Patent GB-576361-A (GB)
Title: Hydrazino-1,3,5-triazino derivatives of substituted phenylarsenic compounds
IPC: C07F9/74
Filed: 1943-02-17
Abstract: 1 : 3 : 5-Triazine compounds of the formula <FORM:0576361/IV/1> are prepared by treating a 1 : 3 : 5-triazine compound of the formula <FORM:0576361/IV/2> with a phenylarsenic compound of the formula W-C6H2(D,E)-As=X wherein Y and Z may be halogen, amino, substituted amino, or hydrazino radicals.  C6 represents a benzene ring, D and E may be H or -OH, -As=X represents -AsO3H2 and its salts, -AsO, arsenic dihalides and radicals of the formul  <FORM:0576361/IV/3> One of the radicals T and W is a halogen radical and the other is a -NH-NH2 radical.  If necessary, the products of the above reaction are subjected to the action of a reducing agent to convert a pentavalent arsenic radical into a corresponding trivalent arsenic radical.  This reduction may be carried out with SO2 in hydrochloric acid solution in the presence of hydriodic acid, or by the action of hypophosphorous acid or stannous chloride in hydrochloric acid solution in the presence of hydriodic acid as a catalyst or by the action of sodium hydrosulphite in neutral or alkaline solution.  In cases where the triazine nuclei carry one or more halogen atoms, these may be replaced by amino, substituted amino, or hydrazino groups.  In examples: (1) Arsanilic acid is treated with sodium nitrate, and reduced with Na2S2O4 to form p-hydrazino-phenylarsonic acid, which is then reacted with cyanuric chloride in chloroform solution to form [(2 : 4)-dichloro-1 : 3 : 5-triazinyl - (6)] - p - hydrazino-phenylarsonic acid.  (2) The product of example (1) is treated with one mol. of aqueous hydrazine hydrate to form [(2 : 4)-chloro-hydrazino-1 : 3 : 5-triazinyl-(6)]-p-hydrazino-phenylarsonic acid.  (3) The product of example (1) is treated with two mols. of aqueous hydrazine hydrate to form [(2 : 4)-dihydrazino-1 : 3 : 5-triazinyl-(6)]-p-hydrazino-phenylarsonic acid.  (4) Equi-molecular proportions of trihydrazino-triazine and p-bromobenzene-arsonic acid are reacted in monochlorbenzene in the presence of copper powder to form the same compound as is obtained in example (3).  (5) The product of example (1) is treated with aqueous ammonia to form [(2 : 4)-chloro-amino-1 : 3 : 5-triazinyl-(6)]-p-hydrazino-phenyl arsonic acid.  (6) The product of example (1) is treated with an excess of liquid ammonia to form the corresponding 2 : 4-diamino-compound.  The same compound is also obtained by treating the chloro-amino-compound of example (5) with hot concentrated ammonia.  (7) The chloro-amino-compound of example (5) is treated with aqueous hydrazine hydrate to form [(2 : 4) - amino - hydrazino - 1 : 3 : 5 - triazinyl - (6)] - p - hydrazino - phenyl - arsonic acid.  (8) [(2 : 4)-dihydrazino-1 : 3 : 5-triazinyl - (6) - p - hydrazino - phenylarsonic acid obtained as in example (3) is treated with SO2 in hydrochloric acid solution in the presence of hydriodic acid to form [(2 : 4)-dihydrazino-1 : 3 : 5-triazinyl - (6)] - p - hydrazino - phenyldi - chlorarsine.  This on treatment with ammonia gives [(2 : 4)-dihydrazino-1 : 3 : 5-triazinyl-(6)]-p - hydrazino - phenyl - arsinoxide.  (9) [(2 : 4) - diamino - 1 : 3 : 5 - triazinyl - (6)] - p - hydrazino - phenylarsonic acid prepared according to example (6) is reduced with aqueous sodium hypophosphite in methanolic hydrochloric acid solution in the presence of hydriodic acid to give bis-[(2 : 4)-diamino-1 : 3 : 5-triazinyl-(6)-p-hydrazino-phenyl arsine].  (10) 3 : 4-amino-oxyphenylarsonic acid is treated with sodium nitrate and then reduced with Na2S2O4 to form 3 : 4-hydrazino-oxyphenylarsonic acid which is reacted in chloroform solution with cyanuric chloride to form [2 : 4-dichloro-1 : 3 : 5-triazinyl-(6)] - 31 - hydrazino - 41 - oxyphenylarsonic acid.  This compound couples in alkaline solution with diazobenzene-sulphonic acid to form a red azo dye. (11) The product of example (10) is treated with sodium-p-aminobenzene sulphonate to form [2 - amino - 4 - sulphanilino - 1 : 3 : 5-triazinyl - (6)] - 31 - hydrazino - 41 - oxyphenyl - arsonic acid.  (12) The product of example (11) is reduced with stannous chloride in hydrochloric acid solution in the presence of hydriodic acid to form an arseno compound of the formula <FORM:0576361/IV/4>