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Title:Studies on the 1-Aza-1 Prime -Oxa-(3,3)-Sigmatropic Rearrangement: Synthesis of Ortho-(beta-Oxoalkyl) Anilides and Regiospecifically Substituted Indoles
Author(s):Burgoyne, William Franklin, Jr.
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Organic
Abstract:The 1-aza-1'-oxa-{3,3}-sigmatropic rearrangement of N-aryl-O-vinyl-hydroxylamine derivatives has been investigated as a synthetic method for the ortho alkylation of benzene rings. The general approach involved the in situ formation of N-aryl-O-vinylhydroxamates which rearranged under the conditions required for their synthesis. The O-vinylation of N-aryl-hydroxamic acids was accomplished by Michael-type addition of the hydroxamic acids to acetylenic esters, (beta)-chloroacrylates, and (alpha)-allenic esters. The requirements and limitations for the 1,4-addition reaction have been defined. The products obtained from these reactions are substituted anilides which bear (beta)-oxo-alkyl groups ortho to the acetylamino group. The reaction of N-arylacetohydroxamic acids with methyl propiolate or methyl (beta)-chloroacrylate gave 2-(acetylamino)-(alpha)-formylbenzeneacetates. The {3,3}-sigmatropic rearrangement of the O-vinylhydroxamates prepared from the 1,4-addition of N-arylhydroxamic acid to (alpha)-allenic esters occurred entirely with the double bond of the vinyl group in the (beta),(gamma)-position, affording 2-(acetylamino)-(beta)-oxobenzene butanoates in 34-79% yields.
The anilides have been utilized in the preparation of indoles in several cases by the deacylation of the amide group by hydrolysis or catalytic hydrogenation followed by ring closure and dehydration. These sequential reactions thus provide a new synthetic approach for the regiospecific preparation of substituted indoles. Substituents present on the Michael acceptor permit the incorporation of functional groups at the C-2 and C-3 prositions on the indole.
Alternate O-vinylating agents have also been investigated. The reactions of N-arylhydroxamic acids and (alpha)-chloroenamines gave rise to substituted anilides bearing a carboxamidomethyl substituent resulting from the O-vinylation of the hydroxamic acid and {3,3}-sigmatropic rearrangement.
Issue Date:1981
Description:141 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1981.
Other Identifier(s):(UMI)AAI8114395
Date Available in IDEALS:2014-12-13
Date Deposited:1981

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