ORGANIC SULFUR COMPOUNDS . 13 . FREE-RADICAL ADDITION OF THIOLS TO PHENYLACETYLENE
ORGANIC SULFUR COMPOUNDS . 13 . FREE-RADICAL ADDITION OF THIOLS TO PHENYLACETYLENE
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DOI：
10.1021/ja01068a023
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发表时间：
1964-01-01
影响因子：
15
通讯作者：
HUDSON, BE
中科院分区：
文献类型：
--
作者：
OSWALD, AA;GRIESBAUM, K;HUDSON, BE
Nucleophilic addition of thiols to acetylenes is well understood but little is known about the stereochemistry of the free-radical addition. In the present study, therefore, aromatic and aliphatic thiols and thiolacetic acid were added to phenylacetylene by a chain mechanism both in the absence and in the presence of ultraviolet light or hydroperoxide initiation. When equimolar amounts of reactants were mixed at ambient temperatures, mainly trans monoaddition occurred, yielding cis-l-substituted mercapto-2-phenylethenes. The apparent stereoselectivity of the reaction increased when an excess of phenylacetylene was used. The resulting cis adducts were readily isomerized by thiyl radicals to equilibrium mixtures consisting mainly of the trans isomer. The various cis-trans isomer mixtures were analyzed by a combination of the gc and nmr techniques; nmr and infrared spectra of the cis and trans adducts and their mixtures were systematically studied andled to general rules for the identification of the configuration of these adducts.
