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Erstes Beispiel einer H-Verschiebung in ‘Thiocarbonyl-aminiden’(N-(Alkylidensulfonio)aminiden)


Mloston, Grzegorz; Romanski, Jaroslaw; Linden, Anthony; Heimgartner, Heinz (1995). Erstes Beispiel einer H-Verschiebung in ‘Thiocarbonyl-aminiden’(N-(Alkylidensulfonio)aminiden). Helvetica Chimica Acta, 78:1067-1078.

Abstract

First Example of an H-Shift in ‘Thiocarbonyl Aminides’ (N-(Alkylidenesulfonio)aminides) Reaction of benzyl azide (15a) with the sterically hindered C=S group of 4,4-dimethyl-1,3-thiazole-5(4H)-thiones 14 (Scheme 3) and 1,1,3,3-tetramethylindane-2-thione (17, Scheme 4) at 80° leads to the corresponding imines in high yield, without formation of any by-product. In contrast, 15a and 2,2,4,4-tetramethyl-3-thioxocyclobutanone (7) under the same conditions yielded, in addition to imine 19, products 20a and 21 (Scheme 5). For the formation of 20a, a reaction mechanism via [1,4]-H shift in the intermediate ‘thiocarbonyl aminides’ 23 is proposed (Scheme 6). Product 21 as well as the dithiazole derivative 22, which is formed only in the reaction with 4-nitrobenzyl azide (15c), are formal adducts of the dipole 23. Whereas precedents are known for the formation of cycloadducts of type 22, the pathway to 21 is not known. Two possible mechanisms of its formation are proposed in Schemes 8 and 9.

First Example of an H-Shift in ‘Thiocarbonyl Aminides’ (N-(Alkylidenesulfonio)aminides) Reaction of benzyl azide (15a) with the sterically hindered C=S group of 4,4-dimethyl-1,3-thiazole-5(4H)-thiones 14 (Scheme 3) and 1,1,3,3-tetramethylindane-2-thione (17, Scheme 4) at 80° leads to the corresponding imines in high yield, without formation of any by-product. In contrast, 15a and 2,2,4,4-tetramethyl-3-thioxocyclobutanone (7) under the same conditions yielded, in addition to imine 19, products 20a and 21 (Scheme 5). For the formation of 20a, a reaction mechanism via [1,4]-H shift in the intermediate ‘thiocarbonyl aminides’ 23 is proposed (Scheme 6). Product 21 as well as the dithiazole derivative 22, which is formed only in the reaction with 4-nitrobenzyl azide (15c), are formal adducts of the dipole 23. Whereas precedents are known for the formation of cycloadducts of type 22, the pathway to 21 is not known. Two possible mechanisms of its formation are proposed in Schemes 8 and 9.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:German
Date:1995
Deposited On:04 Dec 2013 13:32
Last Modified:05 Apr 2016 17:12
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Polnisches Nationalkomitee zur Förderung der wissenschaftlichen Forschung, Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung, F. Hoffmann-La Roche AG, Basel
Permanent URL: https://doi.org/10.5167/uzh-85763

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