Rate and Product Studies with Benzyl and p-Nitrobenzyl Chloroformate under Solvolytic Conditions
- Title
- Rate and Product Studies with Benzyl and p-Nitrobenzyl Chloroformate under Solvolytic Conditions
- Author
- 경진범
- Issue Date
- 2000-12
- Publisher
- The American Chemical Society
- Citation
- JOURNAL OF ORGANIC CHEMISTRY, v. 65, issue. 23, page. 8051-8058
- Abstract
- The specific rates of solvolysis of p-nitrobenzyl chloroformate are well correlated using the extended Grunwald-Winstein equation, with a high sensitivity (l) to changes in solvent nucleophilicity (N(T)) and a moderate sensitivity (m) to changes in solvent ionizing power (Y(Cl)). The values are consistent with a rate-determining association within an association-dissociation pathway. The selectivity values (S) for the attack at the acyl carbon show a modest preference for ethanol over water and a relatively high preference for ethanol over 2,2,2-trifluoroethanol (TFE). The solvolyses of benzyl chloroformate show similar characteristics in solvents of relatively high nucleophilicity and/or low ionizing power. In solvents with considerable fluoro alcohol content, an ionization mechanism, accompanied by loss of carbon dioxide, leads to benzyl chloride, benzyl alcohol, and benzyl alkyl ether. A new correlation now applies, with a much lower l value and somewhat higher m value. The S values for this pathway are close to unity, even in TFE-ethanol mixtures, consistent with the components of the binary solvent capturing a highly reactive carbocation.
- URI
- https://www.scopus.com/record/display.uri?eid=2-s2.0-0034680621&origin=inward&txGid=c591281ad17f738666971671b6369adchttps://repository.hanyang.ac.kr/handle/20.500.11754/162318
- ISSN
- 0022-3263
- DOI
- 10.1021/jo005630y
- Appears in Collections:
- COLLEGE OF SCIENCE AND CONVERGENCE TECHNOLOGY[E](과학기술융합대학) > CHEMICAL AND MOLECULAR ENGINEERING(화학분자공학과) > Articles
- Files in This Item:
There are no files associated with this item.
- Export
- RIS (EndNote)
- XLS (Excel)
- XML