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Umsetzung von Di(tert-buty1)- und Diphenyldiazomethan mit 1,3-Thiazol-5(4H)-thionen: Isolierung und Kristallstruktur des primären Cycloadduktes


Mloston, Grzegorz; Petit, Mireille; Linden, Anthony; Heimgartner, Heinz (1994). Umsetzung von Di(tert-buty1)- und Diphenyldiazomethan mit 1,3-Thiazol-5(4H)-thionen: Isolierung und Kristallstruktur des primären Cycloadduktes. Helvetica Chimica Acta, 77(2):435-444.

Abstract

Reaction of Di(tert-butyl)- and Diphenyldiazomethane and 1,3-Thiazole-5(4H)-thiones: Isolation and Crystal Structure of the Primary Cycloadduct Reactions of diazo compounds with C=S bonds proceed via the formation of thiocarbonyl ylides, which, under the reaction conditions, undergo either 1,3-dipolar cycloadditions or electrocyclic ring closure to thiiranes (Scheme 1). With the sterically hindered di(tert-buty1)diazomethane (2c), 1,3-thiazole-5(4H)-thiones 1 react to give spirocyclic 2,S-dihydro-1,3,4-thiadiazoles 3 (Scheme 2 ). These adducts are stable in solution at -20", and they could be isolated in crystalline form. The structure of 3c was established by X-ray crystallography. In CDCI3 solution at room temperature, a cycloreversion occurs, and the adducts of type 3 are in an equilibrium with 1 and 2c. In contrast, the reaction of 1 with diphenyldiazomethane (2d) gave spirocyclic thiiranes 4 as the only product in high yield (Scheme 3). The crystal structure of 4b was also determined by X-ray analysis. The desulfurization of compounds 4 to 4,5-dihydro-5-(diphenylmethylidene)-1,3-thiazoles 5 was achieved by treating 4 with triphenylphosphine in boiling THF. The crystal structure of 5f is shown.

Abstract

Reaction of Di(tert-butyl)- and Diphenyldiazomethane and 1,3-Thiazole-5(4H)-thiones: Isolation and Crystal Structure of the Primary Cycloadduct Reactions of diazo compounds with C=S bonds proceed via the formation of thiocarbonyl ylides, which, under the reaction conditions, undergo either 1,3-dipolar cycloadditions or electrocyclic ring closure to thiiranes (Scheme 1). With the sterically hindered di(tert-buty1)diazomethane (2c), 1,3-thiazole-5(4H)-thiones 1 react to give spirocyclic 2,S-dihydro-1,3,4-thiadiazoles 3 (Scheme 2 ). These adducts are stable in solution at -20", and they could be isolated in crystalline form. The structure of 3c was established by X-ray crystallography. In CDCI3 solution at room temperature, a cycloreversion occurs, and the adducts of type 3 are in an equilibrium with 1 and 2c. In contrast, the reaction of 1 with diphenyldiazomethane (2d) gave spirocyclic thiiranes 4 as the only product in high yield (Scheme 3). The crystal structure of 4b was also determined by X-ray analysis. The desulfurization of compounds 4 to 4,5-dihydro-5-(diphenylmethylidene)-1,3-thiazoles 5 was achieved by treating 4 with triphenylphosphine in boiling THF. The crystal structure of 5f is shown.

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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 12:16
Last Modified:21 Nov 2017 17:00
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung, F. Hoffmann-La Roche AG, Basel, Polnisches Komitee zur Förderung der wissenschaftlichen Forschung (KBN)
Publisher DOI:https://doi.org/10.1002/hlca.19940770204

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