The thermodynamic effect of fluorine as a substituent. Vinylic CF2 and CFH and allylic CF2C

Document Type

Article

Publication Date

1-1-1982

Abstract

I2-catalyzed isomerizations of 3-fluoropropene and 3,3 - difluoropropene, and a Cope rearrangement of 1,1 - difluoro - 1,5 - hexadiene provide thermodynamic data which allow the determination of a number of important group values for contributions to ΔHo f which when combined with those determined in the preceding paper allow the calculations of ΔHo f's of most simple F-substituted hydrocarbons: [Cd(F)(H)] = - 38.4, [Cd(F)2] = - 88.0, [C(F)2(C)(Cd)] = - 103.9, [C(F)2(C)2] = - 104.9 kcal/mole. A kinetic study of the conversion of 1,1 - difluoro- to 3,3 - difluoro - 1,5 - hexadiene provided activation parameters for the process: Log A = 10.8, Ea = 33.0 kcal/mole and ΔS≠ = - 12.2 e.u. Incremental geminal stabilizations of F and other substituents are discussed and contrasted. © 1982.

Identifier

0001239092 (Scopus)

Publication Title

Tetrahedron

External Full Text Location

https://doi.org/10.1016/0040-4020(82)87020-8

ISSN

00404020

First Page

2415

Last Page

2420

Issue

15

Volume

38

Fund Ref

National Science Foundation

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