Studies on the 1-Aza-1 Prime -Oxa-(3,3)-Sigmatropic Rearrangement: Synthesis of Ortho-(beta-Oxoalkyl) Anilides and Regiospecifically Substituted Indoles
Burgoyne, William Franklin, Jr.
This item is only available for download by members of the University of Illinois community. Students, faculty, and staff at the U of I may log in with your NetID and password to view the item. If you are trying to access an Illinois-restricted dissertation or thesis, you can request a copy through your library's Inter-Library Loan office or purchase a copy directly from ProQuest.
Permalink
https://hdl.handle.net/2142/67256
Description
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.
Issue Date
1981
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
Language
eng
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.
Use this login method if you
don't
have an
@illinois.edu
email address.
(Oops, I do have one)
IDEALS migrated to a new platform on June 23, 2022. If you created
your account prior to this date, you will have to reset your password
using the forgot-password link below.
