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Note on the Constitution of Diparabromben-Zylcyanamide Author(s): C. Loring Jackson and R. W. Fuller Reviewed

Note on the Constitution of Diparabromben-Zylcyanamide Author(s): C. Loring Jackson and R. W. Fuller Reviewed work(s):

Source: Proceedings of the American Academy of Arts and Sciences, Vol. 35, No. 11 (Dec.,

1899), pp. 231-236 Published by: American Academy of Arts & Sciences

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CONTRIBUTIONS

FROM THE

CHEMICAL

LABORATORY

OF HARVARD

COLLEGE.

NOTE

ON

THE

CONSTITUTION OF DIPARABROMBEN

ZYLCYANAMJDE.

By

C.

Lorlng

Received November

Jackson

24,1899.

and

Presented

R.

W.

December

Fuller.

13,1899.

The

silver

of

the

work

salt

of

described

cyanamide

of

in

into

this

this

a

body.

paper

consists

of

the

and

conversion

the

this

of

determination

work

the

was

dialkylcyanamide,

Last

" Berichte

of

constitution

a

paper

obtained

For

we

fear

shall

alkyl

this

summer

der

a

of

the

of

(after

deutschen

number

cyanogen

field

thus

finished)

Gesellschaft,"

in

appeared

which

by

in

Wallach*

the

the

action

of

approaching

abandon

the

compounds

Laboratory;

chemischen

of

substituted

on

secondary

reserved

by

but

will

substance

be

is

described

bromide

near

too

study

cyanamides

amines.

Wallach

further

dialkylcyanamides,

and dicyanimide

latter

the study of

taken

up

in

of

in

dicyandiamide

fact

work

on

this

already

in

progress.

Theoretically

a

cyanamide

might

dialkylcyanamide

have

either

of

the

derived

following

from

the

formulas

silver

salt

R-N=C=N-R

of

or

R2=N-CN,

formulas

this

and

is

has

it

is

easy

to determine

by

So

far

as

we

can

tried;

this

was

published

who

prepared

cyanamide

ether,

and

the

point

of

experiment

find,

but

which

a

single

of

these

two

of

and

ethyl

was

correct.

been

experiment

by

Fileti

of

product

was

sort

some

years

ago

by

hours.

portions

Cloez

and

cyanamide,

Robert

iodide

extracted

and

gave

prepared'it

point

Schiff,f

on

of

argentic

with

a

boiling

by

190?.

diethyl cyan amide

100?

for

into

whereas

some

two

of

ethyl

the action

;

The

one

10.11

a

at

divided

186?,

distilled,

t who

boiling

Cannizzaro,

found

decomposition

Fileti and R. Schiff analyzed their distillate, and ob

instead of 10.30.

tained carbon 60.66

instead of 61.22

and hydrogen

* Ber.

t Id.,

X Ann.

d.

X.

chem.

425

Ges.,

>(1877).

Chem.,

XC.

XXXII.

95.

1872.

232 PROCEEDINGSOF THE AMERICAN ACADEMY.

The

other

decomposed

chlorides

converted

obtained

portion

of

their product

by

means

of

hydrochloric

obtained

into

by

chlorplatinates

evaporating

two

end

fractions

in

and

which

the

following

results:

?

(which

acid

had

on

the

hydrochloric

crystallized

the

platinum

not

the

been

water

acid

distilled)

bath;

solution

fractionally,

was

when

determined

was

the

were

they

with

Platinum

44.04

*

I.

42.51

Found.

(NH4)2PtCl6 II.

36.3

((C2H5)2NH2)2PtCl6

35.30*

(C2H5NH3)2PtCl6

In

considering

requires

these

results

39.24

of

* per cent

Fileti

and

R.

of platinum.

