Abstract
| Language | English |
|---|---|
| Pages | 1405-1410 |
| Number of pages | 5 |
| Journal | Journal of the Chemical Society, Perkin Transactions 2 |
| Volume | 1999 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - Jul 1999 |
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Keywords
- substitution-reactions
- para-nitrobenzoates
- solvent assistance
- solvolysis
- ion
- ethers
- carbon
- acetonitrile
- mechanism
- chloride
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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 journal › Article
TY - JOUR
T1 - The acid-catalysed rearrangements of 4,5-bis(2-thienylhydroxymethyl)-1,3-dithiole-2-thione
AU - Serebryakov, I.M.
AU - Skabara, P.J.
AU - Perepichka, I.F.
PY - 1999/7
Y1 - 1999/7
N2 - 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.
AB - 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.
KW - substitution-reactions
KW - para-nitrobenzoates
KW - solvent assistance
KW - solvolysis
KW - ion
KW - ethers
KW - carbon
KW - acetonitrile
KW - mechanism
KW - chloride
UR - http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleForFree.cfm?doi=a901178a&JournalCode=P2
UR - http://dx.doi.org/10.1039/a901178a
U2 - 10.1039/a901178a
DO - 10.1039/a901178a
M3 - Article
VL - 1999
SP - 1405
EP - 1410
JO - Journal of the Chemical Society, Perkin Transactions 2
T2 - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
SN - 1472-779X
IS - 7
ER -