Patent GB-507207-A (GB)
Title: Manufacture of hydrohalides of substituted iso-thioureas
IPC: C07C335/30
Filed: 1937-12-08
Abstract: 507,207. Wetting &c. agents. GROVES, W. W. (I. G. Farbenindustrie Akt.-Ges.) Dec. 8, 1937, No. 33980. [Classes 2 (iii) and 15 (ii)] Hydrohalides of substituted isothioureas are made by reacting thiourea or a derivative thereof containing at least one reactive hydrogen atom and capable of reacting in the isoform with a halogen-methyl compound of the general formula wherein R stands for an aliphatic, aliphaticcycloaliphatic or aliphatic-aromatic radical containing at least eleven carbon atoms, which may contain substituents and/or may contain an oxygen, sulphur or nitrogen atom as a hetero-atom in an aliphatic carbon chain or as a bridge directly linking an aliphatic portion of the radical to a cycloaliphatic or aromatic nucleus, R1 stands for an alkyl radical which may contain a substituent, X stands for oxyphenyl in which the hydroxyl group is in ortho- or para-position to the halogen-methyl group, or for R2 stands for hydrogen or alkyl, and Hal means a halogen atom. The halogenmethyl starting materials are stated to include the reaction product from formaldehyde or a polymer thereof and a hydrohalic acid with stearic acid nitrile, but are generally made by the reaction of formaldehyde or a polymer and a hydrohalic acid on a phenol, a carboxylic acid amide, a carbamic acid ester or a urea containing a reactive hydrogen atom. The reaction may be effected by kneading the components, if desired with heating up to about 120‹C., or in a solvent such as methylene chloride, carbon tetrachloride, benzene, toluene, xylene, solvent naphtha, benzine or ethyl acetate. Starting materials specified are on the one hand: N - methyl - N- chlormethyl - lauric acid amide, N - chlormethyl - p - isooctylphenoxyacetic acid amide, N - chlormethylhydroxystearic acid amide, N - octadecyl - N - chlormethyl - carbamic acid ethyl ester, N-chlormethyl-carbamic acid 9.10-dichloroctadecyl ester, 1-chlormethyl-2- hydroxy-5-isododecyl-benzene, and on the other hand ethylthiourea, benzylthiourea, triethylthiourea, diphenylthiourea or ethylene-thiourea. The products are soluble in, or capable of being emulsified with, water and may be used in the treatment of textiles. In examples, thiourea is reacted with the chlormethyl compounds obtained by the reaction of hydrogen halides and paraformaldehyde on (1) stearic acid amide (in which case the hydrochloric acid may be replaced by hydrofluoric or hydrobromic acid) ; (2) 9.10-dichlorstearic acid amide ; (3) the N-dodecyl carbamic acid ester of hydroxystearic acid amide; (4) N-dodecylacetamide; (5) p-isotetradecylphenoxyacetic acid amide ; (6) carbamic acid octadecyl ester ; (7) monoctadecyl-urea; (8) stearic acid nitrile (in which case the 'thiourea may be replaced by sym.-diphenylthiourea or N-benzyl-N<1>-ethylthiourea); (9) p-n-dodecylbenzoic acid amide ; (10) adipic - acid di-dodecyl-amide. Also in examples: (11) the amide from hardened train oil fatty acid is converted to its N-chlormethyl compound and the latter is reacted with triethylthiourea; (12) an alkyl phenol prepared by condensation of phenol in presence of boron trifluoride with an olefine obtainable by dimerisation of an olefine fraction containing mainly isohexylene and isoheptylene (formed by the dehydration of the corresponding alcohols formed in the catalytic reduction of carbon monoxide) is converted to its chlormethyl derivative, which is reacted with ethylene thiourea. Specification 497,353 is referred to. 9.10-Dichlorstearic acid amide is obtained by addition of chlorine to oleic acid amide. The N-dodecyl-carbamic acid ester of hydroxystearic acid amide is obtained by the action of dodecyl isocyanate on the amide of hardened ricinoleic acid. p-Isotetradecylphenoxyacetic acid is obtained by the condensation of p-isotetradecylphenol with chloracetic acid.