通过碱催化反应合成和分离非发色团笼状重排倍半硅氧烷
Synthesis and isolation of non-chromophore cage-rearranged silsesquioxanes from base-catalyzed reactions.
作者信息
Hanprasit Sasikarn, Tungkijanansin Nuttanee, Prompawilai Arisa, Eangpayung Supattra, Ervithayasuporn Vuthichai
机构信息
Department of Chemistry, Center of Excellence for Innovation in Chemistry (PERCH-CIC), Center for Catalysis, Center for Inorganic and Materials Chemistry, and Center of Intelligent Materials and Systems, Nanotec Center of Excellence, Faculty of Science, Mahidol University, Rama VI road, Ratchathewi, Bangkok 10400, Thailand.
出版信息
Dalton Trans. 2016 Oct 18;45(41):16117-16120. doi: 10.1039/c6dt02585d.
The nucleophilicity of both ortho- and meta-nitrophenolate anions is strong enough to give substituted products, but their basicity also facilitates cage-rearrangement reactions in polyhedral oligomeric silsesquioxanes (POSS). Anions having a stronger basicity, but weaker nucleophilicity, such as CO, gave products only from cage-rearrangement, with the cage expansion products being isolable in multi-gram quantities using conventional column chromatography.
邻硝基苯酚根阴离子和间硝基苯酚根阴离子的亲核性都很强，足以生成取代产物，但它们的碱性也促进了多面体低聚倍半硅氧烷（POSS）中的笼重排反应。碱性较强但亲核性较弱的阴离子，如CO，仅通过笼重排生成产物，使用传统柱色谱法可分离出多克量的笼扩展产物。
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