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Publication numberUS1106455 A
Publication typeGrant
Publication dateAug 11, 1914
Filing dateSep 5, 1818
Publication numberUS 1106455 A, US 1106455A, US-A-1106455, US1106455 A, US1106455A
InventorsLadislaus Karczag, Eduard Kopetschni
Original AssigneeLadislaus Karczag, Eduard Kopetschni
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the production of acid chlorids of the oxyacids.
US 1106455 A
Abstract  available in
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Description  (OCR text may contain errors)

.- *srarpsairam ormoa.

LamsL'aUs macz'ao, or cnanno'r'ramaono, Am) normal) xorE'rsonm, or


- mas ron 'rriaraonoc'rrox ,or ACID CHLORIDE-OF THE oxracms.

I Drawing.

To all whom it may concern: f1

Be 't ;known' that we, DrfLAoIsmUs Kanczacand Dr. EDUARD Kora'racnm, both subjects of the King of Hungary, Emperor of Austria, residing, respectively, at 49 'Schlueterst'rasse, Charlottenburg, and 40 Kaiserring, Mannheim, both in the Ger- ,man Empire, have invented a certain new etc.) has as is known, established the fact that it is not-the simple acid ch'lorids but chemical compounds 0 amjore complex nature that are formed, these compounds containing phosphorus and in which the chlo-.

rina'ting agent has entered the molecule of the oxyac'ids. .In the comprehensive publication of these operations (Br Anschutz .Ueber ein 'Gesetz" der Bildung. freier Phenolkarbonsiiurechloride Bemkte 30.221

(1897),;th'e said author states that chlorids' 0f thejsing'le .phenol 'cai'boxylic acids .can-

' ception not be'pzoduced in this way, the only exing'those oxy carbonic acids which are' substituted in the. ortho position to the phenol hydroxyl and owing to this protectiye action of the substitute are capable of for free phenoljcarboxylic chlorids (see also erman Patent No. 89596).

The operations .of Hans Meyer Ueber cine all'gemein anwendbare' Methode -zur 'Darstellu von Chloriden der organischen Siu en, iemrjMomts/zefte 22, 415 1901) in-which he endeavored to utilize thionyl chlorid as a generally utilizable chlorinating a ent in substitution of carboxyl hydroxy curiously afi'orded'an exception preciscly for the mono-ox benzoic'" acids. In the chlorination of that ree isomeric monoo benzoic acids by means of'thionyl chlo- HQMeyer ascertained that although m-ox' benzoic acid furnished the correspozi ing chlorid, salicylic acidafter long continued boiling furnished a new chlor'id (not salicyl chlorid) but a sulfurous acid ester of salicylchlorid of unknown constitution, while p-oxybenzoic acid does not re- Speciflcatton ot Lctters ratent.

.\ Applicationflled September 5, 1812. Serial No. 718,0;8. V

Patented Aug. 11, 1914.

act at all with thionyl boilin for da s.-

If t io'nyl clilorid is caused toactjon salipglic acid in the presence ofitertiary bases,

chlorid m F n in the manner-described in German Patent N o. 211403"anhydriaing of the salicylic acid always takes place and (in this case). the formation of salicylo salicylic acid. The latteris also obtained according to' the said atentby the action of not more than the t eoretical of thionyl chlOlld upon neutral and basic salicylates. Now the surprising fact has been, noted that by causing'neutralsalts of quantity (:1. half molecule) 1 aromatic or alip'atio oxy carboxylic acids an oxychlorid whose products of decomposition resulting from this reaction are gaseous at ordinary temperature lt'he chlorids, of the correspondin oxysacids arer at, once reached. Thus, in example, the neutral salts of salicylic acid of the type C,H, (0H) COO M (M being ametal), in contradistinction to the free acid thionyl chlorid in excess readily in a cold to be acted upon by at least one molecule-of? react with state in forming the long sought for sali-.

