of heat
and diminution
evolution of hydrogen
all
of
2C 2 H 5 .OH + 2Na = 2C 2
or ethoxides,
96
alcohol,
C 2 H 5 .OH + HI = C 2 H 5 I + H 2 0.
When treated
is
it
converted into
is
readily oxidised
by chromic
is
acid,
C 2 H5
OH +
= C 2 H4
+ H2
C 2 H4 +
By
= C 2 H4
Acetic Acid.
Acetaldehyde.
mycoderma
aceti, it
is,
under
The presence
may be
detected
small quantity of
by Lieben's iodoform reaction (p. 178).
iodine is placed in the solution, and after warming gently potash
is added drop by
drop until the colour of the iodine disappears.'
If alcohol be present in considerable
quantity, a yellow precipitate
of iodoform
is
In
appearance
of
By
its
possible to detect
part of
97
little
colourless
its
and
its
six
atoms of hydrogen
close
it
is
dis-
H H
H
is
resemblance to methyl
placeable by
alcohol in chemical properties, lead to
metals,
C O
H,
or
H i
C 2 H 5 -OH.
It
may be
regarded
stitution product of ethane.
When
ordinary
the juice
as
monohydroxy-sub-
Alcoholic Fermentation.
of grapes
it
temperatures,
and fructose
glucose
is
called fermentation,
change
is
termed a ferment.
by the
process of fermentation.
The ferment which brings about the conversion of grapewine is present on the grapes and stalks and in
the air
it is a living
organism, and during fermentation
mineral
it
and
rapidly grows
multiplies, feeding on the sugar,
In
in
the
and
contained
substances
salts,
juice.
nitrogenous
order that fermentation may take place, the conditions must
juice into
;
Org.
98
be favourable to the
life
of
The malt
tion
and
is
now heated
at
50-100 in order
to stop germina-
which
it
The
solution
('wort')
diastatic fermentation,
are
added in order
sets in,
the
to
is
now
the
After
the preservative properties of the hops.
cooling to from 5 to 20, yeast is added, when alcoholic fermentation sets in, the sugar maltose being gradually converted
account of
to give
it
a flavour.
The production
the
first
of beer involves
two
malt
is
distinct fermentations.
In
3(C 6 H 10
Starch.
5)
+ H 2 = C ls Hn O u + C 6 H 10
Maltose.
5 ;
Dextrin.
yeast,
C 12 H 22 O n + H 2 - 4C 2 H 6 + 4C0 2
by the
99
One of the ferments cannot do the work of the other ; yeast cannot
convert starch into maltose, nor can diastase set up the alcoholic
Diastase is an amorphous substance,
fermentation of sugar.
without definite form or structure, and apparently lifeless. Such
ferments are termed enzymes, in contradistinction to living organised ferments of definite structure, of which yeast is an example.*
figs.
18 and 19.t
Fig. 18.
When
Burton Yeast.
Fig. 19.
London Yeast.
between about 5
and 30;
if
it
fructose
or
fruit-sugar,
C 6 H 12
and maltose,
C ]2 H 22 O n
the
Brewery.
100
yeast,
C 12 H 22 O n + H 2 = C 6 H 12
Sucrose.
The
alcoholic
+ C 6 H 12
Glucose.
fermentation of
Fructose.
these
sugars
is
expressed
oil,
Fusel
oil
(p.
106)
and
is
a
;
of
is
sulphuric
and,
after
when
neutralising
methods
is
spirits, liqueurs,
and other
articles
101
For
this
purpose
spirit is
over
')
being
collected
spirit is
employed
and in the
as a solvent for
In this country a
&c., and is also used in spirit-lamps.
heavy excise duty has long been levied on spirit of wine, a
fact which acted as a serious impediment to its extended use ;
but since 1856 the Government has permitted the manufacture
and
sale of
methylated
it is so much cheaper.
Methylated spirit
cannot be separated into its constituents by any commercial
process, but the water and tarry impurities can be got rid of
ever possible, as
but
its
purification is troublesome
Alcdholometry.
sample of alcohol
and wasteful.
is,
of a
102
aqueous
spirit,
it is
its specific
weight.
The standard
scale.
is
such a
being
spirit as shall at a temperature of 51 F. weigh
exactly ^fths of an equal measure of distilled water.'
Spirits
are termed under or over proof according as they are weaker
thus 20 over proof means
stronger than proof-spirit
that 100 vols. of this spirit diluted with water would yield
or
120
100
of
If
alcohol is found
by
.Distillation
necessary
is
because
the
sugary
and
other
103
no value.
of
The percentage
known fermented
follows
of
alcohol
in
by weight
some
of
the best-
may
liquors
Port
50%
%
40%
Brandy
50
Whisky
Gin
Hock
8%
3%
Lager-beer
The members
7%
Claret
20%
16 %
Sherry
of the series
from
of
HO-
is
Propane,
form,
CH
iso-
CH3 .CH.CH3
or
may
be derived from
of
it
and isopropyl
OH
In order to distinguish between the various isomerides, the
may be considered as derivatives of methyl alcohol
alcohols
f
or
carbinol,
CH 3 -OH
or
"FT
CJ
Thus,
propyl
alcohol,
[OH
CH
- groups
for
Such names
as
C 4 H 9 -OH,
104
Normal butyl
alcohol, or
propyl carbinol
(primary).
pfi
'**
>CH.CH
or
.OH,
cJ
TT
^n 3
Isobutyl alcohol,
or
isopropyl carbinol
(primary).
CH 3
or
,H-OH,
/C-UH,
The
C2 H 5
Methylethyl carbinol
(secondary).
d^
x^ OTJ
CX
Trimethyl carbinol
,^.13
(tertiary).
*
propyl alcohol,
example, normal
contain the group -CH 2 -OH, and may be
considered as mono-substitution products of carbinol.
On
Primary
CH 3 .CH
-CH 2 .OH,
2
aldehydes
(p.
(p. 145),
first
into
the group
s-TT
-CH 2 -OH
into
being transformed
first
into
~C\Q
an(*
then
-CX/i
Secondary
*
The
alcohols, as,
CH 3 -CH(OH).CH 3
'
'
105
number
group
alcohols,
Tertiary
- CH 3 .CO-CH 3 + H 2 0.
CH 3 .CH(OH).CH 3 +
such
as
tertiary
butyl
alcohol,
be
(CH 3 ) 3 C(OH),
smaller
number
re-
oxida-
garded as tri-substitution
tion they yield both ketones
they are derived, the molecule of the latter being broken up.
Tertiary butyl alcohol, or trim ethyl carbinol, (CH 3 ) 3 C(OH),
for
example,
yields
CH 3 -CO-CH 3
acetone,
acetic
acid,
CH3 -CO-OH,
is
which
it
formed
when
is
prepared by
propyl iodide
fractional
is
It
distillation.
is
and water,
C 3H 7 I + Ag-OH = C 3H r OH + Agl.
It is a colourless liquid of sp. gr.
On oxidation
miscible with water in all proportions.
with chromic acid, it is converted first into propaldehyde and
and
is
CH 3 .CH 2 .CHO + H
Propaldehyde.
0.
Propionic Acid.
best
CH 3 -CO-CH 3 + 2H = CH 8 -CH(OH).CH 8
106
oxidation
it
yields acetone,
- CH 3 .CO-CH 3 + H 2 0,
CH 3.CH(OH).CH 3 +
it
gives propylene,
CH,.CH(OH).CH 8 = CH 3 -CH:CH 2 + H 2 0.
C 4 H 9 -OH. Normal
CH3 'CH -CH -CH -OH,
alcohol
',
be
or
carbinol,
propyl
may
prepared
is
Methylethyl carbinol,
-CH(OH)-C 2 H 5 is obtained by
ketone, CH 3 -CO-C 2 H 5 (p. 137), with
CH
It boils at 99
(CH
Trimethyl carbinol,
3) 3
(740 mm.).
the
CH
at
25, and
boils
83-84.
Amyl alcohols, C 5
isomerides theoretically
two occur in fusel oil
H n -OH.
capable
Of
of
the
eight structural
the following
existing,
CH 3v p
CH/
Isobutyl carbinol,
(Isoamyl alcohol.)
^ >CH-CH
r^TT
nTT
p'H 2 .UH
p 2 -UH.
.OH.
B.p. 129.
L/xlg'Uxlg
= C 5 H n .HS0 4 + H 2O.
107
By
neutralising these
salts,
C 5 H n .HS0 4 + H 2 = C 5 H n -OH + H 2 S0 4
Commercial amyl alcohol is prepared from fusel oil by fracand is a mixture of about 87 per cent, of isobutyl
It has
carbinol and about 13 per cent, of active amyl alcohol.
a pungent, unpleasant smell, boils at about 130, and is used as a
solvent, and in the preparation of essences and perfumes (p. 193).
tionation,
letters p.,
s., t.,
and
tertiary respectively.
(p.) ...........
Isopropyl alcohol
Butyl alcohol (p.)
(s.) ........
............
\PHOH
j^s^rv
f4,
w nw
0-812 at
78
0-806
97
82
107
<i
other
little
isornerides
of
importance .........
'
..
"
((
,.
816
Q 827
131
Six
0-823
0-786
129
n-
817
816
83-
Isoamyl alcohol
'
ggo
.-.
(p.) .........
-i
r ^Jtiii-uri,
Sp. gr.
66
117
>,
IP
B.p.
afc
2QO
.,
"
0-825
..
'
108
C 2 H 5 I + C 2 H 3 O 2 Ag = C 2 H 5 -C 2 H 3
Silver Acetate.
C 2 H 5 .C 2 H 3
+ Agl
Ethyl Acetate.
= C 2 H 5 -OH + C 2 H 3
2 + KOH
K.
This method gives very good results, and is much used in the
preparation of the higher alcohols, because the halogen derivatives
of the higher paraffins (such as hexyl chloride, C 6 13 C1), wheni
treated directly with alkalies, are mainly converted into olefines,
CH
CH
3
3
water,
C 3 H 6 + H 2 S0 4 = C 3 H 7 .HSO 4
C 3 H 7 .HS0 4 + H 2 = C 3 H 7 -OH + H 2S0 4
and when aldehydes and ketones are reduced with nascent hydrogen, aldehydes giving primary, ketones secondary, alcohols,
CH
crystalline
compound,
CH
which
/0-Zn-CH
^0
+Zn(CH =CH -C^CH
XC1
X C1
3 -C<;
3 )2
is
methyl,
/0-Zn.CH 3
/~^TT
f*i
f^TT
\P1
-U 7"iiff"^T-T
\J\.
323
^
OTT
/0-Zn-CH3
C^~-
Ol-T
/^TT
7-n C^\
8
v^Xlo
This product
X)-Zn.CH3
~,
^CH 3
/OH
+2H 2 O = CH 3 -C^CH3 + Zn(OH) 2 + CH 4
109
The
.CH :CH 2 + H 2 O.
olefine is
hydrogen atoms,
34
PTT 3
:
>CH -S0 H.
4
H+H =
2
a secondary
*>CH.OH + H2 S0 4
SO 4 H
~*
OH
CH3
No
The
gaseous alcohols are known.
members up to C^H^O are, with few exceptions, neutral, colourless
liquids, possessing a characteristic odour and a burning taste.
Trimethyl carbinol and all the higher alcohols, such as cetyl
alcohol, C^Hgg-OH, which occurs in spermaceti in combination
with palmitic acid, and melissyl alcohol, C 30 61 -OH, which is found
in beeswax, also in combination with palmitic acid, are solids.
Methyl, ethyl, and the propyl alcohols are miscible with water,
but as the series is ascended the solubility in water rapidly
Physical Properties.
decreases, the
soluble.
The
The sp. gr. gradually increases, and the boilingpoint rises on passing up the series ; the primary alcohols, however,
boil at a higher
temperature than the secondary, and the latter at
a higher temperature than the tertiary isomerides, as shown in the
organic liquids.
table
(p. 107) ; the regular variation in physical properties is, thereobvious only when alcohols of similar constitution are comIt may also be pointed out that, as a rule, the first member
pared.
of a homologous series shows a somewhat abnormal behaviour ;
fore,
110
example, methyl alcohol has a higher sp. gr. than ethyl alcohol,
its boiling-point is only 12 lower than that of ethyl alcohol
in the case of the higher homologues, the difference between the
boiling-points of two consecutive normal alcohols is about 20.
Chemical Properties. The fact that the alcohols interact with
other compounds so much more readily than the paraffins is due to
the presence of the hydroxyl- group, the rest of the molecule
remaining unchanged, except under exceptional circumstances.
In many reactions the alcohols behave as alkyl substitution products of water in others, their similarity to metallic hydroxides
is more marked.
They dissolve sodium and potassium with evolution of hydrogen,
for
and
CH
3 C1,
C 2 H 5 Br, C 3 H 7 .HSO 4
CH r COOC H
2
5.
of the paraffins
foot-note p. 92),
amorphous
They
CH
The
same number
by their
different
THE ETHERS.
CHAPTER
Ill
VII.
THE ETHERS.
The
ethers, such as
CH
ether,
-0'C 2
5,
CH
methyl
ether,
&c., are
same way
Methyl
of sulphuric acid
the action
on methyl alcohol,
a gas which
liquefies at
readily in water (1
ether at 18).
vol.
23
of water dissolves 37
C 2 H 6 -ONa + C 2 H 5 I
---
C 2 H5 -O.C 2H 5 + Nal.
is
2C 2 H 5 .OH _ C 2 H 5 .0-C 2 H 5 + H 2 0.
Ethyl ether is prepared by the following method
A mixture of five parts of 90 per cent, alcohol and nine
parts of concentrated sulphuric acid is heated in a flask fitted
:
now
112
THE ETHERS.
is
sulphur dioxide.
purified
by
redistillation
from a water-bath.
by adding pieces
The
ether
may be
still
got rid of
some
Fig. 20.
(p.
185),
compound then
sulphuric acid,
and
THE ETHERS.
113
is
Now,
when
the latter
is
process*
Ether
is
colourless,
mobile,
neutral,
pleasant-smelling
its
CH
4
10
air or
oxygen,
+ 60 2 = 4C0 2 + 5H 2 0,
Ether
and
all
is
is
all
proportions.
Compared with
is
THE ETHERS.
114
Ether
an
5) 2
(C 2
H
H
5) 2
is
anaesthetic,
when
+ 2H 2 S0 4 = 2C 2 H 5 -HS0 4 + H 2
+ 2HI = 2C 2 H 5 I + H 2 0.
(C 2
inhaled
since,
;
it is
as a solvent
employed
is produced by the
on sodium ethoxide, C 2 5 -ONa,
it may be concluded that it is formed by the substitution
of the monovalent C 2 5- group for the sodium atom, and its
constitution may be expressed by the formula C 2 5 -0-C 2 5
C 2 H 5 I,
When
represented by
the behaviour of ether are brought to mind.
Ether, unlike
alcohol, contains no HO- group, and therefore it is not
acted on by sodium or potassium, or by phosphorus pentachloride ; and, not being a hydroxide, it does not interact
Ether was formerly
with acids to form a salt and water.
from alcohol
from
same way
as nitric anhydride
is
formed
nitric acid,
2C 2 H 5 .OH = (C 2 H 5 ) 2
+ H2
It is better
hydroxides,
C2 H 5 -OH
K-OH
Finally, it
C 2 H 5 .0-C 2 H 5
K-O-K
.
may be regarded
or
or
(C.H^O
K 0.
2
as a di-substitution product of
H.OH
C 2 H 5 .O.H
C 2 H 5 -O.C 2 H 5
THE ETHERS.
The
115
properties.
of the
Dipropyl ether
ether
Di-isopropyl
)2
>CH)
.............................
B.p. 90-7
...........................
69
>CH.CH ) O .......................
H
n O ......................................
Di-isoamyl ether (C
3
Di-isobutyl ether
122
2 2
)2
173
CH3 -O-C 2 H
5.
The formation
All
5,
contain
hydrocarbon groups are termed mixed ethers, to distinguish them from simple ethers, such as ethyl ether, C 2 H 5 -O-C 2 H 5
and those given in the above table, which contain two identical
Mixed ethers can also be obtained by treating the sodium
groups.
compounds of the alcohols with alkyl halogen compounds,
two
different
+ Nal.
THE ETHERS.
116
(C H O + 2H S0 4 = 2C H .HS0 4 + H O
CH -O -C2 H 5 + 2HBi CH 3Br + C H Br + H
2
5 ).2
2 0.
CH
The
C1.0.CH 3
CH
formula
compounds
of the
CH3 .O.CH
.CH 2 .CH 3
are, for
C4 H 10 0,
CH .O.CH< ui3
3
3
CH
example, three
Ethyl Ether.
These three ethers are also isomeric with the four butyl alcohols
C 4 H 9 -OH
(p. 104).
RADICLES.
On
of organic
is
particularly noticeable.
Ethyl chloride, for example, may be
converted into ethyl alcohol, the latter may be transformed
into
ethyl
butane,
iodide,
but during
and
all
this again
may
be converted into
these
single atom,
of
similar kind
might be quoted;
CH
CH
and
.CH 3 may
3
8 J,
3
be successively transformed one into the other.
Groups of atoms, such as C 2 5 and CH 3 -, which act
,
of
radicles.
CH
117
RADICLES.
its
valency equivalent,
as
or alcohol radicle is given to all the monoatoms which are, theoretically, obtained on
taking away one atom of hydrogen from the paraffins, methane,
valent groups of
radicles
CH -CH2-;
3
C3 H 7 -
thus
yl,
propyl,
CH - ethyl, C H 5- or
CH3 -CH -CH - isopropyl,
C4 H 9- or CH 3 .CH -CH 2 .CH -;
methyl,
or
or
isobutyl,
C 3H r-
&c.
of these hypo-
H -C1,
5
letter
are
is
alkyl radicle,
as, for
R-O-R
(simple
represent any
frequently employed
example, in the formulae R-OH (alcohols) and
ethers).
C 3 H 7 -C1,
The
CH 3-, C H
instead of
radicle
case
(CH
Pr3
The name alkylene
3)2
is
(except methylene)
is
may be
CH =
2
C 4 H 8 =,
chlorine, for
ethylene,
paraffins.
C2H 4 =
The alkylenes
propylene,
C3H 6=
are
buty-
&c.
such as glyceryl,
=CO
carboxyl,
-CO-OH
are.:
hydroxyl,
cyanogen,
-CN
C 3 H5 =
-OH;
acetyl,
118
-CO-CH3
nitro,
-NH
-N0 2
2,
and
groups.
One of
CHAPTER
determine the
VIII.
primary
two atoms
of
series
of the general
CnH2n O,
formula
or
Alcohols.
Paraffins.
Aldehydes.
H-CH3
H-CH 2 -OH
H-CHO
CH 3 .CH3
CH 3 .CH .OH
CH 3 .CHO
C H .CHO
C 2H 5 .CH 2 -OH
C 2 H 5 .CH 3
it
is
by a process of oxidation.
Formaldehyde, or methaldehyde,
is
H-CHO,
is
said to occur
those
plant
Formaldehyde
cells
is
is
reduced,
is
passed over
warm
palladium.
119
the change
a process of oxidation,
is
30-40 per
as
On
alcohol.
solution
which
collects in the
may
much
The formation
strated
and
taking place.
is a gas at ordinary temperatures, but when
condenses to a liquid, boiling at -21.
Even at
Formaldehyde
cooled
this
(p.
it
121),
rapidity,
of heat.
H.CHO + O=H.COOH.
When
its
aqueous solution
is
mercurous chloride,
is
is
then to mercury.
Formaldehyde
*
and
is fatal
to
120
preservative,
and
as a reducing agent.
a substance which
it
very readily
Constitution.
Since carbon is tetravalent, there is only
one way of expressing graphically the constitution of formal-
dehyde,
CH 2 0,
formation
alcohol,
group
is
/TT
H-C.
In the
CH -0-H,
compound,
and
poses into
2
atom in formaldehyde
decom-
oxygen
it
indicates the
is
evaporated
it is
a colour-
121
(CH 2 0) 2
Trioxymethylene, or metaformaldehyde, (CH 2 0) 3 is formed
by the polymerisation of anhydrous liquid formaldehyde (p. 1 1 9),
and also when paraformaldehyde is carefully heated ; it is an
.
indefinitely crystalline
melts at 171.
When
strongly heated
it
is
readily,
and
completely de-
Polymerisation.
It will be seen
140,
it
is
also converted
stated, that
the latter.
thus
it is
may show no
whatsoever
collections of
chemically to
122
whose
merely an
formation of
is,
then,
in
the
resulting
molecular
is
weight
ordinary chemical
a new compound,
of
multiple
that
of
the
latter
which
it
undergoes polymerisation
most
its
When
is
one of
aqueous solution
its
means
272).
(p.
Methylal,
CH (OCH
2
3 ) 2,
It
be
is
an important derivative of
obtained by boiling aqueous
formaldehyde.
may
formaldehyde with methyl alcohol and a small quantity
of sulphuric acid, but is usually prepared by oxidising
methyl alcohol with manganese dioxide and sulphuric acid,
the formaldehyde first produced combining with the un-
may be
CH
the
'first
spirit (p.
alcohol
filtration
through charcoal;
123
formate
di-
of
aldehyde
ammonia
transferred to a
washed with
This substance
is
ether,
Acetaldehyde,
a colourless,
at
and
0;
it
or
mobile,
boils
suffocating
at
aldehyde,
as
is
it
usually
called,
is
odour,
somewhat
like
that
of
sulphur
it
CH 3 .CHO + Ag
= CH 3 .COOH + 2Ag.
124
When
it
is
con-
When
aldehyde
sodium
JN
Jtifj
being regenerated.
Aldehyde very readily undergoes polymerisation on treatment with acids, dehydrating agents, and other substances
Its behaviour
(see below).
when
in,
it is
with alkalies
is
is
very characteristic
its
'
'
follows
Sulphurous acid
of rosaniline
Constitution.
ethyl
alcohol,
Aldehyde
just
as
is
formaldehyde
is
produced
by
the
125
CH 3 .CH .OH +
2
two hydrogen
+ H 2 0,
= CH 3 -C
= CH 3 .CH<
CH
the
hydroxyl-group.
of
constitution
this
aldehyde
view
accords very
well with
chemical behaviour of
is
the
whole
similar to
that of formaldehyde.
Aldehyde, unlike alcohol, does not
contain a hydrogen atom displaceable by sodium or potassium, and does not form salts with acids; these facts are
displaced
a
by
two
change
chloride),
atoms of chlorine
which
is
very
(giving
different
ethylidene
that
from
This point
is
CH
The
ftict that
aldehyde has the power of combining directly
with nascent hydrogen, ammonia, sodium hydrogen sulphite,
126
alcohol
must be concluded,
ammonia, &c.
-C/y
which
usually written -CHO (not COH, which might be confused with C - OH) ; it is the presence of this aldehyde
is
which
group
because
determines
the
all
nearly
undergo are
both
contain;
they
their
changes
limited
hydes
all
to
characteristic
properties,
which
two
the
these
group
-CHO
alde-
which
kind.
of
Polymerisation
poly me rides
of
Acetaldehyde.
are
aldehyde
known
Three
namely,
well-defined
aldol,
par-
CH
is produced
Aldol, (C 2 4 0) 2 or
3 .CH(OH>CH 2 .CHO,
dilute
or
of
action
of
zinc
the
acid,
chloride,
hydrochloric
by
,
is
a colourless,
shows
the
all
It can be distilled
under
H 0)
Paraldehyde,
a
drop
ordinary
It
place.
at
its
as
is
124, and
cold
it
is
distilled
of
saturated
less
colourless,
solidifies in
solution
soluble
in
acic
is
it
medicine as a
into
aldehyde.
127
Paraldehyde
is
used
in
soporific.
Paraldehyde
properties of aldehydes,
-CHO group ; in other
Metaldehyde
144).
(p.
Derivatives
of
it
md
CH 3 .CH(OC H
Acetal,
Aldehyde.
when a mixture
100, or when alcohol is
produced
and alcohol
of aldehyde
is
5) 2 ,
is
heated
104; when
id into alcohol
distilled
and aldehyde,
Chloral,
loral alcolwlate,
mtrated
sulphuric
CC1 3
OP 2 TT 5
-CH<^
acid,
and the
is
oily
distilled
distillate
chloral
listilled
with sulphuric
acid,
when pure
128
The formation
by the action
of chloral alcoholate
of chlorine
on alcohol involves a long series of reactions, which it is unnecessary to describe in detail because they are not sufficiently typical ;
it may be noted, however, that the chlorine acts here both as
an oxidising and as a chlorinating agent.
Chloral
at
97.
is
an
It has
a penetrating
and
irritating smell,
and in
sulphite,
it is
hyde
is
CC1 3 -CHO +
On
(p.
= CC1 3 .COOH.
undergoes polymerisation,
being
it very readily
transformed into a white
with
behaviour
decomposed,
boiling
giving
by which
potash,
chloroform
(p.
175)
it
and
is
quickly
potassium
formate,
is often
prepared in this way.
When chloral is poured
Chloral Hydrate, CC1 3 .CH(OH) 2
into water it sinks as an oil at first, but in a few seconds the
.
oil
a considerable rise in
hydrate melts
decomposed
on
at
57,
is
distillation
with
and
is
chloral
sulphuric acid,
In some respects it is a very stable substance ;
passing over.
it does not polymerise, and does not give the rosaniline
These facts point to the conclusion
reaction of aldehydes.
that chloral hydrate does not contain the aldehyde group,
129
but that by combination with water the chloral has been converted into a substance of the constitution
Chloral
hydrate
is
extensively
CCl 3 -CH<
OTT
used in medicine
.*
as
soporific.
CH
100;
it
boils at
medicine.
CH -CHO + CH
3
C1-CHO = CH 3 .CH:CC1.CHO + H 2 0,
Homologues of Acetaldehyde.
the
2
of
13
-COOH
(p. 160),
and on
C 6 H 13 -CH 2 -OH.
*
Very few compounds containing two hydroxyl - groups united to the
same carbon atom are known as a rule such compounds are very unstable
and readily lose the elements of water, the group >C(OH) 2 giving
;
>CO + F2
Oi*
130
KETONES.
The
CH3 -CO-CH 3
may
united
two
with
C 2 H5 ^CO-C 2 H5 and
alkyl
radicles,
as
their composition
in
CH3 -CO-C H5
2
may be
expressed by
the general formula C n 2n O ; they are isomeric with the
aldehydes containing the same number of carbon atoms.
,
Dimethyl ketone,
H 8-
occurs
in
Acetone
is
is
oxidised with
and
is
distillation of
from
and
acetone.
may be
may then be
the bisulphite
Acetone
by the dry
is
barium) acetate,
131
aqueous
distillate of
Acetone
it
is
centrated
direct
ment
of heat,
sodium
and a
bisulphite,
separates.
CH 3 .CO.CH3 ,NaHS0 3
This compound
quickly decomposed
by
being regenerated.
59.
When
treated with
formed,
is
hydroxide
agents,
by which
it is
its
molecule
CH .COCH 3 + 40 = CH 3 .COOH + C0 + H
3
0.
132
and is employed
(p. 96),
for the preparation of iodoform, chloroform, and sulphonal ;
it is also used as a solvent and in gelatinising gun-cotton in
Acetone
Constitution.
~s\CH-OH
oxidation
282).
alcohol,
loses
105),
(p.
(p.
is
it
>CH-OH
change, which
is
shown by the
the alcohols, does not form salts with acids. That the oxygen
atom is combined with carbon only that is, that acetone
-CO-
contains a
group
is
shown by
behaviour with
its
phosphorus pentachloride, which is similar to that of aldeFurthermore, the -CO- group must be united with
hyde.
two methyl -groups, as in the formula CH 3 -CO-CH 3 because
,
if
it
hyde,
CH 3 CH 2 'C^TT
-
(? 105).
These
facts,
p-rr/C
3
or
(CH 3) 2 CO
acetone
its
has
the
characteristic
>C = 0,
ketones.
The
graphic formulas
/1TT
Acetone,
TT
3
>C =
Aldehyde,
f;
>C =
therefore
those
changes,
common
which
in
133
only this
group
Such changes
to both substances.
many
acetone behaves
other reactions,
As
compound.
two compounds
as
an unsaturated
between the
group, and does not combine with oxygen without the molecule being broken up; it is therefore less readily acted on
Acetone
than aldehyde, and does not reduce silver oxide.
and many other ketones give Schiff's reaction, but the
colour usually reappears more slowly than with aldehydes ;
by far the best means of distinguishing between an aldehyde
and a ketone is to study the behaviour of the compound on
oxidation (p. 142).
Condensation of Acetone.
certain
When
acetone
is
treated with
it
dehydrating agents
undergoes peculiar changes,
two or more molecules combining together with elimination
of
2(CH 3 ) 2 CO = C 6H 10
+ H2
3(CH 3 ) 2 CO = C 9 H 14 + 2H 2 0.
Phorone.
Mesityl Oxide.
When
it is saturated with
interesting condensation products.
dry hydrogen chloride, and the solution kept for some time, a
mixture of mesityl oxide and phorone is formed, in accordance
with the above equations; but when distilled with concentrated sulphuric acid, acetone yields a hydrocarbon, mesitylene,
(Part II. p, 348), a derivative of benzene,
3(CH 3 ) 2 CO = C 9 H 12 + 3H 2 0.
134
CH3
stitution
melting at 28
is
acetone.
of
NH
H .NH-NH
with phenylhydrazine, C 6
ing condensation products.
This property
and
135
The oximes
NH
CH 3 .CH:N-OH + HC1 + H
They
which
CH 3 .CH:]ST .ONa
and
(CH 3 ) 2 C:N-OK
136
One important
difference
is,
(p.
294),
(p.
302), giving
alkyl-substituted amides,
Acetoxiine.
Metliylacetamide.
>C
as, for
1*2
They
are
iN-NH.C 6 H 5 = >C:N-NH.C 6 H 6 + H 2 0,
CH3 -CH:N-NH-C 6 H6
H5 The hydraC:N-NH-C
(CH 3 ) 2
6
importance.
compounds (compare
is
up
H-CHO
-21
CH -CHO
CH .CH -CHO
-CH 2 .CHo-CHO
)
^^u... /CH
\ (C H 3 CH.CHO
J
\ r TT n /CH3 -CH .CH .CH .CHO
2
+20-8
49
Isobutaldehyde,
Valeraldehyde,
)2
c*
H O
CH
TJ
OTT
12
C7Hl4
or (Enanthol, /
10
IsovaleraldehydeJ
C6
Capraldehyde,
rieptaiueiiycie,
B.p.
CH
CHO
CHO
Formaldehyde,
Acetaldehyde,
Propaldehyde,
Butaldehyde,
137
Wrf***r^wo*
r\
rf'TT
74
63
102
92
128
i
KX
(CH 3 2 CO
B.p. 56-5*
H
(C H
(C H
(C n H
(C H
(C H
(C 2
\
Isobutyrone, or di-isopropyl ketone/
(Enanthone, or dihexyl ketone
Laurone
Palmitone
Stearone
15
17
5 )2
CO
CO
..
"
-f
103
144
n
125
M.p. 30-5
69
83
88
CO
23 2 CO
31 2 CO
35 2 CO
13 ) 2
..
)
)
When
C 3 H 6 O, C 4 H 8 O, C S H 10 0, C 6 H 12 O,
in
of
CH
&c.,
The
isomerism occur.
first
two
members,
Methylpropyl Ketone.
Methylisopropyl Ketone.
3
,
on passing
up the series.
Both aldehydes and ketones may be regarded as derived from
the paraffins, by substituting one atom of oxygen for two atoms of
*
[CH 2]5
is
a convenient
way
of writing
138
displaced,
giving
CH
giving
is
Nomenclature.
H-COOH.
H-CHO, giving formic acid,
Formaldehyde,
CH 3 -COOH.
acetic acid,
Acetaldehyde, CH 3 .CHO,
Propaldehyde, C 2 H 5 -CHO,
propionic acid, C 2 H 5 .COOH.
,,
of
'
'
of
primary alcohols,
CH
Aldehydes
may
(C 3
In
its
to the
may
139
considered,
Stearone.
+ Zn (C 2 H 5 2 = C 2 H 5 CG1<
-
ALDEHYDES AND
140
and
ether.
Chemical Properties.
Owing to the presence of this group, they have the power of combining directly under certain conditions with two monad atoms or
their valency equivalent.
All the lower aldehydes and many* of the lower ketones form
crystalline additive compounds when shaken with a concentrated
aqueous solution of sodium bisulphite. This property is of great
value in purifying aldehydes and ketones, and especially in
separating them from substances which do not form 'bisulphite
compounds,' as illustrated in the preparation of acetone (p. 131).
These bisulphite compounds are soluble in water, but usually insoluble, or nearly so, in alcohol and ether.
They may be regarded
as salts of hydroxy-sulphonic acids^ the compounds formed by
aldehyde and acetone respectively being
'
'
CH
-CH(OH)-S0 3 Na
All
these
compounds
are
>C(OH)-S0 2 Na.
Sodium Hydroxyisopropylsulphonate.
Sodium Hydroxyethylsulphonate.
readily
With few
exceptions,
(Part
II. p. 392).
ketones
only those
containing the
group
S0 2 -OH
141
A secondary
alcohol
is
CH
-CH(OH)-CH3
The formation
of
a pinacone
may
a ketone, a substance,
T>^C<C
f^TT
>
is
momentarily produced by combination with one atom of hydroThis hypothetical intermediate product may then combine
gen.
with another atom of hydrogen to form a secondaiy alcohol
T?
OTT
or two molecules may unite to form a pinacone,
^>C<CTT
IV
-tl
-,
D ^>C
K
C-^T*.
.K
and that
142
by two atoms
of halogen.
CH
.CHBr2 ,*
CH3 .CHO + PC1 5 = CH3 .CHC1 2 + POC13
ethylidene bromide,
This reaction
may be
-CN
CH
-COOH
(compare
p. 287),
Aldehydes
differ
They
CH
Propaldehyde.
CH
Propionic Acid.
Heptaldeliyde.
-CO.CH 3 + 40 = CH 3 -COOH + CO 2 + H 2 O.
= CH 3 -COOH + CH3 .[CH 2] 3 .COOH.
3 .CO.;[CH 2 ] 4 .CH 3 + 30
CH
CH
CH 3 -CH<
is
termed ethylidene.
143
+ C0 2
is
am-
an example, are
R.CH<^
isation is the
144
O /
CH -CH, CH-CH
H-CH/ CH-H
CH
Paracetaldehyde, or Paraldehyde.
Trioxymethylene.
The method
were unknown.
their constitutions
hydrogen
place,
>CO
groups
R.C;H2 ;.CO.R')
V
R.C;H 2 ;.co.R'
R'-C;0 !-CiH 2 :]
R-CH 2 .C;O
!]
R-C-CO-R'
(Type of Mesityl Oxide).
II
R'.fc.CH 2 .R
R.C-CO-R'
R'-C-C.R
R-CH
.(
(Type
of Phorone).
THE FATTY
145
ACIDS.
identical;
CHAPTER
THE FATTY
The
fatty acids
formula
IX.
ACIDS.
form a homologous
C nH 2n+1 -COOH,
C n H2n
or
may be
they
re-
Paraffins.
H-CH 3
CH
CH
2
.CH 3
5 -CH 3
3
The term
Aldehydes.
Fatty Acids.
H.CH 2 .OH
H-CHO
H-COOH
CH -CHO
C H .CHO
CH3 -COOH
C 2 H -COOH.
C 2 H 5 .CH 2 .OH
'fatty'
was given
to
because
many
CH
nettles,
ants
When
distilled,
weak aqueous
CO + KOH = H.COOK.
When
THE FATTY
146
ACIDS.
or
C0 2 + 2H + KOH = H.COOK + H 2 0,
4C0 2 + 4K + 2H 2 = 2H-COOK + 2KHC0 3
evolved
The
acid may be obtained from the potassium salt by diswith dilute sulphuric acid.
Formic acid can also be obtained by oxidising methyl
alcohol or formaldehyde with platinum black (precipitated
tilling
platinum),
CH .OH + 20 = H-COOH + H 2
H-CHO +
- H-COOH,
HCN + 2H
and
by
decomposing
= H-COOH + NH 3 ,*
chloroform
with
alcoholic
potash
(p. 176).
Formic acid
(glycerin)
it
c.c.)
is
below this temperature, evolution of carbon dioxide commences, and dilute formic acid distils, but after keeping for
some time at 100-110 action ceases. A further quantity of
oxalic acid
is
carbon dioxide
is
again evolved, and a more concentrated
solution of formic acid collects in the receiver.
By adding
obtained
ammonia
is
an ammonium
salt are
produced.
liberated,
is
THE FATTY
the manufacture of ether
(p.
ACIDS.
147
latter distils
glycerol, to
C 2 4 H ,2H 2 O = H-COOH + CO 2 + 2H 2 O
C 3 H 5 (OH) 3 + H-COOH = C 3 H 5 (OH) 2 .O-CHO + H 2 O.
On adding more crystallised oxalic acid, the monoformm is decomposed by part of the water expelled from the oxalic acid crystals,
yielding glycerol and formic acid,
boiling
Formic acid
is
sp. gr.
0; it solidifies at low temperatures, melting
It has a pungent, irritating
again at 8, and boiling at 101.
odour, recalling that of sulphur dioxide, and it blisters the
skin like a nettle sting; it is miscible with water and
1-241 at
THE FATTY
148
ACIDS.
with litmus,
metallic
acid.
precipitates silver
hydroxide, being
itself
of
ammoniacal
silver
it is
rapidly
H.COOH = CO + H 2 0,
and when heated alone at 160
carbon dioxide and hydrogen,
in closed vessels,
it
yields
H-COOH = C
The Formates, or salts of formic acid, are prepared
neutralising the acid with alkalies, hydroxides, &c., or
by
by
salt,
250, they
H-COOK,
are deliquescent;
may be made
2H-COONa - C 2
When ammonium
is
when heated
formate
is
Na 2 + H 2
(p. 165),
(p.
288),
H-COONH4 = H.CO-NHa + H2
H-CO.NH2 = HCK + H 2 0,
Silver formate,
crystals
on adding
H-COOAg,
on exposure
is
precipitated in colourless
a neutral concentrated
silver nitrate to
it
is
unstable,
THE FATTY
149
ACIDS.
In order to
of silver
is
confirmed
is
evolved, and
may be
Constitution.
CH3 for
constitution,
H
0=i-0-H
But the second formula does not correctly indicate the behaviour of formic acid ; it represents the two hydrogen atoms
as being in the same state of combination, which is very
improbable, since one of them is, the other is not, readily
displaced by metals ; it does not recall the fact that formic
acid behaves in
indicated in the
first
H
group
=C
formula,
H-COOH.
of
the
HO-
group,
which
is
CH
THE FATTY
150
ACIDS.
of
many
and
plants,
is
It can be
organic substances.
CH
also
.ONa + CO = CHg-COONa
(p.
mineral acids,
CHg-ON" +
C 2H6 + 20 = C 2 H4
air,
C 2H4
H2
2 +
= C 2 H4
This liquid
of lime,
The
rises as a scum and is skimmed off.
evaporated to dryness, and the calcium salt
distilled with concentrated hydrochloric acid from copper vessels,
care being taken not to employ excess of acid,
'
'
empyreumatic matter
solution
is
finally
(C 2 H 3 2 2 Ca + 2HC1 = 2C 2 H 4 O 2 + CaCl 2
The concentrated aqueous acetic acid which collects in the
receiver is now mixed with a little potassium permanganate or
dichromate, and again distilled, by which means most of the
impurities are oxidised, and commercial acetic acid is obtained.
.
Vinegar.
When
beer,
or a
as claret, is
left
to
the air
C 2 H6 +
it
= C 2 H4
+ H2 0.
THE FATTY
ACIDS.
151
alcohol,
by strong
since
alcohol,
and cannot
live in
nitrogenous substances,
mineral
'
process being repeated at intervals until the vat is about halfmost of the vinegar is then drawn off, and the operaj
tions repeated with fresh quantities of wine.
full
top,
THE FATTY
152
ACIDS.
The
much more
This process
is
is
25-40.
acetic acid.
commercial acetic
Pure
acid.
by
distilling
anhydrous sodium
by neutralising the impure commercial acid with sodium carand then fusing to expel the water of
from this process contains only
The
distillate
crystallisation.
a small quantity of water, and solidifies, when cooled, to a
mass of colourless crystals ; it is then termed glacial acetic
acid in contradistinction to the weaker acid, which does not
bonate, recrystallising,
crystallise so readily.
of water in glacial
necessary.
Anhydrous
acetic
acid
is
scopic solid, melts at 16-5, boils at 118, and has the sp. gr.
L080 at 0; it has a pungent, penetrating smell, a burning
when near
flame.
its
boiling-point, burning
It is miscible
it
is
inflammable
all
proportions,
and
is
THE FATTY
153
ACIDS.
iodine, &c.,
acid,
hydroxides
unlike formic acid, it has not reducing properacid does not decolourise potassium perman-
The pure
ties.
The Acetates,
or
of
salts
acetic
acid,
are prepared
by
Sodium
acetic acid.
acetate,
C2H3
Na + 3H 2 0,
2
liberation of
is
extensively
The anhydrous
drating agent.
Ammonium
(p.
salt is hygroscopic,
Potassium
acetate is gradually
and water
164)
acetate,
CH -CO-NH + H
0.
2
on
dry
and
C 2H3
is
2
used as a dehy-
K,
is
deliquescent.
C 2H 3
.]SrH 4
precipitated in colour2
3
less crystals on adding silver nitrate to a concentrated neutral
solution of an acetate ; it is moderately soluble in cold water,
Silver acetate
is
2) 2
Cu + H 2 0,
acetic acid
it
is
is
light.
Copper
acetate,
is
2) 2
Verdigris
con-
Cu + Cu(OH) 2
manufactured by
leaving sheet-copper in contact with vinegar, or with grapeskins, the sugars in which have undergone fermentation first
into alcohol, then into acetic acid.
When washed with
is
known
salt,
(CoH 3
2) 2
Cu + (As0 3 ) 2 Cu 3
THE FATTY
154
ACIDS.
and
poisonous,
as it is liable to
decompose in presence
of hydrogen
of
or
Lead
acetate,
'
of
sugar
solving
(sugary)
solution
formed.
lead,'
is
Ferric acetate
is
dis-
and excess
iron,
ferric
clear
this property is
made use of
'
an
acetate,
it is
portion
of
the
solution
is
if
necessary,
Because of
its
THE FATTY
155
ACIDS.
of
tion
ethyl
alcohol
is
clearly
the
constitution
of
acetic
acid
will
be expressed by the
H
H-C Of^O
MJH.
H
I
formula
CHg-CO-OH,
or
Expressing
these
CH3 -CN + 2H 2
= CH 3 .CO-OH + NH3
the
If
now
by the
with the
various
its
it
will
other, affords a
proper interpretation or
summary
of all the
facts.
From
in
quoted (1) Acetic acid contains the group HO-, because its
behaviour with phosphorus pentachloride is similar to that of
:
CH
or
alcohols (pp. 96, 161).
3
(2) It contains a methyl
group that is to say, three of the four atoms of hydrogen
in acetic acid are directly
This
is
THE FATTY
156
ACIDS.
by
also
CH
CH3a
CH3 .COOK
CH o3 -COOK
C02
C0 M2
contains a
constitution
CH 3-
CH 3 -(X~.pT,
previously arrived
The
which
confirms
conclusion
at.
relation
the
acetic acids,
and their
H <OOH
CH
and
The
which
has
not
compounds
yet
that
fore,
the
to
contain
met
with
;
it
characteristic
their
presence
the
been
considered
of
this
group.
group -C\.pp
in
may be
acid
As,
concluded,
moreover,
but do not
there-
are
properties
due
aldehydes
contain
hydrogen
displaceable
the
salts.
HO-
is
-CO -OH,
named
As
all
is
-COOH.
THE FATTY
157
ACIDS.
it is
With
tain a carboxyl-group.
they may, in fact,
he
by the substitution of the monovalent carboxylgroup for one atom of hydrogen; acetic acid, CH 3 -COOH,
from methane, CH 4 ; propionic acid, C 2 H 5 'COOH, from ethane ;
and so on. They form, therefore, a homologous series of
the general formula C M H2M+1 -COOH, or C n H 2n 2 and are
paraffins,
monobasic or monocarboxylic
all
As
acids.
members
exist in
The two
primary alcohols.
example,
correspond
isomeric
acids,
butyric
acid,
isobutyric acid,
with
the
3
and
two
primary
>CH.CH 2 .OH,
alcohols
respectively.
Those
paraffins
hydrogen
normal
group,
butyric
acid,
CH3 .CH
contain
the
normal
atom of
termed normal acids,
-COOH
are
the
for one
normal
2 -COOH,
.CH 2 .CH 2 .CH 2 .CH 2 .COOH; those
acid,
f^TT
which
derived from
are
as
heptylic
which
isomerides
group
n
^ M 3 /CH-
are
usually
termed
/~1TT
iso-acids,
as,
iso valeric
acid,
p "^
r^iT
3
^CH-CH 2 -COOH,
is
not
well-known
iso-acids,
it is
name
usual,
formula,
C 5 H 10
2,
named
as follows,
THE FATTY
158
CH3 .CH
ACTDS.
Valeric Acid
(Propylacetic Acid).
Normal
CH3
H.COOH
X>C
Trimethylacetic Acid.
Methylethylacetic Acid.
C 3H 6 O 2
CH 3 .CH
exists in
Propionic acid,
2 .COOH,
acid
it is
crude
in
occurs
and
one
;
pyroligneous
form,
only
formed when acrylic acid (p. 263) is reduced with sodium
,
or
lactic
acid (p.
is
231)
two
stages,
CH 3 .CH(OH).COOH + HI = CH 3 .CHLCOOH + H 2
CH 8 .CHLCOOH + HI = CH 8 .CH2 -COOH + 12
.
It is
acid,
but on adding a
little
This property
is
surface,
forming an
acids.
Normal butyric
acid,
CH 3 -CH
.CH 2 .COOH,
occurs in the
of butter.
lactose or
it
THE FATTY
lactic acid
is
159
ACIDS.
present in the
Lactose.
The
lactose
besides
Lactic Acid.
lactic
into
lactic
now
If
acid.
little
decaying
2C 3 H 6
= C4H 8
+ 2C0 2 + 2H 2
Butyric acid
is
and
stale perspiration,
with water in
all
in
which
proportions,
it
occurs
but
it
separates
is
on
miscible
adding
calcium chloride.
solution
is
heated,
separates
in
crystals,
closely,
but
is
acid, is
all
5H
act
if
C 5 H 10 2
(CH 3 ) 2 CH-CH 2 -COOH,
THE FATTY
160
ACIDS.
most important.
are the
acids
of
water
is
known
liquid,
boiling
acids
(p.
The hexylic
the
C 6 H 12
acids,
2,
seven
isomerides
eight
Palmitic acid,
C 18 H 36
2,
or
and vegetable fats and oils (p. 169), from which they are
prepared on the large scale principally for the manufacture
stearin candles ; they are colourless, waxy substances,
melting at 62 and 69 respectively, and insoluble in water,
but soluble in alcohol, ether, &c. Their sodium and potassium
of
salts
and
was
stituents of
soaps
(p.
at one time
named margaric
ficially
thought to
add; this
prepared acid,
C lY H
;34
or
C 16 H 33 -COOH, which
in the series,
stands
and which
THE FATTY
161
ACIDS.
Acid Chlorides.
to
is
+ 3HC1.
Another method of preparation consists in dropping phosphorus oxychloride (4 parts) on to anhydrous sodium acetate
(15 parts), and then distilling, as before,
Acetyl chloride
boils
at
it
is
Acetyl chloride
the same
relation
to acetic
acid as
it
P-
191),
Acetyl chloride
is
0.
more or
less rapidly,
by
all
compounds
THE FATTY
162
containing
one
or
ACIDS.
more liydroxyl-groups
the
interaction
CH
3 -C\^
is
displacing
be recovered unchanged, indicating that it is not a hydroxycompound, or it may be converted into a new substance,
stance
estimated
alkali or acid,
acetic
in chemical properties,
of
Anhydrides.
-COOH
*
is
Except when the acetyl derivative has the same, or nearly the same,
composition as the original substance, in which case the
number of acetyl-groups in the molecule is determined by the second
percentage
method,
THE FATTY
163
ACIDS.
CHo-COOK
+ CH,yO COC1 = CH o3 -CO.O.CO.CH 3 + KC1.
O
>
acetate
in
this
way may
12 u
C 2H6 -OH _ C2 H5 \^
CA-OH-c^A
Ho
with more
salt,
which
or,
inter-
expressed
in one equation,
is
and by
all
it is
decomposed by
alkalies,
by
described.*
All the fatty acids, except formic acid,
*
The action of
groups
is
may be
converted into
THE FATTY
164
ACIDS.
anhydrides by treating the acid chloride with the alkali salt of the
acid, or by heating excess of the alkali salt with phosphorus oxyIf an acid chloride be treated with a salt of a different
chloride.
acid, mixed anhydrides, corresponding with the mixed ethers, are
All these anhydrides resemble acetic anhydride in
obtained.
chemical properties.
as derived
and
is
named
acetamide,
(p.
under pressure,
but
ammonium
acetate
0.
complete decom
position, that portion of the distillate boiling above 140 is collected
separately and redistilled, these operations being repeated three or
As one
four times.
or
alkalies
it
is
decomposed
into
acid
acetic
and
on
water, and
is
distillation
THE FATTY
ACIDS.
