5H-dibenzo[b,d]silole | 244-96-2

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 5H-dibenzo[b,d]silole
• 英文别名: Silafluoren；5H-benzo[b][1]benzosilole
• CAS: 244-96-2
• 化学式: C₁₂H₁₀Si
• 分子量: 182.297
• InChiKey: KFCMUZONUPOPAC-UHFFFAOYSA-N

物化性质

• 沸点：
  60-80 °C(Press: 0.01 Torr)
• 熔点：
  36.5 °C

计算性质

• 辛醇/水分配系数(LogP)：
  0.79
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5H-dibenzo[b,d]silole 在 palladium dichloride 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 3.0h， 生成 9-isopropoxy-9-silafluorene
  参考文献：
  名称：

  9,9-二烷氧基-9-硅芴的合成、结构和反应性

  摘要：

  AbstractA series of novel 9,9‐dialkoxy‐9‐silafluorenes were synthesized, and their structures and reactivity were studied. Dehydrogenative alkoxylation of 9,9‐dihydro‐9‐silafluorene with various alcohols in the presence of PdCl2 gave the corresponding dialkoxylated products in good yields. The structures of some of the novel 9,9‐dialkoxy‐9‐silafluorenes were analyzed by X‐ray crystallography. The 9,9‐dialkoxy‐9‐silafluorenes show remarkably high reactivity toward phenylmagnesium bromide to afford substitution products.

  DOI：

  10.1002/hc.21478
• 作为产物：
  描述：

  2,2'-双溴双苯 生成 5H-dibenzo[b,d]silole
  参考文献：
  名称：

  具有双功能硅中心的三环杂环

  摘要：

  所述diorganometallic试剂缩合（ø -MC 6 ħ 4）2 X（M锂，氯化镁）与HSiCl 3，接着用还原的LiAlH 4提供dibenzosilacycles，I（A，X - ; B，XNME; C， X ＝ CH 2； d，X ＝ CH 2 CH 2），带有两个环外H-取代基。确定了将I逐步转化为混合双官能体系（II，XCl，Br; III，X）OR）和双官能衍生物（IV，XCl; V，XOR）的条件。尽管CCl 4为1摩尔当量的SO 2 Cl 2或NBS可实现I至II的受控卤化在ClRh（PPh 3）3或PdCl 2的存在下导致缓慢的单氯化作用。I与过量的SOCl 2或SO 2 Cl 2的反应将I转化为III，但是后者更快并且提供更少的副反应。用ClRh（PPh 3）3高产率地将I与IV转化为IV，而使用H 2 PtCl 6则低产率地进行I至IV的转化。除t

  DOI：

  10.1016/s0022-328x(00)99678-5

文献信息

• Lewis acid-catalyzed synthesis of silafluorene derivatives from biphenyls and dihydrosilanes <i>via</i> a double sila-Friedel–Crafts reaction
  作者：Yafang Dong、Yuta Takata、Yusuke Yoshigoe、Kohei Sekine、Yoichiro Kuninobu

  DOI：10.1039/c9cc07692a

  日期：——

  The synthesis of silafluorene derivatives from aminobiphenyl compounds and dihydrosilanes via a double sila-Friedel–Crafts reaction using a borane catalyst has been achieved. This method is applicable to the synthesis of a variety of silafluorene derivatives, such as multisubstituted silafluorenes, spirosilabifluorenes, and silicon-bridged terphenyl compounds, which are not readily obtained using conventional

  通过使用甲硼烷催化剂的双sila-Friedel-Crafts反应，由氨基联苯化合物和二氢硅烷合成了silafluorene衍生物。该方法适用于各种硅芴衍生物的合成，例如多取代的硅芴，螺硅双芴和硅桥联的三联苯化合物，这些都是使用常规合成方法不易获得的。另外，我们已经证明了这些硅芴衍生物中的氨基转化为其他取代基。
• Synthesis of six-membered silacycles by borane-catalyzed double sila-Friedel–Crafts reaction
  作者：Yafang Dong、Masahiko Sakai、Kazuto Fuji、Kohei Sekine、Yoichiro Kuninobu

