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THE

SYNTHETIC USE OF METALS

IN

OKGANIC CHEMISTEY

ARTHUR

J.

HALE,

B.SC.(LOND.),

A.I.O.

FELLOW OF THE OHKMIOAL SOOU'lTY; LHOTURKK, A.TST)

IN CHicariaTRy AT THK crr Y AND aviu)H

COLLKGK,

l^INHBUltY,

LONDON

TKOiiwroA.L

LONDON

J .

&

A.

CHURCHIL L

7, aREA.T MARLBOKOUO-H

STEEET

l-0

5

/*""

V

LIBRARY

PKEFACE

THE student of Organic Chemistry will probably be impressed at an early stage with the importance of metallic sodium and its compounds in synthetic work, and will subsequently mark the value of such substances as acetoacetic-, malonic-, and cyanacetic- ester and their sodium compounds. He will notice the use of aluminium chloride in the preparation of various aromatic compounds, will hear the story of the discovery of the zinc alkyls, and will possibly be attracted by those interesting bodies, the organo-rnetals. Various metals arid metallic, derivatives have been utilised in the development of Organic Chemistry, and during recent years, much attention has been given to the use of magnesium in the Grrignard reaction and to the value of the carbides in the fixation of atmospheric nitrogen, while the reduction and synthesis of organic compounds in tlio presence of reduced nickel and other metals has, by develop- ment, led to the discovery of numerous catalytic changes in the presence of certain metallic oxides.

VI

PREFACE

In this volume an attempt has been made to present an account of the uses to which the metals and certain of their compounds have Tbeen put, and the work is based upon a course of lectures, on this subject, recently given by the author to the advanced students of Finsbury Technical College. Each chapter is supplemented by an appendix of practical work exemplifying the methods mentioned in the text. Most of the preparations have been carried out in the College laboratories, and in connection with fthis part of the work the author desires to acknowledge the valuable assistance of two advanced students, Messrs. T. McLachlan and E. Mendoza. He is also indebted to Mr. F. W. Streatfeild, F.LC., Senior Demonstrator, for help during the reading of the proofs.

LONDON;

February, 1914.

A. J.

H.

CONTENT^

CHAPTER

I.

SODIUM AND POTASSIUM.

Synthetic Use of the Metals—Sodium ethylate—Sodamide —Sodium hydroxide—Potassium cyanide—Potassium "bisulphate—Potassium hydroxide —Potassium nitrate —Potassium and sodium disulphates

1

 

CHAPTER

II.

COPPER AND SILVHXt.

 

Use of the

Metals—Copper

acetylene

derivatives—Silver

cyanide—Silver hydroxide

 

35

 

CHAPTER

III.

MAG-NESIUM, CALCIUM AND BARIUM.

Applications of the Grignard reagent—Carbides of Calcium and Barium—Nitrogen fixation—Calcium and Mag- nesium nitrides—Hydroxides of the metals . 42

Metallic

Zinc—Zinc

mercury

CHAPTER

IV.

ZINO AND MERCURY.

chloride—Mercuric

oxide—Metallic

^

V1U

CONTENTS

CHAPTER

V.

ALUMINIUM, TIN AND LEAD.

PAGE

Aluminium chloride—Aluminium-mercury couple—Tin and lead organo-metallie compounds—Tin tetrachloride— Lead oxide—Antimony and the chlorides of antimony— Vanadium pentoxidc

11

CHAPTER

VI.

IRON, NICKEL

AND PLATINUM.

Ferrous sulphate—Ferrous potassium oxalate—Iron and ferric chloride—Reduction by reduced iron, nickel or cobalt

88

APPENDIX

I.

PRACTICAL WORK:

SODIUM—POTASSIUM.

Ethyl benzene—Anisole—Benzoic anhydride—Hexamethy- lene—Trimethylene dicarboxylic acid—Chlorof ormic ester—Carbonyl chloride—• Ethyl benzoate—Toluic ethyl ester—Aeetoacetic ester—Ethyl acetoacotic ethyl ester —Aceto-succinic ester—Malonic ester—Ethyl malonic ester—Diaceto-succinic ester—Ethane tetra-carboxylic ester —Acetyl-acetoacetic ester—Antipy rine—Methyl succinic ester—Succino-succinic ester—Tin tetraphenyl —Lead tetraphenyl—Mercury diphenyl—Silicon tetra- phenyl—Oxalyl-acetic ester—Hydroxy-methylene cam- phor—Acetyl-acetophenone—Ethyl acetophenone—Fur- furol acrolein—Cinnamyl-vinyl-methyl ketone—Acetic anhydride — Benzoin — Desyl-acetophenone — Phonan- throxylene-acetoacetic ester

104

APPENDIX

II.

PRACTICAL WORK :

COPP1R—SILVER.

Acrolein—Acrylic

acid

acid—Di-o-nitro-

phenyl-diacetylene — o-Chlor -toluene — o-Chlor-benzoio

—Carbazole—o-Nitrophenyl-propiolic

acid—/3-Iodopropionic

acid—Adipic

CONTENTS

IX

APPENDIX III.

PRACTICAL

WORK:

MAGNESIUM—CALCIUM.

Benzoic acid—Phenyl-ethyl-carbinol—Trimethyl carbinol— Triphenyl carbinol—Camphoric anhydride—Homo-cam- phoric acid—Camphor—Pentamethylene—Cyanamide .

APPENDIX

IV.

PRACTICAL

WORK :

ZINC—MERCURY.

Citric acid—Use of Zinc alkyl iodide—Naphthalene—Iso-

quinoline—ITuorescein—Malachite

a-Methyl-indole—Propyl chloride—a-Ethoxy-quinoline —Phthalic acid

green—Acridine—

APPENDIX

V.

PRACTICAL

WORK:

ALUMINIUM—TIN—LEAD.

Dimethyl-aniline-phosphor-chloride — jp-Tolxiic-aldehyde — Diphenyl-methane—a-Hydrindone—Triphenyl-methane —Acetophenone—o-Benzoyl-benzoic acid—Anthraqui-

anisole—Toluene—Diphenyl—

none —Hydrolysis

Oxalic acid

of

APPENDIX

VI.

PRACTICAL

WORK:

IRON—NICKEL.

o-Amino-benzaldehyde—o-Amino-cinnamic

acid—Mannose

PAGK

137

144

153

—Hexahydrobenzene—Hexahydrophenol

.

.

.16 2

INDEX

167

ABBREVIATIONS

USED

IN

THE

BIBLIOGRAPHY.

Ann.

=

«

=

Liebig*s Annalen der Chemie.

Ann. Ch. Phys.

Annales de Chimie et de Physique.

Ber.

Berichte der deutsohen chemischen

Bull. Soc. chim.

