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Reaktion von Phenyldiazomethan mit 1,3-Thiazol-5(4H)-thionen: Basenkatalysierte Ring-Öffnung des Primäradduktes


Petit, Mireille; Linden, Anthony; Mloston, Grzegorz; Heimgartner, Heinz (1994). Reaktion von Phenyldiazomethan mit 1,3-Thiazol-5(4H)-thionen: Basenkatalysierte Ring-Öffnung des Primäradduktes. Helvetica Chimica Acta, 77(4):1076-1086.

Abstract

Reaction of Phenyldiazomethane with 1,3-Thiazole-5(4H)-thiones: Base-Catalyzed Ring Opening of the Primary Adduct Reaction of 1,3-thiazole-5(4H)-thiones 1 and phenyldiazomethane (2a) in toluene at room temperature yields the thiiranes trans- and cis-1,4-dithia-6-azaspiro[2.4]hept-5-enes (trans- and cis-4; Scheme 2). With Ph3P in THF at 70°, these thiiranes are transformed stereospecifically into (E)- and (Z)-5-benzylidene-4,5-dihydro-1,3-thiazoles 5, respectively. In the presence of DBU, 1 and 2a react to give 1,3,4-thiadiazole derivatives 6 or 7 via base-catalyzed ring opening of the primary cycloadduct (Scheme 3). In the case of 2-(a1kylthio)-substituted 1,3-thiazole-5(4H)-thiones 1c and 1d, this ring opening proceeds by elimination of the corresponding alkylthiolate, yielding isothiocyanate 7. The structures of (Z)-5c and 6b have been established by X-ray crystallography.

Abstract

Reaction of Phenyldiazomethane with 1,3-Thiazole-5(4H)-thiones: Base-Catalyzed Ring Opening of the Primary Adduct Reaction of 1,3-thiazole-5(4H)-thiones 1 and phenyldiazomethane (2a) in toluene at room temperature yields the thiiranes trans- and cis-1,4-dithia-6-azaspiro[2.4]hept-5-enes (trans- and cis-4; Scheme 2). With Ph3P in THF at 70°, these thiiranes are transformed stereospecifically into (E)- and (Z)-5-benzylidene-4,5-dihydro-1,3-thiazoles 5, respectively. In the presence of DBU, 1 and 2a react to give 1,3,4-thiadiazole derivatives 6 or 7 via base-catalyzed ring opening of the primary cycloadduct (Scheme 3). In the case of 2-(a1kylthio)-substituted 1,3-thiazole-5(4H)-thiones 1c and 1d, this ring opening proceeds by elimination of the corresponding alkylthiolate, yielding isothiocyanate 7. The structures of (Z)-5c and 6b have been established by X-ray crystallography.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:German
Date:1994
Deposited On:17 Dec 2013 12:18
Last Modified:05 Apr 2016 17:15
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung, F. Hoffmann-La Roche AG, Basel, Polnisches Komitee zur Förderung wissenschaftlicher Forschung (KBN)
Publisher DOI:https://doi.org/10.1002/hlca.19940770421

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