PREPARATION OF DIMETHYL 2-(PHENYLTHIO)MALEATE, DIMETHYL 2-(PHENYLTHIO)FUMARATE, AND THEIR SULFOXIDES
PREPARATION OF DIMETHYL 2-(PHENYLTHIO)MALEATE, DIMETHYL 2-(PHENYLTHIO)FUMARATE, AND THEIR SULFOXIDES
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DOI：
10.1021/jo00155a033
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发表时间：
1983-01-01
影响因子：
3.6
通讯作者：
SMITH, DL
中科院分区：
文献类型：
--
作者：
KAYDOS, JA;SMITH, DL
对这些同分异构体的合理方法是氧化相应的硫化物la和2a。从二甲基乙炔二羧酸酯中制备了硫化Z 2a，但尚未发现纯的E异构体la。我们现在报道了E -烯烃la的合成以及另外两种制备2a的方法。Newton等人1已经证明，通过核磁共振测定，将等量的苯硫醇加入到二甲基乙炔二羧酸盐中，会得到85:15的2a/la混合物。虽然这种混合物是不可分离的蒸馏（热异构成1:1的混合物发生）和柱层析，皂化的混合酯，然后净化二酸Z和再酯化确实产生2a无任何污染的la。1
A reasonable approach to these isomers is oxidation of the corresponding sulfides la and 2a. The Z sulfide 2a has been prepared from dimethyl acetylenedicarboxylate, 1 but pure E isomer la is not known. We now report the synthesis of the E olefin la as well as two additional means for the preparation of 2a.Newton et al. 1 have already demonstrated that nucleo-philic addition of 1 equiv of benzenethiol to dimethyl acetylenedicarboxylate results in an 85: 15 mixture of 2a/la, as determined by NMR. Although this mixture is unseparable both by distillation (thermal isomerization to a 1: 1 mixture occurs) and by column chromatography, saponification of the mixed esters followed by purification of the Z diacid and reesterification does yield 2a free of any contaminating la. 1