=

=

=

~

G-esellschaft. Bulletin de la Soci6t6 chimique de Paris.

Chein. Centr.

Chemisches Centralblatt.

Chem. Zeit.

Chemiker-Zeitung.

Compt. rend.

Comptes

rendus

de

TAcad&nie

des

Sciences.

 

D.R.P.

German Patent.

J.

Am. Chem. Soc

~

Journal

of

the

American

Chemical

Society.

 

J.

Soc. Chem. Ind.

=

Journal

of

the

Society

of

Chemical

Industry.

 

J.

prakt. Chem.

=

Journal fur praktische Chemie.

Monats.

=

=

«

Monatshefte fur Chemie.

Phil. Trans.

Philosophical Transactions.

Proc.

Proceedings of the Chemical Sooiety.

Rec. Trav. Chim.

Recueil des travaux chimiques des Payw- Bas.

= Zeit. ang-ew. Chem. =

Trans.

Transactions of the Chemical Society. Zeitschrift fur angewandte Chemie.

Zeit. phys. Chem.

»

Zeitschrift fur physikalische Cheniie.

THE

SYNTHETIC

IN

ORGANIC

USE OF METALS CHEMISTRY

CHAPTER* I

SODIUM

AND

POTASSIUM

ALMOST the first metal to Tbe used for organic synthesis, sodium continues to hold a foremost posi- tion among all the metals utilised as synthetic agents in organic chemistry. Although potassium was the first used, being applied by Frankland and Kolbe in 1848 to the preparation of hydrocarbons by heat- ing the metal with alkyl nitriles^ yet sodium has always received a far wider application. Twenty- three parts by weight of sodium suffice to bring about a chemical change which would require tho use of thirty-nine parts of potassium^ and thin fact, together with the lower price of sodium, gives tho metal an economic advantage. Another reason for the priority of tins metal is that in many cases the more electro-positive and moro chemically active potassium proves to be too violent

2 SYNTHETIC

USE

OF

METALS

in its action, and renders the control of the reaction difficult. After the investigation of Frankland and Kolbe mentioned above, Frankland in the following year heated metallic zinc with alkyl iodides, and besides preparing paraffin hydrocarbons in this way, he also discovered the zinc alkyl s, the first of the organo-metallic compounds. In 1850, Williamson prepared certain ethers by the interaction of alkyl iodides and sodium ethoxide, a method of preparation which rendered evident the constitution of these bodies :

1

C 2 H 5 I + C 2 H 6 O]Sra

=

]STaI + C 2 H 5 .O.C 2 H 5 .

In 1855, Wurtz emphasised the importance of

sodium for preparing the paraffin hydrocarbons, and prepared di-isobutyl, by the action of the metal

upon isobutyl iodide

3

:

2(CH a ) 2 CH.CH 2 I + 2Na -

(CH 3 ) 2 CH.CHo.CH 2 .CH(CH 3 ) 3 + 2NaI.

A few years later, Fittig applied this reaction to the synthesis of aromatic hydrocarbons by condensing aryl and alkyl radicles. The following reactions will indicate the usefulness of this method 8 :

C 6 H 6 Br

+

Brombenzene.

C B H 4 Br 2

Dibrom-benzene.

+

CH 3 Br Methyl bromide. 2C 2 H fi I + 4Na Ethyl iodide.

+

2Na

-

C 6 H B *CH 3 + 2NaBr.

Methyl benzene (toluene). C 6 H 4 (C a H 6 ) a + 2NaI + 2NaBr Diethyl-benssene.

=

the

benzene

nucleus. After 1850, various compounds were prepared by

positions occupied by the halogens in the

In these changes the alkyl groups take up

SODIUM

AND POTARBIUM

3

the agency of sodium and potassium, and tin* follow- ing are examples of some of the bent known reactioiiH of this class:

Phenol and other formation :

CflHftONn

+ Oir,I

Sodium phonate,

«

(yr fi .O.0H 3

+ Nal

AtitHolo (methyl phonyl othor).

The samo exchango is offoctod

by lining an alkyl

sulphate or an alkyl liydrogon nulphato :

CaH 4 OK

+

O a ir B nS0 4

-

Ethyl hydrogon

sulphate.

2C 2 II 5 OK + (Cir 8 ),so 4

«

Methyl Htilphato.

CaUft.O.O.jlT, + KHHO,

2cyr & .o.air 3 + K a so 4

Ethyl mothyl othor.

The

following

aro

chai*actoriHtic

alkyl potassium sulphates:

When

hoatod alone tht^y yield OI

C a ri 6 KSO 4

«

iUU

roacjtionn

of

When boiled with water tjuvy yit^ld alcohols:

O a II ft KS() 4

•»• II a O

'

cyiftO H

-i- KUBO 4 .

When treated with KI, KCJN, K 2 H, KHH, thisy yield alkyl iodidos, nitriloH, thio-others and mor- captans respectively:

RKSO 4 + icr

^

m + K a so 4

RKHO 4

2KKS<) 4 +

KKBO 4 + KSII « K.H.II. + K 9 H() 4 .

ak 3 HO 4

*.

+ KXIN

IC,8

IU1N

i

K

K.H.R +

S()

4

™.

When heated with the alkali salfcH of organic ncidH, esters are obtained ;

RKSO 4 +

OH 8 OO()K

s

Cir s COOR

+ K.HO,

KKSO 4 + OflllflCOO^a

 

-

fl ir

*

Sodium bonzoato.

4 SYNTHETIC

USB

OF METALS

Acid anhydrides are produced by distilling a mixture of the acid chloride with an alkali salt of the acid :

CH 3 COC1

+

CH 3 COONa

=

(CH 3 CO)X>

+

NaCl

Acetyl chloride.

Acetic anhydride.

C 6 H 5 COC1 +

C 6 H 5 COOK

-

(C C H 5 CO) 2 O

+ KC1

Benzoyl chloride.

Benzoic anhydride.

 

Numerous hydrocarbons can be prepared by the action of sodium upon halogen substitution products. In addition to those already mentioned, un- saturated hydrocarbons can.be synthesised in this way:

2CH 2 : CH.CH 2 I + 2Na Allyl iodide. 2CH 2 : CHBr + 2Na Vinyl bromide.

«

CH 2 : CH.CH 2 .CH 2 .CH: CH 2 + 2NaI Diallyl.

=

CH-: CH.CH: OIL Divinyl.

+ 2NaBr

Sodium has played an important role in the pre- paration of many polymethylene hydrocarbons and their derivatives. The first member of this series of hydrocarbons

was prepared by Freund (1882), by allowing sodium

to act upon trimethylene bromide

4

:

yCH 2 Br CH / \CH 2 Br

+ 2Na

==

y CIL

I

"\CH 3

Oil /

" + 2NaBr.

