Abstract
The specific rates of solvolysis of 2-thiophenecarbonyl chloride are very well correlated by the extended Grunwald-Winstein equation over a wide range of solvents; contrary to previous claims of an SN2 mechanism, the solvolyses are predominantly by an ionisation mechanism aided by nucleophilic solvation.
References
1.
Sohn J.-E.
,
Yoon S.-K.
, and
Lee I.
, J. Korean Chem. Soc. , 1979 , 23 , 339 .
2.
Oh J.
,
Yang K.
,
Koo I. S.
, and
Lee I.
, J. Chem. Res. (S) , 1993 , 310 ; J. Chem. Res. (M) , 2040.
3.
Kevill D.N.
, and
D'Souza M. J.
, J. Phys. Org. Chem. , 2002 , 15 , 881 .
4.
Winstein S.
,
Grunwald E.
, and
Jones H. W.
, J. Am. Chem. Soc. , 1951 , 73 , 2700 .
5.
Kevill D.N.
, in Advances in Quantitative Structure-Property Relationships , ed.
Charton M.
, JAI Press , Greenwich, Connecticut , 1996 , vol. 1 , pp. 81 –115 .
6.
Kevill D.N.
, and
Anderson S. W.
, J. Org. Chem. , 1991 , 56 , 1845 .
7.
Kevill D.N.
, and
Anderson S. W.
, J. Chem. Res. (S) , 1991 , 356 .
8.
Bentley T.W.
, and
Llewellyn G.
, Prog. Phys. Org. Chem. , 1990 , 17 , 121 .
9.
Kevill D.N.
, and
D'Souza M. J.
, J. Chem. Soc., Perkin Trans. 2, 1997 , 1721 .
10.
Kevill D.N.
, and
D'Souza M. J.
, J. Org. Chem. , 1998 , 63 , 2120 .
11.
(a)
Bentley T.W.
, and
Carter G. E.
, J. Am. Chem. Soc. , 1982 , 104 , 5741 .
12.
Kevill D.N.
, and
D'Souza M. J.
, J. Chem. Res. (S) , 1993 , 174 .
13.
Lomas J.S.
,
D'Souza M. J.
, and
Kevill D. N.
, J. Am. Chem. Soc. , 1995 , 117 , 5891 .
14.
Kevill D.N.
, and
Abduljaber M. H.
, J. Org. Chem. , 2000 , 65 , 2548 .
15.
Bentley T.W.
,
Carter G. E.
, and
Harris H. C.
, J. Chem. Soc., Chem. Commun. , 1984 , 387 .
16.
Bentley T.W.
, and
Koo I. S.
, J. Chem. Soc., Perkin Trans. 2, 1989 , 1385 .
