bis(benzyloxy)(methyl)(phenyl)silane | 86934-36-3

• 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
• 英文名称: bis(benzyloxy)(methyl)(phenyl)silane
• 英文别名: methylphenyldi(benzyloxy)silane；Bis(benzyloxy)(methyl)phenylsilane；methyl-phenyl-bis(phenylmethoxy)silane
• CAS: 86934-36-3
• 化学式: C₂₁H₂₂O₂Si
• 分子量: 334.49
• InChiKey: NDHBRYZHYFWGIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  甲基苯基二氯硅烷 在 甲基苯基二氯硅烷 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 6.5h， 生成 bis(benzyloxy)(methyl)(phenyl)silane
  参考文献：
  名称：

  O-甲硅烷基烯酮缩醛化学1 ; 二乙烯基氧基硅烷衍生物作为新型且有用的用于h-酸性材料的双官能保护剂

  摘要：

  新型试剂双（1-甲氧基-2-甲基-1-丙烯氧基）硅烷（）已被证明是非常有用的双官能保护剂，适用于各种类型的H酸性材料，例如二醇，二硫醇，二酸及其组合材料。反应在温和条件下迅速进行，以几乎定量的产率得到相应的亚甲硅烷基衍生物。

  DOI：

  10.1016/s0040-4039(00)81633-0

文献信息

• PRODUCTION METHOD FOR ALKOXYSILANES
  申请人：NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY

  公开号：US20160002271A1

  公开（公告）日：2016-01-07

  Provided is a method for efficiently producing alkoxysilanes that are useful as various functional chemicals. In order to produce alkoxysilanes efficiently, an ethoxy- or methoxysilane and an alcohol are caused to react using, as a catalyst, for instance an inorganic solid acid having a regular-pore and/or layered structure. Zeolites, montmorillonites or the like can be used as the inorganic solid acid. When a zeolite is used as the catalyst, the silica/alumina ratio of the zeolite ranges preferably from 5 to 1000. The reaction can be promoted through irradiation of microwaves.

  提供了一种有效生产作为各种功能化学品有用的烷氧基硅烷的方法。为了有效地生产烷氧基硅烷，可以使用乙氧基或甲氧基硅烷和醇作为催化剂，例如具有规则孔隙和/或层状结构的无机固体酸。沸石、蒙脱石或类似物可以用作无机固体酸。当沸石用作催化剂时，沸石的硅铝比最好范围为5至1000。通过微波辐射可以促进反应。
• Sodium Hydroxide Catalyzed Dehydrocoupling of Alcohols with Hydrosilanes
  作者：Anton A. Toutov、Kerry N. Betz、Michael C. Haibach、Andrew M. Romine、Robert H. Grubbs

  DOI：10.1021/acs.orglett.6b01687

  日期：2016.11.18

  An O–Si bond construction protocol employing abundantly available and inexpensive NaOH as the catalyst is described. The method enables the cross-dehydrogenative coupling of an alcohol and hydrosilane to directly generate the corresponding silyl ether under mild conditions and without the production of stoichiometric salt byproducts. The scope of both coupling partners is excellent, positioning the

  描述了使用大量可用且廉价的NaOH作为催化剂的O-Si键构建方案。该方法使得醇和氢硅烷的交叉脱氢偶联能够在温和条件下直接产生相应的甲硅烷基醚，而不会产生化学计量的盐副产物。两种偶合剂的作用范围都非常好，这为在复杂分子和材料科学应用中使用的方法奠定了基础。还报道了一种新型的基于Si的交叉偶联试剂。
• Catalytic reduction of benzoate esters and lactones in the presence of PhMeSiH₂ and a titanocene-based catalyst
  作者：Ronghua Shu、John F Harrod、Anne-Marie Lebuis

  DOI：10.1139/v02-047

  日期：2002.5.1

  PhMeSiH₂ reduces ethyl benzoate in the presence of a Cp₂TiMe₂ (Cp = η⁵-cyclopentadienyl) catalyst to give PhMeSi(OEt)(OCH₂Ph) (1). Small to moderate amounts of toluene are also produced, depending on the reaction conditions. Under 40 psi of H₂ the same reaction gives quantitative reduction of the ester to toluene. PhCHO is reduced, under the same conditions as the ester, to a mixture of PhMeSi(OCH₂Ph)₂ and toluene in proportions similar to that observed with the ester. A stoichiometric reaction of PhMeSiH₂, PhCOOEt, and Cp₂TiMe₂ resulted in the formation of known [Cp₂Ti(OEt)]₂ (2) in 75% isolated yield. A mechanism is proposed in which the C=O of the ester inserts into a Ti–H bond. A Ti-mediated transfer of the ethoxy group from the resulting (α-ethoxy)benzyloxytitanium intermediate to silicon produces PhMeSi(OEt)H and PhCHO. 1 is generated via hydrosilation of PhCHO by PhMeSi(OEt)H. Both β- and γ-butyrolactones react with PhMeSiH₂ in the presence of a catalytic amount of Cp₂TiMe₂ to produce copolymers -[O-PhMeSi-O(CH₂)₃CHR]_n- (R = H, 3; R = Me, 4) (M_w [Formula: see text] 1 × 10³; M_w/M_n [Formula: see text] 1.3). A mechanism analogous to that proposed for the ethyl benzoate reduction is proposed. A reaction of PhMeSiH₂ and γ-butyrolactone with a stoichiometric amount of Cp₂TiMe₂ in the presence of tetrahydofuran (THF) produces Cp₂Ti(µ-H)(µ-η¹,η⁵-C₅H₄)Ti(OC₄H₈)Cp(5) (65% isolated yield) whose structure is determined by X-ray crystallography.Key words: hydrosilation, esters, lactones, titanocene, catalysis.

