Patent GB-611215-A (GB)
Title: Manufacture of new amide-like derivatives
IPC: C07C233/00
Filed: 1945-07-13
Abstract: New amide-like derivatives are prepared by reacting an aliphatic or cycloaliphatic carboxylic acid amide or hydrazide, urea, or an aliphatic or cycloaliphatic urea or urethane, containing at least one hydrogen atom attached to at least one amido-nitrogen atom, with a mercaptan and an aldehyde containing at least two directly connected carbon atoms or an acetal of such an aldehyde.  Reaction is advantageously effected at raised temperature, for example, from 60 DEG  to 100 DEG  C. and, if desired, in the presence of a solvent such as water, methanol, ethanol, acetone, dioxane or glacial acetic acid and of acids acting as catalysts.  The reactants may be brought into reaction simultaneously or in succession.  When a reactant, for example, the aldehyde, contains an ethylenic double bond, additive combination may occur between the double bond and the mercaptan if enough of the latter be present.  The preferred products are those derived from mercaptans containing a carboxylic or sulphonic acid group, the alkali metal salts thereof being soluble.  Enhanced solubility results when products containing an ethylenic double bond are treated with a bisulphite or when products containing an hydroxyl group are converted into sulphuric acid esters.  In examples: (1) commercial stearic acid amide and thioglycollic acid are melted together, crotonaldehyde added and the mixture heated, thereafter, the product is added to water, neutralized with sodium carbonate and evaporated to dryness yielding a sodium salt which gives foaming aqueous solutions and from which salt the free acid can be obtained by treatment with a mineral acid; similar products are obtained when the crotonaldehyde is replaced by acrolein, cinnamic aldehyde, anhydrous glucose, butyraldehyde or acetaldehyde.  (2) Commercial coconut oil fatty acid amide, crotonaldehyde and thioglycollic acid are reacted as in (1) above to yield a similar product.  The condensation products derived from acrolein and crotonaldehyde respectively as described in (1), are each reacted either (3) with more thioglycollic acid to yield products soluble in dilute alkalies or (4) with sodium bisulphite to yield products isolated as free sulphonic acids or sodium salts thereof.  (5) A condensation product obtained by heating coconut oil fatty acid hydrazide with anhydrous glucose in absolute alcohol in presence of boric acid is heated with thioglycollic acid and the resulting product isolated in the form of its sodium salt.  (6) Stearic acid hydrazide and crotonaldehyde are heated together in absolute alcohol and then refluxed with thioglycollic acid yielding a monocarboxylic acid product which on heating with excess thioglycollic acid yields a dicarboxylic acid. Other amido starting materials specified are amides derived from formic, acetic, acrylic, caprylic, lauric, oleic, linoleic, maleic and adipic acids, hardened train oil fatty acid, resin or naphthenic acids, chloracetic acid and glycollic acid; their N-substitution products such as N-methyl, N-oxyethyl and N-phenyl lauric acid amides; N : N1-diacylated methylene diamides; urea, mono-ethyl urea and dodecyl-urea; octadecyl urethane and methylene di-octadecylurethane; hydrazides corresponding to the above-mentioned amides, for example, lauric acid hydrazide. Additional aldehydes referred to include lauric aldehyde, chloral, benzaldehyde, furfural, aldehydes containing at least one sulphonic acid group such as acetaldehyde and benzaldehyde sulphonic acids and aldehydes containing at least one hydroxyl group, including semi-acetals thereof, such as oxy-benzaldehydes, l-arabinose, d-glucose and maltose.  Further examples of mercaptans are oxyethyl, 2 : 3-dioxypropyl and hexadecyl mercaptans and b -mercapto-ethane sulphonic acid or its salts.  The Specification as open to inspection under Sect. 91 includes the use of amides generally as starting materials and states that the process may include the step of introducing into the products a group imparting water solubility. Additional amides specified include aromatic and heterocyclic carboxylic acid amides such as benzoic acid amide, para-stearylamino benzoic acid amide; cyclic amides, for example phthalamide and diketopiperazine; monophenyl urea, thiourea, dicyandiamide and melamine; and paraffinic and aromatic sulphonamides.  The aldehydes used may contain a substituent convertible into a group imparting water-solubility, for example, chloracetaldehyde.  Those products containing a reactive halogen atom may be treated with sulphites, thiosulphates or tertiary amines.  This subject-matter does not appear in the Specification as accepted.ALSO:New amide-like derivatives are prepared by reacting an aliphatic or cyclo-aliphatic carboxylic acid amide or hydrazide, urea, or an aliphatic or cyclo-aliphatic urea or urethane, containing at least one hydrogen atom attached to at least one amido-nitrogen atom, with a mercaptan and an aldehyde containing at least two directly connected carbon atoms or an acetal of such an aldehyde.  