Patent GB-762187-A (GB)
Title: Metal complexes of hydrazide-hydrazones and process for producing the same
IPC: C07D213/86
Filed: 1953-10-09
Abstract: The invention comprises metal complexes of hydrazones of hydrazides of heterocyclic carboxylic acids, the metals being of the fourth Period and Groups 2 to 8 of the Periodic Table. Suitable metals are iron, cobalt, zinc, manganese, vanadium and nickel.  The complexes are prepared by reacting a compound of the metal, e.g. a salt, with the hydrazone, in water or other solvent such as alcohol.  The heterocyclic acid radical may be derived from nicotinic, isonicotinic, alkylisonicotinic, pyromucic, and quinoline, thiophene, pyrazole and pyrimidine carboxylic acids. Particularly useful products are obtained when the hydrazone is derived from an aldehyde or ketone which bears in the 2-position to the oxo group a substituent capable of participating in the complex formation. Examples of such aldehydes and ketones are o-hydroxybenzaldehyde and its derivatives, e.g. the 3,5-dichloro- and 6-nitro-derivatives, 2-naphthol-1-aldehyde, o-amino-benzaldehyde, pyridine-2-aldehyde, pyrrole-2-aldehyde, furfural, resorcylaldehyde, phthalaldehyde acid, p-chloro-phenyl glyoxal, resacetophenone, o-quinones, glycol aldehyde, dextrose, glyceryl aldehyde, glyoxalic acid and diacetylmonoxime and bilateral reaction products of such o-dioxo compounds as glyoxal and diacetyl with the hydrazides.  In the examples: (1) the compound <FORM:0762187/IV(b)/1> is obtained from ferric ammonium sulphate and o-hydroxy-benzalisonicotinic acid hydrazide hydrazone; (2) (a) the chloride salt is obtained starting from ferric chloride, (b) the corresponding complex is obtained from ferric chloride and fural-isonicotinic acid hydrazide-hydrazone; (3) the compound having the approximate formula <FORM:0762187/IV(b)/2> is obtained from iron butylate and o-hydroxybenzalisonicotinic acid hydrazide-hydrazone.  Analogous results are obtained using iron acetyl acetonate or other non-ionic metal compounds; (4) the same hydrazone as in (3) is reacted with cobaltous chloride to form a complex; (5) using the same hydrazone and manganese chloride, a complex is obtained which contains 2 chlorine atoms to 1 molecule of hydrazone and which on boiling yields a complex of lower chlorine content; (6) the compound of the formula <FORM:0762187/IV(b)/3> is prepared from ammonium vanadate and the same hydrazone as in (1); (7) a complex is obtained from ferric chloride and o-hydroxypyromucic acid hydrazide-hydrazone; (8) the hydrazone used in (1) is reacted with zinc chloride to give a complex containing 4 mols. of hydrazone to 3 mols. of zinc chloride; (9) nickelous chloride is reacted with (a) the hydrazone of isonicotinyl hydrazide and 2-hydroxynaphthaldehyde-1, (b) the hydrazone used in (1), (c) the hydrazone of o-hydroxypyromucic acid hydrazide; (10) a bivalent iron complex is prepared from iron chloride and benzal-isonicotinyl hydrazide hydrazone; (11) the bilateral reaction product of diacetyl and isonicotinyl hydrazide is refluxed with iron chloride to give a soluble complex; (12) ferric chloride is reacted with the isonicotinyl hydrazide-hydrazone of (a) resorcaldehyde, (b) 2-hydroxy-3-methoxy-benzaldehyde, and (c) 2-hydroxy-4-methoxy benzaldehyde.  Also specified is the complex <FORM:0762187/IV(b)/4> prepared from the hydrazone <FORM:0762187/IV(b)/5> which is obtained from 2,4-dihydroxyacetophenone; and the complex <FORM:0762187/IV(b)/6> prepared from the hydrazone <FORM:0762187/IV(b)/7> which is obtained from 2-hydroxy-4-methoxy benzaldehyde.