Reaction of Endic Anhydride with Hydrazines and Acylhydrazines.

Abstract

2005 Bridged compounds Q 0060 Reaction of Endic Anhydride with Hydrazines and Acylhydrazines. -The products of the title reactions represent interesting synthons and possible pharmaceutical agents. -(KRISHCHIK, O. V.; TARABARA, I. N.; KAS'YAN, A. O.; SHISHKINA, S. V.; SHISHKIN, O. V.; ISAEV, A. K.; KAS'YAN, L. I.; Russ.

Structure and Reactivity of Bicyclo[2.2.1]hept-2-ene-endo-5,endo-6-dicarboxylic (endic) Acid Hydrazide

“…Both compounds we have previously prepared by reaction of endic anhydride with acylhydrazides, and they have been described in [4]. Their ppreparation by a new method was an additional confirmation of their structure.…”

“…The reactions of endic anhydride with alkyl-and arylhydrazines under mild conditions in contrast to reactions with amines furnished imide forms. The intermediate hydrazidoacids were isolated only seldom [4].…”

“…Note the shift of the absorption bands of benzoylhydrazines Va and Vb compared with sulfonylhydrazines from the region 3250-3240 to the region 3520-3470 cm -1 indicating the presence of an enol tautomer. The existence of a tautomeric equilibrium in amides of this series obtained by another procedure had been considered before basing on the analysis of the 13 C NMR spectra [4]. The characteristic feature of the IR spectra of aminoalcohols VIIIa and VIIIb is the presence of absorption bands belonging to hydroxy and amino groups in the region 3350-3250 cm -1 .…”

“…To establish the structure of the reaction product of anhydride I and hydrazine hydrate we first evaluated the Hydrazinolysis of anhydride I was carried out by two known procedures (heating of the anhydride mixture with 25% water solution of hydrazine in alcohol [7] or boiling equimolar amounts of the anhydride with 80% aqueous hydrazine hydrate in alcohol for 5 h [5]), and also similarly to the conditions we had previously used in reaction of the endic anhydride with monosubstituted hydrazines (in the cold in a benzene solution [4]). In all cases were isolated identical reaction products in respective yields 94.3, 91.0, and 92.5%.…”