The same method was used in 1888, for preparing methyl tetra-methylene from 1 : 4-dibrompentane

5

:

CH 3 .CHBr.CHo.CH fl .CH 2 Br

+ 2Na

»

CH 3 .CH. . CH C 2

2

I

I

| CH 2 .CH .CH

2

2

+ + 2NaBr,

and again in 1894 for preparing hexamethylene from the corresponding dibromide :

SODIUM

AND

CH 3 .CH 2 .CH 2 Br

|

+ 2Na

-

OH 2 .CH 2 .CH 2 Br

POTASSIUM

CH 2 .CH 2 .CH S

| OH 2 .CH 2 .OH 2 Cyclohexane.

|

+

2NaBr.

0

Many polymethylene carboxylic acids can bo pro- pared by the aid of di-sodium malonato :

CIl.Br

/COOC.JIs

CHa\

/COOOIIj

+ 2NaBr

OH 2 Br

\COOCaH 6

0H 2 /

\CO0C a H s

Triinetliylene dicarboxylic oatoir.

The condensation product when hydrolysod givon the corresponding acid and the latter on heating, passes to a monocarboxyl compound :

CHo\ | CH 2 /

"

yCOOH

N C X

\COOH

Heat

->

CPL>\

N

CH.CO0H -i- COo. CIL/

|

"

Similar compounds are formed by using triinothy- lene dibromide and pentamethyleiio dibromido. Numerous acids may bo prepared by tlio action of carbon dioxido upon aromatic halogen compounds, in the presence of sodium. This method was first used by Kekule iu 186(3 for preparing benzoic and toluic acids from brombonzouo and bromtoluene:

0

CoHfiBr + CO 3 + 2Na /OH 3

C 6 H 4 < x B r

+

COo + 2N a

== C (5 H ft COONa + NaBr .CH,

=

C () II 4 < XiOONa

+

NaBv.

Magnesium is now used instead of aodium for this type of reaction (see later). Wurtz, by the aid of chloroformic oalor, prepared the corresponding esters of these itcids:

C 6 H 5 Br + 2N"a + CICOOC-H5

«

0^.0000 ^

-I- NaCl + Kalir.

6 SYNTHETIC

TTSJE OF

METALS

USES

OF

ACETO-ACETIC

ESTEB.

This useful reagent was discovered by G-euther in 1863, who pi*epared it by the action of sodium upon ethyl acetate. About the same time Frankland and Duppa, using the same reaction, discovered that the hydrogen atoms of the raethylene group are replaceable by sodium and various organic radicles. G-euther represented the substance as OH 3 .C(OH)

: CH.COOC 2 H 6 , that is /3-hydroxycrotonic ester, but

Frankland and Duppa preferred the keto formula OHg.CO.OHg.OOOOgHg, and represented it as aceto- acetic ester. 7 The formation of the substance may be represented thus:

CH 3 .COOC 2 H 5 + CH 3 .COOC 2 H 5 = CH 3 .CO.CH 2 .COOC 3 H 6 + OftOH.a

Wislicenus had by 1877, investigated the substance and shown that other substances contained methy- lene groups, the hydrogen of which could be replaced by sodium. 9 A few years later, Conrad showed that an alcoholic solution of sodium ethoxide would suffice, in place of metallic sodium or the dry ethoxide, for this type of reaction; he applied his method in particular to the preparation of alkyl malonic esters. 10 Not only does condensation take place between two molecules of an ester such as acetic ester, but also be- tween an ester and a ketone. Acetyl acetone can be prepared, for example, from acetic ester and acetone :

OH 3 .COOC 2 H 5 + CH 3 .CO.CH 3 « CH 3 .CO.CH 2 .CO.CH 3 + C 2 H 5 OH.

same

type of

Propionic

and

butyric

esters

undergo

the

condensation:

SODIUM AND POTASSIUM

7

2CH 3 .CH 2 .COOC 2 H 5 «

CH 3 .CH 2 .CO.CH.COOC 2 H 6 + C 2 H 6 OH

2C,H B .CH a .COOC 3 H s

CH 3 Propio-propionic ester. == C,H fi .CH a .CO.CH.CO0C a H 5

+

GftO H

C 2 H 5 Butyrobutyric ester.

Iii both cases the carboxyl group of one molecule of the ester attaches itself to the a-carbon atom of the other. The yields in both cases are lower than that obtained with acetic ester, which is about 25 per cent, of that calculated. Isobutyric and isovaleric esters were found by

Hantzsch

The compound which might be expected when using isobutyric ester could not be isolated, and was apparently reduced by the sodium present to eth- oxycaprylic ester, while simultaneously some of it becamo hydroiysed to hydroxycaprylic acid thus :

11

to follow a different course.

(CH a ) 2 CH.C(OH)(OC 2 H 6 ).C(CH 3 ) 2 .COOC 2 H s Not isolated.

Partly reduced to

(CH 3 ) 2 CH.CH.(OC 2 H 6 ).C(CH 3 ) l ,COOC 2 H 6 Etlioxycaprylic ester.

Partly hydroiysed to .

.

(CH 3 ) 2 CH.CH(OH).C(CH 8 ) 2 .COOH Hydroxycaprylic acid.

Similar changes occurred when using isovaleric ester and are represented by the following equations :

2(CH 3 ) 2 CH.CH 2 .COOC 2 H 5

- •

(CH 3 ) 2 CH.CH.vC(OH)

(OC 2 H 6 ).CH.C 3 H 7 .COOR

Not isolated. (CXr 3 ) 2 CH.CHo.CH(OC 2 H 6 ).CH.C 3 H 7 .COOCoH 5

Ethoxycapvic ester.

(CH 8 ) 2 CH.CH 2 .CH(OH).CH.C 3 H 7 .COOH

Hydroxycapric acid.