  DOI：10.3762/bjoc.16.39

  日期：——

  We have developed a catalytic synthetic method to prepare phenoxasilins. A borane-catalyzed double sila-Friedel–Crafts reaction between amino group-containing diaryl ethers and dihydrosilanes can be used to prepare a variety of phenoxasilin derivatives in good to excellent yields. The optimized reaction conditions were also applicable for diaryl thioethers to afford their corresponding six-membered

  我们已经开发了一种催化合成方法来制备苯那西林。含氨基的二芳基醚和二氢硅烷之间的硼烷催化的双硅烷-Friedel-Crafts反应可用于制备各种苯氧西林衍生物，并具有良好的产率。优化的反应条件也适用于二芳基硫醚，以提供其相应的六元硅环产物。代表性的双（二甲基氨基）苯恶沙林的克级合成及其氨基的转化也得到了证明。
• Conjugate Addition of Perfluoroarenes to α,β-Unsaturated Carbonyls Enabled by an Alkoxide-Hydrosilane System: Implication of a Radical Pathway
  作者：Weilong Xie、Sung-Woo Park、Hoimin Jung、Dongwook Kim、Mu-Hyun Baik、Sukbok Chang

  DOI：10.1021/jacs.8b05744

  日期：2018.8.1

  reagents to α,β-unsaturated carbonyls is a key strategy for the construction of carbon-carbon bond in organic synthesis. Although direct C-H addition to unsaturated bonds via transition metal catalysis is explored in recent years, electron-deficient arenes that do not bear directing groups continue to be challenging. Herein we disclose the first example of a conjugate addition of perfluoroarenes to α,β-unsaturated

  有机金属试剂与α,β-不饱和羰基化合物的共轭加成是有机合成中碳-碳键构建的关键策略。尽管近年来探索了通过过渡金属催化将 CH 直接加成到不饱和键，但不带有导向基团的缺电子芳烃仍然具有挑战性。在本文中，我们公开了由醇盐-氢硅烷系统实现的全氟芳烃与 α,β-不饱和羰基的共轭加成的第一个例子。该反应可方便地在室温下在广泛的底物和反应物上进行，以提供高产率到极好的合成多功能产品。结合计算研究的机械实验表明，在这种转变中最有可能是一个激进的途径。
• Ruthenium-catalysed double trans-hydrosilylation of 1,4-diarylbuta-1,3-diynes leading to 2,5-diarylsiloles
  作者：Takanori Matsuda、Sho Kadowaki、Masahiro Murakami

  DOI：10.1039/b703397d

  日期：——

  Dihydrosilanes undergo double trans-hydrosilylation with 1,4-diarylbuta-1,3-diynes in the presence of a cationic ruthenium catalyst to afford 2,5-diarylsiloles: in particular, 9-silafluorene is a good hydrosilylating agent to produce spiro-type siloles in good yield.

  二氢硅烷在阳离子钌催化剂的存在下与1,4-二芳基丁-1,3-二炔发生双转式氢硅化反应，生成2,5-二芳基硅烯；尤其是，9-硅氟烯是一个良好的氢硅化试剂，可以高产率地生成螺旋型硅烯。
• Metallocene compositions
  申请人：——