Reaction is advantageously effected at raised temperature, for example, from 60 DEG  to 100 DEG C. and, if desired, in the presence of a solvent such as water, methanol, ethanol, acetone, dioxane or glacial acetic acid and of acids acting as catalysts.  The reactants may be brought into reaction simultaneously or in succession.  When a reactant, for example, the aldehyde contains an ethylenic double bond, additive combination may occur between the double bond and the mercaptan if enough of the latter be present.  The preferred products are those derived from mercaptans containing a carboxylic or sulphonic acid group, the alkali metal salts thereof being soluble.  Enhanced solubility results when products containing an ethylenic double bond are treated with a bisulphite or when products containing an hydroxyl group are converted into sulphuric acid esters.  The products may be used as textile assistants and those containing an aliphatic residue of at least 12 carbon atoms which are water-soluble may be used as wetting, washing, dispersing, softening or dyeing assistants and as agents for opening up agglomerations of coherent fibres in the manufacture of regenerated cellulose staple fibre; they may be used with other textile assistants.  In examples: (1) commercial stearic acid amide and thioglycollic acid are melted together, crotonaldehyde added and the mixture heated; thereafter, the product is added to water, neutralized with sodium carbonate and evaporated to dryness yielding a sodium salt which gives foaming aqueous solutions and from which salt the free acid can be obtained by treatment with a mineral acid; similar products are obtained when the crotonaldehyde is replaced by acrolein, cinnamic aldehyde, anhydrous glucose, butyraldehyde or acetaldehyde.  (2) Commercial coconut oil fatty acid amide, crotonaldehyde and thioglycollic acid are reacted as in (1) above to yield a similar product.  The condensation products derived from acrolein and crotonaldehyde p  respectively as described in (1), are each reacted either (3) with more thioglycollic acid to yield products soluble in dilute alkalies or (4), with sodium bisulphite to yield products isolated as free sulphonic acids or sodium salts thereof.  (5) A condensation product obtained by heating coconut oil fatty acid hydrazide with anhydrous glucose in absolute alcohol in presence of boric acid is heated with thioglycollic acid and the resulting product isolated in the form of its sodium salt.  (6) Stearic acid hydrazide and crotonaldehyde are heated together in absolute alcohol and then refluxed with thioglycollic acid yielding a monocarboxylic acid product which on heating with excess thioglycollic acid yields a dicarboxylic acid.  (7) Wool yarn is washed in an aqueous solution of the product of (1) derived from crotonaldehyde.  Other amido starting materials specified are amides derived from formic, acetic, acrylic, caprylic, lauric, oleic, linoleic, maleic and adipic acids, hardened train oil fatty acid, resin or naphthenic acids, chloracetic acid and glycollic acid; their N-substitution products such as N-methyl, N-oxyethyl and N-phenyl lauric acid amides; N : N1-diacylated methylene diamides; urea, mono-ethyl urea and dodecylurea; octadecyl urethane and methylene dioctadecylurethane; hydrazides corresponding to the above-mentioned amides, for example, lauric acid hydrazide.  Additional aldehydes referred to include lauric aldehyde, chloral, benzaldehyde, furfural, aldehydes containing at least one sulphonic acid group such as acetaldehyde and benzaldehyde sulphonic acids and aldehydes containing at least one hydroxyl group, including semi-acetals thereof, such as oxy-benzaldehydes, l-arabinose, d-glucose and maltose.  Further examples of mercaptans are oxyethyl-, 2 : 3-dioxypropyl- and hexadecylmercaptans and b -mercapto-ethane sulphonic acid or its salts.  The Specification as open to inspection under Sect. 91 includes the use of amides generally as starting materials and states that the process may include the step of introducing into the products a group imparting water solubility. Additional amides specified include aromatic and heterocyclic carboxylic acid amides such as benzoic acid amide, para-stearylamino benzoic acid amide; cyclic amides, for example phthalimide and diketopiperazine; monophenyl urea, thiourea, dicyandiamide and melamine; and paraffinic and aromatic sulphonamides.  The aldehydes used may contain a substituent convertible into a group imparting water-solubility, for example, chloracetaldehyde.  Those products containing a reactive halogen atom may be treated with sulphites, thiosulphates or tertiary amines.  This subject-matter does not appear in the Specification as accepted.ALSO:New amide-like derivatives having surface-active properties are prepared by reacting an aliphatic or cycloaliphatic carboxylic ac