2,2-dimethyl-1-trimethylsiloxypropane | 18246-63-4

• 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: 2,2-dimethyl-1-trimethylsiloxypropane
• 英文别名: 1-trimethylsilyloxy-2,2-dimethylpropane；trimethyl(neopentyloxy)silane；(2,2-dimethyl-propoxy)-trimethyl-silane；2,2-dimethyl-1-trimethylsilanyloxy-propane；Trimethyl-neopentyloxy-silan；Silane, (2,2-dimethylpropoxy)trimethyl-；2,2-dimethylpropoxy(trimethyl)silane
• CAS: 18246-63-4
• 化学式: C₈H₂₀OSi
• 分子量: 160.332
• InChiKey: CFUAMMVVJMPPLD-UHFFFAOYSA-N

物化性质

• 沸点：
  121-122 °C
• 密度：
  0.7632 g/cm3
• 保留指数：
  778

计算性质

• 辛醇/水分配系数(LogP)：
  2.88
• 重原子数：
  10
• 可旋转键数：
  3
• 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

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-1-trimethylsiloxypropane 生成 2-氟-2-甲基丁烷
  参考文献：
  名称：

  Une evaluation du

  摘要：

  DOI：

  10.1016/s0040-4020(01)83214-2
• 作为产物：
  描述：

  新戊醇 、 四丁基溴化铵 在 三甲基氯硅烷 作用下， 以94%的产率得到2,2-dimethyl-1-trimethylsiloxypropane
  参考文献：
  名称：

  Process for the preparation of O-silylated hydroxyl compounds and their

  摘要：

  这项发明涉及一种制备O-硅烷基脂肪羟基化合物的方法，通过将脂肪羟基化合物与三有机氯硅烷反应，并从反应混合物中去除所得气态氯化氢，其特征在于在无溶剂存在的情况下，在相转移催化剂的存在下进行反应。该发明还涉及利用通过该方法获得的O-硅烷基羟基化合物作为含酯基异氰酸酯的起始原料，通过与异氰酸酯羧酸氯化物反应制备。

  公开号：

  US05142081A1

文献信息

• Mild and efficient silylation of alcohols and phenols with HMDS using Bi(OTf)3 under solvent-free condition
  作者：Santosh T. Kadam、Sung Soo Kim

  DOI：10.1016/j.jorganchem.2009.04.001

  日期：2009.7

  A very efficient and mild silylation of alcohols and phenols with hexamethyldisilazane (HMDS) at rt is developed using Bi(OTf)3 as the catalyst. Primary, secondary and tertiary alcohols as well as phenols are excellently converted into corresponding TMS ethers in a very short reaction time. This procedure can also be applied to large scale silylation for industrial application.

  使用Bi（OTf）3作为催化剂，在室温下使用六甲基二硅氮烷（HMDS）对醇和酚进行了非常高效和温和的甲硅烷基化反应。伯，仲和叔醇以及苯酚在非常短的反应时间内即可出色地转化为相应的TMS醚。该程序也可用于工业应用的大规模甲硅烷基化。
• Nafion® SAC-13: heterogeneous and reusable catalyst for the activation of HMDS for efficient and selective O-silylation reactions under solvent-free condition
  作者：Gurusamy Rajagopal、Hanbin Lee、Sung Soo Kim

  DOI：10.1016/j.tet.2009.04.025

  日期：2009.6

  hexamethyldisilazane (HMDS) for the efficient and selective silylation of alcohols. Primary, secondary, and tertiary alcohols and phenols are efficiently converted to their corresponding silylethers in short reaction times (4–8 min) with excellent yield at rt under solvent-free condition. Simple and clean reactions, high yield of the products and efficient recycling of the catalyst are the salient features of

  Nafion SAC-13可有效活化六甲基二硅氮烷（HMDS），以实现酒精的高效选择性硅烷化。伯，仲和叔醇和苯酚在较短的反应时间（4-8分钟）内可在无溶剂条件下在室温下高效转化为相应的甲硅烷基醚，并具有出色的收率。简单干净的反应，产物的高收率和催化剂的有效循环是该方法的主要特点。
• Cobalt carbonyl catalysed reaction of oxetanes with a hydrosilane and carbon monoxide
  作者：Toshiaki Murai、Kazuyoshi Furuta、Shinzi Kato、Shinji Murai、Noboru Sonoda

  DOI：10.1016/0022-328x(86)80088-2

  日期：1986.3

  The cobalt carbonyl catalyzed reaction of oxetanes with HSiR3 and CO took place at 25°C under 1 atm to give not only 1,4-disiloxybutanes but also 1-siloxypropanes. The product ratio was highly dependent on the solvent used.