  公开号：US20030073568A1

  公开（公告）日：2003-04-17

  This invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization. In one embodiment, the metallocenes of the present invention may be represented by the formula: 1 wherein: M is a metal of Group 4, 5, or 6 of the Periodic Table preferably, zirconium, hafnium and titanium, most preferably zirconium; R 1 and R 2 are identical or different, preferably identical, and are one of a hydrogen atom, a C 1 -C 10 alkyl group, preferably a C 1 -C 3 alkyl group, a C 1 -C 10 alkoxy group, preferably a C 1 -C 3 alkoxy group, a C 6 -C 10 aryl group, preferably a C 6 -C 8 aryl group, a C 6 -C 10 aryloxy group, preferably a C 6 -C 8 aryloxy group, a C 2 -C 10 alkenyl group, preferably a C 2 -C 4 alkenyl group, a C 7 -C 40 arylalkyl group, preferably a C 7 -C 10 arylalkyl group, a C 7 -C 40 alkylaryl group, preferably a C 7 -C 12 alkylaryl group, a C 8 -C 40 arylalkenyl group, preferably a C 8 -C 12 arylalkenyl group, or a halogen atom, preferably chlorine, or are a conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30 atoms not counting hydrogen; R 5 and R 6 are identical or different, preferably identical, are one of a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C 1 -C 10 alkyl group, preferably a C 1 -C 4 alkyl group, which may be halogenated, a C 6 -C 10 aryl group, which may be halogenated, preferably a C 6 -C 8 aryl group, a C 2 -C 10 alkenyl group, preferably a C 2 -C 4 alkenyl group, a C 7 -C 40 -arylalkyl group, preferably a C 7 -C 10 arylalkyl group, a C 7 -C 40 alkylaryl group, preferably a C 7 -C 12 alkylaryl group, a C 8 -C 40 arylalkenyl group, preferably a C 8 -C 12 arylalkenyl group, a —NR 2 15 , —SR 15 , —OR 15 , —OSiR 3 15 or —PR 2 15 radical, wherein: R 15 is one of a halogen atom, preferably a chlorine atom, a C 1 -C 10 alkyl group, preferably a C 1 -C 3 alkyl group, or a C 6 -C 10 aryl group, preferably a C 6 -C 9 aryl group; R 7 is 2 wherein: R 17 to R 24 are as defined for R 1 and R 2 , or two or more adjacent radicals R 17 to R 24 , including R 20 and R 21 , together with the atoms connecting them form one or more rings; M 2 is carbon, silicon, germanium or tin; the radicals R 3 , R 4 , and R 10 are identical or different and have the meanings stated for R 5 and R 6 . Two adjacent R 10 radicals can be joined together to form a ring system, preferably a ring system containing from about 4-6 carbon atoms. Alkyl refers to straight or branched chain substituents. Halogen (halogenated) refers to fluorine, chlorine, bromine or iodine atoms, preferably fluorine or chlorine. The metallocene compositions may also be represented by the formula: 3 wherein: M 1 is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, preferably zirconium, hafnium or titanium, most preferably zirconium; R 1 and R 2 are identical or different, and are one of a hydrogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 2 -C 40 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, an OH group or a halogen atom, or are a conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30 atoms not counting hydrogen; preferably R 1 and R 2 are identical and are a C 1 -C 3 alkyl or alkoxy group, a C 6 -C 8 aryl or aryloxy group, a C 2 -C 4 alkenyl group, a C 7 -C 10 arylalkyl group, a C 7 -C 12 alkylaryl group, or a halogen atom, preferably chlorine; R 3 are identical or different and are each a hydrogen atom, a halogen atom, a C 1 -C 10 alkyl group which may be halogenated, a C 6 -C 10 aryl group which may be halogenated, a C 2 -C 10 alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, a —NR′ 2 , —SR′, —OR′, —OSiR′ 3 or —PR′ 2 radical, wherein: R′ is one of a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group; preferably R 3 is not a hydrogen atom; preferably each R 3 is identical and is a fluorine, chlorine or bromine, atom, a C 1 -C 4 alkyl group which may be halogenated, a C 6 -C 8 aryl group which may be halogenated, a —NR′ 2 , —SR′, —OR′, —OSiR′ 3 or —PR′ 2 radical, wherein: R′ is one of a chlorine atom, a C 1 -C 4 alkyl group, or a C 6 -C 8 aryl group; R 13 is represented by the formula: 4 wherein: R 17 to R 24 are as defined for R 1 and R 2 , or two or more adjacent radicals R 17 to R 24 , including R 20 and R 21 , together with the atoms connecting them form one or more rings; preferably, R 17 to R 24 are hydrogen. M 2 is carbon, silicon, germanium or tin, preferably silicon; R 8 , R 9 , R 10 , R 11 and R 12 are identical or different and have the meanings stated for R 4 to R 7 .

