1-(甲基磺酰基)-1-丙烯和N,N-二甲基-1-丙烯-1-磺酰胺的合成

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引用次数: 0

摘要

各种乙烯基砜和乙烯基磺酰胺具有广泛的生物活性(主要是抑制不同类型的酶),经常用于合成有机化学(作为活性亲二烯试剂,迈克尔受体,通常是1,4加成和电环化反应的活性剂)。然而,尽管有许多这种类型的合成物质,但获得这些化合物的低分子量代表-1-(甲基磺酰基)-1-丙烯和N,N -二甲基-1-丙烯-1-磺酰胺的合成方案似乎仍然知之甚少。本文在2-(4 -溴苯基)-2-羟基-N,N-二甲基-1 -丙烯磺酰胺的初步实验的基础上,提出了一种简单、高效、通用的方法,从相应的1-(甲基磺酰)-2-丙醇和N,N-二甲基-1 -丙烯磺酰胺出发,用MeSO2Cl/有机碱体系分别脱水合成1-(甲基磺酰)-1 -丙烯和N,N-二甲基-2-羟丙烯磺酰胺。从N,N -二甲基甲磺酰胺开始,经N - buli锂化,再经4 -溴苯甲醛作用,再经进一步加工,得到了后者。乙烯基衍生物合成的应用程序允许避免中间甲酰基衍生物的分离,包括离去基的一锅形成及其消除。根据1H NMR谱偶联常数,合成的N,N -二甲基-1-丙烯-1-磺酰胺是E-和z -异构体的混合物(比例为88:12),而分离的1-(甲基磺酰基)-1 -丙烯和2-(4-溴苯基)-N,N -二甲基磺酰胺是最稳定的E-异构体。合成的化合物的结构经核磁共振光谱和质谱分析证实。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Synthesis of 1-(methylsulfonyl)-1-propene and N,N-dimethyl-1-propene-1-sulfonamide
Various vinylsulfones and vinylsulfonamides have a wide range of biological activities (mainly, inhibition of different types of enzymes) and are frequently used in synthetic organic chemistry (as active dienophiles, Michael acceptors and, generally, active agents in 1,4‑addition and electrocyclization reactions). However, despite numerous synthesized substances of this type, the synthetic protocols for the obtaining of the low molecular weight representatives of these compounds – 1‑(methylsulfonyl)-1-propene and N,N‑dimethyl-1‑propene-1-sulfonamide – seem to be still little known. In the present work we report a simple, efficient and general protocol for the dehydrative synthesis of 1‑(methylsulfonyl)-1‑propene and N,N‑dimethyl-1‑propene-1‑sulfonamide starting from corresponding 1-(methylsulfonyl)-2-propanol and N,N‑dimethyl-2‑hydroxypropanesulfonamide, respectively, using MeSO2Cl/organic base system basing on the preliminary experiment of 2‑(4‑bromophenyl)-N,N‑dimethylethenesulfonamide synthesis from 2‑(4‑bromophenyl)-2‑hydroxy-N,N-dimethylethanesulfonamide. The latter in its turn has been obtained starting from N,N‑dimethylmethanesulfonamide by lithiation with n-BuLi, subsequent action of 4‑bromobenzaldehyde and further workup. The applied protocol of vinyl derivatives synthesis allows to avoid isolation of intermediate mesyl derivatives, consisting of one-pot formation of leaving group and its elimination. Accordingly to coupling constants in 1H NMR spectra, synthesized N,N‑dimethyl-1-propene-1‑sulfonamide exists as mixture of E- and Z-isomers (in the ratio 88:12), while isolated 1‑(methylsulfonyl)-1‑propene and 2-(4-bromophenyl)-N,N‑dimethylethenesulfonamide are the most stable E‑isomers. The structures of the synthesized compounds are confirmed by the methods of 1H NMR-spectroscopy and mass-spectrometry.
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