Acetoacetic ester was the first of those compounds

to

be

studied, which contain

the grouping—00 —

8 SYNTHETIC

USE

OF

METALS

CH 2 —CO— , the hydrogen of the methylene group (CH 2 ) being replaceable, entirely or in part, by sodium. Around its constitution and principal re- actions much controversy was destined to take place, and even now the last word has not been heard con- cerning this important and interesting substance. Geuther, endeavouring to show that a second hydrogen atom of acetic acid could be replaced by sodium, caused the metal to act upon acetic ester. Hydrogen was evolved, sodium ethoxide was formed, and a solid sodium compound was isolated, having the composition C 0 H 9 O 3 Na, which on acidifying yielded an oil capable of forming salts with bases. Geuther also proved that by the action of alkyl iodides the sodium was replaced by alky], and this fact was con- firmed shortly after by Frankland and Duppa. Wislicenus next showed that the product under discussion was acetoacetic ester and that two hydrogen atoms were replaceable by sodium in two stages. He represented the reactions in the following manner, adopting the formula of Frankland:

(i) CH a .CO.CHNa.COOC a H 8

+

CHs.CO.CH(C 2 H 6 ).COOC 2 H 6

C 3 H 6 I

+

Na l

-

(ii)

CH 8 .CO.CNa(C 2 H 6 ).COOC 2 H 5

+

C 2 H 5 I

=

CH 8 .CO.C(C 2 H 5 ) 2 .COOC 2 H 5

+

Na l

Geuther ascribed the enolic or hydroxylic formula CH 3 .C(OH):OH.COOC 2 H 6 to the substance, main- taining that it explained better its chemical nature. 12 Claisen was the first to propose an important ex- planation of its mode of formation, and offered a view which is still regarded with favour. 13 This view is, that the condensation of acetic ester, and other con-

SODIUM AND POTASSIUM

9

densations of this type, take place through the formation and subsequent decomposition of an inter- mediate addition compound, in the formation of which sodium ethylato plays an important role. The stages of the reaction may therefore be represented thus:

.ONa CH 3 .COOCJS fi + C a H 6 ONa = CU 3 .C-OC a H fi (Intoraodiato com-

CH 3 .COOC a H B

»

CH 3 .C(ONa): CH.C0O0. 2 H 6 + 2C a H 5 OH. Sodium derivative.

The sodium derivative is decomposed by weak acids yielding acetoacetic ester, for which reason tho derivative is frequently represented with sodium linked to carbon directly and the liberation of tho ester is then represented thus :

CH 3 .CO.CHNa.COOC 2 H 6 + HC1 -

CH :i .CO.CU a .0OOC 3 H b 4- NaCl

The above intermediate compound has not boon isolated; but by tho interaction of bouzoic molhyl- ester and sodium benzylate an analogous compound has been produced and separated.

C 6 H 5 .COOCH 3 + C 0 H 6 .CILONa -

C U H B .C

/

-

Other compounds containing a metliyleno group ; the hydrogen of which is replaceable by sodium aud by alkyl groups, are :

Acetyl acetone Malonic osier Acetone clicarboxylio estor Cyanacotio oster

CH B CO.Cir 3 .OO01I a

0^000.0JJ 3 .COOU s ll fi CoH^OOC.CHa.CO.CH

NC.CIt

COOC

a Ui

Benzyl cyaixido

^ ;

Deoxybenzoin

1 0

SYNTHETIC

USE

OF METALS

A few applications illustrating the value of these

sodium derivatives may now be outlined. The sodium derivative of acetoacetic ester, pre- pared by treating the ester with an alcoholic solution of sodium ethylate, is converted into an alkyl sub- stituted ester by boiling with any alkyl iodide:

CH 3 .CO.CH 2 .COOaH 5 -> CH 3 .CO.CH]Sra.COOC 2 H5 -* CH 3 .CO.CHR.COOC 2 H 6

A second radicle II 1 may be caused to replace the

second hydrogen of the methylene group, by repeat- ing the treatment with sodium ethylate and an alkyl iodide E a I.

CH3.CO.CHRCOOC0H5 -» CH 3 .CO.CNaR.COOC 2 H 5

These substituted esters, like aceto-acetic ester itself, can be hydrolysed in two different ways and thus yield a variety of ketones and acids of the acetic series. 14 Boiling with dilute acid or dilute alkali brings about ketonic hydrolysis chiefly :

R

CH 3 .CO.C.COOC a H 6 + Sift I

= CH3.CO.CHRR 1 + CO 2 + C 2 H 6 OH, Kotone

while boiling with strong alkali favours lysis :

R

acid hydro-

CH 3 .CO.C.COOCoH 5 + 2H 2 O - CH 3 COOH + CHRR^COOII + C 2 H 3 OH.

I

-

Acid

R 1

Malonic ester in particular can be used for pre- paring higher acids of the acetic series by first

SODIUM

AND POTASSIUM

1 1

replacing one or both of the methylene by an alkyl group :

hydrogens

yCOOC H CH 2 ; \COOC 2 H

2

5

5

/COOC 2 H 5 -* CHR X \COOC 2 H

5

or C&R 1

yCOOC 3 H 6

(

\COOC 2 H 5

On hydrolysis these substituted malonic esters give the corresponding acids and the latter on being heated to 200° lose carbon dioxide :

yCOOH

CHEf

\COOH

/COOH

-»B.CH,.CO0H; CKBF "

\COOH

-» ER l CH.COOH

of aceto-acetic ester

on treatment with iodine undergoes condensation to a dibasic ester (diaceto-succinic ester).

The

monosodium derivative

CH 3 .CO.CHNa.COOC,H 5

+

I 2

»

CH.,.CO.CHN*a.COOC 2 H 5

CH 3 .CO.CH.COOC 2 H | CH 3 .CO.CH.COOC 2 H

5

+ 2NaI

6

The mono-sodium compound of malonic ester gives a tetra-carboxylic ester when similarly treated (ethane tetra-carboxylic ester):

C

OC 2 H

OC 3 H

5

6

CH(COOC 2 H 6 ) 2

+

Io ==• | OH(COOC 2 H 6 ) 2

"

+ 2NaI

Acetyl aceto-acetic ester is prepared by the action of acetyl chloride upon the compound 0H s .0O.0H Na.COO0 3 H 5 , and on hydrolysis gives acetic and aceto-acetic acids :

CH3.CO.OH.COOC3HB

I

+ 2H 2 O

=

COCH, CH3.COOH + CH3.C6.CH3.COOH + O 2 H C OH

In a similar manner, by using a-monochloracetone,

the y-diketone, acetonyl acetone, is obtained after

hydrolysis 15 :

1 2

SYNTHETIC USE OF METALS

CH 3 .CO.CHNa.COOCoH (5 + CICH3.CO.CH3 = CH3.CO.CH.COOC3H5 + NaCl

CHa-COCHa

Heating with water at 160° is sufficient to hydro- lyso the substitution compound and eliminate carbon dioxide :

CH3.CO.CH.COOC3II5

cH3.co.CH3

CH3.CO.CH.COOH

CH S .CO.CH 3 "*

CH 3 .CO.CH 3 .CH 2 .CO.CH 3 + CO 3

Acetonyl acetone affords a means of passing tu furf urane, thiophbne, and pyrrol derivatives. Heated with dehydrating agents such as zinc chloride or phosphorus pentoxide, it yields dimethyl furfurane, a change which is sometimes explained by the following steps:

1

6H3.CO.CH3

CH3COCH3

CII:

->

0 H

C /

OH~" >

O

y °

OH : V

.CH a

Heated with phosphorus pentasulphide it yields the corresponding thiophene compound, while the action of alcoholic ammonia solution forms a pyrrol compound:

