Acyclic Imidate and Thiomidate Normal-Oxides: Nitrones of Esters and Thioesters (alpha-Alkoxynitrones, Alpha-Alkylthionitrones, Normal - Alkylthiohydroxamic Acids, X-Ray)
Firsan, Sharbil Jurji
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https://hdl.handle.net/2142/70324
Description
Title
Acyclic Imidate and Thiomidate Normal-Oxides: Nitrones of Esters and Thioesters (alpha-Alkoxynitrones, Alpha-Alkylthionitrones, Normal - Alkylthiohydroxamic Acids, X-Ray)
Author(s)
Firsan, Sharbil Jurji
Issue Date
1986
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Abstract
Two N,O-dialkylacetimidate N-oxides and their hydrochlorides, and the hydrochloride of O-ethyl-N-methylpropionimidate N-oxide were prepared in dichloromethane solutions by the acid-catalyzed condensation of N-alkylhydroxylamines with aliphatic orthoesters. The (alpha)-alkoxynitrones and their hydrochlorides were characterized by ('1)H NMR spectroscopy and, in one case, by reaction with ammonia and aniline. In addition, a series of N,S-dialkylthioimidate N-oxides hydroiodides was synthesized by S-alkylation of N-alkylthiohydroxamic acids with methyl and ethyl iodide in acetone. The free (alpha)-alkylthionitrones were liberated from the corresponding hydroiodides with sodium carbonate or bicarbonate in water. The thioimidate N-oxides and their hydroiodides were characterized spectroscopically and their equilibrium ratios were determined in bromobenzene and acetone, respectively. The E/Z stereochemistry of the C-phenyl thioester nitrones is unambiguously established on the basis of an X-ray structural analysis on the N,S-dimethyl compound, and that of the C-alkyl counterparts is tentatively assigned on the basis of long range coupling, nuclear Overhauser effects, and chemical shift correlations. The reactions of (Z)-N,S-dimethylthiobenzimidate N-oxide, with methylmagnesium bromide and aqueous acid and base were investigated.
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