tert-butyl dimethylsilyl ether | 7489-73-8

• 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: tert-butyl dimethylsilyl ether
• 英文别名: t-butyl dimethylsilyl ether；tert-Butoxy(dimethyl)silane；dimethyl-[(2-methylpropan-2-yl)oxy]silane
• CAS: 7489-73-8
• 化学式: C₆H₁₆OSi
• 分子量: 132.278
• InChiKey: BFFJBAVNIXLGLQ-UHFFFAOYSA-N

物化性质

• 沸点：
  78 °C

计算性质

• 辛醇/水分配系数(LogP)：
  1.78
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-3-((R)-2-((1R,2S)-2-(benzyloxy)-1-hydroxypropyl)hexanoyl)-4-isopropyloxazolidin-2-one 、 tert-butyl dimethylsilyl ether 在 lithium hydroxide 、 双氧水 作用下， 生成
  参考文献：
  名称：

  2 Methoxy antimycin a derivatives and methods of use

  摘要：

  披露了调节细胞凋亡的2-甲氧基抗霉素衍生物或类似物，通过结合Bcl-2家族成员蛋白（例如Bcl-2或BCl-xL）的疏水槽来调节细胞凋亡。这些2-甲氧基抗霉素衍生物或类似物用于治疗与凋亡相关的疾病的方法，例如肿瘤性疾病（如癌症）或其他与Bcl-2家族成员蛋白过度表达相关的增生性疾病。

  公开号：

  US20050239873A1
• 作为产物：
  描述：

  dimethylsilylene 、 叔丁醇 以 正己烷 为溶剂， 生成 tert-butyl dimethylsilyl ether
  参考文献：
  名称：

  Fast Kinetics Study of the Reactions of Transient Silylenes with Alcohols. Direct Detection of Silylene−Alcohol Complexes in Solution

  摘要：

  The kinetic behavior of dimethyl-, diphenyl-, and dimesitylsilylene in hexanes solution in the presence of methanol (MeOH), tert-butanol (t-BuOH), and the respective O-deuterated isotopomers has been studied, with the goal of elucidating a detailed mechanism for the formal O-H insertion reaction of transient silylenes with alcohols in solution. The data are in all cases consistent with a mechanism involving the intermediacy off lie corresponding silylene-alcohol Lewis acid-base complexes, which have been detected directly for each of the SiMe2-ROL and SiPh2-ROL (L = H or D) systems that were studied. Complexation proceeds effectively irreversibly (K-cq >= 2 x 10(5) M-1) and at close to the diffusion-controlled rate in these cases. I it contrast, the kinetic and spectroscopic behavior observed for SiMes(2) in the presence of these alcohols indicates the SiMes(2)-ROL complexes are involved its steady-state intermediates. Formed reversibly and 10-100 times more Slowly than is the case with SiMe2 and SiPh2 Product formation from the silylene-alcohol complexes is shown to proceed via catalytic proton transfer by it second molecule of alcohol, the rate of which exceeds that of unimolecular intracomplex H-migration in all cases, even at submillimolar alcohol concentrations. The catalytic rate constants range from 10(9) to 10(10) M-1 s(-1) for the SiMe2-ROH and SiPh2-ROH complexes, sufficiently fast that the isotope effect ranges from ca. 2.5 to close to unity for all but the SiPh2-t-BuOL complex, where it is remarkably large (k(HH)/k(DD)= 10.8 +/- 2.4). The value is consistent with a mechanism for catalysis involving double proton transfer within it cyclic five-membered transition state. The isotope effects on the ratio of the rate Constants for Catalytic proton transfer and dissociation of the SiMes(2)-MeOH and SiMes(2),-t-BuOH complexes suggest that a different mechanism for catalytic proton transfer is involved in the case of the sterically hindered diarylsilylene.

  DOI：

  10.1021/om9009747
• 作为试剂：
  描述：

  2-(羟基甲基)苯甲酸 、 3-formylaminosalicylic acid 、 Fmoc-Thr-OMe 在 tert-butyl dimethylsilyl ether 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 二乙胺 、 N,N-二异丙基乙胺 作用下， 生成 3-formamido-2-hydroxy-N-((3R,4S)-3-methyl-1,5-dioxo-1,4,5,7-tetrahydro-3H-benzo[g][1,5]dioxonin-4-yl)benzamide
  参考文献：
  名称：

  2 Methoxy antimycin a derivatives and methods of use

  摘要：

  披露了调节细胞凋亡的2-甲氧基抗霉素衍生物或类似物，通过结合Bcl-2家族成员蛋白（例如Bcl-2或BCl-xL）的疏水槽来调节细胞凋亡。这些2-甲氧基抗霉素衍生物或类似物用于治疗与凋亡相关的疾病的方法，例如肿瘤性疾病（如癌症）或其他与Bcl-2家族成员蛋白过度表达相关的增生性疾病。

  公开号：

  US20050239873A1

文献信息

• Substituent Effects on the Reactivity of the Silicon−Carbon Double Bond. Resonance, Inductive, and Steric Effects of Substituents at Silicon on the Reactivity of Simple 1-Methylsilenes
  作者：William J. Leigh、Rabah Boukherroub、Corinna Kerst

  DOI：10.1021/ja981435d

  日期：1998.9.1

  -diazomethanes leads to the formation of reactive silenes which can be detected directly in solution, allowing detailed studies of the kinetics and mechanisms of their reactions with nucleophiles. Over 30 transient silenes have now been studied by these methods, providing the opportunity to systematically assess the effects of substituents at silicon and carbon on the reactivity of the Si=C bond.

