US2010731A - Esters of substituted saturated fatty acids having 12 to 18 carbon atoms - Google Patents

Description

acid radical.

Patented Aug. 6, 1935 s PATENT'OFFICE ESTERS 0F SUBSTITUTED SATURATED FATTY ACIDS HAVING 12 ATOMS,

l Wolfgang Liib hauer, Dussel ors to firm Henkel & Cie.

dorf, Germany bert, Dusseldorf, and Erich dorf-Benrath. Germany,

To 18 cannon Rosenas i G. m. b. 11., Dussel- No Drawing. Application November 29, 1932,

Serial No. 644,912. In

.' i 9 Claims. (Cl. 260-103) The application Serial No. 6ll,911 discloses a process for the manufactureof esters of aliphatic or hydroaromatic hydroxypounds, the said esters being or mercapto-comsubstitutedyin the The process consists in that hydroxyor mercapto-fatty acids, whichare arylated at the oxygen or sulphur, or their der stitution products, are phatic v or' tainat least one hydroxyland at least 6 carbon atoms. It has now been found ivatives or sub- A esterified with such alihydroaromatic compounds as conmercapto-group,

further that likewise valuable organic compounds are obtained when aliphatic compounds which contain at least one hydroxylor mercapto-group and less than 6 carbon atoms are esterified with such fatty acids,

which are substituted by alkyl-oxy-,

or hydro-aryl-oxy-radicals, or the aralkyl-oxyaryl-oxy-,

corresponding mercapto-compounds, as contain in the fatty acid radical 6 or more carbon atoms.

Instead of the aforesaid fatty acid derivatives, it is also possible to employ their substitution hydroxy-, hydrocarbon radicals,

As such come into consideration, for

ecifie'cl, which are sulphonic ossible to employ with normal or branched or more carbon atoms, such as, for example, the stearic acids which are substituted in the a-position or in other positions by one or more alkyl-oxy-, aryl-oxy-,

aralkyl-oxymercapto-compounds and hydro-aryl-oxy-radicals, or the corresponding to stearic acids, furthermore a-methoxylauric such acid or a-phenoxylauric acid or u-ethyl-thiostearic acid or the a-tolylthiolauric acids and the like.

As aliphatic compounds containing groups, it is possible to employ ondary or tertiary alcohols or ing mercaptans, provided 6 carbon atoms. polyvalent alcohols or type.

The compounds containing groups or mercapto-groups may ed or unsaturated nature.

The said compounds, which droxylor mercapto-groups may all kinds, such as caror their derivatives, halogen atoms,

possess substituents of boxyl-groups ether groups, sulphonic acid-groups The esterification of the com hydroxylprimary, secthe correspondthey contain less than It is also possible to employ mercaptans of the said the hydroxylbe of a saturatcontain the hyin their turn and the like. ponents is efiect- Germany December 16,

ed in knownmanner with the free acids, if desired, in the presence of catalysts. It is also possible to employ derivatives of the fatty acids obtained by modifying the carboxy-group of the acids, such as chlorides, anhydrides, or the principle of alcoholysis may be employed, or the process may be carried out in such a manner that, instead of the hydroxy-comp0unds,their reactive derivatives, such as mineral acid esters or ester salts or alcoholates are employed.

Thus, for example, n butyl a phenoxylauric ester is obtained by the interaction of a-phenoxylauric acid chloride, obtainable from a-phenoxylauric acid and thionyl chloride, with n-butyl alcohol in carbon tetrachloride as solvent and diluent.

The new compounds possess to some extent emulsifying properties. They may be employed in the perfume industry, as softening agents and the like. Provided they possess groups which render them soluble in water, they have saponaceous properties. In addition, they serve as starting substances for further conversion products.

27.9 parts of a-bromolauric acid are dissolved in about 100 parts of alcohol, and there are added thereto 9.4 parts of phenol and, gradually, 8 parts of NaOH, dissolved in about parts of aqueous alcohol. The mixture is then heated to boiling on a water bath for five hours. 7

After evaporation of the alcohol and water in a vacuum, the sodium salt which is formed is re-crystallized from '96 per cent. alcohol, the halogen-free product is thereupon dissolved in water and is acidified with the calculated amount of hydrochloric acid. The freeacid is extracted with ether.

After drying the ether extract with sodium sulphate and evaporation of the ether, the acid is treated with thionyl chloride. The acid chloride which is formed is added to an excess of n-butanol and the mixture is heated for 1 hour almost to boiling. Thereupon, the reaction product is diluted with water, is washed neutral with bicarbonate solution and the ether is evapo- (2) Preparation of ethyl a-phenylmercapt stearic ester I 27 parts of u-bromostearic acid are dissolved in about 150 parts of alcohol, 82; parts ofthiophenol are added thereto andthe whole is mixed with 6 parts of NaOH in about parts of alcohol. After about 5 hours boiling on a water bath,

a-phenylmercapto-stearic acid, the acid chloride is heated for about 1 hour with absolute alcohol on the water bath. The reaction product is water, the oil which separates out is takenup with ether; is washed neutral with sodium bicarbonate to remove hydrochloric acid, and after drying with sodium sulphate, the ether is distilled 0th The ester remains as a yellowish oil. TWe clairlm-f 1. The esters'having the formula 1 R X- R -aCoOR and "the sodium salt of acid, whereupon the said free in which R 000 represents the acid radical of a saturated fatty acid having 12 to 18 carbon atoms, X represents 0 or S, R represents a radical of a benzene hydrocarbon and R an alkyl radical containing less than 6; carbon atoms.

2. The esters set forth in claim 1 wherein X is oxygen.

' 3. The esters set forth in claim 1 wherein X is sulphur.

fl. The esters set. forth in claim 1 wherein R is a phenyl radical.

csafiocaimqoocmt.

'9. Ethyl a-phenylmercaptostearic ester which may be represented by the formula CeI-IsSCni-IsrCOOCzHs.

O FGANG LiiBBERT. ERICH R SEN A E