  氧杂环丁烷与HSiR 3和CO的羰基钴催化反应在25℃，1个大气压下进行，不仅得到1,4-二甲硅烷丁烷，而且还产生了1-甲硅烷氧基丙烷。产物比例高度取决于所用溶剂。
• Turning the Nitrogen Atoms of an Ar₂ P−CH₂ −N−N−CH₂ −PAr₂ Motif into Uniquely Configured Stereocenters: A Novel Diphosphane Design for Asymmetric Catalysis
  作者：Eva Diehl née Knobloch、Reinhard Brückner

  DOI：10.1002/chem.201706160

  日期：2018.3.7

  Hexahydropyridazines with CH2PAr2 groups at both N atoms are newly designed 1,4‐diphosphanes and were synthesized for the first time. Their N atoms assume a single configuration under the influence of stereocenters at C‐5 and C‐6. In the solid state, these N‐atoms bind the CH2PAr2 substituents axially. Combined with Pd0, N,N′‐chiral diphosphanes of this kind catalyzed Tsuji–Trost type allylations of dialkyl malonates

  在两个N原子上均具有CH 2 PAr 2基团的六氢哒嗪是新设计的1,4-二膦烷，是首次合成。它们的N原子在C-5和C-6的立体中心的影响下呈单一构型。在固态下，这些N原子轴向结合CH 2 PAr 2取代基。与此类的Pd 0，N，N'-手性二膦烷结合，可有效地与乙酸外消旋1,3-二苯基烯丙基乙酸酯催化二甲基丙二酸酯的Tsuji-Trost型烯丙基化，且ee高达91％  。
• Synthesis and properties of 2′-O-neopentyl modified oligonucleotides
  作者：Gérald Mathis、Stéphane Bourg、Samia Aci-Sèche、Jean-Christophe Truffert、Ulysse Asseline

  DOI：10.1039/c2ob26871j

  日期：——

  2′-O-Neopentyldeoxyuridine (Un) was synthesized and incorporated into a series of oligodeoxyribonucleotides. Single and triple incorporations in various arrangements were performed. The Watson and Crick pairing properties with complementary DNA and RNA were investigated by UV melting curves, CD spectroscopy, and molecular dynamic simulations. The results were compared to those obtained with DNA–DNA and DNA–RNA duplexes involving dU at the same positions. Oligonucleotides containing Un clearly demonstrated their ability to form duplexes with both complementary DNA and RNA but with higher stabilities for the DNA–RNA duplexes similar to the one of the parent DNA–RNA duplex. Investigations into the thermodynamic properties of these 17-base-pair duplexes revealed ΔG values (37 °C) that are in line with the measured Tm values for both the DNA–DNA and DNA–RNA duplexes. CD spectroscopic structural investigations indicated that the conformations of the DNA–DNA and DNA–RNA duplexes involving Un are similar to those of the dT–rA and dU–rA containing duplexes. Only small changes in intensities and weak blue shifts were observed when three Uns were incorporated into the duplexes. The results of the molecular dynamic simulations showed, for the six duplexes involving the modified nucleoside Un, calculated curvatures similar to those of the corresponding unmodified duplexes without base-pair disruption. The neopentyl group is able to be accommodated in the minor grooves of both the DNA–DNA and RNA–DNA duplexes. However, molecular dynamic simulations indicated that the Uns adopt a C2′-exo sugar pucker conformation close to an A-helix type without perturbing the C2′-endo sugar pucker conformations of their 2′-deoxynucleoside neighbours. These results confirm the potential of 2′-O-neopentyldeoxyuridine as a nucleoside surrogate for oligonucleotide based therapeutic strategies.

  2'-O-新戊基脱氧尿苷（Un）被合成并纳入一系列脱氧寡核苷酸中。进行了不同排列的单次和三次纳入。通过UV熔解曲线、圆二色光谱和分子动力学模拟研究了其与互补DNA和RNA的沃森-克里克配对特性。结果与在相同位置包含dU的DNA-DNA和DNA-RNA双链体所获得的结果进行了比较。含有Un的寡核苷酸明显表现出形成与互补DNA和RNA双链体的能力，但对DNA-RNA双链体具有更高的稳定性，类似于亲本DNA-RNA双链体的稳定性。对这些17个碱基对双链体的 thermodynamic 性质的调查揭示了与DNA-DNA和DNA-RNA双链体的测定 Tm 值一致的 ΔG 值（37 °C）。圆二色光谱结构研究表明，涉及Un的DNA-DNA和DNA-RNA双链体的构象与包含dT-rA和dU-rA的双链体相似。只在双链体中纳入三个Un时观察到强度的小变化和微弱的蓝移。分子动力学模拟的结果显示，对于涉及修饰核苷Un的六个双链体，计算的曲率与相应的未修饰双链体相似，没有碱基对断裂。新戊基团能够适应DNA-DNA和RNA-DNA双链体的小沟。然而，分子动力学模拟表明，Un采取接近A型螺旋的C2'-外糖环构象，而不干扰其2'-脱氧核苷邻位的C2'-内糖环构象。这些结果证实了2'-O-新戊基脱氧尿苷作为寡核苷酸为基础的治疗策略的核苷替代品的潜力。