Photocycloaddition of 2,3-Dihydro-2,2-dimethyl-4H-thiopyran-4-one (a 4-Thiacyclohex-2-enone) to bona fide Triplet Quenchers. A Contradiction?

Paul Margaretha; Kerstin Schmidt; Jürgen Kopf; Volker Sinnwell

doi:10.1055/s-2007-965998

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Photocycloaddition of 2,3-Dihydro-2,2-dimethyl-4H-thiopyran-4-one (a 4-Thiacyclohex-2-enone) to bona fide Triplet Quenchers. A Contradiction?

Paul Margaretha*, Kerstin Schmidt, Jürgen Kopf, Volker Sinnwell
Fachbereich Chemie, Universität Hamburg, M. L. King Platz 6, 20146 Hamburg, Germany
Fax: +49(40)428385592; e-Mail: Paul.Margaretha@chemie.uni-hamburg.de;

Abstract

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Abstract

2,3-Dihydro-2,2-dimethyl-4H-thiopyran-4-one undergoes regiospecific photocycloaddition to 2-chloroacrylonitrile as well as regio- and stereospecific photocycloaddition to ethylidenemalononitrile. On irradiation in the presence of either 2,3-dimethylbuta-1,3-diene or isoprene, the same enone affords mainly [2+2]-cycloadducts and only minor amounts of (stepwise) [2+4]-cycloadducts, whereas quantitative quenching is observed in the presence of 2,5-dimethylhexa-2,4-diene. In contrast, the corresponding pyran is almost quantitatively quenched in the presence of any of the enenitriles or dienes mentioned.

Key words

[2+2] photocycloaddition - 1-chlorocyclobutanecarbonitriles - vinylcyclobutanes - 1,4-biradicals

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