ELECTROPHILIC REACTIONS AT SINGLE BONDS .25. NITRATION OF ADAMANTANE AND DIAMANTANE WITH NITRONIUM TETRAFLUOROBORATE

被引：60

作者：

OLAH, GA ^{[1
]}

RAMAIAH, P ^{[1
]}

RAO, CB ^{[1
]}

SANDFORD, G ^{[1
]}

GOLAM, R ^{[1
]}

TRIVEDI, NJ ^{[1
]}

OLAH, JA ^{[1
]}

机构：

[1] UNIV SO CALIF,DEPT CHEM,LOS ANGELES,CA 90089

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1993年 / 115卷 / 16期

关键词：

D O I：

10.1021/ja00069a024

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The slow reaction of adamantane with nitronium tetrafluoroborate at room temperature in purified, nitrile-free nitromethane or in nitroethane gives 1-nitroadamantane in 66% and 74% isolated yield, respectively. Similar reaction of diamantane gives 62% 1- and 5% 4-nitrodiamantane. Initial reaction upon aqueous workup gives 1-adamantanol with 1-fluoroadamantane, 3-fluoro-1-adamantanol, and adamantanone as byproducts. Upon prolonged reaction 1-nitroadamantane is formed in good yield. The experimental data are in accord with intermediate formation of the 1-adamantyl cation (by hydride abstraction or cleavage of initially formed 1-nitroadamantane) followed by reaction with HNO2 or NO2- formed in the reaction, giving 1-adamantyl nitrite, which then undergoes cleavage-rearrangement to give 1-nitroadamantane. A small kinetic hydrogen isotope effect of k(H)/k(D) = 1.2-1.3 is indicative of a nonlinear highly unsymmetrical transition state in the rate-determining step of the reaction.

引用

页码：7246 / 7249

页数：4

共 39 条

[21] ELECTROPHILIC REACTIONS AT SINGLE BONDS .10. HYDROGEN TRANSFER, ALKYLATION, AND ALKYLOLYSIS OF ALKANES WITH METHYL AND ETHYL FLUOROANTIMONATE [J].