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Reactions of stable alpha-chlorosulfanyl chlorides with C=S-functionalized compounds


Majchrzak, Agnieszka; Janczak, Aleksandra; Mloston, Grzegorz; Linden, Anthony; Heimgartner, Heinz (2003). Reactions of stable alpha-chlorosulfanyl chlorides with C=S-functionalized compounds. Helvetica Chimica Acta, 86:2272-2283.

Abstract

The smooth reaction of 3-chloro-3-(chlorosulfanyl)-2,2,4,4-tetramethylcyclobutanone (3) with 3,4,5-trisubstituted 2,3-dihydro-1H-imidazole-2-thiones 8 and 2-thiouracil (10) in CH2Cl2/Et3N at room temperature yielded the corresponding disulfanes 9 and 11 (Scheme 2), respectively, via a nucleophilic substitution of Cl- of the sulfanyl chloride by the S-atom of the heterocyclic thione. The analogous reaction of 3-cyclohexyl-2,3-dihydro-4,5-diphenyl-1H-imidazole-2-thione (8b) and 10 with the chlorodisulfanyl derivative 16 led to the corresponding trisulfanes 17 and 18 (Scheme 4), respectively. On the other hand, the reaction of 3 and 4,4- dimethyl-2-phenyl-1,3-thiazole-5(4H)-thione (12) in CH2Cl2 gave only 4,4-dimethyl-2-phenyl-1,3-thiazol-5(4H)-one (13) and the trithioorthoester derivative 14, a bis-disulfane, in low yield (Scheme 3). At -78°, only bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutyl)polysulfanes 15 were formed. Even at -78°, a 1 : 2 mixture of 12 and 16 in CH2Cl2 reacted to give 13 and the symmetrical pentasulfane 19 in good yield (Scheme 5). The structures of 11, 14, 17, and 18 have been established by X-ray crystallography.

Abstract

The smooth reaction of 3-chloro-3-(chlorosulfanyl)-2,2,4,4-tetramethylcyclobutanone (3) with 3,4,5-trisubstituted 2,3-dihydro-1H-imidazole-2-thiones 8 and 2-thiouracil (10) in CH2Cl2/Et3N at room temperature yielded the corresponding disulfanes 9 and 11 (Scheme 2), respectively, via a nucleophilic substitution of Cl- of the sulfanyl chloride by the S-atom of the heterocyclic thione. The analogous reaction of 3-cyclohexyl-2,3-dihydro-4,5-diphenyl-1H-imidazole-2-thione (8b) and 10 with the chlorodisulfanyl derivative 16 led to the corresponding trisulfanes 17 and 18 (Scheme 4), respectively. On the other hand, the reaction of 3 and 4,4- dimethyl-2-phenyl-1,3-thiazole-5(4H)-thione (12) in CH2Cl2 gave only 4,4-dimethyl-2-phenyl-1,3-thiazol-5(4H)-one (13) and the trithioorthoester derivative 14, a bis-disulfane, in low yield (Scheme 3). At -78°, only bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutyl)polysulfanes 15 were formed. Even at -78°, a 1 : 2 mixture of 12 and 16 in CH2Cl2 reacted to give 13 and the symmetrical pentasulfane 19 in good yield (Scheme 5). The structures of 11, 14, 17, and 18 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
Uncontrolled Keywords:Physical and Theoretical Chemistry, Inorganic Chemistry, Organic Chemistry, Biochemistry, Drug Discovery, Catalysis
Language:English
Date:2003
Deposited On:11 Sep 2013 14:49
Last Modified:18 Aug 2018 11:07
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Rector of the University of Lodz (Research Grant No.505/465), Swiss National Science Foundation, F. Hoffmann-LaRoche AG, Basel
OA Status:Green
Free access at:Official URL. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/hlca.200390183
Official URL:http://onlinelibrary.wiley.com/doi/10.1002/hlca.200390183/pdf
Project Information:
  • : Funder
  • : Grant ID
  • : Project TitleRector of the University of Lodz (Research Grant No.505/465)
  • : FunderSNSF
  • : Grant ID
  • : Project TitleSwiss National Science Foundation
  • : Funder
  • : Grant ID
  • : Project TitleF. Hoffmann-LaRoche AG, Basel

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