Synthese von Fluorsilylenolaten, Aminosilylenolaten, -ethern und Aldolkondensaten/Synthesis of Fluorosilylenolates, Aminosilylenolates, -ethers, and Aldol Condensates
作者:Thomas Büschen、Wibke Dietz、Uwe Klingebiel、Mathias Noltemeyer、Yvonne Schwerdtfeger
DOI:10.1515/znb-2007-1103
日期:2007.11.1
(Me3C)2SiF2. A side reaction of the enolate formation is often a condensation releasing water. For that reason, acyclic and cyclic siloxanes may appear as by-products, e. g. disiloxane (17) using (Me3C)2SiF2, cyclotrisiloxane (Me3C(C6H5)Si-O)3 (18) using Me3(C6H5)SiF2, or cyclotetrasiloxane (Me3CSiF-O)4 (19) using Me3CSiF3 in these reactions. Attempts to prepare the enolate of cyclopentanone in the reaction
根据反应条件,酮与正丁基锂、叔丁基锂或二异丙基氨基锂反应生成烯醇化物或醇化物。在叔丁基甲基酮与 n-BuLi 和氟硅烷的反应中,氟甲硅烷基烯醇化 H2C=C(O-SiFRR')CMe3 (1 - 4) 和氟甲硅烷基醚 Me3C(CH3)(n-C4H9)CO-SiFRR' ( 5 - 8) [R,R' = Me (1, 5); F, CMe3 (2, 6); F, C6H5 (3, 7); F, CHMe2 (4, 8)] 形成。使用叔丁基甲基酮、n-BuLi 和 (Me3C)2SiF2、异丁烯和乙醛 H2C=CH-O-SiF(CMe3)2 的氟甲硅烷基烯醇化物 (9)。二异丙基酮与 Me3CLi 和氟硅烷反应生成氟甲硅烷基烯醇化物 Me2C=C(O-SiFRR')CHMe2 (10, 11) 和 -ethers,Me3C(Me2HC)2C-O-SiFRR' (12, 13) [R,R