SB*

CH • C<

-^ x h

'

\QT-J

diniothyl-tliiophene

 

CH : CV.CHJI

CH

* c^

^ *

-Cri^

'

dimothyl-pyrrol

SODIUM

AND POTASSIUM

1 3

The behaviour of sodium ethyl aceto-acetate to- wards chloracetic ester and chloroformic ester respec- tive! j y indicates that the compound exhibits dynamic isomerism because in the first reaction it behaves as though sodium were directly united to carbon, and in the second reaction as though the sodium were united to oxygen :

CH 3 .CO.CHNa.COOG>H 5 + C1CH 2 .COOC 2 H 5 =rCH :} .CO.CH.COOC 2 H 6

CH ? .COOC 2 H 5

Aceto-succinic ester

, CH 3 .C £

OCOOGft

CH 3 .CONa : CH.COOC,H 5 + C1COOC 2 H S =

^CH.COOC 2 H fi /3-carbethoxy-crotonic ester

acetyl-acetone a series of j3- or 1: 3-di-

ketones can be obtained by treating the mono-sodium compound with alkvl iodides :

From

I 3

+ CHJE

=

CH 3 .CO.CH(C2H B ).CO.CH 3 +

Nal

Treatment

of the sodium derivative with iodine

gives tetra-acetyl ethane :

CH 3 .CO.CH.CO.CH 3

CH a .CO.CHNa.CO.CH 3 + * " CH 3 .CO.CH.CO.CH f

CH3.CO.CHNa.CO.CH3

Aceto-acetic ester is technically valuable in the preparation of antipyrine. The ester is first allowed to react with phenyl-hydrazine, and the ring com- pound formed is then convex'ted into antipyrin by inethyl iodide and sodium :

CH 3 .CO.CH 3 .COOC S H 5 +

CflH fi .NH.NH

" CH

f.-

2 ' CO -° CiI15+

2

1 4

The

SYNTHETIC

hydrazone

then

USE

OF METALS

loses C 2 H 5 OH

and

forms

l-phenyl-3-rnethyl pyrazolon :

CH 3 .C : CH.CO

"L-J.Q.B.

which then passes to 1 : 2 : 3-phenyl dimethyl-pyra- zolon. From benzylcyanide and deoxybenzoin alkyl derivatives can be formed by the action of sodium and alkyl halides:

C 6 H 5 .CH 3 .COC fl H 5 -> C C H 5 .CHR.COC G H 6

dimethyl succinic ester will

illustrate the use of cyanacetic ester. 16 The sodium compound is condensed with a-brom- propionic ester to form cyano-methyl succinic ester :

The preparation

of

CN

CHNa + Br.CH

COOC 2 H 5

CH a

COOC 2 H 5

-

CN

CH

CH 3

CH

+

NaBr

COO 2 II fi COOC 2 H 5

This substance is then treated with ISTaOEt and OH3I and the product hydrolysed with loss of carbon dioxide:

CN

CH,

COOC H

-

-

2

5

/inn p TT

COOCjHg

+

Hydrolysis

"*

COOH

6.CH 3

COOC 2 H 5

The

synthesis

of

CH 8 I

«

CN

I

C.CH 8

nC\(

COOCaHa

CH.,

I

CH

COOC 2 H 5

+

Nal

CH 3 CH COOC 2 H 6

-CO 2

~>

CH 3

CH 3

CH

COOC 2 H 5 COOCjHs

CH

S-keto-hexahydrobenzoic

acid

further illustrates the use of cyanacetic ester. 17

SODIUM AND POTASSIUM

1 5

The di-sodium derivative is condensed with /3-iodo- propionic ester to form y-cyanopentane-a-ye-tricar- boxylic ester :

C 2 H 5 OOC.C(CN)NA 2 + 2CH 2 I.CH 2 .COOC 2 H 5 /CI1 2 .CH 2 .COOC 2 II,

= C 2 H 5 OOC.C(CN) \CH 2 .CH 2 .COOC 2 H 5

+ 2TSM

Hydrolysis of this cyano-ester gives pentane-ayc- tricarboxylic acid, which on digestion with acetic anhydride and subsequent distillation yields S-keto- hexahydro-benzoic acid:

,CH 2 .CH 2 .COOH HOOC.CH \CH 2 .CH 2 .COOII

,CH 2 .CH 2 = HOOC.CH \C

Nc O + CO 2 + H 2 O.

Further examples of the synthesis of cyclic com- pounds are :

The formation of butane tetra-carboxylic ester from ethylene dibromide and mono-sodium-malonic ester:

OHjBr

| C!HI 2 Br CH(lSra) (COOC 2 H 5 ) 2 CH 2 .CH(COOC 2 H 5 ) 2

CH 2 .CH(COOC 2 H 6 ) 2

CH(Na) (COOC 2 H 6 ) 2

+

I

=

I

+

2NaBr

When the sodium derivative of butane tetra- carboxylic ester is acted upon by bromine, the result- ing product is tetramethylene-1 : 2-tetracarboxylic ester:

CH 2 .CNa(COOC 2 H 6 ) 2 CH 2 .C(COOC 2 H 5 ) 2

CH 2 .CNa(COOC 2 H 5 ) 2 +

^

"

CH 2 .C(COOC 2 H 5 ) 2

The

use

of

trimethylene

bromide

with

sodium

16

SYNTHETIC

USE OF METALS

malonic

ester

will

make

the

following

reactions

possible:

 

.

CH 2 .CH(COOC 2 H 5 ) 2

y

CH 2 .C(COOC 2 H 5 ) 2

CH 2

- » OHo

J

 

\

CH 2 .CH(COOC 2 H r ,) a

\

CH 2 .C(COOC 2 H 6 ). 2

Pentametliylene-tetracarboxy] ic ester

Using methylene

iodide

instead

of

bromine,

a

cyclohexane-tetracarboxylic ester results:

CH. 2

+

CH a I 2

\cH 2 .CNa(COOC 2 H B ) 2 / CH 2 .C(COOC 2 H 5 ) 2

CH 2 \cH 2 .d(COOC 2 H fi ) 2

Succino-succinic ester

is formed by the

condensa-

tion of succinic ester in the presence of sodium : 1S

C 2 H 6 OOC.CH 2 .CHo.COOC 2 H 5 C 2 H 6 OOC.CH a .CHj.COOC 4 H 5

,

^

C

2 H 5 OOC.CH /

OC

2 \ C O

+

2O,II 5 OH

CH.COO0jH 5

and this on oxidation is converted into 2 : 5-dihydroxy- terephthalic ester:

C-COOC a H 6

HC

II

HO.C

^C.OH

I

CH

/

C--COOC2H5

Succino-succinic ester can also be prepared by the action of sodium upon a-bromaceto-acetic ester.