Schiff,

it

is

to

be

observed

that

terion

the

of

diethylcyanamide

was

purity

given

was

not

(Wallach

purified,

states

and

that

that

no

these

very

sharp

substances

cri

are

decomposed

point

the

It

obtained

yield

We

 

by

distillation

under

ordinary

pressure,

so

that

the

boiling

of much

value

in

this

respect),

further

that

their

analyses

 

salts

did

not

give

numbers

 

very

near

to

those

calculated.

to

us,

therefore,

wrorth

while

to

try

similar

experiments

with,

a

crystalline

disubstituted

cyanamide,

 

which

could

therefore

in

a

state

of

undoubted

purity,

 

and

also

with

one

which

amines

more

easily

separated

than

ammonia

and

diethyl

selected

for

this

purpose

the

diparabrombenzylcyanamide,

the

the

parabrombenzyl

diparabrombenzylamine,

compounds

if

show

formed,

a great

could

tendency

to

be

b e r e c o g n i z e d

recognized

crystallize,

by

is not

platinum

seemed

if possible,

be

would

amine.

since

and

melting

zylamine,

point,

if

melting

from

point,

ammonia.

50?

that

and

(dibenzylamine

were

both

the

these

product,

amines

is

a

liquid),

gives

could

a

be

while

carbonate

separated

the

parabromben

a

with

definite

without

difficulty

of

its

The

diparabrombenzylcyanamide

melting

at

133?.

diparabrombenzylamine,

reaction

?

:

On

decomposition

ammonia,

proved

with

to

be

dilute

and

carbonic

a well

crystallized

sulphuric

dioxide

by

acid

the

it

solid,

gave

following

(C6H4BrCH2)2NCN

+

2H20

=

(C6H4BrCH2)2NH

+ NH3

+ C02.

Our

no

amides

doubt

ment

of

results,

that

and

the

therefore,

confirm

those

of

Fileti

and

R.

Schiff,

the

not

silver

dialkyl

derivatives

carbodiimides.

from

argentic

If

they

are

formed

cyanamide

by

direct

in

argentic

cyanamide

by

the

alkyl

radicals,

*

what

These

altered

are

by

the

using

numbers

modern

given

by

atomic

Fileti

weights.

and

R.

Schiff.

They

would

and

are

leave

cyan

replace

the

be

same

some

JACKSON

constitution

amide.

additions

disubstituted

carbodiimide

If,

of

AND

(Ag2NCN)

FULLER.

must

on

the

other

hand,

the

alkyl

cyanamides

formula,

bromide

as

could

is

shown

?

DIPARABROMBENZYLCYANAMIDE.

be

ascribed

to

these

with

be

compounds

splitting

formed

this

off

are

of

from

by

the

following

substance

formed

argentic

silver

reactions:

a

233

and

to

cyan

by

successive

bromide,

the

salt

?

with

a

*

C

^

//

C

NAg

+RBr=C

NAg

NR

+ RBr

NAg

=

Br

\ /

^

Br

\ /

C

R

NAg

=AgBr+C

NAg

R

NR

=

/

C

NAg

NR2

N

NR

//

^

NAg

+ AgBr.

Our

results,

therefore,

prove

cyanamide.

 
 

Preparation

of

nothing

in

regard

to

Diparabrombenzylcyanamide,

(C6H4BrCH2)2NCN.

the

true

formula

of

The

Walther,#

yellow

was

in

the

proportion

which

with

the

a

full

replaced

tate

the

was

filtrate

oil

yellow

be

yellow

by

the

then

and

was

the

strong

at

first

pouring

appear.

the

dried

silver

salt

of

with

two

cyanamide,

a

benzol

molecules

Ag2NCN,

solution

of

of

the

mixture

until

prepared

according

to

mixed

of

finely

color

yellowish

filtered

washings

left.

parabrombenzylbromide

to

one

heated

four

or

of

in

five

the

a

salt,

flask

hours

been

hot

completely

The

precipi

benzol,

and

in

a

hot

thick

reddish

alcohol,

and

oil

was

deposited

was

obtained

crystals

melting-point

began

constant.

