Studies of 1,2-quinone monooximes and their metal complexes
type: CreativeWork
description: The chemistry of 1,2-quinone monooximes hi« been reviewed. The synthesis of 5-amlno, 5-alkylamino and 5-acylamino substituted 1,2-benzoquinone monooximes was systematically studied. Thus, It has been found that 5-amino-1,2-benzoquinone-2-oxime (5-AqoH), 5-ethylamino-4-methyl 1-1,2- benzoquinone-2-ox I me (5-Et-4-MeqoH), 5-hexylamino-1,2-benzoquinone-2-oxime (5-HxqoH) and 5-heptylamino-1,2-benzoquinone-2-oxime (5-HptqoH) were best prepared by the reaction of the corresponding phenol with sodium nitrite In the presence of concentrated hydrochloric acid. Under these conditions, N-nitrosation was inhibited and the 1,2-benzoquinone- 2-oxlme hydrochlorides were formed. The 5-acylaminc1,2-benzoqulnone-2- oximes, 5-propionylamino-1,2-benzoquinone-2-oxime (5-PrqoH), 5-butyrylamino-l,2-benzoquinone-2-oxime (5-BuqoH), 5-pentanoylamino-1,2-benzoquinone-2-oxime (5-PeqoH), and 5—heptanoylamino-1,2-benzoquinone-2-oxime (5-HpqoH) were obtained from their metal complexes, since the direct reaction of the phenol with sodium nitrite failed to give the compounds giving the corresponding l,4-benzoquinone-4-oximes,3- proplonylamino-1,4-benzoquinone-4-oxime (3-PrqoH), 3-butyrylamino-1,4- benzoquinone-4-oxlme (3-BuqoH), 3-pentanoylamino-1,4-benzoquinone-4- oxime (3-PeqoH) and 3-heptanoylamino-1,4-benzoquinone-4-oxime (3-HpqoH) instead. Spectroscopic analysis has shown the compounds to exist in the quinone oximic rather than In the nitrosophenollc form. X-ray crystallographic studies of 5-HxqoH, 5-Et-4-MeqoH and 5- Et-4-MeqoH.HCI have shown ail three compounds to have some 1,4-oxime- imino character. The synthesis of nlckel(ll), copper(ll), palladium(ll) and platinum(ll) complexes of the acylamino and alkylamino substituted 1.2- benzoqulnone-2- oximes both by the direct and nitrosation methods was examined. The nitrosation method gave rise to complexes NI(qo)2.nH20, Cu(qo)2.nH20 and Pd(qo)2 but failed to give the corresponding platinum complexes. The latter were only obtained by the direct …
abstract: The chemistry of 1,2-quinone monooximes hi« been reviewed. The synthesis of 5-amlno, 5-alkylamino and 5-acylamino substituted 1,2-benzoquinone monooximes was systematically studied. Thus, It has been found that 5-amino-1,2-benzoquinone-2-oxime (5-AqoH), 5-ethylamino-4-methyl 1-1,2- benzoquinone-2-ox I me (5-Et-4-MeqoH), 5-hexylamino-1,2-benzoquinone-2-oxime (5-HxqoH) and 5-heptylamino-1,2-benzoquinone-2-oxime (5-HptqoH) were best prepared by the reaction of the corresponding phenol with sodium nitrite In the presence of concentrated hydrochloric acid. Under these conditions, N-nitrosation was inhibited and the 1,2-benzoquinone- 2-oxlme hydrochlorides were formed. The 5-acylaminc1,2-benzoqulnone-2- oximes, 5-propionylamino-1,2-benzoquinone-2-oxime (5-PrqoH), 5-butyrylamino-l,2-benzoquinone-2-oxime (5-BuqoH), 5-pentanoylamino-1,2-benzoquinone-2-oxime (5-PeqoH), and 5—heptanoylamino-1,2-benzoquinone-2-oxime (5-HpqoH) were obtained from their metal complexes, since the direct reaction of the phenol with sodium nitrite failed to give the compounds giving the corresponding l,4-benzoquinone-4-oximes,3- proplonylamino-1,4-benzoquinone-4-oxime (3-PrqoH), 3-butyrylamino-1,4- benzoquinone-4-oxlme (3-BuqoH), 3-pentanoylamino-1,4-benzoquinone-4- oxime (3-PeqoH) and 3-heptanoylamino-1,4-benzoquinone-4-oxime (3-HpqoH) instead. Spectroscopic analysis has shown the compounds to exist in the quinone oximic rather than In the nitrosophenollc form. X-ray crystallographic studies of 5-HxqoH, 5-Et-4-MeqoH and 5- Et-4-MeqoH.HCI have shown ail three compounds to have some 1,4-oxime- imino character. The synthesis of nlckel(ll), copper(ll), palladium(ll) and platinum(ll) complexes of the acylamino and alkylamino substituted 1.2- benzoqulnone-2- oximes both by the direct and nitrosation methods was examined. The nitrosation method gave rise to complexes NI(qo)2.nH20, Cu(qo)2.nH20 and Pd(qo)2 but failed to give the corresponding platinum complexes. The latter were only obtained by the direct …
author: Thomas, Terrance Augustine
keywords: 540 Chemistry & allied sciences
date published: 1993-08
date modified: 2026-07-24T02:54:30Z
provider: London Metropolitan University
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of North London