Patent GB-449865-A (GB)
Title: Agents of capillary activity
Filed: 1934-12-28
Abstract: An alkylated or cycloalkylated aromatic hydrocarbon, having at least four carbon atoms in the alkyl or cycloalkyl group, is condensed with a functional derivative of an acid of the formula COOH(CH2)nCOOH, where n is 2, 3 or 4, and the keto group in the ketocarboxylic acid so obtained is reduced.  Acids of the formula RA(CH2)nCOOH, where R is an alkyl or cycloalkyl group of at least four carbon atoms, A is an aryl group, and n is 3, 4 or 5 are obtained, and these may be hydrogenated to convert the group A into a hydroaryl group.  In a modification, the acids of the formula given in which R and A are both hydroaryl groups may be obtained by starting from an arylated aromatic hydrocarbon and afterwards hydrogenating the two aryl nuclei simultaneously. As functional derivatives of the acids of the formula COOH(CH2)nCOOH, use may be made of the anhydrides, chlorides or ester-chlorides, subsequent saponification being necessary in the last case.  The reduction of the keto group in the ketocarboxylic acids first obtained may be effected with catalytically activated hydrogen or with zinc dust in an alkaline medium.  If the alkylaryl (or cycloalkylaryl) aliphatic acids so obtained are to be hydrogenated, to convert the aryl groups into hydroaryl groups, the acids are preferably first esterified with a mono- or poly-hydric alcohol, and the esters are hydrogenated in the liquid phase at 130--200 DEG  C. under pressure in the presence of a nickel catalyst; the esters are then saponified.  The alkali salts of any of the products obtained as described above are useful as foaming, wetting, emulsifying and washing agents, and the nuclearly hydrogenated acids are useful as lubricants, e.g. for wool.  In the examples: (1) n-butylbenzene and succinic anhydride, heated in tetrachlorethane in the presence of aluminium chloride, yield g -4-butylphenyl-g -oxobutyric acid, which is then reduced with hydrogen, in the presence of a nickel catalyst, to yield g -(4-butylphenyl)butyric acid; (2) the g  - (4 - butylphenyl)butyric acid obtained in example 1 is esterified with methanol and the ester is hydrogenated at 130--200 DEG  C. and 50--150 atm. in the presence of a nickel catalyst; the ester is then saponified and g -(4-butylcyclohexyl)butyric acid is obtained; (3) cyclohexylbenzene is treated as in example 1 and yields, in turn, g -4-cyclohexylphenyl-g -oxobutyric acid and g -(4-cyclohexylphenyl)-butyric acid; (4) the end product of example 3 is esterified, hydrogenated and saponified as in example 2, and yields g -(4-cyclohexylcyclohexyl)butyric acid; the same product is obtainable by condensing diphenyl with succinic anhydride to yield g -4-phenylphenyl-g -oxobutyric acid, reducing this to g -(4-phenylphenyl)butyric acid, and hydrogenating the phenyl nuclei. Products momologous with those of examples 1 and 2 have been prepared, by the reactions described in those examples, from sec.-butylbenzene, isoamylbenzene, n-hexylbenzene, n-octylbenzene, and n-dodecylbenzene.  Other specified products are g -(4-b -decahydronaphthyl)butyric acid, g -(2-butylnaphthyl-6)butyric acid, and dicyclohexylmethane-4-g -butyric acid.  Other specified starting materials are the products obtained by reaction of benzene, naphthalene or phenanthrene with mixtures of alcohols containing at least four carbon atoms, such as isobutyl oil or the alcohols obtained by hydrogenating fatty acids or by oxidizing paraffin, and also the products obtained by reacting the specified aromatic hydrocarbons with olefines containing at least four carbon atoms or their polymerization products, such as diisobutylene, or with oil of turpentine.  According to the Provisional Specification, (1) any alkylated aromatic hydrocarbon may be used as starting material, reference being made to the use of toluene, ethyl- and propyl-benzenes, and methylnaphthalene, and (2) derivatives of higher homologues of the aliphatic dicarboxylic acids specified above may be used, 4-ethylphenyl-e -caproic acid being specified as one of the products obtainable.ALSO:An alkylated or cycloalkylated aromatic hydrocarbon, having at least four carbon atoms in the alkyl or cyclo-alkyl group, is condensed with a functional derivative of an acid of the formula COOH(CH2)nCOOH, where n is 2, 3 or 4, and the keto group in the ketocarboxylic acid so obtained is reduced.  Acids of the formula RA(CH2)nCOOH, where R is an alkyl or cycloalkyl group of at least four carbon atoms, A is an aryl group, and n is 3, 4 or 5 are obtained, and these may be hydrogenated to convert the group A into a hydroaryl group.  In a modification, the acids of the formula given in which R and A are both hydroaryl groups may be obtained by starting from an arylated aromatic hydrocarbon and afterwards hydrogenating the two aryl nuclei simultaneously. The alkali salts of any of the products obtained as described above are useful as emulsifying agents, and the nuclearly hydrogenated acids are useful as lubricants, e.g. for wool.  In the examples: (1) n-butylbenzene and succinic anhydride yield g -4-butylphenyl-g  oxobutyric acid, which is then reduced to yield g -(4-butylphenyl) butyric acid; (2) the g -(4-butylphenyl)butyric acid obtained in example 1 is esterified with methanol and the ester is hydrogenated and then saponified; g -(4-butylcyclohexyl)butyric acid is obtained; (3) cyclohexylbenzene is treated as in example 1 and yields, in turn, g -4-cyclohexylphenyl-g -oxobutyric acid and g -(4-cyclohexylphenyl)butyric acid; (4) the end product of example 3 is esterified, hydrogenated and saponified as in example 2, and yields g -(4-cyclohexylcyclohexyl)butyric acid; the same product is obtainable by condensing diphenyl with succinic anhydride to yield g -4-phenylphenyl-g -oxobutyric acid, reducing this to g -(4-phenylphenyl)butyric acid, and hydrogenating the phenyl nuclei. Products homologous with those of examples 1 and 2 have been prepared, by the reactions described in those examples, from sec.-butylbenzene, isoamylbenzene, n-hexylbenzene, n-octylbenzene, and n-dodecylbenzene.  Other specified products are g  - (4 - b  - decahydronaphthyl)butyric acid, g -(2-butylnaphthyl-6)butyric acid, and dicyclohexylmethane-4-g -butyric acid.  Other specified starting materials are the products obtained by reaction of benzene, naphthalene or phenanthrene with mixtures of alcohols containing at least four carbon atoms, such as isobutyl oil or the alcohols obtained by hydrogenating fatty acids or by oxidizing paraffin, and also the products obtained by reacting the specified aromatic hydrocarbons with olefines containing at least four carbon atoms or their polymerization products such as diisobutylene, or with oil of turpentine.  According to the Provisional Specification (1) any alkylated aromatic hydrocarbon may be used as starting material, reference being made to the use of toluene, ethyl- and propyl-benzenes, and methylnaphthalene, and (2) derivatives of higher homologues of the aliphatic dicarboxylic acids specified above may be used, 4-ethylphenyl-e -caproic acid being specified as one of the products obtainable.