It

by

to

of

was

?

bromide

was

after

had

bromide.

with

when

dissolved

yellow

which

as

sort

the

the

remained

results:

should

return-condenser

powdered.

of

on

the

The

steam-bath,

out

the

white

and

argentic

color

washed

of

evaporated

purify

to

this

cool

crystalline

from

the

it

to

was

slowly;

a

oil

where

substance,

soon

this

it

as

of

the

following

cyanamide

argentic

thoroughly

dryness,

To

allowed

a white

off

raised

analyzed

solution

by

solution

repeated

was

and

followed

the

By

recrystallizations

to

133?,

with

substance

in

vacuo

*

Journ.

prakt.

Chem.,

1896,

510.

234 PROCEEDINGS

OF

THE

AMERICAN

ACADEMY.

 

I. 0.1508

gram

of

the substance gave

by

the method

of Carius

0.1494

 

gram

of

argentic

bromide.

 

II.

0.3041

 

gram

of

the

substance

 

gave

20.2

cc.

of

nitrogen

at

a

tem

 

perature

of

18?.6

and

a

pressure

of

760.4

mm.

 

Calculated for

 

Found.

(C7H6Br)2NCN

II. I.

 

Bromine

 

42.11

 

42.18

 

Nitrogen

7.377.64

 

In

view

of

the

great

tendency

 

of

cyanamides

to

polymerize,

it

was

 

*

thought

safer

to

determine

the

molecular

weight

of

the

body

by

 

the

method

of

freezing

a benzol

solution,

which

gave

the

following

results

?

:

0.375

gram

of

the

substance

dissolved

in

16.25

grams

of

benzol

produced

 

a

depression

 

of

0?.28

in

the

freezing

point.

 
 

Calculated

for (C7H6Br)2NCN.

 

Found.

 
 

Molecular

weight

 

337380

There

can

be

no

doubt,

therefore,

that

the

substance

is

really

(C6H4BrCH2)2NCN.

 
 

Properties

of

Diparabrombenzylcyanamide.

 

The

substance

crystallizes

 

from

benzol

in

sheaves

of

white

crystals

 

shaped

like

the

blade

of

a

lancet,

sometimes

united

laterally

 

into

groups

with

comb

ends.

It

melts

at

133?.

It

is

freely

soluble

in

benzol,

chlo

roform,

acetone,

or

acetic

ester;

soluble

in

toluol;

slightly

soluble

in

cold

ethyl

or

methyl

alcohol

or

glacial

acetic

acid,

freely

soluble

in

these

solvents

when

they

are

hot;

slightly

soluble

in

ether,

carbonic

disulphide,

 

or

in

hot

or

cold

water;

essentially

insoluble

in

ligroine.

 

It

is

slowly

decomposed

by

cold

strong

sulphuric

 

acid;

apparently

unaffected

 

by

hydrochloric

acid

or

nitric

acid

in

the

cold.

The

best

solvent

for

it

is

hot

alcohol.

 

In

order

to

see

if

it

could

form

a

chloride,

a

portion

 

of

the

dipara

 

brombenzylcyanamide

 

was

dissolved

in

anhydrous

benzol

and

saturated

with

dry

hydrochloric

acid

gas.

No

precipitate

was

formed

even

after

the

mixture

 

had

stood

for

two

weeks,

and

on

evaporating

 

off

the

benzol

the

original

substance

was

recovered

unaltered.

It

would

seem

from

this

experiment

 

that

the

diparabrombenzylcyanamide

cannot

unite

with

hydrochloric

 

acid.

 

*

This

work

was

done

before

the

appearance

of Wallach's

 

statement

that

di

substituted

cyanamides

show

no

tendency

to polymerize.

 

JACKSON

AND

FULLER.

?

DIPARABROMBENZYLCYANAMIDE.