19

SODIUM AND POTASSIUM

1 7

CH 3 .CO.CHBr.COOCoH

+

C 2 H 5 OOC.CHBi\CO.CH

5

a

 

CO

 

/

\

^

H 2 C

CH.COOC 2 H 6

C 2 H 5 OOC.HC

CH 2

 

CO

When hydrolysed with sodiam hydroxide the ester passes to the corresponding acid ; and this is decom- posed when heated to 200° into £>-diketohexaniethy- lene and carbon dioxide :

CO

CO

H,C

I I

HOOC.HC

v

CH.COOH

CH 2

->

H 2 C

I

H 2 C

CH 2

I

CH 2

v

+ CO 2

The latter substance was used by Baeyer in preparing dihydro-, tetrahydro-, and hexahydro- benzene. Succino-succinic ester was also used by Baeyer for synthesising the terpene hydrocarbon p-men- thadiene. Succino-succinic ester, like phloroglucin, exhibits dynamic isomerism (tautomerism), behaving under some conditions as a keto-body ; and under other conditions as a hydroxylic, or phenolic body having this structure:

20

21

II 2 C

C.OH C.COOC 2 H 6

C.OH

A farther example ol ester and kefcone condenaa-

o

1 8

SYNTHETIC

USB OP METALS

tion is afforded by the syntliesis of acetyl-pyroracemic ester, from acetone and oxalic ester :

CH 3 .CO.CH 3

+

COOC 2 H 5 j

iooc 3 H 5

cc

=

CH 3 .CO.CH 3 .CO.COOC 2 H 5

+

C 3 H 6 OH

By using mesityl oxide and oxalic ester the con- densation product is mesityl-oxide-oxalic ester :

CH 3V >C : CH.CO.CH 3 + I

CK/

COOC 2 H

5

COOC 3 H 5

CH

C

CH 3

3

: CH,CO.CH 2 .CO.COOC 2 H 6 + C 3 H 8 OH

A case of internal condensation similar to that of succinic ester^ is the formation of keto-pentamethy- lene carboxylic ester from 1 : 4-butane dicarboxylic ester:

CH 3 - CH 2 COOC 3 H 5

CH 2 - CH.COOC 2 H 6

 

=

|

NC O

+ C 2 H 5 OH

CH 2 - CH 2 COOC 3 H 5

CH 2 - CH 3

Sometimes condensation products are formed by

the elimination of water.

For example:

C 6 H 6 .CHO + CH 3 .COOC 2 H 6 = C 6 H 5 .CH: CH.C0OC a H 6 + H 2 O

Benzaldehyde

Acetic ester

C6H5.CHO + CH 2

^COOCjjHfi

Cyanacetio ester

»

Cinnamic ester

C 6 H 5 CH : o /

X COOC 3 H 5

+

H8 °

Benzylidene cyanacetic ester

Sodium has been widely used in the synthesis of various organo-metals and organo-metalloids, by causing the halides of the elements to react with organic halogen compounds. The following are ex- amples of this type of reaction : 23

SODIUM AND POTASSIUM

1 9

S21CI4 +

4C 6 H 5 Br

+

8Na

=

Sn(C 6 H 5 ) 4 +

4NaBr + 4Na01

SiCl 4 +

4C 6 H 6 Br

+

8Na

=> Si(C c H 5 ) 4 +

4NaBr + 4NaCl.

Sometimes the sodium alloy of the metal is utilised, as in the preparation of tin, lead, and mercury com- pounds, by means of tin-sodium, lead-sodium, and sodium amalgam respectively : 33

Pb

+ 4Na + 4O 3 H 7 I

=

Pb(C 3 H 7 ) 4 + 4NaI

Sn + 4Na + 4C 6 H 5 Br

=

Sn(C 6 H 6 ) 4 + 4NaBr

It

is advisable

to accelerate these

reactions by

means of a small quantity of acetic ester.

SODIUM BTHYLATE.

The value of this sodium derivative was first extensively illustrated by Claisen. 2 * I t may be used for condensing esters and ketones, and esters by themselves as well as with aldehydes, in much the same manner as sodium itself. Benzoic ester and acetone yield benzoyl-acetone.

C 6 H 5 .COOC 2 H 6 + CH3.CO.CH3 =

C 6 Hfi.CO.CH 2 .CO.CH 3 + C 2 H 6 OH

Sucoinio ester and acetone yield teraconic

ester.

CH 3 .COOC 2 H 5

co+

1

-

(CH 3 ) 2 C: C.COOC 2 H 5

I

+H 2 O

CH 2 .COOC 2 H 5

CH 2 .COOC 2 H 8

Benzoic ester with acetic ester yields benzoyl-acetic ester, while with acetophenone it gives dibenzoyl- methane :

06115.00.0^.0000^5 +C 2 H 5 OH C 6 H 6 .CO.CH 2 .CO.O 0 H 6 + C 2 H 6 OH.

ester with other monocar-

boxylic esters, aldehyde esters result, while by using oxalic ester, ketonic dibasic esters are formed:

By condensing formic

2 0

SYNTHETIC

HCOOC 2 H 5 + CH 3 .COOC. 2 H 6

COOC,H 5 " COOG 2 H 6

|

+

CH a COOC,H 5

CII 3 GOOC 2 II 5

USE

OF METALS

=

-

HCO.CH. 2 .COOC 2 H S + C 3 H 6 OH Formyl acetic ester. CO.OH 3 .COOC 2 H 5

|

+ 2C 2 H 5 OH

CO.CH 2 .COOC 2 U 5 Diacetyl dicarboxylic ester.

Pormyl acetone may be prepared by using formic ester and acetone:

HCOOC 2 H 5 + CH3.CO.CH3 =

HCO.CH S .CO.CH 8 + C 2 H 5 OII

This substance can be farther condensed by acetic acid to triacetyl-benzeno:

 

CH

 

/CH O CH,.CO.CH 3

CH a CO.C

C.COCH 3

I

->

II

I

+3H 2 O

OHO

OHO

HC

CH

CH 2 .CO.CH 3

 

C

Similarly acetophenono and formic ester yield forniyl-acetophenone, which may bo condensed further to tribenzoyl benzone. Bing condensations with oxalic ester are : Diketo- cyclopentane dicarboxylic ester from oxalic and glutaric esters :

25

COOC 2 II 5

CH 2 —COOC.J-I5

v

cir 2

CO—CH~-COOO 2 H 5

\

Oils

+ 2C 2 H 5 OH.

