Journal of Fluorine Chemistry p. 217 - 241 (1993)
Update date:2022-08-11
Topics:
Brace, Neal O.
The free-radical addition of 2-(perfluoroalkyl)ethanethiols (RFCH2CH2SH) to alkenes, cycloalkenes, alkadienes and alkynes has been studied to determine: (1) the mode of reaction, i.e. the stereochemistry, regiochemistry and any skeletal changes: (2) the relative reactivity towards unsaturates of differing structures and classes as affected by the presence of the RF group; and (3) the influence of the reaction conditions on the rate of addition or selectivity for different products.Adducts from 2-(F-hexyl)ethanethiol (1) and alkenes have been obtained in high yield,but containing small amounts of regio isomers.For example compound 1 with 1-heptene gave 1-<2-(F-hexyl)ethanethio>heptane (3, 96percent yield) as well as 2-<2-(F-hexyl)ethanethio>heptane (4, O.61percent) and 3-<2-(F-hexyl)ethanethio>heptane (5, 2.22percent). 1,6-Hexadiene and 1,7-octadiene gave chiefly linear adducts, i.e.RFCH2CH2S(CH2)nCH=CH2 (7, n=4; or 12, n=6, respectively) and RFCH2CH2S(CH2)nSCH2CH2RF (8, n=6; or 14, n=8, respectively).A small amount (2-3percent) of cis- and trans-1-methyl-<2-(F-hexylethanethiomethyl>cyclohexane (13) isomers were present in 12.Compound 1 with 1,6-heptadiene gave 7-<2-(F-hexyl)etanethio>-1-heptene (9), the bis adduct, 1,7-bis-<2-(F-hexyl)ethanethio>heptane (11) and the cyclic adducts, cis- and trans-1-methal-2-<2-(F-hexyl)ethanethio>methylcyclopentane (10).The relative amounts of cyclic isomers depended on the reactant ratio.Compound 1 added readily with free-radical initiation to vinyl monomers such as styrene and vinyl acetate, and to phenyl acetylene, propargyl acetate and ethyl propynoate.These new addition products are useful as models for further study.
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