16f)
Formic acid and all the higher fatty acids may be converted into
amides by methods similar to those given above fomnamide,
H-CO'NH2 for example, may be prepared by distilling ammonium
These amides closely resemble acetamide in chemical
formate.
and physical properties, but their solubility in water rapidly
diminishes on passing up the series. It is a remarkable fact that
the melting-points of the amides of the fatty acids lie very close
together, most of them melting between 95 and 110, and all
within the limits of 79 and 129.
;
tion
it
might be expected to give
halogen substitution products, just as does methyl chloride.
As a matter of fact, acetic acid yields three substitution pro-
ducts
when
it is
and
of these three
com-
This again is the fact; the three substitumonobasic acids, similar to acetic acid and
to one another in chemical properties.
anhydrides, &c.
The
by
iodine chloride
direct
combination
is
again
THE PATTY
166
ACIDS.
II. p. 352).
CH
it
Chloracetic acid,
is a crystalline substance
2 C1-COOH,
melts at 62, and boils at 185-187.
Dichloracetic acid,
at
190-191;
it
is
KCN + CC1
CHC1 2 -COOH,
best prepared
is
by heating
(or ferrocyanide) in
aqueous solution,
Trichloracetic
acid,
CC1 3 -COOH,
is
best
prepared
by
= CC1 3 -COOH.
CClg-CHO +
It melts
at
55,
boils at
three bromacetic and iodacetic acids are similar in proOn treating any of these halogen substitution products
CH
named
The
/3-bromisopropylacetic acid.
fatty acids (and other saturated
for
example,
is
THE FATTY
167
ACIDS.
it
into
an
^H
ester,
>CBr.COBr + CH 3 .OH =
^2 5
the second method
is a liquid because
>CBr-COOCH 3 + HBr
^2 H 5
generally used when the substituted acid
is
its ester is
more
by fractional
easily purified
distillation.
may
general formula
members
Formic
of this
acid,
homologous
Butyric acid,
C 3H7
^TT (Normal
-COOH,{ Iso
nu
Valeric acid, C 4 H 9 rv^TT /Normal
-COOH,| Iso
Heptylic acid, C 6 H 13 -COOH, Normal
Laurie acid, C n H 23 -COOH,
Myristic acid, C 13 Ho 7 -COOH,
Palmitic acid, C^H^-COOH,
Stearic acid, C 17 H 35 -COOH,
.
101
1-241^0
118
1-080
-36
141
1-013
- 4
_ 7go
163
0-978
-59
186
0-957
..
0>947
|(
223
0-945
_ gr
- 10-5
It is
sV
+43-6
+ 54
+62
+69
in this
Q>965
'
875>
|
862
U|
0-853
-
13 g,
0-845 J <
members named
+16-5
H-COOH,
CH3 -COOH,
acid, C H -COOH,
r.Ti
Acetic acid,
Propionic
THE FATTY
168
ACIDS.
By heating those dicarboxylic acids in which the two carboxylgroups are combined with one and the same carbon atom (p. 240),
CH3 .CO.CH(C H
3
Physical
(p. 193),
At
Properties.
ordinary
temperatures
the
lower
solid,
C 12 H 24 O 2
43-6
CjgH^Og
C 14 H 28 O 2
C 15 H 30 O 2
40-5
54
51
C 16 H 32 O 2
62
C 17 H 34 O 2
60
THE FATTY
169
ACIDS.
Chemical Properties. The fatty acids are very stable, and are
only with difficulty oxidised and broken up ; nevertheless, owing to
the presence of the carboxyl-group, they readily undergo a variety
of double decompositions.
They are all monobasic acids, but the
acid character becomes less and less pronounced on passing up
the series; whereas formic and acetic acids readily decompose
carbonates, and dissolve metals and metallic hydroxides, the higher
members, such as palmitic and stearic acids, are with difficulty
recognised as acids by ordinary tests. The metallic salts of the
lower members are soluble in water ; but on passing up the series
the solubility decreases, until, in the case of the higher acids, only
especially in
presence of
When
on distillation with an alkali salt of a fatty acid they yield anhydrides of the acids,
again are readily converted into ethers and olefines, all these compounds may be obtained from the fatty acids.
The reactions by which a fatty acid may be converted into the
next lower, or higher, homologue are described later (p. 205).
Composition of Fats
and
Oils.
and
When
Butter.
is
fat
THE FATTY
170
as
The
tallow.
manner,
is
When
fat
much
tallow
obtained
from pig
and
called lard.
softer,
is
pressure at about
'
and ' fatty acids
is
suet,
in a similar
200,
it is
now
the mixture be
if
ACIDS.
(p.
254)
distilled in highly
superheated steam
takes place
when
tallow
it is
fats,
is
such as
lard,
acids of the
C n H 2w
and
oils,
The occurrence
and the
of these
members
of
Glycerol
acid,
forming neutral
salts,
hydroxide,
171
stearic acid,
tristearin,
when, however,
proportion of triolein
it
contains
it
soft
is
and pasty
large
or liquid
relatively
(lard),
(olive-oil).
CH2 .OCO.C H
CH -OH
2
35
]7
CH.O.CO.C^ +3H
Tristearin.
oils
CH -OH
CHa-O-CO-C^H^
Since fats and
Stearic Acid.
Glycerol.
are
When
the
weak
ammonia
sufficient
when
it
is
converted after
C^H^-COOH
(p. 264), is
is
to
acids.
say,
the
Some
THE FATTY
172
ACIDS.
common
sodium
water and
When
and
oleic acids
with
with potash,
instead of with soda, similar chemical changes take place, and
the potassium salts of the acids are formed ; if common salt
be
alkali.
now added
salts,
is finally
obtained
is
above-named
acids,
tion,
Hydrolysis
of
of glycerides
expressed
by
by water,
the
acids,
following
and
alkalies,
equations,
examples
of
hydrolysis,
H
(p.
(p.
189)
275)
(p. 289).
acid,
THE FATTY
173
ACIDS.
After distilling the products in a current of superfirst acidifying with sulphuric acid, if lime
above).
heated steam
much
is
of the liquid
ole'ic
acid as possible.
little paraffin to
make
it less brittle,
and employed
in
The
large quantities in the manufacture of stearin candles.
or
of
mass
and
acids
stearic
oleic,
palmitic,
pasty
liquid
separated from the stearin is known as olem, and is employed
for the preparation of soap.
Glycerol
(p.
254)
is
by
evaporated to a syrup.
Butter.
Butter, prepared from cream, is a mixture of fat
(about 82-5 per cent.), water (about 14-5 per cent.), and small
quantities of casein, milk-sugar, and salts.
contains about 92 per cent, of a mixture
Pure
butter-fat
of
tristearin,
tripalmitin,
flavour
it differs
from
all
oils,
in containing a
174
CHAPTER
X.
It has
and water,
salts
forming
C 2 H 5 .OH + HC1 = C 2 H 5 C1 + H 2
C 2 H 5 .OH + H 2 S0 4 = C 2 H 5 .HS0 4 + H 2
CH3 -OH + CH 3 .COOH = CH3 .COOCH 3 + H2 0.
These compounds are called ethereal salts or esters, in contradistinction to the metallic salts,
chloride,
di-,
tri-,
paraffins,
form,
CH3C1
C2 H5 C1
C3 H 7 C1
Propyl
The
be
related to
X = C1,
series
Br, or
Methyl bromide,
Ethyl
Propyl
of
the
general
I.
CH 3Br
C2H 5 Br
C3 H 7Br
Methyl
iodide,
Ethyl
Propyl
CH 3 I
C2 H5 I
C3 H 7 I
such
CHC1 3
cannot
homologous
formula,
Methyl
Ethyl
form
they
paraffins;
<c.
as
CH
methyl alcohol
is
acid,
175
methyl
alcohol,
CH 3 C1 + H 2 = CH 3 .OH + HC1.
Methyl chloride
is
of organic dyes, the compressed gas being also used for the artificial
production of a low temperature ; for these purposes it is manu-
(p.
211) with
hydrochloric acid,
chloroform with
solution,
CHC1 3 + 2H = CH 2 C1 2 + HC1
it is
a colourless,
heavy
liquid, boiling at
Chloroform, or trichloromethane,
41.
CHC1 3
is
formed when
176
pure substance
hydrate
(p.
is
separated in the
manner
just described,
and
chloride,
(Part
smell
II. p.
is
of phenylcarbylamine or phenylisocyanide*
207).
drop of
if
possible,
is
177
thetic,
Carbon tetrachloride,
final
CH
product
C1 2 and
,
of
or
the action
CHC1 3
is
tetrachloromethane,
of chlorine on
the
which
CC1 4
CH4 CH 3 C1,
sulphur dichloride
tetrnchloride
76-77
at
verted into
inverse
CHC1 3 CH 2 C1 2
,
substitution.
It
CH 3 C1,
is
and CH 4 successively, by
decomposed by hot alcoholic
potash,
CC1 4 +
4KOH = 4KC1 + C0 2 + 2H 0.
CH
CH
2
Br (b.p. 4-5),
ethereal salts, methyl bromide,
3
and methyl iodide,
I
are
prepared by methods
3
(b.p. 42),
The halogen
similar to those
ethyl
salts
(see
Khemical properties.
:
especially
is
Org.
178
lodoform, or triiodomethane,
tion product of
may
methane,
be considered here.
is
CHI 3
a halogen tri-substitu-
CH
bonate
lodoform
aqueous
is
solution
odour
it
is
volatile in steam.
It
is
temperatures,
The
flask is connected
provided with
8-
safety tube.
190),
is
and
is
saturated
it is
gently
179
warmed on
the water-bath,
when ethyl
chloride
cooled in
into the flask.
is
C 2H 5 -OH + HC1 - C 2 H 5 C1 + H 2 0.
Ethyl chloride
may
also
and sodium
at
12-5;
C 2 H5 C1 + H 2 = C 2 H 5 .OH + HC1
on treatment with chlorine in sunlight,
substitution products of ethane.
cipitate
it
It gives
nitrate,
di-, tri-,
&c.
no immediate
pre-
gives
is
quickly
remaining in solution,
ordinary temperatures,
C 2 H 5 .OH + PBr 5 = C 2 H 5 Br +
It
may
POBr^
+ HBr.
180
mixture
after
is left
3C 2 H 5
for about
OH + P + 3Br = 3C H5 Br + H P0
is
to
The
free
distillate
it
C 2 H 6 I,
is
it is prepared
;
by
gradually adding iodine (65 grams), in small quantities at a
time, to a mixture of alcohol (25 grams) and amorphous
phosphorus (5 grams), and then distilling from a water-bath,
is
3C 2 H5 .OH + P + 31 = 3C 2 H5 I + H3 P03
Ethyl iodide
is
it
nearly
all
organic
it
properties
compounds containing
closely
resembles
ethyl
iodine.
chloride
In chemical
and ethyl
bromide.
Other halogen ethereal salts or halogen mono-substitution products of the paraffins, such as propyl bromide, C 3 7 Br, butyl
iodide, C 4 9 I, &c., may be prepared by methods similar to those
all
colourless,
neutral, pleasant-smelling
181
are insoluble,
C 3 H 7 I + KOH = C 3 H6 + KI + H 2 O.
They do not give an immediate
of silver nitrate
a halogen silver
remains in solution,
Sp. gr.
atO"
Methyl chloride,
Methyl bromide,
Methyl iodide,
CH C1
CH3 Br
CH 3 I
Sp. gr.
T,
atO"
-22
:}
1-73
2-33
Ethyl chloride,
Ethyl bromide,
Ethyl iodide,
+4-5
42
C2 H5 C1 0-921
C 2H 5 Br 147
C2 H 5 I 1-975
a>1) -
12-5
39
72
and
normal butane
>CX.CH3
CH
^>CH-CH 2X
from isobutane.
It
may be
also
)3
+ H 2 O.
MHEBEAL
182
It is
a colourless
oil,
SALTS OR
boils at 100,
decomposing
slightly,
and
is
The
warmed with
formed when
silver nitrate in
alcoholic solution,
C 3 H 7 .OH + HM) 3 = C 3 H r N0 3 + H 2 0.
Ethyl nitrate, C 2 H 5 -N0 3 is formed when alcohol
is
treated
acid,
much
heat
is
reduced
to
nitrous
acid,
which then
If,
(p.
interacts
with
however, the
301), a substance
the
nitric
which
the
reaction
takes
place quietly,
the
is
principal product.
Ethyl nitrate
and boils at 87
is
;
it
183
&c.
It
by hot
alkalies,
it
yields Tiydroxyl-
amine,
nitrate,
CH
-N0 3
(b.p.
The
of nitrous acid
on the
by the action
alcohols,
nitrite,
C 2 H 5 -N0 2
is
(2 c.c.),
The
from a water-bath.
and
distillate consists of a
its
prepare pure ethyl nitrite, a mixture of alcohol and dilute sulphuric acid is added to a solution of potassium nitrite ; the
product
Ethyl
is
and
distilled.
0-947 at 15-5;
+ 2HNO,,.
184
it
boils at
apples
it is
nitrite,
resemble ethyl
CH
nitrite.
Angina
Pectoris.
equation,
nitrite
nitrogen,
in constitution
and isomeric
^
The
^ O1
one a ^ om
hydrogen.
and
without decomposing, but their boiling-points are much
higher than those of the corresponding nitrites ; nitro-ethane, for
example, boils at 114, ethyl nitrite at 17. They differ from the
nitro- paraffins are colourless, pleasant-smelling-liquids,
distil
nitrite.
The
amines on reduction,
C 2 H 5 .N0 2 + 6H = C 2 H 5 -NH 2 + 2H 2 O,
whilst the nitrites yield hydroxylamine
an alcohol,
(p.
183) or
ammonia, and
185
C2
^ >S0
Ethyl sulphate (C 2 H 5 ) 2 S0 4
TT
Ethyl hydrogen sulphate, ethylsiilphuric acid, or sulphoacid (from sulphuric acid and spirit of wine),
C 2 H 5 -HS0 4 is formed when ethylene is passed into fuming
sulphuric acid, or heated with ordinary sulphuric acid,
vinic
C 2 H 4 + H 2 S0 4 = C 2 H 5 -HS0 4
It is prepared
acid,
C 2 H 5 .OH + H 2 S0 4 = C 2 H 5 .HS0 4 + H 2 0.
mixture of equal volumes of alcohol and concentrated sulphuric acid is heated at 100 for about an hour, when part of the
is converted into ethyl hydrogen sulphate.
The solution is
then cooled, diluted with water, and treated with a slight excess of
barium carbonate, when barium sulphate and barium ethylsulphate
are formed,
alcohol
carbonates,
186
may
car-
with
ness
it is
as it is
obtained from
its
+ H 2 S0 4
yields ethylene,
Ag2 SO 4 + 2C 2 H 5 I = (C 2 H 5 ) 2 SO 4 + 2AgI.
a colourless liquid, and boils at 208, decomposing slightly.
MERCAPTANS AND SULPHIDES.
the
hydrogen
sulphides
classes of organic
hydrosulphides as
ETHEREAL SALTS
Oft
187
ESTERS.
C2
f Ethyl hydrosulphide,
\ Potassium hydrosulphide,
f Ethyl
hydrosulphides
organic
(C 2 H 5 ) 2 S
C2H5
hydroxide,
\Potassium hydroxide,
The
K-SH \Potassium
or
sulphide,
5 )2
are
sulphhydrates
KS
H O
K
2
(C 2
usually
C 2 H 5 -SH, may
Ethyl mercaptan,
be obtained by treating
5C 2 H 5 -OH + P2 S 5 = 5C 2 H 5 .SH + P 2
it
is
by the interaction of ethyl chloride and potassium hydroIt is a colourless liquid, has a most offensive smell,
sulphide.
or
and
boils at
36.
displaceable by metals
group of the alcohols ;
sodium or potassium,
tide,
C2 H 5 -SNa,
or
when
it
C 2 H 5 -SK,
a crystalline
compound, which
is
decomposed by hydrogen
(C 2
5 -S) 2
characterised
188
5(C 2 H5 ) 2
and by
obtained by heating
+ P2 S 5 = 5(C2H5 ) 2 S + P2
distilling a concentrated
5,
2C 2 H 5 .KS0 4 + K 2 S - (C 2 H 5 ) 2 S + 2K 2 S0 4
It
is
boils at
91;
displaceable
by metals, and
is
it
liquid,
and
an example.
an important and interesting
compound, first prepared by Baumann, arid largely used as a
Although acetone and other ketones do not interact
soporific.
readily with alcohols giving acetals, as aldehydes do (p. 143),
they condense with mercaptans in presence of hydrogen chloride
acetone and ethyl mercaptan, for example, give acetone mercaptole
of
Sulphonal,
) 2,
is
is
(b. p.
190-191),
When
Ethyl acetate,
when
acetyl
alcohol,
C 2H3
chloride
-C 2
or
5,
or
acetic
CH3 -CO-OC H5
anhydride
is
is
formed
treated
with
189
also
halogen
a metallic
salt
acetic acid
of
heated with
is
is
The
distillate
is
of
sodium
which
it is
by hot
and by water,
hydrolysed
acids,
CH3 -COOC 2 H5 + H
When
It is readily
alkalies,
ammonia
it
yields acetamide
and alcohol,
acid or an acetate
the so-called
<
may be
acetic-ether
readily detected
by
this reaction,
'
test.
many
other operations,
190
as, for
(p. 162)
and
it
always employed.
With
appara-
be
may
for
days
attention.
esters
of
mineral
The
may
all
be produced by treating an
alcohol,
when an
alcohol
is
mixed with an
191
CH .OH + C H O = C H .CH + H O
C 2 H 2 .CH + H 2 = CH .OH + C H 4 O
3
is
equation thus,
CH .OH + C H
3
C 2 H 3 O 2 .CH3 + H 2 O,
'
'
'
'
it
An
ester.
as a rule, however,
when
esterification is at
recently advanced.
192
by
filtration
is
(if
if it be soluble in water).
only a small quantity of acid is at disposal, and it is
desired to prepare one of its esters, it is converted into the silver
salt, and the latter is warmed with a halogen ethereal salt, such
liquid, or
When
as methyl iodide.
Esters are usually colourless, neutral, pleasant-smelling liquids,
sparingly soluble or insoluble in water ; they distil unchanged under
They
important respects.
The hydrogen
are
ethereal salts
usually
and alkalies
The
are soluble.
ammonia
(p. 205),
= C 2 H 5 .NH 8
HI.
193
CH
CH
propionate,
C 2 H 5 -COOCH 3 and
,
so on.
Many
occur
esters
in
'
as 'apple-oil.'
CHAPTER XL
SYNTHESIS OF KETONES AND FATTY ACIDS WITH THE AID
Ethyl acetoacetate,
with loss of
representing
the
p.
is
reaction
in
its
simplest
form
(compare
199),
-CO.CH 2 .COOC 2 H 5
+ C 2 H 5 .OH.
* Et is used to
represent C 2 5 in this and in
formulae for the sake of clearness.
many
of the following
194
An
separately.
of acids, but
it is
it
contains a
The sodium
is
so
much used
or benzene
metal
195
A solution of the
when its aqueous solution is boiled.
sodium derivative is easily obtained by mixing ethyl acetoacetate with a cold alcoholic solution of sodium ethoxide,
dL-CO-CEL-COOEt + NaO-C 9 H, CH3 .CO-CHNa.COOEt + C 2 H 5 -OH.
When
acetate,
(C 6 9 3 ) 2 Cu.
This property of forming metallic derivatives is due to the
presence of the group -CO-CH 2 -CO- ; all substances which
contain this, or the group
-CO-CH-CO-,
yield derivatives
by the metal.
sodium
is
employed,
CHg-CO-CHPr-COOCaHs,
results,
ethyl propyl-
and
so on.
All the alkyl wzowo-substitution derivatives of ethyl acetoacetate contain the group -CO-CH-CO, and are therefore
l
&c.,
From
-CH-
by the action
group.
of
alkyl
&c., are
196
CH .CO.CNaMe.COOC H + EtBr =
CH 3 .CO-CEtMe.COOC H 5 + NaBr.
3
Ethyl Ethylmethylaceioacetate.
CH 3 .CO.CNaPr-COOC H5 + PrI =
CH3 .CO-CPrPr.COOC H + Nal.
2
Ethyl Dipropylacetoacet&te.
pound;
the introduction
carried
out in
does
one
not form a
is
The
The ethyl
(1 mol.),
theoretical quantity
its
is
weight of absolute
thoroughly cooled.
and a
now gradually added, the whole being well cooled during the
operation ; the flask is then connected with a reflux condenser,
and carefully heated on a water-bath until neutral to litmusIn order to isolate the product, the alcohol is distilled from
paper.
are
a water-bath, the residue mixed with water to dissolve the precipitated sodium salt, and the whole extracted with ether ; the
ethereal solution is washed with water, dried with anhydrous
by fractional
off,
oil purified
distillation.
The following
are
some
of the
di-sub-
B.i.
Ethyl we%Jacetoacetate,
Ethyl dimethyla,cetoa,ceta,te,
Ethyl e%Zacetoacetate,
Ethyl cfte%Jacetoacetate,
Ethyl />r0p^acetoacetate,
Ethyl wo^rop^acetoacetate,
CH -CO-CHMe-COOC H
CH -CO-CMe2-COOC2 H
CH -CO-CHEt-COOC2 H5
CH COCEt2-COOC2H
CH -CO CHPr*-COOC2 H
CH .CO-CHpr/3.COOC2 H5
3
3
3
187
184
198
218
209
201
The mono-substituted ethyl acetoacetates resemble ethyl acetoacetate in chemical behaviour and give a characteristic bluish-
197
One
acetate
of the most important changes which ethyl acetoand its derivatives undergo is that which takes place
when
they
are
with
treated
alkalies
mineral acids.
or
Potassium Acetoacetate.
On
When
heated with alkalies, ethyl acetoacetate and its derivatives are decomposed in two ways, the course of the decomposition depending to a great extent
concentration of the alkali used.
hydrolysis),
=
CHg-CO-CHajCOOEt + 2KOH CH3 -CO.CH 3 + K 2 C0 3
+ Et-OH
CH3 .CO.CEt2 |COOEt + 2KOH = CH3 -CO.CHEt2 + K2 C08
+ Et-OH.
Ketonic hydrolysis
dilute mineral acids.
is
also brought
If,
(compare
p. 166).
is
198
CH3 .COiCH
.COOEt +
+ Et 2 CH.COOK + C 2 H5 -OH.
Potassium Diethylacetate.
Ethyl acetoacetate is, therefore, a very important compound, as with its aid any fatty acid, or any ketone (containing the group CH 3 -CO-), can be synthetically prepared,
provided the requisite
alkyl
compound
halogen
can
be
obtained.
ethyl
CH
If
Example.
namely, butyl
5 )(C 3
a ketone
of the constitution
acetone
be
ethyl
required,
).COOK + C 2 H 5 -OH.
3 -CO-CH 2 -C 4 H 9
CH
butylacetoacetate,
CH
sulphuric acid,
CH
.CO.CH(C4 H 9 ).COOC 2 H 5
The
employed.
On hydrolysis with
converted into a salt of
is
199
CH 3 .CO-CH2 -COOC 2 H 5
-CO-
seems
to
be
CH 3 .CH(OH).CH
its
In many of
ethyl salt.
acetoacetate behaves as if it
its
reactions,
-COOH,
however,
contained a hydroxylethyl
group, and had the constitution represented by the formula
These facts have led to the
3 .C(OH):CH.COOC 2
5
CH
compounds hydrogen directly united with carbon is not displaceable by metals. At first sight it might seem absurd to represent
the sodium derivative by the formula CH 3 .C(ONa):CH.COOEt,
when this compound interacts with alkyl halogen compounds the alkyl-group does not become united to oxygen but to
carbon; this might be explained, however, by assuming that the
first change consisted in a direct addition of the alkyl halogen
compound to the unsaturated sodium derivative, giving an unstable
product which immediately underwent decomposition,
because
A similar
200
CH3 C(OH)3
CH3 .COOEt + NaOEt = CH3 .C(OEt) 2 .ONa
hydroxycrotonate),
CH
Many
R-CO-CH
group
isomeric hydroxy-compounds,
which
R-C(OH) = CH-
or
R-C(OH) = C<,
be reconverted into the keto-derivatives ; such isomerides differ from isomeric compounds generally, in the readiness
with which they are changed one into the other by heat or by the
action of various chemical agents, and are termed tautomeric forms
or
'
may
tautomerides.
enol
'
When
'
under ordinary conditions, the latter is often called the labile modification
but, as a rule, it is difficult to say which is the more
stable form, as it all depends on the conditions under which the
;
is
formed by
means
).COOH, the
.COOH,
201
from which
it
was
first
obtained.
fatty acids.
chloracetate
is digested with potassium
potassium
in
cyanide
aqueous solution, potassium cyanacetate is pro-
When
duced,
This
salt,
acid
(p.
acid, yields
malonic
239),
CH (CN)-COOK + 2HC1 + 2H
2
but
if
malonate
is
produced,
Preparation.
heated
in
commences.
large
As soon
evaporated on
constantly stirred
with
thermometer until
the temperature
202
boiling at
Ethyl malonate,
the
contains
derivative
CH
group
when
it
<
c*o or^ TT
**
'~
treated
with
the
forms
metal
sodium
with
or
sodium ethoxide,
CH (COOC H
2
and
it
because
its alkali
it
derivatives are
decomposed by water,
Ethyl Ethylmalonate.
these mono-substitution derivatives, like those of ethyl acetoacetate, are again capable of forming sodium derivatives,
Ethyl Propylethylma.loua.te.
may be obtained,
the syntheses being carried out exactly as described in the
case of the substitution products of ethyl acetoacetate.
Ethyl malonate and its derivatives are hydrolysed by
of derivatives
boiling
salts of
the
of
203
potassium
E thylpropylmalonate.
This behaviour
is
shown by
all
it
are
with
240),
CH (COOH) 2 = CH 3 -COOH + C0 2
2
CEtPr(COOH) 2 = CEtPrH-COOH + C0 2
Ethylpropylmalonic Acid.
Ethylpropylacetic Acid.
ketones are
products.
The value
much enhanced by
is
CH
5 )2
hydrolysed
ethyl propylmalonate,
3 .CH 2 .CH 2 .CH(COOC 2
with boiling alcoholic potash.
The propylmalonic acid obtained
from the potassium salt is heated at about 200, or distilled, when
it
ETC.
CHg-CO-CHNa-COOEt + CH 3 -COC1 =
CH3 .CO.CH(CO.CH 3 ).COOEt + NaCl
CHNa(COOEt) 2 + CH 3 .COCl = CH(CO.CH 3 )(COOEt) 2 + NaCl,
and with halogen derivatives of esters, such as ethyl chloracetate
the compounds thus obtained undergo hydrolysis in
(pp. 240-41)
much the same way as the simple alkyl derivatives of the two esters.
;
CHAPTER
XII.
simple inorganic
example,
may be
regarded
as
derivatives
as
of
derivatives
of
ethers, for
the
water,
sulphuretted
hydrogen,
C 2 H 5 -OH
H-O-H
H'S-H
C 2H 5 .0-C 2 H 5
C 2 H5S C 2 ri5.
<
Cfjiig'SH
Primary.
Methylamine,
Ethylamine,
Propylamine,
Secondary.
NH -CH3
NH -C H
NH -C H
Dimethylamine,
Diethylamine,
Dipropylarnine,
NH(CH8
)2
NH(C 2 H ),
NH(C3 H 7 ) 2
5
ETC.
205
Tertiary.
Trimethylamine,
Triethylamine,
N(CH3 ) 3
N(C 2 H 5 ) 3
Tripropylamine, ^(CgHi^g
The methods of formation and general character
of the amines
be
best
understood
from
a
will, perhaps,
description of the
ethyl compounds.
-C 2 5 was first obtained by Wiirtz, by
Ethylamine,
2
NH
CO:N.C 9 H, +
2KOH = NH 2 -C H5 + K C0 3
2
salt,
C 2 H5 I + NH 3 - NH 2 -C 2H5
HI.
amide
is
ETC.
possible, therefore, to
it is
CH
-CH 2 .COOH
CH
Propionic Acid.
CH 3 .CH2 .NH CH
.CH 2 .CO.NH 2
-CH 2 .OH
Ethyl Alcohol.
Ethylamine.
Propionamide.
CH3 -COOH.
Acetic Acid.
As, moreover, the amides of other fatty acids behave in this respect
like propionamide, it is clear that a given fatty acid may be converted into the next lower homologue, and so on down the series.
Conversely, a given fatty acid may be transformed into the next
The calcium salt of
higher homologue in the following manner
the acid is distilled with calcium formate, and the resulting aldehyde converted into the corresponding alcohol by reduction ; the
alcohol is then transformed into the iodide, the latter treated with
potassium cyanide, and the resulting cyanide hydrolysed with
alkalies or mineral acids,
:
Acetaldehyde.
Ethyl Alcohol.
CH 3 .CH
2I
Ethyl Iodide.
CH3 .CH.CN
Ethyl Cyanide.
.COOH.
Propionic Acid.
paraffins,
C 3 H7 .O.N0 2 + NH 3 =C 3 H 7 .NH2
HNOy
salts,
207
ETC.
amine, therefore,
are even
salts
oil
carbonate
it
is
very hygro-
scopic,
is
air,
ammonia and
nitrite)
nitrous
acid
(ammonium
heated
are
together,
NH N0
4
or tf
+ HO-NO = 2H-OH + N 2
reaction),
C 2 H 5 -NC + 3KC1 + 3H 2 0.
amines
into
hydroxy-compounds,
the
second
for
their
detection.
CO^Qjj ^
-^
ETC.
;
they usually differ from ammonium
in being soluble in alcohol, a property which is frequently made use of in isolating the amine.
at ordinary temperatures
salts
80, and
has
is
similar
deliquescent.
properties.
ammonium
double
-NH 2 2 H 2 PtCl 6
(NH3 2 H 2 PtCl 6
C 2H5 -NH2 HAuCl4
Ethylamine platinichloride, (C 2
Ammonium
platinichloride,
Ethylamine aurichloride,
Ammonium
NH
aurichloride,
3,
HAuCl 4
and
isolating the
amines
on
is
salt,
the other
2C 2 H5 I + NH 3 = NH(C 2 H5 ) 2 HI + HL
,
salts.
It is readily distinguished
from
(C 2
it
since, instead of
being con-
yields diethylnitrosamine,
H NH + HO.JSTO = (C H N-NO + H 0.
5) 2
5) 2
209
ETC.
-NO
for the
atom
of
hydrogen which
is
nitrogen.
soluble.
Triethylamine,
amines,
is
N(C 2 H 5 ) 3
like the
ammonia,
3C 2 H 5 I + NH 3 = N(C 2 H 5 ) 3 HI + 2HL
,
The
salts of
5) 3
+ C 2 H 5 I = N(C 2H 5 ) 4 I
NH
+ HI = NH4 I.
with
Org.
freshly precipitated
silver
hydroxide,
double
clecom-
position results,
ammonium
ETC.
ammonium
bases, or
in
Tetrethylammonium hydroxide,
N(C 2 H 5 ) 4 -OH,
for
ex-
air,
and
liberates
when
salts
of
iodide
is
resolved into
N(C 2 H 5 ) 4 C1 = N(C 2 H 5 ) 3 + C 2 H 6 G1
chloride,
NH4C1 = NH
+ HC1.
amines
may be
converted
into
secondary,
and
those
of
the
tetrethylammonium com-
typical
pounds may
be
taken as
ammonia
ETC.
211
the corresponding
NH
latter,
that
detailed description
and triMethylamine,
2 -CH 3
dimethylamine, NH(CH 3 2
methylamine, N(CH 3 3 are usually produced in small quantities
during the decomposition of nitrogenous organic substances, and
;
may
Methylamine, CH 3 .NH 2
Ethylamine, C 2 H 5 .NH 2
Propylamine, C 3 H 7 -NH 2
Butylamine, C 4 H 9 .NH 2
B.p.
-6
+19
49
76
The higher amines, like the higher ethers, esters, &c., exist in
there are, for example, three compounds
various isomeric forms
of the molecular formula C 3 9
The amines, like the
(see below).
ethers, may be classed into simple amines, such as propylamine,
:
HN
or of different kinds.
Some of the
Preparation and Identification of Amines.
methods actually used for the preparation of
primary amines have already been described namely, the
principal
and potash
reactions.
(p.
205), both of
which
are
important general
ETC.
zinc dust
acetic acid.
in
and then
when
reactions
such as the
following occur,
The
latter
may
with hydrochloric
alcohol.
The
acid,
ETC.
213
base
may
(C 2
H )N-NO + H
5
= (C 2 H5 ) 2 .NH + HO-NO.
amides,
+H
first
carbylamine or isocyanide
primary amine.
If
(p.
As most amines
ETC.
Phosphines.
PH
hydrogen,
Tertiary phosphines, such as triethylphosphine, are not produced under the above conditions, but may be prepared by
is
a mixture of
PH4 I + 3C H 5 I = P(C2 H5
2
With
)3,
HI + SHI
and
PH
-CH 3 which
,
tertiary phosphines
is
are
liquids
only sparingly soluble, in water (PH3 unonly sparingly soluble), and in readily undergoing
oxidation on exposure to the air ; in many cases so much
rule, insoluble, or
like
heat
fire
NH
is
3,
is
that
is to say,
many
ETC.
215
When tertiary phosphines undergo slow oxidation in presence of air, they are converted into stable oxides,
such as triethylphosphine oxide, P(C 2 5 ) 3 0.*
inflammable.
PH(C 2 H 5) 2
hydriodide,
phine
just as those of the corresponding tetralkylbases are more stable than those of ammonia.
salts,
ammonium
Arsines.
The hydrogen atoms of the hydrides of arsenic and antimony, and the chlorine atoms of bismuth trichloride, may be
(indirectly) displaced by alkyl groups ; but although in the
*
Tertiary amines give similar oxidation products, termed oxamines, on
treatment with hydrogen peroxide.
ETC.
arsenious
tertiary arsines are obtained by treating
chloride with the zinc alkyl compounds (p. 220), or by heat-
The
+ 3ZnCl 2
It is a
fire
It differs
ignite spontaneously.
phines in being a neutral
hydrogen,
it
as a typical
colourless,
with
tertiary amines and phosphines in combining readily
alkyl iodides, forming salts of quaternary arsonium hydroxides,
As(C 2 H 5 ) 3 + C 2H 5 I = As(C 2 H 5 ) 4 I.
Tetrethylarsonium iodide, As(C 2
5 ) 4 I,
for example,
is
tetrethylarsonium hydroxide,
neut-
The
such
as
Bi(CH 3 ) 3
217
ETC.
atom
pentavalent
also
Cl
+ C1 =
derivatives
of
dimethylarsine
are
of
considerable
interest,
Dimethylarsine oxide,
or
cacodyl oxide,
As4
This liquid has an intensely obnoxious smell,* and is excessively poisonous, for which reasons its preparation, except
in minute quantities, should not be attempted ; its formation
due care be
is
***$?,
'stinking.'
ETC.
substance prepared in the above-mentioned manner is spontaneously inflammable owing to the presence of cacodyl, but
In chemical properties cacodyl
the pure compound is not.
2HC1 = 2As(CH 3) 2 Cl + H 2 O.
When cacodyl chloride is heated with zinc in an atmosphere of carbon dioxide, it yields cacodyl or diarsenic tetramethyl, a change which is analogous to the formation of
ethane from methyl iodide,
on exposure
to the air.
is
+ 2Hg + Ha = 2
it
is
CH 2 AsO.OH + 2Hg
3)
is
poisouous.
The
organic compounds of silicon are of exceptional inbecause their study exhibits in a very strong light the
close relationship between silicon and carbon.
Just as the
terest,
may be
however,
only
considered as
radicles
those
compounds
as,
containing
for example,
four
alkyl
silicon tetra-
SiH 2 (CH 3 ) 2
carbons
&c.,
CH(CH3 ) 3 CH 2 (CH 8
,
Silicon tetramethyl,
tetrachloride
is
219
ETC.
is produced
heated with zinc methyl,
SiCl4 +
Si(CH 3 ) 4
when
silicon
30, and
SiCl 4
it
153, and
at
boils
nonane, C 9 20
as derived from the as yet
,
unknown
isomeride of nonane,
the
of one atom
substitution
tetrethylmethane,
2
5 ) 4 by
of silicon for one atom of carbon; for this reason it is
C(C H
The great similarity between silicononane and nonane is strikshown by the following facts Silicononane, like nonane, is
ingly
acetate,
Si(C 2
5 ) 3 .C 2
4 Cl
+ C 2H 3
Ag= Si(C2 H 5 3 .C 2 H
)
is
.C 2
+ AgCl.
readily hydrolysed by
silicononyl alcohol, just as ethyl acetate gives ethyl alcohol,
Si(C 2
5 ) 3 .C 2
4 -C 2
HO
3
alkalies, yielding
+ KOH = Si(C 2 H 5
)3
.C 2
-OH + C 2 H 3 O 2 K
C n 2n +i-OH.
Organic silicon compounds, such as Si2 (C 2 H 5 ) 6 corresponding with
are known, but are of less importance,
formula
ETC.
Many
there
is
If,
in fact,
the
a gradual change in properties, just as do the elements themselves, and pass into organo-metallic compounds without any
C(CH3 )4
Si(CH3) 4
Sn(CH 3 ) 4
Pb(CH 3) 4
N(CH3
)3
P(CH8) 3
As(CH3)3
Sb(CH3 ) 3
but in the
Bi(CH 3 ) 3
is practically impossible to
say which of them,
should be classed as organo-metallic compounds.
it
The
if
any,
been given
already
iodide
ETC.
221
is
formed,
= Zn(C 2 H 5 ) 2 + ZnI 2
2Zn< j
Zinc filings (100 grams) and an equal weight of ethyl iodide are
placed in a flask connected with a reflux condenser, and the air is
completely expelled from the apparatus by passing a stream of dry
carbon dioxide through a narrow tube which runs through the condenser to the bottom of the flask. The condenser is then quickly
fitted with a cork through which passes a tube, dipping under mercury, in order to prevent access of air ; the materials and the
air,
clouds
Zn(C H
2
and
as
it
is
also
and
zinc hydroxide,
2H 2 = 2C 2 H6 + Zn(OH) 2
5) 2 +
decomposed by
alcohol,
by water,
Zn(C 2 H6 ) 2 + 2C 2 H5 .OH = 2C 2 H 6 +
OP
TT
Zn<^g.
as,
compounds
it is
exten-
Zinc methyl,
and
or,
Zn(CH 3 ) 2
resembles
zinc
ethyl
in
most
respects,
is
liquid, boiling at
but
it
is
sodium amalgam,
is
gr.
244;
it
boils
at
159
It is much less
ignites readily when strongly heated.
active than zinc ethyl, does not oxidise on exposure to the air,
and is not decomposed by water, in which it is only sparingly
it
soluble
On
H6 + C
Mercuric Ethochloride.
These
and
at
ordinary
temperatures,
Mercuric Ethiodide.
and by treating
di-alkyl
Hg(C 2 H 5 ) 2 + 1 2 =
H g<
Hs + C
HL
5
They
223
ETC.
sodium hydroxide,
+ AgOH = Hg<
Hg<
+ Agl.
The
organo-metallic
compounds
are
of
great
service
in
of
metallic
without decomposing;
compounds,
CHAPTEK
XIII.
224
As an example,
CH3 -CH
3,
may be
con-
This hydrocarbon, as already shown, may be sucinto ethyl chloride, CH 3 -CH 2 C1, ethyl
transformed
cessively
alcohol, CH 3 -CH 2 .OH, and acetic acid, CH 3 -CO-OH, by
sidered.
CHg
"
^-H- 3
'
CH
CH3
^^-3
CH2 -OH
C1
T*
^-i}
'
COOH
it
CH
CH
.OH
C1.CH 2 C1 (ethylene dichloride),
2 (OH)-CH 2
2
(dihydroxyethane), and COOH-COOH (oxalic acid) might
also be obtained,
such as
CH3
CH3
"
CH C1
CH C1
2
"
" *
CH 2 -OH
CH2 -OH
"
'
COOH
COOH
close relationship
products.
The
discovered
point
CnH2M(OH) 2
is
225
Ethylene glycol
rather sweet taste ;
is
it
in
ether.
Although
C 2 H4
From
its
Na2 + 2H 2 = C 2H6
it
re-
+ 2NaOH.
glycol contains hydroxyl-groups, and that it gives ^'-substitution products (whereas the monohydric alcohols yield only
it
*
If the solution be kept in rapid ebullition, a considerable quantity of
the glycol escapes with the steam.
Org.
226
groups.
like alcohol,
Again,
is
also
is
C 2 H4 Br2 + 2C 2 H3
Ag = C 2 H4 (C 2 H3
2) 2
+ 2 AgBr
which was
first
The
Constitution
of Giycol.
CH
or HOCH^CH^OH.
This point is
on considering the formation of giycol from
ethylene dibromide; since the latter has the constitution
CH 2 Br'CH 2 Br, and its conversion into giycol may be regarded
tution
.CH(OH) 2
easily decided
by the formula
or
may be
2
.
CH OH
represented
This
con-
compounds,
dihydroxy-derivatives
Glycol.
the
The higher
paraffins,
as,
227
glycols,
for
or
example,
a/3-propylene glycol,
glycol,
tin saturated
they
may
a,
/3,
y,
&c. to
commencing
at
;
they are usually prepared by treating
bromine, and decomposing the dibromoadditive products obtained in this way by boiling with alkali
carbonates (compare also pinacones, p. 141).
the
olefmes with
of
by the case
of ethylene glycol.
of formation and of one or
From a
is
well
consideration of
method
two simple reactions, it
concluded that glycol has the constitution OH.CH 2 .CH 2 .OH.
Assuming this to be true, its behaviour under given conditions can
be foretold with tolerable certainty from the facts established in the
case of ethyl alcohol, because the constitutional formula of a compound is a summary of its whole chemical behaviour. Ethylene
glycol contains two -CH 2 -OH groups, each of which is similar to
that in ethyl alcohol it may be supposed, then, that those properties of ethyl alcohol which are dependent on the presence of this
group will also be exhibited by glycol. Since, for example, alcohol
acts like a metallic hydroxide, and forms salts with one molecule of
a monobasic acid, ethylene glycol, which contains two hydroxylgroups, should behave as a cfo'acid hydroxide, and form salts with
two molecules of a monobasic acid.
When hydrogen chloride is passed into glycol heated at about
its
is
is
formed,
228
Again, when ethyl alcohol is carefully oxidised, it is first converted into aldehyde (the group -CH 2 -OH being transformed into
-CHO), and then into acetic acid (by the oxidation of the -CHO
This also
is
the fact
on oxidation with
nitric acid
CH2 -OH
CH2 -OH
CHO
COOH
Glycollic
CHO
CHO
COOH
COOH
CHO
COOH
Glyoxal.
Glyoxylic Acid.
Oxalic Acid.
any sub-
Ethylene.
CH .CH:CH2 + HOC1 = CH
3
.CHC1.CH 2 .OH.
Propylene Chlorohydrin.
Propylene.
CH2 .OH
I
C H2C1
+KOH=
CH2\
Ethylene Oxide.
CH2 -OH
CHC1
CH2\
+KOH = CH2X
+KC1 + H 2O.
CH3
Propylene Oxide.
*
is
229
boils at 13-5,
into glycol.
glycol,
CHO-CHO,
it
is
is
O.
ether
it
Hydroxycarboxylic Acids.
Glycollic acid, OH-CH^COOH, may be obtained by the
oxidation of glycol, OH-CH 2 'CH 2 'OH, with nitric acid, just
as
acetic
acid
CH 3 'CH 2 -OH,
is
produced by the oxidation
with suitable agents,
of
alcohol,
CH2-OH
CH 2 -OH
of the acid
It is also
(glycine, p. 299)
is
CH -NH
2
Glycollic acid
is
CH -OH
atom
salt of
is
sub-
230
CH -OH
CELC1
melts at 80
ether.
is
it
is
Assuming that
constitution
its
is
and
and
correctly represented
constitutional formula.
and forms
salts
-CH
it
On
it
and
oxalic
CH 2 -OH
+
600H
CH-OH
CHO
COOH
"
*'
i
COOC 2 H 5
+CHo-COCl=
2>
i
COOC 2 H 5
+ HCl.
Homologues of Glycollic Acid. Glycollic acid may be regarded as hydroxyacetic acid, or acetic acid in which a
231
hydroxyl-group has been substituted for one atom of hydrogen ; as, moreover, other fatty acids yield similar hydroxyderivatives, a
homologous
be obtained.
may
of
the
glycols
also
members
of the series
may
a
OH-CH 2 -COOH.
OH-C 2 H 4 -COOH.
-CH -OH
2
group to
-COOH.
of this series, carbonic acid or hydroxyis not known in the free state, since,
OH COOH,
when
is
these
shown
CH 3 -CH 2 .COOH
Propionic Acid.
CH
CH 3 -CH(OH).COOH
-Hydroxypropioiiic or Lactic Acid.
(OH).CH 2 -COOH.
CH
matter,
acid
acid,
by heating
a-chloro-
CH -CHBr.COOH + H
3
= CH 3 .CH(OH)-COOH + HBr
232
acid,
It
is
0.
proportions; it cannot be distilled, as it undergoes decomposition into aldehyde, water, carbon monoxide, and other
When heated with dilute sulphuric acid it is
products.
acid,
acids,
which
fact
acid
lactic
is
very unstable,
Lactic acid
ethereal
is
salts.
lactate,
Calcium
+ 3H 2 O,
CH
contains a
^>CH(OH)
acid,
CH3
CH 3 .CH<^Q H
CH .CHLCOOH + HI = CH
8
On
oxidation
with
potassium
-CH 2 .COOH + 1 2
permanganate,
lactic
acid
233
0.
II. p. 545).
COOH,
CH X-CH
2
-COOH,
-with
0.
CH
example,
it
Since lactic
formulae
namely,
CH 8 ..CH(OH).COOH
i.
and
CH
(OH).CH 2 .COOH
ii.
234
already settled
if
or amido-propionic acids be taken as known ; supposing, however, this were not the case, the following syntheses of the
it
with hydrochloric
CH3 .CH(OH)-CN + 2H 2
acid,
= CH 3 -CH(OH).COOH + NH 3
represented by formula i., a conclusion which is fully borne out by all other facts.
When ethylene is treated with an aqueous solution of
Lactic acid, therefore,
hypochlorous
this
acid,
is
ethylene chlorohydrin
interacts
compound
CH
which,
into
hydracrylic acid,
CH
(OH)-CH 2 .CN.+ 2H 2
hydroxypropionic
acids.
is
CH
-CH 2 -CH2-.
Dicarloxylic Acids.
CH
CH
Glycollic acid,
being derived from
2 (OH)-COOH,
ethylene glycol,
by the oxidation of
2 (OH).CH 2 -OH,
one of the -CH 2 -OH groups, it might be concluded that the
other -CH 2 -OH group would be capable of undergoing a
similar change
this
is
found
to
As,
be
so,
since
oxalic -acid,
such
as
on oxidation
COOILCOOH.
ay-propylene glycol,
235
homologous
of
series
dicarboxylic
acids
of the
...........
..........
COOH
C2H2
or
C3 H 4
or
H O 4 or
6
CH2
CH 2 -COOH
CH 2 -uUuH
I
H O4 or C
Glutaric acid .................................... C H O
Adipic acid ...................................... C H O
Isosuccinic, or a-carboxypropionic, acid.C 4
10
Oxalic acid,
C2H2
4,
COOH
or
COOH
I
f^OOTT
calcium oxalate;
filtered
solution
when
gives
of
calcium oxalate.
instructive.
It is
is
in
is
to about
2H-COONa = C 2
Na 2 + H 2
quickly heated
236
it
also
is
when an aqueous
other compounds,
many
solution of cyanogen
(p.
285)
is
kept for
some
Ammonium
Each
Oxalate.
means of synthesising
elements, since carbon dioxide, formic
acid, and cyanogen may be obtained from their elements.
Oxalic acid may be prepared by gently warming sucrose
of these three reactions affords a
oxalic acid
from
its
as soon as
after
are separated
purified
may
by
filtration
by
crystallisation
when
C2
Ca + H 2 SO 4 = C 2 O 4 H 2 + CaSO 4
and evaporated to
is
then
crystallisation.
filtered
237
is
of oxalic acid
When
C2
the
- ILCOOH + C0 2 = H 2
anhydrous acid
is
+ CO + C0 2
and a
very hygroscopic,
powerful
dehydrating agent.
Oxalic acid is decomposed by concentrated sulphuric acid,
but only when heated moderately strongly (distinction from
formic acid),
it
is
its solu-
and
is
ganate solutions,
The
Ammonium
giving
oxalate,
oxamide, when
C2
(NH 4 2 + H 2 0,
carefully
is
heated, just as
salts
decomposed,
ammonium
238
it
gives cyanogen
285).
