烯丙基苯基二氯硅烷 | 7719-03-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 中文名称: 烯丙基苯基二氯硅烷
• 中文别名: 粉末硫磺；硫磺石；硫沉降；沉淀硫磺；硫磺升华；硫磺软膏；硫黄粉；α型硫磺；胶态硫；胶体硫；沉降流磺；硫磺胶悬剂；沉降硫磺；沉降硫
• 英文名称: allyl (phenyl)-dichlorosilane
• 英文别名: allyldichlorophenylsilane；allylphenyldichlorosilane；phenylallyldichlorosilane；allyl-dichloro-phenyl-silane；Allyl-dichlor-phenyl-silan；(2-Propenyl)phenyldichlorsilan；dichloro-phenyl-prop-2-enylsilane
• CAS: 7719-03-1
• 化学式: C₉H₁₀Cl₂Si
• mdl: MFCD00053191
• 分子量: 217.17
• InChiKey: IGFFTOVGRACDBL-UHFFFAOYSA-N

物化性质

• 熔点：
  <0°C
• 沸点：
  100-102°C 8mm
• 密度：
  1,168 g/cm3
• 闪点：
  76°C

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.111
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• TSCA：
  Yes
• 危险类别码：
  R34
• 危险品运输编号：
  UN 2987
• 安全说明：
  S26,S36/37/39
• 储存条件：
  储存温度应维持在2-8°C之间，并需确保容器密封且环境干燥。

反应信息

• 作为反应物：
  描述：

  烯丙基苯基二氯硅烷 在 正丁基锂 、 三氟化硼乙醚 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 234.0h， 生成 difluorophenyl[2-((E)-phenylazo)phenyl]silane
  参考文献：
  名称：

  Intramolecular allylation of the azo group of 2-(allylsilyl)azobenzenes and its photocontrol

  摘要：

  Pentacoordinate allylsilanes bearing an azobenzene moiety were synthesized and their structures were elucidated. The reaction of allyldifluorosilane (E)-7a with BF3 center dot OEt2 did not proceed, but (E)-7a was allowed to react with a fluoride ion to give tetrafluorosilicate 8a via intramolecular allyl-migration from the silicon atom onto the azo group. Activation of both the nucleophilic and electrophilic parts by the Si center dot center dot center dot N interaction was found to be important for promotion of the allyl-migration reaction. The azobenzene moiety of the allylsilane was reversibly isomerized by photoirradiation. The (Z)-7a formed by photoirradiation of (E)-7a is in a tetracoordinate state in contrast to the (E)-7a, and it did not react with a fluoride ion at all under the conditions where (E)-7a reacted quantitatively. The reactivity was successfully controlled without changing any conditions other than the change of the coordination number of the silicon atom induced by photoirradiation. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.08.045
• 作为产物：
  描述：

  丙烯基三氯硅烷 在 C₆H₅MgBr 作用下， 以 not given 为溶剂， 以46%的产率得到烯丙基苯基二氯硅烷
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Si: MVol.C, 58, page 165 - 167

  摘要：

  DOI：

文献信息

• Reactivity of dichlorosilanes with lithium ester enolates: synthesis of 3,3-disubstituted 3-silaglutarates
  作者：Abdelhafid Djerourou、Luis Blanco

  DOI：10.1016/0022-328x(94)24757-a

  日期：1995.1

  3,3-Disubstituted 3-silaglutarates were synthesized by reaction of the lithium enolate of ethyl acetate with diclorosilanes at −94°C. When a phenyl group is linked to the silicon atom the reaction in THF gave mainly the silaglutarate. In other cases alkylsilylketene acetals were formed in proportions similar to or greater than that of the silaglutarate. The presence of HMPA increased the ratio of C-

  通过使乙酸乙酯的烯醇锂与二氯硅烷在-94℃下反应，合成3，3-二取代的3-硅戊二酸酯。当苯基连接到硅原子上时，在THF中的反应主要产生硅谷氨酸盐。在其他情况下，烷基硅烷基烯酮缩醛的形成比例与硅谷氨酸盐相似或更高。HMPA的存在增加了C-与O-甲硅烷基化产物的比例，并允许以高收率制备3-硅烷基戊二酸酯3，3-二烷基酯。
• Controlled introduction of allylic group to chlorosilanes
  作者：Zhifang Li、Xiaojun Cao、Guoqiao Lai、Jinhua Liu、Yong Ni、Jirong Wu、Huayu Qiu

