Secondary deuterium isotope effects in solvolysis of cyclopentyl p-bromobenzenesulfonate. Stereochemistry of E1 and SN1 reactions
Journal Article
·
· Journal of the American Chemical Society
Secondary alpha - and BETA -isotope effects in solvolysis of cyclopentyl1-d, cis-cyclopentyl-2-d, trans-cyclopentyl-2-d, and cyclopentyl(E -- W) and trifluoroethanol-- water (TFE -- W) mixtures. The magnitude of the effects indicates that in the E--W mixtures the products are derived by rate- determining substitution and elimination on the reversibly formed intimate ion pair. However, the change to TFE-W mixtures causes a change in mechanism; in these solvents the formation of the solvent separated ion pair is rate determining and the products are formed in fast subsequent attack on this lntermediate. Consistent with this interpretation of the isotope effects, the elimination in E--W mixtures was found to be stereospecifically trans, while in TFE--W mixtures it is nonstereospecific. It was also determined that the configuration of the cyclopentanol formed in both types of solvents was inverted in comparison to the starting material. A detailed analysis provides an estimation of the isotope effects in each of the individual steps in the reaction.
- Research Organization:
- Rudjer Boskovic Inst., Zagreb
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-29-002483
- OSTI ID:
- 4408713
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 23 Vol. 95; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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