Potassium oxalate, C 2 4 2 + 2 0,
water, but potassium hydrogen oxalate,
occurs in
many
plants,
is
readily
C2
KH,
soluble
a salt
is
in
which
the latter
KH
+ C2 4
position C 2 4
or potassium quadroxalate
mould and
2
;
+ 2H 2 0, known
'
as
salts of sorrel,'
removing
iron-
potassium oxalate.
C2
Silver oxalate,
Ag2
is
an oxalate
it is
only
cells
decomposed by
and a sulphate.
poisonous.
The
chiefly based
on
its
is
Methyl
oxalate,
C2
(CH 3 ) 2
is
is
acid.
by heating
239
it
is
is
sometimes
readily
(p. 90).
The
tion
from
and formates
by
it
is
its
forma-
a dibasic
acid because
anhydride
it
is
Oxamide,
2
,
is
from ethereal
C2
in.
4 (C 2
5) 2
+ 2NH3 = C 2
2 (NHjj)
+ 2C 2 H 5 -OH.
that undergone
C2
by acetamide
2
(p.
164),
(NH 2 ) 2 + 2H2 = C 2
CH (COOH)
+ 2NH3
Malonic acid,
If instead of the
240
CH 2 (COOH) 2 = CH 3 .COOH + C0
All other dicarboxylic acids, in which both the carboxylgroups are united to one and the same carbon atom, are
decomposed in a similar manner under the influence of heat.
Succinic acid,
and
C 4H 6
4,
or
CHg-COOH^
occurg
CH2 .COOH
ambe ^
many
with nitric
It
manner
hydrogen,
also
when
fats
are oxidised
acid.
acetylene,
is
its
reduced to ethylene,
the
latter
passed into
is
formed,
compound
mineral acids,
(compare foot-note,
p.
146),
.COOH
COOC 2 H 5
COOC 2 H 5 + NaCl
241
+ 3KOH =
197).
COOK
+ CHg-COOK + 2C 2 H 5 .OH.
Succinic acid
iron retorts
insoluble in water.
Ammonium succinate, C 4 H 4
the iron
is
sometimes employed
manganese, as, on adding a
(NH4
) 2,
ammonium
is
succinate, the
salt,
whole of
which
is
The
by
its
forma-
tion from ethylene dibromide, and by the fact that the only
alternative formula for a dicarboxylic acid of the molecular
composition
C4H6
must be assigned
below).
Succinic anhydride,
acid
is
distilled,
C 4H6
.CO X
>0.
CH
= C4H4
is
+ H 2 0,
but a large
pro-
It is prepared
portion of the acid passes over unchanged.
for some
chloride
by heating the acid with phosphorus oxy
time and then distilling, the oxychloride combining with the
water which
is
242
CH -C
CH 2 -CCK
CH -COOH
CH,COOHCH,CO
CHg-COOH
>0 +
CH2 .COC1
Succinyl chloride.
CH2 .COC1
is
is
treated with two molecules of phosphorus pentachloride,* the interaction recalling that which occurs in the formation of acetyl
chloride,
CH2 -COOH
+ 2PCL=
CH2 .COOH
CH2 .COC1
I
CH2 -COC1
+ 2POCL+2HC1.
succinate.
*
The product is probably a mixture of succinyl chloride and a dichloro-substitution derivative of succinic anhydride of the constitution
CH2-CC12\
I
CH2 -CO
'>0,
243
CH2 .CONH2
Succinamide,
CH2 -CO'NH2
is
oxamide
is
CH2 .CO-NH2
I
CH 2 .CO-NH2
converted into
+ 2H 2 =
ammonium
oxalate,
CH2 .COONH4
I
CH2 .COONH
4.
heated,
it is
Succinimide,
CH2 -CO\
CH2 -CO /NH,
I
is
also
dride
is
CH2 .CO\
CH2 -COOH
>NH + 2H 0= CH
CH .CCr
2
+NH
.COOH
3.
The
just as an amide
CH2 -CO-
is
a mono-
CH2 .CO\
imide,
CH 2 CO
-
)*NK,
is
produced
this
compound
interacts with
244
and the
latter,
on treatment
>NH
HO
known
CH3 .CH.COOH
CH2 .COOH
Normal Glutaric Acid.
Pyrotartaric Acid or
Metliylsuccinic Acid.
COOH
Ethylmalonic Acid.
C 6 H 10 O 4
Adipic acid,
on oxidising fats with
is of
Dirnethylmalonic Acid.
nitric acid
it
may be
is
often obtained
produced synthetically
by heating
245
Hydroxydicarboxylic Acids.
may be
hydroxymalonic
CHC1(COOH) 2
;
succinic acid
CH(OH)-COOH
or
CH .COOH
C4 H
5,
fi
a rnonohydroxy-
name (acidum
mountain
ash.
may be
It
of lactic acid
from a-bromo-propionic
CHBr-COOH
i
CH2 .COOH
As,
+ Ag-OH =
bromosuccinic
therefore,
acid,
'
CH(OH)-COOH
v
+AgBr.
CH 2 -COOH
i
acid
is
easily
prepared
by
is
aspartic acid (a
acid, or
indirectly
from asparagus*), with nitrous acid, just as lactic acid may
Asparayin,
occurs in asparagus
aspai-tic acid,
when
246
=
2
It is usually
mountain
CH -COOH
CH .COOH
ash.
The expressed
juice is boiled with milk of lime and the crystalsparingly soluble calcium salt, C 4 4 O 5 Ca + 2 0, which is
precipitated, dissolved in hot dilute nitric acid ; the calcium
line,
Malic acid
is
100, and
is
importance.
Many
a consideration of
methods
its
constitution,
of formation.
derivative
of
succinic
be foretold from
may
which
is
established
by
its
lactic into
bromopropionic
place,
not identical in
all
(Part II.
p. 545).
malic acid is heated for a long time at 130 it does not
form malic anhydride, as might have been expected from the
When
is
CH(OH).COOH
CH-COOH
CH .COOH
CH.COOH
247
+ H2
CH.COOH CH-COOHx
=11
>0 + H20.
CH-COOH CH-eOOHx
II
Maleic anhydride
acid,
CH(OH>COOH
,
or
is
II. p. 558).
dihydroxy succinic
acid,
C4 H6
or
CH(OH)-COOH
vegetable acids, and is contained in grapes, in the berries of
the mountain ash, and in other fruits ; during the later stages
of the fermentation of grape-juice a considerable quantity of
'
argol,' or
and
it is
obtained.
therefore,
from
can be
its
and amorphous phosphorus (p. 166), and two hydroxylgroups are then substituted for the two atoms of bromine in
the usual way
namely, by heating the dibromo-derivative
with water and silver hydroxide,*
CHBr-COOH
CH(OH)-COOH
v
+ 2AgBr.
+ 2Ag-OH =
CHBr-COOH
CH(OH)-COOH
i
*
The tartaric acid obtained in this way is optically inactive, and
inixture of racemic acid and mesotartaric acid (p. 251).
is
ft
248
Tartaric acid
(p.
=;
hydrogen cyanide,
CHO
CH(OH)-CN
decomposed by mineral
is
cyanoacetic acid
yields
malonic acid,
CH(OH). CN
CH(OH).COOH
CH(OH).CN
CH(OH)-COOH
Tartaric acid
is
when
is
its
partially purified
aqueous solution
is
by
is
This
recrystallisation
precipitated, neutral
2C 4 H 5
K + CaC0
= C4 H 4
Ca + C 4H 4
+ C0 2 + H 2
separated, and
a second precipitate of calcium tartrate
is
calcium chloride,
when
is
obtained,
C 4 H4
+ CaCl 2 = C 4 H 4
Ca + 2KC1.
soluble in water
is
;
readily
it
melts
among
Tartaric
*
acid
This acid
(p. 251).
acid,
is
like
other
and
pyrotartaric acid.
dicarboxylic
and
is
acids,
forms both
some
salts,
of
which are
249
of considerable
importance.
respect
C 4H 4
known
+ HC1 = C 4 H 5
'
K + KC1
it is
'
in
'
'
crystals,
Calcium
tartrate,
C 4H4
(p.
and
is
employed in the
268).
Ca + 4H 2 0, being
insoluble
in
is
which
is
made use
C 4H4
tartrate,
K(SbO) + JH 2 0,
is
as a mordant.
The
is
based
(a)
ammoniacal solution of
*
The precipitation
is
silver nitrate,
250
is
solid
the
it
acid;
is
is
is
compound.
On
first
is
converted
+ 2H[=
CH .COOH
COOH
=
CH 2 -COOH
CH(OH>COOH
CH(OH)-COOH
it
CH(OH).COOH
CHB,COOH
CHBr-COOH
CH(OH).COOH
acid are
compound
namely,
dextrotartaric
(the
that
and
is to say,
they are
all
dihydroxy-derivatives of
by the formula,
COOH-CH(OH).CH(OH).COOH
they
acid
mesotartaric acid.
stitution
known
differ,
example,
especially in their behaviour towards polarised light ; compounds which show a relationship of this kind are called
The
salts of
the
acids-
251
obtained synthetically by heating an aqueous solution of dibromosuccinic acid with silver hydroxide, as described above ; also from
Racemic acid may be resolved into dextro- and levoglyoxal.
tartaric acids (Part II. pp. 542, 557).
Mesotartaric acid, like racemic acid, is optically inactive, but it
cannot be resolved into the two optically active modifications ; it
is formed, together with racemic acid, when dextrotartaric acid is
heated for a long time with a small quantity of water at about 165,
and when dibromosuccinic acid is heated with silver hydroxide.
Hydroxytricarboxylic
A cids.
state
in
It is prepared
on the
large scale
first
and then neutralised with calcium carbonate ; the calsalt, which is precipitated from the hot solution, is washed
matter,
cium
also prepared
citromycetes.
which contain
and
acid,
fairly so in alcohol,
acids, it
Like
tartaric
252
citric
acid
and
acid
tartaric
are
employed
in
analytical
acid
is
a tricarboxylic acid,
C 6 H 6 7 K 2 and C 6 H 7 7 K, all
salts, C 6 H 5 7 K 3
which are readily soluble in water. Calcium citrate,
(C 6 H 5 7 ) 2 Ca 3 + 4H 2 0, is not precipitated on adding a solu-
potassium
of
tion of
solution
of a citrate,
water; on heating,
readily
however, a crystalline precipitate is produced, as the salt
is less soluble in hot than in cold water.
This behaviour,
because
it
soluble
is
in
cold
and the
Citric
acid
may
reactions which
be
show
it
the constitution,
CH2 -COOH
(OH)-COOH.
CH2 -COOH
Symmetrical dichloracetone, CH2 C1-CO-CH2 C1, which may be
obtained by oxidising aa-dichlorohydrin (p. 257) with chromic acid,
like other ketones, combines with hydrogen cyanide, forming
OTT
the cyanohydrin, (CH 2 Cl) 2
this product, like other comC<^p,,, ;
-CN
group,
is
CH2C1
CH2-CN
CHa -CN
this dicyano-derivative
by boiling
it
253
citrio acid
CH 2 COOH
CH2 CN
CH2 -CN
CH2 -COOH
This view of the constitution of citric acid is borne out by all the
reactions of the compound ; it is shown to contain one hydroxylgroup by the fact that ethyl citrate, C 3 4 (OH)(COOC2 5 ) 3 yields
a monacetyl-derivative with acetyl chloride. When heated alone
at 175, citric acid is converted into aconitic acid, just as malic is
converted into fumaric acid,
CHCOOH
CH2 -COOH
C(OH)-COOH = C-COOH + H2 O
CH2 COOH
CH2 COOH
when
+ CO + H 2 O,
C(OH)-COOH = CO
CH2-COOH
on
reduction
acetone-
CH 2 -COOH
CH2 -COOH
and
with
CH2 -COOH
hydriodic
acid
it
is
converted
into
CH2 COOH
tricarballylic acid,
CH-COOH.
CH2 COOH
CHAPTEK
XIV.
it
it is
atoms of hydrogen
254
may be converted
latter to the
Propyl Alcohol.
Propylene Alcohol.
CH3 .CH(OH).CH
.OH
Propenyl Alcohol.
CH
(OH).CH(OH).CH 2 .OH.
oils,
investigation.
C 3 H 5 (OH) 3
CH
and
tristearin,
which
oils,
and
consist
triolein (esters of
essentially
of
tripalmitin,
which glycerol
is
the base)
The concentrated
fractions,
may
series of reactions
tribromide,
CH 2 Br CHBr-CHgBr
is
obtained,
255
^CH
Pure glycerol
is
17;
pressure, without
traces of salts
it
decomunder-
and
mixing with
insoluble in
it
also
ether,
compounds.
Glycerol
(p.
readily
undergoes
decomposition
into
acrolein
C 3 H5 (OH) 3 = C3 H4 + 2H 2
when impure
and
completely
readily
distilled,
glycerol
when glycerol is heated with potassium hydrogen sulphate,
this
change
takes
place
but
is
to
slight
extent
much more
CH 3 -CO -
is
represented by
Ac
in this formula.
256
CH
(OH).CH(OH)-CH 2 .OH + 40 =
CH 2 (OH)-COOH + C0 2 + 2H 2
CH 2 (OH).CH(OH>CH2 .OH + 60 =
2
COOH-COOH + C0 2 + 3H 2 0.
is
Glycerol
it
is
extensively used
in
the
preparation
of
nitro-
glycerin
(p.
hydrogen
is
C 3 H 5 (OH) 2 'ONa,
is
hygroscopic, and
is
the product,
immediately decom-
posed by water.
Again, the behaviour of glycerol with acids is analogous to
that of alcohol and of glycol ; when heated with acetic acid,
for example,
it
and water,
is
may
yield
compounds, such as monacetin and diacetin, by the displacement of only one, or of two, atoms of hydrogen,
257
all be
prepared by heating
higher the temperature and
the larger the relative quantity of acetic acid employed, the
Acetic anhydride
larger the proportion of triacetin produced.
acts more readily than acetic acid, but gives the same three
glycerol with
acetic
acid,
may
the
products.
The
Chlorohydrins.
acid on glycerol
is
at
moderately
is
acid,
Glyceryl
CH
2 C1,
it
chloroform.
The name
'
glycerylj or propenyl,
is
like
sometimes
may
be
CH2 (OH).CH(OH).CH2C1
/3-Chlorohydrin,
a-Chlorohydrin.
CH 2 C1-CH(OH) CH2C1
a/3-Dichlorohydrin.
-Dichlorohydrin.
*
'
'
'
'
and
originally
dichlorohydrin
chlorohydrin
given to these glycerol derivatives (and still used) are not satisfactory,
and do not express their relation to glycerol.
or*.
258
CH 2C1.CO CH2C1.
ap-Dichlorohydrin
with chlorine ;
is
on
260)
CH
When treated
2 C1-CHC1-COOH.
a/3-dichloropropionic acid,
with potash, both aa- and a/3-chlorobydrin yield epichlorohydrin,
CH2C1-CH-CH
When
glycerol
is
p. 228).
it
triacetin, as
alcohols,
di-
)2
C1
+ H 2 0.
similar behaviour.
C 3 H 5 (0-N0 2 ) 3
oil,
its
preparation
259
and
is
It explodes
explosion, and
is
even rather
with great
subjected to per-
burns without
it
difficult to ignite.
alkalies,
and ammonia,
12S.
but, being so
correct names,
Nitro-glycerin
is
extensively employed
as
an explosive,
An
alkali
nitrite
is
also
The presence
260
makes it liable to undergo spontaneous decomposition and explosion ; great care must therefore be taken in washing it thoroughly.
Nitro-glycerin is
of acids in nitro-glycerin
mixed with gun-cotton (p. 282), as blastingand in the preparation of smokeless gunpowder
also employed,
gelatine,
(cordite)
is
it
CH
:CH-CH 2 .OH,
is
to Glycerol.
glycerol
slowly heated with crystallised oxalic acid until
the temperature rises to about 260, and :the distillate then
is
fractionated
in the
first place,
the glycerol
is
converted into
formic acid
(p.
147),
0.
It is a colourless,
all
proportions.
Allyl alcohol is an unsaturated compound, and has therefore not only the properties of a primary alcohol, but also
those of
character
Its alcoholic
unsaturated compounds in general.
shown by the following facts it dissolves sodium
is
with acids,
salts
261
is
converted,
:CH.CH 2 C1 + H 2
first
acrylic acid,
- CH 2 :CH-CHO + H 2
.bH + 20 = CH 2 :CILCOOH + H 2 0.
CH.,:CILCH 2 .OH +
CH2 :CH-CH
In
all
these reactions
its
behaviour
is
so closely analogous to
That
it
is
an unsaturated compound
is
shown by
it
its
be-
combines
directly,
CH
CH 2 :CH-CH 2 I,
an unsaturated ester,
is
same way as ethyl iodide to
It may be obtained by treating allyl alcohol
ethyl alcohol.
with iodine and phosphorus, but is more conveniently prepared directly from glycerol.
Allyl
iodide,
parts),
is
formed,
262
When
it is
CH
and
boils at
70-71.
it is
known
therefore
as oil of garlic.
It is a colourless, very
Another allyl
unpleasant-smelling liquid, boiling at 140.
derivative
namely, allyl isothiocyanate, occurs in nature in
considerable quantities in black mustard-seeds, and
as oil of
mustard
(p.
is
known
298).
C 3 H 5 (OH) 3 = C 3 H 4 + 2H 2 0.
Acrolein
the same
is
an aldehyde, and
is
related to
allyl alcohol
in
as aldehyde to ethyl alcohol; it is a colourless liquid, boils at 52, and has an exceedingly irritating and
way
an amorphous,
brittle substance
named
disacryl ;
it
also gives
it
on treatment with
on exposure to the
air,
or
undergoes oxidation,
263
CH Br.CHBr.CHO.
2
Crotonaldehyde, CH 3 CH:CH CHO, is a homologue of acraldeit is obtained on heating acetaldehyde with dilute
;
hydrochloric acid, or with a solution of zinc chloride, aldol being formed
as an intermediate product (p. 126),
hyde
CH
CHO + H
2 O.
Acrylic acid,
allyl
CH 2 :CH-COOH,
and of
alcohol
CH
acrolein,
which on
233),
distillation
loses
the
is
formed from
ethyl bromide,
Acrylic acid
139-140;
all
is
it
proportions,
and
its
It
is
in being an unsaturated
additive-products.
It
dibromopropionic acid,
CH :CH.COOH + Br
2
CH Br.CHBr.COOH
2
264
CH :CH-COOH + HC1 = CH
2
C1-CH 2 .COOH,
acid,
acid,
may
general behaviour.
Ole'ic
series,
PolyJiydric Alcohols.
The
existence of
they might
still
them occur
it
not that
many
in nature,
they
may
xylose,
265
all
be repre-
CH 2 (OH).CH(OH)-CH(OH).CH(OH).CH(OH).CH
.OH;
may
also be
When
CH
(OH).CH(OH).CH(OH).CH(OH)-CH(OH).CH 2 .OH
*
The term ' secondary ' which is always applied to this compound is
rather misleading, and seems to be based on the fact that the iodide may be
regarded as a derivative of secondary hexyl alcohol,
CH
THE CARBOHYDRATES.
266
CHAPTER
XV.
THE CARBOHYDRATES.
The word
'
'
same
as in water.
glucose,
C 6 H 12
6,
for
example,
might be
represented
as
To
includes
organic chemistry, as
stituents of
plants.
this
many
group belong
(a)
the sugars,
due
(b)
all
foods
and
form of cotton, paper, wood, &c., are of the greatest importance in daily
life.
The Sugars.
C 12 H 22 O n
THE CARBOHYDRATES.
267
MONOSES.
C 6 H 12
Glucose,
or
dextrose,
6,
or
CH
(OH).[CH-OH]}.CHO,
also called
is
grape-sugar,
many sweet
Alcohol
90 per cent.
(1 litre,
c.c.),
which melt
146;
it
is
at
and purified by
mol.,
2 0,
recrystallisa-
in warty masses
at
in about its
the
not
It is
being less sweet than that of sucrose.
carbonised when gently warmed with sulphuric acid
solution
that
is,
of
known
Compare
+ Mr>=
length.
foot-note, p. 1 37.
+52-7 in 10 per cent, aqueous solution.
for
THE CARBOHYDRATES.
268
called
this purpose
is
the operation
itself,
Glucose
and
is
a saccharimeter or polarimeter,
saccharimetry.
strong reducing
silver,
cipitates gold,
on warming.
potash, and then copper sulphate added, -a deep-blue solution
is obtained, and on gently warming, a bright-red precipitate
salts
of cuprous oxide
colourless
if
Cu 2 0,
sufficient
is
glucose
be added
moreover,
as,
and
as it
decomposes on keeping,
is
it is
charged
by 0-05 gram
of dextrose, or
by 0-0475 gram
of sucrose
(after inversion).
but at the
same
lic
time
of
Like sucrose, glucose combines readily with certain metalhydroxides, forming glucosates, such as calcium glucosate,
C 6 H n (CaOH)0 6
these
and
compounds are
composed by carbonic
H n (BaOH)0
barium glucosate, C 6
readily soluble in water,
acid,
and
are de-
showing that
it
is
there-
THE CARBOHYDRATES.
269
formula,
CH
which
is
(OH).CH(OH)-CH(OH).CH(OH).CH(OH).CHO,
based on a number of facts, only a few of which
CH
it
=
(OH).[CH-OH] 4 .CHO + 2H
CH
atoms as
shows
glucose,
and not a
ketone
such as nitric
(p.
acid,
that
142).
convert
the
the
latter
an aldehyde
is
Powerful
glucose
oxidising agents,
into saccharic acid,
-CH2 -OH
group, as well as
group, undergoing oxidation ; ultimately it is resolved into oxalic acid.
Glucose, like other aldehydes, inter-
COOH-[CH.OH] 4 .COOH,
the
-CHO
acts readily
(p.
272),
Mannose,
from which
which
it differs
it is
is
a sugar
identical in chemical
in its action
on polarised
it
is
CH
is formed by
Galactose, C 6 12 6 or
2 (OH).[CH.OH] 4 -CHO,
the hydrolysis of lactose, together with glucose, from which it may
be separated by crystallisation from water. It is also formed by
boiling gum-arabic
acid.
THE CARBOHYDRATES.
270
Fructose,
C 6 H 12
6,
or
CH 2 (OH).[CH.OH] 3 .CO-CH
.OH
sugar
(p.
compound
glucose
is
readily soluble.
is
dissolved
in
water (50
c.c.),
the
solution well cooled with ice, and slaked lime (6 grams) added
in small quantities at a time, with constant stirring.
The
Pure
(C 6
10
fructose
crystallised
5 )ft,
starch
which
is
from
prepared
occurs
in
(C 6
An
H 0> + rcH
10
mulin,
plants, and
the inulin is
many
= raC 6 H 12
is
melts at 95
glucose,
and
its
taste is just
THE CARBOHYDRATES.
Fructose
latter.
by which
is
levorotatory*
271
also
glucose
(p.
268).
is a strong
reducing agent,
solution
CH2 (OH).CH(OH).CH(OH).CH(OH)-CO.CH
When
it
digested
and
zinc
.OH.
chloride,
C 6 H 7 0(C'CO-CH 3 ) 5
a fact
CH
just
as
alcohol.
it
acetone, under
When
CH
and
glycollic acid,
(OH).CH(OH).CH(OH).CH(OH).|CO.CH 2 .OH + 40
COOH.CH(OH).CH(OH).COOH + CO'OH-CH 2 .OH + H2
2
when
=
;
["]D
-93
THE CARBOHYDRATES.
272
CH 2 (OH).CH(OH).CH(OH).CH(OH).;CO-CH .OH + 20 =
CH2 (OH).CH(OH).CH(OH).COOH + COOILCH .OH.
2
a ketone,
is
and not an
aldehyde
CH
the composition
C 6 H 12
6,
of
formaldehyde,
6CH 2 - C 6H 12
From
called a-acrose,
numerous to discuss
glucose and fructose.
here,
which
when
glycerose is treated with caustic soda it undergoes condensation, giving a mixture of sugars, among others, a-acrose.
When
(1
THE CARBOHYDRATES.
*M-CH(OH)
273
CHO + C6 H -NH-NH =
2
M-CH(OH).CH:N 2 HC 6 H 5 + H 2 O.
Glucose.
Glucosephenylhydrazone.
M-CO CH 2
H .NH-NH = M C(N HC H
5
Fructose.
).CH 2 .OH + H 2 0.
Fructosephenylhydrazone.
Hydrazones.
M
CHOH
c^
H:N2 HC 6 H,
:N 2 HC 6 H 5
CH:N 2 HC 6 H 5
C:N2 HC 6 H 5
C:N 2 HC 6 H 6
CHo-OH
CHO
terminal groups.
Many other sugars yield hydrazones or osazones according as
The hydrazones
1 inol., or excess, of phenylhydrazine is employed.
are usually readily soluble in water, but the osazones are only
sparingly soluble ; the latter are therefore of the greatest service,
offering a
The group
CH2 (OH).CH(OH).CH(OH)-CH(OH)-,
by M,
THE CARBOHYDRATES.
274
M.COCHO + 2C H .NH-NH 2
6
HC1.
Glucosone.
zinc dust
and acetic
may
Glucosone.
strawberries, pine-apples,
and other
fruits.
is
to
obtain
the
largest
possible
yield
of
crystallised
sucrose.
THR CARBOHYDRATES.
275
At about 200-210
gradually becomes opaque and crystalline.
sucrose loses water, and is gradually converted into a brown
mass called caramel,
which
is
largely
C 12 H22 U + H 2 = C 6 H 12
Sucrose.
Now,
left to
+ C6 H12
Glucose.
Fructose.
which
product,
fructose,
is
[]p= +66-5
of
slightly levorotatory.
consists
which
is
in 10 per cent,
parts of
When, there-
equal
dextrorotatory*
aqueous solution.
is
boiled
THE CARBOHYDRATES.
276
with
to
'
(sp.
gr.
1-1) con-
an enzyme,
verts
which is present in the yeast, conand fructose, and then alcoholic fermenWhen boiled with acetic anhydride and
invertase,
into glucose
it
tation
sets
sodium
in.
sucrose
acetate,
is
converted into
octacetylsucrose,
C 12 H 14 O 3 (0-CO-CH 3 ) 8 and
,
and
formed by the condensation of one molecule
of glucose with one molecule of fructose, but its constitution
has not yet been clearly established.
groups
this fact,
show that
it
is
Strontium sucrosate,
C 12 H 20 (SrOH) 2 O 11
Maltose,
C 12 H 22 O n
is
its
a granular substance of
use in separating sucrose
is
3(C 6
10
6 )n
+ nR 2
= C ia HM O u + wC 6 H 10
5,
THE CARBOHYDRATES.
and spirituous
liquors, it is
is
277
and
is
dextrorotatory
two-thirds as
ferments
with
readily
When
yeast.
boiled
C 12 H 22 O n + H 2 = 2C 6 H 12
a change
with
dilute
is
6,
an anhydride of the
latter.
C 12 H 20
maltose,
C 12 H 14 (C 2 H 3 O2 8 O 3
)
mammals
22
It occurs in the
as a by-product in the
When
H On
milk
is
and
is
obtained
manufacture of cheese.
and
on
the
crude
;
sugar
evaporation,
which are readily purified by re-
deposited in crystals,
crystallisation from water.
is
it
is
dextrorotatory.!
but
much more
It reduces
slowly than
10 per cent, of
C 12 H22 O 11
THE CARBOHYDRATES,
278
charic
and mucic
acids,
COOH{CH-OH] 4 -COOH,
like
the
Lactose
tartaric
is
acids,
in
their action
on polarised
light.
and galactose
into glucose
(p.
C 12 H 22 O n + H 2 = C 6 H 12
Lactose.
acid,
269),
6
+ C 6 H 12
Glucose.
6
Galactose.
POLYOSES.
Starch, dextrin, and
cellulose are all highly complex substances, the molecules of which seem to consist of combina-
monoses or
bioses,
with
loss of
example, in
as potatoes
The potatoes
in
fine
sieves,
The grain
which favours the subsequent washing of the starch, an operation which is carried out in the manner described above.
Starch
is
the
THE CARBOHYDRATES.
279
size,
as
diameters),
those
Fig. 22.
(a)
Barley Starch
(b)
Potato Starch
(c)
Wheat
Starch.
large,
those
The contents
water the granules swell up and then burst.
of the cells, or the granulose, dissolves, but the cell-wall,
or starch cellulose, is insoluble, and can be separated by
filtration;
THE CARBOHYDRATES.
280
precipitated as
as soluble starch.
is
is
known
is
is
10
(C 6
5 )ft,
acids, starch is
H 0> + wH
10
= wC 6 H 12
first
converted
glucose,
6
Malt
3C 6 H 10
+ H 2 = C 6 H 10
+ C 12 H 22 O n
The
is
C 6 H 10
the molecular
formula has not as yet been determined, but as it is undoubtedly many multiples of the empirical formula, it is
usually expressed by (C 6
Gluten.
Wheaten
10
5 )w.
flour contains
about by kneading flour in a thin calico bag under water, when the
starch passes through with the water, forming a milky liquid, from
which it is deposited on standing. The gluten remains in the bag
as a tenacious, sticky, gray mass, which soon decomposes and
smells disagreeably.
Both starch and gluten are very valuable food-stuffs.
Dextrin, (C 6
10
5 )rc,
is
the
name given
to the substance,
THE CARBOHYDRATES.
281
It
is
it
in the
Dextrin
is
a colourless,
amorphous substance,
soluble
in
and
water,
is
is
Cellulose, (C 6 10 6 )w, like starch, occurs very widely distributed throughout the vegetable kingdom. It is the principal
constituent of cell membrane and of wood, and constitutes,
and drying
Cellulose
is
at
100.
insoluble in
all
it dis-
is
powder.
Concentrated sulphuric acid gradually dissolves cellulose,
and if the solution be diluted with water and boiled, dextrin
and ultimately dextrose are produced. It is thus possible to
convert
wood
into sugar,
alcohol.
THE CARBOHYDRATES.
282
C 6 H 10
but
5,
greater than
its
this,
and
is
more frequently (C 12 H 20
When
chloride,
10 )ft.
by
is certainly
very much
therefore written (C 6 10 6 )?, or
molecular formula
which
C 12H 10 (0-CO-CH3 ) 10
is
alkalies.
and sulphuric
acids,
better,
or,
nitrates of
When
cotton-wool
is
with a mixture of
nitric
of variable
com-
cellulose
position are produced, according to the amount and concentration of the acids employed, and the length of time
This
thoroughly washing and drying, constitutes gun-cotton.
substance has, approximately, the composition C 12 14 (N0 3 ) 6 4
and
is,
It is insoluble in a
a flame
mixed with
it is
known
as ballistite or blasting-gelatine.
Cordite
is a
powder.
mixture of gun-cotton with camphor constitutes the
substance known as celluloid, which, although readily com-
When
of
of
THE CARBOHYDRATES.
283
The
the biases
(c)
by
The polyoses do not ferment with yeast, and do not reduce Fehling's
solution.
284
THE CARBOHYDRATES.
and also by the fact that they interact with phenylhydrazine, hydroxylamine, &c. ; that they contain hydroxyl-groups
is proved by their conversion into acetyl-derivatives (and in the case
of the polyose, cellulose, by its conversion into various nitrates).
reduction,
cyanohydrins
(p. 142),
When
CH
obtained
formed,
CH
+ 6I2
and consequently the fatty acid finally produced would not have
been normal heptylic acid, but one of its isomerides. Obviously.
also, the conversion of fructose into methylbutylacetic acid, taken
in conjunction
shows that
facts,
285
this sugar is a
constitution
ketone
expressed by the
formula already given (p. 271). In addition to this evidence, the
fact that glucose and fructose may be converted into secondary
hexyl iodide (p. 265) shows them to be derivatives of normal
its
is
hexane.
II. p. 555).
CHAPTER
XVI.
-CiN
(Gay-Lussac),
radicle,
as
although they
tain the
single
examples,
Cljj,
This fact brings out very clearly the meaning of the term
radicle,' the monovalent group -CN* playing much the
same part as the atom of chlorine, just as the radicle ammonium may play the part of a single atom of an alkali metal.
'
N=C
Cyanogen, dicyanogen, C 2 N 2 Cy 2 or
C=N, is produced in small quantities when the electric arc passes between
carbon poles in an atmosphere of nitrogen,
,
also
when ammonium
oxalate
is
phoric anhydride,
NH OOC-COONH4 = N=C
4
Cy
is
C=~N + 4H2 0,
-ON,
286
the nitrile
(p.
289) of oxalic
it
acid.
it
is
is
first
precipitated undergoing decomposition into
and
cuprous cyanide (compare behaviour of potassium
cyanogen
is
a colourless gas,
ammonium
contains
When
N=C C=N + 4H
*
= NH 4 OOC-COONH 4
many of
its
287
ammonium
in a
C1 2
Cyanogen
chloride,
CNC1,
is
of chlorine
on
by aqueous
C 3 N 3 C1 3 + 3H 2 O = C 3 N 3 (OH) 3 + 3HC1.
Cyanuric acid
is
on distillation
it is
(p. 295).
(or
free
state
more frequently
the
form of
the
glucoside* amygdalin
and
cherry kernels contain
(Part
418).
this glucoside; when macerated and kept in contact with
water, fermentation soon sets in, due to the presence of a
benzaldehyde in
II. p.
Bitter almonds
* The term
rjlucoside is applied to all those vegetable products which,
on treatment with acids or alkalies, yield a sugar, or some closely allied
carbohydrate, and one or more other substances (frequently phenols or
p. 298).
288
emulsin,
Amygdalin.
Hydrogen cyanide
is
Benzaldehyde.
Glucose.
and
also
is
is
heated
with phos-
which can
0.
or,
acid,
Potassium Ferrocyanide.
Ferrous Potassioferrocyanide.
hydrogen cyanide.
(10 parts) is mixed with concentrated sulphuric acid (7 parts) previously diluted with water
10-40 parts, according to the desired strength of the hydrocyanic
acid), and the mixture is distilled from a retort connected with a
The anhydrous acid may be prepared from the aqueous
condenser.
(
and dehydration
over calcium chloride, but very special precautions must be taken
to avoid accidents.
at
289
Hydrogen cyanide
solution
HCN + 2H
= H-COONH 4
On
if
a trace of some
if
the
solution be
alkalies.
is
The
constitution of
the formula
H-C:N
ammonium
produced from
that
hydrogen cyanide
formate,
acetate
(p.
may
be expressed by
The
is
acid
is
by a change similar to
formed from ammonium
293),
CH .COONH4 = CH
3
acids
acid, just as
is
methyl cyanide
-CN + 2H 2
it
is
H.CN + 2H 2 o = H.COOH + NH S
CH 3 -CN + 2H 2 - CHg-COOH + NH3
As, moreover,
many
facts
as
if
it
had the constitution H-NIC; its silver salt, for example, seems
to contain the metal directly united with nitrogen (compare p. 295).
Hydrogen cyanide is sometimes called formonitrile, the nitrile
of formic acid, or rather of ammonium formate, the name nitrile
being given to those compounds which are derived from ammonium
salts
on.
290
of the acid,
air,
cyanide.
KCN, may
be obtained synthetically by
in
It is prepared on a
cyanogen.
gently heating potassium
large scale by strongly heating potassium ferrocyanide alone,
Potassium cyanide,
After allowing to
settle,
is
air,
run
off
+ Fe.
carbide, or iron
The pure
salt
may
is
manu-
crystals
which are
precipitated.
Potassium cyanide
and
is
'
'
tailings
by the MacArthur-Forrest
cyanide process.
An
nitrate, a
Silver cyanide
plating.
to silver
that
KAg(CN) 2 which
,
is
it is
is
used in electro-
chloride,
when heated
291
it
its
properties
differs in this,
silver
and
cyanogen,
Mercuric cyanide,
Hg(CN) 2
is
made
cyanide
is
thus formed
ferric chloride,
blue
is
is
ferric chloride
an intense blood-red
produced.
The cyanides
of
many
of the
metals,
like
many
of the
'
is
salt of
may
cyanide,
Au(CN) 3
'
in
potassium
cyanide.
These
'double
decomposed
crystallise unchanged from
by mineral acids in the cold, with evolution of hydrogen
Like the soluble simple cyanides, they are excescyanide.
salts
sively poisonous.
292
salts,
K Fe(CN)
4
is
K Fe(CN)
4
potassium cyanide,
in an
is
crude
potashes
iron
pot
blood, &c.),
carbonate), and iron
(containing potassium
hair,
K Fe(CN)
4
from the
acid,
which
is
is
not anhydrous.
when
cyanide.
Solutions of ferric salts
ferrocyanide
precipitate
in
it
293
gives hydrogen
excess
of
ferrocyanide,
Fe4 [Fe(CN) 6 ] 3
Potassium
K Fe(CN)
3
6,
ferricyanide,
red
or
prussiate
of
potash,
is
The transformation
3KCN + Fe(CN) 3
is
formed.
in presence of
potassium ferrocyanide,
nitriles,
KCN + C H I = C H
2
or
by
distilling
pentoxide,
the
ammonium
-CN + KI,
salts,
some dehydrating
or the amides,
-COO]SrH4 = CH 3 .CN + 2H 9
3
C 2H5 .CONH 2 = C,H 5 -CN + H 2 0.
CH
of the
294
They
when
81) and
(b.p.
possessing a
readily soluble in water
octyl cyanide,
When
C 8 H 17 -CN,
-COOH
group,
= CH 3 .COOK + KH3
=
2H
H5 -COOH + NH4C1.
C
HC1
-CN +
+
2
2
5
For
this reason,
the
ammonium
the
after
and
salts of
which
acids
cyanide,
CH 3 'CN,
cyanide,
C2H
may be
obtained from
named
methyl
for example,
On
is
the nitriles
(p. 207),
The
isonitriles or
soluble in water
poisonous properties.
They boil at lower temperatures than the isomeric cyanides
methyl isonitrile, CH 3 -NC, for example, boils at 58 ; ethyl
isonitrile, C 2 5 -NC, at 82.
They differ from the nitriles, inasmuch
;
by boiling alkalies
295
HN=C.
In order to explain the difference in the constitution of the
products obtained by the action of alkyl halogen compounds on
potassium and silver cyanide respectively, it is necessary to assume
either that in the formation of silver cyanide from potassium
cyanide by precipitation, intramolecular change (p. 302) has taken
place, K-C=N yielding Ag-N==C, or that silver cyanide, Ag-C=N,
with the alkyl halogen compound, an additive profirst yields,
duct, which is then decomposed, yielding the isonitrile,
Ag-G=N + C 2 H 5 I = Ag-C
(p.
N<
= C=N.C2 H 5 + Agl.
C 3 N 3 (OH) 3 = 3HO-CK
It is a strongly acid,
above
and therefore the acid cannot be prepared by the decomposition of its salts with mineral acids.
Potassium cyanate,
KO-CN
(or
KN:CO),
is
air,
;
it
produced when
and
is
also
when
usually pre-
alcohol,
296
It is a colourless,
and dilute
aqueous
solution
ammonium and
rapidly
decomposes
with
formation
2KO-CN + 4H 2 = (NH4 ) 2 C0 3 + K 2 C0 3
"When a
of
potassium carbonates,
is
NH
Constitution of Cyanic Acid. Although cyanic acid is a comparatively simple substance, there is some doubt as to whether
its constitution should be expressed by the formula HO-C:N or
H-N:CO. The fact that it contains a hydrogen atom displaceable
by metals, and the formation of potassium cyanate from cyanogen
chloride, (Cl-C-N), point to the first formula; the following facts,
however, point to the alternative constitution.
HN:CO,
first
when
with sulphur,
the change being analogous to the formation of cyanates by
the oxidation of cyanides.
Thiocyanic acid
may
thiocyanate
dilute
sulphuric
acid;
it
is
297
a liquid,
It is
12-5, and has a very penetrating odour.
concentrated
with
acid,
by
moderately
decomposed
sulphuric
solidifies at
Potassium thiocyanate,
NH
ferric
salts,
)2
S.
caused
colouration,
as 'rhodanates.'
of ferric hydrate.
cyanide),
'
ammonium
ferrosalts,
CuS-CN,
is
ammonium
salt
by decomposing
is
it
'
298
evaporated.
Alkyl thiocyanates are produced by distilling the alkyl iodides
with potassium thiocyanate, or from the mercaptides (especially
lead mercaptide), by the action of cyanogen chloride,
(C 2
5 S) 2
shows that the alkyl-group is united with sulphur, and that the
esters are derived from an acid of the constitution HS-C N.
Tiheal/cyl isothiocyanates, or mustard-oils, are produced by heating
the normal thiocyanates at 180, or by simply repeatedly distilling
them, intramolecular change (p. 302) taking place,
C 2 H 5 .S-C;N
>
S:C:N-C2 H5
is
steam.
Mustard
seeds
contain
glucoside,
'potassium
'
myrosin
'),
C 10 H 18 NS 2
10
K = C H -N:CS + C H
3
12
+ KHS0 4
when
CHAPTER
299
XVII.
Two
-NH
classes
of
2,
(p.
less rapidly
by boiling aqueous
an alkali
stable
salts,
the
bases
and, although they form salts with strong acids, their salts
are very unstable ; for this reason and because they show a
These
facts afford a
good
illustration of the
manner
in
which
pound
group,
atom in an alkyl halogen commay be displaced by the amidohalogen atom of a substituted acid
Now,
so
may
the
166)
is
dissolved in concentrated
ammonia
the
at
ammonium
ordinary
salt
of
-CH 2 .COONH4 + NH 4 C1
+ 3H 2 0.
Glycine, or amido-acetic acid,
CH (NH
2
)-COOH, can be
300
it
prepared from this ammonium salt as described below
found in certain animal secretions, usually in combination.
;
is
As hippuric add
II. p. 430), it
(Part
urine of horses, and it may be prepared by heating hippuric
acid with hydrochloric acid,
HC1.
Glycine Hydrochloride.
in water,
The
properties.
H-CH 2 -NH2
confers basic
is
which
salt,
The
acid
is
sulphide
into
sulphide,
and evaporating.
its
aqueous
solution,
H N0
filtering
from
copper
its
(p.
229),
0.
301
acid,
with nitrous acid they yield the corresponding hydroxyacids (p. 232).
ammonium
The
esters of
NH
OH
Urea, or carbamide,
CH4 N"
or
CO(NH 2
) 2,
is
compound
human
urine, of
first artificially
p. 2).
Ammonium
CON H
302
differently
within
the
molecule,
transformed into
NH
NH
-0-C:N
-CO-NH
2
(or
NH4 -N:C:0)
being
.
>2
in
crystallises
is
in ether;
one of
132, and
at
dilute acids,
(or
and
it is
its salts),
when heated
but
alone
it
yields
ammonia, cyanuric
acid,
biuret,
is
is
produced.
Carbonyl chloride
p.
177).
Urea
303
is
dioxide,
hydroxyl-groups,
when
takes
similar
0} +
urea
change
place
solutions of hypochlorites or hypobromites,
is
2N 2 + 2H2
with
treated
off,
the
Urea possesses
basic
properties,
CO(NH 2 2,HN0 3
)
is
which
and
therefore be represented
may
by the formula
C0<^ fl
2
-
urea
and
H N4
Uric acid, C 5 4
urine, from which
it
and
reptiles.
The excrements
urate,
of
is
304
Uric acid
is
insoluble
in
alcohol
and
ether,
on
and very
addition
of
ammonia,
(murexide
reaction).
Uric acid
carbonate
it
is
weak
the acid
is
dibasic acid
yields an acid
salt,
C 5 H 2 N4
when
salt,
itself,
dissolved in sodium
C 5 H 3 N 4 3 Na + JH 2
Na 2 + H 2 0, is formed when
3
sodium
The
metallic
salts, like
by heating
ORGANIC CHEMISTRY.
PART
II.
CHAPTER
XVIII.
air,
it
When
and
the coal
is
The hot
exposure to the
it
Org.
Chem.
306
MANUFACTURE, PURIFICATION,
= 1,N 2
4,
4,
but
its
composition
(acetyis
very
variable.
The
coal-tar
two layers
liquor (a yellow, unpleasant-smelling, aqueous solution of ammonium carbonate, ammonium sulphide, and numerous other
considered to be an
source
sole
of
very
obnoxious by-product,
many
substances of
it
is
now
the
industrial
great
importance.
In order to partially separate the several constituents, the
tar is
are
it is
heated in large
wrought-iron
or retorts,
In
this
fractions
I.
IT.
III.
way
the tar
is
Heavy
oil
or creosote
IV. Anthracene
V. Pitch
oil
Collected up to 170.
between 170 and 230.
,.
oil
Residue
230
above 270 Q
it
270.
in
the
still.
which
is
oil.
This
oil
is
redistilled
307
distillate
collected in three
caustic soda,
The
collected
oil
obtained in this
between 82
'
'
acid.
On cooling,
and
finally
crystals
*
Commercial '90 per cent, benzol' contains about 70 per cent., and '50
per cent, benzol' about 46 per cent., of pure benzene; the terms refer to
the proportion of the mixture which passes over below 100 when the commercial product is distilled. Benzene, toluene, and xylene are known
commercially as benzol, toluol, and xylol respectively.
308
MANUFACTURE, PURIFICATION,
then drawn
off
an
which
is
oil
is
and
distilled
acid
and
270,
is
than water;
IV. The
crude
fourth
of
upwards, consists
fraction,
collected
270
at
and
on;
Y. The pitch in the
still is
still
hot,
and
is
obtained.
C6H 6
The crude
'
'
substances
on further fractional
distillation
in
specially
309
i
-2
, to
-ill
270
ove
RACENE
-27
arate
te.
tl
3
&
II II*
_32
<
-o
0*
rf.3
>>
llUli
-a
f l^lllf ^
O
e
310
MANUFACTURE, PURIFICATION,
constructed apparatus, it is
pletely into its constituents.
separated
more
or
less
com-
in this
way
still
the impurities
separately.
many
fact,
311
shown
(fig.
is
a piece
of
23).
Fig. 23.
rise,
and was
first
is
a process of poly-
accomplished by Berthelot.
It
is,
at
Pure
I. p.
81).
benzene
be
(C 6
2NaOH = 2C 6 H6 + CaC0 3 + Na 2 C0 3
C 6 H 5 .COOH = C 6 H 6 + CO,,
-COO) 9 Ca +
or
312
MANUFACTURE, PURIFICATION,
The
CH
density of
weight
C 6 H6
is
benzene, however,
is
which corresponds
78,
39,
that
so
its
molecular
refractive,
sp. gr.
is a colourless, highly
0-8799 at 20, but when
it solidifies
to a crystalline mass,
It has a burning
melting again at 5-4, and boiling at 80-5.
taste, a peculiar, not unpleasant smell, and is highly inflammable, burning with a luminous, very smoky flame, which is
its richness in carbon ; the
luminosity of an
ordinary coal-gas flame is, in fact, largely due to the presence
of benzene.
Although practically insoluble in water, benzene
mixes with liquids such as ether and petroleum in all pro-
indicative of
portions;
iodine,
and
for
is
like
the
latter,
it
readily
dissolves
fats,
resins,
derivatives.
and
even
solutions
of
such
powerful oxidising agents as chromic acid or potassium permanganate, it is only very slowly attacked and decomposed,
ordinary temperatures, converts the hydrocarbon into nitrobenzene by the substitution of the inonovalent nitro-group
-N0 2
for
an atom of hydrogen,
C 6 H 6 + HN0 3 m C 6 H 5 -N0 2 + H 2 0,
and concentrated sulphuric
313
it
into benzene-
sulphonlc acid,
C 6 H 6 + H 2 S0 4 = C 6 H 5 -S0 3 H + H 2 0.
action of chlorine and
The
remarkable
bromine on benzene
is
very
at moderately
ever,
the
hydrocarbon
is
only
slowly
attacked,
C 6 H 5 Br,
benzene,
again,
C 6 H 4 C1 2
dichlorobenzene,
some halogen
yielding
C 6 H 5 C1,
,
&c.
bromo-
when,
CHAPTER
XIX.
It will
benzene,
like
certain
conditions
if,
again,
its
properties
be compared
carbon
when
to
it is
CONSTITUTION OF BENZENE,
314
C 6 H 6 would seem
,
hydrocarbons.
In order, then,
to obtain
some
from benzene
(Part
I.
p.
compound dipfopargyt,
87),
may
be chosen, as
the former
is
is
it shows,
immediately oxidised even by weak agents
an unsaturated hydrocarbon of
;
the
acetylene series.
Benzene, on
the
other hand,
is
ex-
therefore,
dipropargyl
formula in order to
tion
account
CHs-CiC-C-C-CHg
or
CH 2 :C:CH.CH:C:CH
2,
form a
is
represented
may be
315
there
which has
still
is,
to
constitution of benzene
permit.
carbon
The point
is
referred to
one
another.
The whole
Now,
if
this
that two of
carbon atom
is
is
clear
two
represented
so
as
to
behaviour of benzene*?
give
the
Many
clearest
indication
of
the
316
CONSTITUTION OF BENZENE,
in 1865,
H-C
H-C
C-H
II
C-H
i
Clans.
