Patent GB-484910-A (GB)
Title: Improvements in or relating to the manufacture of acid amides
Filed: 1936-11-09
Abstract: Amides are obtained by the reaction of carboxylic acids or their derivatives with hydroaromatic primary or secondary amines substituted in the nucleus by an aliphatic hydrocarbon radicle containing at least four carbon atoms.  Products useful as emulsifying and dispersing agents are obtainable from carboxylic acids containing a hydrophile group or a radicle which facilitates the introduction of a hydrophile group, i.e. an additional free acid group or a hydroxyl, ether, mercapto, amino or ester group. In this connection reference is made to the following processes: (1) the hydroaromatic amine, e.g. 4-sec.-decyl-2-methylcyclohexylamine, is reacted with a polybasic carboxylic acid, e.g. oxalic, malonic, succinic, adipic, sebacic, phthalic, sulphoacetic, sulphophthalic, thiodiglycollic or sulphobenzoic acid to yield an amide containing a free acid group; (2) the hydroaromatic amine, e.g. a mixture of 4-sec.-hexyl,- sec.-octyl-, sec-decyl-and sec.-dodecyl-2-methylcyclohexylamines, is acylated by reaction with glycollic acid, lactic acid, hydroxyethoxyacetic acid lactone, thioglycollic acid, salicylic acid, or anthranilic acid, preferably in the form of isatoic anhydride, and a hydrophilic group is introduced into the amide (a) by sulphonation, or (b) by reaction with an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, epichlorhydrin, or cyclohexene oxide, or (c) by reaction with a halogenated carboxylic or sulphonic acid, such as chloracetic or bromethanesulphonic acid, or (d) by conversion of an amino group, if present, into a quaternary ammonium group by treatment with an alkylating or aralkylating agent; (3) the hydroaromatic amine, e.g. a mixture of homologous-4-alkylcyclohexylamines containing at least four carbon atoms in the alkyl groups, is acylated by reaction with a halogenated carboxylic acid or a derivative thereof, e.g. chloracetyl chloride, a -chlorophenylacetyl chloride, chloropropionic acid or 2-bromolauric acid bromide, and a hydrophile group is introduced into the amide by reacting the latter with a sulphite, a thiosulphate, an alkali alcoholate, particularly an alkali-metal compound of a polyhydric alcohol or an etheralcohol, a mercaptide, or a primary, secondary or tertiary amine, e.g. trimethylamine, triethanolamine, dimethylbenzylamine, diethylallylamine, methylglucamine, glycine, sarcosine, alanine, taurine, methyltaurine, sulphanilic acid or aspartic acid; (4) the hydroaromatic amine, e.g. a mixture as specified at (3) above, is acylated by reaction with an unsaturated carboxylic acid, e.g. acrylic, crotonic, oleic or cinnamic acid, and a hydrophile group is introduced into the amide by sulphonation, sulphitation, or addition of a mercaptocarboxylic or mercaptosulphonic acid; (5) an amide prepared as described above from a carboxylic acid containing an aromatic nucleus is sulphonated.  In the examples, (1) 4-sec.-octylcyclohexylamine is heated with phenoxyacetic acid, and the amide so obtained is sulphonated with sulphuric acid; 4-sec.-dodecyl-2-methylcyclohexylamine may be similarly treated; (2) 4-sec.-octylcyclohexylmethylamine is heated with cresoxyacetic acid and the amide so obtaieed is sulphonated with sulphuric acid; (3) 4 - sec. - octylcyclohexylamine is is condensed with chloracetyl chloride in the presence of dimethylaniline, and the amide so obtained is heated with sodium sulphite solution; 4-sec.-octylcyclohexylmethylamine, or a mixture of 4-sec.-hexyl-, sec.-octyl-, sec.-decyl- and sec.-dodecyl-2-methylcyclohexylamines, may be similarly treated; (4) 4-sec.-octylcyclohexylmethylamine is heated with succinic acid to yield a monoamide containing a free carboxylic acid group; a similar product is obtained if phthalic anhydride is used in place of succinic acid.  Mention is made also of the manufacture of carboxylic amides from hydroaromatic amines containing a decahydronaphthalene or a dodecahydro-diphenyl nucleus substituted as described above.  