The acid-catalysed rearrangements of 4,5-bis(2-thienylhydroxymethyl)-1,3-dithiole-2-thione

I.M. Serebryakov, P.J. Skabara, I.F. Perepichka

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Under strongly acidic conditions, the title compound 1 readily participates in several possible rearrangement pathways, affording a product distribution which is relative to the choice of solvent and acid catalyst. Thus, using chloroform or acetone as the solvents and HBr or HClO4 as the catalysts, compounds 2-4 have been isolated and fully characterised; in addition, compound 5 was identified in the reaction mixture and characterised by H-1 NMR spectroscopy. The reaction kinetics of the transformations have been studied by H-1 NMR spectroscopy, using deuterated chloroform or acetone as the NMR solvents. A key intermediate in the reaction mechanisms is the allylic carbocation 6, which rearranges to give the fused system 3; in the presence of bromide anions, the carbocation forms an ion-pair intermediate 7, leading to the formation of compounds 2, 4 and/or 5, depending on the solvent.
LanguageEnglish
Pages1405-1410
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 2
Volume1999
Issue number7
DOIs
Publication statusPublished - Jul 1999

Fingerprint

Thiones
Acids
Chloroform
Acetone
Nuclear magnetic resonance spectroscopy
Catalysts
Bromides
Reaction kinetics
Anions
Nuclear magnetic resonance
Ions

Keywords

  • substitution-reactions
  • para-nitrobenzoates
  • solvent assistance
  • solvolysis
  • ion
  • ethers
  • carbon
  • acetonitrile
  • mechanism
  • chloride

Cite this

Serebryakov, I.M. ; Skabara, P.J. ; Perepichka, I.F. / The acid-catalysed rearrangements of 4,5-bis(2-thienylhydroxymethyl)-1,3-dithiole-2-thione. In: Journal of the Chemical Society, Perkin Transactions 2. 1999 ; Vol. 1999, No. 7. pp. 1405-1410.
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abstract = "Under strongly acidic conditions, the title compound 1 readily participates in several possible rearrangement pathways, affording a product distribution which is relative to the choice of solvent and acid catalyst. Thus, using chloroform or acetone as the solvents and HBr or HClO4 as the catalysts, compounds 2-4 have been isolated and fully characterised; in addition, compound 5 was identified in the reaction mixture and characterised by H-1 NMR spectroscopy. The reaction kinetics of the transformations have been studied by H-1 NMR spectroscopy, using deuterated chloroform or acetone as the NMR solvents. A key intermediate in the reaction mechanisms is the allylic carbocation 6, which rearranges to give the fused system 3; in the presence of bromide anions, the carbocation forms an ion-pair intermediate 7, leading to the formation of compounds 2, 4 and/or 5, depending on the solvent.",
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The acid-catalysed rearrangements of 4,5-bis(2-thienylhydroxymethyl)-1,3-dithiole-2-thione. / Serebryakov, I.M.; Skabara, P.J.; Perepichka, I.F.

In: Journal of the Chemical Society, Perkin Transactions 2, Vol. 1999, No. 7, 07.1999, p. 1405-1410.

Research output: Contribution to journalArticle

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KW - solvolysis

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KW - ethers

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KW - acetonitrile

KW - mechanism

KW - chloride

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