GAS-PHASE CHEMISTRY OF LI+ WITH MONOFUNCTIONAL AND ALPHA,OMEGA-BIFUNCTIONAL ORGANIC-MOLECULES - HOW DOES THE PRESENCE OF A 2ND FUNCTIONAL-GROUP ENHANCE REACTIVITY

被引：22

作者：

LARRIVEE, ML ^{[1
]}

ALLISON, J ^{[1
]}

机构：

[1] MICHIGAN STATE UNIV,DEPT CHEM,E LANSING,MI 48824

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1990年 / 112卷 / 20期

关键词：

D O I：

10.1021/ja00176a008

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

It is surprising that both univalent transition-metal ions and alkali ions can induce the dehydrohalogenation of some alkyl halides (RX) in the gas phase. The mechanisms must certainly be very different. The surface on which [Li+ + RX] reactions occur has been established. The initial step following complexation involves X- transfer/charge transfer to form [LiX]R+. If sufficient charge can be generated on the alkyl group, the reaction usually proceeds to products. When R contains a halogen (R = (CH2)nY), the mechanism is substantially altered. Following charge generation, haloalkyl cations rapidly cyclize, which has dramatic effects on subsequent mechanistic steps, final reaction products, and their distributions. The chemistry of Li+ with a series of α, ω-bifunctional compounds is presented. The results provide additional insights into the mechanisms by which alkali ions can react. © 1990, American Chemical Society. All rights reserved.

引用

页码：7134 / 7140

页数：7