Ladenburg.
(Prism formula.)
(Diagonal formula.)
It will
molecule
of
all
represent the
it
clear,
lies in
In Kekule's formula,
between
which
is
analogous to that
olefmes; in
other hand,
two
cases).
As
it
would be impossible
by
Baeyer,
the
that
constitution
of
317
benzene
A
Armstrong, Baeyer (Centric formula).
The fourth
the short
lines)
in order to
carbon atom.
formula, summarises
all
facts
than, any
formula,
it
'
bindings
of
unlike Kekule's
'
some indication
and the olefines
ness
the
a point in
of chemical
of
the
great
centric formula
its
difference
in chemical behaviour
may, in
affinity,
and
it
is,
is
between benzene
the very indefinite-
fact,
known
therefore,
be regarded as
of the nature
generally adopted
consists of a symmetrical closedchain of six carbon atoms, each of which is united with
one atom of hydrogen ; also to point out how simply and
accurately this view of its constitution accounts for a number
318
CONSTITUTION OF BENZENE,
In the
which would
pounds,
all
six carbon
it
easily
six,
but not
less
than
six,
fact
of,
but
HX
atom or group, so
pound of the type,
as to
form
com-
319
of benzene
that
it
possible to substitute
is
1, 2, 3, 4, 5,
or 6 monovalent
An
produced
that
is
products of
benzene exist only in one form ; when, for example, one atom
of hydrogen is displaced by a nitro-group, no matter in what
way
this
change
nitrobenzene,
CH
6
substance,
stance
is
is
it
In the case
is invariably produced.
has been shown that the same sub-
displaced.
320
CONSTITUTION OP BENZENE,
The only
is,
H-C
(a)
H <y
ll
H H
|
\C-H
(a)
in
it
the
(a),
(&),
hydrogen atoms.
are in the
same
state of combination,
321
manner
can be
it
C6 H4 (OH) 2
C 6 H 4 (N0 2)-OH
and
so on.
Now
the
existence
three
these
of
isomerides
can
be
simplicity.
C 6 H 5 X,
which,
HX
2, 3, 4, 5,
might be
-x
I.
II.
These
five
stances,
Org.
III.
IV.
V.
and
Chem.
CONSTITUTION OF BENZENE,
322
compound
relative
it
will
and I.
Each of the formulae i., n., and in., on the
respectively.
other hand, represents a different substance, because in no
two cases are all the atoms in the same relative positions
be seen at once that they are identical with
n.
experience has
different,
in
the
above
five
but that
i.,
of the atoms
ii.,
and
that
is
i.
identical with
is
v.,
and
n.
with
iv.,
arrangements
them by name
products which are found to have the constitution represented by formula i. are called ortho-compounds, and the
substituting atoms or groups are said to be in the ortho- or
1 2-position to one another ; those substances which may be
:
it
is
323
assumed,
instead of
directly united;
atoms
molecule
is
by
is
it
reason para-compounds may be represented by placing the substituting atoms or groups in the 1:4, 2:5, or 3:6-position.
When
substituted, it has
differs
according as the
identical or
by three
not.
identical
By
be easily accounted
for,
since
their
constitutions
may be
represented as follows,
-x
-x
1:2:3- or Adjacent.
1:2:4- or
Asymmetrical.
1:3:5- or Symmetrical.
324
No
CONSTITUTION OP BENZENE,
matter in what other positions the substituting atoms or
it will be found that the arrangement is
groups be placed,
x1:2:3:5.
1:2:3:4.
When, however,
by
five or six
identical
is
very considerable
HX
in the case of
any
tri-
in
also
for example,
325
and
two
As,
are
isomeric with the three (ortho-, meta-, and para-) ethylmethylbenzenes, C 6 4 (C 2 5 )-CH 3 and also with the three (ad-
jacent,
C 6H
the
OH
ci
- H
!
~CH 3
Chlorobenzene.
The omission
Trimetliylbenzene.
Nitroplienol.
Pyrocatechol.
of the symbols
C and
is
attended by no
convert the
because, in order to
disadvantage whatsoever,
above into the ordinary molecular formulae, it is only necessary
to write C 6 instead of the hexagon, and then to count the
is
C 6 H 5 C1
tri-
C 6 H 3 (CH 3 ) 3
is
326
CONSTITUTION OP BENZENE,
and
Cl
as l:2-chloronitrobenzene, as
C 6 H 4 <,,,.~
(i)
,
or as
C 6 H 4 C1-N0 2
C6B^<9^
(1)
,
or as
C 6 H 4 C1-N0 2
tri-
and adjacent
Br
246
as
but
it is
or
of course quite
numbering
is
commenced.
C 6 H 4 (OH) 2
benzene nucleus
it is
at the constitution of
327
Now
into
many
series; or^o-dinitrobenzene,
same
may
methylbenzene,
C 6 H 4 (CH S ) 2 and
,
constitution
of
other
di-substitution
product
di-substitution
belongs,
or
it,
is
known
must
also be
meta-compounds
it
would
also
be
other two dinitrobenzenes, melting at 116 and 173 respectively, in a similar manner must be either ortho- or para-
compounds
respectively.
be quoted.
Of the three dicarboxybenzenes, C 6 4 (COOH) 2
one namely, phthalic acid (p. 438) is very readily converted
,
CONSTITUTION OF BENZENE,
328
the
other two
acid.
compared,
Ul 2 -cooH
CH
X^^\_coo:
COOH
L2-COOH
coo
COOH
^v
COOH
COOH
stated here, phthalic acid
and
other
reasons
not
this,
as
an
be
ortf/io-dicarboxybenzene.
may
provisionally regarded
Again, the hydrocarbon mesitylene or trimethylbenzene,
C 6 3 (CH 3 ) 3 may be produced synthetically from acetone
formation in this way can be explained in
(p. 348), and its
For
simple
-CH 3
CH*
-CH 3
CH
COOH
Mesitylenic Acid.
-CH 3
CH 3 -
Dimetliylbenzene.
(m-Xylene.)
COOH
-COOH
Isophthalic Acid.
is
329
When
this
hydrocarbon
is
carefully oxidised,
it
yields an acid
matter which of the original three methyl-groups in mesitylene has been finally displaced by hydrogen, the remaining
two must occupy the m-position. Now when this dimethyl-
benzene
is
it
is
converted into a
oxidation,
difficulty,
provided that
it
is
possible
by simple reactions.
As the methods which have just been indicated are based
entirely on arguments drawn from analogy, or from deductions
as to the probable course of certain reactions, the conclusions
to which they lead cannot be accepted without reserve ; there
are,
by
further
displacement
of
hydrogen
of
the
330
CONSTITUTION OF BENZENE,
number
nucleus, the
from an
the
ortho-,
three
of isomerides
or
raeta-,
so
para-compound
that
the
in
different
number
of
by ascertaining
these products the constitution of the original di-derivative
may be established. In the investigation of the dibromocases,
C 6 H4Br2
benzenes,
- 1,
for
+1,
the or^/w-dibromo-compound,
it
is
it
-Br
-Br
-Br
Br
Br-
Br-
IV.
III.
the
Br
compound
of the constitution
in.
is
and
compound,
tri-derivatives,
Br
-Br
Finally,
if
BrBr
Br-
the substance in
Br
question
be
-Br
331
-Br
>i
>^
fT-
-Br
Br-
Br
1
Experiments showed that the compound melting at
two
tribromobenzenes
it
is
therefore
the
ortho-com;
gave
The dibromobenzene melting at +1 gave three
pound..
to
which
may
also
the
series
any
di-
be employed in
tri-derivatives
in
similar manner.
At
derivative
is
known
many compounds
of
constitution.
CHAPTER
XX.
derivatives
synthetically,
still
retain
much
or
may be
prepared
332
and
its
C nH 2n
series
(Part
I. p.
145),
now used
is
compounds which may be considered as derivatives of marsh-gas, and which cannot be regarded as directly
derived from benzene ; all the compounds described in Part I.
belong to the fatty group or division. Benzene and its
derivatives, on the other hand, are classed in the aromatic
to denote all
'
first
'
The fundamental
distinction
CH
CH (OH).CH(OH).CH
2
do
and
2 (OH),
carbon atoms
but an open-chain* of
may be regarded
terms.
it is
a closed-chain
compound,
333
is
clearly
member
may
group
all
be
also
by simple reactions, arid, conversely, many aromatic compounds may be converted into those of the fatty series.
Some examples of the production of aromatic from fatty
compounds have already been given namely, the formation
of benzene
by the polymerisation of
of mesitylene by the condensation of
may be
changes
manner,
expressed
acetylene,
acetone
in
graphically
the
following
H
C
CH
'
U
CH 3
CH 3
CO
CH 3
H;
CH 3-CO
CO-C 3
CO-CH
reactions, because
formations.
converted
leaving
and that
these two
it
may be
caused
Bromacetylene,
into
to
undergo
CBriCH,
(symmetrical)
many
analogous
for example,
tribromobenzene,
other
and acetone
trans-
may be
simply
by
and methylethyl ketone (a homologue of acetone) is transformed into symmetrical triethylbenzene (a homologue of
334
it
with sulph-
then,
more
is
very
characteristic,
+ H2
= C 6H 2 (OH)(N0 2) 3 + 3H 2
are
reduced,
C H 6 .N0 2 + 6H = C 6H 5 .NH + 2H 2
C 6H4 (N0 2 ) 2 + 12H = C 6 H 4 (NH 3 ) 2 + 4H 2 0.
fl
they are
335
at least
381) on treatment withbehaviour is highly charand the diazo-compounds form one of the most
acid
acteristic,
in
the
cold
(p.
this
additive
compounds
is
(b.p.
162),
composed
of six
compound
336
C 6 H 10 Br2 = C 6 H 8 + 2HBr
at 84-86, combines directly with bromine, giving a crystalline tetrabromide, C 6 8 Br4 and rapidly oxidises on exposure to the
it boils
air,
CH2
CH
CHBr
[<^T^>CH
CH 2
X^ NCH
CHx' |^>|CH
CH 2
^^
CHi
CH 2
^JcH 3
CH 2
^\CH
Benzene.
JcH2
L^^
CH 2
CH 2
CH
Hexahydrobenzene.
Bromohexahydrobenzene.
(Hexainethylene.)
(Broinohexamethylene.)
CH
CH
CHBr
CH 2
CH
CH 2
^ ^^ CH
CH 2
Tetrahydrobenzene.
CH
CH 2
CHjj
1JOI1
CH2
CH 2
Dibromohexahydrobenzene.
Dihydrobenzene.
(Dibroinoliexaniethylene.)
It is very important to note that dihydro- and tetrahydrobenzene, which must be regarded as incompletely or partially
reduced benzene, differ very much from the original hydrocarbon,
the difference being, in fact, much the same as that which exists
between unsaturated and saturated compounds in other words,
when benzene combines with two or four atoms of hydrogen, the
product is no longer characterised by great stability, but shows the
ordinary behaviour of unsaturated compounds, inasmuch as it is
;
is
also
337
When
in the
same way
as in ethylene.
these
alcohol,
contain a side-chain,
ethylbenzene,
methyl-
C 6 H 5 -OH, nitrobenzene,
where the substituting groups are comparatively simple, and do not contain carbon atoms.
Now the character of any particular atom or group in the
side-chain, although influenced to some extent by the fact
that the group is united with the benzene nucleus, is on the
whole very similar to that which it possesses in fatty combe applied in the case of phenol,
C 6 H 5 N0 2
&c.,
The consequence
pounds.
is
that aromatic
compounds con-
also,
to a certain extent,
the behaviour
when
Ortt.
ethylbenzene.
Chem,
C 6 H 5 -CH 2 -CH 3
V
or
propylbenzene,
338
C 6 H5 -C 6 H 5
dipTienyl,
for example,
which, theoretically,
CH -CH
3
two methyl-groups,
3,
is
can only be
re-
The hydrocarbon
C 6 H5 -
is
groups, just as
assumed,
as,
and anthracene
(p.
470),
Anthracene.
Naphthalene.
and there
CHfe
Qninoline.
many
closely in constitution.
HOMOLOGOES OF BENZEXE,
CHAPTER
339
ETC.
XXI.
is
from marsh-gas.
C 6 H 5 -CH 3
benzene,
like
benzene
higher
itself,
exists
homologue,
in
which
only one
has the
namely, as ethylbenzene,
series,
the
number
increases.
namely,
benzene,
C 6 H 3 (CH 3
of foreign substances.
340
HOMOLOGUES OF BENZENE
The
homologues
of
^(1)
may be
benzene
obtained
by the
By
halogen
chloride (Friedel and Crafts' reaction) ; under these conditions the hydrogen atoms of the nucleus are displaced by
alkyl-groups, benzene and methyl chloride, for example, giving
advisable.
is first
CH
Anhydrous
aluminium
(2)
By
tive of
Al a Cl s +
CH3 C1 = C H
may
-CH 3 + A1 2 C1 6
benzene or of one of
its
341
halogen compound, with sodium or potassium (Fittig's rethis method of formation is similar to that by which
action)
higher paraffins
yield
o-,
m-, or ^-ethylmethylbenzene,
^
pTT
+ KBr + KI.
^2^5
By
(3)
heating
carboxy-derivatives
homologues with
soda-lime,
benzene
of
method
analogous
and
to
its
that
paraffins (Part
I.
By
passing
benzene and
its
C H 5 .OH + Zn - C 6 H 6 + ZnO
C 6 H 4 (CH 3 ).OH + Zn = C 6 H 5 -CH 3 + ZnO.
tt
(5)
By
many
fatty
compounds through
General Properties.
colourless, mobile
are
crystalline
out
nt
Most
homologues of benzene
one or two, however, are
of the
liquids
ordinary temperatures.
decomposing,
are
volatile
in
They
steam,
all
distil
with-
and
burn
with
HOMOLOGUES OF BENZENE
342
?ttcw0-substitution products of
H
H
Benzene, C 6 6
Toluene, C 7 8
Ethylbenzene, C 8
Propylbenzene, C 9
benzene
may be
considered
H
H
10
12
B.p., 80-5
110-3
0-883
..
0-881
..
134
158
There
three hydrocarbons
isomeric with
are, however,
ethylbenzene (p. 347), whilst propylbenzene has seven isomerides (p. 339), so that the original homologous series
given above branches into a number of series, in which the
there
is
physical properties,
rather variable ; the three xylenes,
show the following differences
C 6 H 4 (CH 3) 2
for example,
Orthoxylene.
Metaxyleiie.
Sp. gr. at
0-893
0-881
B.p.
142
139
As
Paraxylene.
880
138 (M.p. 15)
a general rule, to which, however, there are some expara-compounds melt at a higher temperature than
ceptions,
ortho-compounds;
and sulphonic-derivatives
toluene,
for
toluene-
sulphonic
xylene,
343
nitro-
(5
'
In these, and
product invariably
a rule, the greater the number of alkyl-groups in the hydrocarbon, the more readily does it yield nitro- and sulphoiiicderivatives.
All the homologues of benzene are very stable, and are with
compounds containing a smaller number
of carbon
atoms
chromic
act
(p.
436),
C 6 H 5 -CH 3 + 30 = C 6 H 5 -COOH + H 2
C 6 H 5 .CH 2 .CH3 + 60 = C 6 H 5 .COOH + C0 2 + 2H 2
C 6 H 4 (CH 3 ) 2 + 60 = C 6 H 4 (COOH) a + 2H 2 0.
Although in most cases oxidation leads to the formation of a
carboxy-derivative of benzene, the stable nucleus of six carbon
atoms remaining unchanged, some of the homologues are completely oxidised to carbon dioxide and water (compare p. 347),
and benzene itself undergoes a similar change on prolonged and
vigorous treatment.
HOMOLOGUES OP BENZENE
344
These
hydrocarbons by taking away atoms of hydrogen.
radicles have no actual existence, but the assumption is useful
in
di-substitution
products of benzene, for example, may be regarded as compounds of the monovalent radicle phenyl, C 6 5 -, or of the
divalent
radicle pheni/lene,
C 6 4 <, respectively, as in
phenylamine
(aniline),
C 6 H 5 -NH 2 and
,
in
o-,
m- and
jp-phenyl-
CH
called
The
alcohol.
benzyl
isomeric
hydroxy-compounds,
C 6 H 4 (CH 3 )-OH,
cresols (p.
f^TT
xylylene,
C 6 H 4 <C ri -rj 2
are
also
made
OJtlo
of.
or phenylmethane, C 6 H 5 -CH 3
from
the 90 per cent, benzol
although always prepared
separated from coal-tar (p. 307), can be obtained by any of
Toluene,
methylbenzene,
'
the
reactions
general
distillation of
other resins.
Pure toluene
Tolu, or
It is a
110;
it
345
very closely in
some
of
paraffin.
The hydrogen
be
may
displaced by chlorine, for
a
and
the
latter
by
hydroxyl- or amido-group, by
example,
methods exactly similar to those employed in bringing about
this
similar
methyl-group
changes
C 6 H 5 .CH 2 C1,
in
compounds, substances
fatty
such as
C 6H 5 -CH 2 .NH 2
being
This behaviour was of course to be expected, since
toluene or phenylmethane is a mono-substitution product of
obtained.
CH 3
Ortho-xylene.
Meta-xylene.
Para-xylene.
in coal-tar,
Elhylbenzene.
'
o-
and ^-compounds
HOMOLOGUES OF BENZENE
346
all impurities by further distillaby any simple means, although it is possible to obtain
a complete separation by taking advantage of differences in
tion, or
chemical behaviour.
7/i-Xylene is readily separated from the other isomerides by digesting with dilute nitric acid, which oxidises o- and ^?-xylene to the
corresponding toluic acids, C 6 4 (CH 3 )-COOH, hut does not readily
attack w-xylene ; the product is rendered alkaline by the addition
hydrocarbon purified by
The
isolation of o-
distilla-
and ^?-xylene
The
three xylenes
may
all
^-compound
are obtained,
;
in these
two
cases
shows that
C6H4
PTT
PTT
+ ffaBr + Nal,
347
is
easily
The
inflammable
some
CH 3
-COOH
COOH
\
I
COOH
Ortho-toluic Acid.
On
Meta-toluic Acid.
Para-toluic Acid.
C 6 H 4 (COOH) 2
The
are
formed
436).
show
three hydrocarbons
(p.
more
Etliylbenzene, or plienylethane, C 6 5 -C
5
of the xylenes, is not of much
importance ;
coal-tar,
and may
be
obtained
an isoineride
it
by the general
occurs
in
methods.
348
It
HOMOLOGUES OF BENZENE
a colourless liquid, boiling at 134,
nitric acid or chromic acid it
is
with dilute
and on oxidation
is
converted into
benzoic acid,
C 9 H 12 and
,
pointed out
exists, as already
(p.
339), in eight
isomeric forms,
of
CH 3
J-CH 3
CH 3 -L
occurs in small quantities in coal-tar, but is most conveniently prepared by distilling a mixture of acetone (2
concentrated sulphuric acid (2 vols.), and water
vols.),
(1 vol.),
3(CH 3 ) 2 CO = C 6 H 3 (CH 3 ) 3 + 3H 2 0.
The formation of mesitylene in this way is of interest not only
because it affords a means of synthesising the hydrocarbon from its
elements, but also because it throws light on the constitution of
the compound.
Although the change is a process of condensation,
and is most simply expressed by the graphic equation already given
(p. 333), it might be assumed that the acetone is first converted
into CH 3 -C CH, or into CH 3 -C(OH): CH 2 (by intramolecular change),
and that mesitylene is then produced by a secondary reaction
whatever view, however, is adopted as to the actual course of the
reaction (unless, indeed, highly improbable assumptions be made),
the final result is always the same, and the constitution of the
for this
product is best expressed by a symmetrical formula
i
is
trimethyl benzene.
Mesitylene
is
boiling at 164-5,
it
yields
nitric
converted
into
C 6 (]Sr0
trinitromesitylene,
it
349
(CH 3 ) 3
)3
On
by the conversion
of one or
by treating a mixture
aluminium chloride,
of isopropyl
C 6 H 6 + C 3 H7 Br = C 6 H 5 .C 3 H7 + HBr,
and by the action of sodium on a mixture of bromobenzene
and isopropyl bromide,
C 6 H 5 Br + C 3 H r Br + 2Na = C 6 H 5 .C 3 H 7 + 2NaBr.
It is a colourless liquid, boiling at
with dilute
Cymene,
is
CioH 16
= C 10 H 14 + H 2 0,
HOMOLOGUES OF BENZENE
350
is
boils at
175-176; on
C 6 H 4 (COOH) 2
acid,
terepMhalic
hydrogen
aromatic
C 6 H 5-C 6 H 5
Diphenyl,
is
2C 6 H 5 Br + 2^"a = C 6 H 5 .C 6 H 5 + 2NaBr,
the
reaction
(dimethyl)
(Part
I. p.
from methyl
58).
purified
fractionated,
alcohol.
yields
destroyed.
benzoic
Its
acid,
one
of
the
benzene nuclei
nitric
being
acid,
and
sulphuric
is
similar
that of
to
351
benzene,
substitution
zene nuclei
it
benzyl chloride
is
crystalline
treated with
nitric
usual way, and on oxidation with chromic acid it is converted into diphenyl ketone or benzophenone, C 6 5 -CO-C 6 5
424).
(p.
Triphenylmethane, (C 6
5) 3
CH,
is
the
parent substance
of an important group of
It
three benzene nuclei.
362)
(p.
is
chloride,
C 6 H 5 -CHC1 2 + 2C 6 H 6 = (C 6 H 5 ) 3 CH + 2HC1,
it is usually prepared by heating a mixture of chloroform
and benzene with aluminium chloride,
but
CHC1 3 + 3C 6 H6 = (C 6 H 5 ) 3 CH + 3HC1.
Aluminium
chloride (5 parts)
of chloroform (1 part)
at about 60
is
and benzene
(5 parts),
by
recrystallisation
352
HOMOLOGUES OF BENZENE,
When
a
treated with
yellow,
fuming
crystalline
acid
nitric
ETC.
is
it
converted into
CH(C 6 H 4 -N0 2
tfn'wfro-derivative,
) 3,
On
employed as dyes
(p.
519).
CHAPTER
5)3
is
con-
C-OH.
XXII.
The
ITS
HOMOLOGUES.
action of halogens on benzene has already been re(p. 313), and it has been pointed out that the
ferred to
antimony;*
The homologues
when treated with
of benzene also
chlorine or bromine at ordinary temperatures in absence of direct sunlight, they are converted into
substitution products by the displacement of hydrogen of
the nucleus, and, as in the case of benzene itself, interaction
is
greatly
ETC.
353
of o-
C 6 H 5 .CH 3 + C1 2 = C 6 H4
<^ +HC1.
C C H 5 .CHC1 2 and
,
xylene, again,
benzotrichloride,
when heated
chloride,
formed ;
and treated
at its boiling-point
n H <,CH 2 Br
C
6
4
CH 3
and
n _
H4 <,CH2 Br
C
6
CH
'
Br
ducts,
are obtained.
of the
derivative,
and reconverts
it
however, iodic acid, or some other substance which decomposes hydrogen iodide, be present, iodo-derivatives may
if,
Org.
Chem.
354
Chloro-
Preparation.
and
its
homologues may
and bromo-derivatives
be prepared by direct
'
of
benzene
clilorination
'
'
or
bromination,' the conditions employed depending on
whether hydrogen of the nucleus or of the side-chain is to
be displaced ; if, for example, it were desired to convert
toluene
into
chloride,
p-chloro'benzyl
the
hydrocarbon might be
C 6 H 4 C1-CH 3
first
after having been separated from the accompanying ortho-compound, would then be heated to boiling in
a flask connected with a reflux condenser, and a stream of
,
it.
damp
coke.
(p.
381),
method is used
iodo-compounds, and that
that this
it
is
in
only necessary
the preparation
affords a means
of nearly all
it
of indirectly substituting any of the halogens, not only for
hydrogen, but also for nitro- or amido-groups.
*
HIO 3 + 5HI = 3I2 + 3H2 O. lodo- substitution products are also frequently formed on employing FeCl 3 or A1C1 3 as a carrier, because the IC1
which is formed has a much more energetic substituting action than the
iodine itself, owing to the simultaneous formation of HC1,
,
C6 H 5
AND
The conversion
ITS
HOMOLOGUES.
355
Nitrobenzene.
C 6 H 5 -N 2 C1 -> C 6 H 5 C1
Amidobenzene.
Diazobenzene
Chlorobenzene.
Chloride.
Toluene.
Nitrotoluene.
The preparation
Diazotoluene
Bromide.
Aniidotoluene.
of a ^'-halogen derivative
Broniotoluene.
may sometimes
it is
atom
C 6 H 5 Br
C H4 <
NO>
Broino-
Nitrobromo-
Amidobromo-
benzene.
benzene.
benzena
fl
C6 H4 <
N H2
C 6 H4 <
r
N 2C1 ->C H <cl
l
DiazobromoBromochlorobenzene Chloride.
benzene.
Halogen derivatives of benzene and its homologues are sometimes prepared by treating hydroxy-compounds with pentachloride
or pentabromide of phosphorus, the changes being similar to those
which occur in the case of fatty hydroxy-compounds; if the
hydroxyl-group be present in the nucleus, the halogen naturally
takes up the same position, phenol, for example, giving chlorobenzene, and cresol, chloro toluene,
an aromatic alcohol
may
also be obtained
by
distilling
C 6 H 4 Br.COOH = C 6 H 5 Br + CO 2
halogen
356
by heating sulphonic
chlorides
(p.
chloride,
At ordinary
benzene and
homologues are
its
colourless
They
liquids ; the majority, however, are crystalline solids.
are all insoluble, or nearly so, in water, but readily soluble
in alcohol, ether, &c.
Many are readily volatile in steam,
and distil without decomposing, the boiling-point being
higher and the specific gravity greater than that of the parent
and rising also on
for bromine.
or
iodine
chlorine,
hydrocarbon,
substituting
Bromobenzene.
bromine for
lodobenzene.
Benzene.
Chlorobenzene.
B.p
80-5
132
155
188
Sp.gr. at
0-899
1-128
1-521
1-857.
They
vapours
it
is,
and cannot
at
high
phenols,
C 6H 4 C1-N0 2
temperatures,
yielding
C 6 H4 (OH)-N0 2 and
,
the
corresponding
nitranilines,
w-chloronitrobenzene, however,
is
nitro-
C 6 H 4 (NH 2 )-N"0 2
AND
conditions, a fact
ITS
HOMOLOGUES.
357
H
H
C 6 H 5 .CH 2 .NH 2
it
yields benzyl-
380).
(p.
however, are
C 6 H 5 C1, may
be de-
may be
trichlorobenzenes,
C1 2
also
from ethyl chloride and from other fatty alkyl halogen compounds in being unacted on by water and alkalies, or by
358
metallic salts
it is
CH -COOC H
acetate,
is
easily obtained
from ethyl
Bromobenzene, or phenyl bromide, C 6 5 Br, may be prepared from diazobenzene sulphate by Sandmeyer's reaction,
using cuprous bromide (p. 384)-; also by brominating benzene
in presence of iron.
part) is placed in a flask, provided with a reflux
together with a little iron wire, and the bromine
(2 parts) is added gradually from a stoppered funnel, the bent stem
of which passes through the cork of the flask ; the hydrogen
bromide which is evolved is absorbed by leading it into a tower
Benzene
(1
condenser,
Bromobenzene
is
As a rule,
closely resembles chlorobenzene in all respects.
more
the
bromo-derivatives
readily, and
however,
crystallise
have a higher melting-point than the corresponding chlorocom pounds.
lodobenzene,
C 6 H 5 I,
iodine alone on benzene, but it is formed when the hydrocarbon is heated with iodine in presence of iodic acid at
about 220
C 6 H 5 .N 2 HS0 4 + KI = C 6 H 5 I + KHS0 4 + N 2
Aniline
is
AND
It
359
is
when
HOMOLOGUES.
ITS
it
Cl
the
into
well -cooled
solution,
the
C 6 H 5 I<Cpn
dichloride
separates in crystals (Willgerodt), the iodine becoming trivalent, as it probably is in iodine trichloride, IC1 3
lodobenzene dichloride is slowly decomposed by dilute
.
C 6 H 5 IO,
is
colourless,
amorphous sub-
salt
C 6 H 5 IO + 2C 2 H 4
it
also
is
an oxidising
and water,
2
= C 6 H 5 I(C 2 II 3
agent,
and
2)2
+ H2
liberates
iodine
from
C 6H 5 IO + 2HI - C 6 H 5 I + 1 2 + H 2 0.
When
iodosobenzene
is
undergoes a most interesting decomposition giving iodobenzene, which distils over with the water, and iodoxybenzene,
it
which
is
non-volatile,
lodoxybenzene, C 6 5 I0 2
the aqueous solution
,
when
and
then
allowed
about 230.
properties,""
to
cool
separates
is
;
in
colourless
needles
360
This product
is
investi-
separately
(p.
C6H4
<J + PC1
= C6H4
<cH
cresols
+ POCI 3 + HC1,
3
64
Toluidine.
64
O
Diazotoluene Chloride.
64 CH
O
Chlorotoluene.
AND
ITS
HOMOLOGUES.
361
(p.
phorus pentachloride,
is
by passing
always prepared
toluene,
chlorine
into
boiling
The toluene is contained in a flask which is heated on a sandbath and connected with a reflux condenser; a stream of dry
chlorine is then passed into the boiling liquid until the theoretical gain in weight has taken place and the product is purified
by fractional distillation ; the action takes place most rapidly in
strong sunlight.
Benzyl chloride
boiling at
176;
alcohol, ether,
is
it
is
benzene, &c.
compounds towards
It
nitric acid,
by which
it
converted into
is
common with
is
the
chloride,
it
corresponding
415),
compounds
slowly decomposed by boiling
alkyl
ing the
(p.
halogen
like
in
ethyl
water, yield-
benzyl alcohol
hydroxy-compound,
C 6 H 5 .CH 2 C1 + CH 3 -COOAg =
Benzyl chloride
importance,
is
(p.
418).
-C 6
+ AgCl.
inasmuch as
benzaldehyde
CH3 .COOCH
it
is
362
Benzol chloride,
C 6 H 5 -CHC1 2 may
,
ETC.
be obtained by treating
206, and
it is
is
extensively
C 6 H 5 -CC1 3
it
boils at
is
also
213, and
CHAPTEK
XXIII.
NITRO-COMPOUNDS.
It has already
properties of aromatic
they
may
way
more
it
is
especially because
'
Preparation.
Many aromatic compounds may be nitrated
that is to say, converted into their nitro-derivatives, by dissolving them in concentrated nitric acid (sp. gr. 1-3 to 1-5),
in the cold or at ordinary temperatures, and under such
conditions a mononitro-compound is usually produced ; benzene, for example, yields nitrobenzene,
of o- and p-nitrotoluenes,
C 6 H 6 + HN0 3 = C 6 H 5 .N0 2 + H 2
C 6 H 5 -CH 3 + HN0 3 = CgH^CHgJvNOj + H 2 0.
363
NITRO-COMPOUNDS.
Some
acid,
and
the substance
is
When
interaction.
and
is
trinitro-derivatives
of
when heat
especially
three
dinitro-benzenes,
C 6 H 6 + 2HISr0 3 = C 6 H 4 (N0 2 ) 2 + 2H 2 0.
As soon as nitration is complete (portions of the product may be
tested from time to time), the solution or mixture, having been
cooled if necessary, is poured on to ice or into a large volume of
water, and the product, which is usually precipitated in crystals,
separated by filtration, or
some other manner.
Generally
if
an
speaking, the
oil,
by extraction with
number
of
ether, or in
hydrogen atoms
dis-
when
as,
for
w-nitro-derivative
example,
is
-N0 2 -COOH,
,
formed, whereas,
when
and
-S0 3 H,
in question is a halogen, an alkyl, or an amido- or hydroxylgroup, a mixture of the o- and j9-nitro-derivatives is produced.
This directing influence of an atom or group already combined with the nucleus, on the position which is taken up by
a second atom or group, is by no means restricted to the case
364
NITROCOMPOUNDS.
of nitro-compoimds, but
is
all
it is
groups,
Cl,
Br,
N0 2 S0 3 H,
,
of the nucleus,
displacing hydrogen
NH
CH
compound.
When, on the other hand,
A = N0 COOH, S0
2,
a raeta-derivative
small
quantities
is
of
H,
formed.
These statements
also
hold good
when two
identical
atoms
many
liquids;
of
them
exception of certain
mono-nitro-derivatives, cannot
be
dis-
and
is
I.
is
by the hydroxyl-group on
365
NITRO-COMPOUNDS.
treatment with aqueous or
alcoholic
temperatures.
namely,
(p.
reaction
on
behaviour
368).
the
of
reduction,
nitre-compounds
is
described
later
C 6 5 -N0 2 is usually prepared in the laboratory by slowly adding to benzene (10 parts) a mixture of
nitric acid of sp. gr. 1-45 (12 parts) and concentrated
Nitrobenzene,
benzene which
produced
this
three
is
different.
a current of steam.
it
is
poisonous,
it
is
often employed
(p.
of
oil
of
bitter
almonds
for
373).
366
NITRO-COMPOUNDS.
nitrobenzene
is
part)
(1
completely
when
stirred
the
first
is
w-phenylenediamine
(p.
(p.
375),
meta-diamidobenzene,
C 6 H 4 (NH 2
)2
376).
o-D'mitrobenzem and p-dinitrobenzene are colourless, crystalcompounds, melting at 118 and 173 respectively; they
line
on reduction, and
however,
much
(p.
as
differs
it
o-Dinitrobenzene,
respects.
interacts
405), and,
most other
in
the w-dinitro-compound
anhydrosulphuric
acids
The halogen
at
it
crystallises
in colourless plates
121-122.
by chlorinating or brominating
nitro-
367
NITRO-COMPOUNDS.
C 6 H 4 Cl-ISr0 2
C 6 H 4 Br-N0 2
C 6 H 4 LN0 2
Chloronitrobenzene,
Bromonitrobenzene,
lodonitrobenzene,
They
are,
Ortho.
Meta.
Para.
32-5
444
41-5
56
126
49
33
171
properties,
except that, as already pointed out (p. 356), the o- and pcompounds differ from the m-compounds in their behaviour
recalls
it
Many
CHAPTER XXIV.
AMIDOCOMPOUNDS AND AMINES.
The hydrogen atoms
in
ammonia may be
displaced
by
as,
differ in
is
however, those
directly united
many important
respects
368
A mido-compo unds.
The
amido-compounds
may,
be
therefore,
as
regarded
C 6H4 (NH 2 ) 2
Amidobenzene
With
H (NH
6
3
2 )3
Triainidobenzeiie.
Diamidobenzene.
(Aniline).
three or
fourth
isomeride
C 6 H 5 .CH 2 .NH 2
of
(p.
the
380)
toluidines
namely,
benzylamine,
The amido-compounds
and hydrochloric
C 6H 5 -N0 2 + 6H = C 6 H 5 .NH 2 + 2H 2
C 6 H 4 (CH 8 ).ff0 2 + 6H = C 6 H 4 (CH 3 )-NH 2 + 2H 2
C 6 H 5 .N0 2 + 3SnCl 2 + 6HC1 = C 6 H 5 -NH 2 + 3SnCl 4 + 2H 2 0.
Reduction is usually effected by simply treating the nitro-compound with the reducing mixture without a special solvent, when
a vigorous reaction often ensues, heating being seldom necessary
except towards the end of the operation. The solution contains the
amido-compound, combined as a salt with the acid which has been
when, however, tin or stannous chloride and hydroemployed
chloric acid have been used, a double salt of the hydrochloride of
the base and stannic chloride is produced in the reduction of nitrohas
benzene, for example, the double salt, aniline stannichloride,
;
369
The amido-compound
the composition (C 6 H 5 -NH2 HC1) 2 SnCl 4
liberated by adding excess of caustic soda or lime, and distilled
,
is
The reduction
the
first
there
is
of
in
is
converted
p-Phenylhydroxylamine
and, like hydroxylamine,
hydrochloride
C6H
it is
Nitro-com pounds
may
also
be reduced to amido-compounds
off,
When
so
that
only
Org.
partial
Chem.
reduction
takes
place.
Dinitrobenzeno,
for
370
fl
H <** + 3SH
4
= C6H4
<]*? +
2H2 + 3S.
PTT
CH
H, HC1 -.
p-Toluidiue Hydrochloride.
Methylaniline Hydrochloride.
C6H 5 .N(CH3 ) 2
v^
\NH 2
Methyl-p-toluidine.
Dimethylaniline.
Xylidine.
The diamido-compounds, such as the 0-, m-, and ^-diamidobenzenes or phenylenediamines, C 6 4 (NH 2 ) 2 are prepared
by
either
reducing
C 6 H4 (N0 2 ) 2
the
generally
acid.
The monamido-compounds
Properties.
less
dinitrobenzenes,
C 6 H 4 (N0 2 )-NH 2
or the nitranilines,
corresponding
which
liquids,
specifically heavier
distil
without
than water
and dissolve
They
are
litmus, in
black.
comparatively weak
which
-respect
bases,
to
371
will
phenyl
radicle,
for this
(p.
is
and other
regarded
When two hydrogen atoms in ammonia are displaced by phenyl(p. 379), the product is so
groups, as in diphenylamine, (C6 5 ) 2
Triphenylfeebly basic that its salts are decomposed by water.
does not form salts at all.
amine, (C 6 5 3
(p. 380), moreover,
H NH
H N
)
N0 2-,
C1-, &c.,
I.
p.
207),
when
372
It will be evident
are
nevertheless, except as
regards
its state of
those
combina-
points already
tives,
C 6H 5 -N(CH 3 ) 2
and
&c.,
also
trimethylammonium iodide,
spond with the quaternary ammonium salts (Part I. p. 210).
They are also readily acted on by acid chlorides and
anhydrides, and even by acids on prolonged heating, yielding
substances such as acetanilide and acetotoluidide, which are
closely allied to the fatty amides (Part I. p. 164), and from
which they may be regarded as derived,
Aceto-p-toluidide.
these
compounds
are crystalline,
and serve
with acids or
alkalies,
The amido-compounds,
the carbylamine reaction
is
when
nauseous smell
carbylamine (Part
I.
O.
373
C 6 H 3 (NH 2 ) 8
(o.
m.%).)
C 6 H 4 (NH 2 ) 2 and
,
the
as
C 6 H 3 (NH 2 ) 3 2HC1,
,
Aniline and
its
acid.
Derivatives.
first
benzene was
Aniline
is
its
first
is
tin
and hydrochloric
acid,
C6 H 5 .N0 2 + 6H = C 6 H 5 -NH 2 + 2H 2 0,
2C 6 H B -N0 2 + 3Sn + 12HC1 = 2C 6 H 5 -NH 2 + 3SnCl 4 + 4H 2 0.
Nitrobenzene (50 grams) and granulated tin (80 grams) are placed
in a flask, and concentrated hydrochloric acid (290 grams) added
in small quantities at a time ; at first the mixture must he cooled
if
when
all
the product is gently heated on a water-bath until drops of nitrobenzene are no longer visible. The solution of aniline stanniis now treated with soda until strongly alkaline, the
liberated aniline distilled in steam, and, after saturating the distillate with salt, the base is separated with the aid of a funnel,
chloride
and purified by
distillation.
a faint,
oil, boiling at 184 ; it has
odour, and is sparingly soluble in water, but
readily in alcohol and ether ; it gradually turns yellow when
exposed to light and air, becoming ultimately almost black.
Aniline
is
a poisonous
characteristic
374
aniline
as
hydrocliloride,
soluble
sparingly
salts
?,
(C^-NH^ H
former, like
double
C 6 H 5 -NH.
sulphate,
S0 4
The
&c.,
forms
on treating a
(C 6
.NH 2 ) 2
When
H PtCl
2
which
is
6)
alcoholic
it
produced.
When
nitrous
at
of
diazo-com-
pounds (p. 381) are formed ; but on warming, the latter are
decomposed with formation of phenol (p. 404).
Aniline is very largely employed in the manufacture of
dyes, and in the preparation of a great number of benzene
derivatives.
formed
is
of water.
by
The product
recrystallisation
is purified by
from boiling water,
distillation or
simply
It crystallises in
glistening plates, melts at 112, and is
sparingly soluble in cold, but readily in hot water; when
heated with acids or alkalies it is rapidly hydrolysed, giving
*
Compare Part
I.
p. 176.
AM DO-COMPOUNDS
I
and
aniline
acetic acid.
375
J\XD AMINES.
It is used in medicine,
under the
name
C 6 H5 -NH-CHO,
Formanilide,
and
oxalic acid,
the
CgH^NH-CO-CO-NILC^,
oxanilide,
may
body
the
anilide
of
be similarly prepared.
Aniline and, in
fact, all
amido-
When
treated with
so
indirect
The
di-substitution
products
o-
Chloraniline.
Chloracetanilicle.
The
is
effect of introducing
acetanilide,
Nitranilines,
C 6 H 4 (ISr0 2 )-NH 2
The
the
m-Nitraniline
is
very
readily
376
C 6 H 4 (N0 2 ) 2
duction of w-dinitrobenzene,
with
ammonium
sulphide
(p. 369).
o-Nitraniline melts at
71,
in- at
114, andjp-
at
147;
they
o-,
m-,
and
Homologues of Aniline.
C 6 H 4 (CH 3 )-NH 2
o-,
m-,
and
The
toluidines, or amido-toluenes,
are prepared
jp-nitrotoluenes
from nitrobenzene,
C'H
3
6H = C
*<N0 +
2
^X
+ 2H2
and ^-compounds may also be prepared from methylBoth o- and m-toluidine are oils boiling at
(p. 370).
197 and 199 respectively, but ^9-toluidine is crystalline, and
When treated with nitrous
melts at 45, boiling at 198.
acid the toluidines yield diazo-salts, from which the corresponding cresols, C 6 H 4 (CH 3 )-OH, are obtained, and in all
the
o-
aniline
Diamidobenzenes.
The phenylenediaminea, C 6 4 (NH 2 ) 2 are
obtained by the reduction of the corresponding dinitrobenzenes, or the nitranilines, and a general description of their
o-phenyleneproperties has already been given (p. 373)
,
377
Alkyl anilines.
action of
the
371)
they
are, in
fact,
its
converted
into
yellowish
with nitrous acid,
378
Metliylaniline.
(CH 3
)2
NH + HO-NO = (CH
8) 2
.N.NO + H 2 0.
Nitrosodiinetliylamine.
Dimetliylainine.
is
a colourless liquid
which
boils at
to
its
solution
in
hydrochloric
acid,
nitrosomethyl-
aniline,
192
it is
is
Nitrosodimethylaniline.
Dimethyl-p-phenyleneclitiniine.
p-Nitrosodimethijlamline,
C 6 H 4 <Cxr/nTT
>
*s
prepared by
dis-
solving dimethylaniline (1 part) in water (5 parts), and concentrated hydrochloric acid (2-5 parts), and gradually adding to the
well-cooled solution the calculated quantity of sodium nitrite,
dissolved in a little water.
The yellow
crystalline precipitate of
379
it is
monoxime (compare
p. 426),
of
may
also be displaced
C 6 H 5 C1,
a method which
employed in the prepara-
is
It is
and
is
Diphenylamine
is
largely used in
When
5)2
NK,
380
>NH
(C 6
It
is
H NK + C H
6
5) 2
Br - (C 6 H 6 ) 8 N
colourless, crystalline
+ KBr.
Aromatic Amines.
treating the
(p.
442) with
are
similar
to
those
187;
respects,
it
and
I.
in
the
pp. 211-212).
Benzylamine
at
employed
is
differs
(aniline,
are treated
it
is
p. 415),
381
diazo-compound.
Secondary and tertiary aromatic amines are formed when a
primary amine is heated with an aromatic halogen compound,
containing the halogen in the side-chain; when, for example,
henzylamine is heated with henzyl chloride, hoth dibenzylamine
and tribenzylamine are produced, just as diethylamine and triethylamine are obtained when ethylamine is heated with ethyl bromide,
CHAPTER XXY.
DIAZO-COMPOUNDS AND THEIR DERIVATIVES.
It has already
they yield
phenols;
if,
however,
warm aqueous
a
well-cooled,
added to
set
and the solution contains an unstable substance called diazobenzene chloride, the formation of which may be expressed
by the equation,
C 6 H 5 .NH 2 ,HC1 + N0 2 H - C 6 H 5 .N 2 C1 + 2H 2 0.
In
fatty
amines
amido-compounds
differ
from the
cold,
less readily
first
usually only on
with formation of
the
-NH
382
behave in this way, and yield diazo-salts similar to diazobenzene chloride in constitution.
The diazo-salts were discovered in 1860 by P. Griess, and
may
C 6 H 5 -N 2 -OH, and
its derivatives.
The bases or hydroxides from which these salts are derived have
not yet been isolated, as when liberated from their compounds they
immediately change into highly explosive, very unstable products
which seem to be their anhydrides.
The
may
diazo-salts (usually
be isolated without
spoken of
much
as the
difficulty,
diazo-compounds)
although, as a matter
ordinary temperatures.
Diazobenzene chloride and diazobenzene nitrate may be obtained
in a similar manner, employing alcoholic solutions of hydrogen
chloride and of nitric acid in the place of sulphuric acid.
Diazobenzene nitrate, C 6 5 -N 2 -NO 3 may also be conveniently
isolated as follows Aniline nitrate is suspended in a small quantity
of water, and the liquid saturated with nitrous acid (generated
from As 4 6 and
3 ), when the crystals gradually dissolve with
HN0
Amyl
in alcohol.
nitrite is
it is
soluble
formation
nitrate
383
and
dry
it
parative safety
if
may
kept moist.
384-385).
The
Properties.
com-
(p. 398),
C 6 H 5 .N 2 .S0 4 H + H 9 - C 6 H 5 .OH + N 2 + H 2 S0 4
C 6 H 4 (CH 3 ).N 2 C1 + H 2 = C 6 H 4 (CH 8).OH + N2 + HC1,
2>-Diazotoltiene Chloride.
but
if
^-Cresol.
halogen derivatives,
.N 2 .S0 4 H + HI = C 6 H 5 I + N 2 + H 2 S0 4
tion
of
made use
iodo-derivatives
(p.
358),
because
when
the other
halogen acids are used, the product contains the corresponding phenol.
384
which
is
decomposed
therefore,
the
reaction
is
continuous,
Additive Compound.
C 6 H5 .N 2 C1,
2CuCJST
Additive Compound.
nitrile is
is
value.
is
of great practical
readily obtainable
from
of a halogen, cyanogen, or other derivative from the amido-compountl involves two distinct reactions firstly, the preparation of a
:
of the diazo-salt, the following m.iy serve: Aniline (1 part) is dissolved in a mixture of ordinary concentrated hydrochloric acid
385
*
quantity of sodium nitrite is slowly run in from a tap-funnel,
and keeping the temperature as low as possible.
The solution now contains diazobenzene chloride ; if sulphuric had
stirring constantly
In
all
tion in
Hydrazine Hydrochloride.
Br,
one
I,
N0 3 HS0 4
of
nucleus
much
diazo-salts
-N:NR (where
R = C1,
is
clearly
&c.),
shown by many
facts
as, for
example, by
the conversion of the diazo-salts into rawzo-halogen derivatives, monohjdric phenols, &c., and by their conversion into
well
Org. Chetn.
stirring
386
proved by
many
the following
and
this substance,
>-phenylenediamine
C 6 H 6 .N:N.C
fl
H .N(CH
4
388),
8) 2
+ 4H =
a
as in the formula
C 6 H 5 -NC1:N,
a
There
is,
suggested by Bloomstrand.
C 6 H 5 -NR:N, namely,
quaternary
such as C 6 H 5 -NR=(CH 3 3 in which the acid
directly united to pentavalent nitrogen.
Probably, there-
ammonium
radicle is
salts,
fore,
Although some
of
the
more
characteristic
reactions
of
which occurs
(p.
387
432),
and
= C 6 H6 .N 2 .NH.C H + HC1
6
5
Diazoamidobenzene.
As, moreover,
diazo-compounds and other amidocompounds interact in a similar manner, numerous diazoamidocompounds may be obtained.
Diazoamidobenzene, C 6 II5 -N 2 -NILC 6 H 5 may be described
other
as a typical
compound
of this class
it
is
salts
with
acids.
Amidoazobenzene,
diazoamidobenzene
is
C 6 H 5 .NH-N 2 -C 6 H 5
Diazoamidobenzene.
C 6 H 5 .NH-CH 3
Methylaniline.
C6 H4
<N
H
2
c6 H5
p- Amidoazobenzene.
C6 H 4
<^
p-Toluidine.
388
also be prepared
by nitrating
and
then reducing with ammonium
(p.
391),
sulphide the p-nitroazobenzene, C 6 H 5 -N 2 -C 6 H 4 -N0 2 which is
thus produced ; these changes are analogous to those which
occur in the formation of aniline from benzene and the
Amidoazobenzene
may
azobenzene
that
way proves
it
is
an amido-derivative of azobenzene.
Amidoazobenzene
crystallises
from
alcohol
in
brilliant
'
dye
(p.