OIL—COOC 2 H 5

OO—CH— COOC 2 H h

By using /3j3-dimethyl glutaric ester, Konnnpa

ester which was used

obtained diketo-apocamphoric

for the synthesis of camphoric acid : 26

COOC 2 H 5 CH 2 .COOC. 2 H 6 CO—CH.COOC.ir 6

COOC 2 H 5

C(CII 3 ) 2

CHo.COOC 2 H 5

era

(CH a ) 2

+

20Jtl k OK

CO—OH.COOC 2 H 6

SODIUM AND

POTASSIUM

2 1

A methyl group was introduced into the latter compound by the aid of sodium and methyl iodide, and the resultant compound reduced and then hydrolysed to dihydroxy-camphoric acid:

CH 3

CH 3

CO—C—COOCUHs C(CH 3 ) 2

->

CHOH—C—COOH C(CH 3 ) 2

CO—CH—COOCUH5

CHOH—CH—COOH

On boiling the last product with phosphorus and hydrogen iodide, the result was dehydrocamphoric acid, which was then combined with hydrogen brom- ide to form j3-brom-camphoric acid. The last named substance was reduced by zinc dust and acetic acid to racemic camphoric acid :

CH,

I

CH 3

I

CH 3

I

CH—C—COOH

C(CH :{ ) 2 CH—CH—COOH

Sometimes the oxalic ester only undergoes half- condensation as in the formation of oxalyl acetic ester:

I"

CH 2 —C—COOH ""

CH 2 —C—COOH

C(CH,)o

I

CH 2 —CH—COOH

C

CHBr—CH—COOH

COOC 2 H

ft

CO.CIL,.COOC 2 H r)

+

CH 3 .COOCjH 6

=

+

C 2 IT r ,OII.

COOC 2 H 5

COOCaH 6

By means of sodium ethylate or sodium, Claisen

prepared hydroxymethylene camphor by condensing

camphor with amyl formate

: 27

2 2

SYNTHETIC

USE

OF METALS

Clio + HCOOC 5 H n

C: CHOH

C S H 14 \

CO

\ CO

C f> K n OH.

This substance is strongly acid, forming salts and esters, in which the hydroxyl hydrogen is replaced by metals and by organic radicles respectively. The reaction led to the discovery of many other hydroxy- methylene bodies possessing similar properties. Claisen also obtained nitroso-ketones by the use of amyl nitrite in the presence of sodium ethylate :

CflH 5 .CO.CH 8 + CcH^.O.NO «

C C II 5 .CO.CH: NOH + C 6 H n OH

An example of this class of condensation with elimination of water is the formation of a-phenyl- cinnamic nitrile, from benzaldehyde and benzyl nitrile:

 

C (1 H,

C C H 5 .CH : C.C fl H 5

C (! H 6 .CHO

+

|

«

|

+ H.O.

 

CH a .CN

CN

SODAMIDB

AS

A SYNTHETIC

AGENT.

This substance was utilised by Claisen in 1905, for alkylatin g ketones and for preparing 1 :3-diketones. Its action seems to bo quieter and more regular than that of sodium or sodium ethylate. 28 One or two ethyl groups may be introduced into acetophenone by using ethyl iodide with sodamide :

C fl H 5 .CO.CH 3 + C 2 H 6 I - C fl H 6 .CO.CH 3 + 2C 2 H 6 I -

C 0 H 5 .CO.CH 2 .C 2 H 6 +

C^CO.CSEiQJS:^

H I

+ 2HI.

By using benzyl chloride the benzyl group can be introduced:

t

C 6 H 5 .CO.CH 3 + C 6 H 6 .CH 2 C1 « C 6 H fi .CO.CH 2 .(CH 2 C fi H B ) + HC1.

SODIUM

AND POTASSIUM

2 3

1: 3-Diketones are prepared by condensing ketones with esters. Acetyl acetone from acetic ester and acetone:

CH 3 .COOC 2 H 5 +

OH 8 .CO.CH 3 = CH 8 .CO.CH 2 .CO.CH 3 +

GftOH.

Benzoyl

phenone:

CH3.COOC0H5 +

The powdered sodamide is added gradually to the mixed substances, cooled in ice, and after standing for some time, the mixture is treated Avith ice-cold water and the product precipitated by acidifying with acetic acid. Hydroxymethylene ketones are formed by using formic ester:

aceto-

acetone

from

acetic

ester

and

CH 3 .CO.C C H 5 =

CH 3 .CO.CH 2 .CO.O G H 5 + C 2 H 5 OH.

CH3.CO.CH3 + HCOOR =

CH3.CO.CH : CHOH + EOH.

Sodamide has been technically applied in at least two instances, namely, the production of cyanide by Castner's process and also the production of indigo. In the preparation of cyanide, the sodamide is mixed with carbon and the mixture subjected to a dull red heat, when the following reaction takes place:

NaNH 2 + C =» NaCN

+

H 2

Indigo can be synthesised according to the German Patent 158,089, by heating sodamide with the diethyl ester, or the diamido-derivative, of phenyl-glycocoll-carbonic acid, in benzene solution :

.NH.CH 2 .COOH

4 <

XJOOH

-> C fl H 4 <

.NH V >CH 2 + MX) '

Indoxyl

H.>0 + COo.

The indoxyl formed exposure to air.

is converted into indigo by

2 4

SYNTHETIC USB OF METALS

Metallic sodium has recently received important application as a polymerising agent in the transfor- mation of isoprene into artificial rubber. 29 The steps in this important synthesis, starting from starch, are as follows :

The starch is fermented to fusel oil and acetone, and from the former liquid, isoamyl alcohol is separated. By treatment with hydrogen chloride, isoamyl alcohol is converted to the monochloride, and the vapour of this when acted upon by chlorine gas leads to the formation of three isoamyl dichloindes :

(CH : 0 2 CH.CK,CH 2 OH + HC1 =

(CH :l )oCH.CHo.CH 2 Cl + H 3 O

S (CH :) ) 2 CH.CHC1.CH 2 C1 + HC1

(CH.)) 3 CH.CH n .CH 2 Cl + Cl ^

^ :<N >CH.CHo.CH 2 Cl + HC1 CHoCK

These isoamyl dichlorides, when heated with lime,

(methyl

lose hydrogen chloride and pass to isoprene diviflyl) :

*\c.CH : CH 2

CH/'

Isoprene on standing for some time with metallic sodium becomes converted into synthetic rubber.

SODIUM HYDROXTDE.

This sodium derivative is generally utilised in aqueous solution for condensation work, the concen- tration often being 10 per cent.

was the first to use the reagent, in 10

Schmidt 30

SODIUM AND POTA8STUM

2 5

per cent, aqueous solution, for condensing together furfurol and acetaldehyde :

>CHO

C H : c<(

|

J>0

+ CII;,.CHO =

til :

dH

.CH : CH.CHO

C H :

Furfurol acrolein.

