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Effects of Bridgehead Substitution on Structure and Reactivity of the 7-Norbornyl Cation (CROSBI ID 201663)

Prilog u časopisu | izvorni znanstveni rad | međunarodna recenzija

Sunko, Dionis E. ; Vančik, Hrvoj ; Mihalić, Zlatko ; Shiner, V.J.Jr. ; Wiglis, F.Pz. Effects of Bridgehead Substitution on Structure and Reactivity of the 7-Norbornyl Cation // Journal of organic chemistry, 59 (1994), 23; 7051-7055. doi: 10.1021/jo00102a033

Podaci o odgovornosti

Sunko, Dionis E. ; Vančik, Hrvoj ; Mihalić, Zlatko ; Shiner, V.J.Jr. ; Wiglis, F.Pz.

engleski

Effects of Bridgehead Substitution on Structure and Reactivity of the 7-Norbornyl Cation

A systematic investigation was undertaken of the effect of bridgehead substitution on the solvolytic reactivity of 7-norbornyl triflates in aqueous TFE. Methyl substitution increases the rate 60-fold and the effect of multiple substitution is additive. Chlorine, on the other hand, exhibits a combined inductive and resonance effect and decreases the reactivity 1700 times. The observed normal secondary P-deuterium isotope effect of the 1, 4-d(2) derivative can be rationalized by assuming a tilted C-s geometry for the cationic transition structure which is only slightly higher in energy than the nonclassical intermediate cation of C-1 symmetry. Bridgehead methyl-d(3) kinetic isotope effects are similar to those associated with the nonmigrating methyl group in neopentyl ester solvolyses. These results are in agreement with the recently published structure of the 7-norbornyl cation calculated at the highest ab initio level which has confirmed its nonclassical nature as originally proposed by Winstein.

7-norbornyl cation ; solvolysis ; neigboring group participation

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Podaci o izdanju

59 (23)

1994.

7051-7055

objavljeno

0022-3263

1520-6904

10.1021/jo00102a033

Povezanost rada

Kemija

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