535).
amidoazobenzene,
C 6 H 5 -N 2 C1 + C 6 H 5 .N(CH 3 ) 2 - C6 H 5 .N 2 .C 6
.N(CH3
)2,
HC1,
formed, because
or
2
group.
In this case also the diazo-group, C 6 5 -N 2-, takes up the
^-position to the N(CH 3 ) 2 group, as is shown by the fact that,
on reduction, dimethylamidoazobenzene is converted into aniline
and dimethyl-j9-phenylenediamine, the latter being identical with
the base which is produced by reducing jt?-nitrosodimethylaniline
being
NH<
NH
(p. 378).
Phenylhydrazine,
C 6 H 5 -NH-NH 2
practical importance,
is
easily prepared
compound of great
by the reduction of
diazobenzene chloride,
HCL
dissolved in concentrated hydrochloric acid
(1 part)
(20 parts), and diazotised in the usual way (p. 384) ; the solution
of diazobenzene chloride is then mixed with stannous chloride
Aniline
(45
is
389
distillation, preferably
hydrochloride,
colourless
C 6H 5 -NH-NH 2
and
solutions of the
HC1,
which
crystallises
in
needles,
is
The
constitution of phenylhydrazine
is
and
hydrochloric acid, it is converted into aniline and ammonia.
Phenylhydrazine interacts readily with aldehydes, ketones,
and most substances containing a carbonyl- group, with
elimination of water and formation of phenylhydrazones
established
by the
fact that,
zinc-dust
(hydrazones)
soluble
Benzylidene Hydrazone.
Benzaldehyde.
Acetophenone Hydrazone.
Acetophenone.
Many
phenylhydrazine,
H6 + H 2
6 .CH:N.NH-C 6
+ HC1 =
C 6 H 5 .CHO + C 6H5 .KH-NH 2 HC1;
,
imines,
6
Benzylidenehydrazone.
390
The value
of phenylhydrazine as a
means
of detecting and.
I. p.
272).
that
stated
when mtro-compoimds
and hydrochloric
acid,
when
taking place
alcoholic
ammonium
in
these
reactions
two
2C 6 H 6 .NO a + 6H = C 6 H 5 .N<.>N-C 6 H 5 + 3H 2
Azoxy benzene.
2C 6 H 5 .N0 2 + 8H = C
fl
.N:N.C 6 H 6 +
4H 2 0.
Azobenzene.
Azoxybenzene,
C 6 H 5 -N<C
_ >N-C H
is
5,
is
391
azoxybenzene
which melts
at
131,
C 6 H5 .N:N.C 6 H 5 + 2H = C 6 H 5 .NH.NH-C 6 H5
it,
in a similar manner.
holic solution.
When
air is
passed through
it
is
its alco-
undergoes
converted
into ^-diamidodiphenyl or benzidine, a strongly basic substance largely used in the preparation of azo-dyes (p. 537),
Beuzidine.
Hydrazobenzene.
<2>CH 3
__...
of diazoarnidobenzene into ^-amidoazo-
C6 H 5 .NH-NH.C 6 H 5
"tT
CHAPTER XXVI.
SULPHONIC ACIDS AND THEIR DERIVATIVES.
for
an atom of hydrogen,
C6 H 6 + H 2 S0 4 = C 6 H 6 .SO S H + H 2 0.
The homologues
general behave
of benzene
in a similar manner,
from
fatty,
compounds.
The sulphonic
acids (Part
I.
tion of
an aromatic
radicle for
Sulphuric acid,
SO^r:
U-tl
Sulphonic
S0 2 < OTT
T>
acid,
Preparation.
Carboxylic acid,
393
phuric acid,
C 6 H 5 .CH3 +
S0 4 = C 6 H 4 <
pTT
+ H2
H+H
C 6 H 6 + 2H 2 S0 4 = C 6 H 4 (S0 3 H) 2 + 2H 2 0.
The number
groups
of
depends
is
and the acid isolated as described later (p. 395). In the case of a
substance which is insoluble in water or dilute sulphuric acid, the
point at which the whole is converted into a monosulphonic acid is
easily ascertained by taking out a small portion of the mixture and
adding water ; unless the whole is soluble, unchanged substance is
still
present.
Sometimes chlorosulphonic acid, C1-SO 3 H, is employed in sulphonating substances, and in such cases chloroform or carbon
disulphide may be used as a solvent to moderate the action,
Sulphonic acids
are,
as
rule,
crystalline,
in water,
when
pose
have a sour
all
394
mineral acids, they undergo certain changes of great importWhen fused with potash they yield phenols (p. 398),
ance.
ferrocyanide,
(or nitriles,
p.
434),
they
which
are
distil
converted
off,
or with
into
cyanides
leaving a residue of
potassium sulphite,
This
sulphuric acid.
The sulphonic
many
chlorides
are
acids,
other compounds.
decomposed by water am
by
alkalies,
salts,
are usualb
Benzeiiesulphonamide.
The
395
some
difficulty,
non-
evaporating.
chloride
these
and generally
and
boiling
lead
salt,
both of
which
are
soluble
in
water.
It
396
with 1|
crystallises
plates,
potash
it
mols.
and dissolves
freely
in
in
C 6 H 5 -S0 2 C1,
is
is crystalline,
an
oil,
colourless,
alcohol;
when
BenzenesulpJionic chloride,
and melts
at
hygroscopic
fused with
C 6 H 5 -S0 2 -NH 2
150.
Benzene-ra-disulphonic acid, C 6 4 (S0 3 H) 2 is also prepared by heating the hydrocarbon with concentrated sulphuric
is
acid, but a larger proportion (two volumes) of the acid
employed,
is
when
is
easily
for
some
prepared by
time.
Sulphanilic
acid
crystallises
with 2 mols.
H 0,
2
and
is
When
solution
sulphanilic
acid
mixed with a
is
dissolved
p.
299),
is
397
acid, diazobenzene-p-
formed,
O=C
this
loses water,
verted into
its
anhydride,*
C 6 H4 < Q
and
>, which
is
con-
separates
crystals.
phonic acid
(p.
408),
N"
whereas when
heated
hydrobromic acid
it
with concentrated
hydrochloric
or
sulphonic acid,
interacts
it
(p.
536).
may
acids.
Many
*
The existence of this anhydride (and of that of amidobenzene-msulphonic acid) is a very interesting fact because, as a rule, anhydride
formation takes place only between groups in the o-position to one
another (compare p. 437).
PHENOLS.
398
CHAPTER XXVII.
PHENOLS.
The hydroxy-compounds
of
phenol or hydroxy-benzene,
derived from
the
such as
series,
toluenes,
are
the aromatic
C 6 H 5 -OH,
in benzene,
make some
it
is
convenient,
there-
alcohols
(p.
distinction
414).
The phenols,
then, are
which
C 6 H 5 -OH,
they
for example,
contain.
is
C 6 H 4 (CH 3 )-OH
(OH) 2
on the
399
PHENOLS.
other
are
hand,
C 6 H 3 (OH) 3
Many of
,
compounds
whereas phloroglucinol,
dihydric phenols,
is
carbolic
for
acid,
is
prepared from
and thymol occur in
instance,
carvacrol
of
HC1 + HO-NO =
the
+ ^2 + H 2 + HC1.
It is possible, therefore,
the
CH<
to prepare
may
compounds,
C 6 H6
C 6 H 5 .N0 2
C 6 H 5 -NH 2
C 6 H 5 -OH.
Benzene.
Nitrobenzene.
Amidobenzene.
Phenol.
The conversion
transformed into a
its
salt of a
400
PHENOLS.
soda, which dissolves out the phenol, leaving most of the impurities
in the ether.
Dihydric phenols
may sometimes be
C 6H 6
C 6H 4 <
Benzene.
Dinitrobenzene.
also
They may
Diamidobenzeue.
Diazo-salt.
Dihydric Phenol.
C 6 H 5 -OH C 6 H 4
Phenol.
Nitrophenol.
Amidophenol.
Diazo-salt.
Dihydric Phenol.
carbons
is
often
easily
accomplished, since
3-
The sulphonic
In all cases the phenols are present in the product as alkali salts.
f Caustic alkalies readily attack platinum and porcelain at high temperatures, but have little action on nickel and none on silver.
401
PHENOLS.
*
Dihydric phenols
may
often
be
(p. 399).
obtained
in
temperature at
high
Owing
be carried out, secondary changes very often occur.
the sulphonic
similar
acids,
When
latter
are
For
reason
this
nitrobenzene
phenols
(p.
also,
compounds such
as o-
and
^>-chloro-
be converted into the corresponding nitro405), even by boiling them with concentrated
may
potash, the presence of the nitro-group facilitating the displacement of the halogen atom ; m-chloronitrobenzene, on
the other hand, is not acted on under these conditions. Sometimes also the process is not one of direct substitution only
that is to say, the hydroxyl-groups in the product are not
united with the same carbon atoms as those with which the
bromobenzenesulphonic
the
cinol,
C 6 H 4 (OH) 2
acids, for
because the
o-
* As the mixture is
very liable to spirt, the eyes of the operator must be
protected by spectacles or by a sheet of glass placed suitably before him,
Org.
Chem.
PHENOLS.
402
which are first produced from the corresponding bromomore stable ra-derivasulphonic acids, are converted into the
tive by intramolecular change.
There are several less important methods by which phenols may
be obtained, as, for example, by distilling hydroxy-acids, such as
salicylic acid, with lime,
C 6 H 5 .OH + C 2 H 5 .OH = C 6 H 4
Most phenols are
Properties.
stances, readily soluble in alcohol
in water
groups
in
<
+ H 2O.
colourless, crystalline
and ether
sub-
their solubility
number of hydroxyl;
and the
Conversely,
trihydric compounds are readily soluble.
their volatility diminishes ; so that although phenol and cresol
distil without decomposing, and are readily volatile in steam,
deep
violet
colouration
^?-dihydroxy-compounds give
when
dissolved
ii
403
PHENOLS.
concentrated sulphuric acid and treated with a nitroso-compound or a nitrite, they yield coloured solutions, which, after
diluting and adding excess of alkali, assume an intense blue
or green colour.
test
nitroso-compounds (Part
I.
p. 209).
The reason
of this
is,
HON0
phenylene,
C6H4<,
&c.,
being therefore
regarded as acid-
forming.
The acid character of the hydroxyl-group in phenols
is
shown
with caustic
alkalies, in
when
as, for
picric
acid,
enhanced
example, in nitro-
C 6 H 2 (N0 2 ) 3 .OH,
to such
an extent
and
esters respectively,
404
PHENOLS.
C 6 H 5 -OK + CH 3 I = C 6 H 5 .O.CH 3 + KI
C 6H4<
CH
OK +
3
-COC1 = C 6 H 4
<
C 0>C
C.Ht<Jg
=
W H + KOH C H <|
+ C 2H3 2K.
When
heated with
acids,
however,
the
phenols
are
not
changed
any appreciable extent, because, being less basic
in character than the alcohols, they do not so readily form
to
salts.
they
are,
tion to the tertiary alcohols, and, like the latter, they often
undergo complex changes on oxidation.
Monohydric Phenols.
diazobenzene
Compare
is
foot-note, Part
p. 92.
405
PHENOLS.
(compare
p.
307),
which
in
it
in 1834.
which
and turn pink on exposure to air and light ; it
It has a very characterboils at 183, and is volatile in steam.
istic smell, is highly poisonous, and has a strong caustic action
Phenol
melt at 42
Owing
phenol.
phenol
is
dissolved
in
potash and
Phenyl methyl
ether, or anisole,
it
is
decom-
C 6 H 5 -0-CH 3 may be
,
pre-
series
it
also
it
yields phenol
C 6 H 5 .0-CH 3 + HI = C 6 H 5 .OH + CH 8 L
Phenyl ethyl ether, or phenetole, C 6
>btained in a similar manner; it boils at
-0-C 2
5,
can
be
172.
Nitrophenols,
mating
406
PHENOLS.
it is
frequently shaken,
dark-brown
oil or
>ara-nitro-
resinous mass.
This product is allowed to settle, washed with water by decantaand then submitted to distillation in steam, whereupon the
or^Ao-nitrophenol passes over as a yellow oil, which crystallises on
cooling ; the solution in the flask is heated to boiling, and filtered
from tarry matter, the jmra-iiitrophenol which separates on cooling
being purified by recrystallisation from boiling water with addition
of animal charcoal.
tion,
Meta-nitropUenol is prepared by reducing meta-dinitrobenzene to meta-nitraniline (p. 375), and treating a solution of
the latter in excess of dilute sulphuric acid with nitrous acid ;
the solution of the diazo-salt is then slowly heated to boiling,
The
The
compounds
are
recrystal-
Ortho-nitrophenol,
Meta-nitrophenol,
Para-nitrophenol,
45.
96.
114.
having an
effect
nitric acid,
H0-N0 2
itself,
taking place
o-
and
not
it
may be
>-nitro phenols,
very
easily
is
an equal weight
with
purified from
same time.
resinous
substances
which
407
PHENOLS.
groups,
C 6H 4
Picric
122-5.
acid
is
2 )3
.OH + H 2 S0 4 + 2H 2 O.
but moder-
ately easily in hot, water, and its solutions dye silk and wool
(not cotton, p. 514) a beautiful yellow colour; it is, in fact,
one of the
earliest
known
artificial
organic dyes.
It has very
C 6 H 3 (NO 2
)3 ,
OH
NO,
408
PHENOLS.
Picric acid has the curious property of forming crystalline compounds with benzene, naphthalene, anthracene, and many other
hydrocarbons, so that it is sometimes used in detecting and also in
purifying small quantities of the substances in question the compound which it forms with benzene, for example, crystallises in
yellow needles, is decomposed by water, and has the composition
;
C 6 H 2 (N0 2 3 .OH, C 6 H 6
)
PJienol-o-sulpJionic
when
primary product,
is
acid.
Phenol-m-sulphonic acid
is
C 6 H4
The
e\O
TT-
=
<gQJ + 2KOH C6H4
o-acid is interesting
OT^
<^K + K S0 + H
2
on account of the
0.
fact that it is
converted into the p-acid when boiled with water, and also
because it is used as an antiseptic under the name aseptol.
C6H4<
+ KOH = C 6 H 4 <
+ K2 S0 3
409
PHENOLS.
On
displacement of the hydrogen of the hydroxyl-group.
distillation with zinc-dust they are all converted into toluene,
and they
One very
this is
constitution.
also
If,
group
is
manner
are
methoxybenzoic
acids,
C 6 H 4 (OCH 3 )'COOH.
boiling
given below.
Ortho-cresol.
Meta-cresol.
M.p.
31
B.p.
188
201
Para-cresol.
36
198
may be mentioned
CH3
fT"
LJ
'
CH(CH 3>2
CH(CH3>2
in oil of
Carvacrol.
Thymol.
Thymol occurs
by the formulae,
CH 3
410
PHENOLS.
C6
= C 6 H 4 (OH)-CH 3 + C 3H 6
H,(OH)<^
easily prepared
+ 1 2 = C 10 H 14 + 2HI
CioH 16
an
237, and
is
oil
boiling at
its
When
is
it
phosphoric anhydride,
o-cresol.
Dihydric Phenols.
The
OH
OH
OH
^
I
-OH
Catechol
Resorcinol
Hydroquinone
(Ortho-dihydroxybenzene).
(Meta-dihydroxybenzene).
(Para-dihydroxybenzeue).
and was
first
vegetable product
sulphonic acid,
it
C 6 H 4 (OH)-S0 3 H,
is
most
+ HI = C6 H 4 <
+ CH 3 I
411
PHENOLS.
It is a colourless, crystalline substance, melting at
104, and
for
as,
displaced,
C 6 H4 (OCH 3 ) 2
there
no
is
C 6 H 4 (OH) 2
Resorcinol,
colouration.
,
is
C6 H4
<g
J + 2KOH
= C 6H4
<JJ + 2K
S03>
but
it
(compare
401).
p.
and a
C 6 HBr 3 (OH) 2
When
with
ferric
precipitate of tribromoresorcinol,
bromine water.
resorcinol is
crystalline
there
results
brownish-red
solution,
which when
(p.
532).
reaction,
reaction
may
also
412
PHENOLS.
is
bear-berry
boiled
with water,
C 12H 16
+ H 2 = C6 H 4 (OH) 2 + C6 H 12
C 6 H4
+ H 2 S0 3 + H 2 = C 6 H 4 (OH) 2 + H 2 S0 4
169,
readily soluble in water, and when treated
with ferric chloride or other mild oxidising agents it is con-
It melts at
is
C 6 H 4 (OH) 2 +
= C6 H4
+ H 2 0.
Trihydric Phenols.
The
exist
three
in
trihydric
accordance
phenols,
respectively represented
Pyrogallol.
1:2: 3-Trihydroxybenzene.
Pyrogallol,
by the following
-OH
-OH
C 6H 3 (OH) 3 which
I
HO L
should
known, and
are
formulae,
^~
J OH
Plilordglucinol.
1:3: 5-Triliydroxy benzene.
C 6 H 3 (OH) 3 sometimes
,
all
Hydroxyhydroquinone.
1:2: 4-Trihydroxybenzene.
is
and
is
is
413
PHENOLS.
Pyrogallol has
and mercury
from
solutions
of
their
silver,
being itself
other phenols,
salts,
many
the dimethyl-deiiv&tive,
wood
C 6 H 3 (OCH 3 ) 2 -OH,
occurs in beech-
tar.
C 6 H 3 (OH) 3
It
is
parts) for
evolution of
(6
is
dissolved in water,
acidified
taste, gives,
with
that
when
it
with
hydroxylamine
it
trioxime,
414
PHENOLS.
C 6 H 6 (N-OH) 3
it
behaves as though
OH
and
it
readily
may be assumed
convertible
into
the
I. p.
is
by
200).
or l:2:4-trihydroxybenzene, is formed
fused with potash. It melts at 140, is very
soluble in water, and its aqueous solution is coloured greenishbrown by ferric chloride, but on the addition of sodium bicarbonate
Hydroxyhydroquinone,
when hydroquinone
is
CHAPTER
(p. 402).
XXVIII.
The aromatic
by
:
benzyl alcohol, C 6 5 .CH 2 -OH, for example, is derived
from toluene; tolyl alcohol, C 6 4 (CH 3 )-CH 2 .OH, from xylene;
and so on. The compounds of this kind are very closely
chain
substances.
415
nucleus,
alcohols
are
usually colourless
water
their behaviour
liquids
or
with alkali
few well-known
may be
(p.
418) with
sodium amalgam,
it is
The aldehyde
(9 parts) in
which
is
416
by
distillation.
with evolution
potassium
which
derivatives
are
of
hydrogen,
decomposed
yielding
metallic
it
is
converted into
benzyl chloride,
On
gives benzyl acetate, C 6 5 .CH 2 .0-CO.CH 3 (b.p. 206).
oxidation with dilute nitric acid, it is first converted into
benzaldehyde and then into benzoic
acid,
glucose,
Ci 3
It
(p.
may
H O
18
+ H2 = C6H 4
<jj
QJJ
+ C 6 H 12 O 6
422) with
417
(p.
423)
they
is
C6 H 4
< CHs QH + CH
It is crystalline,
it
3I
= C 6 H4
yields anisaldehyde
and
anisic acid,
on oxidation
C 6 H 4 (OCH 3 ).COOH.
Aldehydes.
The
benzaldehyde,
and so
Now
on.
those
importance than those in which the aldehyde-group is combined with a carbon atom of the side-chain, as in phenylacet-
418
(p.
In the
or copper nitrate.
nitrate
chloride
is
probably
first
first
dihydroxy-derivative of toluene,
by the equation,
+ 3H 2 0.
Benzyl chloride
(4 parts) are
is
a stream
of carbon
419
dioxide being passed into the liquid all the time, in order to expel
the oxides of nitrogen, which would otherwise oxidise the benzaldehyde to benzoic acid ; the process is at an end when the oil
contains only traces of chlorine, which is ascertained by washing
a small portion with water, and boiling it with silver nitrate
The benzaldehyde
the
ethereal
extract
is
solution of
distilled.
Benzaldehyde
sp. gr.
1-05 at
is
15;
ether,
&c.,
in
all
proportions.
is
It
is
to the air,
C 6 H 5 -CHO +
= C 6 H5 -COOH,
On
reduction
they
are
converted
of silver
the
into
corresponding alcohols,
When
treated
with
phosphorus
pentachloride,
two
atoms
of
chlorine
being
substituted
they give
C 6 H 5 -CHC1 2
for
one
atom
oxygen.
Benzylidenehydrazone.
420
They combine
directly
sodium
with
compounds, and
crystalline
with
bisulphite, forming
hydrogen cyanide they
yield
C 6 H 5 -CH(OH)-CN.
with
many
(m.p. 42),
is
formed.
the
differ
as
hydrobenzamide,
(C 6
H -CH) N
5
2,
which
is
When
obtained by
shaken with
p.
415),
Nitrobenzaldehydes,
C 6 H 4 (N0 2 )- CHO.
When
treated
with
and sulphuric acids, benzaldehyde yields w-nitrobenzaldehyde (m.p. 58) as principal product, small quantities of
o-nitrobenzaldehyde (m.p. 46) being formed at the same time.
jo-Nitrobenzaldehyde (m.p. 107), and also the o-compound, are
most conveniently prepared by the oxidation of the corresponding
mixture of
nitric
nitrocinnamic acids
*
(p.
which
is
C 6H 5 -CH=,
421
is
it is
This
soda, a precipitate of indigo-Uue gradually forms (Baeyer).
important synthesis of this vegetable dye may be represented by
the equation,
Indigo-blue.
+2CH 3 .COOH + 2H 2 0.
Hydroxy-aldehydes.
The hydroxy-derivatives
hydro xybenzaldehydes,
of
the
aldehydes,
C 6 H 4 (OH)-CHO, which
such as the
contain the
and aldehydes.
aldehyde,
As, however, such alcohols are not easily obtained, and indeed
in many cases have only been produced by the reduction of
the hydroxy-aldehydes, the latter are usually prepared by
heating the phenols with chloroform in alkaline solution
(Keimer's reaction),
<
+ 3KC1 + 2H 2 0.
422
+ HC1,
which by the further action
of the
alkali
OH
is
converted into a
C 6 H 5 -CHC1.2
is
trans-
/OH
/OH
As a
it
is
reaction.
over.
The
and
by
distillation.
with
its
ferric chloride.
yields saligenin,
it
is
at
196,
moderately
When
C 6 H 4 (OH>CH 2 .OH
boils
C 6H 4 (OH)-COOH.
423
It crystallises
is
C 6 H 4 (OCH3 ).CH:CH-CH 3
anetkole,
21
(m.p.
C
),
group.
substance
crystalline
is
-CH:CH-CH 3
be
may
prepared
j9-hydroxybenzaldehycle
synthetically
by digesting
and methyl
iodide,
<ft<CHO
+ CH ^ = C
A<CH0
+ KL
alcohol,
convert
it
Ketones.
The ketones
R-CO-R',
where
and R'
re-
course, be aromatic.
Acetophenone,
phenylmethyl
ketone,
or
acetylbenzene,
C 6 H 5 -CO-CH 3 may
It
is
(C 6
It is
424
(1
aluminium
mol.)
in
presence of
chloride,
chlorides
used
it is
Its
as a hypnotic in medicine, under the name of hypnone.
chemical behaviour is so similar to that of the fatty ketones
its reactions, or at any rate those which are
determined by the carbonyl-group, might be foretold from a
consideration of those of acetone on reduction with sodium
that most of
HC H
On
respectively.
hydrazone, C 6 5 .C(N 2
6
5 )-CH 3
oxidation it is resolved into benzoic acid and carbon dioxide,
the
just as acetone
is
C 6 H 5 .CO-CH 3 + 40 = C 6 H 5 .COOH + C0 2 + H 2 0.
Acetophenone shows also the general behaviour of aromatic
compounds, inasmuch as it may be converted into nitro-,
amido-, and halogen-derivatives
of the nucleus.
The homologues
C 6H 5 -CO-C 2 H 5
of
by displacement
of
hydrogen
butyrophenone,
C 6 H 5 .CO-C 3 H 7
&c.,
are
of
Benzophenone,
C 6 H 5 -CO-C 6 H 5
or
ketone,
benzoylbenzene,
diphenyl
be
obtained
by distilling calcium
may
benzoate,
arid
425
most respects
when
is
into diphenylmethane,
C 6 H 5 -CH 2 -C 6 H 5
351).
(p.
Quinones.
When
hydroquinone
is
oxidised
with
excess
of
ferric
chloride in aqueous solution a yellowish colouration is produced, and the solution acquires a very penetrating odour ;
if
The substance formed in this way is named quinone (benzoquinone), and is the simplest member of a very interesting
class of
compounds
equation,
its
formation
C 6 H 4 (OH) 2 +
may be
= C 6H4
expressed by the
+ H 2 0.
Quinone, C 6 4 2
usually prepared by oxidising aniline
with potassium dichromate and sulphuric acid.
is
(1
part) is dissolved in
acid (8 parts),
and very
characteristic smell,
and
is
only
if it
contained two
426
with ^>-nitrosophenol,
The two
379),
p.
C 6 H4^f ^ ^^
(identical
to one another, as is
is
reduced
it
gives
of ordinary ketones
>CO
group
is
been expected.
This curious behaviour, and the close relation between
hydroquinone and quinone, is explained by assuming that in
the conversion of the former into the
latter
by oxidation
is
it
change
by the centric formula
is again established
formulas indicate the nature of these changes,
the following
OH
in
Hydroquiuone.
Quiuoiio.
Dichloroben/eue.
The
constitution of
quinone
may
427
also be represented
by the
following formula,
which was
first
/N.OH
constitution of quinone
monoxime would
be,
C 6 H 4<
and
C 6 H 4<f
C6H4
its
<^Q,
monoxime would be
'
occur during
principal
p. 336).
T
CgH^NH^-CHg, [NH 2 :1S H 2 :CH 3 = 1:4:2], yield
=
CH
All
toluquinone [0:0:
joara-quinones resemble
3
1:4:2].
diamine,
*
Other quinones, of a somewhat different class from benzoquinone, are
described later (pp. 468, 483).
428
ETC.
being readily
NH
2 .C 6
NH
2 -C 6
H 4 .NH
Quinone Dichlorocliimide.
many
respects
and are respectively converted into jo-amidophenol andj^-phenylenediamine or their derivatives on reduction.
Chloranil, or tetrachloroquinone, O:C 6 C1 4 :O, is produced when
chlorine acts on quinone, but it is usually prepared by treating
phenol with hydrochloric acid and potassium chlorate, oxidation
oxidising agents
is
undesirable.
CHAPTER XXIX.
CARBOXYLIC ACIDS.
benzoic acid,
C 6 H 6 -COOH,
plitlialic acids,
429
CARBOXYLIC ACIDS.
C 6 H 4 (COOH) 2
&c., but
rise
to
toluene (and
derivatives of
both
kinds
as,
for
example, the
phenylacetic acid,
C 6 H 5 -CH 2 .COOH.
Although there are no very important differences in the
properties of these two classes of acids, it is more convenient
to describe them separately, taking first those compounds in
which the carboxyl-groups are directly united with carbon
of the nucleus.
Such acids
Preparation.
the alcohols or aldehydes,
may be
obtained by oxidising
nitriles
(p.
433) with
alkalies
or
mineral acids,
which
I. p.
employed in the
168).
always oxidised to
groups
may
benzene which
it
-CO OH,
contain
-CH 2-
is
attacked, so that
by stopping the
430
CARBOXYLIG ACIDS.
is
obtained,
Properties.
The aromatic
and gener-
and ether. As regards, all those properties which are determined by the carboxyl-group, the aromatic acids are closely
analogous to the fatty compounds, and give corresponding
derivatives, as the following
examples show,
Ethyl berizoate,
C 6 H 5 .COOH
Benzoyl chloride, C 6 H 5 -COC1
C 6 H 5 -COONa Benzamide,
C 6 H 5 .CO-NH 2
C 6 H 5 .COOC 2 H 5 Benzoic anhydride, (C 6 H 5 -CO) 2 0.
When
Benzoic acid,
Sodium benzoate,
distilled
loss of
dioxide and formation of the corresponding hydrocarbons, just as acetic acid under similar circumstances yields
carbon
marsh-gas,
C 6 H 5 .COOH = C 6 H 6 + C0 2
C 6 H 4 (CH3 )-COOH = C 6 H 5 -CH3 + C0 2
Benzoic acid, C 6 H 5 -COOH, occurs in the free state
many resins, especially in gum benzoin and Peru balsam
.
is
also
in
;
it
CARBOXYLIC ACIDS.
or benzoylglycine,
about 2 per cent.
It
may be
431
C 6 H 5 -CO-NH.CH 2 .COOH,
obtained by subliming
gum
to the extent of
(Parti,
p.
300),
=
,
Benzoic acid
is
(p.
HC1.
+ HC1,
or
It
at
about 350,
.
or benzaldehyde,
soda,
C 6 H 5 .CO.(m + 2H 2 = C 6 H5 .COOH + NH 3
caustic
but
and
and
an
coughing.
ether.
irritating
Most
is
of
Its
the
and
metallic
salts
crystallise well
of
acid
benzoic
calcium benzoate,
I. p.
191).
The alcohol is then distilled, the oily residue poured into water,
and shaken with dilute sodium carbonate until free from acids the
ester is next washed with water, dried with calcium chloride, and
;
432
CARBOXYLIC ACIDS.
alcoholic potash.
Benzoyl chloride,
C 6 H 5 -COC1,
is
obtained
by
treating
The dry acid is placed in a distillation flask, and about 5 per cent,
more than one molecular proportion of the pentachloride is added
the fumes which are evolved are passed into water or dilute soda
;
(care being taken that the liquid is not sucked into the flask), the
whole operation being conducted in the fume cupboard. When the
reaction is finished, the mixture of phosphorus oxychloride (b.p.
107) and benzoyl chloride is submitted to fractional distillation.
and
boils
at
198;
it
is
most
irritating odour,
gradually decomposed
by water,
chloride
dride
and amido-compounds,
C 6 H 5 -CO-,
group,
monovalent lenzoyl-
hydroxyl- or amido-group,
(C 6
.CO) 9
As such
433
CARBOXYLIC ACIDS.
may be prepared by heating the hydroxyamido-compound with benzoyl chloride or with benzoic anhyA more convenient method, however, is that of Baumann
dride.
and Schotten it consists in adding benzoyl chloride and 10 per cent.
potash alternately, in small quantities at a time, to the compound,
which is either dissolved or suspended in water, the mixture being
well shaken and kept cool during the operation.
Potash alone is
then added until the disagreeable smell of benzoyl chloride is no
longer noticed, and the solution remains permanently alkaline;
Benzoyl-derivatives
or
the product
is finally
The
to those
as, for
but
it is
C 6 H 5 .CO-NH 2 + C0 2 + H
It is a crystalline substance, melts at
130, and
is
amides,
and an
it is
decomposed by boiling
sparingly
like other
alkalies, yielding
ammonia
alkali salt,
obtained
C 6 H6 .CO-NH 2 = C 6 H 5 .CN + H2 0.
cannot be prepared by treating chloro- or bromoAlthough
benzene with potassium cyanide (the halogen atom being so
it
Chem.
no interaction occurs),
2 B
it
may be
obtained by
434
CARBOXYLIC ACIDS.
It
(1
part)
is
(p.
384),
of the diazo-chloride is
cyanide,
Benzonitrile
is
a colourless
nitrobenzene.
which
aromatic
C 6H4 (CH3)-CN~,
acetonitrile
nitriles,
are
known,
such
also
as
the
three
compounds such
tolunitriles,
as phenyl-
acid
is
CABBOXYLIC ACIDS.
435
and water
is
at
formed.
at
(m.p.
the
by
(p.
oxidation
367)
when
H (NH
salts
giving
and
aniline
carbon
dioxide.
which
which
is
remarkable
is
known
for possessing
as saccharin.
The sulphobenzoic
an exceedingly sweet
(p.
taste,
when fused
and
COOK + K SO
2
+ H2 O.
be
o-
CARBOXYLIC ACIDS.
436
corresponding toluidines (ra-toluidine cannot easily be obtained) into the nitriles by Sandra eyer's reaction (p. 384), and
The
alkalies,
respectively,
Dicarboxylic Acids.
dicarboxylic
acids
are
the three
COOH
which
COOH
sCOOH
COOH
>COOH
COOH
Phthalic Acid.
Isophthalic Acid.
Terephthalic Acid.
They
&c.,
which
a.
CARBOXYLIC ACIDS.
same reactions
as,
437
I.
p. 234).
its
I.
240),
p.
is
con-
S ^x-CCX
COOH
O-COOH
but
it is
>
k^^
+ H 2 0,
J CO/
iso-
from one molecule of the acid takes place only when the two
carboxyl-groups in the benzene nucleus are in the o-position,
never when they occupy the m- or ^-position.
= C6 H 6 .COOH + C0 2>
this
all
dicarboxy-
derivatives of benzene.
When
is
To convert the
phthalic acid
itself,
438
CARBOXYLIC ACIDS.
anhydrides formed from one
may be
is
\vith
acid
sulphuric
mercury
C 10H8 C1 4
in
presence
of
small
quantity
of
and the residue distilled, the phthalic anhydride (see below), which
passes over, being reconverted into phthalic acid by boiling it with
caustic soda ; the acid is then precipitated by adding a mineral
acid, and the crystalline precipitate purified by recrystallisation
from boiling water.
Phthalic acid crystallises in colourless prisms, and melts at
184, with formation of the anhydride, so that, if the melted
substance be allowed to solidify, and the melting-point again
determined, it will be found to be about 128, the meltingpoint of phthalic anhydride.
Phthalic acid is readily soluble in hot water, alcohol, and
ether, and gives with metallic hydroxides well-characterised
salts
the barium
precipitate
the
salt,
C 6 H 4 <C.^>Ba,
ammonium
salt, is
obtained as a white
to a neutral solution of
295.
CC1
C 6 H 4 <\ nr 2 ^0
I.
p. 242).
439
CARBOXYLIO ACIDS.
CO
Phthalic
C 6 H 4 <p~>0,
anhydride,
is
when
formed
284, and
it
is
CO
C 6 H 4 <C r r,^>NK,
GO
a great similarity
thus
cinimide (Part
I. p.
a sub-
is
229, and
CO
CgHxC^^^NH,
\j\j
There
suc-
243).
Potassium phthalimide interacts with various halogen derivaas, for example, with ethyl iodide and with ethylene
tives,
Ethylphthalimide.
rn
Brometliylphthalimide.
Ethylenediphthalimide.
NH
NH
NH .CH .CH
2
-NH2
Isophthalic
acid,
C 6 H4 (COOH) 2
(benzene-w-dicarboxylic
acid), is
440
It
CARBOXYLIC ACIDS.
needles, melts
in
crystallises
above
in
water.
Methyl
it
isophthalate,
very sparingly
C 6 H 4 (COOCH 3 ) 2
melts at 65.
acid),
and
CH
the ^-position.
when
It
is
heated,
C 6 H 4 (COOCH 3 ) 2
the methyl
salt,
poured into excess of methyl alcohol. As soon as the vigorous reaction has subsided, the liquid is diluted with water, the
crude methyl salt collected, recrystallised, and its melting-point
determined.
acid,
perties in
441
CARBOXYLIC ACIDS.
them
in the
Formic
manner
just mentioned.
H-COOH,
acid,
Benzoic acid,
Acetic acid,
C eH 5 -COOH
CHg-COOH,
Phenylacetic acid,
Propionic acid,
CH
C 6 H 5 .CH 2 -COOH.
.CH 2 -COOH,
Phenylpropionic acid,
Butyric acid,
With
(phenylformic acid).
acids are derived from the aromatic hydrocarbons by the substitution of carboxyl for hydrogen of the side-chain.
They
have not only the characteristic properties of aromatic compounds in general, but also those of fatty acids, and, like the
latter, they may be converted into unsaturated compounds by
loss of
rise to
new
Propionic acid,
CH
-CH 2 -COOH,
Phenylpropionic acid,
Acrylic acid,
CH :CH-COOH,
Phenylacrylic acid,
Propiolic acid,
C 6 H 5 .CH:CH.COOH.
CHiC-COOH,
Phenylpropiolic acid,
C 6 H 5 .C;C-COOH.
group
2H 2 = C 6 H 5 .CH 2 .COOH + NH 3
442
CARBOXYLIC ACIDS.
By the
reduc-
which
(a)
and
is
(Part
I.
given
The
is
thus
produced,
C 6 H 5 .CH 2 C1 + CHNa(COOC 2 H 5 2 =
C 6 H 5 .CH 2 .CH(COOC 2 H5 ) 2 + NaCl,
)
Ethyl Benzylmalonate.
is
is
H CLCH
3,
for example,
of this class
by
fractional distillation,
is
443
CARBOXYLIC ACIDS.
from water,
C 6 H 5 -CH 2 C1
C 6 H 5 -CH 2 .COOH.
C6 H 5 .CH 2 -CN
and forms
salts
When
it
namic
may
also
A mixture of benzaldehyde (3
and anhydrous sodium acetate
flask placed in an oil-bath.
mixture
is
parts), acetic
(3 parts) is
444
CARBOXYLIC ACIDS.
the residue
is
and tarry
and sodium
are obtained.
2
hydrogen
aldehyde oxygen
group which is directly united with the carboxyl-radicle of the
sodium salt.
Phenylisocrotonic acid may, however, be prepared by heating
benzaldehyde with a mixture of sodium succinate and succinic
anhydride, carbon dioxide being eliminated,
302
acids,
CH
3 .C 6
.CH:CH.COOH.
acid,
C 6 H 5 -CHBr.CHBr.COOH,
show
On
CARBOXYLIC ACIDS.
is
445
acid
When
distilled
is
decomposed into
C 6 H 6 -CH:CH.COOH = C 6 H 5 -CH:CH 2 + C0 2
Concentrated nitric acid converts cinnamic acid into a mixture of about equal quantities of o- and p-nitrocinnamic acids,
C 6 4 (N0 2 )-CH: CH-COOH, which may be separated by convert-
them into
(by means of
ing
C 6 H 4 (N0 2 )'CHBr-CHBr.COOH.
dibromopropionic acids,
Phenylpropiolic acid, C 6 5 -C:C-COOH, is obtained by treating phenyldibromopropionic acid, or, better, its ethyl ester, with
alcoholic potash,
a method which
C 6 H 5 .C C-COOH = C 6 H 5 .C CH + C0 2
C 6 H 4 (NO 2 )-C: C-COOH, maybe
i
o-Nitrophenylpropiolic acid,
simi-
aromatic
CARBOXYLIC ACIDS.
446
it is
con-
+ 4H = C 16 H 10 N 2
+ 2C0 2 + 2H 2 O.
CHAPTER XXX.
HYDROXYCARBOXYLIG
ACIDS.
In the
first
same character
phenols and
are
practically
the
same
as
those
between
alcohols.
HYDROXYCARBOXYLIC
447
ACIDS.
those employed in the preparation of phenols from hydrothat is to say, the acids are converted into nitro;
carbons
latter are
COOH
or,
the acids are heated with sulphuric acid, and the sulphonic
way are fused with potash,
C6H6-COOH
-CH
6
It must be borne in mind, however, that as the carboxylgroup of the acid determines the position taken up by the
nitro- and sulphonic-groups (p. 364), only the weta-hydroxy-
compounds
are
conveniently prepared
in this
way
directly
acids.
is
heated at about
+ C 6 H 5 .OH.
Under these conditions half the phenol distils over and is rehut if the sodium compound he first saturated with
covered
carbon dioxide under pressure, it is converted into an aromatic
derivative of carbonic acid, which, when heated at about 130
under pressure, is completely transformed into a salt of the
hydroxy-acid by intramolecular change,
;
448
HYDROXYCARBOXYLIC
ACIDS.
resorcinol,
from phenols consists in "boiling a strongly alkaline solution of the phenol with carbon tetrachloride ; the principal
product is the ortho-acid, but varying proportions of the
are also formed,
<
+ 4NaCl + 3H 2 O.
After the substances have been heated together for some hours,
the unchanged carbon tetrachloride is distilled off, the residue
acidified, and the solution extracted with ether ; the crude acid
obtained on evaporating the ethereal solution is then separated
from unchanged phenol by dissolving it in sodium carbonate, reprecipitated with a mineral acid, and purified by recrystallisation.
The above method is clearly analogous to Eeimer's reaction
(p. 421), and the changes which occur during the process may be
assumed to take place in various stages as indicated below,
< OH
TT ^t-'C'lg
pi H
C
4
6
f\TT
CTT
6 H 5 .<J]
pt TT ^C(OH) 3
C
6H4
< OH
H4 ^COOH
C 6 -p~
< OH
as the
m- and ^>-hydroxybenzoic
HYDROXYCARBOXYLTC
449
ACIDS.
is
salts
salts,
The
di-metallic salts
are
salicylic
acid,
decomposed by carbonic
for
C 6 H 4 (OH)-COONa
acid,
are
this way.
The
the
of
esters
usual manner
ordinary
displaced,
C 6 H 4 (OH)-COOCH 3
such
esters,
being formed;
as
these
methyl
'salicylate,
compounds have
still phenolic properties, and dissolve in caustic alkalies, forming metallic derivatives, such as methyl potassiosalwylate,
C 6 4 (OK)-COOCH3 which, when heated with alkyl halogen
C6 H 4 (OCH3 )-COOCH 3
compounds
On hydrolysing di-alkyl
of this kind with alcoholic potash, only the alkyl
.
The other
with
alkalies,
C 6H 5 -OCH3
into phenol
Org. Chein.
(p.
2 C
HYDROXYCARBOXYLIG ACIDS.
450
hydroxy-acid,
6
,COOH
H4\QQ
H +J:
,COOH
H4\OH
in
considerable
wintergreen
(Part I. p. 89), the solution is acidified with dilute sulphuric acid, and the precipitated salicylic acid purified by
recrystallisation
from water.
C 6 H 5 -OCOONa, which
is
thus
formed, at 120-140 under pressure, when it undergoes intramolecular change into sodium salicylate (p. 447).
Salicylic acid is sparingly soluble in cold (1 in
400 parts
at
it
this
if
the acid be
smell,
for example,
potassium
salicylate,
C 6 H 4 (OH)-COOK, and
HYDROXYCARBOXYLIC
ACIDS.
451
they
are,
The
di-
C 6 H 4 (OK)-COOK and C 6
the
decomposed by carbonic
mono-metallic
acid,
salts,
+ C0 2 + H 2 = 2C 6 H4 <
Methyl
C 6 H 4 (OH)-COOCH 3
salicylate,
manner described
+ K 2 C0 3
prepared in the
an agreeably-smelling
C 6 H4 (OH)-COOC 2H 5
oil,
boiling at
boils at
224;
ethyl salicylate,
223.
Methylsalicylic acid,
C 6 H 4 (OCH 3 COOH,
)
is
obtained
when
its
solution
by adding hydrochloric
acid,
and
purified
by
HYDROXYCARBOXYLIC
452
ACIDS.
is
acid,
it
when
may
the group
also
-CH:CH-CH 3
is
converted into
-COOH
by
means
of reactions analogous to those employed in the formation of methylsalicylic acid from salicylic acid (p. 451).
Anisic acid melts at 185, and when distilled with lime
is decomposed, with formation of anisole (p. 405) ; when
heated with fuming hydriodic acid, it yields jp-hydroxy ben zoic
it
protocateclmic acid,
[OH:OH:COOH = 1:2:4],
It crystallises
it
is
very soluble, in
needles, melts at 199, and when strongly heated it is decomposed into catechol and carbon dioxide ; its aqueous solution
is
HYDROXYCARBOXYLIC
453
ACIDS.
from solutions
silver,
and platinum
of their salts.
Tannin, digallic
C 14 H 10
9,
occurs in
When
Tannin
'
'
animal skin or membrane, after suitable preliminary operais placed in a solution of tannin, or in contact with
tions,
acid), is
It
may be
obtained
I. p.
234),
454
HYDROXYCARBOXYLIC
ACIDS.
C6 H 5 .CH(OH)-COOC 2 H 5
Mandelic
acid,
different forms.
The
synthetical acid
is
is
in
three optically
optically inactive,
levo-rotatory.
CHAPTER XXXI.
NAPHTHALENE AND
All the
aromatic
ITS DERIVATIVES.
the exception of diphenyl, diphenylmethane, and triphenylmethane (p. 350), contain only one closed-chain of six
benzene;
may
exceptions
just
mentioned
more
readily,
so that they
benzene derivatives.
are
also,
strictly
The
speaking,
NAPHTHALENE AND
455
ITS DERIVATIVES.
may be
of
benzene,
regarded
as
is
carbons form
and of derivatives of a
different type.
now
in
to be described,
importance
number
number
each forms
the
are perhaps
starting-point
of
great
or sublimed, and
Naphthalene
79, and boils at 218.
smell, and is extraordinarily
at
It
volatile,
(p.
305),
the rest
and even
into
fact,
is
deposited
crystals in cold weather, principally at the
bends of the pipes, frequently causing stoppages.
It is
insoluble in water, but dissolves freely in hot alcohol and
in
ether,
many
it
may be
it
crystallised.
combines with
Like
picric
NAPHTHALENE AND
456
when
acid,
alcohol,
the
ITS DERIVATIVES.
a yellow
in
crystalline
compound
C 10 H 8 ,C 6 H 2 (N0 2 ) 3 .OH,
which melts
at
149.
As
ting coal-gas
is
which
are
Constitution.
when
treated with nitric acid, for example, it yields nitroand with sulphuric acid it gives sulphonic acids.
derivatives,
boiled
with dilute
nitric
is
is
chromic
acid,
or
heated
Now
fact
of
the
formation of phthalic
very great
importance,
naphthalene contains the group,
or
acid
since
it
in
is
this
way
proof
is
that
NAPHTHALENE AND
that
is
to say, that
it
457
ITS DERIVATIVES.
to
one
are
many
different
C 6 H4 <
n
C
for, and
ways in which these might be
group.
these
Now
way
When
nitro-
acid,
C 6 H 3 (N0 2 )(COOH) 2
therefore,
again,
is
other words,
different
two
cases,
to
parts
n
C6 H4 <Cp
remains.
NAPHTHALENE AND
458
The
constitution of naphthalene
by the formula,
ITS DERIVATIVES.
CH
CH
CH
CH
This will be evident
if
When
(see below),
nitroriaphthalene
is
NO
COOH
Nitrophthalic Acid.
Nitrouaphthalene.
Naphthalene.
NH 2
COOH
COOH'
Phthalic Acid.
Amidonaphthalene.
The
this
atoms
condensed*
since
together
in
the
o-position,
as
common
to,
signifies that
both nuclei.
NAPHTHALENE AND
its
derivatives,
459
ITS DERIVATIVES.
conclusively by
the
study
The
difficulty of
H
H
6
(or
310),
/CH:CH
C6 H5 .CH 2 .CH 2 .CH:CH 2 -C 6 H4<
+2H 2
X CH:CH
most important synthesis of naphthalene was accomby Fittig, who showed that a-naphthol (a-hydroxynaphthalene) is formed on boiling phenylisocrotonic acid
This change probably takes place
(p. 444) with water.
in two stages, the first product being a keto-derivative of
plished
and
NAPHTHALENE AND
460
ITS DERIVATIVES.
I. p.
200),
CH
CH
C(OH)
As in the case
study of the isomerisrn of the substitution products affords the most convincing evidence that the
accepted constitutional formula of naphthalene is correct.
Isomerism of Naphthalene Derivatives.
of
In
benzene,
the
the
first
yielding
two
place,
isomeric
tional formula
of naphthalene,
written,
or
numbered
relatively
the
to
hydrogen
the rest
atom
of
(1)
the molecule.
were
displaced
If,
for
example,
by chlorine
or
NAPHTHALENE AND
461
ITS DERIVATIVES.
atom
or group
so.
it
ducts
are, therefore,
a and p.
When
two
the system of
would
be,
1:2, 1:3, 1:4, 1:4', 1:3', 1:2', 1:1', 2:3, 2:3', 2:2',
all
2:4', for
The
however,
is
different
from any of
these,
and
is
termed
naphthalene nuclei.
462
NAPHTHALENE AND
ITS DERIVATIVES.
Derivatives of Naphthalene.
+ C 2 H 5 I = C 10 H 7 -C 2 H 5 + HI,
a-Methylnaphthalene,
is
colourless
liquid,
at
boiling
melts at
occur in coal-tar.
The halogen
the hydrocarbon,
at
its
with
the
treating
halogens
by
C 10 H r ]m 2
-i
C 10 H 7 .K2 C1
C 10 H7 C1.
a-Chloronaphthalene,
C 10 H 7 C1,
is
NAPHTHALENE AND
463
ITS DERIVATIVES.
by hydroxyl-groups
Naphthalene tetrachloride, C 10 H 8 C1 4
is
on
and
which shows
that all the chlorine atoms are present in one and the same
nucleus ; the constitution of the compound is therefore
.
The formation
_ .CHCLCHCk
^e^^Tri P
_,
lene derivative, are known, and it has been found that when one
of the nuclei is thus fully reduced, the atoms or groups directly
united to it acquire the character which they have in fatty compounds, whereas those united to the unreduced nucleus retain the
character which they have in simple substitution products of
benzene.