  PhMeSiH₂在Cp₂TiMe₂（Cp = η⁵-环戊二烯基）催化剂存在下还原苯甲酸乙酯，生成PhMeSi(OEt)(OCH₂Ph)（1）。根据反应条件的不同，也会产生少量至适量的甲苯。在40 psi的H₂下，相同的反应会将酯定量还原为甲苯。在与酯相同的条件下，苯甲醛被还原为PhMeSi(OCH₂Ph)₂和甲苯的混合物，比例与观察到的酯相似。PhMeSiH₂、PhCOOEt和Cp₂TiMe₂的化学计量反应导致已知的[Cp₂Ti(OEt)]₂（2）以75%的分离产率形成。提出了一种机理，酯的C=O插入Ti-H键。Ti介导的α-乙氧基苄氧基钛中间体向硅的乙氧基转移产生PhMeSi(OEt)H和PhCHO。通过PhMeSi(OEt)H对PhCHO的氢硅烷基化生成1。在Cp₂TiMe₂的催化下，β-和γ-丁内酯与PhMeSiH₂反应，产生共聚物-[O-PhMeSi-O(CH₂)₃CHR]_n（R = H, 3; R = Me, 4）（M_w [公式：见文本] 1 × 10³；M_w/M_n [公式：见文本] 1.3）。提出了与苯甲酸乙酯还原相似的机理。PhMeSiH₂和γ-丁内酯在四氢呋喃（THF）存在下与化学计量的Cp₂TiMe₂反应，生成Cp₂Ti(µ-H)(µ-η¹,η⁵-C₅H₄)Ti(OC₄H₈)Cp（5）（65%的分离产率），其结构由X射线晶体学确定。关键词：氢硅烷基化，酯，内酯，二茂钛，催化。
• Photoactivated silicon–oxygen and silicon–nitrogen heterodehydrocoupling with a commercially available iron compound
  作者：Matthew B. Reuter、Michael P. Cibuzar、James Hammerton、Rory Waterman

  DOI：10.1039/c9dt04870g

  日期：——

  Silicon-oxygen and silicon-nitrogen heterodehydrocoupling catalyzed by the commercially available cyclopentadienyl dicarbonyl iron dimer [CpFe(CO)2]2 (1) under photochemical conditions is reported. Reactions between alcohols and PhSiH3 with catalytic 1 under visible-light irradiation produced silyl ethers quantitively. Reactions between either secondary or tertiary silanes and alcohols also produced

  报道了在光化学条件下由市售的环戊二烯基二羰基铁二聚体[CpFe（CO）2] 2（1）催化的硅-氧和硅-氮杂脱氢偶联。在可见光照射下，醇与PhSiH3与催化剂1的反应定量生成了甲硅烷基醚。仲硅烷或叔硅烷与醇之间的反应也产生了甲硅烷基醚，但是，这些反应的特点是反应时间更长且转化率较低。伯胺或仲胺与硅烷与催化剂1的反应显示出混合效率，其转化率为20-100％。机理研究表明，甲硅烷基铁化合物在键形成步骤中不重要，并提出了亲核性醇盐或酰胺中间体。最重要的，
• Hydridosilylamido complexes of Ta and Mo isolobal with Berry's zirconocenes: syntheses, β-Si–H agostic interactions, catalytic hydrosilylation, and insight into mechanism
  作者：Nicolas A. McLeod、Lyudmila G. Kuzmina、Ilia Korobkov、Judith A. K. Howard、Georgii I. Nikonov

  DOI：10.1039/c5dt04548g

  日期：——

  Group 6 hydrosilylamido complexes of the type R(ArN)MN(tBu)SiMe2–H}X (M = Ta, R = Cp; M = Mo, R = ArN; X = Cl, H, OBn, Me) are described. The various substituents in the X position seem to play the key role in determining the extent of β-agostic interaction with the Si–H bond. The Mo agostic hydrido complex (ArN)2Moη3-N(tBu)SiMe2–H}H is a pre-catalyst for the hydrosilylation of carbonyls. The stoichiometric

  R（ArN ）M N（t Bu）SiMe 2 -H} X类型的新型5和6组氢化硅酰胺基配合物的合成（M = Ta，R = Cp; M = Mo，R = ArN; X =描述了Cl，H，OBn，Me）。X位置的各种取代基似乎在决定与Si–H键的β-声波相互作用的程度中起关键作用。莫agostic氢基络合物（ARN ）2沫η 3 -N（吨丁基）森达2 -H} H是羰基的氢化硅烷化的预催化剂。苯甲醛和（ARN之间的化学计量反应）2沫η 3 -N（吨丁基）森达2 -H} H，使得所述复合苯甲酸基（ARN）2 Mo N（t Bu）SiMe 2 -H}（OBn），与母体氢化物相比，显示出相似的催化反应活性。机理研究表明，非氢化物机理是有效的。