REARRANGEMENTS OF 1-CYCLOHEXENYLMETHYLENES AND THEIR RELEVANCE TO THE MECHANISM OF THE PHENYLCARBENE REARRANGEMENT

被引：10

作者：

MILLER, PC ^{[1
]}

GASPAR, PP ^{[1
]}

机构：

[1] WASHINGTON UNIV,DEPT CHEM,ST LOUIS,MO 63130

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 17期

关键词：

D O I：

10.1021/jo00017a021

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Gas-phase pyrolysis of 1-cyclohexenyldiazomethane (17) and (2-methyl-1-cyclohexenyl)diazomethane (36) leads to the generation of cyclohexenylmethylenes, 13 and 27, respectively, whose intramolecular rearrangement mechanisms can be inferred from the stable end products. These substituted vinylmethylenes undergo intramolecular pi-addition, but apparently do not participate in an all-carbon Wolff rearrangement. The relevance of these results to the mechanism of the phenylcarbene rearrangement is discussed, and it is suggested that a pi-route with a bicycloheptatriene-like transition state may operate. An attempt to generate 1,3-cyclohexadienylmethylene is described.

引用

页码：5101 / 5107

页数：7

共 37 条

[11]

Harding K. E., 1974, SYNTHETIC COMMUN, V4, P297

[12]

HODGKINS E, 1963, J ORG CHEM, V28, P3356

[13]

HSU JP, 1981, THESIS WASH U, P79

[14]

KABALKA GW, 1984, ORG PREP PROCED INT, V16, P321, DOI 10.1080/00304948409457889