235

A

of

sic

in

weeks

number

the

hydrate

the

cold

with

from

of

experiments

were

tried

A

the

hydrate,

only

in

the

dilute

hope

of

solution

obtaining

of

by

was

taken

was

polymeres

or

potas

standing

for

replace

two

the

the

color

diparabrombenzylcyanamide.

produced

or

a

by

solution

boiling

no

of

which

escaped,

white

to

point

alone

pale

of

was

effect

the

ammonic

but

the

brown,

the

also

sodic

long

boiled

to

that

on

mixture.

substance,

The

care

either

the

substance

being

observed

to

due

cyanamide

boiling

ammonia

turned

since

tered.

the

change

evidently

a

slight

decomposition,

 

was

essentially

unal

point,

but

produced

no

melting

Water

substituted

tried

at

change.

unaltered

Upon

to

temperatures

not

tained

cases

a

bring

into

when

it

seemed

polymerization,

that

Wallach

heating

160?

the

substance

this

point

for

cooling

analysis.

was

a

above

it

its melting

first

point

it

remained

at

we

; above

red,

and

on

a

the

fit

state

substauce

evident

these

and

that

our

turned

an

A

with

oily

similar

sodic

had

therefore,

no

yellow,

and

which

product

higher

was

could

ob

these

than

of

gave

product,

viscous

acetate.

taken

confirm

tendency

heated

In

place

the

both

rather

statement

to

polymerize.

decomposition

show

experiments,

dialkylcyanamides

Decomposition

of

Diparabrombenzylcyanamide.

As

amide

some

was

preliminary

decomposed

experiments

with

difficulty

showed

that

by

hydrochloric

the

acid

substituted

in

open

cyan

vessels,

we

which

adopted

has

of

acid

in

a

dilute

sulphuric

frequently

given

good

the

diparabrombenzylcyanamide

with

in

a flask

a

the

hot

acid

an

given

oily

which

cooling,

off

with

drops

did

reduced

whole

the

precipitate;

and

the

isolate

portion

which

solidified

boiling

To

washed

obtain

with

in

dissolved

acid

having

a

specific

results

in

were

was

this

gravity

of

1.44,

Laboratory.

boiled

Soon

with

after

a

the

observed,

to

be

was

and

upon

carbonic

continued

did

a

not

entirely

voluminous

white

to

stop

could

acid.

consist

the

process

be

easily

This

of

quantity

;

its

of

amount

filtered

it

from

the

adhering

few

black

then

filtered,

Several

excess

grams

of

melted

large

this

gas

the

return-condenser.

on

effervescence

water,

of

it

the

oil,

filled

therefore,

hot

seemed

a

substance

testing

dioxide.

for

remove

at

ten

it.

crys

this

separated

latter

sub

crystalline

insignifi

and

the

acid,

lumps

the

acid

and

of

sul

the

As

hours,

On

talline

point

from

stance

baryta

proved

heating

but

with

which

sulphuric

to

fresh

acid

it

was

free

behind

was

not

the

disappear,

amount

became

liquid

we

this

undissolved

determined,

in

crystalline

cooling,

as

again

with

the

a

hot

crystalline

little

cold

water,

cyanamide.

substance,

the

undecomposed

the

was

from

diparabrombenzylcyanamide,

product

cant.

on

it gave

sulphuric

product

water

which

The

left

solution

to

liquid,

then

undecomposed

236 PROCEEDINGS

phate

which

base,

decomposed

set

after

free

the

purification

by

the

base

by

as

OF

THE

addition

of

AMERICAN

AMERICAN

a

strong

ACADEMY.

solution

of

sodic

a

pasty

mass

crystallization

solidifying

from

alcohol,

on

cooling.

showed

hydrate,

the

This

con

*

stant

melting

point

50?,

which

is

that

of

the

diparabrombenzylamine

 

(C6H4BrCH2)2NH.

 

For

greater

 

security

the

chlorplatinate

 

was

pre

pared

and

analyzed.

Chlorplatinic