The amido-group
x
the constitution
in the tetrahydro-^-naphthylamine of
.
C EL<
fi
X CH
same
.CH 2
tetrahydro-p-naphthylamine,
/CH^-CHa
NHa-CeHg^
I
^CH^-CELj
the
NAPHTHALENE AND
464
ITS DERIVATIVES.
(ac.-)>
according
as
the substituent
is
contained in the
according
to
more atoms
of
the concentration
of
quantities
On
nitric
with
nitrite,
The amido-derivatives
of naphthalene
79.
are very similar in
NAPHTHALENE AND
465
ITS DERIVATIVES.
by
amidoazo-compounds, &c.,
employed
in the case of
the
250,*
C 10 H 7 .OH + NH 3 = C 10 H r NH 2 + H 2 0,
but
is
it
iron-filings
and
acetic acid,
C 10 H 7 .N0 2 + 6H = C 10 H 7 -NH 2 + 2H 2 0.
It is a colourless, crystalline substance, melting at 50, and
boiling at 300; it has a disagreeable smell, turns red on
air, and its salts give a blue
and other oxidising agents.
exposure to the
chloride
ferric
(p.
/3-Naphthylamine
acid, it is
precipitate with
On
oxidation
converted into
468).
is
294
it
differs
odourless,
and
chloride.
On
oxidation
with potassium
permanganate,
it
water
is
formed,
Ammonium
as
acetate
may be employed
Chem.
is less
it
dissociates
energetic.
NAPHTHALENE AND
466
ITS DERIVATIVES.
or monohydroxy-derivatives of naph-
amines,
or
C 10H r NH 2
C 10 H 7 -N 2 C1
C 10 H r OH,
(compare
p.
400),
by carbonic
acid
the naphthols
may
by an alkyl-group, just
it
were, a connecting-link
NAPHTHALENE AND
in the a-position
is
it
467
ITS DERIVATIVES.
It is a colour(p. 468).
substance, melting at 94, and boiling at 280 ;
it has a faint smell, recalling that of phenol, and it dissolves
freely in alcohol and ether, but is only sparingly soluble in
less, crystalline
hot water.
violet,
is
^'^'fro-derivative,
yellow needles, and melts at 138; this nitrocompound, like picric acid, has a much more strongly marked
acid character than the hydroxy-compound from which it
crystallises in
is
derived,
salts
derivative,
as
the
potassium
of
salt
C 10 H 4 (N0 2 ) 2 (OK).S0 3 K;
dinitro-a-naphtholsulphonic acid,
the acid itself is manufactured
by
ing
a-naphthol
with
anhydrosulphuric
(prepared by heatacid),
in
which
and a flocculent
precipitate
of
/3-di-naphthol,
OH.C 10 H 6 .C 10 H 6 -OH.
Sulphonic Acids.
itself,
NAPHTHALENE AND
468
ITS
DERIVATIVES.
is
with
concentrated
sulphuric
acid
80;
at
if,
phenol-o-sulphonic
by
heating.
The
acid
two
is
Di-sulphonic acids
acids
naphthalenesulphonic
may be
show
all
are
the charac-
theoretically be obtained
acids,
namely,
as
One
of the most important, perhaps, is l:4-naphthylamineacid, or naphthionic acid, which is the sole
monosulphonic
The napJitholmonosidphonic
acids
correspond
acids,
in
and
number
are
also
NAPHTHALENE AND
groups occupy the a-positions
469
ITS DERIVATIVES.
a-naphthylamine,
and
4-amido-
for
example, may
l:4-diamidonaphthalene,
As a rule, however, naphthalene itself is
be employed.
oxidised with a boiling solution of chromic acid in acetic
naphthol,
acid (a
is
quinone
then easily obtained in a
state of purity.
a-Naphthaquinone
crystallises
in steam.
acid,
naphthalene,
C 10 H 6 (OH) 2
as
just
it
into
quinone
is
4-dihydroxytransformed
a-naphthaquinone
may be
/5-Naphthaquinone, C 10 6 2 isomeric with the a-comis formed when a-amido-/?-naphthol is oxidised with
,
pound,
potassium
ferric
dichromate and
chloride
at about
115
phurous
acid,
dilute
crystallises in
it
is
NAPHTHALENE AND
470
quinone
tution
is
ITS DERIVATIVES.
may be
its
consti-
unknown.
The above description
affinities is
of
some
of the
more important
number of isomeric forms, they are, as a rule, prepared by the same methods as their analogues of the benzene
series, and resemble them closely in chemical properties.
larger
may, in fact, be stated that, as a rule, all general reand generic properties of benzene derivatives are met
with again in studying naphthalene derivatives.
It
actions
CHAPTEK XXXII.
ANTHRACENE AND PHENANTHRENE.
Anthracene,
C 14H 10
is
known
471
which
is
and
phenanthrene,
the phenanthrene dissolves, leaving the anthracene, which
is further purified by crystallisation from benzene.
Crude anthracene contains considerable quantities
C 6 H 4\
C 6 H 4 //NH,
I
of cavbazole,
On treatment with
is
which remains
C 6 H 4 //NK,
on
other
heating many
decomposed
impurities,
which cannot readily be separated by crystallisation, are also got
rid of in this way.
converted into a potassium derivative,
in the retort, or is
Anthracene
crystallises
from benzene in
colourless, lustrous
picric
Constitution.
and bromine
is,
The behaviour
to that of
benzene and
naphthalene
that
is
to say,
it
472
quinone,
C 14 H 8
two atoms
when
of
2,
two atoms
oxygen;
or
employed,
and
occurs
the
in
as
of
this
is
it
closely analogous
conversion of naphthalene,
C 10 H 6
agent, is
that which
to
C 10 H 8
into
a-
468), it is an indication of
the presence of a closed-chain, oxidation processes of this
kind (namely, the substitution of oxygen atoms for an equal
naphthaquinone,
(p.
number
of
fatty
of
(open-chain)
as,
however,
side-chains in benzene
carboxyl (compare
p.
all
experience has
shown
and in naphthalene
are
such
that
oxidised to
facility,
it
is
impossible to assume their presence in anthracene, a compound which is always oxidised to the neutral substance
kind
of anthracene
nuclei
as,
assumed that
all
the
closed-chains
are
composed
of
six
473
following
CH
formulae
OH
CH
mula
ii.
expressing that of phenanthrene, p. 481), because it
accounts satisfactorily for all known facts amongst others,
for a number of important syntheses of the hydrocarbon
and
lene
state
is,
as,
of combination
different
are generally attacked first), and that the two carbon atoms
of these groups are directly -united, the above formula (i.)
is
usually written,
or
C 6H 4
affinities of the
carbon atoms
474
the two
in
C 6 H 4<
It is
chloride,
3C 6 H 6 .CH 2 C1 = C 6
the hydranthracene
Hc
X UJ /
(p.
which
475),
+ C 6 H 5 .CH 3 + 3HC1,
is
formed as an
inter-
mediate product,
C1C
*
=C
A<
H + 2HC1
4
'
first
equation.
Anthracene
is also
hydranthracene and phenanthrene (p. 481), when ortho-hromobenzyl bromide (prepared by brominating boiliny o-bromotoluene,
C 6 H 4 Br-CH 3 )
is
and from
BrCHBr
All these methods of formation are accounted for in a simple
manner with the aid of the above constitutional formula, the
last one especially indicating that the two central carbon
atoms
will,
are
directly united
therefore,
the
formula
/ CH \ H
/C 4
/
C 6 H 4<^
derivatives.
*
The letters or numbers serve to denote the constitution of the anthracene derivatives (p. 475).
"
475
in support of the
the molecule;
OTT 2
Hydranthracene,
C 6 H 4 <^pTT ^>C 6 H 4 a
may
be obtained.
substance of
little
im-
portance, is formed on reducing anthracene with boiling concentrated hydriodic acid, or with sodium amalgam and water.
It is a
colourless, crystalline compound, melting at 106-108, and when
Anthracene dichloride,
C6 H 4
r^irf^i
it is obtained when
passed into a cold solution of anthracene in carbon
disulphide, whereas at 100 substitution takes place, monockloranthracene and dickloranthracene,
is
chlorine
is
/CC1\
and
/CC1
Anthraquinone,
C 6 H4
CO
H
<_>C
6
4,
is
formed, as already
parts)
in glacial
476
by
recrystallisation
from
acetic acid.
Anthraquinone
is
a damp
produced,
= C6H4
o-Benzoylbenzoic Acid.
CCH
4<QQQfl^
molecule of water,
C6 H 5 =
B
VoH-^gQ^CoH-t
A
+ H 2 0.
bromanthraquinone,
of this substance
477
C0<^ groups
is
it is
and
this,
CO
A
in
f^OOTT
with nitric acid, yields phthalic acid, ~, TT>C 6 H 4 the
.
two CO<^ groups are attached to B, as well as to A, in the o-position, and anthraquinone
has the constitution represented above, a conclusion which affords
group
being oxidised
therefore the
Anthraquinone
crystallises
from
yellow needles, melts at 285, and sublimes at higher temperatures; it is exceedingly stable, and is only with difficulty
attacked by oxidising agents, by sulphuric acid, or by nitric
In all those properties which are connected with the
acid.
quinone, therefore,
When
is
it is
C6 H 4
<T^r,Q77T^>C 6
as in
4,
it
one of the
the reduction of
C6 H4
/^TT/QTT\
C 6 H/
^
^CH
4,
">C 6
loses
4,
sulphonic acid,
at
is dis-
CO
C H <^,,>C H
6
which
is
Anthraquinone
phuric acid even
one
'
is finally
tilled
<\,C H
478
160-170, it
6
2 (S0 3 H) 2
used in such
is
is
pre-
pared by heating anthraquinone with an equal weight of anhydrosulphuric acid (containing 50 per cent, of SO 3 ) in enamelled iron
The product is diluted with water, filtered from
pots at 160.
unchanged anthraquinone, and neutralised with soda ; on cooling,
sparingly soluble sodium anthraquinone-monosulphonate separates
in glistening plates, and is collected in filter-presses.
The more
soluble sodium salts of the anthraquinone-disulphonic acids, which
When
mixed with
in solution.
a trace of finely-divided
soda, a little zinc-dust
dilute
anthraquinone
added, and the mixture heated to boiling, an intense red
colouration is produced, but on shaking in contact with air,
the
solution
is
is
(p. 477)
forming a deep-red solution
is
on shaking with
air,
however,
it
precipitate.
Alizarin,
C 6 H4
r*o
<^>C H (OH)
6
2,
or l:2-dihydroxy anthra-
C 26 H 28
14
glucose,
+ 2H 2 - C 14 H 8
Ruberythric Acid.
+ 2C 6 H 12
Alizarin.
it
synthetically.
This was
first
accomplished in 1868
479
C 6 H4
PO
PO
+ 2KBr,
At
Anthracene
is
first
oxidised
to
anthraquinone,
and the
by the
is
is
(p.
23
+ 2H 2
from this sodium
When
salt alizarin is
anthraquinonesulphonic
-SO 3 H group
is
displaced
by
acid
-ONa
is
in
and hydrogen,
C6 H 4
PO
PO
follows.
480
water, and sent into the market in the form of a 10 or 20 per cent,
From this product alizarin is obtained in a pure state by
paste.
recrystallisation
Alizarin
which melt
crystallises
at
It is a dihydroxy-derivative
moderately soluble in alcohol.
of anthraquinone, and has therefore the properties of a
dihydric phenol;
it
dissolves in potash
are
soluble
With
acetic
in
water,
anhydride
CO
which
it
when
distilled
with zinc-dust
it
is
The value
compound
blue,
and the
tin
and aluminium
compounds
different
short
is
given
Constitution of Alizarin.
Alizarin may be prepared by
heating a mixture of phthalic anhydride and catechol with
CO'
^>^
iOH
Now,
C 6H4
alizarin
yields
two isomeric
ro
2,
481
?7zowo-nitro-derivatives,
such nitro-derivative.
Besides alizarin, several other dihydroxy- and also trihydroxyanthraquinones have been obtained, but only those are of value as
dyes which contain two hydroxyl-groups in the same positions as in
alizarin ; two such derivatives, which possess very valuable dyeing
properties, may be mentioned.
Purpurin,
C6 H 4
< CO
CO >C H(OH)
6
3,
or
:2:4-trihydroxyanthraquin-
Anthrapurpurin,
purpurin, and
acid,
is
C 6 H3 (SO 3
is
isomeric with
H)<Q>C H .SO H,
6
C 14 H 10
an isomeride of anthracene,
is
it
Phenanthrene,
50 per
cent, anthracene/
It
from which
is
it from anthracene picrate, and then decomthe hydrocarbon being finally purified by
ammonia,
posed by
alcohol, to free
recrystallisation.
Phenanthrene
Org.
Chem.
2 E
99,
482
and
is
first
about 340
at
distils
ether,
is
it
When
and benzene.
(p.
350)
it is
therefore diphenyl-
and
its
latter contains
formation
two benzene
nuclei.
is
formed, for example, on passing o-ditolyl (prepared by treating o-bromotoluerie with sodium) or stilbene* through a
since these two hydrocarbons give the same
;
product, the reactions must be expressed as follows,
red-hot tube
fi
(-'Ho
=
I
C 6 H4
C 6H4
CH3
C 6H 5
CH
2H2
II
^^
Phenanthrene.
o-Ditolyl.
CgHg
CgH,
CH
=
CgH 4
I
li
C 6 H4
CH
CH
H2
II
CH
Phenanthrene.
Stilbene.
Br
Br
C6H4
C 6H4
CH
CH
Br
+
2
C 6H4
CH
C 6 H4
CH
'
Br
5,
may
be prepared by
crystallises
C6H 5 -CHBr-CHBr-C6 H 5
(m.p. 237),
483
For these and many other reasons, the constitution of phenanthrene is expressed by the formula,
CH = CH
When
the hydrocarbon
is
oxidised to phenanthraquinone,
co -co
C0 2 H C0 2 H
Diphenic Acid.
Phenanthraquinone.
C,H 4
Phenanthraquinone,
C 6H4
i
CO
CO
I
like
anthraquinone,
is
crystallises
or to a-naphthaquinone, but
quinone
(p.
469),
(ortho-quinone)
when
it
and
is,
is closely related to
/?-naphthalike the latter, an ortho-diketone
The hydroxy-derivatives
yields a dioxime, C 12 8 (C:NOH) 2
of phenanthraquinone, unlike those of anthraquinone, possess
no
tinctorial properties.
484
C 6H4
Diphenic acid,
C 6H4
I
COOH
COOH
it
is
PO
C 12 H 8 <:|::>0
anhydride,
\j\j
(m.p. 217).
This fact
is
remarkable, because
rivatives of hydrocarbons
CHAPTER XXXIII.
PYRIDINE, QUINOLINE,
AND ISOQUINOLINE.
Pyridine, quinoline, and isoquinoline are three very interesting aromatic bases, which, together with their numerous
derivatives, form a group of great theoretical interest, and of
scarcely less importance than that of the aromatic hydrocarbons ; many of these derivatives occur in nature, and
belong to the well-known and important class of compounds
known
as 'alkaloids.'
Coal-tar,
AND ISOQUINOL1NE.
PYRIDINE, QUINOLINE,
485
tional
distillation
stituents
of
this
quinoline, &c.,
oil
may
some of these
is
bone-tar
Dippel's
in
oil.
Pyridine and
Pyridine,
C 5 H 5 N,
is
its
Derivatives.
distilla-
Pure pyridine
by
is
acid,
may be
prepared from
C 6 H 4 N.COOH - C 5 H 5 N + C0 9
C 5 H 3 N(COOH) 2 = C 5 H 5 N + 2C0 2
For commercial purposes
it is
which
is
separated
486
AND ISOQUINOLINE.
PYRIDINE, QUINOLINE,
from bone-oil or
of
consists
together with
pyridine,
the product
small quantities of
its
homologues.
a colourless, mobile liquid of sp. gr. 1-003 at
115, is miscible with water in all proportions,
0;
and possesses a pungent and very characteristic odour. It
is an exceedingly stable substance, as it is not attacked by
is
Pyridine
it
boils at
boiling nitric or chromic acid, and only with difficulty by halogens; in the latter case substitution products such as mono-
C 5 H4 BrN, and
dibromopyridine, C 5 3 Br2 N,
however, a solution of pyridine in hydrochloric acid be treated with bromine, a crystalline, unstable
additive product, C 5 5 NBr 2 is precipitated, even from very
bromopyridine,
are formed.
If,
dilute
sometimes used as a
When
dissolved
(p.
of
substance
this
is
in
alcohol
sodium,
is
pyridine
solutions,
(C 5
S0 4
5 N) 2 ,H 2
crystallises in
in water
sparingly soluble
fact
C 5 H 5 Isr,HCl, and
(C 5
platinichloride,
when,
The
however,
yellow
its
solution
the
sulphate,
N) 2 ,H 2 PtCl 6
is
readily soluble
is
boiled,
N) 2 PtCl 4
a very
separates, a
use of for the detection of pyridine
(C 5
salt,
a,
when
contents
of
test tube
with methyl
C 5 H 5 N,CH 3 I,
now
is
pro-
is
at once noticed.
PYRIDINE, QUINOLINE,
AND ISOQUINOLINE.
487
Constitution.
Pyridine is a strong base, has a pungent
odour, and turns red litmus blue, properties which at once
It is not, however, a
suggest some relation to the amines.
primary amine, because it does not give the carbylamine re-
action
by
nor
is it
nitrous acid
tertiary base
is
its
behaviour towards
If,
moreover,
it
be borne in
mind
because
The grounds
are, in fact,
for
doubting
much
its relation to
is
totally different
by
closed-chain
or
nucleus,
as
represented
by the following
formula,
and
this
488
compound which
constitution
and which
(i.)
is
is
(11.),
CH 2
CH^
CH
>H
CHL
JCH 2
CH 2 k
NH
JOB
N
Pyridine
Piperidine (L).
(II.).
CH<;
groups.
is
CH
OH
cn
CH
en
Korner.
Dewar.
CH
K^J
">I
Centric Formula.
The mowo-substitution
PYBIDINE, QUINOLINE,
numbered or lettered *
C and H being omitted
AND ISOQUINOLINE.
489
These substitution products being formed by the displaceof any one of the five hydrogen atoms, it is evident
that the following three, but not more than three, isomerides
ment
may
be obtained,
The
aft ay,
the
substituents
in
the
All other positions are identical with one of these ; aft for
example, is the same as a'ft, and fly is identical with f$'y.
As regards the isomerism of its derivatives, pyridine may
C 5 H 10 NH,
Piperidine, or hexahydropyridine,
formed,
already stated, when pyridine is
reduced with sodium and alcohol ; it is usually prepared
is
as
* In the
pyridine derivatives letters are generally used instead of
numerals, the latter being conveniently reserved for benzene derivatives.
490
PYRIDINE, QUINOLINE,
AND ISOQUINOLINE.
ammonium
chloride which
is always
then evaporated, the
residue distilled with solid potash, and the crude piperidine purified
hy fractional distillation over potash.
present.
The
filtered alcoholic
solution
is
it
acid,
at
218;
C 5 H 10 N-NO,
an
oil,
boiling
C 5 H 10 N-CH 3
with
it
is,
and
the
in
2KCN =
2KBr,
(Part
it is
a heavy, colourless
oil,
and
boils at 164.
PYRIDINE, QUINOLINE,
a substance which,
AND ISOQUINOLINE.
491
011
+ 8H =
im .CH
2
during
diamine
this
is
same change
occurs,
but
much more
completely,
when
the
is distilled,
r^
^CH -CH
2
'^CH^CH/
3"
of their salts.
C 5 H 3 N(CH 8 ) 2
or
lutidines,
collidines,
C 5 H 2 N(CH 3 ) 3
potassium permanganate, and are converted into pyridinecarboxylic acids, just as the homologues of benzene yield
benzenecarboxylic acids, the alkyl-groups or side-chains being
oxidised to carboxyl-groups,
C 5 H4 N-CH3 + 30 = C 5 H 4 N-COOH + H 2
C 5 H 3 N(CH 3 ) 2 + 60 = C 5 H 3 N(COOH) 2 + 2H 2 0.
is of great use in determining the positions of
the alkyl-groups in these homologues of pyridine, because the
carboxylic acids into which they are converted are easily
This behaviour
isolated,
and
by
their
melting-points
-192
AND ISOQUINOLINE.
PYRIDINE, QUINOLINK,
many
of
the alkaloids.
The
three
(a, /?,
acid
is
known
from
prepared
The a-carboxylic
as picolinic acid, because it was first
usually
is
a-picoline
called
(a-methylpyridine),
nicotinic
^-compound
obtained by the oxidation
acid,
because
whereas the
it
was
first
COOH
COOH
J
COOH
Picolinic Acid, or
Nicotinic Acid, or
Pyridine-a-carboxylic Acid
(111.
p. 136).
Isonicotinic Acid, or
Pyridine-/3-carboxylic Acid Pyridine-y-carboxylic Acid
(in. p.
229).
which
The
acid.
C5 H 3N(COOH) 2
(pyridine-a/3-dicarboxylic
acid),
iCOOH
COOH
PYRIDINE, QUINOLINE,
a
AND ISOQUINOLINE.
493
of quinoline with
the most important of the six isoIt crystallises in colourless prisms,
potassium permanganate,
meric dicarboxylie acids.
only sparingly soluble in water, and gives, with ferrous sulphate, an orange colouration, one of the carboxyl-groups being
is
When
in the a-position.
heated at 190
it
decomposes into
benzenedicarboxylic
its
anhydride
acetic
(p.
anhydride,
CO
,
at
134.
acid
439)
as
the
latter
nevertheless,
quinolinic
acid
is
converted into
gives
an
anhydride,
(as
in
the case of
Quinoline.
between 236
and 243
as,
however,
it is difficult
by Skraup
and nitrobenzene.
494
PYRIDINE, QU1NOLINE,
AND ISOQUINOL1NE.
gr.
Qninoline
1-095 at
is
colourless,
highly
at
refractive
239.
of
oil,
sp.
has a peculiar
It
but
it
the platinichloride,
(C 9
it
it
just as naphthalene
PYRIDINE, QU1NOLINE,
CH
AND ISOQUINOLTNE.
CH
495
01 1
CH
on
Now,
differs
ganate
is
shown by
its
is
by formula
I.
(the
all
substance,
benzene,* loses
under the oxidising action of the nitrotwo atoms of hydrogen, and is converted into
quinoline,
CH
CH
CH
-jun
+ H 2 0.
as in
496
Many
reaction,
itself
is
AND ISOQUINOLINE.
PYRIDINE, QUINOLINE,
(p. 376)
formed, the position of the
of course, united with the benzene,
employed, a methylquinoline
is
Isoquinoline,
depending on which of
taken.
is
C 9 H 7 N,
may
236-243,
and
thus obtained
fied
by
is
distillation.
Isoquinoline
241,
is
it
is
also
is
solid,
slightly
puri-
quinoline (239).
The constitution of isoquinoline is very clearly proved by
its behaviour on oxidation with permanganate, when it yields
C 5 H 3 N(COOH) 2
or pyridine-^y-dicarboxylic acid ; oxidation takes place, therefore, in two directions, in the one case the pyridine (Py), in
CH
CH
CH
CH
CH
CH
^CH
c-COOH
Isoquinoline.
Phthalic Acid.
COOH-c
CH
Cinchomeronic Acid.
^N
closed-chain
as open-chain,
secondary, or tertiary bases respectively, as far as these particular
groups are concerned.
The secondary bases, such as piperidine, which contain the
AND ISOQUINOLINE.
PYRIDINE, QUINOLINE,
497
>NH-group,
an
giving triethylamine,
(C 2
H NH + C H I = (C H
5 )2
5 )2
N.C 2 H 5 ,HI.
ammonium
salts (Part
I.
is
of the
also displaceable
or
>N(CH
3 ) 2 I.
>NH-group
by
radicles.
The
nitrogen atom
is
CHAPTER XXXIV.
ALKALOIDS.
The term alkaloid is generally applied to those basic nitrogenous substances which occur in plants, irrespective of any
similarity in properties or constitution ; as, however, most
substances of this kind have some important physiological
volatile
liquids
Chem.
498
ALKALOIDS.
well-
many
derivatives
are
alkaloids
of
quinoline,
pyridine,
or
isoquinoline.
It is a remarkable fact that
of the
number
C 6 H5 -0-CH3
of such
p.
405),
groups in
the molecule
is
of
the
of.
The
fact that
equation,
<-OCH
by estimating
the
3)
methyl
iodide
obtained
from a given
molecular weight, it is
quantity of a compound of known
of methoxy-groups
number
the
determine
to
therefore,
easy,
in the molecule ; ethoxy-groups may also be determined in a
similar manner.
as
it
first
affords a
means
is
of general
of accurately determining
ALKALOIDS.
the
number
499
it
is
carried
in 12 c.c. of water).
About 0-3 gram of the substance
the flask
(a),
together with 10
under examination
placed in
is
gradually raised, until the acid just boils, carbon dioxide, at the
rate of about 3 bubbles in 2 seconds, being passed all the time.
The methyl iodide is carried forward through the 'potash bulbs,'
is
acid,
iodide,
stance was
The
C 8 H 4 O 3 (OCH 3
) 2.
ALKALOIDS.
501
occur together, partly because of the neutral and acid substances, such as the glucosides, sugars, tannic acid, malic acid,
finally purified
and
isolation.
in
the
following pages.
oil,
it
may
boiling at
be prepared by distillation
167, and
is
readily soluble
in water
it
C 8 H ir N,HCl, which
base and
its
salts are
to
* In
cases of alkaloid poisoning it is usual, after using the stomach-pump,
wash out the stomach with dilute tannic acid, or to administer strong
tea (which contains tannin), in order to render the alkaloids insoluble, and
therefore harmless.
502
ALKALOIDS.
is
dextrorotatory a-propyl-
CH 2
NH
and has succeeded in preparing
it
synthetically,
the
first
heavy type
compare
obtained by synthesis,
may
be resolved into
components by crystallisation
is
atom (shown
and
p. 544),
of its tartrate
its
two
optically active
(compare
p. 557).
Nicotine, C^H^l^,
plant (Nicotiana tabacum), combined with malic or citric acid.
posed with potash, and the free nicotine extracted with ether.
The- ethereal solution, on evaporation, deposits the crude alkaloid,
which is purified by distillation in a stream of hydrogen.
oil, which boils at 241, possesses a very
and
pungent odour,
rapidly turns brown on exposure to air ;
it is readily soluble in water and alcohol.
It is a strong
di-acid base, and forms crystalline salts, such as the hydro-
It is a colourless
chloride,
C 10 H 14 N" 2 ,2HC1
it
two
H N
base
(p.
nicotinic
497).
acid
When
(pyridine-/?-carboxylic
acid,
p.
492)
it
;
yields
it
is,
therefore, a
Nicotine
into
is
exceedingly poisonous, two or three drops taken
the stomach being sufficient to cause death in a few
minutes.
It
shows no very
503
ALKALOIDS.
presence
(which
may be
Piperine,
cent,
detected
by
its
C 17 H 19 N0 3
from which
it is
easily extracted.
The pepper is powdered and warmed with milk of lime for fifteen
minutes ; the mixture is then evaporated to clryness on a waterbath, extracted with ether, the ethereal solution evaporated, and
the residual crude pipeline purified by recrystallisation from alcohol.
It
in
crystallises
insoluble in water
melts at
prisms,
is
it
128, and
is
almost
it is
when
(p.
C 17 H 19 N0 3 + H 2 = C 5 H U N + C 12 H 10
Piperidine.
Atropine, or daturine,
although
it
belladonna).
is
C^H^NOg,
4
Piperic Acid.
and
intramolecular
undergoes
treatment with bases.
readily
liyoscine,
change
into
The plant is pressed, the juice mixed with potash, and extracted
with chloroform (1 litre of juice requires 4 grams of potash and
30 grams of chloroform)
the chloroform is then evaporated, the
atropine extracted from the residue with dilute sulphuric acid, the
solution treated with potassium carbonate, and the precipitated
alkaloid recrystallised from alcohol.
;
It crystallises
melts at
115;
and
insoluble in water.
When
boiled
C 1Y H23 N0 3 + H 2 = C6 H5 'CH<
Tropic Acid.
Atropine
is
+ C8 H 16 NO.
Tropine.
504
ALKALOIDS.
causing death.
on the
when
its
solution
is
placed
eye.
H N0
The coca-leaves are extracted with hot water (80), the solution
mixed with lead acetate (in order to precipitate tannin, &c.),
filtered, and the lead in the filtrate precipitated with sodium
sulphate ; the solution is then rendered alkaline with soda, the
cocaine extracted with ether, and purified by recrystallisation
from alcohol.
is
salts,
of
C 17 H 2] N0 4 ,HC1,
and
is
Cocaine
is
is
most
local application
takes
all
sensation
of
as
it
away
pain
however, poisonous, one grain injected subcutaneously
having been attended with fatal results.
its
is,
When
and ecgonine,
C 17 H 21 N0 4 + 2H 2 = C 6 H 5 -COOH + CH 3 -OH + C 9 H 15 N0 3
C 20 H 24 N 2
505
ALKALOIDS.
some
The
of
which contain
alkaloids
are
as
much
contained
in
the
bark,
combined with
may
be obtained as an amorphous
melts at 177
2 0,
when
H N
many
in
Quinine
is
it
H N
acid
it
yields
acid),
>~\
COOH
^
CHj
N
Quinine contains one methoxy-group, as has been demonstrated by Zeisel's method (p. 498), and it is a methoxycinchonine, because on oxidation it yields the methoxyderivative of quinoline-y-carboxylic acid (see below).
If a solution of a salt of quinine be
Tests for Quinine.
mixed with
chlorine- or bromine-water,
506
ALKALOIDS.
produced
dilute
quinine
solutions
of
salts
its
emerald-green colouration is
by the fact that
characterised
also
is
show a
beautiful
light-blue
fluorescence.
C 19 H 22 N 2 0,
Cinchonine,
all
the
and
cinchona-barks,
is
but are
antipyretics,
much
less
at
255,
salts,
active
for
than
those of quinine.
COOH
The formation
of this
is
quinoline-derivative.
H N
Strychnine, C 21 22 2 2 and brucine, two highly poisonous alkaloids, are contained in the seeds of Strychnos nux
vomica and of Strychnos Ignatii (Ignatius' beans), but they
are usually extracted
is
The
pre-
507
ALKALOIDS.
The
strychnine
purified
by
is
part in
bitter taste,
one of
C 21 H 22 N 2
iodide
C 21 H 22 N 2 2 ,CH3 I.
When distilled with
products, quinoline
to
,HC1
many
of
the salts
it
com-
probably, therefore,
it
is
among
other
a derivative of
this base.
is
Strychnine
reactions,
it
of
which the
When
a small quantity
in a porcelain basin, a
is placed
concentrated sulphuric acid added, and then a little
an
powdered potassium dichromate dusted over the liquid,
of
powdered strychnine
little
is
produced.
H N
H 0, and
Brucine, C 23
with 4 mols.
It
is
more
26
4,
crystallises
melts,
in
colourless
prisms,
178.
and in alcohol than
when anhydrous,
at
508
ALKALOIDS.
C 23 H 26 N 2
,HC1
it
is
C 23 H 26 N 2
,CH 3 L
now
is
is
is
if
produced.
This colour reaction serves as a delicate
it
may
test,
both for
The
juice of certain kinds of poppy-heads (Papaver somcontains a great variety of alkaloids, of which
niferum)
is
the most important, but code'ine, narcotine,
and
thebdine,
papaverine may also be mentioned. All these
are
present in the juice in combination with
compounds
meconic acid* and partly also with sulphuric acid.
When
incisions are made in the poppy-heads, and the juice which
exudes is collected and left to dry, it assumes a pasty conAn alcoholic tincture of
sistency, and is called opium.
morphine
grain of
opium in 15 minims,
is
Meconic acid,
C 5 HO 2 (OH)(COOH) 2
acid,
and
all
the alkaloids,
is
which
it
509
ALKALOIDS.
Morphine,
with 1 mol.
C 17 H 19 N0 3
and
2 0,
in
crystallises
is
only
I.
p. 107).
colourless
slightly
soluble
prisms,
in
water
salts
crystallises
in medicine.
Morphine is a tertiary
and when treated with methyl iodide it yields morphine
commonly employed
base,
C ir H 19 N0 3 ,CH 3 I.
methiodide,
Morphine has
a bitter taste,
and
is
excessively poisonous,
opium
that, after a
may be taken
is extensively
in
cases of intense pain.
soporific, especially
Tests for Morphine.
Morphine has the property of liberat-
effects.
Morphine
If a little iodic
ing iodine from a solution of iodic acid.
and a few drops of a solution
at
once produced,
is
starch-paste, the
to
obtained.
solution of morphine, or of a
colouration with ferric
deep -blue
morphine
salt,
gives a
but
perhaps
the following
If a trace of morphine be dissolved in concentrated sulphuric
acid, the solution kept for 15 hours, and then treated with
the most
nitric
delicate
acid,
it
chloride,
alkaloid
gives a bluish-violet
is
colour,
which changes
510
to
ALKALOIDS.
This reaction
blood-red.
is
is
well
of morphine.
a phenol;
it
C 17 H] 7 NO(OCH 3 )-C 2 H 3 O 2
H N
Tea
2 0,
melts at 225, and at higher temperatures sublimes unit has a bitter taste, and is
;
sparingly soluble
decomposed
in cold water
forms
salts
C 8 H 10 ]\T4
and
only
2 ,HC1,
is
alcohol.
with
at
Caffeine
strong
acids
is
the
hydrochloride,
very closely
by E.
allied.
it
ALKALOIDS.
acid),
violet
(murexide reaction)
I. p.
of
this reaction is
303).
511
water
red colouration.
Theobromine, C 7 H 8 N 4 O 2 occurs in cocoa-beans, from which it
be obtained by treatment with lime, and extraction with
It crystallises from water, and shows the greatest resemalcohol.
blance to caffeine in properties ; the latter is, in fact, methyltheobromine, and may be obtained directly from theobromine in the
,
may
following
way
Theobromine contains an
^>NH
is
C 7 H 7 N 4 O 2 Ag + CH 3 I = C 7 H 7 N 4 O 2 -CH 3 + Agl.
Silver Theobromine.
Caffeine.
The
/NH CO
/NH-CO-C-NH,
C0<\NH
>CO
C-NH/
C0<
C-N (CHA
>CH
||
\N(CH 3
is
Theobromine.
Uric Acid.
,N(CH 3 ).CO.C.N(CH 3 k
co<;N(C H 3
II
>CH
C
Caffeine.
Antipyrine,
C 11 H 12 N 2 0,
is
'
hydrazine (p. 388), and then heating the product (plienylmetliylpyrazolone) with methyl iodide,
C 6 H 10
+ C 6 H5 .NH.KE 2 = C 10 H 10 N2 + C 2 H5 .QH + H 2
C 10 H 10 N 2 + CH 3 I = C n H 12 N" 2 0,HI.
512
ALKALOIDS.
and its salts dissolve freely in water. Its aqueous solution gives a deep-red colouration with ferric chloride, and a
bluish-green colouration with nitrous acid.
Antipyrine is
base,
for lower-
CJioline, Betaine,
compounds
really belong,
or
hydroxyethyltrimethylammonium hydroxide,
) 3 .OH, occurs in the blood, bile, brainof
substance, yolk
egg, and in other parts of animal organisms,
in
form
of lecithin (a compound of choline,
the
usually
it also
glycerol, phosphoric acid, and various fatty acids)
It may be prepared synthetioccurs in mustard and in hops.
cally by warming trimethylamine with ethylene oxide in
Choline,
aqueous solution,
N(CH 8 ) 8 + C 2 H 4 + H 2 = C 5 H 15 N0 2
aqueous solution having an alkaline reaction, and absorbing carbon dioxide from the air ; with hydrochloric acid it
its
OH-CH
H N0
loses
ALKALOIDS.
513
salt-like
sweet
0.
When
may
COOH-CH 2 .N(CH 3
) 3 C1,
betame is converted
and this compound
with chloracetic
Neurine,
(vmyltrimethylammonium
CH LCH 2 .N(CH 3
2
)3
+ 2AgOH =
CH 2 :CH.N(CH 3 ) 3 .OH + 2AgI + H2
Neurine
is
only
known
soluble,
salts,
CH2 :CH.N(CH 3
its
) 3 C1, are
crystalline.
NH
and decomposes
at about
240, and
is
it
forms
salts
When
treated
NH CH
2
-CH 2 S0 3 H + HO
matter are
known
collectively as ptomaines,
poisonous.
Or. Chem.
2 G
of animal albuminoid
and many
of
514
CHAPTER XXXV.
DYES AND THEIR APPLICATION.
colourless,
some,
is coal-tar
coal-tar colours.'
is,
of course,
does not
fulfil
is
acid,
does not
it,
a behaviour which
is
fabric,
cotton,
it is
evident that
of
minute
515
fibres,
which may
membrane, allow
by
crystalloids
or, of course, of
diffusion,
matter in suspension.
If,
it
;
would, on wash-
The nature
dyed in
this
of the insoluble
way
is
itself)
some constituent
this
of the fibre
516
mordants.
Dyes, therefore,
may be roughly
under-
first
often obtained.
As an example
be taken, as
it
may
mordants.
is easily
got rid of
Substances
certain
salts
if,
again, the
would
salt instead, it
*
A colouring matter such as alizarin, which can thus be used for the
'
a dye
production of different colours, is sometimes termed polygenetic
'
which gives only one colour is then named monogenetic.'
'
517
and alums,
which undergo decomposition on treatment with water or
with steam, yielding either an insoluble metallic hydroxide
or an insoluble basic salt.
The
firstly,
salt
is
treated
way
is
accomplished in
is
many ways.
One
of the simplest
salt,
some
some
salt
an insoluble
action of steam, at a suitable temperature ; under these conditions the metallic salt dissociates, the acid volatilises with
metallic salt
fibre
salt.
518
material
is
metallic hydroxide
fixes the dye.
The coloured substances produced by the combinadye with a metallic hydroxide are termed lakes, and
those dyes which form lakes are called acid dyes.
Tannin (p. 453) is an example of a different class of
the
fibre.
tion of a
The
fabric is
of tannin,
All colouring matters are converted into colourless compounds on reduction ; in the case of some dyes, the reduction
product cannot be directly reconverted into the dye by oxidation, as, for example, in that of amidoazobenzene, which,
when
the colourless
leuco-compound.
519
of which
is
benzene
may be
H N
indigo-white
in dyeing with
white
is prepared by
with grape-sugar and sodium hydroxide, or ferrous sulphate
and sodium hydroxide, and the fabric is then passed through
formulae
factorily established.
Derivatives of Triphenylmethane.
Triphenylmethane,
C 6 H 5 -CH(C 6 H 5) 2
(p.
351),
or,
more
strictly
is
520
great technical
and rosaniline
be described.
may
dye
itself.
The
leuco-base (p. 518) is an amido-derivative of triphenylin the case of malachite green, for example, the
;
methane
leuco-base
The
and
is
tetramethyldiamidotriphenylmethane,
colour-base
is
methane
(p.
example,
is
Both the leuco-base and the colour-base are usually colourand the latter also yields colourless, or only slightly
when warmed
coloured, salts on treatment with cold acids
less,
with
salts,
however,
C 23 H 26 N" 2 + HC1 = C 23 H 25 N 2 C1 + H 2 0.
Malachite Green Base.
This change
atoms
or
is
groups
(p.
521
428),
(p.
and
C 6 H 5 .C(OH).C 6 H 4 .N(CH 3 ) 2
(CH 3 ) 2 N, HC1
(CH 3 ) 2 NC1
Chloride of Malachite Green.
Hydrochloride of Colour-base.
as derivatives
of quinones.
is
a double
salt,
formed by
is
methyl-p-diamidotriphenylmethane,
Leuco-malachite green
is
C 6H 6 -CH< r 6
TT
4
with hydrochloric
acid,
C6 H 5
r<
TT
p
H5
C 6 TT
molecule
of
water,
intensely
green
solutions
being
522
obtained;
the
formation
of the
chloride,
for
example,
is
C 23H26 N 2 + HC1 = C 28 H 26 N 2 C1 + H 2 0,
and
its
double
salt
base), constitutes the malachite green (Victoria green, benzaldehyde green) of commerce.
steam, to get rid of the unchanged dimethylaniline, and after coolThis product is
ing, the insoluble leuco-compound is separated.
washed with water, dissolved in as little hydrochloric acid as
possible, the solution diluted considerably, and the calculated
quantity of freshly precipitated lead dioxide added. The filtered
dark-green solution is then mixed with sodium sulphate, to precipitate any lead, again filtered, and the colouring matter precipitated
in the form of its zinc double salt, 3C23H 25 N 2 Cl,2ZnCl 2 + 2H 2 0, by
the addition of zinc chloride and common salt ; this salt is finally
by recrystallisation.
Malachite green, and other
purified
oxalate,
2C 23 H 24 N 2 ,3C 2 H 2
tetramethyldiamidotri-
phenyl carbinol.
Malachite green dyes silk and wool directly an intense
dark-bluish green, but cotton must first be mordanted with
tannin and tartar emetic (p. 518), and then dyed in a bath
gradually raised to 60.
other dyes, closely allied to malachite green, are prepared
tertiary alkylanilines (p. 377).
Brilliant green, for example, is finally obtained when diethylaniline is employed instead of dimethylaniline in the abovedescribed process, whereas acid green is obtained from benzal-
Many
* Produced
by treating aniline with benzylchloride and ethyl bromide
successively.
t>YES
523
for this reason, the bases are treated with anhydrosulphuric acid,
of <imf/i?'cfo-triphenylmethane, the rosanilines are all triamidotriphenylmethane derivatives, as will be seen from the follow-
ing formulae,
Triphenyhnethane.
Tolyldiplienylmethane
(Methyl triphenylmethane).
Leuco-rosaniline
Leuco-pararosaniline
(Paraleucaniline).
(Leucaniline).
Triamiclotriphenylmetliane.
Triamidotolyldiphenylmethane.
Pararosaniline Base.
Triamidotriphenyl Carbinol.
Rosaniline Base.
Triamidotolyldiphenyl Carbinol.
Rosaniline Chloride.
Pararosaniline Chloride.
In
all
these
position to the
is
most conveniently
>-toluidine
(1
pre-
mol.) and
+ 2H0.
524
NH
The
salts of pararosaniline
are soluble in
warm water
described
is,
the
in
case
of
methane,
NH
NH
9 .C 6
-C(OH)(C 6 H 4 .NH 2 ) 2 +
NH
2H =
-C 6
2
.CH(C 6 H4 .]S H 2) 2 + H 2 0.
T
H N
salts,
CH(C 6 H 4 -N 2 C1) 3
aurin, C 19 H 14 3
it
is
which,
(p.
530),
alcohol, is
first
derivative
established
of
this
hydrocarbon
by E. and 0. Fischer
it
has
been shown
that
all
the
nitro-groups
are
in
the
fuming
to
nitric acid
a substance which
525
which, on oxidation,
is
base,
triamidotriphenyl
with
acids,
elimination
of water,
HC1,NH 2 -C 6 H 4
.<
<
Hydrochloride of Pararosaniline
Chloride of Pararosaniline.
is
the
portions of aniline, o-toluidine, and j>toluidine (with nitrobenzene, arsenic acid, mercuric nitrate, &c.), the reaction
being similar in
rosaniline base
all
(1 mol.),
o-Toluidine.
TSJTT
2'
P
PTT 4H4' CH
C 6 TT
3 +
6432
c 6H 5 .NH 2
Qf)
Aniline.
p-Toluidine.
NH -C
2
A-qOHK^J^'
+ 2H 2 0.
Kosaniline Base.
Rosaniline
what
is
is
acid process.
To
* Crude
has sometimes been
'aniline-oil,' a mixture of these three bases,
526
and steam
is
recrystallisation.
quantity of iron
The
salts
is
necessary.
ficent crystals,
equivalent of
C 20 H 20 N3 C1,
warm
they dissolve in
and dye
silk,
malachite green.
The addition of alkalies to the saturated solution of the
rosaniline destroys the colour, and causes the
precipitation of the colour-base, triamidotolyldiphenyl car-
chloride of
binoly
needles,
into
and hydrochloric
aniline,
which,
C 20 H 21 N 3
when
acid,
(p.
is
again converted
into rosaniline.
The
deduced in the
same way
of
the
into
diphenyl-m-tolylmethane,
)2
leuco-
CH
(i>
salts are
/CH.NH
(4)
527
and rosaniline may be displaced by methyl- or ethylgroups, by heating the dye with methyl or ethyl iodide
under these conditions tri-alkyl
(chloride or bromide) ;
aniline
of the
displaced.
for
When,
it
methyl chloride,
of
PTT ATTT
64:
633
This compound
is
triethyl-TossLmline
NH(CH 8 )C1.
chloride
Hofmann's
stance
is
used
it
compound
C 20 H 16 N 3 (CH 3 4 I,CH 3 I + H 2 0,
of the composition,
'
is
green, and
iodine green.'
when
as
in
528
Lastly,
is
interesting to note
like tetramethylrosaniline,
it
compound,
is
that
when
a violet dye,
somewhat
however,
'
it is usually manufactured by
;
mixture of dimethylaniline, potassium chlorate,
of &e:m?fteA?//-pararosaniline
heating
for about
(p.
522).
When
aniline at
100, in the
529
are
reddish-violet
and
bluish-violet
Aniline bine,
ros-
180
dilute
acids,
crystallises out in
Aniline blue
dyeing with
solution.
dye
it,
is
the names
'
alkali blue,'
In dyeing
material
is
silk
first
'
water
blue,'
&c.
salts,
when
The
is
first
developed.
Cotton
is
dyed in
530
Trihydroxytriplienyl Carbinol.
These compounds
may
Trihydroxytolyldiplienyl Carbinol.
tri-
in
constitution,
Rosolic Acid.
Aurin.
owing to the
difficulty
them.
The Phthaleins.
compound formed
loss of
one mole-
cule of water,*
co<$l
*
Compounds produced
acid,
by
loss
of water,
I. p.
are
called
166).
^ H** + HjA
CO
y-Bntyrolactone.
The fatty lactones are mostly neutral volatile liquids, but those belonging to the aromatic series are crystalline solids ; all lactones dissolve in
caustic alkalies, yielding salts of the hydroxy-acids from which they are
derived.
Phthalophenone
phthalyl
chloride
is
by acting on
prepared
(p.
531
a mixture of
with aluminium
chloride,
=
CO<5J^>Ca + 2C H CO<5>C(
6
It
crystallises
dissolves
in
in
colourless
melts at
needles,
salts
yielding
alkalies,
W, + 2HCL
of
115, and
triphenylcarbinol-o-
COOH.C 6 H4 -CH(C 6 H 5 ) 2
carljoxylic
acid,
distillation
is
from which, by
obtained a proof
14
4,
is
.OH =
CO<>C(C H .OH)
6
+ H 2 O.
solutions
the
;
use
it is,
of phenolphthalein as an
however, of no value as a dye.
The conversion of feebly coloured phenolphthalein into an intensely coloured salt is probably due to its transformation into
a derivative of quinone, just as in the case of the conversion of
the colourless salt of tetramethykliamidotriphenyl carbinol into
the green dye
(p. 521),
follows,
c
Intermediate Product.
Phenolphthalein.
'
Coloured
Salt.
H =O
4
+ H2O
fi
.OH
532
Fluorescein,
C 20 H 12
5,
is
resorcinol,
Fluorescein.
this Change,
a
phthalic anhydride (as in the formation of phenolphthalein),
second molecule of water being eliminated from the hydroxyl-
it
C 20 H 10
impart fluorescence.
the fact that
Eosin,
its
CO<
>C<>0
(tetrabromoflum-
placed.
Fluorescein
is
533
extent as
solutions of fluorescein.
its potassium
brownish
and
is
much used
(a
powder),
for dyeing silk, wool, cotton, and especially paper, which
fixes the dye without the aid of a mordant.
Silk and wool
are dyed with eosin directly in a bath acidified with a little
salt,
C 20 H 6 Br 4
K2
5
acetic
lead,
or
fluorescence.
Tetriodofluorescem,
sodium
name
salt,
C 90 H .I 4
C 20 H 8 I 4 5 is also a
Na 2 comes into the
5
,
valuable dye.
Its
'
erythrotdn.
of
azo-com pounds,
it is intensely
coloured (compare p. 514), and this is true also of other
neutral azo-compounds
if, however, one or more hydrogen
atoms in such compounds be displaced by amido-, hydroxyl-,
all
is
Amidoazobenzene,
Hydroxyazobenzene,
Azobenzenesulphoriic acid,
are yellow or
brown
for example,
as,
CH
CH
CH
6
-N:N-C 6 H 4 -NH 2r
H4 -OH,
.N:N.C
5
6
H4 -S0 3 H,
-N:N-C
5
6
5
dyes.
by one of two
general
534
methods
compound,*
C 6H 6 .N,C1 + C
CH8 .C H 4 .N
tf
Cl
.N(CH 8 ) 2 = C
.H .N(CH
.N:N.C 4
3 ),,HC1,
5
(3
Dimethylaiaidoazobeiizeiie Hydrochloride.
