Patent GB-494249-A (GB)
Title: Manufacture of amino-substituted arsenobenzene formhaldehydebisulphite compounds
IPC: C07F9/74
Filed: 1937-04-23
Abstract: Arsenobenzene derivatives are prepared by (1) reducing a hydroxyalkylamino-hydroxybenzene-arsonic acid together with an aminohydroxybenzene-arsonic acid, which may also contain a hydroxyalkyl residue, and treating the resulting arsenobenzene with sodium formaldehyde-bisulphite; (2) condensing the arsine corresponding with one arsonic acid of (1) with the arsenoxide or arsine dichloride corresponding with the other; (3) interaction of a symmetrical hydroxyalkylamino-hydroxy-arsenobenzene with a symmetrical amino-hydroxyarsenobenzene, which may also contain a hydroxyalkyl residue, in equimolecular proportions and treating the unsymmetrical product with sodium formaldehyde-bisulphite; the latter treatment may be dispensed with if one of the arsenobenzene starting materials is used in the form of its sodium formaldehyde-bisulphite compound.  According to the examples, (1) a mixture of 3-(dihydroxypropyl) amino - 4 - hydroxybenzene - 1 - arsonic acid and 3 - amino - 4 - hydroxybenzene - 1-arsonic acid is reduced with hypophosphorous acid or a hydrosulphite and the product treated with sodium formaldehyde - bisulphite; (2) 3 - (dihydroxypropyl - hydroxyethyl) amino - 4 - hydroxybenzene - 1 - arsonic acid (see Specification 447,773) and 3-hydroxy-4 - aminobenzene - 1 - arsonic acid are reduced with hypophosphorous acid and the product reacted with sodium bisulphite and formaldehyde; (3) 3 - (bis - dihydroxypropyl)amino-4 - hydroxybenzene - 1 - arsonic acid (see Specification 447,773) and 3 - (dihydroxypropyl) amino - 4 - hydroxybenzene - 1-arsonic acid are reduced and treated with sodium formaldehyde - bisulphite; (4) 3-hydroxy - 4 - (dihydroxypropyl - hydroxyethyl) aminobenzene - 1 - arsonic acid is reduced with potassium iodide and sulphurous acid to the arsenoxide and reacted in hydrochloric acid solution with 3-amino-4-hydroxybenzene - 1 - arsine (see Specification 11625/11, [Class 2 (iii)]); (5) 3 : 31-diamino-4 : 41-dihydroxyarsenobenzene (see Specification 13485 /10, [Class 2 (iii)]) and 3 : 31-bis-(dihydroxypropyl)amino-4 : 41 - dihydroxyarsenobenzene, prepared by reducing the corresponding arsonic acid, are heated in the form of their hydrochlorides in aqueous solution and the rearrangement product reacted with sodium formaldehyde-bisulphite; (6) 3 : 31-di-(bis-dihydroxypropyl)amino - 4 : 41 - dihydroxy - 5 : 51 - di(acetylamino)-arsenobenzene is heated in aqueous solution with sodium 3 : 31-dihydroxy4 : 41-diamino-arsenobenzene-di-(formaldehydebisulphite), prepared by reducing 3-hydroxy-4-aminobenzene-1-arsonic acid and treating with sodium formaldehyde - bisulphite; (7) 3 : 31-bis - (dihydroxypropyl - hydroxyethyl)amino-4 : 41 - dihydroxyarsenobenzene dihydrochloride is heated with the dihydrochloride of 3 : 31 - diamino - 4 : 41 - dihydroxy - 5 : 51-dimethoxy - arsenobenzene, prepared from the arsonic acid described in Specification 373,085, and the product transformed with sodium formaldehyde-bisulphite. Specification 372,213 also is referred to.  Arsonic acids.-3 - (Dihydroxypropyl)amino-4 - hydroxybenzene - 1 - arsonic acid is obtained by the action of 1 mol of glycide on 3 - amino - 4 - hydroxybenzene - 1 - arsonic acid.  3 - (Bis - dihydroxypropyl)amino-4-hydroxy - 5 - acetylaminobenzene - 1 - arsonic acid is prepared by nitrating 4-hydroxy-5-acetylaminobenzene - 1 - arsonic acid, reducing the 3-nitro product and treating it with 2 mols of glycide. 3-Hydroxy-4-(dihydroxypropyl - hydroxyethyl)aminobenzene - 1 - arsonic acid is obtained by the action of 1 mol of ethylene oxide and 1 mol of glycide on 3-hydroxy-4-aminobenzene-1-arsonic acid.