Evidence for Cyclohexyne and Cyclopentyne as Intermediates in the Coupling Reactions of Phenyllithium with 1-Chlorocyclohexene and 1-Chlorocyclopentene
Abstract
Phenyllithium and 1-chlorocyclohexene and 1-chlorocyclopentene react at 150º in ether to form 1-phenylcyclohexene and 1-phenylcyclopentene, respectively. A 1:1 mixture of 1-chlorocyclohexene-2-^(14) and 1-chlorocyclohexene-6 ^(14)- with phenyllithium yielded 1-phenylcyclohexene-x-^(14)C which contained 23 % of the ^(14)C label in the 1-position. When 1-chlorocyclopentene-1-^(14)C was heated with phenyllithium, extensive rearrangement of the ^(14)C label occurred with 48.9, 36.2, and 14.9% of the ^(14)C distributed in the 1-,2-, and 5-positions of 1-phenylcyclopentene, respectively. The observed ^(14)C rearrangements which accompanied these nucleophilic substitution reactions are best rationalized in terms of an elimination-addition mechanism involving cycloalkyne intermediates.
Additional Information
© 1965 American Chemical Society. Received November 21, 1964. Supported in part by the National Science Foundation and the Petroleum Research Fund administered by the American Chemical Society. Grateful acknowledgment is hereby made to the Donors of the Petroleum Research Fund. General Electric Company Fellow, 1959-1960; National Science Foundation Predoctoral Fellow, 1954-1955.Additional details
- Eprint ID
- 61175
- DOI
- 10.1021/ja01087a015
- Resolver ID
- CaltechAUTHORS:20151015-104931160
- NSF
- American Chemical Society Petroleum Research Fund
- General Electric
- NSF Predoctoral Fellowship
- Created
-
2015-10-15Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Gates and Crellin Laboratories of Chemistry
- Other Numbering System Identifier
- 3191