(
+ CH8 .C 6 H 4 -NH 2 =
p-Diazotoluene Chloride.
o-Tolnidine.
Amidoazotoluene Hydrochloride.
or
In the
preparation of azo-dyes
sists in treating
(p.
SOsH-CgH^Na-OH + C 6 H 5 .NH 2 =
S03H.C6H4.N:N.C6H4.NH2 + H 2 0.
Ainidoazobeiizenesulplionic Acid.
azo-com pounds.
In
all
these
the
reactions
diazo-group,
displaces
is
difficulty.
excess of the
amido-compound
is
The
535
the alkaline solution of the phenol, or its sulphonic acid, care being
taken to keep the solution slightly alkaline, otherwise the liberated
After a
hydrochloric acid prevents combination taking place.
short time the solution is mixed with salt, which causes the
colouring matter to separate in flocculent masses ; the product is
then collected in filter-presses and dried, or sent into the market in
The combination
of
is
Acid azo-colours (that is, hydroxy- and sulphonic-derivataken up by animal fibres directly from an acid
are principally employed in dyeing wool ; they
and
bath,
can be fixed on cotton with the aid of mordants (tin and
tives) are
aluminium
a mordant.
Basic azo-dyes are readily fixed on cotton which has been
mordanted with tannin, and are very largely used in dyeing
calico and other cotton goods.
At the present time a great many azo-colours are manufactured, but only a few of the more typical are mentioned
here.
Aniline
yellow,
is
not
a
,
fast,
is
is
(p.
536
is
yellow colour.
Bismarck brown,
NH -C H -N:N.C H
2
(NH 2 ) 2
(triamidoazo-
benzene), is prepared by treating w-phenylenediamine hydrochloride with nitrous acid, one half of the base being con-
The hydrochloride
used
in
is
(NH 2 ) 2 =
a dark-brown powder, and is largely
(mordanted) and leather a dark
cotton
dyeing
brown.
solution,
which
hence
use as an indicator.
dye,
its
is
on account of
seldom employed as a
It is
of acid.
Its
sodium
salt is a
not readily
acted on by acids ; it is chiefly employed, mixed with other
dyes of similar constitution, in the production of olive-greens,
is
maroons, &c.
By
as in the
in order, however, to
537
done by combining a benzenediazo-compound with a naphthylamine, naphthol, naphthaleriesulphonic acid, &c., just as
The dyes thus obtained give various shades
described above.
of reddish-brown or scarlet, and are known collectively as
;
Ponceaux
'
or
'
Bordeaux.'
When,
example, diazoxylene chloride is combined
with /3-naphtholdisulphonic acid, a scarlet dye (scarlet R)
of the composition C 8 8 (CH 8 ) 2 .N:N.C 10 4 (S0 8 H) 2 .OH is
formed; another scarlet dye (Ponceau 3R) is produced
for
by the combination
/?-naphtholdisulphonic
of
compound
pro-
natural dye, cochineal, which rocellin and other allied azocolours have, in fact, almost superseded.
Within recent years a great number of exceedingly valuable colouring matters have been prepared from benzidine,
-C 6 4 .C 6 4 -NH 2 (p. 391), and its derivatives.
2
NH
Benzidine
may
C1N 2 .C 6 H 4 .C 6 H 4 -N 2 C1.
Congo-red, a dye produced by the combination of tetrazodiphenyl chloride with naphthionic acid, is one of the most
valuable compounds of this class.
Its
sodium
salt,
538
is
blue,
The congo-dyes
which are
cotton,
fast
soap.
brownish-red
producing
are
They
much used
shades
for dyeing
which contains
air of
to
The Benzopurpurins
ditolyl salts
amine, and
are, therefore,
the congo-group
stitution.
shades,
scarlet
sodium
during nitration.
C 10 H 5 (N0 2 ) 2 -ONa
is
the
salt,
readily soluble in water,
and dyes silk and wool directly an intense golden yellow.
When a-naphtliol-trisulphonic acid is nitrated, two of the
it is
it is
its potassium salt, C
;
10
4 (N0 2 ) 2 (OK).S0 3
very largely used, as the yellow shades are faster to light
than those of Martins' yellow.
form of
Methylene
C 16 H 18 N 3 SC1, was
blue,
first
prepared by Caro,
is
539
in
(p.
sulphide.
Nitrosodimethylaiiiline (p. 378) is reduced in strongly acid solution with zinc-dust, or with hydrogen sulphide, and the solution
of dimethyl-j9-phenyleiiediamine thus obtained is treated with
ferric chloride in presence of excess of hydrogen sulphide.
The
intensely blue solution thus obtained is mixed witli salt and zinc
chloride, which precipitate the colouring matter as a zinc double
which form
salt, in
it
Methylene blue
valuable
tannin,
soap
is
cotton-blue,
a beautiful
it is
Indigo,
not
C 16 H 10 N 2
blue,
much used
is
2,
which
in
earliest times.
is
dyeing
is
with
silk or wool.
natural
aniline,
when
as
a dark-blue crystalline
made
air, is
use
substance
(p.
solves indigotin
C 16 H 8 N 2
rapidly reconverted
in dyeing with
of
'
indigo carmine.'
540
Baeyer succeeded
methods, two of
which have already been described (pp. 421 and 446), but these and
several other methods subsequently discovered were found to be
unsuitable for the manufacture of the dye at a price which would
enable it to compete with the natural product.
Recently, however, by the application of scientific knowledge
of untiring energy, processes have been worked out in Germany
by which it seems possible to produce indigo-blue synthetically
on the large scale and at a profit.
The most important of these methods is based on a discovery
of Heumann, who found that indigo-blue could be obtained
and
follows
it
+ NaOCl + H 2 O = C 6 H 4
Anthranilic acid
is
+ NaCl + CO 2
<
phenylglycinecarboxylic acid,
This compound, like phenylglycine itself, is converted into indigoblue when it is fused with alkalies, the change taking place in
several stages which may be indicated as follows
:
Indoxylic Acid.
Phenylglycinecarboxylic Acid.
Indoxyl.
Indigo-blue.
Indoxyl.
The
541
namely, the conversion of indoxyl into indigoblue is carried out ly dissolving the fused mass in water and
passing a stream of air through the alkaline solution.
last reaction
CHAPTER XXXVI.
OPTICAL-
AND STEREO-ISOMERISM.
remember.
to
The
little,
limited
significance
of
diffi-
graphic
formulas was
H
H
H C
!
H
are employed,
Cl
it
Cl
OH
are intended
plane
facts,
542
and
AND STEREO-ISOMERISM.
OPTICAL-
is,
moreover,
shown
some
which
siderations,
of
be
incorrect
will be
mentioned
to
by many conlater.
Tartaric acid, C 4 6
that is to say,
active
6,
its
may
be
The mother
ing the plane of polarisation of polarised light.
liquors from which this tartaric acid is obtained contain an
acid, originally called para-tartaric acid,
but
now known
as
NaNH
the composition C 4 4 6
4H 2 were obtained these
4 +
like
the
acids
salts,
themselves, differed in their action on
:
discovered
fact
that
salts,
the
two
but
salts
in
1848
also
Pasteur
differed
in
crystalline structure ; he found that all the perfect or wellgrown crystals of the salt obtained from tartaric acid had
manner,
acid, the
other having
in the crystal
the
particular
salt
faces
(a,
of
1>)
L (fig. 25).
arranged as shown
The two kinds of crystals obtained from racemic acid were,
in fact, found to be related to one another as an object, such
is
related to
its
mirror-image
543
a left
hand held
directly.
of
two kinds of
crystals,
was
the other
levorotatory.
D.
Fig. 25.
by heating
the
cinchonine
salt
it
of
to the right.
tartaric
acid,
Further,
Pasteur
544
OPTICAL-
AND STEREO-ISOMERISM.
is
from which
was formed, this salt
ammonium
salt
by
substance
different
when
is
its
molecule contains
atoms or groups.
there
is (at least)
namely,
CH 3v
/H
CH3\
/OH
c
H
Lactic Acid.
H\ /CH^COOH
C
/OH
C
H/ \COOH
HO/ ^COOH
Tartaric Acid.
Malic Acid.
OgK^
OPTICAL-
AND STEREO-ISOMERISM.
545
active,
U1
CH3\x//OH
Hx
H/ \!OOH
^COOR
Active.
Malic
acid, again,
active succinic acid
Inactive.
is
is
/H
CH,\
H\^ /CH 2
Hs^ /CHg-COOH
Active.
still
C2
CH3\
/H
U/
Amyl
\CK,.OK
C2
amyl
y\
H/ ^CH,!
Iodide.
CH3v /H
H/ VCH .CN
2
Amyl
active
/H
Amyl
Alcohol.
CH3\ /H
C2
.COOH
Inactive.
CH3X
in-
H/ \IOOH
HC/ \X)OH
alcohol
on reduction
formed,
Cyanide.
C2
H/
^COOK
Methylethylacetic Acid.
546
OPTICAL-
CH
\/H
C
C 2H5
CH3
Diniethylethylmethane.
substance
The
is
formed which
relation
is
optically inactive.
is
polarised light
that it may now
is
situated at
which
atom
to
OPTICAL-
AND STEREO-ISOMERISM.
547
to such
CH
CH
2 ClBr,
CH
arrangements
C1 2
CH(CH3
)2
exist in one
form
such as the
following,
to be different
on paper, are in
reality
identical.
ally
Hatton Garden, London, E.C.), from whom they may be obtained at a cost
of eighteenpence.
Such sets contain sufficient models for the study of the
isomerism of the tartaric acids, but larger sets suitable for the study of the
sugars
may
also be obtained.
548
OPTICAL-
(3)
AND STEREO-ISOMERISM.
of the type C, R, X, Y, Z
in which the
united with four different atoms or groups
Compounds
carbon atom
is
may
forms.
These
another, in the
that
is
be distinguished by
or d, the other
by
or
/,
may
the actual
two
it
is
now known
- ) to exactly
rotatory (d or + ), the other levorotatory (/or
the same extent.
These two forms may be represented by
the figures just given, and they are called optical (physical, or
The two optical isomerides havt
stereochemical) isomerides.
the same chemical properties and chemical constitution, am
molecules differ only as regards the arrangement ii
space.
They have also the same melting-point and boilingtheir
OPTICALpoint,
and
if
that,
AND 8TBREO1SOMER18M.
549
solids,
Such
atom
be enantiomorplious or Tiemihedral.
substance
any
containing one asymmetric carbon
prepared synthetically, the product is found to be
When
is
optically inactive.
When,
the
d and
solution,
an
When, however,
it is
often
found to
differ
and a
d and
when,
for example, a
solution containing the sodium ammonium salts of both dand Z-tartaric acids is evaporated, the crystals are deposited
separately, side by side, if the temperature of the solution
is kept below 28
during crystallisation
mixture is termed externally compensated.
it
(p.
557).
Such a
contain, or
be, as
550
OPTICAL-
AND STEREO-ISOMERISM.
above three
racemic
or
optically
forms
different
compensated
externally
namely, d, I, and
substance of the
constitution,
C- COOH,
OH
example, would not form a larger number of optical
isomerides than a simple substance such as lactic acid.
for
manner
model on the
This
1%-w
two
when
it
or
Modification
I.
The
letters r, 6,
iv,
and y
and yellow
balls
AND STEREO-TSOMERISM.
OPTICAL-
asymmetric
with
(r),
and
(b), (w),
is
and
551
(C,
r,
b,
w\
the
instead of
(?/).
will be,
or
r
.
This form
possibly be
is
made
Modification
II.
II.
r,
now
r will
upwards in
mirror,
it
downwards
point
I.;
if,
in
its
II.,
model
in fact, this
it is
(II.)
mirror-image
identical with
its
mirror-
I.
viewed
directly.
III.
C,
?*,
b,
If
now two
u\ y,
different
asymmetric
carbon
atoms,
- , be joined in the
w, or + and
as before, another modification will be obtained,
and C,
same manner
which is quite
r,
y,
Z>,
different
from
I.
and
II.,
represented thus,
r
or
to
Modification
III.
552
OPTICAL-
No
structed.
two
AND STEREO-ISOMER1SM.
asymmetric
modifications.
because
it
carbon
One
contains
of
then, that a
atoms
these
compound containing
may form
will
(I.)
two identical
+)
three
distinct
be dextrorotatory,
asymmetric carbon
compound
therefore inactive.
The same
One
OPTICAL-
AND STEREO-ISOMERISM.
553
Tartaric acid,
of the tartaric acids investigated by Pasteur.
COOH.CH(OH)-CH(OH).COOH, contains two carbon atoms,
each of which is united with four different atoms or groups
namely,
COOH
tf-Tartaric Acid.
COOH
Z-Tartaric Acid.
COOH
Mesotartaric Acid.
may be more
COOH
554
OPTICAL-
but in
AND STEREO-ISOMERISM.
all
water.
salts,
C4H6
Mesotartaric acid,
form of
tartaric acid
all
their
directions.
6,
is
that is to say,
it is
inactive
by
internal
compensation.
differs
perties,
perties,
and of those of
it
is
its
identical with
salts,
and
tain
solid
it
behaves as
exists in the
if
it
were a
is
also perfect.
in space of three dimensions is also strongly supported by considerations based on the phenomenon of structural isomerism, because
an arrangement
of the
atoms or groups
in
OPTICAL-
AND STEREO-ISOMERISM.
555
shown that isomerism does not occur in the case of the compound
C 2 H 4 C1 2 for example, two structural isomerides, namely, CH 3 -CHC1 2
and CH 2 C1-CH 2 C1, are known, in accordance with theory were all
;
the atoms arranged in one plane, the following^ve isomeric compounds should be capable of existence,
H H
C C-H
H H
H C-C-C1
Ai H
Ai Ai
Cl
C-H
i
Ai
H
H-C
Cl
C-C1
AH
H Cl
H C-C-H
A Ai
I. p.
269),
COOH.OH(OH).CH(OH).CH(OH).CH(OH>COOH,
which contains four asymmetric carbon atoms,
is capable of
existing in ten optically isomeric forms (which may be constructed with the aid of models) ; many other examples of
optical isomerism occur among the polyhydric alcohols (Part I.
p.
I.
p. 266).
As
dimethylsuccinic acid,
inactive, the
duced,
all of
which would be
number
different,
556
OPTICAL-
AND STEREO-ISOMERISM.
molecule.
attraction or repulsion on those united with the other if, then, the
carbon atoms be capable of free rotation about an axis, a certain
;
position of equilibrium,
be attained.
which
is
by one
or other
(1)
of
its
of one
This
OPTICAL-
method was
first
AND STERKO-ISOMKK1SM.
employed
by Pasteur
in
557
the
case
of
racemic (tartarie) acid, it depends on the fact that if a solution of the sodium ammonium salt be allowed to crystallise
at
and left-handed,
(right-
racemic acid be
If,
optically
for example,
active
base
similar
may
(p.
manner the
be resolved into
its
constituents
by
(p.
501)
fractional crystallisa-
558
OPTICAL-
AND STEREO-1SOMERISM.
Compounds.
The occurrence of isomerism among certain unsaturated compounds was observed long ago, but for many years a satisfactory
explanation of the existence of such isomerides could not be given.
Fumaric acid and malei'c acid, for example, are both unsaturated
compounds of the constitution COOH-CH:CH COOH (Part I.
pp. 246-247) ; their isomerism is not structural that is to say,
it is not due to the atoms being in a different state of combination as is proved by their methods of formation and by their whole
chemical behaviour ; arid yet the isomerides differ considerably in
properties, botli physical
readily converted into
is
and
'COOH
Malei'c Acid.
The
HK~
^COOH
COOH
Fumaric Acid.
is
therefore explained,
OPTICAL-
AND STEREO-ISOMER1SM.
559
H-C COOH
H-C-COOH
H C COOH
COOH-C H
Maleic Acid.
Fumaric Acid.
On
reduction, maleic and fumaric acids give one and the same
product, namely, succinic acid, COOH-CH 2 -CH 2 -COOH, because as
soon as the carbon atoms become singly bound they regain the
property of free rotation, and by the mutual actions of the different
p. 556).
is
generally called
CHEMISTRY.
APPENDIX.
THE CONSTITUENTS OF PLANTS AND ANIMALS.
INTRODUCTORY.
IT has been pointed out in Chapter I. that the peculiar composition of those substances which are obtained directly or
regard them
562
up
APPENDIX.
into simpler
but still very complex decomposition pro;
they are also, as a rule, insoluble in water and other
ducts
and do not
liquids,
culty
them
synthetically.
or three noteworthy
Two
mentioned.
i.
p. 281), which play such an important part
in the vegetable world, and which form such a large proportion by weight of all plants, are both well-known substances
cellulose (part
word
that
is
to
say,
their ordinary
has only been proved that they are both highly complex substances, which break up into simpler ones (dextrin, maltose,
glucose)
APPENDIX.
the
H O
of
563
it
for
starch,
example,
at least
is
10
5 ) 200
it
much
is
associated in nature.
of Plants.
The Carbohydrates.
Although, then, owing to our incomplete knowledge of the
structure of the more complex vegetable substances, a clear
and satisfactory system of classification is quite impossible at
the sugars, starches, and celluloses, which are the
principal constituents of all plants, are conveniently placed
*
together in one large group, and are classed as carbohydrates
present,
'
(part
i.
p. 266).
It
is,
is
known
of
their
structure or
con-
stitution.
lactic acid,
C3H6
3,
&c.,
which have no relation whatever to the principal naturallyFor this reason the term is
occurring members of the group.
564
APPENDIX.
which most
of the
C^
^>C
CHO,
Inulin (C 6
which
is
i.
p. 270), is
a starch
many
by
is
5) n,
other plants;
yellow
acid it
10
it
is
i.
270).
p.
is
powder
but
it
and
soluble
starch,
as
is
on
(part
by
or
i.
p.
is
broken down
When
it
is
the highly-complex
not immediately re-
565
APPENDIX.
at
acids
or
diastase,
are
may
therefore be regarded
as forming
'
'
either
dissolve, giving
sticky solution,
or swell
up
to a jelly-like, sticky
i.
p. 264:),
CH 2 (OH>CH(OH).CH(OH).CH(OH>CHO.
Wood gum,
on
or xylan,
is
another
occurs in
many
more
xylose, C 5 10
with arabinose.
(part
i.
p. 264),
The
The name
to
gum which
plants,
a group
which
is
optically isomeric
Glucosides.
glucose
APPENDIX.
566
and salicin, C 13 H 18 T
(p. 418),
two of the best-known members of this
group the former, on hydrolysis, is resolved into benzaldehyde, hydrocyanic acid, and glucose,
C 20 H 2r NO n
Amygdalin,
= C 6 H 5 -CHO + 2C 6 H 12
C 20 H 27 NO n + 2H 2
HCN;
latter,
C 13 H 18
C 16 H 20
= C 6 H4
OH
<g|*-
+ C 6 H 12
Coniferin,
in the coniferse
CHO
CH=CH-CH.OH
)H
Coniferyl Alcohol.
other compounds.
substances which
pronounced physiological
action.
Essential Oils.
Nearly
all
plants contain in
their seeds,
fruit,
flowers,
having a charac-
APPENDIX.
567
which
many
of
them
essential oils
given,
oil
would be impossible
to
ones.
Now, most
in
common,
'
turpentine,'
which
is
and on
called
distilling
568
APPENDIX.
crude
in
turpentine
current of
oil
is
On
ally changes
and
is
exposure to moist air, oil of turpentine gradudarkens in colour, becomes more viscous,
it
converted
into resin
arid
a variety
of
oxidation
and caoutchouc;
tion of varnishes
and
oil paints.
'
The Terpenes.
The
compound
thyme.
Pinene
it is
tine/
20).
is
C 10 H 16
and
is specifically lighter
It boils at
155, and
is
than water
(sp.
gr.
0-858 at
.,
APPENDIX.
569
CTL
It also combines
CHBr
Br
when
unsaturated compound,
/CH
C 8 H 14<||
X
CH
H
+1 =C 8 H
/CH
Cl
(NOC1), giving a crystalline compound, C 10 16 NOC1, melting at 103, which is called pinene nitrosochloride.
These additive compounds are of great use in detecting and
recognising pinene, which, being a liquid, is not so easily
identified as these crystalline solids of definite melting-point.
When
high temperature it
hydrogen bromide,
r
R - P TT
HU
H 16 Br
C 10 TI
10
2
also produced, together
cymene
is
carbons,
when pinene
is
L 9TT-Rv
-f
2HBr
Pinene readily undergoes oxidation, yielding various products according to the conditions of the experiment among
these may be mentioned terephthalic acid (p. 440) and two
other important oxidation products namely, terpenylic and
;
terebic acids,
follows,
the
constitutional formulae
of
which
are
as
570
CH
CH 2
COOH CH
COOH CO-O
CO-0
Terpenylic Acid.
Terebic Acid.
and
line
from which
it
can be
is
obtained by
oxidising
with
potassium permanganate.
As
tive or
-piriene.
a very interesting
fact, as it
mixtures.
Camphene, C 10 H 16
is
a solid hydrocarbon
which occurs in a
APPENDIX.
number
oil),
and
571
of essential oils (ginger-, citronella-, spike-, valerianwhich can also be obtained artificially from various
160,
Camphene
at
one,
it
chloride, as represented
C 10 H 17 C1 = C 10 H 16 + HC1;
but
149-151;
also
it
camphor
(p.
it
gives
579).
Camphene, like pinene, exists in two optically active (d- and 1-)
forms, and in one externally compensated (inactive or i-) modification.
Limonene,
of essential
C 10 H 16
oils,
like pinene, is
an important constituent
104
it
also unites
melts at
APPENDIX.
572
or
C 10 H 18 C1 2
it
yields cymene.
it
is
treated in a similar
also produced
a fact
manner
when pinene
or
camphene
is
is
when
C 10 18 Br2 is optically inactive, and is named dipentene dihydrochloride or dihydrobromide as the case may be ; in the formation
of these derivatives the asymmetric carbon atom in limonene (comor
like the
word carbohydrate,
are all
pounds
chloride,
and they are all unsaturated comthey all combine directly with bromine, hydrogen
hydrogen bromide, and nitrosyl chloride, or at least
readily volatile,
APPENDIX.
these
573
reagents,
forming crystalline
additive products which serve for their isolation and identiBut whereas some of the terpenes combine directly
fication.
GROUP
I.
Pinene.
GROUP
Camphene.
II.
The behaviour
and the
if
the
hydrocarbons
they should unite directly
with six atoms of bromine or with three molecules of a
;
for,
C 10 H 16
one treble
3
:
574
APPENDIX.
produced,
Among
the
the
most
found
is
the
well-known
p-isopropylmethylbenzene, C 10 14
(p. 349), which, as will be seen, contains only two atoms of
hydrogen less than the terpenes, and which is represented
hydrocarbon
by
cymene
or
CH 3
Cymene
or Para-methylisopropylbenzene.
cymene, and also the fact that cymene itself often occurs
together with the terpenes in essential oils, have led to the
conclusion that the terpenes are probably derivatives of, or
that is to say, that they probably
closely related to, cymene
manner.
APPENDIX.
few of
conclusion
the
may be
facts
and
575
arguments
on this
In order to
bearing
the
formula
C 10H 18
CH
CH3
Hexahydrocymene,
CH
CH 3
Tetrahyclrocymenes,
By
C^H^.
two atoms
C 10 H 10 would be
obtained,
as,
for
576
APPENDIX.
CH 3
CH 3
CH 3
CH
4
CH
CH 3
CH3
Dihydrocymenes, CioHjg.
double linkings or ethylenic bindings, and they would combine directly with four atoms of bromine or with two molecules
of a halogen acid ; they would all be readily converted into
APPENDIX.
chain
may
be
hydrocarbons
577
C 10 H 16
CH 3
CH 3
OF!
CH.,
CH 3
CH
CH 3
CH
chains,
far
CH3
CH3
Pinene.*
578
APPENDIX.
CampJiene.*
Sesquiterpenes
The
and Polyterpenes.
C 10 H 16
are
often
generally
that all
C 15 H24
or
C20H32
It has
hydrocarbon isoprene,
various
hydrocarbons
of
the
molecular
formula
APPENDIX.
579
C 15 H
The two
best -known
canjopliyllem, both of
are
sesquiterpenes
cadinene
and
liquids, boiling at
respectively.
Compounds
and menthol
see below), or ethereal salts of
these alcohols, and most of them are closely related to the
Some of the more important of
terpenes in constitution.
as borneol
dissolves
readily in
alcohol
solvents; it is extensively used in medicine, in the manufacture of xylonite, and also in the preparation of a few
explosives.
oxidising
C 10H 16 +
camphene
acid,
= C 10 H16 0;
(p.
571)
580
APPENDIX.
it
(p.
is
also
583),
is
C 10 H 18
+ O = C 10 H 16
a ketone
is
camphor interacts
camphoroxime (m.p. 118),
instance,
C 10 H 16
and on reduction
is
its
;
H 0.
NH .OH
2
= C 10 H 16 :N-OH +
oxime,
H 0;
2
C 10 H 16
When
= C 10 H ir .OH.
it
is
converted into
carvacrol or
C 10 H 16
= C 10 H 14 +
it
is
trans-
0.
CH3
CH 3
CH 3
CH 3
CH 2
CH3
Carvacrol.
CH 3
APPENDIX.
There
are,
however,
many
that
is
581
not a
camphor
clearly
derivative, as represented above, and that its conversion into
these benzene derivatives is not nearly so simple a change as
appears to be.
In the first place, camphor behaves like a saturated ketone,
and forms substitution, not additive, products when treated
with bromine, chlorine, &c., whereas in accordance with
it
Kekule's formula
it
in
the
C 10 H16
4,
so = r
+ 30
H
C 8 TT
a.
ou
and
this
acid,
C 9 H 14
6,
called
C 10 H 16
Now,
it
<
UCOOH
camphoronic
+ 50 = C
that
yields a tricarboxylic
acid,
14
+ C0 2 +
0.
following constitution,
COOH,
it
of a true cymene or
camphor has not the
constitution assigned to it by Kekule
nevertheless, it is
related
to
doubtless very closely
cymene, as Kekule sup-
possibly be obtained
carvacrol derivative,
by the oxidation
it
follows that
582
APPENDIX.
and
posed,
CH
The
relation
camphoronic acid
between
may
COOH
OH
CHs-C-CH 3
CH
2,
.COOH
^C^
CH3
CH 3
Camphoric Acid.
Camphoric
acid,
duct of camphor,
it
is
is
Camplioronic Acid.
the
first
oxidation pro-
readily converted
into
CO
its
anhydride
C 8 H 14 <CpQ^>0
(m.p. 221).
Camphoronic acid, C 6H n (COOH) 3 is a crystalline compound which melts at 137 and is readily soluble in water;
when submitted to dry distillation it is decomposed into
,
and carbon,
*
These formulae are identical ; many other formulae for camphor have
been suggested.
APPENDIX.
:
CH 3
CH 3 CH3
COOH-CHa-i-C
I
583
COOH
COOII
zinc to form a
compound,
CH 3
which, when
trimethylglutarate,
o-
j8
C 10 H 17 -OH,
it
also
camphora, a
Borneol
camphor,
tree
can
obtained
and
sodium
with
by
reducing
alcohol
(see
the
ketone,
It
above).
it
is
is
more
some-
mint.
It melts at
203,
boils at
212, and
is
readily volatile
in steam.
Borneol
is
secondary
phosphorus pentachloride
it is
alcohol;
when
treated
with
584
APPENDIX.
and when
this product is heated with aniline it gives camphene, with elimination of the elements of hydrogen chloride,
C 10 H 17 C1 = C 10 H 16 + HC1.
From
these,
described,
it
camphene
are
related
closely
to
one another, as
may
be
CO
C 8 H 14
/CH-OH
<J
C 8 H 14
Borneol.
Camphor.
Menthone, C 10H 18 0,
is
/CH
Camphene.
Menthone
is
206, and
its
Menthone
may
CH 3 -CH-CH 3
CH 3 -CH CH 3
CH
CH
,CH-OH
CH.A
CI
H3
CH 3
Menthone.
Menthol.
camphor;
it
occurs in
oil
related
to
related
to
APPENDIX.
and as menthyl
Menthol is a
state
salt.
acetate,
585
C 10 H 19 -0-CO-CH 3
crystalline
solid
an ethereal
is
On
into
hexahydrocymene
evidence that
its
constitution
is
one
least
two forms
is
principal
may
of the
consist
many
of
them can be
Secondly,
lisation,
the
distillation,
gums
&c.,
known.
It must be borne
may have been produced by the above demerely because more is known of the simpler
impression
scription ; it
than of the
is
586
APPENDIX.
may be
accepted.
now
proteids
(p.
610),
it
Partly on
a
matter
of the
generally
these complex substances in
as well.
is
purity
further,
as
they
known
APPENDIX.
Animal
established.
f>{>7
(b)
Complex substances
The
of
unknown
of
known constitution.
constitution.
differences
illustrate
down
animals
which
so
is
known
is
little
subdivide them
it
is
possible,
however,
known
constitution, and to
into various groups according to their chemical
to classify those
compounds
of
relationships.
Lecithine
The
four
first
group
which
CH 3 -CH 2 .N(CH 3
)3
the Ptomaines.
will
be
considered
compounds which
simple
important
and
.OH;
are
contains
derivatives
ethyltrimetliylammonium hydroxide,
they are all closely related to one
CH
Muscarine,
Betdine,
Neurine,
~CHO.CH 2 .N(CH 3
COOH.CH 2 .N(CH 3
CH = CH.X(CH
)3
)3
-OH.
.OH.
3 ) ?/
OH.
588
APPENDIX.
These
section, are
of
them
of animal matter;
they are nearly all
classed as the ptomaines or toxines.
is
poisonous, and
are
many
of the
it
as the result of
putrefactive decomposition.
H NP0
Lecithine (Protagon), C 44 90
is a substance contain9
ing phosphorus, which is very widely distributed throughout
the animal and vegetable kingdoms.
It is found in small
in
bile
and
in
most
quantities
organs of the body, and is
,
especially prominent in the brain substance, the bloodcorpuscles, and in the nerve tissues ; it occurs in considerable quantities in yolk of egg (hence the name from \extOos,
yolk of egg), and is also found in plants, particularly in the
seeds.
Lecithine
is
substance, soluble
water it swells up
stitution is indicated
of emulsion.
Some forms
Its con-
undergoes on
when
it
it is decomposed
and choline,
acid.
t Glycerophosphoric acid, C3 5 (OH)2-O-PO(OH)2, is a thick syrup, prepared by combining glycerol with metaphosphoric acid.
APPENDIX.
= 2C 18 H 36
Stearic Acid.
589
C3H 9 P0 6 + C5H 16 N0
2 ;
Choline.
Glycero-
phosphoric Acid.
is thus probable
that the constitution
represented by the following formula,*
of
it
lecithine
is
X).CO.C 17 H 35
C 3 H5<-O.CO.C ir H 35
X
PO(OH).0-CH 2 .CH 2 .N(CH 3 ) 3 .OH.
or
Choline,
CH
hydroxyethyltrimethylammonium
called
hydroxide,
or
sinkaline
bilineurine, has just been mentioned as one of the decomIt is widely distributed in
position products of lecithine.
the animal and vegetable kingdoms, and was discovered by
Strecker in bile
Choline
(xW)
its
by
is a constituent
Baeyer.
of the alkaloid sinapine which occurs in mustard-seeds.
It is
also produced in corpses, as the result of putrefactive changes.
is
C 5 H 14 NOC1.
Choline
is
it is
It forms salts
the
hydrate,
ammonium
attached to nitrogen
hydroxyl group
being
from water in
choline
is
plates.
boiled, glycol
Compare the
When
strong
aqueous solution of
are formed,
and trimethylaniine
i.
p. 171).
590
APPENDIX.
3)3
CH
QH 2 + N(CH3 3 + H
)
is
Betalne,
or
oxyneurine
pTT
or
CO<C^QJP>N(CH 3 ) 3
lycine,
it
was
Preparation.
beetroot sugar,
The mother-liquor,
H NO
out.
APPENDIX.
591
It is very soluble in
represented by the second formula.
and
well-characterised
salts, such as the chloride
water,
gives
COOH-CH2 -N(CH 3
betaine
is
as
is
)3
CH 2 :CH.N(CH
solution,
3) 3
.OH,
is
one
of
the
most
crystalline salts.
It has been
When
prepared synthetically as follows
heated with hydrobromic acid the two hydroxyl
groups are displaced by two atoms of bromine, and a substance
Br.CH 2 -N(CH 3 ) 3 Br is formed; this, when
of the formula
2
choline
is
CH
CH
is
592
APPENDIX.
and forms
salts
NH
p.
240).
mentioned, and
also been given
(p. 490).
It is a syrup which boils at
it is a diacid base.
178-179, and,
like putrescine r
Derivatives.
Emil
compounds
is
mainly due
Fischer.
N = CH
I
(2)
CH
II
(3)
(5)C
II
C
(4)
Purine.
(6)
O
KHX
W>CH
(9)
(8)
APPENDIX.
593
The
NH CO
NH CO
C!H
CO
NH\
W>H
II
II
-- C
NH X
}CH
||
NH
Xanthine or 2,6-Dioxypurine.
Hypoxanthine or 6-Oxypurine.
NH CO
CO
I
NH
C
II
NH
>co
NH7
NH CO
CO
II
CH 3 -N
||
-N
Tbeobromine or
Caffeine or
1,3,7-Trimethylxanthine.
NH CO
CH C NH
II
>H CH
N/
3,7-Dimethylxanthine.
N=C-NH
II
CO C.N(CHA
C-N(CHA
II
CH3 -N CO
^CH
Adenine or 6-Amidopurine.
NH
IIC
-C
||
||
NH X
^CH
Guanine or 2-Amido-6-oxypurine.
acid
is
oxidised
594
APPENDIX.
by means
and urea.
of
acid
nitric
The
first
acetyl chloride,
CH 3 -COC1
NH
.CO-NH 2 =
Oxalylurea, or parabanic
2
2
obtained by treating a mixture of urea and oxalic acid with
,
phosphorus oxychloride,
COOH H 2 K
+
>CO
CO NH X
>CO + 2H 2 0,
CO NH/
COOH H 2 N/
a
synthesis
Parabanic acid
this
ureid.
When
united to nitrogen.
CO
|
CO
NHX
CO
>CO + H 2
is
and
NHV
>CO.
NH/
it
COOH NH/
Oxaluric Acid.
NH
2 .CO.JSTH.CO.COOH +
Alloxan,
= C2H2
/NH-COx
C0<
x>C(OH) 2 + 3H 2 0,
+
is
CO(NH2 ) 2
mesoxalyl-
* It
will be noticed that parabanic acid does not contain a carboxyl
group, and is therefore not a true organic acid. Substances, however,
which contain
properties, the
APPENDIX.
since
urea,
urea,
on hydrolysis
it
595
yields
add* and
mesoxalic
x-v
C0<
>C(OH) 9 + 2H 2
COOHv
;>C(OH)
COOH/
It
crystallises
from water in
owing
colourless
The
constitutional
prisms which
water of crystallisation.
formula for
uric
acid
its
aqueous
ferrous salts
given
ahove
Alloxan Fragment.
NH
CO:
'
596
APPENDIX.
CH
NH .CO-NH
.C(OH)
II
CH-COOC 2 H 5
3
YCH-COOC H +H
2
0.
This on hydrolysis yields the corresponding acid, /3-uramidowhich readily loses water and forms methyl-
crotonic acid,
uracil,
NH
COOH
=
CH
CO
II
NH
When
is
group
is
CO
C(
CO
CH
NH
C-CH3
/3-Uramidocrotonic Acid.
group
NH
+H 0.
2
II
C-CH 3
Methyluracil.
NH CO
CO
I
NH
NH CO
=
C-NOo
II
CO
C-JST
COOH
Nitrouracilic Acid.
+ C0 2
II
NH CH
Nitrouracil.
Ethylic acetoacetate,
CH3 -C(OH):CH-COOC2 Hg
(part
i.
p. 199).
as
if
APPENDIX.
NH CO
CO
C(NH
CO
II
597
NH CO
NH-CH
C(OH)
II
NH CH
Amidouracil.
Hydroxyuracil.
NH CO
NH CO
CO
C(OH)
NH
NH
C(OH)
JXHf
CO
NH
Dialuric Acid.
NK
CO + 2H0
Uric Acid.
Since this synthesis was discovered, uric acid has been synthesised
in other ways, notably from pseudouric acid; but it is not
possible
to ghr e these methods here.
Xanthine, or 2,6-dwxypurine,
CgH^Og,
occurs in small
guanine
(p.
acid,
the amido-
iodide
When
alloxan.
Synthetically
in the following
way
it
it
In this and in many other cases it will be noticed that the group
sometimes reacts as if it were N=C(OH), and vice versd; these
two forms are distinguished as lactam NH-CO- and lactim N=C(OH).
Compare the somewhat similar case of ethylic acetoacetate (part i. p. 200).
NH-CO-
598
APPENDIX.
N-CC1
I
cic
C.NH
N = C-OC H
2
C 2 H5 O.C
II
C
II
TH
NHX
^CCl
N^
CO
gives
NH
HN
CO
C-KH\
\CH.
C N^
||
the nuclei of
converts
by
purine
it
(p.
597), which
when
6-amido-2,8-dichloropurine
hydriodic acid gives adenine.
gives
this
on
ammonia
reduction
with
HN
Hypoxanthine, sarkine, or
is
mentioned.
Guanine,
C 5 H 5 N 5 0,
APPENDIX.
C8 H 10 N4
C r H8 N4
2,
and
599
or
theobromine,
3,7-dimethylxanthine,
(p.
511).
HN
Purine, C 5 4 4
substance of all the
Emil
2J.
properties.
At
is
given of
These substances, the latter especiare related to guanine and other members of the uric
ally,
acid group.
NH
i.
p.
i.
p.
301), namely,
297),
when
undergoes intramolecular
salt
change,
NH
The only
.S-CN =
difference in the
NH .CS-NH
2
two reactions
is,
it is
Thiois
very
APPENDIX.
600
it
598)
NH
first
(p.
It
acid.
is
may be
with ammonia,
by treating cyanogen iodide
cyanamide being formed as an intermediate product,
synthesised
NH.C;N
Guanidine
most
ammonium
is first
the
ammonium
NH
.CS-NH 2 +
Guanidine
is
NH ,HCNS
3
colourless
crystalline
NH .C(]SrH).NH ,HN0
nitrate,
characterised
When
substance,
and
is
is
it
3,
acids
guanidine
it
NH
guanidine,
with acids
NH
and
this
NH
yields
it
.C(NH).NH-NH 2
When
the latter
is
digested
.C(NH)-NH.NH 2 +
on further treatment
is
NH
.CO-NH.NH 2 +
NH
3>
NH .CO.NH.NH
2
HO
2
NH
of iodine
+ CO, +
(p.
it is
-NH 2
388), interacts
in colourless needles
;
NH
very poisonous.
with alde-
on heating a mixture
601
hydes and ketones to form crystalline compounds (semicarbazones),
and is now much used in the isolation of such substances. Benz-
NH
2 .CO-NH.N:CH.C 6
5 (m.p. 214), for
aldekyde semicarbazone,
example, separates at once in crystals, when benzaldehyde is
shaken with an aqueous solution of semicarbazide hydrochloride
and sodium acetate. Like the hydrazones, the semicarbazones are
decomposed by treatment with acids, yielding the aldehyde or
ketone and a salt of semicarbazide.
their Derivatives.
described below.
CH
was first
Sarcosine, or methylglycine,
3 -NH-CH 2 -COOH,
obtained by Liebig in 1847, by boiling creatine with baryta
water (p. 603) ; it is also formed when caffeine is subjected
in
alcohol,
compose
1862
HC1.
is
and
at
anhydride,
Like glycine,
it
and forms
602
and
APPENDIX.
the
Cu(C 3 H 6 N0 2 ) 2 + 2H 2
salt
copper
the
CH 3 -CH(NH
NH
latter
).COOH,
ammonia.
i.
pp. 232-233) by treatment with
have
They
properties very similar to those of
acids
(part
glycine.
rates
CH8 .C(NH
2)
COOH
C(NH 2 ).CH 3
COOH
The amido-derivatives
physiological interest.
Leucine, or a-amidocaprdic
acid,
CH 3 -[CH 2 3 -CH(NH
]
2 )-
in small quantities in
many
organs,
panied by tyrosine
(p.
605).
Leucine
when
carefully
270, and
when
rapidly
APPENDIX.
heated
CH
It dissolves in
soluble
in
2 -CH.,-
but
Its
is
very sparingly
in hydrochloric acid is
leucine is boiled with
baryta
solution
when
becomes optically
it
CH3 -CH
carbonic anhydride.
alcohol.
dextrorotatory;
water
603
it
Inactive
inactive.
leucine has
levorotatory.
NH:C(NH2 ).N(CH 3 ).CH2 .COOH, is a very important substance found in the muscles, nerves, and blood,
and also in considerable quantity in meat extract, from which
it was isolated
by Chevreul in 1834. Muscles contain about
0-3 per cent, of creatine, and it has been calculated that the
Creatine,
total
muscles of a full-grown
grams
man
The name
of this substance.
meat.
Preparation.
Meat
is
dissolved in water
and basic lead acetate added until no further prethe filtrate is freed from lead by passing
produced
(800 grams),
cipitate is
with
equivalent
of
baryta water
it is
an
acid,
When
but
it
604), and
decomposed into urea
(p.
does not
when
and
appear to
it
is
digested
sarcosine,
con-
with
604
APPENDIX.
NH
Creatine has been prepared synthetically by heating together cyanamide and sarcosine in alcoholic solution,
^NH
Creatinine,
CO
the anhydride (lactam)
NH:C\
acids
from
creatine.
HN
of an
acid.
When
zinc chloride
is
added
to its solution in
HN
(C 4
and
p.
0) 2 ,ZnCl 2
this
268),
is
and
gives,
NH
(p.
in
two
.CH.COOH
CH -CO-NH
2
contains
501),
2,
prepared.
is
formed
APPENDIX.
605
peas,
is
sparingly soluble
levorotatory, but
becomes dextrorotatory on the addition of hydrochloric acid.
When treated with acids or alkalis, asparagine is converted
into
p.
acid,
/-aspartic
is
(part
i.
245).
occurs
^.-Asparagine
young shoots
in
of lupines,
together
and
is,
It is noteworthy that
ordinary properties.
in equal quantities in aqueous solution d- and
Z-asparagine do not, like the tartaric acids, combine to form
latter
all
when mixed
or
Tyrosine,
p-hydroxyphenyl-a-amidopropionic acidr
is
formed together with
(p.
in the liver in
cheese (the
some
name
is
found
and in
was first
it is
derived from
rvpos,
cheese)
it
its
with dilute
this
is used
and
Tyrosine decomposes at 270 into carbonic anhydride
reaction
ip-hydroxyplienyletliylamine,
and
when
fused
reactions,
proved
APPENDIX.
606
carried
by Erlenmeyer and
out
C 6 H 5 'CH 2 -CHO,
Lipp.
with hydrocyanic
yields,
Phenylacetaldehyde,*
acid, the nitrile of
propionic acid,
NO
tyrosine.
Compounds of Unknown
Constitution
known
constitution
having
been"
found in
of
Bile.
animal origin of
section
this
described,
occur together in
bile.
The
Glycocholic acid,
colourless needles,
and
alcohol,
solution
its
is
sodium
named
cholesterine.
and melts
at
133;
it
is
its alcoholic
form of
dextrorotatory.
salt,
crystallises in
soluble in water
crystallises in
stellate
groups.
Preparation.
chloric acid
Fresh bile
and rapidly
is
filtered
through sand.
Phenylacetaldehyde,
C 6 H 5 .CH 2 -CHO,
is
The
of hydrofiltrate is
APPENDIX.
The
607
which separate on standare washed with water containing hydrochloric acid and ether.
of bile.
ing,
Taurocholic acid
When
is
C 24 H 39
-NH.CH 2 .COOH +
= C 24 H 40
Taurocholic acid,
human
+ NH .CH .COOH.
H
O 4 .NH.CH .CH .S0 H, occurs in
C 24
2
39
bile,
and
It
is
H NaN0
water
it is
decomposed into
C 24 H 39
and
cholalic acid
taurine,
Taurocholic Acid.-
= C 24 H 40
NH
Cholalic Acid.
Cholalic acid,
which
ether
C 24 H 40
Taurine.
manganate
it
NH
Taurine,
it
NH
synthetically
trioxide,
when
CH
carefully
bases.
608
APPENDIX.
Avith
phosphorus
acid,
CH
pentachloride,
C1-CH 2 -S0 3 H,
ammonia, taurine
is
yields
from
which,
diloretliylsulphonic
by
with
treating
obtained.
bile
fat
distils at
appreciably.
Hcemoglobins.
Haemoglobin
is
the
name given
to the
corpuscles of the blood. 'It exists in the blood in two conditions ; in arterial blood it is loosely combined with oxygen,
and
is
called
oxyhcemoglobin
the
other condition
is
the
A substance
or phytosterine,
very similar to Cholesterine, and named paracholesterinefound in the seeds of certain plants.
is
APPENDIX.
which
609
defibrinatecl
blood
by
mixing
it
versa,
converted
oxide
carbonic
this
an
into
substance
led
loses
into
its
solution
oxygen
of
oxyhaemoglobin
compound
oxygen
poisonous
is
like
not
of
capable
haemoglobin
action
of
carbonic
and giving up
which explains the
absorbing
fact
oxide,
since
this
gas
by
610
APPENDIX.
is.
crystal of
easily identified
When
and distinguished
oxyhaemoglobin or dried
warmed with
common
H N
H N
colourless,
it,
now
is
mass, .which,
however,
still
611
APPENDIX.
suffice to
substance, and
its
to say
whether or not
it
is
it
in
little
during
this process.
As
known
practically nothing is
of
the constitution of
little
success.
what
is
meant by
Proteids differ in
and these
in order to subdivide
them
As
regards
their chemical behaviour little can -be said, except that they
all
and sulphur.
The determination
nitrogen,
proteid
is itself
of the
percentage
of
As found
in
composition
612
APPENDIX.
following numbers
50
Carbon
-55
percent.
6-9- 7-3
Hydrogen
Nitrogen
15
Oxygen
19
it
-19
-24
n
.,
0-3- 2-4
Sulphur
in
crystalline
its
condition;
is
composition
C = 51-48,
S = 0-96 percent.
composition
members
like
C 146 H 226 N 44 S0 50
H = 6-6,
as
= 0-9
N=18-0,
much value,
as a
having
analytical
results
would make
very great
difference
in
the formula.
The molecular
formulae
of
the
proteids
are
unknown
number which
will afford
the proteids.
The
proteids
are
insoluble
but
in
many
alcohol
of
salts
them
and
ether,
and
dissolve in salt
proteids
is
is
somewhat
between
613
APPENDIX.
55 and 75
some proteids
by alcohol and
by mineral acids.
heat
are,
for
(a)
magnesium
(b)
To
salt or
sulphate.
by heat
are
water and in
salt solutions,
action of alkalis
4f)}
they are
first
water and
precipitated
ammonium
Besides those
classes
salt solutions
by
alcohol,
sulphate solution.
of proteids,
Physiological Chemistry
When
must be consulted.
subjected to hydrolysis
ammonia and
614
APPENDIX.
tyrosine
602),
(p.
(p.
605),
acid
aspartic
605),
(p.
and*
influence of certain organisms, probesides fatty acids, phenylacetic acid (p. 442) and
substances of more complicated structure, such as
teiids yield,
phenol,
indole,
C 8 H 7 N,
and
skatole,
C 9 H 9 N.
of
ammonia becomes
bright orange.
Thi
Gelatin
is
to>
Gelatin
which
*
is
When
urea
is
is
contains biuret,
APPENDIX.
615
destroyed.
with tannic
acid,
Gelatin forms
an insoluble compound
is
given,
is
in
PAGE
Acetal
127
84, 96, 122
Acetaldehyde
Acetaldehydehydrazone
Acetaldoxime
136
164
96, 149
Acetamide
Acetone
Acetone
Acetone
Acetone
Acetone
Acetone
Acetone
58
of.
cyanohydrin
153
163
189
193, 199
89, 130
142
dichloride
142
hydrazone
mercaptole
pinacone
sodium bisulphite
136
188
141
131
253
Acetonedicarboxylic acid
Acetonitrile
372, 374
Acetals
Acetic anhydride
Acetic ether
Acetoacetic acid
124, 134
143
Acetanilide
Acetic acid
Acetic acid, electrolysis
Acetic acid, salts of.
PAGE
Acid
Acid
Acid
Acid
Acid
164,
294
423
- Acrose
............................ 272
Acrylaniline ........................ 405
Acrylic acid ........................ 263
Active amyl alcohol ........ 106, 544, 545
Acetophenone
Acetophenonehydrazone
Acetophenoneoxime
424
424
Acetotoluidide
372
Acetoxime
135
Acetyl chloride
Acetylbenzene
161
423
282
510
Acetylcellulose
Acetylcode'ine
Acetylene
Acetylene series
Acetylformic acid
Acetyl fructose
Acetylglucose
j3- Acetylpropionic acid
Acid amides
Aldehyde
80
144
Aldehydes, condensation of. .........