  各种有机硅化合物（例如芳基、乙烯基和炔基乙硅烷、硅杂环丁烷和硅杂环丁烯以及 α-甲硅烷基烯酮和 -重氮甲烷）的激光闪光光解导致形成可直接在溶液中检测到的反应性硅烯，从而可以对动力学进行详细研究以及它们与亲核试剂的反应机制。现在已经通过这些方法研究了 30 多种瞬态硅烯，提供了系统评估硅和碳上的取代基对 Si=C 键反应性的影响的机会。
• J-Cross polarization in silanes
  作者：P. Dubois Murphy、T. Taki、T. Sogabe、R. Metzler、T. G. Squires、B. C. Gerstein

  DOI：10.1021/ja00509a006

  日期：1979.7

  cross-polarization NMR experiment between /sup 1/H and /sup 29/Si in the liquid state with rare-spin observation is reported. A line-shape-fitting technique is employed to directly measure the spin coupling constant, J, from the experimental results of initial magnetization vs. cross-polarization contact time. The technique has been used to enhance sensitivities of /sup 29/Si measurements in Si-O-model compounds

  报道了液态 /sup 1/H 和 /sup 29/Si 之间的第一次交叉极化 NMR 实验，并进行了稀有自旋观察。采用线形拟合技术从初始磁化与交叉极化接触时间的实验结果直接测量自旋耦合常数 J。该技术已用于提高 Si-O 模型化合物中 /sup 29/Si 测量的灵敏度。
• Cyclo-hydrosilylation: A novel route to siloxetanes and silanones
  作者：Thomas H. Lane、Cecil L. Frye

  DOI：10.1016/s0022-328x(00)81049-9

  日期：1979.6

  A novel and convenient method for the apparent liquid phase generation of dimethylsilanone, Me2SiO (D1), based on readily obtainable reactants and employing conventional temperatures (50–150°) is reported herein. Platinum catalyzed hydrosilylation of vinyldimethylcaarbinoxydimethylsilane (I) appears to proceed by an exclusively intramolecular path to produce not only the expected 5-membered heterocyclic

  一种新颖和表观液相代dimethylsilanone的方便的方法中，Me 2 SiO（d 1系），在容易获得的反应物和使用常规温度（50-150°）在本文中报道。铂催化的乙烯基二甲基caarbinoxy二甲基硅烷（I）的氢化硅烷化似乎是通过分子内唯一途径进行的，不仅产生了预期的5元杂环，1,1,3,3-四甲基-2-氧杂-1硅杂环戊烷（V），异构体和高度不稳定的4元硅氧烷，1,1,3,3,4-五甲基-2-氧杂-1-硅环丁烷（IV）。IV的中间体由以下产物暗示：即2-甲基-2-丁烯，其被认为是由于IV的断裂而与Me 2 Si 3 O一起出现的；D 3和D4从d 1自耦合; 由D 1插入IV的Si-O键衍生而来的6元环，即1,1,3,3,5,5,5,6，七甲基-2,4-二氧杂-1,3-二硅环己烷（ VI）; 碱性裂化后产生更多6环（VI）但很少或没有5环（V）的聚合物，表明该聚合物是由D 1，D
• Alkoxyhydrosilanes as Sources of Silylene Ligands: Novel Approaches to Transition Metal–Silylene Complexes
  作者：Takahiro Sato、Masaaki Okazaki、Hiromi Tobita

  DOI：10.1246/cl.2004.868

  日期：2004.7

  Irradiation of Fe(CO)5 and HSiMe2OR (R = alkyl or aryl group) together with hexamethylphosphoric triamide (HMPA) produces (CO)4Fe=SiMe2·HMPA and SiMe2(OR)2. Even in the absence of HMPA, irradiation of Fe(CO)5 and HSiMe2O(2-C5H4N) affords (CO)3(H)FeSiMe2···O(2-C5H4N)···SiMe2}. In these reactions, the alkoxyhydrosilanes act as sources of the silylene ligand.

  将 Fe(CO)5 和 HSiMe2OR（R = 烷基或芳基）与六甲基磷酸三酰胺（HMPA）一起辐照会产生 (CO)4Fe=SiMe2-HMPA 和 SiMe2(OR)2。即使没有 HMPA，Fe(CO)5 和 HSiMe2O(2-C5H4N)经过辐照后也会产生 (CO)3(H)FeSiMe2--O(2-C5H4N)--SiMe2}。在这些反应中，烷氧基氢硅烷是硅烷基配体的来源。
• Insertion of dimethylsilylene into OH and NH single bonds
  作者：Tai-yin Yang Gu、William P. Weber

  DOI：10.1016/s0022-328x(00)94358-4

  日期：1980.1

  dodecamethylcyclohexasilane, inserts efficiently into OH single bonds of alcohols to yield alkoxydimethylsilanes. Use of ethanol-O-d1 yields ethoxydimethylsilane-Si-d1. Dimethylsilylene also inserts into OH single bonds of water or D2O to yield respectively tetramethyldisiloxane or tetramethyldisiloxane-Si2-d2. Dimethylsilylene also inserts into NH bonds of primary and secondary amines to yield aminodimethylsilanes

  由十二甲基环己硅烷的光解反应生成的二甲基甲硅烷基可有效地插入醇的OH单键中，生成烷氧基二甲基硅烷。使用乙醇-O- d 1产生乙氧基二甲基硅烷-Si- d 1。二甲基亚甲硅烷也插入到水或dOH单键2 O操作得到分别四甲基二硅氧烷或四甲基二硅氧烷-硅2 - d 2。二甲基亚甲硅烷基也可插入伯胺和仲胺的NH键中，从而生成氨基二甲基硅烷。该反应提供了双官能硅烷的有效途径。