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Secondary steric effects in S<SUB>N</SUB>Ar of thiophenes: a coordinate kinetic, thermodynamic, UVVIS, crystallographic and ab initio study
- Source :
- Journal of the Chemical Society, Perkin Transactions 2; February 1, 1997, Vol. 1997 Issue: 2 p309-316, 8p
- Publication Year :
- 1997
-
Abstract
- The reactivity of some dinitro-benzene and -thiophene derivatives with piperidine and sodium benzenethiolate has been examined giving evidence that benzenes show large and thiophenes show small kinetic secondary steric effects, respectively. The acid dissociation reaction and the UVVIS spectra of some nitrothiophenamines have also been studied. The crystal structure and the absolute conformation of 2-iodo-3,5-dinitrothiophene and of 2-iodo-4-methyl-3,5-dinitrothiophene have been determined. For different conformations of the analogous chlorodinitro derivatives in the thiophene and benzene series, ab initio energy calculations have been performed. The results collected show that steric strain among adjacent groups affects the benzene and thiophene compounds and the kinetic, thermodynamic and spectroscopic properties of the molecules examined differently. Differences in geometry of the two aromatic rings and then in rotation of nitro groups with respect to the rings themselves as well as differences along reaction coordinates (essentially depending on hybridation changes) are used to explain the above data.
Details
- Language :
- English
- ISSN :
- 1472779X and 13645471
- Volume :
- 1997
- Issue :
- 2
- Database :
- Supplemental Index
- Journal :
- Journal of the Chemical Society, Perkin Transactions 2
- Publication Type :
- Periodical
- Accession number :
- ejs1711879