期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 74, 期 10, 页码 3659-3664出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo9004316
关键词
-
资金
- National Science Foundation [CHE0445847]
- NIH [NIGMS068649]
- Procter & Gamble Pharmaceuticals, Mason, Ohio
The reaction of benzoyl chloride with methanol catalyzed by pyridine is 9 times more rapid than is the same reaction with thiobenzoyl chloride. The difference in reactivity, as well as the dealkylation reactions that occur when the reaction of thiobenzoyl chloride is catalyzed by bases such as Et(3)N, can be understood in terms of the charge distributions in the intermediate acylammonium ions. The reaction of PhNCO with ethanol occurs at a much higher rate (4.8 x 10(4)) than that of PhNCS, corresponding to a difference in activation free energies for the additions of 6 kcal/mol. Transition states for each of these reactions were located, and each involves two alcohol molecules in a hydrogen bonded six-membered ring arrangement. Information concerning differences in reactivity was derived from analysis of Hirshfeld atomic charge distributions and calculated hydrogenolysis reaction energies.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据