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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 |
Department / Program: | Chemistry |
Discipline: | Chemistry |
Degree Granting Institution: | University of Illinois at Urbana-Champaign |
Degree: | Ph.D. |
Genre: | Dissertation |
Subject(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. |
Issue Date: | 1986 |
Type: | Text |
Description: | 185 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986. |
URI: | http://hdl.handle.net/2142/70324 |
Other Identifier(s): | (UMI)AAI8623296 |
Date Available in IDEALS: | 2014-12-15 |
Date Deposited: | 1986 |
This item appears in the following Collection(s)
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Dissertations and Theses - Chemistry
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Graduate Dissertations and Theses at Illinois
Graduate Theses and Dissertations at Illinois