Rearrangements of azidoquinones VI. Thermal rearrangement of azido-1,4-quinones to 2-cyano-1,3-cyclopentenediones
1969; Elsevier BV; Volume: 10; Issue: 45 Linguagem: Inglês
10.1016/s0040-4039(01)88583-x
ISSN1873-3581
AutoresHarold W. Moore, Walter Weyler, H. Raymond Shelden,
Tópico(s)Chemical Reactions and Mechanisms
ResumoTetralledron Letters No.45, pPO 3947-3950, 1969. Pergamon Press. Printed in Great Britain. REARRANGEMENTS OF AZIDGQUINONlB VI. THERMAL REARRANGEMENT OF AZIDO-1, I-QUINONES TO 2-CYANO-1,3-CYCLOPENTENEDIONES Harold W. Moore, Walter Weyler, Jr., and II. Raymond ShelQn Department of Chemistry University of California Irvine, California 92664 (Xeceived in USA 18 July 1969; received in UK for publication 25 August 1969) Previously it was shown that azido-1,4-quinones undergo a highly stereoselective catalyzed ring contraction to y- cyanoalkylidlne- A Q’ ’ - butenoH&s. ’ acid Reported in the present communication is an investigation of the thermal decomposition d selected azido-1,4- quinones ( 1 ), a reaction also resulting in ring contraction giving the 2-cyano-1,3-cyclopen- tenedione ( 3) ring system. This rearrangement provides a new example of a very limited number of known methods in which thermal conversion of a six to a five membered ring can be accomplished. The general structures ( 1) and ( 3) illustrate the overall chemical transformation as indicated by the following possible mechanistic scheme (Scheme I).
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