Investigation into thiol-(meth)acrylate Michael addition reactions using amine and phosphine catalysts
Investigation into thiol-(meth)acrylate Michael addition reactions using amine and phosphine catalysts
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DOI：
10.1039/c0py00100g
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发表时间：
2010-10-01
影响因子：
4.6
通讯作者：
Haddleton, David M.
中科院分区：
文献类型：
--
作者：
Li, Guang-Zhao;Randev, Rajan K.;Haddleton, David M.
本文研究了硫醇-烯的Michael加成反应。研究了不同的催化剂，伯胺、叔胺和膦，用于一系列硫醇与一些（甲基）丙烯酸酯的二聚体和低聚物的反应。伯胺和叔胺是硫醇-烯反应的有效催化剂，尽管这些催化剂需要几个小时才能达到高转化率。此外，对膦催化剂二甲基苯基膦（DMPP）和三-（2-羧乙基）膦（TCEP）进行了详细的研究。DMPP是一种有效的催化剂，在优化的条件下在几分钟内完全转化。重要的是，DMPP的浓度应保持在催化水平，以避免形成源自DMPP加成到乙烯基上的副产物。此外，当介质的pH高于8.0时，TCEP是水性介质中硫醇-烯反应的有效催化剂，因为在酸性pH下观察到副产物的形成。
This work describes a study into thiol-ene based Michael addition reactions. Different catalysts, primary and tertiary amines and phosphines, were investigated for the reaction of a range of thiols with dimers and oligomers of some (meth)acrylates. Primary and tertiary amines are efficient catalysts for the thiol-ene reaction, although these catalysts require several hours to reach high conversion. Moreover, the phosphine catalysts, dimethylphenylphosphine (DMPP) and tris-(2-carboxyethyl)phosphine (TCEP), were investigated in detail. DMPP is an efficacious catalyst yielding complete conversion in few minutes under optimized conditions. Importantly, the concentration of DMPP should be kept at catalytic levels to avoid the formation of by-products, originating from the addition of DMPP to the vinyl group. Furthermore, TCEP is an efficient catalyst for thiol-ene reactions in aqueous media when the pH of the medium is higher than 8.0 since at acidic pH the formation of by-products is observed.