Patent GB-536011-A (GB)
Title: Process for the production of colourless halogen substituted urea sulphonic acids, and the resulting products
IPC: C07C309/51
Filed: 1939-06-15
Abstract: 536,011. Halogenated urea sulphonic acids. GEIGY AKT.-GES., J. R. June 15, 1939, Nos. 17505 and 17506. Convention dates, June 16, 1938, and Dec. 31, 1938. Samples furnished. [Class 2 (iii)] [Also in Group VIII] Colourless halogen substituted urea sulphonic acids of the benzene series are made by treating with phosgene colourless mono-amines or monoaminosulphonic acids of the benzene series, which in the case of polynuclear compounds contain directly linked benzene nuclei or as linking members between the benzene nuclei the atoms O or S or the groupings SO, SO 2 , NH, CH 2 , CONH, or NH-CO-NH, the reaction components being so selected that at least one halogen atom and one sulphonic group are present in the final product ; alternatively these may be introduced by subsequent halogenation or sulphonation. Heterocyclic compounds of the general formula where X is a direct linkage or O, and Y is O or S, may also be employed as parent materials. Amino-sulphonic acids of diphenyls, diphenylethers, diphenylmethanes, diphenylsulphides, diphenylsulphoxides, diphenylsulphones, di - phenylamines, benzanilides, and diphenylureas may be used as parent materials, as well as simple sulphonic acids of aniline, anisidine and nitraniline. The products may be used for protecting wool and other substances against damage by moths, and also as disinfectants, bactericides, fungicides and seedsteeping materials. In examples (1) 4-amino- 4<SP>1</SP> - chloro - 5<SP>1</SP> - methyl - 1 : 11 - diphenylether - 2 - sulphonic acid is treated with phosgene ; a large number of other chlorodiphenylether sulphonic acids is specified ; these may be made by condensing o- and p-chloronitrobenzene sulphonic acids with phenols and reducing; (2) 2-amino-4:4<SP>1</SP>-dichlor-1:1<SP>1</SP>-diphenylether-2<SP>1</SP>- sodium sulphonate is treated with phosgene ; the parent material is made by sulphonating 2-amino-4:4<SP>1</SP>-dichloro-1:1<SP>1</SP>-diphenyl ether, a long list is given of similarly obtained chloraminodiphenylether sulphonic acids which may be used; (3) 3-amino-4<SP>1</SP>-chlor-4-(4<SP>11</SP>-chlor-5<SP>11</SP>- methyl-2<SP>11</SP> sulpkophenoxy)-1:1<SP>1</SP>-diphenylsul - phone, made by condensing 4:4<SP>1</SP>-dichlor-3- nitro-1:1<SP>1</SP>-diphenylsulphone with 3-methyl-4- chlorphenol, reducing, and sulphonation, is treated with phosgene ; other phenoxydiphenylsulphone sulphonic aids, which may be used, are specified; (4) 2-amino-4<SP>1</SP>-chlor-1:1<SP>1</SP>-diphenylsulphide - 4 - sodium sulphonate, made by condensing 4-chlorthiophenol with o-chlorntrobenzene-sulphonic acid and reducing, is treated with phosgene ; a long list is given of similar aminochlordiphenylsulphide sulphonic acids which may be used ; (5) 4-amino-41- chlor-1:1<SP>1</SP>-diphenylamine-2 sulphonic acid, made by condensing p-chloranilinewith p-chlornitrobenzenesulphonic acid and reducing, is treated with phosgene; other aminochlordiphenylamine sulphonic acids are specified ; (6) 4-amino-4<SP>1</SP>-chlor-1:1<SP>1</SP>-diphenylsulphone-2- sulphonic acid is treated with phosgene ; (7) 2-amino-4:4<SP>1</SP>-dichlor-1:1<SP>1</SP>-diphenylmethane- 2<SP>1</SP>-sulphonic acid (made by condensing nitrop-chlorbenzylchloride with chlorbenzene, reducing and sulphonating, is treated with phosgene ; (8) 3<SP>1</SP>-methyl-4-amino-1:1<SP>1</SP>-diphenylether-2-sulphonic acid is treated with phosgene, and the product is chlorinated introduce .4 or 8 chlorine atoms per molecule. Samples have been furnished under Sect. 2 (5) of the products obtained by treating with phosgene (1) 4 -chlor - 3<SP>1</SP> - aminodiphenyleneoxide sulphonic acid, made by sulphonating 4-chlor-3<SP>1</SP>-aminodiphenylene-oxide, and (2) 3- aminophenothioxene sulphonic acid; the product is chlorinated. The Specification as open to inspection under Sect. 91 comprises the production of halogensubstituted acylamino sulphonic acids of aromatic and heterocyclic compounds in general, by reacting carbonic or thiocarbonic acid derivatives capable of reaction, or substances forming these compounds, on isocyclic or heterocyclic amines. Carbonic and thiocarbonic acid derivatives include chlorides, esters, amides, imides and anhydrides of obeseacids, and aromatic compounds treated include those of the naphthalene series. In further examples (1) 4 - amino - 4<SP>1</SP> - chlor - 1 : 11 - diphenylether is treated with carbon disulphide, and the thiourea obtained is sulphonated ; (2) 4-amino- 4<SP>1</SP>-chlor-1:1<SP>1</SP>-diphenylether-2<SP>1</SP>-sodium sulphonate is treated with phenyl mustard oil to yield a thiourea ; (3) 4-amino-4<SP>1</SP>-chlor-1:1<SP>1</SP>-diphenylether-21-sodium sulphonate is treated with carbon disulphide; (4) 4-amino-4<SP>1</SP>-chlor-1:1<SP>1</SP>- diphenylether is condensed with urea, and the product is sulphonated; (5) 4-amino-4<SP>1</SP>-chlor- 1:1<SP>1</SP>-diphenylether-2-sulphonic acid is treated with thiophosgene to yield a thiourea, and (6) a urethane sulphonic acid is obtained by condensing 2-amino-4:4<SP>1</SP>-dichlorphenylether-2<SP>1</SP>- sodium sulphonate with 4-chlorphenol carbonic acid chloride. The Specification also includes. the subject-matter of Specification 536,047. This subject-matter does not appear in the Specification as accepted.