DICHLOROCARBENE, FREE OR COMPLEXED - RELATIVE REACTIVITIES OF FREE CCL2

被引：47

作者：

SKELL, PS

CHOLOD, MS

机构：

[1] Department of Chemistry, Pennsylvania State University, University Park

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1969年 / 91卷 / 22期

关键词：

D O I：

10.1021/ja01050a017

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

High-temperature pyrolysis of CHCI3 or CCl4 produces CCl2. Dichlorocarbene molecules issuing from a 1500° furnace zone into a high vacuum chamber experience collisionless flight to the wall. Wescott demonstrated that this free CCl2 reacts stereospecifically with cis- and trans-2-butene when it is cocondensed with the cold olefin. Since the graphite furnace provides a surface for spin equilibration, it was concluded that the ground state of CCI2 is singlet. This same technique has been employed to determine the relative reactivities of olefins in reaction with this variety of CCl2. Dichlorocarbene intermediates generated from MCX3 in similar media18 show the same relative reactivities, suggesting that free CCl2 is the active reagent in dichlorocyclopropanation of olefins. © 1969, American Chemical Society. All rights reserved.

引用

页码：6035 / &

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