The Nature and Transmission of Substituent Electrical Effects in Alicyclic Solvolysis

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Title:The Nature and Transmission of Substituent Electrical Effects in Alicyclic Solvolysis
Creators:
Charton, Marvin
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 64, 11, pp. 1849-1876
Uncontrolled Keywords:Norbornanes, Electrical effect transmission, Solvolysis, Modified field effect, Bicyclo[2,2,2]octanes, Steric effects, Substituent effects

Abstract

The correlation of rate constants taken from the literature for 2-<i>exo</i>- and 2-<i>endo</i>-norbornyl derivatives substituted in positions 1, 4, 5-<i>exo</i>, 6-<i>exo</i>, 6-<i>endo</i>, and 7-<i>anti</i> with the triparametric LDR equation and relationships derived from it has been carried out. A delocalized (resonance) electrical effect has been found in all but the 4-substituted derivatives. The resonance effect may be somewhat greater when the leaving group is <i>exo</i> than when it is <i>endo</i>. Steric effects occur in the 6-<i>endo</i>-substituted derivatives. The transition state resembles a classical carbocation rather than the nonclassical norbornyl carbocation. The correlation of solvolysis rate constants for 2- and 3-substituted 1- and 4-<i>exo</i>-substituted 2-<i>exo</i>-adamantyl derivatives gave no reliable indication that a delocalized electrical effect existed in these systems. A study of solvolysis rate constants for 4-substituted 1-[2.2.2]bicyclooctanyl, 6-<i>exo</i>-substituted [2.2.2]bicyclooctan-2-<i>exo</i>-yl and 6-<i>exo</i>-substituted [2.2.2]bicyclo- octan-2-<i>endo</i>-yl derivatives showed a delocalized electrical effect only in the latter of these systems. Such an effect was also observed in 4-substituted 2-chloro-2-methylbutane solvolyses. The transmission of electrical effects is by a modified field effect. It is dependent on 1/<i>n</i> where <i>n</i> is the number of bonds intervening between substituent and reaction site. <p>

Title:The Nature and Transmission of Substituent Electrical Effects in Alicyclic Solvolysis
Creators:
Charton, Marvin
Uncontrolled Keywords:Norbornanes, Electrical effect transmission, Solvolysis, Modified field effect, Bicyclo[2,2,2]octanes, Steric effects, Substituent effects
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:64
Number:11
Page Range:pp. 1849-1876
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19991849UNSPECIFIED
ID Code:1601
Item Type:Article
Deposited On:06 Feb 2009 17:10
Last Modified:06 Feb 2009 16:11

Citation

Charton, Marvin (1999) The Nature and Transmission of Substituent Electrical Effects in Alicyclic Solvolysis. Collection of Czechoslovak Chemical Communications, 64 (11). pp. 1849-1876. ISSN 0010-0765

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