STEREOSPECIFIC REACTIONS OF NUCLEOPHILIC AGENTS WITH ACETYLENES AND VINYL-TYPE HALIDES .4. THE STEREOCHEMISTRY OF NUCLEOPHILIC ADDITIONS OF THIOLS TO ACETYLENIC HYDROCARBONS
STEREOSPECIFIC REACTIONS OF NUCLEOPHILIC AGENTS WITH ACETYLENES AND VINYL-TYPE HALIDES .4. THE STEREOCHEMISTRY OF NUCLEOPHILIC ADDITIONS OF THIOLS TO ACETYLENIC HYDROCARBONS
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DOI：
10.1021/ja01593a029
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发表时间：
1956-01-01
影响因子：
15
通讯作者：
SIMMS, JA
中科院分区：
文献类型：
--
作者：
TRUCE, WE;SIMMS, JA
对甲苯硫醇与苯乙炔和2-丁炔的碱催化加成反应分别生成了c-ŋS-α-苯乙酰对甲苯硫醚和2-对甲苯硫醇Ŧi-2-丁烯。苯乙炔和甲硫醇生成甲基硫醚，对甲苯硫醇与1-己炔反应生成2-甲苯硫基-L-己烯和1-^-甲硫基-L-己烯的混合物。碱催化的乙炔加成反应生成相应的乙烯基化合物已有多年的研究，但这种加成反应的立体化学还没有得到系统的研究。6文献中有几个迹象表明，这种反应可能不会产生可能的顺式和反式烯烃的混合物。例如，对硝基苯乙炔和苯硫酚的碱性溶液以41%的产率形成纯的苯基%硝基-铜-苯乙烯硫化物，其几何构型尚未确定。此外，当乙醇在乙醇钠存在下加到苯乙炔中时，两种可能的乙氧基苯乙烯中只有一种生成。8常压蒸馏导致异构化为几何异构体的混合物。
The base-catalyzed addition of p-toluenethiol to phenylacetylene and to 2-butyne yields cŋs-a.-styryl^-tolyI sulfide and2-p-tolylmercapto-lraŦi-2-butene, respectively. Phenylacetylene and methanethiol yieldmethyl ct'i--styryl sulfide, p-Toluenethiol reacts with 1-hexyne to produce a mixture of 2-/>-tolylmercapto-l-hexene and 1-^-tolylmercapto-l-hexene.Base-catalyzed additions to acetylenes to form the corresponding vinyl compounds have been known for many years3-6; however, the stereo-chemistry of such additions has not been system-atically studied. 6 There are several indications in the literature that such reactions may not pro-duce a mixture of the possible cis-and transolefins. For example, an alkaline solution of p-nitrophenylacetylene and benzenethiol forms a pure phenyl% nitro-cu-styryl sulfide, of undetermined geometry in 41% yield. 7 Also, only one of the two possible-ethoxystyrenes is formed when ethanol is added to phenylacetylene in the presence of sodium ethoxide. 8 Distillation at atmospheric pressure caused isomerization to a mixture of geometrical isomers.