US815548A

US815548A - Process of producing aromatic alcohols and their derivatives.

Info

Publication number: US815548A
Application number: US23114904A
Authority: US
Inventors: Charles Mettler
Original assignee: Individual
Current assignee: Individual
Priority date: 1904-11-02
Filing date: 1904-11-02
Publication date: 1906-03-20
Anticipated expiration: 1923-03-20

Description

. CHARLES METTLER OF MUNICH;y GERMANY i! "ai f i `P'RocfEss oiPRoDUciNG AROMATICALCQHOLSANDTHEIR D iR|vAT|i/5's.f

Beit known that LCHARLES MErTIiEn,

chemist, aciti'z'enof Switzerland, vof No.1?` Marsstra'ss'e, Munich, rinthe Kingdom' of. Ba-f f yVaria and Empire of Germany, hayeinyented lcertain new and useful improvements in Proc-1 es seslfor the Production of'Aromatic Alco-4 f hols` and their Derivativ lowing isaspecication. f

It has nothitherto been known that aire-7" duction ofY aromatic esters to f alcoholspforg ex- Y, `ample, vfromy ethyl-ester of benzoic' acidto `benzylaloohol t i (1,115*oooomflwni:CGHEomOH-Fcuon f has eyerbeen realized.y i

I have new yfound i that i minnie sjeefs lhave'they 'roperty,'` under thefconditions suit-y able fort e saine, of taking upjhydrogen `and changing into compounds comparatively poor in oxygen. y; Th1-'secours when arornaticesters g are reduced atinetal cathodes-'for i example,y

at lea'd `cathodeS- by means of yelectrolyti'c- .ally-separated hydrogen. For thiS purpose it t cornes into consideration, concentrated Sul-y furie acid which can be diluted with watera`l 1 o' i coholo r acetic acid. In lieu'thereof an aque'- f alsobe carried out in'an alkaline or neutral so@ i Intiem, in whichv case anf aqueous solution 7 which contains the electrolyte s-rnixed withv the quantity of alcohol nec'eSSaryforthe soluv tion of the ester'.4 Ifone operates in yana'cid sol lution andreducesfplyway .of example ethyl after'afeufcient time.V l my i is advantageous. to'v employ a dissolving agent for the ester, which iS at' the Sametime capable l Y of conducting theielect'ric current, as Such ous alcoholic .solutiony of hydrochloric acid can be' employed, andfinally such a reduction `can specification of retten;"Patent l' L r i Application illallNmvitilier@@9044k Serial Noi-231,149. 'V

es,of which the fol@ a 1k w This courseof reactionsisgnotjonly vfthe Variousethylestersofbenzoicacid;'1butiity t methyl estei' o1 aniscpaeid. 'i

limited .150,

relates to. anew general class reaction of Varoi -In'atic`z-este1s.-` {It} isA particularly of value in that-it also holds'goodfor'substituted aronatic esters. `Thus whenusin halo enfsub'stituted and I I ethyl athen-.of meta-'- meta-bror'n'lben-y brom-be zoic acid.

1 Withregard tothe riroportionsi of :etherl andofalcoholthe`se epend uponl uite" af lI iurr'lberof'cir'cumstances.v Forexai'n'p e, con-y Patented l f formed out `'of',Inethylester of 'b enzoic acid,

' l oon I' iethyl ether otanisic alco- `h 225 f.

`diluted with water.

velectrolyti`c reduction of substances which stitution and temperature play an important part. If the methyl ester of benzoic acid is treated, the-production of alcohol .prevails formed, (two parts alcohol, one part ether,) whereas out of ethyl ester of benzoic acid under analogous conditions more etheris formed (one part alcohol, two parts ether.) The formation of ether is still more predominant in the case of the halogen-substituted compounds. Thus, for example, the ethyl ester of meta-chlor-benzoic acid is exclusively reduced to ethyl ether of meta-chlor-benzyl alcohol. The reduction of the esters can also be carried out in an alkaline solution. As main products alcohols are obtained.

By means of suitable oxidizing agents the ethers, like the alcohols, can easily be converted into aldehydes, and these form a suitable material for the dyeing industry for triplienyl-'methan dyestuffs and for artificial 1n 1go.

The following examples will now be given:

1. The cathode-space of an electrolyzing a paratus is charged with a solution having tlIie following composition: three hundred grams of ethyl ester of benzoic acid, three. hundred and iifty grams 'of concentrated sulfuric acid, five hundred grams of alcohol of ninety-six per cent., one hundred grams of water. (In place of water acorrespondinglydilute solution of sulfuric acid can of course beemployed.) The anode-space separated by an earthenware cell contains sulfuric acid It is known that the are not readily and easily reduced can be facilitated by employing for the cathode a metal having a high cathodic tension. Therefore the cathode of my apparatus consists of pure sheet-lead, which is suitably prepared according to Tafels prescription, (Berichte der Deutschen Chem. Gesellschaft 332215,) and pure lead is employed for the anode. A current of seven amperes per one hundred square centimeters cathode-surface is sent through the liquid; but the streng-th of the current can be materially varied without disadvantage. By means of cooling the temperat-ure is kept between 20 and 30 centigrade. `When no more hydrogen is absorbed,

`grams of alcohol.

the-cathode liquid is neutralized with about thirty per cent. soda-lye. Two layers are formed, of which the upper one consists of alcohol and the products of reduction of the ethyl ester of benzoic acid. This is separated distilled, and fractionized. The benzyl-ethyl ether boils at 184, the benzyl alcohol at 205.

2. Under similar conditions as in Case 1 a cathode liquidy of the following compositionnamely, one hundred and seventy grams of ethyl ester of meta-brom-benzoic acid, three hundred grams of concentrated sulfuric acid, five hundred grams of alcohol of ninety-six per centis reduced at a lead cathode with the aid of the electric current. During the electrolysis the reaction product is se ara-ted for the greater art on the bottom of tiie cathodespace as oi It is drawn off and distilled. Between 235 to 239 the ethyl etherof metabrom-benzyl alcohol distils. At 250 a small quantity of meta-brom-benzyl alcohol passes over.

3. In the cathode-space of an electrolyzing apparatus a solution as follows is laced: one hundred grams ofethyl ester of enzoic acid, six hundred grams of thirty-per-cent. aqueous sal-ammoniac solution, six hundred The anode-space separated by an earthenware cell contains dilute sulfuric acid or ammonium-sulfate solution. Cathode and anode consist of urelead. Electrolysis proceeds while the iquid is cooled, the current having a strength of six amperes per one hundred square centimeters cathodesurface. When no more. hydrogen is absorbed, the alcohol is distilled off and the liquid is acidulated. Benzyl alcohol separates for the most part. It is removed and disuned. (195%0 205.)

What I claim is- Process for the roduction of aromatic alcohols and their et ers, which consists in exposing the aromatic esters in a dissolving agent, capable of conducting the electric current in the cathode-space of an electrolytic apparatus in using for the cathode a material of a specially-high cathodic tension, then neutralizing the cathode liquid, then se arating the reaction product and finally distilling, substantially as described.

In witness whereof I have hereunto set my hand in the presence of two witnesses.

CHARLES METTLER.

Witnesses:

ULYssEs J. BYWATER, ABRAHAM ScHLEsiNGER.

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