  DOI：10.1016/j.jorganchem.2006.07.023

  日期：2006.11

  controlled manner. Thus allylation of trisubstituted chlorosilanes (R3SiCl) afforded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. Dichlorosilanes (R2SiCl2) can either afford monoallylated silanes or diallylated silanes depending on the amount of allylsamarium bromide used. Similarly, trichlorosilanes (RSiCl3) can selectively afford mono-, di-, and tri-allylation products. Finally

  用烯丙基溴化mar已经实现了氯硅烷的烯丙基化，特别是以可控的方式。因此，三取代的氯硅烷（R 3 SiCl）的烯丙基化得到各种芳基，芳烷基和烯基取代的烯丙基硅烷。根据所用的烯丙基溴化amount的量，二氯硅烷（R 2 SiCl 2）既可以提供单烯丙基化的硅烷，也可以提供二烯丙基化的硅烷。类似地，三氯硅烷（RSiCl 3）可以选择性提供单，二和三烯丙基化产物。最后，使全氯硅烷（SiCl 4）逐步烯丙基化，并以令人满意的产率获得相应的分别含有一个，两个，三个或四个烯丙基的硅烷。
• Pentacoordinate Silicon Complexes with<i>N</i>-(2-pyridylmethyl)­salicylamide as a Dianionic (<i>ONN′</i>) Tridentate Chelator
  作者：Dana Schwarz、Erica Brendler、Edwin Kroke、Jörg Wagler

  DOI：10.1002/zaac.201200084

  日期：2012.9

  six-membered chelate is formed by the dianion, and smaller rings are not present in the compound), the poor electron withdrawal from silicon by its C– or H– substituents and the flexible methylene bridge between the salicylamide and the pyridine moiety, the pyridine N donor atom furnishes pentacoordinate silicon coordination spheres in all of these compounds 2a–2f. The coordination number of the silicon atom

  标题化合物 N-(2-吡啶基甲基) 水杨酰胺 (1) 通过水杨酸甲酯和 2-甲基吡啶胺的酯氨解合成。在三乙胺作为载体碱存在下，水杨酰胺部分与有机二氯硅烷 RR'SiCl2 反应形成所需的 RR'Si-O-(o-C6H4)-C(=O)N( pic)，其中 pic 是 2-吡啶甲基（即 2-吡啶甲基）部分，并且 RR' = Me, Me (2a)；我，博士（2b）；博士，博士（2c）；Bn, Bn (2d); 所有，Ph（2e）和Ph，H（2f）。尽管不存在显着的环应变释放路易斯酸性（即，二价阴离子仅形成六元螯合物，化合物中不存在较小的环），但硅的 C– 或 H– 取代基从硅中提取的电子较差以及水杨酰胺和吡啶部分之间的柔性亚甲基桥，在所有这些化合物 2a-2f 中，吡啶 N 供体原子提供了五配位的硅配位球。硅原子的配位数通过固态的单晶X射线衍射分析和溶液态的29Si NMR光谱证实。
• New Insights into Hexacoordinated Silicon Complexes with 8- Oxyquinolinato Ligands: 1,3-Shift of Si-Bound Hydrocarbyl Substituents and the Influence of Si-Bound Halides on the 8-Oxyquinolinate Coordination Features
  作者：Erik Wächtler、Alexander Kämpfe、Katrin Krupinski、Daniela Gerlach、Edwin Kroke、Erica Brendler、Jörg Wagler

  DOI：10.5560/znb.2014-4170

  日期：2014.12.1

  The transsilylation reaction between allyltrichlorosilane and 8-trimethylsiloxyquinoline in the molar ratio 1 : 3 yields the hexacoordinated silicon tris-chelate (oxinate)₂Si(adho) (“oxinate” = 8- oxyquinolinate, “adho” = di-anion of 2-allyl-1,2-dihydro-8-oxyquinoline) comprising an SiO₃N₃ skeleton. The identity of this complex was established by single-crystal X-ray diffraction analysis and ²⁹Si CP=MAS NMR spectroscopy of its chloroform solvate. Benzyltrichlorosilane and dibenzyldichlorosilane, comprising benzyl (Bn) as an “aromatically stabilized allyl moiety” did not undergo such rearrangement. Instead, the complexes (oxinate)₂SiBnCl and (oxinate)₂SiBn₂ were obtained even upon using three molar equivalents of 8-trimethylsiloxyquinoline.

