Patent GB-278037-A (GB)
Title: Manufacture and production of carbazides and thiocarbazides of the naphthalene series
IPC: C07C281/06
Filed: 1926-05-25
Abstract: 278,037. British Dyestuffs Corporation, Ltd., Dyson, G. M., Mason, F. A., and Renshaw, A. May 25, 1926. Samples furnished. Carbazides and thiocarbazides of the naphthalene series are obtained by the action of phosgene or thiophosgene on hydrazines of the general. formula where n is an integer greater than one, P is a sulphonated naphthalene or acenaphthene residue,. Q and R are same or different aryl, aralkyl or aralkylene residues, and X and Y are either carbonyl, -CO-, or sulphonyl, -SO2-. The hydrazines are obtained by condensing nitroarylolefinic-carboxylic acid chlorides, nitroaryl fatty acid chlorides, nitroaroyl chlorides, nitroarylsulphochlorides, nitronaphthoyl chlorides, nitronaphthalene sulphochlorides or their substitution products with naphthylamine sulphonic acids or their substitution products or with aminoacenaphthene sulphonic acids or their substitution product, followed by reduction of the nitro group, diazotization and further reduction. Before diazotization the amino bodies formed bv the first reduction may be again condensed with nitroacidyl halides and reduced, this process being repeated several times, if desired, before converting into the hydrazines by diazotization and reduction. The following parent materials are specified :-2-, 3-, and 4-nitrocinnamyl chlorides, 1-nitronaphthalene-5-sulphochloride, 1 : 5-nitronaphthoyl chloride, 2- and 4-nitrophenylacetyl chlorides, nitrobenzoyl, chlorides, nitroanisoylchlorides nitrotoluyl chlorides, nitrobenzene sulphochlorides. chlor-, brom-, and iodo-nitrobenzoyl chlorides, 1: 8-aminonaphthol-3 : 6-disulphunic acid, 1-naphthylamine-4:8-disulphonic acid, 1-naphthylamine-3 : 6 : 8-and-4 : 6 : 8-trisulphonic acids, chlor-, brom-. or iodo-naphthylamine sulphonic acids (obtained by halogenating naphthylamine sulphonic acids by known methods, or by halogenating acetylnaphthylamine sulphonic acids by known methods. or by halogenating acetylnaphthylamine sulphonic acids and hydrolyzing the products), alkoxynaphthylamine sulphonic acids. 1 : 5-aminonaphthol-7-sulphonic acid, 2 : 8-aminonaphthol-3 : 6-disulphonic acid, 4-aminoacenaphthene-3-and 5-sulphonic acids, 4- aminoacenaphthene 3 : 5-disulphonic acid, and 4- aminoacenaphthene-trisulphonic acids (obtained by further sulphonating 4-aminoacenapthene-5- sulphonic acid of 4-nitroacenaphthene-5-sulphonic acid with oleum, and reducing the product if necessary). The products may be used as therapeutic agents for the destruction of blood parasites. or as intermediate for the manufacture of colouring matters. In an example, 1-naphthylamine-4 : 6 : 8-trisulphonic acid is condensed with o-nitro-p-toluyl chloride in alkaline solution, the product is acidified, reduced with iron. further condensed with m-nitrobenzoyl chloride in alkaline solution, again reduced, then diazotized and reduced to the hydrazine compound with sodium hydrosulphite; finally the hydrazine compound is converted into the carbazide by treating with phosgene dissolved in toluene. The product is a pale red powder. By employing thiophosgene in place of phosgene the corresponding thiocarbazide is obtained. Specifications 9472/14, 20192/14, and 224,849 are referred to.