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Bildung von 1,2,4-Trithiolanen in Dreikomponenten-Gemischen aus Phenyl-azid, aromatischen Thioketonen und 2,2,4,4-Tetramethylcyclobutanthionen: Eine Schwefel-Transfer-Reaktion unter Bildung von ‘Thiocarbonyl- thiolaten’ ((Alkylidensulfonio)thiolaten) als reaktive Zwischenstufen


Mloston, Grzegorz; Heimgartner, Heinz (1995). Bildung von 1,2,4-Trithiolanen in Dreikomponenten-Gemischen aus Phenyl-azid, aromatischen Thioketonen und 2,2,4,4-Tetramethylcyclobutanthionen: Eine Schwefel-Transfer-Reaktion unter Bildung von ‘Thiocarbonyl- thiolaten’ ((Alkylidensulfonio)thiolaten) als reaktive Zwischenstufen. Helvetica Chimica Acta, 78:1298-1310.

Abstract

Formation of 1,2,4-Trithiolanes in Three-Component Reactions of Phenyl Azide, Aromatic Thiones, and 2,2,4,4-Tetramethylcyclobutanethiones: A Sulfur-Transfer Reaction to ‘Thiocarbonyl-thiolates’ ((Alkylidenesulfonio)- thiolates) as Reactive Intermediates The reaction of PhN3 and aromatic thioketones 18 (two-component reaction) at 80° yields only the corresponding imines 22, S, and N2. Under similar conditions, in the prescnce of sterically crowded 2,2,4,4-tetramethyl- cyclobutanethiones 19 (three-component reaction), 1,2,4-trithiolanes of type 20 are formed in good yields in addition to imines 22 (Scheme 4). In case of 19a and 19c (X = CO, CS), the symmetrical trithiolanes 21a and 21b, respectively, are also isolated. With 4,4-dimethyl-2-phenyl-l,3-thiazole-5(4H)-thione (24) instead of aromatic thioketone 18, imine 25, trithiolane 21a, and 1,4,2-dithiazolidine 26 are formed (Scheme 5). A reaction mechanism for the formation of 1,2,4-trithiolanes 20 and 21, including an S-transfer to generate ‘thiocarbonyl-thiolates’ 2b and/or 2c and 1,3-dipolar cycloaddition with a thioketone, is proposed in Scheme 7.

Formation of 1,2,4-Trithiolanes in Three-Component Reactions of Phenyl Azide, Aromatic Thiones, and 2,2,4,4-Tetramethylcyclobutanethiones: A Sulfur-Transfer Reaction to ‘Thiocarbonyl-thiolates’ ((Alkylidenesulfonio)- thiolates) as Reactive Intermediates The reaction of PhN3 and aromatic thioketones 18 (two-component reaction) at 80° yields only the corresponding imines 22, S, and N2. Under similar conditions, in the prescnce of sterically crowded 2,2,4,4-tetramethyl- cyclobutanethiones 19 (three-component reaction), 1,2,4-trithiolanes of type 20 are formed in good yields in addition to imines 22 (Scheme 4). In case of 19a and 19c (X = CO, CS), the symmetrical trithiolanes 21a and 21b, respectively, are also isolated. With 4,4-dimethyl-2-phenyl-l,3-thiazole-5(4H)-thione (24) instead of aromatic thioketone 18, imine 25, trithiolane 21a, and 1,4,2-dithiazolidine 26 are formed (Scheme 5). A reaction mechanism for the formation of 1,2,4-trithiolanes 20 and 21, including an S-transfer to generate ‘thiocarbonyl-thiolates’ 2b and/or 2c and 1,3-dipolar cycloaddition with a thioketone, is proposed in Scheme 7.

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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 14:05
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-85770

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