[EN] PROCESS FOR THE STEPWISE SYNTHESIS OF SILAHYDROCARBONS [FR] PROCÉDÉ DE SYNTHÈSE SÉQUENTIELLE DE SILAHYDROCARBURES
摘要:
本发明涉及一种逐步合成在硅原子上带有最多四种不同有机基团取代的硅氢化物的过程,其中该过程包括至少以下步骤:a) 通过重分配反应、使用醚/HCI试剂对氢硅烷进行选择性氯化,或者通过使用四氯化硅对氢硅烷进行选择性氯化来制备双功能氢氯硅烷;至少一个步骤 b) 将双功能氢氯单硅烷进行氢硅化反应;至少一个步骤 c) 对氯代单硅烷进行氢化;以及步骤 d) 在氢硅化反应中获得硅氢化物化合物。
[EN] PROCESS FOR THE STEPWISE SYNTHESIS OF SILAHYDROCARBONS [FR] PROCÉDÉ DE SYNTHÈSE SÉQUENTIELLE DE SILAHYDROCARBURES
摘要:
本发明涉及一种逐步合成在硅原子上带有最多四种不同有机基团取代的硅氢化物的过程,其中该过程包括至少以下步骤:a) 通过重分配反应、使用醚/HCI试剂对氢硅烷进行选择性氯化,或者通过使用四氯化硅对氢硅烷进行选择性氯化来制备双功能氢氯硅烷;至少一个步骤 b) 将双功能氢氯单硅烷进行氢硅化反应;至少一个步骤 c) 对氯代单硅烷进行氢化;以及步骤 d) 在氢硅化反应中获得硅氢化物化合物。
A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes
作者:Yuki Naganawa、Kei Sakamoto、Yumiko Nakajima
DOI:10.1021/acs.orglett.0c04175
日期:2021.1.15
Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si–Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5
由于难以裂解牢固的Si-Cl键,氯硅烷直接催化转化为有机硅化合物仍然具有挑战性。我们在本文中报道了氯硅烷与有机铝试剂的钯催化交叉偶联反应。[Pd(C 3 H 5)Cl] 2和DavePhos配体的组合催化了各种二氯硅烷1,三氯硅烷5和四氯硅烷6的选择性甲基化,得到了相应的一氯硅烷。
Ectopic salivary gland tissue in the anterior mandible: a case report
作者:M Dorman、D Pierse
DOI:10.1038/sj.bdj.4801629
日期:2002.11
Ectopic salivary gland inclusions in the mandible are a rare phenomenon. Classically as described by Stafne1 they have been found in the posterior mandibular region. Cases affecting the anterior mandible are even more unusual. We report a case of ectopic salivary gland tissue in the anterior mandible. In our discussion we emphasise the need for a thorough history, examination and relevant investigations. Mandibular radiolucencies can prove a pitfall for the unwary.
Arenium-ion-catalysed halodealkylation of fully alkylated silanes
作者:Tao He、Hendrik F. T. Klare、Martin Oestreich
DOI:10.1038/s41586-023-06646-9
日期:2023.11.16
molecules. Yet these methods often suffer from challenging separation problems5. Conversely, silanes with four alkyl groups are considered synthetic dead ends. Here we introduce an arenium-ion-catalysed halodealkylation that effectively converts Me4Si and related quaternary silanes into a diverse range of functionalized derivatives. The reaction uses an alkyl halide and an arene (co)solvent: the alkyl
“有机硅”在自然界中并不存在,但现代化学很难想象没有硅与碳结合的情况。虽然含硅商品化学品(例如通过“直接工艺” 1,2,3,4产生的那些)看起来很简单,但选择性制备芳基取代和烷基取代(官能化)硅化合物(称为硅烷)并非易事。氯硅烷如 Me 4− n SiCl n ( n = 1–3) 以及 SiCl 4 ( n = 4) 是合成含硅分子的常见起点。然而这些方法常常遇到具有挑战性的分离问题5 。相反,具有四个烷基的硅烷被认为是合成的死角。在这里,我们介绍了芳烃离子催化的卤代脱烷基化反应,可有效地将 Me 4 Si 和相关的季硅烷转化为各种官能化衍生物。该反应使用烷基卤和芳烃(共)溶剂:烷基卤是卤化物源,最终与芳烃进行弗里德尔-克来福特烷基化以再生催化剂6 ,而芳烃离子则充当强布朗斯台德酸原脱烷基化步骤7 。例如,在硅药物前体的合成中,证明了自上而下的卤代烷基化方法相对于报道的自下而上程序的优势。此外,连接到烷基链上的相当惰性的Me
Synthesis of triorganylchlorosilanes by catalytic reaction of triorganylsilanes with chlorobenzene
作者:Yu. I. Khudobin、N. A. Andreeva、N. P. Kharitonov、M. G. Voronkov
DOI:10.1007/bf00923508
日期:1974.4
Selective synthesis of halosilanes from hydrosilanes and utilization for organic synthesis
作者:Atsutaka Kunai、Joji Ohshita
DOI:10.1016/s0022-328x(03)00254-7
日期:2003.11
Selective synthesis of halosilanes has been examined. Various types of halosilanes and halohydrosilanes, such as R3SiX, R2SiHX, R2SiX2, RSiH2X, RSiHX2 (X = Cl, Br, F), were obtained by the reactions of the corresponding hydrosilanes with Cu(II)-based reagents selectively in high yields. This method could be also applied to the synthesis of chlorofluorosilanes and chlorohydrogermanes. On the other hand, iodo- and bromosilanes and germanes were obtained by Pd- or Ni-catalyzed hydride-halogen exchange reactions of hydrosilanes with alkyl or allyl halides. Their synthetic applications have been demonstrated by using iodo-and bromosilanes and chlorofluorosilanes. (C) 2003 Elsevier Science B.V. All rights reserved.