1,3-bis(tert-butyldimethylsiloxy)butane | 122795-02-2

• 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: 1,3-bis(tert-butyldimethylsiloxy)butane
• 英文别名: 1,3-Butanediol, bis-DMTBS；tert-butyl-[4-[tert-butyl(dimethyl)silyl]oxybutan-2-yloxy]-dimethylsilane
• CAS: 122795-02-2
• 化学式: C₁₆H₃₈O₂Si₂
• 分子量: 318.648
• InChiKey: DFMVMAAKZHEQMZ-UHFFFAOYSA-N

物化性质

• 沸点：
  308.8±25.0 °C(Predicted)
• 密度：
  0.844±0.06 g/cm3(Predicted)
• 保留指数：
  1497.8

计算性质

• 辛醇/水分配系数(LogP)：
  5.81
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-bis(tert-butyldimethylsiloxy)butane 在 sodium hydride 作用下， 以 六甲基磷酰三胺 为溶剂， 反应 10.0h， 以69%的产率得到1,3-丁二醇
  参考文献：
  名称：

  氢化钠对丁基丁基二甲基甲硅烷基醚的还原裂解

  摘要：

  -将丁基二甲基甲硅烷基醚在六甲基磷酸三酰胺（HMPA）或N，N'-二甲基丙烯脲（DMPU）中用氢化钠裂解。

  DOI：

  10.1016/s0040-4039(00)82294-7
• 作为产物：
  描述：

  1,3-丁二醇 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以96%的产率得到1,3-bis(tert-butyldimethylsiloxy)butane
  参考文献：
  名称：

  使用甲酸作为叔丁基二甲基甲硅烷基伯醚的温和高效脱保护剂选择性保护仲醇

  摘要：

  描述了一种用于选择性保护仲羟基的温和、高效且环保的方法。该方法包括将伯羟基和仲羟基保护为叔丁基二甲基甲硅烷基 (TBDMS) 醚，并在乙腈/水中用甲酸对伯 TBDMS 基团进行选择性脱保护。测定了不同浓度甲酸对初级和次级 TBDMS 醚的脱甲硅烷基化速率。发现浓度为 5-20% 的甲酸可以选择性地对初级 TBDMS 醚进行脱保护，同时保持 95% 以上的二级对应物完好无损。

  DOI：

  10.1055/s-0037-1611757

文献信息

• Silicon-29 NMR Spectra of tert-Butyldimethylsilyl and Trimethylsilyl Derivatives of Some Non-Rigid Diols
  作者：Magdalena Kvíčalová、Vratislav Blechta、Krzysztof Kobylczyk、Ryszard Piekos、Jan Schraml

  DOI：10.1135/cccc19970761

  日期：——

  ²⁹Si NMR spectra of trimethylsilyl (TMS) and tert-butyldimethylsilyl (TBDMS) derivatives of selected diols were measured under standardized conditions (i.e., in diluted CDCl₃ solutions). Application of the recently reported correlation between the chemical shifts in TMS and TBDMS derivatives revealed considerable and systematic deviations which exceeded experimental errors and error estimates from the correlation. Two possible explanations of the deviations are considered: interaction between the two bulky substituent groups and invalidity of the reported correlation for simple hydroxy derivatives. An independent study of analogous derivatives of monohydroxy compounds has shown that the linear correlation holds but the slope and intercept are significantly different from those reported previously on the basis of a study of amino acid derivatives. The data obtained for the diol derivatives fit the new correlation very well and no indication of an interaction between the bulky TBDMS groups was noticed. However, deviations do occur in branched diol derivatives in which branching reduces accessibility of the oxygen atoms surface to associate with proton donors. The largest deviation was found when intramolecular hydrogen bond was formed.

  29Si核磁共振谱测定了选定二醇的三甲基硅基（TMS）和叔丁基二甲基硅基（TBDMS）衍生物在标准化条件下（即在稀释的CDCl3溶液中）。应用最近报道的TMS和TBDMS衍生物化学位移之间的相关性显示出明显和系统性的偏差，超过了实验误差和相关性误差估计。对偏差的两种可能解释是：两个笨重取代基之间的相互作用以及对简单羟基衍生物的报道相关性的无效性。对单羟基化合物的类似衍生物的独立研究表明，线性相关性成立，但斜率和截距与以前基于氨基酸衍生物研究所报告的值显著不同。对二醇衍生物获得的数据非常符合新的相关性，没有发现叔丁基TBDMS基团之间的相互作用的迹象。然而，在支链二醇衍生物中确实存在偏差，其中支链减少了氧原子表面与质子供体结合的可及性。当形成分子内氢键时，发现最大的偏差。
• A Mild and Efficient Desilylation of <i>O</i>-<i>tert</i>-Butyldimethylsilyl Ethers Mediated by Chlorotrimethylsilane and Potassium Fluoride Dihydrate in Acetonitrile
  作者：Wei-Dong Li、Yu Peng

  DOI：10.1055/s-2006-932474

  日期：——

  Desilylation of O-tert-butyldimethylsilyl ethers was achieved by a reagent system consisting of chlorotrimethylsilane and potassium fluoride dihydrate in acetonitrile. This alternative desilylation procedure is chemoselective, generally effective and operationally simple, and should find practical applications in organic synthesis.

  O-叔丁基二甲基甲硅烷基醚的脱甲硅烷基化是通过由氯三甲基硅烷和二水合氟化钾在乙腈中组成的试剂系统实现的。这种替代的脱甲硅烷化过程具有化学选择性，通常有效且操作简单，应该在有机合成中找到实际应用。
• [EN] NRF2 ACTIVATOR<br/>[FR] ACTIVATEUR DE NRF2
  申请人：BIOGEN MA INC

  公开号：WO2018140738A8

  公开（公告）日：2019-08-15
• Lee, Adam Shih-Yuan; Yeh, Hsiu-Chih; Yeh, Ming-Kuo, Journal of the Chinese Chemical Society, 1995, vol. 42, # 6, p. 919 - 922
  作者：Lee, Adam Shih-Yuan、Yeh, Hsiu-Chih、Yeh, Ming-Kuo、Tsai, Ming-Hung

  DOI：——

  日期：——
• Intramolecular Oxyallyl–Carbonyl (3 + 2) Cycloadditions
  作者：Elizabeth H. Krenske、Shuzhong He、Jian Huang、Yunfei Du、K. N. Houk、Richard P. Hsung

  DOI：10.1021/ja312459b

  日期：2013.4.10

  Cycloadditions involving oxyallyl intermediates typically require an electron-rich diene or alkene, but we have discovered the first examples of the cycloaddition of heteroatom-stabilized oxyallyls onto carbonyl groups. An oxazolidinone-substituted oxyallyl undergoes chemoselective (3 + 2) cycloaddition onto the carbonyl group of a tethered dienone in preference to formation of the expected (4 + 3) cycloadduct. Density functional theory calculations indicated that the (3 + 2) cycloaddition takes place through a concerted, highly asynchronous mechanism. The transition state features simultaneous interactions of the oxyallyl LUMO with the carbonyl pi and lone-pair orbitals, making this reaction "hemipseudopericyclic" (halfway between purely pericyclic and purely pseudopericyclic). Further (3 + 2) cycloadditions involving tethered phenyl ketones and a tethered enone were predicted theoretically and verified experimentally.