cylic chlorid, which latterdifiers distinctly from Meyers sulfurousacidester of salicylic chlorid in its roperties. Y If on the otherhand, thionyl c lorid is caused to act on basic salicylates (sodium disalicylate for example), bu t small quantities of chlorid" are obtained and princi ally other products,


Ina similar manner the salts of mand -which have not been cosely examined, are

oxybenzoic acid react with thionyl chlorld so that mand the hitherto unknown poxybenzoyl chlorid are formed. Llkewise (in order to adduce arexample from the aliphatic series also) when thionyl chlorid acts on salts of glycolic acid, glycolic chlorid, which ha: not hi'therto been known in a pure form, Charm I l' The reaction of thionyl chlorid generally takes place more readily'with the salts of the oxycarboxylicacids and at lower ternperatures'thanthe action on the free'aclds.

is prakt.

In view of the deoom posibility of the ch10;

rids obtained and the fact that under the influence of. the thionyl chlor1d 1n excess the latter are apparently further modified in part the advantage results that by employmg the salts purer; products are obtained. Thus the preparation of m-oxy benzoyl chloridfrom the salts presents the advantage as compared-with the employment of free m-oxybenzoic acid (according to H. Meyer) of rendering it possible to operate with the theoretical quantity of thionyl chlorid at a low temperature and consequently to repress the formation of sulfurous acid ester which Otherwise forms as a by-product. Phosgene can also be used instead of thionyl chlorid.

The chlorids of the oxy acids thus pro duced are generally very freely capable of reac but are also partially sensitive bodies.- Salicylic chlorid for example forms at ordinary indoor temperatures an oily colorless llquid of a characteristic but not I unpleasant smell. In a cooling mixture the oil sets into a crystallinemass of felted or matted well-defined white needles which melt at about 9 to 1l C. Upon distillation .(also in cacao) the salicylic acid chlorid decomposes in separating hydrochloric acid. Mixed with methylalcohol Gautheria oil (methyl salicylate) with its very characteristic'odor forms at once and salicylic ethylester forms with ethyl "alcohol. r-react withanilin salicylic anilid is formed Caused to which is identical with that already described in technical literature which is obtained in a different way. Meta and para oxy benzoyl chlorid are tear-inducing strongly smelling oils which do not set even in a cooling mixture of l5-20 CJ Chemically they behave like salicylic chlorid and are also decomposable. When treated with methyl alcohol abs. (in which a vigorous reaction begins even at ordinary indoor temperature) the corresponding methyl esters of mand p-oxy benzoic acid are fo ed. Glycolic acid chlorid, which has hither not been known, is a penetratively. acid smelling colorless oil.

' Examples.

1. 16 parts of sodasalicylate are introduced into 25 parts of thionyl chlorid in small portions. In developing sulfurous acida vigorous reaction takesplace. It is preferable to provide that a heating of the reaction mass over 30 does not take place. lhe reaction takes place in accordance with the following equation.


' .HOCJLCO Cl+Na c1+so disulfid or ligroin. The solvent is then driven off completely by distillation in vacuo at as low a temperature as possible, the salicylic chlorid remaining behind as an oily liquid.

2. To a mixture of 110 g. of thionyl chlorid and- 120 ccm. of benzol .100 g. of sodium salicylate are added gradually in slowly shaking the liquid. The reaction mass swells into a colloidal mass which is allowed to stand for an hour in a cold temperature; Thereupon the unutilized thionyl chlorid and the benzol re distilled over in a rarefied chamber and t e residuum leached with benzol. The solution of the salicylic acid chlorid in benzol .is then again freed from the solvent in 'vacuo, the operation being carried out with a high vacuum and low temperature. The yield amounts toapproximatcly 85-90% of the theoretical yield, relatively to the salt used.