Specification 482,580, [Group IV], is referred to.ALSO:Amides are obtained by the reaction of carboxylic acids or their derivatives with hydroaromatic primary or secondary amines substituted in the nucleus by an aliphatic hydrocarbon radicle containing at least four carbon atoms.  The acids may be aliphatic or aromatic carboxylic acids such as acetic acid, methoxyacetic acid, alkylmercaptoacetic acids, pyromucic acid, propionic acid, stearic acid, behenic acid, montanic acid, abietic acid, benzoic acid, phenoxyacetic acid or cresoxyacetic acids.  Products useful as wetting, washing, emulsifying and dispersing agents are obtainable from carboxylic acids containing a hydrophile group or a radicle which facilitates the introduction of a hydrophile group, i.e. an additional free acid group or a hydroxyl, ether, mercapto, amino or ester group.  In this connection reference is made to the following processes: (1) the hydroaromatic amine, e.g. 4-sec.-decyl-2-methylcyclohexylamine, is reacted with a polybasic carboxylic acid, e.g. oxalic, malonic, succinic, adipic, sebacic, phthalic, sulphoacetic, sulphophthalic, thiodiglycollic or sulphobenzoic acid to yield an amide containing a free acid group; (2) the hydroaromatic amine, e.g. a mixture of 4-sec.-hexyl-, sec.-octyl-, sec.-decyl- and sec.-dodecyl-2-methylcyclohexylamines, is acylated by reaction with glycollic acid, lactic acid, hydroxyethoxyacetic acid lactone, thioglycollic acid, salicylic acid, or anthranilic acid, preferably in the form of isatoic anhydride, and a hydrophilic group is introduced into the amide (a) by sulphonation, or (b) by reaction with an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, epichlorhydrin, or cyclohexene oxide, or (c) by reaction with a halogenated carboxylic or sulphonic acid, such as chloracetic or bromethanesulphonic acid, or (d) by conversion of an amino group, if present, into a quaternary ammonium group by treatment with an alkylating or aralkylating agent; (3) the hydroaromatic amine, e.g. a mixture of homologous 4-alkylcyclohexylamines containing at least four carbon atoms in the alkyl groups, is acylated by reaction with a halogenated carboxylic acid or a derivative thereof, e.g. chloracetyl chloride, a -chlorophenylacetyl chloride, chloropropionic acid or 2-bromolauric acid bromide, and a hydrophile group is introduced into the amide by reacting the latter with a sulphite, a thiosulphate, an alkali alcoholate, particularly an alkali-metal compound of a polyhydric alcohol or an ether-alcohol, a mercaptide, or a primary, secondary or tertiary amine, e.g. trimethylamine, triethanolamine, dimethylbenzylamine, diethylallylamine, methylglucamine, glycine, sarcosine, alanine, taurine, methyltaurine, sulphanilic acid or aspartic acid; (4) the hydroaromatic amine, e.g. a mixture as specified at (3) above, is acylated by reaction with an unsaturated carboxylic acid, e.g. acrylic, crotonic, oleic or cinnamic acid, and a hydrophile group is introduced into the amide by sulphonation, sulphitation, or addition of a mercaptocarboxylic or mercaptosulphonic acid; (5) an amide prepared as described above from a carboxylic acid containing an aromatic nucleus is sulphonated.  In the examples, (1) 4-sec.-octylcyclohexylamine is heated with phenoxyacetic acid, and the amide so obtained is sulphonated with sulphuric acid; 4-sec.-dodecyl-2-methylcyclohexylamine may be similarly treated; (2) 4-sec.-octylcyclohexylmethylamine is heated with cresoxyacetic acid and the amide so obtained is sulphonated with sulphuric acid; (3) 4-sec.-octylcyclohexylamine is condensed with chloracetyl chloride in the presence of dimethylaniline, and the amide so obtained is heated with sodium sulphite solution; 4-sec.-octylcyclohexylmethylamine, or a mixture of 4-sec.-hexyl-, sec.-octyl-, sec.-decyl- and sec.-dodecyl-2-methylcyclohexylamines, may be similarly treated; (4) 4-sec.-octylcyclohexylmethylamine is heated with succinic acid to yield a monoamide containing a free carboxylic acid group; a similar product is obtained if phthalic anhydride is used in place of succinic acid.  Mention is made also of the manufacture of carboxylic amides from hydroaromatic amines containing a decahydronaphthalene or a dodecahydro-diphenyl nucleus substituted as described above.  Specification 482,580 is referred to.