Przybylska Agnieszka, Szymańska Anna, Maciejewski Hieronim
Faculty of Chemistry, Adam Mickiewicz University Uniwersytetu Poznańskiego 8 61-614 Poznań Poland.
Poznań Science and Technology Park, Adam Mickiewicz University Foundation Rubież 46 61-612 Poznań Poland
RSC Adv. 2023 May 9;13(20):14010-14017. doi: 10.1039/d3ra01583a. eCollection 2023 May 2.
A simple and efficient method for the synthesis of organofunctional silanes by the thiol-(meth)acrylate addition reaction is presented. At first, systematic studies were carried out to select an optimum initiator/catalyst of the addition reaction for the model reaction involving 3-mercaptopropyltrimethoxysilane (MPTMS) and hexyl acrylate. Photoinitiators (in the presence of UV light energy), thermal initiators (such as aza compound and peroxide) as well as catalysts (primary and tertiary amines, phosphines and Lewis acid) were studied. After selecting an effective catalytic system and optimizing the reaction conditions, reactions between the thiol group ( 3-mercaptopropyltrimethoxysilane) and (meth)acrylates containing various functional groups were carried out. All derivatives obtained were characterized by H, C, Si NMR and FT-IR analysis. In reactions carried out at room temperature, in an air atmosphere and in the presence of dimethylphenylphosphine (DMPP) as a catalyst, quantitative conversions of both substrates were obtained within a few minutes. The library of organofunctional silanes was expanded by compounds (containing various functional groups, alkenyl, epoxy, amino, ether, alkyl, aralkyl, fluoroalkyl) which were obtained in the thiol-Michael addition of 3-mercaptopropyltrimethoxysilane to a group of organofunctional (meth)acrylic acid esters.
本文提出了一种通过硫醇-（甲基）丙烯酸酯加成反应合成有机官能硅烷的简单高效方法。首先，针对涉及3-巯基丙基三甲氧基硅烷（MPTMS）和丙烯酸己酯的模型反应，进行了系统研究以选择加成反应的最佳引发剂/催化剂。研究了光引发剂（在紫外光能存在下）、热引发剂（如氮杂化合物和过氧化物）以及催化剂（伯胺和叔胺、膦和路易斯酸）。在选择了有效的催化体系并优化反应条件后，进行了硫醇基团（3-巯基丙基三甲氧基硅烷）与含各种官能团的（甲基）丙烯酸酯之间的反应。通过氢、碳、硅核磁共振以及傅里叶变换红外光谱分析对所有得到的衍生物进行了表征。在室温、空气气氛以及以二甲基苯基膦（DMPP）作为催化剂进行的反应中，几分钟内两种底物都实现了定量转化。通过3-巯基丙基三甲氧基硅烷与一组有机官能（甲基）丙烯酸酯的硫醇-迈克尔加成反应得到的化合物（含有各种官能团，如烯基、环氧基、氨基、醚基、烷基、芳烷基、氟烷基）扩展了有机官能硅烷库。