3. For the production of m-oxy chlorid 15 g. of sodium m-oxy benzoate in the finest state of pulverization are slowly introduced into 60 g. of thionyl chlorid, the temperature of the reaction mass bein kept low by cooling with ice. As' soon as t e salt is consumed the thionyl chlorid in excess is at once distilled over in 'vacuo as by its action when the reaction is terminated a parently a further modification of the benzoyl chlorid formed is produced. The residuum .is extracted with low .boiling ligroin, the solution is filtered and then the m-oxy ben- Zoyl chlorid is, freed in vacuo from ligroinJ 4. 20 g. of potassium p-oxy benzoate are slowly introduced in a finely pulverized form into 60 g. of thionyl chlorid in small portions; tion, which commences violently, the reaction vessel is cooled with ice. sium chlorid separates out in a white amorphous and voluminous form. When the first operation is finished, the thionyl chlorid in excess is' immediately distilled over in the rarefied chamber, and .the p-oxy benzoyI chlorid is extracted from the residuum by means of ligroin, this chlorid remaining behind as a strongly-smelling yellowish oil after the elimination of thesolvent.

5. Phosgene is introduced preferably into an ice-cooled suspension of salicylate of sodium in a small, quantity of benzol (toluol and so forth) or the SOdlllIIl salicylate is introduced into toluol saturated with phosgene and the mixture is then left for some hours. The further treatment .is identical with that already described in connection with thionyl chlorid.

6. The process for the formation of glycolic chlorid is quite analogous to the examples already described. 20 g. ofsoda glycolate are gradually introduced into g. of .thionyl chlorid and in order to prevent excessive heating of the reaction mass, simul- In order to moderatethe reac The potaslaneously cooled with ice. The excess is distilled over with thionyl chlorid, extraction with ligroin is then effected and the latter is then driven oil coma in the manner repea tedly described above. The colorless, oily glycolir. chlorid remains in the residuum.

What we claim and desire to secure by Letters Patent of the United States is:

l. The process for the manufacture of acid c-hlorids 11 the. oxy acids which consist in causing one molecule of a neutral salt of an cxy carhoxylic acid to be acted upon by at least one molecule of an oxychlorid whose {)Wull-PJS of decomposition resulting from this reac ion are gaseous at ordinary temlrt!" j,

1 e vrocess for the manufacture of U .loz'ids of the oxy acids which consisis in causing at least one molecule of thi- (my! rhloiid to act upon one molecule of u alt oi d1 oar carboxylic acid.

3. p cess for the manufacture of. -Ill. "l vzlti nh ch consists in causing one niUit'i'hM' a neutral salicylate to he acted r l l l the presence of an indifl'erent diluent, by at least one molecule of an oxychlorid whose products of decomposition resulting from this reaction are gaseous at ordinary temperature.

6. The process for. the manufacture of salicylic chlorid which consists in causing at least one molecule of thionyl chlorid to act upon one molecule of a neutral salicylate in the presence of an indifferent diluent.

T. The process for the manufacture of salicylic chlorid which consists in gradually introducing 16 parts of sodium salicylate into parts of thionyl chlorid, distilling over the thionyl chlorid in excess in wacuo,

- removing the salicylic'chlorid formed from the residuum by means of a neutral solvent and driving the solvent off by distillation in wzcuo.

R. The herein described product consisting of salicylic acid chlorid, the same being an oil) colorless liq id forming, when Pooled. white needles melting at from 9 t0 ll dear. (1. decomposing upon dislillatiomeven 1". I'IHHU. forming when mixed with ethyl alcohol. salicylic ethyl ester.

in testimony whereof we aiiix our signatures in presence of two witnesses.

DR. LADISLAUS KARCYAG. Du. EDUARD KUPETSCHNI. itnesscs to signature of Dr. Karczag:

\Vo: an: M .in H l\ 1 PT, Au'rurn Sonata-mun. Witnesses to signature of Dr. Kopelschni:

S. H. ll-unit, .losnrn PEIFFF"

U.S. Classification562/840, 562/857, 562/862
Cooperative ClassificationC07C51/62