  本发明涉及金属茂组成物及其在烯烃聚合催化剂系统制备中的应用，尤其是丙烯聚合。 在一种实施方式中，本发明的茂金属可以用以下公式表示： 其中：M是周期表中第4、5或6组的金属，优选锆、铪和钛，最优选锆；R1和R2相同或不同，优选相同，它们是氢原子、C1-C10烷基，优选C1-C3烷基，C1-C10烷氧基，优选C1-C3烷氧基，C6-C10芳基，优选C6-C8芳基，C6-C10芳氧基，优选C6-C8芳氧基，C2-C10烯基，优选C2-C4烯基，C7-C40芳基烷基，优选C7-C10芳基烷基，C7-C40烷基芳基，优选C7-C12烷基芳基，C8-C40芳基烯基，优选C8-C12芳基烯基，或卤原子，优选氯原子，或是具有一个或多个烃基、三(烃基)硅基团或烃基、三(烃基)硅基团烃基的共轭二烯，所述二烯不计算氢原子最多有30个原子；R5和R6相同或不同，优选相同，它们是氢原子、卤原子，优选氟、氯或溴原子，C1-C10烷基，优选C1-C4烷基，可以卤代，C6-C10芳基，可以卤代，优选C6-C8芳基，C2-C10烯基，优选C2-C4烯基，C7-C40芳基烷基，优选C7-C10芳基烷基，C7-C40烷基芳基，优选C7-C12烷基芳基，C8-C40芳基烯基，优选C8-C12芳基烯基，或者是—NR215、—SR15、—OR15、—OSiR315或—PR215基，其中：R15是卤原子，优选氯原子，C1-C10烷基，优选C1-C3烷基，或C6-C10芳基，优选C6-C9芳基；R7是 其中：R17到R24如R1和R2中所定义，或两个或更多相邻的基团R17到R24，包括R20和R21，与连接它们的原子形成一个或多个环；M2是碳、硅、锗或锡；基团R3、R4和R10相同或不同，并且具有R5和R6中所述的含义。两个相邻的R10基团可以连接在一起形成环系，优选含有约4-6个碳原子的环系。烷基是直链或支链取代基。卤素(卤代)是氟、氯、溴或碘原子，优选氟或氯。茂金属组成物也可以用以下公式表示： 其中：M1选自钛、锆、铪、钒、铌、钽、铬、钼和钨的组，优选锆、铪或钛，最优选锆；R1和R2相同或不同，它们是氢原子、C1-C10烷基、C1-C10烷氧基、C6-C10芳基、C6-C10芳氧基、C2-C10烯基、C2-C40烯基、C7-C40芳基烷基、C7-C40烷基芳基、C8-C40芳基烯基、OH基或卤原子，或是具有一个或多个烃基、三(烃基)硅基团或烃基、三(烃基)硅基团烃基的共轭二烯，所述二烯不计算氢原子最多有30个原子；优选R1和R2相同且为C1-C3烷基或烷氧基、C6-C8芳基或芳氧基、C2-C4烯基、C7-C10芳基烷基、C7-C12烷基芳基或卤原子，优选氯；R3相同或不同，它们是氢原子、卤原子，可以卤代的C1-C10烷基、可以卤代的C6-C10芳基、C2-C10烯基、C7-C40芳基烷基、C7-C40烷基芳基、C8-C40芳基烯基、—NR′2、—SR′、—OR′、—OSiR′3或—PR′2基，其中：R′是卤原子、C1-C10烷基或C6-C10芳基；优选R3不是氢原子；优选每个R3相同且为氟、氯或溴原子、可以卤代的C1-C4烷基、可以卤代的C6-C8芳基、—NR′2、—SR′、—OR′、—OSiR′3或—PR′2基，其中：R′是氯原子、C1-C4烷基或C6-C8芳基；R13由以下公式表示： 其中：R17到R24如R1和R2中所定义，或两个或更多相邻的基团R17到R24，包括R20和R21，与连接它们的原子形成一个或多个环；优选R17到R24是氢原子。M2是碳、硅、锗或锡，优选硅；R8、R9、R10、R11和R12相同或不同，具有R4到R7中所述的含义。