142
Aldehydes, oxidation of. .............
Aldol ............................... 126
200
271
Aliphatic
268
Alizarin, 478
72, 81
200
164, 169
480 dyeing
; diacetate,
with .............................. 516
Alkali blue .......................... 529
;
618
INDEX.
PACK
Alkaloids, 497
499
extraction of
;
278
Anethole
423, 452:
162
Anhydrides
Alkyl
Alkyl
Alkyl
Alkyl
Al kyl
78
....,
Amylum
510
acid
PAGE
Amylene
376;
chlorides
117
cyanides
293
phonic acid
396
117
Aniline blue
Aniline yellow
Animal charcoal
529'
hydrides
Alkyl radicles
185
296
117
Alkylanilines
377
Alkylene radicles
117
hydrogen sulphates
80,
isocyanates
86
Allene.
Allyl alcohol
260
Allyl bromide
Allyl iodide
262
261
535
Anisaldehyde
Anisic acid
Anisole
Anisyl alcohol
405
417,423
Anthracene
308, 338, 470
Anthracene derivatives, isomerism
...475
of
Aluminium ethyl
223
Amalinic acid
510
Anthranilic acid
164
Anthranol
262
Allyl sulphide
Allylene
81, 86,
Amides
Amidoacetic acid
Amido-acids
Amidoazobenzene,
phonic acid
87
229, 299
299
387, 533, 535
sul-
534
sul-
7
417, 423
417, 423, 452
Anthracene dichloride
Anthracene disulphonic acids
Anthracene oil
Anthracene picrate
262, 298
Allyl isothiocyanate
475
478
308
471
477
481
Anthrapurpurin
Anthraquinone
Anthraquinone-/3-monosulphonic
."
acid
475
477, 47
Amidoazo-compounds
386
Amidoazotoluene hydrochloride
Amidobenzaldehydes
534
421
Anthraquinonedisulphonic acid
Anthraquinonesulphonic acid,
sodium salt of.
Amidobenzene
Amidobenzenesulphonic acids .. .396,
Amidobenzoic acid
435, 450,
Amido-compounds
alcohol
Amidoethyl
373
Antifebrin
374
397
Antipyrine
Arabinose
511
368
Arabitol
264
439
Arbutin
411
513
Argol
247
301
Amidoethylsulphonic acid
Amidoformic acid
Amidonaphthalene
-
457,
Amido-/3-naphthol
540
465
468
l:4-Amidonaphthol
468
Amidophenol
427
Amidopropionic acid
Amidotoluene
232, 301
376
Amines
Amines,
204, 380
separation
of
Amyl alcohols
Amyl hydrogen
sulphate
primary,
213
287, 418
193
;
478
264
halo-
352
215
408
245
245
544
503
Arsines
Aseptol
Asparagin
Aspartic acid
Asymmetric carbon atom
Atropine
Anrin
Azobenzene
Azobenzenesulphonic acid
cyanide,
481
184
Azo-compounds
106
Azo-dyes
106
Azoxybenzene
524,
530
535
390, 533
533, 534, 535
390
619
INDEX.
PAG
A zoxy-compounds
Azulmicaciil
...286
282
Ballistite
275
Barley-sugar
Basic dyes
Baumann and
518, 534
Scliotteu's
Beer, preparation
Benzal chloride
method
433
OS
of.
362, 418
Benzaldehyde
Benzaldehyde green
Benzaldoxime
Benzamide
308
313
335
339
311
439
Benzene-o-dicarboxylic acid
Benzene-p-dicarboxylic acid
438
Benzenedisulphonic acid
Benzenesulphonainide
Benzenesnlphonic acid
396
Benzenesulphonic chloride
Benzidine
396
440
396
395
391, 537
420
70
Benzoic anhydride
Benzoin
Bromobenzoylbenzoic acid
Bromobenzyl bromide
27
358
435
474,
476
482
178
335
335
463
Brotnohexamethylene
Bromonaphthalenes
Bromonitrobenzenes
367
476
432
/3-Bromopropionic acid
233
420
Bromosuccinic acid
Bromotoluene
245
425
362
Butter
Benzoyl chloride
Benzoyl derivatives
Benzoylbenzene
Benzoylbenzoic acid
Benzoylglycine
Benzoyl-group
432
433
424
476
300
432
231, 232
474
inethiodide
Benzotrichloride
508
129, 137
61,
380
420
.420
67
173
104,
106
129129-
180, 181
SO-
181
211
78
*-Btitylene
344
IG'
Bromoform
Bromohexahydrobenzene
538
167
Bromobenzene
Bromobenzoic acids
Brucine, 507
'.
77
439-
Bntaldehyde
Butane
Benzylamine
Benzylidene radicle
Benzyl ideneacetone. ...
179-
439
Bromethylphthalimide
Bromination of acids
351, 424
radicle
476
Bromethane
Bromethylamine
Bromethylene
434
433
Benzonitrile
Benzophenone
Benzopurpurin
Benzoqninone
166
substitution products of
Boiling-point
333
313
hexachloride
431
217
Bromacetylene
Bromanthraquinone
313
of,
536
522
hexabromide
salts
266, 283
537
313
43fl.;
Bioses
Bismarck brown
Brilliant green
Bromacetic acids
derivatives, isomerism of
Benzine
Benzoic acid,
420'
Bordeaux
Benzene
Benzene
Benzene
Benzene
Benzil
513
chloride
522
85, 307,
hexahydride
Benzene, homologues of.
Benzene, synthesis of.
Benzene-m-dicarboxylic acid
Beta'ine, 512
485
Benzene,
of..
442
Bone-oil, Bone-tar
433
constitution
419
Benzylidenehydrazone
Benzylidenehydroxycyanide
Benzylmalonic acid
418
419
PAGE
1C
390
/3-Butylene
78
y-Bntylene
Butylene dibromide
Bntylene glycol
Butyric acid, normal
78
87
80,
227
158
620
INDEX.
PAGE
159
Butyrone
Butyrophenone
137
530
Cacodyl
Cacodyl chloride
Cacodyl cyanide
Cacodyl oxide
Cacodylic acid
424
Chlorobenzene
Chlorobenzoic acid
218
Chlorobenzyl chloride
Chloroform
218
218
-Chlorohydrin
217
/3-Chlorohydrin
218
Chlorohydrins
Chloromalonic acid
510
Caffeine
PAGE
Chlorine carrier
Chlorine, detection of.
Chlorine, estimation of
Calcium carbide
82
166, 352
16
27
357
360
354
175
258
257, 258
56, 128,
257,
245
Chloromethane
174
517
274
Chloronaphthalenes
Chloronitrobenzenes
462, 463
137
a-Chloropropionic acid
166, 231
160
,3-Chloropropionic acid
166, 233
Caramel
Carbamic acid
Carbamide
275
360
301
Chlorotoluenes
Choline
301
Chrysoidine
535
Carbazole
Carbinol
471
Cinchomeronic acid
496
Cinchona-bark, alkaloids of
Cinchonine
Cinchoninic acid
506
506
Calico-printing
Cane-sugar
Capraldehyde
Caproic acid
89,103
266
Carbohydrates
Carbolic acid
307, 308,
404
14
Carbon, detection of
Carbon, estimation of
Carbon tetrachloride
18
177
Carbonyl chloride
Carbonyl-group
Carboxyl-group
177, 302
Carboxylic,acids
Carbylairiine reaction
156, 428
method
156
176, 207
294
Carbylamines
Carius'
132
of analysis
Carvacrol
Casein
Gatechol
27
34i, 409
277
410, 480
443
251
252
Closed-chain compounds
Coal-tar, distillation of
Coca, alkaloids of.
Cocaine
Codeine
504
510
305
491
Collodion
282
Colour-base
Condensation
Celluloid
Cellulose
281
Cellulose nitrates
282
Cetyl alcohol
Cetyl palmitate
109
192
Chloracetanilide
375
Chloracetic acid
Chloral
166
Chloral alcoholate
Chloral hydrate
Chloranil
Chloranilines
Chlorethane
127
520
19, 20
133
537
468, 537
501
Copper acetylide
Cordite
Cream of tartar
Creosote
Cresols
Crotonaldehyde
Crotonic acid
178
Crotonylene
Crystallisation
48
50
83
260,282
249
308
oil
375
77
504
*
Collidines
410
282
Chlorethylene
332
305, 309
Coke
Catechu
428
417
508,
Combustion apparatus
28
506
Citric acid
452
512
Cinnamic acid
Cinnamic aldehyde
Catecholcarboxylic acid
127
367, 375
408
126, 263
264
81, 87
6
308,
621
INDEX.
PAGE
PAGE
Cumene
349
Cumicacid
349
295
Cyainelido
Dicarboxylic acids
Dichloracetic acid
234, 436
166
134
Dichloracetone, asymmetrical
Cyanic aci'l
Cyanides
Cy;i nides, double
295
Cyanogen
Cyanogen chloride
Cyanogen compounds
Cyanohydrins
285
Diclilorethylene
84
287
Dichlorobenzene
313:
Dichloracetone, symmetrical
134, 252, 258
290
291
Dichloranthracene
285
-Dichlorohydrin
136, 142
/3-Dichlorohydrin
Cyanuric acid
Cyanuric chloride
287
Dichloronaphthalene
287
Cymene
349
/3-Dichloropropane
/3-Dichloropropionic acid
Dahlia
Daturine
527
503
Decane
67
98, 280
267
251, 542, 543
256
Dextrin
Dextrose
Dextvotartaric acid
Diacetin
258
Diacetylchlorohydrin
Diallyl
87
Diallyl tetrabromide
87
536
Diainidoazobenzene hydrochloride
Diainidoazobenzenes
366, 368, 376
373, 376
Diamido-compounds
391
Diainidodiphenyl
l:4-Diamidonaphthalene
1 Marsenic tetrainethyl
468
218
98, 277, 280
387
Diastase
Diazoamidobenzene
Diazoainido-compoimds
Diazobenzene, chloride, 382
382
Diazobenzenesulphonic acid
Diazotoluene chloride
Diazoxylene chloride
Dibasic acids, electrolysis of
Dibenzylamine
Dibromanthraqninone
Dibroinethylbenzene
.Dibroinethylene
Dibromobenzenes
258
Dicyanogen
Diethyl ketone
Diethylamine
285-
Diethylamine, salts of
Diethylnitrosamine
Diethylphosphine
Diethylphosphine hydriodide
209
208
214
Digallic acid
453-
137
208
215
137
Dihexyl ketone
399, 401, 410
Dihydric phenols.
336
Dihydrobenzene
336
Dihydrobenzene tetrabromide
272
Dihydroxyacetone
478, 481
Dihydroxyanthraquinones
534
Dihydroxyazobenzene
410
Dihydroxybenzenes
452
Diliydroxybenzoic acids
469Dihydroxynaphthalenes
48&
Dihydroxyphenanthrene
531
247
382
Di-isobutyl ether
115
..385
537
383, 534
537
115
65
Di-isopropyl
115
Di-isopropyl ether
137
Di-isopropyl ketone
Dimethyl carbinol
103,
Dimethyl ketone
130, 137
105
159
381
Dimethylacetic acid
Dimethylacetylene
479
445
Dimethylamidoazobenzene
Dimethylamidoazobenzene
388
72, 81
84
330
336
Dibroinohexamethylene
Dibromopropionic acid
336
Dibroinosticcinic acid
463
131, 142
Dihydroxysuccinic acid
Di-isoamyl ether
Di brom oh exahydrobenzene
Dibroniopyridine
258
257, 258
Dihydroxyphthalophenone
397, 534
381
Diazo-compounds
Diazo-compounds, constitution of.
Diazopseudocnmene chloride
252, 257,
386
nitrate,
sulphate
475
.263
486
247, 250
87
hydro534
chloride
Dimethylamine
Dimethylaniline
Dimethylarsine oxide
Dimethylbenzidine
536
211
370, 378
217
391, 538
622
INDEX.
PAGE
411
Dimethylcatechol
Dimethylethylamine
211
Diiiietliyletliylinethane
546
Diinethylinalonic acid
241
Dimethyl phenylenediamines
376, 535, 536, 539
491
Dimethylpyridines
4(57
Dinaphthols
Dinitro--naphthol
467, 538
Din itro-<*-naphthol-di.sulphonic acid,
407
potassium salt of
Dinitrobenzene
365, 366
87, 88
Di-olefines
Diphenic acid
482, 483, 484
484
Diphenic anhydride
Diphenyl, 338, 350, 482 ketone, 351, 424
371, 379
Diplienylamine
482
Diphenyldicarboxylic acid
;
Diplieuylethylene
482
Diphenyliodonium hydroxide
Diphenyliodonium iodate
Diphenylmethane
360
351, 425
Diphenyl-m-tolylmethaiie
523, 526
Dippel's
360
485
oil
Dipropargyl
Dipropyl ether
Dipropyl ketone
87,
314
115
137
Dipropylamine
204
Disacryl
262
8
Distillation
Distillation in steam
Distillation of
.'
wood
Ditolyl
Dulcitol
Dutch liquid
Dyes and their application
Dynamite
Earth-wax
Ecgonine
Elementary analysis
Empirical formula
Emulsin
Enantiomorphous crystals
Enzymes
Eosin
90
482
265, 270
71
514
259
67
504
14
32
288
549
99, 276
Epichlorhydrin
532
258
Erythritol
264
Eryth rosin
533
Esterification
191
Esters
174
Ethaldehyde
122
PAGE
Ethane
Ethene
Ethene glycol
58, 67,
84
71
224
Ether
Ethereal salts
Ethers
Ethoxides
Ill
acetate
188
acetoacetate
193
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
174
Ill
95
acetyllactate
alcohol
232
94, 107
394
benzenesulphonate
benzoate
benzylmalonate
bromide
431
442
179, 181
198
butylacetoacetate
carbinol
carbonate
chloride
105
302
178, 181
302
chloroformate
Ethyl copper acetoacetate
Ethyl diethylacetoacetate
Ethyl dimethylacetoacetate
Ethyl dipropylacetoacetate
Ethyl ether
Ethyl ethylacetoacetate
Ethyl ethylmalonate
Ethyl ethylmethylacetoacetati!
Ethyl ethylpropylacetoacetate
Ethyl formate
Ethyl glycollate
Ethyl hydride
Ethyl hydrogen sulphate
Ethyl hydroxycrotonate
Ethyl iodide
Ethyl isocyanate
Ethyl isonitrile
Ethyl isopropylacetoacetate
Ethyl lactate
Ethyl malonate
Ethyl mandelate
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
mercaptan
inethylacetoacetate
195
196
196
196
Ill
196
202
196
198
192
233
58
74,
185
200
180, 181
296
294
196
232
201
454
187
195, 196
nitrate
182
nitrite
183
oxalate
239
438
phthalate
propylacetoacetate
propylethylmalonate
propyl malonate
195, 196
202
203
623
INDEX.
PAGE
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
Ethyl
PAGE
salicylate
451
sodioacetoacetate
194
sodiomalonate
202
Fermentation, butyric
Fermentation, diastatic
Fermentation, frctic
succiniinide
244
Fittig's reaction
sulphate
186
sulphide
188
Formaldehyde
Formaldoxime
Formamide
205
Ethylamiiie
Ethylainiue, salts
208
of.
95
Formauilide
345, 347
522
Formic acid
Formic acid,
Formose
Ethylates
Ethylbenzene
Ethylbenzylauiline
207, 294
Ethylcarbylamiue
Ethyleue
Ethyleue alcohol
Ethylene chlorohydrin
Ethylene cyanohydrin
Ethyleue diaiiiiue
Ethyleue dibromide
Ethyleue dichloride
Ethyleue glycol
Ethyleue oxide
Ethylene series
71, 79
224
227, 228
142
Fusel
oil
272
525
247, 558
98, 100,
106
269
234
452
244
Gas liquor
305
214
215
Gasoline
General formulae
439
152
203
Gluconic acid
Glucosates
269
203
169
193
from ethyl
201
from next
205
from next
206
Fatty compounds
332
Fehling's solution
268
Fermentation, acetic
Fermentation, alcoholic
Fuchsine
Fumaric acid
340, 424
Gallic acid
145
Fatty acids
Fatty acids, electrolysis of
58, 68
from
Fatty acids, synthesis of,
ethyl
Ferment
Galactosazone
Galactose
187
of,
11
142
188
of,
30
Fractional crystallisation
Fractional distillation
270
Elhylideue bromide
Ethylidene chloride
Formula, calculation of a
Fruit-sugar
234
of,
148
122, 272
273
439
acetoacetate
salts of
270
Ethyleuelactic acid
165
375
Fructosephenylhydrazoue
Fructosoxime
Ethyleuediphthaliinide
Fats
120
Fructose
71
Ethylsulphoue
Ethylsulphouic acid
80, 224
228
Ethylpropylacetic acid
Ethylpropylmalouic acid
439
77
Ethyl phosphine
Ethylphosphine hydriodide
Ethylphthalimide
159
341
234
77
Ethylideuelactic acid
Ethyliiialouic acid
159
98, 280
97
96, 150
97-100
270
70
6t>
268
Glucosazone
Glucose
273, 274
Glucosephenylhydrazone
2C9, 272
267
Glucosides
287
Glucosoue
Glucosoxime
274
Glutaric acid
269
235, 244
Gluten
280
Glyceraldehyde
272
256
Glyceric acid
Glycerides
Glycerin
Glycerol
Glycerose
Glyceryl acetate
Glyceryl trichloride
Glyceryl trinitrate
Glycine
Glycine hydrochloride
170
254
170,172,254
272
255, 256
257
258
299
300
624
1XI>K\.
PACK
Glycol diacetate
Glycol, sodium
Glycollic acid
compounds
226
225
of.
228
223, -J24
228, 229, 248
Glyoxal
Glyoxylic acid
Granulose
Hydroximes
134, 212:
430
Hydroxyacetic acid
229, 231
421
Hydroxyaldehydes, aromatic
Hydroxyanthraquinone
477, 479Hydroxyazobenzene
533, 534
Hydroxyazobenzenesulphonic acid ..534
Hydroxybenzaldehydes
422, 423
404
Hydroxy benzene
282
Hydroxybenzoic acids
228
279
267
Grape-sugar
Graphic formula;
Guaiacol
Gum benzoin
Gun-cotton
Hydroqninone
410, 411, 426
Hydroxides, quaternary ammonium .210
216
Hydroxides, quaternary arsonium
Hydroxides,quaternary phosphonium 215-
50
410
450, 451
416, 417
166, 352
174, 352
Halogen
Halogen derivatives
Hard soap
Heavy oil
172
306
536
Helianthin
Hemihedral crystals
Hemimellitene
alkaloids
543, 549
349
Hemlock,
Heptaldehyde
Heptane
Heptyl alcohol, normal
501
of.
Heptylic acid
Hexachloracetone
Hexahydrobenzene
Hexahydropyridine
Hexahydrotetrahydroxybenzoic
Hexamethylene
12!>,
67
Hexylene
Hexylic acids
Hippuric acid
Hofmann's violet
Homologous
series
Hydracrylic acid
Hydrolysis
142
51&
512
414
a-Hydroxypropionic acid
489
/3-Hydroxypropionic acid
Hydroxysuccinic acid
231, 233.
Hydroxysulphonic acids
140, 408
335
412,
142
134, 183
245
231
245
Hydroxy toluenes
408
Hydroxytricarboxylic acids
251
265
201
265
Hyoscine
503
503
424
.528
65, 67
79
160
Hyoscyamine
Hypnone
300, 430
527
66
231. 233
Hydranthracene
474, 475
Hydrazines
385, 388
391
Hydrazobenzene
Hydrazones
134, 136, 272, 389
420
Hydrobenzamide
Hydrocarbons, aromatic, oxidation of 429
443
Hydrocinnamic acid
Hydrogen cyanide
Hydrogen, detection of
Hydrogen, estimation of.
446
142
245
134
acid.. 505
530'
142, 231,
Hydroxycarboxylic acids
Hydroxycyanides
Hydroxydicarboxylic acids
Hydroxyethyl cyanide
Hydroxyethylsulphonic acid
Hydroxyethyltriinethylaimuonium
hydroxide
335
129
486,
199, 264
Hydroxyhydroquinone
Hydroxyisopropyl cyanide
Hydroxylamine
Hydroxymalonic acid
129, 160
Hexamethylpararosaniline chloride
Hexane
Hexyl alcohol
Hexyl iodide
137
/3-Hydroxybutyric acid
y-Hydroxybutyric acid
287
15
18
172,192
Indican
539
Indigo- white
Indigodisulphonic acid
Indigotin
Indoxyl
Indoxylic acid
Inulin
Inverse substitution
Inversion
Invert sugar
Invertase
519, 539
539
539
540
540
270'
57
276
270, 276
100, 276
625
INDEX.
PAGE
PAGE
lodacetic acids
166
Lactic acid
Jodethaue
180
Iodine green
lodobenzene
lodobenzene dichloride
359
178
Laudanum
508
Laurie acid
167
Laurone
Lead ethyl
Le Bel and van't Hoffs theory
137
512
106
Lecithin
Leucaniline
Leuco-base
193
Leuco-compound
27
527, 528
358
lodoform reaction
96
lodoiiitrobenzenes
367
lodosobenzene
359
lodoxybenzene
359
Isethionic acid
513
104
Iso-alcohols
Isoainyl alcohol
Isoamyl isovalerate
78
jS-Isoamylene
Isobutaldehyde
Isobutane
Isobutyl alcohol
Isobutyl carbinol
Lsobutylene
Isobutyric acid
137
61, 65, 67
104, 106
104
78
159, 167
Isobutyrone
Isocyanides
Iso-hydrocarbons
137
294
65
Isomerisni
Isonicotinic acid
64
492
Isonitriles
294
63
Isopentane
Isophthalic acid
Isopropyl alcohol
Isopropyl bromide
Isopropyl carbinol
439
105, 107, 131
80
104, 106
181
Isopropyl iodide
Isopropylacetic acid
158
Isopropylbenzene
Isopropylbenzoic acid
349
Isoquinoline
Isosuccinic acid
349
485,
235,
496
244
Isothiocyanates, alkyl
298
Isovaleraldehyde
137
Kerosene
Ketones
70
130, 423
Ketones, condensation of
Ketones, oxidation of.
144
142
Ketoximes
134
Kjeldahl's method
27
Kb'rner's'method of determining constitution
329
Chem.
7/6
232
Lactones
Lactose
Lakes
Lard
Laubenheimer's reaction
16
lodoforni
530
159, 277
480, 518
170
484
223
544
523, 526
520
518
Leuco-malachite green
Leuco-pararosaniline
Leuco-rosaniline
Levotartaric acid
Levulinic acid
521
524
523, 526
523,
200
Levulose
Liebermann's reaction
270
209, 402
306
Light oil
Light petroleum
70
70
Ligroin
Lutidines
491
Magenta
525
Malachite green
Maleic acid
Malei'c
anhydride
Malic acid
Malonic acid
Maltosazone
Maltose
Mandelic acid
Mannitol
521
247, 558
247, 558
245, 250, 544, 545, 549
235, 239
98,
277
276
453
265, 271
Mannose
269
Margaric acid
Margarine
Marsh-gas
Martins' yellow
160
Meconic acid
508
173
53
538
Melissyl alcohol
109
Melting-point
Mendius* reaction
205
Mercaptans
Mercaptides
Mercuric ethiodide
Mercuric ethochloride
Mercuric ethohydroxide
13
187
187
222
222
223
INDEX.
626
PAGE
PAGE
Mercuric ethyl
Mesityl oxide
Mesitylene
Mesitylenic acid
Mesotartaric acid
Metachloral
Meba-coi n pounds
222
133, 134
Metaldehyde
127
Metanilic acid
397
Methaldehyde
Methane
Methane series
Methene dichloride
118
53, 67
53, 67
175
91
Methoxides
Methoxybenzaldehyde
Methoxybenzoic acids
Methoxybenzyl alcohol
Methoxycinchonine
Methoxy-group
409,
423
452
417
409
Methylene dichloride
175
Methylenitan
Methylethyl
Methylethyl carbinol
Methylethyl ketone
Methylethylacetic acid
Methylethylamine
Methylethylene
Methylisopropyl ketone
Methyl isopropyl benzene
272
.211
78
137
349
490
89, 107
193
94
Methylsalicylic acid
Methylsuccinic acid
Ill
Methylsulphonic acid
Methyltheobrcniine
Methyl triphenylmethane
115
Methylviolet
294
91
177, 181
294
440
116
449, 451
183
184
536
238
449
193
116
449, 451
91
440
136
Middle
91
491
496
449, 451
214
184
510
523
528
306, 307
277
Mirbane, essence of
Mixed amines
365
Mixed anhydrides
Mixed ethers
Mixed ketones
164
Molecular formula
Molecular weight, determination
Molecular weight, determination
by chemical methods
Molecular weight, determination
by physical methods
69
211
115
137
32
of.
32
of,
32
of,
36
Monacetin
256
Monobromopyridine
Monocavboxylic acids
486
134
Monoformin
101
61
137
Milk-sugar
Mineral naphtha
211
370, 378
214
oil
Methylamine
87
462
Methylpropyl
Methylpropyl ketone
Methylpyridines
Methylquinoline
122
spirit
139
Methylpiperidine
Monochloracetone
Monochloranthracene
Methylated
Methylates
60
104, 106
498
Methylacetylene
Methylal
Methylaniline
538
505
177, 181
90,
Methylcresols
Methylene blue
510
193
289,
344
410
444
Methylmorphine
Methylnaphthalenes
Methyl phosphine
Methyl acetate
Methyl alcohol
Methyl bromide
Methyl butyrate
Methyl carbinol
56,
Methyl chloride
Methyl cyanide
Methyl ether
Methyl ethyl ether
Methyl hydrogen sulphate
Methyl iodide.
Methyl isonitrile
Methyl isophthalate
Methyl isopropyl ether
Methyl methylsalicylate
Methyl nitrate
Methyl nitrite
Methyl orange
Methyl oxalate
Methyl potassiosalicylate
Methyl propionate
Methyl propyl ether
Methyl salicylate
Methyl sulphate
Methyl terephthalate
Methylacetamide
Methylbenzene
Methylcatechol
Methylcinnamic acids
Monohydric alcohols
Monohydric phenols
Monohydroxynaphthalenes
157
475
147, 260
89
404
466
627
INDEX.
PAGE
PAGE
266, 283
Mordants
516
Morphine, 509
methiodide
509
Mucic acid
270
Mustard-oil
298
Myristic acid
167
Myrosin
298
307
Naphtha, crude, 306 solvent
Naphthalene
307, 308, 338, 455
Naphthalene, amido-derivatives of... 464
456
Naphthalene, constitution of
462
Naphthalene, derivatives of
Naphthalene derivatives, isomerism
;
of
460
462
Naphthalene, hoinologues of.
.464
Naphthalene, nitro-derivatives of.
456
Naphthalene picrate
467
Naphthalene, sulphonic acids of.
438, 463
Naphthalene tetrachloride
467
Naphthalene yellow
.
Naphthalene-ae-sulphonic acid
468
Naphthalene-/3-sulphonic acid
Naphthalenedisulphonic acids
468
Naphthalic acid
484
468
465, 468
-Naphthaquinone
469
/3-Naphthaquinone
468, 537
Naphthionic acid
-Naphthol, 459, 466; /3-Naphthol. ..467
467, 538
Naphthol yellow
538
-Naphtholdisulphonic acid
537
/3-Naphtholdisulphonic acid
538
flc-Naphtholmonosulphonic acid
.
Naphtholmonosulphonic acids
Naphthol-s
481
Nitrobenzaldehydes
Nitrobenzene
Nitrobenzoic acids
Nitrocinnamic acids
420
445
334, 362
Nitro-conipounds
Nitroethane
184
Nitrogen, detection of
Nitrogen, estimation of
15
23
258
Nitroglycerin
Nitrometer, Schiff 's
/3-Nitro--naphthylamine
a-Nitronaphthalene
/3-Nitronaphthalene
24
464
458, 464
464
184
Nitroparaffins
405
Nitrophenols
Nitrophenyldibromopropionic acids. .445
445
Nitrophenylpropiolic acid
457
Nitrophthalic acid
Nitrosamines
209, 377
Njtrosobenzene
369
378, 539
Nitrosodimethylaniline
Nitrosomethylaniline
Nitrosophenol
Nitrosopiperidine
Nitrotoluenes
378
379
490
367
Nonane
Normal alcohols
Normal butylene
Normal hydrocarbons
Nux
67
104
78
65
vomica, alkaloids of
506
Octacetylmaltose
277
Octacetylsucrose
276
466
-Naphthylamine
458, 465
465
/3-Naphthylamine
Naphthylaininemonosul phonic acids.. 467
1 :4-Naphthylaininesulphonic acid
468
Narcotine
508
Natural gas
69
Neurine
513
502
Nicotine, 502 dimethiodide
;
67
129, 137
137
Oil
of,
89, 450
71
Oleic acid
Oleomargarine
Open-chain compounds
Opium, 508
Nitranilines
375
Nitrates, ethereal
Nitrates of cellulose
182
Optical isomerides
Optically active substances
183
mus-
71
Olefiant gas
Olefines
375
136, 293
169
Oils
503
282
bitter
Nightshade, alkaloids of
Nitracetanilides
Nitrites, ethereal
435
Octane
(Enanthol
GEnanthone
467, 538
Nitriles
365
468
-Naphtholtrisulphonic acid
Nicotinic acid
Nitroalizarin
alkaloids of
171, 264
173
332
508
548
541
188
Organic acids, ethereal salts of
Organic compounds, classification
of...
331
628
INDEX.
PAGE
Organo-metallic compounds.
220
Ortho-compounds
Orthoquinones
Osazones
Osones
322
469
group, 338
iodide, 358
radicle
ether, 405
;
PAGE
methyl
344, 403
Phenylacetaldehyde
Phenylacetic acid
405, 417
273
273
Phenylacetonitrile
434, 442
Oxalic acid
Oxalic acid, salts of
235
236
Plienylacetylene
Phenylacrylic acid
441, 443
Oxamide
Oxamines
239
Phenylamine
373
215
444
Oxanilide
377
Oxanthrol
477
Phenyl-/3-bromopropionic acid
Phenylbutylene, 459; dibromide
Phenylbutyric acid
Phenylcarbinol
92
Oxidising agents
Oximes
.134, 212
67, 70
Ozokerite
442
445
459
441
415
Phenylcarbylamine
Phenylchlorofonn
362
Phenyl-a/3-dibromopropionic acid.
160, 167
Palmitic acid
Palmitone
Papaverine
Paracetaldehyde
Phenylenediamiiies
508
Phenylethane
Phenylethyl alcohol
Phenylethylene
Phenylformic acid
Phenylglycine
126, 143
322
Para-compounds
Paracyanogen
286
53, 66, 67
Paraffins
66
Paraffin-wax
Paraformaldehyde
120
Paralactic acid
233
126
Paraldehyde
523, 524
Paraleucaniline
Phenylene radicle
137
.444
344, 403
373, 376, 426, 536
347
417
445
441
540
Phenylglycinecarboxylic acid
Phenylglycollic acid
540
Phenylhydrazine
Phenylhydrazones
Phenylhydroxylamine
383
Paraqninones
469
Phenylisocrotonic acid
453
369
444, 459
Pararosaniline
523
281
Phenylisocyanide
Phenylmaltosazone
176
Parchment paper
Pentamethylene diamine
Pentane
491
Phenylmethane
344
63, 67
78
277
Pentylene
Pepper, alkaloid of
Perchloracetone
134
Peri-position
Pel-kin's reaction
444
Phenyltrimethylammonium iodide..
430
Phloroglucinol
Phloroglucinol triacetate
Phloroglucinol trioxime
412,
Phorone
133,
503
461
Peru balsam
Petroleum
Petroleum ether
69
70
483
Phenanthraquinone
Phenanthraquinone, bisulphite com-
pound of
Phenanthraquinone dioxime
Phenanthrene
308,
Phenetole
Phenol
Phosphomolybdic acid
483
Phosphorus, detection of
Phosphorus, estimation of.
Phosphotungstic acid
Photogene
Phthaleins
Phthalic acid
405
307,404
Phenolphthalei'n
531
Phenols
398
397, 408
Phenolsulphonic acids
Phenyl, bromide, 358 ; chloride, 357
;
cyanide,
433;
ethyl ether,
405;
413
413
413
1
Plithalic acids
Phthalic anhydride
Phthalimide
34
214
Phosphines
483
474, 481
.372
501
.
18
29
501
70
530
436, 456
327,
436
629
INDEX.
PAGE
Phthalophenone
530
Phthalyl chloride
Physical isomerides
438
PAGE
204, 211
Picolines
491
Propylamine
Propylene
Propylene chlorohydrin..
Propylene dibromide
Picolinic acid
492
a/3-Propylene glycol
227, 231
ay-Propylene glycol
Propylene oxide
Propylmalonic acid
228
548, 568
Picric acid
Pinacoline
Pinacones
141
Piperic acid
490, 503
Piperidine
486, 489
490, 503
Pipeline
Pitch
Polarimeter
Polyhydric alcohols
Polymerisation
Polyoses
349
262
Purification of
121
Purpurin
Potassium ferricyanide
Potassium ferrocyanide
Potassium myronate
Primary alcohols
Primary hydrocarbons
Primula
527
Proof-spirit
102
Propionitrile
Propionyl chloride
Propiophenone
Propyl alcohol
Propyl bromide
Propyl carbinol
Propyl formate
Propyl hydride
Propyl iodide
Propylacetic acid
502
Pseudocumene
Propione
Propionic acid
Propionic acid, salts of
203
-Propylpiperidine, d
268
Potassium, acetylide,
cresate,
403 diphenylamine, 379 phenate,
405 phthalimide, 439 ; picrate
407
Propaldehyde
Propane
Propenyl acetate
Propenyl alcohol
Propenyl chlorohydrin
Propenyl dichlorohydrin
Propenyl iodide
Propenyl tribromide
Propenyl trichloride
Propenyl trinitrate
Propionamide
233
308
537
254
452
537
84
78,
Protocatechuic acid
Prussian blue
Prussic acid
278, 283
Ponceau 3R
Ponceaux
78
228
293
292
293
287
4
compounds
478, 481
tives,
isomerism
of,
488;
homo-
meth iodide
486
Pyridine-/3-dicarboxylic acid
Pyridine-/3-carboxylic acid
Pyridine-/3y-dicarboxylic acid
Pyridiuecarboxylic acids , /3,
492
502
496
491, 492
298
Pyrocatechol
410
104
452
Pyrogalloldimethyl ether
Pyroligneous acid
Pyrotartaric acid
150
244
05
255
412
413
200, 233
Pyruvic acid
Pyruvic acid hydrazone
200
254
Qualitative elementary analysis
257
261
Quinic acid
Quinine, 504 ; dimethiodide
Quininic acid
505
Quinol
411
254
257
.258
206
137
105, 158, 167
158
294
.
14
257
162
424
105, 107
180
104
193
60
181
158
505
505
alkaloids
Quinoline, 338, 484, 493
derived from, 504; y-carboxylic
494
methiodicle
acid, 506
493
Quinolinic acid, 492 anhydride
;
425
Quinone
Quinone chlorimides
Quinone dichlorodiimides
Quinonedioxime
Quinonemonoxime
Quinones
428
428
426
426
425
Racemic acid
.248, 251, 542, 554
549
Racemic compound
Racemic compounds, resolution of. .556
.
630
INDEX.
Radicles
116, 343
Rational formulae
50
Reducing agents
55
70
Refined petroleum
Refined spirit
Reimer's reaction
Resorcin yellow
Resorcinol
101
421, 448
536
410, 411
PAGE
Sodium ammonium racemate
557
Sodium glycerol
256
Sodium hydroxyethylsulphonate
140
Sodium hydroxyisopropylsulphonate..l40
Sodium phenylcarbonate
447, 450
Sodium picrate
407
Soft soap
Solar oil
Resorcylic acids
448
Sorbitol
Rhodonates
172
70
265, 269, 271
297
Spirit of wine
Rocellin
537
Spirits,
Rochelle salt
Rosaniline
Rosolic acid
249
530
Stannic ethyl
Stannous ethyl
Starch
478
Starch cellulose
523, 525
Ruberythric acid
94
manufacture of
100
223
223
278
279
Stearic acid
160, 167
Saccharic acid
Saccharimeter
269
Stearin
268
Saccharin
Saccharosates
Saccharose
435
Stearone
Stereo-chemical isomerides
Stereo-isomerism
276
172
137, 139
558
558
216
Stibines
Salicin
274
416
Salicyl alcohol
416
Storax
422
Strontium sucrosate
Strychnine, 506 methiodide
276
Styrolene
Substitution
445
Salicylaldehyde
Salicylic acid, 450
451
salts of
.417
Satigenin, 416, 421 ; methyl ether.
Sandmeyer's reaction. ..357, 358, 384, 434
.
172
Saponification
Sarcolactic acid
Saturated compounds
Scarlet
537
Secondary alcohols
Secondary aromatic bases
Secondary hydrocarbons
Seminin
Separation of
Side-chains
.124
Stilbene, 482
dibromide
Substitution, rule of
57
364
Succinamide
243
Succinic acid
241
243
28
496
65
Sucrose
...
...
274
269
4
218
Sugars, hydrazones
Sulphanilic acid
Silicononane
219
Sulphates, ethereal
Sulphides
Sulphocyanic acid
Sulphonal
219
Sulphonamides
219
Sulphonation
Sulphones
Skraup's reaction
Soaps
241
Succinimide
219
Silver acetylide
Silver theobromine
72, 76
281
Silicon tetramethyl
Silicon tetrethyl
Silicononyl acetate
Silicononyl alcohol
Silicononyl chloride
240
337
compounds
507
153
104
compounds
Silicon, organic
482
415, 443
of.
219
219
84
511
493
169
Sulphonic,
chlorides
acids,
272
of.
396
185
186
296
188
394
393
188
187,
Sulphovinic acid
Sulphur, detection of
334,
392;
394
185
18
631
INDEX.
PAGE
PAGIi
29
Sulplmr, estimation of
Sulphuric ether
110
Tobacco, alkaloid
Tolidine
391, 538
Toluene
307, 344
170
Toluenesulphonic acids
396, 435
453
Tolnic acids
347, 435
Tallow
Tannic acid
Taimiu
Tartar emetic
453, 518
249, 518
Tartaric acid
247, 271
Toluic aldehydes
Toluidines
Tolunitriles
Tautomeric forms
Tension of aqueous vapour
Toluylenediamine
200
25
Terephthalic acid
Tertiary alcohols
350, 440
496, 497
105
105, 106
65
Tetrabromethane
84,
84
428
Tetrachlorohydroquinone
Tetrachloromethane
177
Tetrachloroquinone
Tetrahydrobenzene
Tetrahydro-/3-napththylamine
Tetrahydroxyhexahydrobenzoic acid
Tetralkylammonium bases
428
336
463
.505
210
car-
Tetramethyldiamidotriphenyl
binol
474
532
Tetrabromofluorescein
Tetrachlorethane
methane
444
368,
427
Toluquinone
Toluyl, chloride, 360
376
434
344
radicle
427
170, 256
Triacetin
Triamidoazobenzene
Triamido-com pounds
536
373
Tribromophenol
Tribromopropane
405
Tribromoresorcinol
Tribu tyrin
411
Tricarballylic acid
Trichloracetic acid
253
Trichloraldehyde
127
254
173
166
Trichloraniline
375
Trichloromethane
175
520, 521
Triethylamine
209
63, 65, 68
Triethylarsine
216
Triethylarsine dichloride
Triethylarsine oxide
217
333
216
Triethylbenzene
Triethylphosphine
Triethylphosphine hydriodide
Triethylphosphine oxide
Tetramethyl-p-diamidotriphenyl-
Tetramethylmethane
442
-Toluic acid
249
Tartaric acid, salts of.
Tartaric acids, optical-isomerism of. 552
513
Taurine
Tertiary hydrocarbons
502
of.
Tetrazodiphenyl chloride
537
Tetrazoditolyl salts
538
Tetrethylammonium hydroxide
210
Tetrethylammoniutn iodide
Tetrethylarsonium hydroxide
Tetrethylarsonium iodide
Tetrethylphosphonuun iodide.... 214,
209
215
Triethylrosaniline chloride
527
Tetriodofluorescein
533
Trihydric phenols
412
Theba'ine
508
481
Theme
510
Theobromine
511
Thio-alcohols
187
Trihydroxyanthraquinones
Trihydroxybenzenes
Trihydroxypropane
Trihydroxytolyldiphenyl carbinol
Thiocyanates, alkyl
Thiocyanic acid
298
529, 530
296
297
Thio-ethers
216
216
214
215
215
412
254
187
Thiophene
310
Trimethylacetic acid
158
Thiotolene
344, 484
Thymol
Trimethylamine
Trimethylamine hydrochloride
211
349, 409
211
632
INDEX.
PAGE
333, 348
Trirnethylbenzenes
Trimethyl carbinol
104, 106
Trimethylene bromide
Trimethylene cyanide
490
78
65
61, 65
Trimethylmetliane
Trimethylpyridines
Trimethylrosaniline chloride
Trinitrobenzene, symmetrical
Triiiitromesitylene
491
527
366, 407
348
406
Trinitrophenol
Triolein
Trioxymethylene
Tripalmitin
Triphenyl carbinol
Triphenylamine
304
of.
349
490
Trimethylethyleiie
Trimethyletliylinetliane
Trinitrotriphenylmethane
PAGE
Uric acid, salts
Uvitic acid..
352, 524
171
119, 121, 144
171
352, 519
Valency of carbon
Valeraldehyde
51
137
Valeric acid
160, 203
160
37
70
Veratrol
411
Verdigris
Victoria green
522
153
150
Vinegar
Vinyl bromide
Vinyl chloride
77
77, 83
371, 380
Triphenylcarbinol-o-carboxylic acid
530
Water blue
Wood
529
89
spirit
307, 345
Xylenes
Tristearin
171
Xylose.
264
264
Tropseolin O
Tropic acid
536
503
Xylyl radicle
Xylylene radicle
344
Tropine
503
Turnbull's blue
293
Urea nitrate
Urethane
Uric acid
303
301
303, 511
Xylitol
344
Yeast.
Zeisel's
.99
method
498, 505
Zinc ethiodide
Zinc ethyl
Zinc methyl
Zinc-copper couple
Zymase
220
220
58,220
54,
222
54
99
INDEX TO APPENDIX.
[Where more than one reference
is
given,
is
in
PAGE
Acetylurea
Adenine
Alanine
Albumin (egg)
Albumin (serum)
Albuminates
Albuminoids
594
593, 598
602
610, 612
^.iloxan
570, 584
Camphene
Camphene, constitution
571
Camphene dibromide
571
Camphene hydrochloride
584
Camphor.
571, 579,
Camphor, Bredt's formula for
582
613
594, 595, 597
Amido-acids
601
Amidocaproic acid
Amidodichloropurine
Amidoguanidine
602
598
600
Amidoissethionic acid
607
Amido-6-oxypurine
593,
Amidophenylamidopropionic acid
Amidopropionic acid
Amidopurine
593,
Amidosuccinamic acid
Amidouracil
598
Amygdalin
579, 584
593, 599, 601
Caffeine
613
613
A.lbumoses
588, 592
613
610, 611
Albumins
PAOI
Cadaverine
Cadinene
606
602
598
004
578
of.
Camphor, constitution of
Camphor, Kekule's formula for
Camphoric acid
Camphoric anhydride
Camphoronic acid
Camphoronic acid, synthesis of
Camphoroxine
580-582
551,
.'.582
581, 582
583
580
Carbohydrates
Carbonic oxide haemoglobin
Caryophyllene
Chlorethylsulphonic acid
596
Cholalic acid
566
580
582
563
609
579
608
607
Amylamine
603
Amylo-dextrin
Arabinose
565
565
Cholesterine
Choline
Choline chloride
Choline platinochloride
Artificial
569
Colophony
604
Coniferin
566
Coniferyl alcohol
Creatine
566
601,
Creatinine
603,
camphor
Asparagine
Aspartic acid
Benzaldehyde semfcarbazone
Betaine
Beta'ine chloride
Biuret
Borneol
605, 614
601
587,590
591
614
Creatinine, salts of
Cyanamide
Cyanogen iodide
583, 584
Cymene
Bornyl acetate
Bornyl chloride
583
Cystine
Bromocapro'ic acid
603
606,
608
587, 589
589
589
568
603
604
604
600, 604
600
574
.602
583
Dextrin
..
...564
634
INDEX TO APPENDIX.
PAGE
PAGE
Dialuric acid
597
Issethionic acid
607
Dibromomalonic acid
595
Isoprene
578
Diethoxychloropurine
598
Digitalin
566
Ketohexahydrocymene
584
Dihydrocynienes
576
Diliyclroxyinalbnicacid
595
Lecitliine
Dihydroxyuracil
Diiodopurine
Diinethylxanthine
Dioxypurine
Dipentene
Dipentene dihydrobromide
Dipentene dihydrochloride
597
Leucine
599
Limonene
593, 599
593, 597
571
Limonene, constitution of
576
Limonene tetrabromide
571
565
584
572
Essential oils
572
Malto-dextrin
572
Menthol
Menthone
566
Menthyl acetate
585
Mesoxalic acid
595
583
Ethylic broiuisobutyrate
Ethylic hydroxytrimethylglutarate .583
596
Ethylic /3-uramidocrotonate
584
594
613
Mesoxalylurea
Methylglycine
Methyltheobromine
Methyluracil
Millon's reagent
Muscarine
587,
Gelatin
614
Neurine
587, 591
Globulins
Glucosides
613
Nitroguanidine
600
565
Nitrophenylamidopropionic acid
606
588
Nitrouracil
596
Mtrouracilic acid
596
Ethyltrimethylammonium
ide
Fibrin-globulin
Glycerophosphoric acid
Glycine
Glycocholic acid
Glycogen
Guanidine
Guanidine nitrate
Guanidine thiocyanate
hydrox587
606
564
600
599,
600
600
593, 597, 598
601
599
596
614
590
Oil of
bergamot
571
Oil of
camphor
579
Oil of
caraway
571
Oil of celery
Oil of citronella
571
565
Oil of cloves
579
565
Oil of
Haematein
610
Oil of ginger
Oil of juniper
Hsemin
610
Oil of laurel
579
568
Oil of lavender
571
Guanine
Gum-arabic
Gums
Haemoglobin
Hexahydrocymene
608, 609
.575, 585
605
Hydroxybenzoic acid
Hydroxyethyltrimethylaimnonium
589
hydroxide
Hydroxyphenylamidopropionic acid. .605
605
Hydroxyphenylethylamine
596
Hydroxyuracil
593, 598
Hypoxanthine
Oil of
Indole
Inulin...
600
614
...564
579
cubeb
571
lemon
571
Oil of lime
Oil of parsley
Oil of peppermint
Oil of pine-needles
Oil of rosemary
thyme
cince,.
568
584
572, 583
583
571, 583
Oil of turpentine
Oil of valerian
Oleum
572,
568
Oil of sage
Oil of spike
Oil of
Imidourea
571
568, 583
567, 570
571, 583
572
INDEX TO APPENDIX.
635
PAGE
Oxaluric acid..
595
Oxalylurea
Oxyhsemoglobin
Oxypurine
594, 595, 598
Parabanic acid
608
Paracholesterine
Pentamethylene diamine
Peptones
Phenylacetaldehyde
613
606
614
Phenylacetic acid
Phenylalanine
Phenylainidopropionic acid
606, 614
606, 614
nitrile of 606
Phenylamidopropionic acid,
Phenyllactic acid, nitrile
Phytosterine
Pinene
Pinene, constitution of
Pinene dibroinide
Pinene hydrochloride
Pinene nitrosochloride
Polyterpenes
Proteids
Proteids, tests for
Pseudouric acid
Ptomaines
Purine
Putrescine
.592
of.
606
60S
568, 570, 584
577
568
569
569
Skatole
Starches
614
564
Taurine
Taurocholic acid
Terebic acid
606, 607
Terpenes
568, 572
Terpenes, constitution of
Terpenylic acid
569, 570
607
569,
570
573-588
575
Tetrahydrocymenes
Tetraniethylene diamine
591
Theobroinine
Thiourea
Toxines
Trichloropurine
588
Triinethylanrine
590
Trimethylsuccinic acid
Trimethylxanthine
Trioxypurine
Turpentine
582
593, 598
593
567
602, 605, 614
Tyrosine
578
610, 611
/3-Uramidocrotonic acid
596
614
Urea
597
614
Urea, biuret test for
Ureids
594
Uric acid
592, 593, 594, 595
Uric acid, constitution of. 593, 594, 595
594-597
Uric acid, synthesis of
587, 588
.567
Vanillin
Salicin
Saligenin
Sarcosine
566
566
Wood-gum
565
Sarcosine nitrate
Semicarbazide
601
Xanthine
600
Xanthoprotei'c reaction
614
Semicarbazones
601
Sesquiterpenes
578
Xylan
Xylose
565
565
THE END.
Edinburgh
& R. Chambers, Limited.
:
Printed by
W.
UNIVERSITY OF TORONTO
LIBRARY