Patent GB-630492-A (GB)
Title: Manufacture of new derivatives of amides
IPC: D06M13/425
Filed: 1946-07-05
Abstract: New amide derivatives are prepared by causing to react at a raised temperature one mol. of an aliphatic carboxylic acid amide or an aliphatic urethane, containing at least one hydrogen atom bound to an amide-nitrogen atom, with at least 1 mol. of an inorganic bisulphite and one mol. of an aldehyde having at least one sulphonic acid group in the form of a water-soluble salt or with at least two mols. of an inorganic bisulphite and one mol. of an aldehyde containing an ethylenic double bond, and if desired, conducting the reaction with the addition of an inert solvent or, as a catalyst, a small quantity of a secondary amine.  The reaction is normally effected by heating the reactants with stirring, for example at 100-200 DEG  C.; instead of using a solvent, the amide may be dissolved or finely dispersed in an aqueous solution of the bisulphite and aldehyde or the aldehyde-bisulphite compound followed by distillation of the water and completion of the reaction by heating for example, to 120-160 DEG C.  To assist the splitting off of water which occurs, reaction may be effected under reduced pressure as with azeotropic distillation with the aid of an auxiliary solvent.  The transfer of heat may be facilitated by addition of finely sub-divided inert solid substances such as sodium sulphate.  The products contain two sulphonic acid groups, the bisulphite combining additively with the double bond in the case of the ethylenic unsaturated aldehydes, and they find application as textile assistants (see Group IV (c)).  According to typical examples: (1) commercial stearic acid amide is dissolved in formyl-morpholine with heating and there are added in portions first crotonaldehyde and then sodium bisulphite and the mixture is heated at 130-140 DEG  C. until it is water-soluble; to isolate the product, alcohol is added and the product filtered off or alternatively the formyl-morpholine is removed by distillation under reduced pressure; (2) oleic acid amide, crotonaldehyde and finely-pulverised sodium bisulphite are heated with slow stirring at 150-160 DEG  C., a small amount of piperidine being added when the mixture has melted; after the reaction mixture has become water-soluble, it is refluxed with absolute alcohol, cooled and the product filtered off; (3) commercial stearic acid amide, sodium bisulphite and sodium benzaldehyde-o-sulphonate or cinnamic aldehyde are reacted as in (1), the solvents used being formyl-morpholine and diethyleneglycol respectively; (4) coconut oil fatty acid amide in diethylene glycol is reacted as in (1) above; (5) crotonaldehyde, sodium bisulphite and a small quantity of piperidine are added to a hot solution of octadecyl urethrane in diethyleneglycol, the mixture heated at 130-140 DEG  C. and the product isolated by extracting the solvent with acetone.  Other amido compounds specified as starting materials are the amides of formic acid, acetic acid, chloracetic acid, propionic acid, chloropropionic acid, glycollic acid, acrylic acid, butyric acid, caprylic acid, lauric acid, palmitic acid, linolenic acid, hardened train oil fatty acid, maleic acid and adipic acid and N-substitution products of such amides for example, N-methyl, N-ethyl, N-oxyethyl, N-oxypropyl, N-dioxypropyl or N-phenyl lauric acid amide; N : N1-diacylated methylene diamines such as N : N1-di-stearyl methylene-diamine; and diurethanes such as methylene dioctadecyl-urethane.  Further examples of the aldehyde reactants are water-soluble salts of acetaldehyde sulphonic acid and the propionaldehyde and butyraldehyde sulphonic acids, acrolein and citronellal.  Alkaline earth metal bisulphites may be used as well as the alkali metal compounds.  Additional amines mentioned as catalysts are di-ethanolamine and di-isoamylamine.  The Specification as open to inspection under Sect. 91 includes the use of amides in general which have at least one-amido hydrogen atom, is not limited to the use of the above-mentioned proportions of reactants and states that pyrosulphites may replace the bisulphites and that the aldehyde sulphonic acids may be used as well as their salts.  The amido starting materials specified include aliphatic aromatic and heterocyclic carboxylic acid amides including, in addition to the above amides, those of benzoic acid, naphthoic acid, para-stearylamino benzoic acid, hexahydrobenzoic acid, tetrahydronaphthyl-acetic acid, resin acids or naphthenic acids such as abietic acid, chlormethyl benzoic acid and N-substitution products of these amides; secondary amides such as dibenzamide; cyclic amides such as phthalimide and diketopiperazine; amides of the urea group such as urea, mono-ethyl-monophenyl-, monododecyl-, monooctadecyl or N : N1-didodecyl urea; thiourea, dicyandiamide and melamine; hydrazides such as lauric acid hydrazide; and sulphonamides such as aromatic sulphonamides and those obtained by reacting paraffin hydrocarbons with chlorine and sulphur dioxide and treating the product with ammonia or a primary amine.  This subject-matter does not appear in the Specification as accepted.ALSO:Textile assistants comprise new amide derivatives obtained in specified manner by reaction between an aliphatic carboxylic acid amide or aliphatic urethane having at least one amidohydrogen atom and an inorganic bisulphite and an aldehyde containing an ethylenic double bond or a sulphonic acid group in the form of a water-soluble salt (see Group IV (b)), the amide derivatives obtained having two sulphonic acid groups.  They may be used, for example, as wetting agents in concentrated solutions of electrolytes for instance in mercerizing liquors.  The preferred compounds have an aliphatic residue of at least 8 carbon atoms. These may be used as wetting, dispersing, washing or softening agents, and dyeing assistants, and as agents for preventing the agglomeration of fibres in the manufacture of staple fibres of regenerated cellulose.  They may be used alone or in conjunction with other additions commonly used with textile assistants. Examples describe products, which are water-soluble and generally give foaming solutions having good washing properties, derived from (1) stearic acid amide, crotonaldehyde and sodium bisulphite; (2), (3) oleic acid, crotonaldehyde and sodium bisulphite; (4), (5) stearic acid, sodium bisulphite and sodium benzaldehyde-o-sulphonite or cinnaldehyde; (6) coconut oil fatty acid amide, crotonaldehyde and sodium bisulphite; (7) octadecyl urethane, crotonaldehyde and sodium bisulphite; (8) the product of (1) is used in aqueous solution with sodium sulphate in the washing of wool. Numerous other starting materials are specified.  The Specification as open to inspection under Sect. 91 relates to products of the above-mentioned type prepared from amides in general, including aliphatic, aromatic and heterocyclic carboxylic acid amides, ureas, urethanes, hydrazides, sulphonamides, thiourea, melamine and dicyandiamide and gives many examples of these starting materials. Reference is made to the use of pyrosulphites in place of bisulphites in the preparation of the compounds.  This subject-matter does not appear in the Specification as accepted.