  We determined the crystal structure of a non-disordered bis-chelate (oxinate)₂SiBnCl with Sibound hydrocarbyl and halogen substituents (the previously published (oxinate)₂SiMeCl was disordered with alternative Me=Cl site occupancies). (Oxinate)₂SiBnCl exhibits surprisingly poor response of the N-Si bonds to the different trans-disposed Si-X (X=Bn, Cl) bonds. For comparison and deeper insights into the coordination chemistry of oxinato silicon complexes with halide substituents, we determined the crystal structures of (oxinate)₂SiPhCl·CHCl₃, (oxinate)₂SiCl₂, (oxinate)₂SiF₂·1.5(CHCl₃), and (8-oxyquinaldinate)₂SiF₂. Furthermore, the crystal structures of BnSiCl₃ and Bn₂SiCl₂ (and its dibromo analog) are reported. The influence of the Si-C-C-C torsion angles of the benzyl group on the ²⁹Si NMR shift of benzylsilanes (which is noticeably upfield with respect to analogous methyl silanes) was analyzed by quantum-chemical calculations.

  摘要 烯丙基三氯硅烷和 8-三甲基硅氧基喹啉以 1 : 3 的摩尔比发生硅烷化反应，生成了以 SiO3N3 为骨架的六配位硅三螯合物 (oxinate)2Si(adho)（"oxinate"=8-氧基喹啉酸盐，"adho"=2-烯丙基-1,2-二氢-8-氧基喹啉的二阴离子）。通过单晶 X 射线衍射分析及其氯仿溶液的 29Si CP=MAS NMR 光谱分析，确定了该复合物的身份。由作为 "芳香稳定烯丙基 "的苄基（Bn）组成的苄基三氯硅烷和二苄基二氯硅烷没有发生这种重排。相反，即使使用三摩尔当量的 8-三甲基硅氧基喹啉，也能得到 (oxinate)2SiBnCl 和 (oxinate)2SiBn2 复合物。 我们测定了带有 Sibound 烃基和卤素取代基的非无序双螯合物 (oxinate)2SiBnCl 的晶体结构（之前发表的 (oxinate)2SiMeCl 是无序的，具有 Me=Cl 的替代位点占位）。(oxinate)2SiBnCl的N-Si键对不同反式分布的Si-X（X=Bn，Cl）键的反应之差令人惊讶。为了比较和深入了解带有卤化物取代基的草酸硅配合物的配位化学性质，我们测定了 (oxinate)2SiPhCl-CHCl3、(oxinate)2SiCl2、(oxinate)2SiF2-1.5( ) 和 (8-oxyquinaldinate)2SiF2 的晶体结构。此外，还报告了 BnSiCl3 和 Bn2SiCl2（及其二溴类似物）的晶体结构。量子化学计算分析了苄基的 Si-C-C-C 扭转角对苄基硅烷 29Si NMR 移位的影响（与类似的甲基硅烷相比，苄基硅烷的 29Si NMR 移位明显上移）。
• Enantioselective Allylation of Aldehydes Using Tartrate Ester Modified Allylsilanes
  作者：Luo Cheng Zhang、Hideki Sakurai、Mitsuo Kira

  DOI：10.1246/cl.1997.129

  日期：1997.2

  Tartrate-ester modified allylsilanes, 2-allyl-1,3,2-dioxasilolane-4,5-dicarboxylic esters, (1), were found to serve as useful reagents for regiospecific and stereoselecive allylation of aldehydes. Reactions of 1 with achiral aldehydes without any catalyst gave the corresponding homoallyl alcohols in good yields (70-90%) with the ee values up to 80%.

  研究发现，酒石酸酯修饰的烯丙基硅烷、2-烯丙基-1,3,2-二氧硅烷-4,5-二羧酸酯（1）可作为有用的试剂，用于醛的区域特异性和立体选择性烯丙基化。在不使用任何催化剂的情况下，1 与非手性醛反应生成相应的均烯丙基醇，收率高达 70-90%，ee 值高达 80%。