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Evidence for Cyclohexyne and Cyclopentyne as Intermediates in the Coupling Reactions of Phenyllithium with 1-Chlorocyclohexene and 1-Chlorocyclopentene

Montgomery, Lawrence K. and Scardiglia, F. and Roberts, John D. (1965) Evidence for Cyclohexyne and Cyclopentyne as Intermediates in the Coupling Reactions of Phenyllithium with 1-Chlorocyclohexene and 1-Chlorocyclopentene. Journal of the American Chemical Society, 87 (9). pp. 1917-1925. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20151015-104931160

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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.


Item Type:Article
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http://dx.doi.org/10.1021/ja01087a015DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja01087a015PublisherArticle
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.
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NSFUNSPECIFIED
American Chemical Society Petroleum Research FundUNSPECIFIED
General ElectricUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
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Caltech Gates and Crellin Laboratories of Chemistry3191
Issue or Number:9
Record Number:CaltechAUTHORS:20151015-104931160
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151015-104931160
Official Citation:Evidence for Cyclohexyne and Cyclopentyne as Intermediates in the Coupling Reactions of Phenyllithium with 1-Chlorocyclohexene and 1-Chlorocyclopentene Lawrence K. Montgomery, F. Scardiglia, and John D. Roberts Journal of the American Chemical Society 1965 87 (9), 1917-1925 DOI: 10.1021/ja01087a015
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61175
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:15 Oct 2015 21:06
Last Modified:03 Oct 2019 09:05

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