New Syntheses and Ring Expansion Reactions of Cyclobutenimines

Ernst Schaumann; Gerrit Oppermann; Michael Stranberg; Harold W. Moore

doi:10.1071/CH10318

RESEARCH FRONT

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New Syntheses and Ring Expansion Reactions of Cyclobutenimines

Ernst Schaumann ^A ^C , Gerrit Oppermann ^A , Michael Stranberg ^B and Harold W. Moore ^B

+ Author Affiliations

- Author Affiliations

^A Institute of Organic Chemistry, Clausthal University of Technology, Leibnizstrasse 6, D-38678 Clausthal-Zellerfeld, Germany.

^B Department of Chemistry, University of California, Irvine, CA 92717, USA.

^C Corresponding author. Email: ernst.schaumann@tu-clausthal.de

Australian Journal of Chemistry 63(12) 1656-1664 https://doi.org/10.1071/CH10318
Submitted: 30 August 2010 Accepted: 1 November 2010 Published: 6 December 2010

Abstract

Two routes are reported for the synthesis of iminocyclobutenones having N-(het)aryl substitution: an addition/substitution sequence starting with cyclobutenediones and an aza-Wittig method. A new synthetic route to N-alkyl derivatives is also presented. This involves O-alkylation of 3-alkylamino-1,2-cyclobutenediones using Meerwein’s reagent and subsequent deprotonation under non-hydrolytic conditions. Lithium organyls were found to add to the remaining carbonyl group. The resulting tertiary alcohols undergo ring enlargement on heating in xylene to give 4-aminophenols, 4-amino-1-naphthols, or cyclopenta-annulated quinolines from 4-vinyl, 4-aryl, and 4-alkynyl derivatives, respectively.

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New Syntheses and Ring Expansion Reactions of Cyclobutenimines

Abstract

References

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