Patent GB-463828-A (GB)
Title: Improvements in the manufacture and production of carboxylic amides containing free carboxylic groups and their salts
Filed: 1936-02-29
Abstract: Products having wetting, washing, and dispersing properties are obtained by the reaction of amines of the type NHRR<1>, where R is an aromatic radicle substituted in the nucleus by a hydrocarbon radicle (other than a purely aromatic or a cycloaliphatic-aromatic radicle) of at least two carbon atoms, and R<1> is hydrogen or a hydrocarbon radicle, with polycarboxylic acids or their acid salts, anhydrides, esters or other functional derivatives, the proportions and other reaction conditions being such that the products contain at least one free or merely neutralized carboxylic group derived from the polycarboxylic acid or derivative; if esters of the polycarboxylic acids are used, the ester group in the products must be saponified, e.g. with caustic soda solution.  The products are of the type RR<1>NCOR<11>COOH, where R and R<1> are as above and R<11> is an aromatic, cycloaliphatic or aliphatic radicle, which may be interrupted by oxygen, nitrogen or sulphur.  The reaction may be effected by heating the components, generally in equimolecular proportions or with the carboxylic acid or its derivative in excess, to 60--250 DEG  C. in the presence or absence of a solvent or diluent, e.g. benzine or a chlorinated hydrocarbon.  The products may be used as free acids or as alkali or ammonium salts or salts with amines such as dimethylamine or ethylamine.  Examples are given of the manufacture of products from (1) p - dodecylmethylaniline and diglycollic anhydride, (2) a mixture of o- and p-isooctylaniline and maleic anhydride, and (3) C-isononylaniline and diethyl oxalate. Other specified products are diglycollic acid mono-(p-butylanilide) and mono-(p-dodecylmethyl-anilide), phthalic acid mono - (C - isooctyltoluidide), and maleic acid mono-(C-dibutylanilide). Other specified amines which may be treated are p-isohexylmethylaniline, p-dodecyl-o-toluidine, 4-hexyl-1-naphthylamine, p-cyclohexylethylaniline, and C - benzylaniline (a mixture of o- and p-benzylanilines).  Other specified acids which may be used, as such or as their functional derivatives, are tartaric, citric, succinic and adipic acids. Specification 449,081 is referred to.  Samples have been filed under Sect. 2 (5) of products prepared from (1) 5 - isooctyl-2-methoxyaniline and hexahydrophthalic anhydride, (2) C-isononylaniline and thiodiglycollic acid dimethyl ester, and (3) C-isononylaniline and a mixture of the ethyl esters of aminodiacetic acid (NH(CH2COOH)2) and aminotriacetic acid (N(CH2COOH)3).  The Specification as open to inspection under Sect. 91 defines R in the formul  above as an aromatic radicle substituted in the nucleus by one or more hydrocarbon radicles, and states that halides of the polycarboxylic acids may be used in the reaction. Ethylene-bis-glycollic acid is an additional acid specified.  This subject-matter does not appear in the Specification as accepted.ALSO:Products having dispersing properties are obtained by reacting of amines of the type NHRR<1>, where R is an aromatic radicle substituted in the nucleus by a hydrocarbon radicle (other than a purely aromatic or a cycloaliphatic-aromatic radicle) of at least two carbon atoms, and R<1> is hydrogen or a hydrocarbon radicle, with polycarboxylic acids or their functional derivatives, free or merely neutralized carboxylic group derived from the polycarboxylic acid or derivatives; if esters of the polycarboxylic acids are used, the ester group in the products must be saponified to yield products of the type RR<1>NCOR<11>COOH, where R and R<1> are as above and R<11> is an aromatic, cycloaliphatic or aliphatic radicle, which may be interrupted by oxygen, nitrogen or sulphur.  The products may be used as free acids or as alkali or ammonium salts or salts with amines such as dimethylamine or ethylamine. Examples are given of the manufacture of products from (1) p-dodecylmethylaniline and diglycollic anhydride, (2) a mixture of o- and p-isooctylaniline and maleic anhydride, and (3) C-isononylaniline and diethyl oxalate. Other specified products are diglycollic acid mono-(p-butylanilide) and mono-(p-dodecylmethylanilide), phthalic acid mono-(C-isooctyltoluidide), and maleic acid mono-(C-dibutylanilide). Other specified amines which may be treated are p - isohexylmethylaniline, p-dodecyl-o-toluidine, 4-hexyl-1-naphthylamine, p-cyclohexylethylaniline, and C-benzylaniline (a mixture of o- and p-benzylanilines).  Other specified acids which may be used, as such or as their functional derivatives, are tartaric, citric, succinic and adipic acids. Specification 449,081 is referred to.  Samples have been filed under Sect. 2 (5) of products prepared from (1) 5 - isooctyl - 2 - methoxyaniline and hexahydrophthalic anhydride, (2) C-isononylaniline and thiodiglycollic acid dimethyl ester, and (3) C-isononylaniline and a mixture of the ethyl esters of aminodiacetic acid (NH(CH2COOH)2) and aminotriacetic acid (N(CH2COOH)3).  The Specification as open to inspection under Sect. 91 defines R in the formul  above as an aromatic radicle substituted in the nucleus by one or more hydrocarbon radicles. Ethylene-bis-glycollic acid is an additional acid specified.  This subject-matter does not appear in the Specification as accepted.