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Addition of Diazomethane to Phosphonodithioformates and Reactions of Phosphonylated Thiocarbonyl S-Methylides


Urbaniak, Katarzyna; Mloston, Grzegorz; Gulea, Mihaela; Masson, Serge; Heimgartner, Heinz (2005). Addition of Diazomethane to Phosphonodithioformates and Reactions of Phosphonylated Thiocarbonyl S-Methylides. Polish Journal of Chemistry, 79(9):1483-1494.

Abstract

The reaction of phosphonodithioformates 14 with diazomethane at –60°C yielded 2,5-dihydro-1,3,4-thiadiazoles 15 as unstable intermediates. Their structure was evidenced by the base-catalyzed elimination of methylsulfane leading to 1,3,4-thiadiazole-2-phosphonates. At ca. –35°C, thermal decomposition of 15 by N2-elimination led to reactive thiocarbonyl S-methylides 17. In the absence of trapping reagents, these 1,3-dipoles undergo a head-to-head dimerization leading to 1,4-dithianes 18. An intermediate zwitterionic dimer 19 was detected by 31P NMR spectroscopy. The initially formed thiocarbonyl S-methylide 17 as well as an open-chain zwitterionic dimer 20 was intercepted by methanol. Stable interception products were also obtained with S- and N-nucleophiles.

Abstract

The reaction of phosphonodithioformates 14 with diazomethane at –60°C yielded 2,5-dihydro-1,3,4-thiadiazoles 15 as unstable intermediates. Their structure was evidenced by the base-catalyzed elimination of methylsulfane leading to 1,3,4-thiadiazole-2-phosphonates. At ca. –35°C, thermal decomposition of 15 by N2-elimination led to reactive thiocarbonyl S-methylides 17. In the absence of trapping reagents, these 1,3-dipoles undergo a head-to-head dimerization leading to 1,4-dithianes 18. An intermediate zwitterionic dimer 19 was detected by 31P NMR spectroscopy. The initially formed thiocarbonyl S-methylide 17 as well as an open-chain zwitterionic dimer 20 was intercepted by methanol. Stable interception products were also obtained with S- and N-nucleophiles.

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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:2005
Deposited On:27 Mar 2013 08:32
Last Modified:18 Apr 2018 11:42
Publisher:Polskie Towarzystwo Chemiczne
ISSN:0137-5083
Funders:Polish State Committee for Scientific Research, French CNRS, European Union (FEDER funding), Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel
OA Status:Green
Related URLs:http://www.ichf.edu.pl/pjch/pj-2005/pj-2005-09c.htm
Project Information:
  • : Funder
  • : Grant ID
  • : Project TitlePolish State Committee for Scientific Research
  • : Funder
  • : Grant ID
  • : Project TitleFrench CNRS
  • : Funder
  • : Grant ID
  • : Project TitleEuropean Union (FEDER funding)
  • : FunderSNSF
  • : Grant ID
  • : Project TitleSwiss National Science Foundation
  • : Funder
  • : Grant ID
  • : Project TitleF. Hoffmann-La Roche AG, Basel

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