Claisen, in the following year, used 10 per cent, aqueous sodium hydroxide to condense furfurol with acetone and thus obtained mono-furfurylidene acetone : 81

C 4 II :i O.CIIO + CH n .CO.CH 3 =

C 4 H 3 O.CH : CH.CO.CH 3 + H U O.

Using benzaldehyde and acetone, he obtained mono- and di-benzylidene acetone. Further examples of condensation of this class ai-e the formation of indigo from o-nifcrobenzaldehyde and acetone, and the formation of quinoline from o-aminobenzaldehyde and acetaldehyde:

.Clio

C G H 4 <

\isro 2

+ CH,.CO.CH., -

'

'

>CHOH.CHo.CO.CHa

C 0 H 4 <

\tfo 2

o-nitrophenyl-lactic acid ketono.

This product is then decomposed by the excess of sodium hydroxide :

C (5 H 4 <

y CHOH.CHo.CO.CH 3

2C 0 H 4 < \NO 2 .CO

.CO v

> C : C <

x

> C (1 H t + 2H«O + 2CH S COOH:

Baryta or ammonium hydroxide may also be used for this reaction. 82 Quinoline and quinoline derivatives are obtained by using o-amino-benzaldehyde : 8S

2 6

SYNTHETIC USB OF METALS

 

CH

HC

C.COH

CH 2 .H

HC

C

|

II

+

|

I

II

HC

C.NHo

CHO

CH

CH

o-amino-benzaldeliyde.

quinoline.

By substituting

aceto-acetic

ester

CH

I I

CH

for

+ 2H 3 O

acetalde-

byde, a quinoline derivative is obtained :

 

CH

CH

CH

"

/

\

^

\

/

-

HC

C.COH

CH,.COOCJI 6

HC

C

C.COO(UI r ,

I

II

+

I

••=

I

II

J

+2H 2 O

HC

C.NIL

CO.CII,

HC

C

C.CH 3

CH

CH

N

rt-metliyl-q[xiinoliiie-/3-carboxylic ostev.

Fischer made use of 1 per cent, sodium hydroxide solution to polymerise a mixture of glyceric aldehyde and hydix)xy-acetone, in the formation of a-acrose. After allowing the mixture to stand for four or five days the transformation was complete : u

CH 2 OH

CH 2 OH

CH 2 OH

CH 2 OH

CHOH

+

CO

~ CHOH

CO

CHO

CH 2 OH

CHOH — OHOH

(Q-lycerose).

a-acrose (inactive fructose).

By the same method ; glycollie aldehyde has been polymerised to erythrose :

CH 2 OH

CHO

CH 2 OH

CHO

CHO

CH 2 OH

CHOH

-

CHOH

Cinnamic aldehyde can be formed

from benzal-

8ODITJM

AND POTASSTTJM

27

dehyde again tX( ^ n ^ed

lOH 0

i * 11

^cetaldehyde , and the product can be

with acetaldehyde or acetone :

C 6 H 5 .CH : CH.CHO + H 2 O

: CH.CHO + CH 3 .CHO = : CH.CH: CH.CHO + H 2 O Cinnamyl acrolein.

: CH.CHO + CH v CO.CH.j -

^ : CH.CH :CH.CO.'CH> + H a O Oinnamyl-vinyl-methyl ketone.

If t\^ c> lu °lecula r quantities of cinnamic aldehyde beused> ^ J " 0 ^ i n th e last case di-cinnamyl-vinyl ketone results. Anofcl* cn * crts e of quinoline formation is the con- ^ Toenzoyl acetone and aniline, resulting in

OH

H C / X <

HC

<

Vr

It

ydr

densing 1

CH

CO.C G H 5

 

HC

CH

CO.CH,

Hi

C

CH

N

2H 2 O

Hhown

solid sodium

"better than sodium ethylate for con- nitrile with methyl iodide :

by

V\ Meyer^ that

36

OHI a I + NaOH = C c H 5 .CHCISr + Nal

QuinotioH ca n be prepared by condensing 1: 2- diketorioH by nquoous sodium hydroxide. In tli o first plac e an unsaturated 1:2 : 5-triketone is fonuocl wliich. Tby further condensation passes to a quinom> # Diacety l gives first dimethyl-quinogen and then ^- x

30

28

SYNTHETIC

USE OF METALS

CO

CH 3 .CO.CO.CH S

->

CH3.CO.CO.CH3

CH 3 .C.CO.CH 3

*II

'

- >

CH.CO.CO.Cir,

CH V C

' II

HC

v

Oil

II

C.CF,

"

Acetyl-propionyl condenses in this way, duroquinone :

CO

forming

CH. } .CO.CO.C1L>.CH,

CH,.C C.CII,

 

'

II

II

+ 2TT,0.

CH.j.CHo.CO.CO.CH-,

CH,.C C.CH,

The reaction may be expi*essed in a general way thus :

CO

X.CHo.CO.CO.Y

X.C.CO.CO.Y

 

XC

CY

 

II

->

II

II

Y.CO.CO.CHo.X

Y.C.CO.CH

X

YC

CX

A further example of condensation by sodium hydroxide is afforded by ionone, used as a substitute for essence of violets, which is formed from citral and acetone. 37 Pseudo-ionone is the first product, and this is then converted to a mixture of a- and j3-ionone by boiling with dilute sulphuric acid :

- (CH 8 ) 2 C:CH.CH 2 .CH 2 .C(CH 3 ):CH.CH:CH.CO.CH 3 + H 3 0.

(CH 3 ) 2 C:CH.CH 2 .CH 2 .C(CH 3 ):CH.CHO

+ CH 3 .CO.CH 8

The next

scheme:

stage

is

explained

by

the

following

CH3

/

HC

H.

I

I

c

c

SODIUM AND POTASSIUM

29

CH3

CH.CH: CH.CO.CH3

+2H 3 O

CH 3

> H,C

|

CH 3

<X>H

/

|

CH 2 .CH : CH.CO.CH 3

XXHH 3

 

V

0H

CH 2

 

I

to

w

0

CH.CH: CH.CO.CH3

H 2 C

C.CH:

CH.CO.CH 3

(C

C.CH3

H2C

C.CH3

 

CHo

 

a-ionone

/3-ionone.

POTASSIUM COMPOUNDS.

Potassium itself is rarely used in synthetic work, but the cyanide, acid sulphate, and hydroxide are often made use of.

A commercial process in which potassium may be

regarded as a synthetic agent is Beilby's process for preparing cyanide, by heating a mixture of potas-

sium carbonate and carbon in ammonia. Potassamide is probably an intermediate compound, and tho method corresponds to Castner's cyanide process:

K a CO 8 + 2NH 3 + 2C

-

2KNH 2

2C

3 0