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New Thiocarbonyl Ylides derived from 3,3-Dichloro-2,2,4,4-tetramethylcyclobutanethione; Generation and reactions


Woznicka, M; Rutkowska, M; Mloston, G; Majchrzak, A; Heimgartner, H (2006). New Thiocarbonyl Ylides derived from 3,3-Dichloro-2,2,4,4-tetramethylcyclobutanethione; Generation and reactions. Polish Journal of Chemistry, 80(10):1683-1693.

Abstract

The reaction of 3,3-dichloro-2,2,4,4-tetramethylcyclobutanethione (1) with diazo compounds yielded spirocyclic 2,5-dihydro-1,3,4-thiadiazoles 3, which decomposed at ca. 45°C to give the corresponding thiocarbonyl ylide of type 4. In the absence of trapping agents, these thiocarbonyl ylides underwent a 1,3-dipolar electrocyclization to yield spirocyclic thiiranes 5. On the other hand, the thiocarbonyl methanide 4a was efficiently intercepted with C C, C=C, C=O, C=S, and N=N dipolarophiles leading to the [2+3] cycloadducts. A non-stereoselective cycloaddition took place when 3a was decomposed
in the presence of the very electron-deficient dicyanofumarate or maleate, indicating a two step mechanism via an intermediate zwitterion. Furthermore, the thiocarbonyl methanide 4a could be trapped by the imidazole-2-thione 7 to give the 1,3-adduct 8. Treatment of 3a with secondary amines led to amidrazones of type 25 via base-catalyzed ring opening and condensation reaction.

Abstract

The reaction of 3,3-dichloro-2,2,4,4-tetramethylcyclobutanethione (1) with diazo compounds yielded spirocyclic 2,5-dihydro-1,3,4-thiadiazoles 3, which decomposed at ca. 45°C to give the corresponding thiocarbonyl ylide of type 4. In the absence of trapping agents, these thiocarbonyl ylides underwent a 1,3-dipolar electrocyclization to yield spirocyclic thiiranes 5. On the other hand, the thiocarbonyl methanide 4a was efficiently intercepted with C C, C=C, C=O, C=S, and N=N dipolarophiles leading to the [2+3] cycloadducts. A non-stereoselective cycloaddition took place when 3a was decomposed
in the presence of the very electron-deficient dicyanofumarate or maleate, indicating a two step mechanism via an intermediate zwitterion. Furthermore, the thiocarbonyl methanide 4a could be trapped by the imidazole-2-thione 7 to give the 1,3-adduct 8. Treatment of 3a with secondary amines led to amidrazones of type 25 via base-catalyzed ring opening and condensation reaction.

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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:English
Date:2006
Deposited On:06 Dec 2011 07:52
Last Modified:05 Apr 2016 15:07
Publisher:Polskie Towarzystwo Chemiczne
ISSN:0137-5083
Funders:Polish State Committee for Scientific Research (grant 3T09A00716)), Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1002/chin.200706033
Related URLs:http://www.ichf.edu.pl/pjch/pj-2006.htm

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