Patent GB-580357-A (GB)
Title: Manufacture of n-acylthiomethyl carbonamides
IPC: C07C327/30
Filed: 1945-02-28
Abstract: N-acylthio-methyl carbonamides are prepared by reacting an aliphatic monobasic thiolcarboxylic acid containing up to six carbon atoms with an N-hydroxy methyl or N-alkoxy methyl carbonamide, the term "carbonamide" including the oxygen carbonamides having the grouping -CO.N:, the thiocarbonamides having the grouping -CS.N:, and the imino carbonamides (amidines).  The reaction may be carried out at any temperature up to the decomposition temperature of the reactants but is generally effected between 20 DEG -100 DEG  C.  An acidic catalyst such as hydrochloric acid, sulphuric acid, p-toluene sulphonic acid, ammonium chloride, and phosphoric acid is preferably employed. An inert organic solvent is present desirably, for example, benzene, dioxane, ether or toluene or excess thiolcarboxylic acid. The reaction materials specified include thiolacetic acid, thiol propionic acid, and thiolbutyric acid and the N-hydroxymethyl and N-alkoxymethyl derivatives of acetamide, propionamide, butyramide, lauramide, palmitamide, stearamide, chloracetamide, cyclohexyl-acetamide, nicotinamide, N-ethylpropionamide, maleamide, undecylenamide, thioacetamide, acetamidine, benzamidine, urethane, the mono- or poly-N-hydroxymethyl and -alkoxymethyl derivatives of amides such as oxamide, glutaramide, sebacamide, phthalamide and phthalimide and the mono- or bis-alkoxy or hydroxy methyl derivatives of open chain ureas such as urea itself, thiourea, N-methyl urea, N-phenylurea, N-phenylthiourea, guanidine, N-ethyl guanidine or such cyclic ureas as the N : N1-bis (alkoxymethyl) urons, for example, N : N1-bis (methoxymethyl) uron, the tetrahydro-1 : 3-bis (alkoxy methyl)-s-triazones-(2) such as tetrahydro-1 : 3-bis (methoxymethyl) - 5 - methyl - s - triazone-(2), and the N : N1-bis (alkoxymethyl) ethylene ureas, for example, N : N1-bis (ethoxymethyl) ethylene urea and the corresponding ethylene thiourea derivative and amino-triazine derivatives such as 2 : 4 : 6-tris (methoxymethylamino)-1 : 3 : 5-triazine.  Polymeric amides such as the N-alkoxymethyl or N-hydroxymethyl polyamides or polyester amides, the urea-formaldehyde resins and the dicyandiamide formaldehyde resins may be used to yield polymeric N-acylthiomethyl amides.  The N-oxymethyl derivatives of oxygen carbonamides are preferred; the N-alkoxymethyl amides preferably contain an alkoxy group which is that of an aliphatic alcohol having up to six carbon atoms.  Suitable amide starting materials are described in Specifications 466,015, 537,971 and 557,932.  The N-acylthiomethyl carbonamides, which are stated to be novel, may be hydrolysed to yield N-mercaptomethyl carbonamides, and may be used in petroleum chemicals and pharmaceuticals; the polymeric acylthiomethyl carbonamides are useful as films and fibres and in coating compositions.  In examples: (1) thiolacetic acid is reacted with N : N1-bis(methoxy methyl)urea in dioxane in the presence of hydrochloric acid yielding N : N1-bis (acetyl-thiomethyl) urea which may be used in alkaline solution in conjunction with an alkylene dihalide in the treatment of wool to give improved resistance to alkali (see Group VIII); (2) N : N1-bis (methoxymethyl) adipamide is reacted with thiolacetic acid as in (1) to yield N : N1-bis (acetyl thiomethyl) adipamide; (3) N-(methoxymethyl) polyhexamethylene - adipamide, prepared by reacting polyhexamethylene-adipamide with formaldehyde and methanol in formic acid solution and in which methoxymethyl substituents are attached to about half of the amide groups, is dissolved in acetic acid and reacted with thiolacetic acid in the presence of p-toluene sulphonic acid, yielding N-(acetylthiomethyl) polyhexamethylene - adipamide which gives elastic and clear films when cast from methanol-water solution and which is readily hydroxlysed by alcoholic potassium hydroxide to yield an N-mercaptomethyl derivative; (4) thiolacetic acid in dioxane containing hydrochloric acid is added to a benzene solution of a butanol modified urea-formaldehyde resin followed subsequently by addition of acetic anhydride to remove water, and the resulting mixture is poured into petroleum ether so precipitating the N-acetyl thiomethyl derivative which when cast from benzene solution yields clear films; (5) N-methylol benzamide is reacted with thiolacetic acid as in (1) above so yielding N-acetyl-thiomethyl benzamide; (6) crystalline, monomeric tris (ethoxymethyl) melamine is reacted with thiolacetic acid as in (1) above yielding a crystalline product in which rather more than two of the ethoxy methylamino groups have been replaced by acetylthio-methylamino groups; instead of the crystalline starting material, there may be used the resinous product obtained by reacting melamine, formaldehyde and alcohol at elevated temperature as described in Specification 466,015.  The Specification as open to inspection under Sect. 91 includes the use of any monobasic thiolcarboxylic acid and specifies, in addition to those mentioned above, thiol lauric acid and thiol-benzoic acid.  This subject-matter does not appear in the Specification as accepted.