1-[(trimethylsilyl)oxy]-1-octene | 71985-43-8

• 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: 1-[(trimethylsilyl)oxy]-1-octene
• 英文别名: (E)-1-(trimethylsiloxy)-1-octene；1-Trimethylsilyloxy-n-octene；trimethyl-[(E)-oct-1-enoxy]silane
• CAS: 71985-43-8
• 化学式: C₁₁H₂₄OSi
• 分子量: 200.396
• InChiKey: NFVWWZAUHAKBPT-ZHACJKMWSA-N

物化性质

• 沸点：
  75 °C(Press: 1 Torr)
• 密度：
  0.815±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.32
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  1-[(trimethylsilyl)oxy]-1-octene 在 tris(cetylpyridinium) 12-tungstophosphate 、 双氧水 作用下， 以 二氯甲烷 为溶剂， 以10%的产率得到1-羟基辛烷-2-酮
  参考文献：
  名称：

  Dehomologation of Aldehydes via Oxidative Cleavage of Silyl Enol Ethers with Aqueous Hydrogen Peroxide Catalyzed by Cetylpyridinium Peroxotungstophosphate under Two-Phase Conditions

  摘要：

  Dehomologation of aldehydes has been first successfully achieved via oxidative cleavage of silyl enol ethers, derived from aldehydes and trimethylchlorosilane, using aqueous hydrogen peroxide in the presence of a catalytic amount of peroxotungstophophate (PCWP) under phase-transfer conditions. For instance, the oxidation of 1-[(trimethylsilyl)oxy]-1-octene resulting from octanal and Me3SiCl with 35% H2O2 catalyzed by PCWP in dichloromethane at room temperature afforded the one-carbon shorter aldehyde, heptanal, in 79% yield. A variety of silyl enol ethers were also converted into one-carbon shorter aldehydes in good yields. The oxidation under homogeneous conditions using tert-butyl alcohol gave hydrolysis products such as 2-oxooctanol and octanal. It is of interest that [1-(trimethylsilyl)oxy]-1,10-undecadiene involving an enol moiety and a terminal double bond afforded exclusively 9-decenal, in which the enol moiety was selectively oxidized. A plausible reaction path for the oxidative cleavage of silyl enol ethers by the present system has been suggested from the oxidation results of alpha-[(trimethylsilyl)oxy]styrene.

  DOI：

  10.1021/jo990477x
• 作为产物：
  描述：

  threo-1-trimethylsilyloctane-1,2-diol 在 sodium hydride 作用下， 以 乙醚 、 Petroleum ether 为溶剂， 反应 24.0h， 以65%的产率得到1-[(trimethylsilyl)oxy]-1-octene
  参考文献：
  名称：

  Elimination reactions of .alpha.,.beta.-dihydroxysilanes: stereospecific synthesis of silyl enol ethers from vinylsilanes

  摘要：

  DOI：

  10.1021/ja00300a031

文献信息

• Silazanes/catalytic bases: mild, powerful and chemoselective agents for the preparation of enol silyl ethers from ketones and aldehydes
  作者：Yoo Tanabe、Tomonori Misaki、Minoru Kurihara、Akira Iida、Yoshinori Nishii

  DOI：10.1039/b203783c

  日期：2002.7.11

  We have developed an efficient method for the preparation of enol silyl ethers using novel agents, silazanes together with NaH or DBU catalyst, wherein TMS and TBDMS groups were smoothly and chemoselectively introduced into ketones and aldehydes under mild conditions.

  我们已经开发了一种使用新型试剂，硅氮烷与NaH或DBU催化剂一起制备烯醇甲硅烷基醚的有效方法，其中TMS和TBDMS基团在温和条件下可以平稳地和化学选择性地引入酮和醛中。
• Selective Oxidation of Vinyl Ethers and Silyl Enol Ethers with Hydrogen Peroxide Catalyzed by Peroxotungstophosphate
  作者：Hiroyo Yamamoto、Masaya Tsuda、Satoshi Sakaguchi、Yasutaka Ishii

  DOI：10.1021/jo970440h

  日期：1997.10.1

  equivalent of 2-hydroxyoctanal, in 70% yield. The oxidation of acyclic silyl enol ethers such as 1-[(trimethylsilyl)oxy]-1-octene under these conditions gave 1-hydroxy-2-octanone in 72% yield, while the same oxidation in dichloromethane alone resulted in cleavage of the enol double bond to form heptanal in 71% yield. Cyclic silyl enol ethers were converted into the corresponding alpha-hydroxy ketones in 48-71%

  首先通过使用过氧钨磷磷酸盐（PCWP）作为催化剂，用过氧化氢水溶液氧化乙烯基和甲硅烷基烯醇醚。例如，在室温下，在甲醇和二氯甲烷的混合溶剂中，在存在PCWP（0.5 mol％）的情况下，化学计量为35％H（2）O（2）的1-乙氧基-1-辛烯的氧化反应1-乙氧基-1-甲氧基-2-羟基辛烷（2-羟基辛醛的合成当量），产率为70％。在这些条件下，无环甲硅烷基烯醇醚如1-[（（三甲基甲硅烷基）氧基] -1-辛烯的氧化以72％的收率得到1-羟基-2-辛酮，而仅在二氯甲烷中的相同氧化导致烯醇的裂解。双键形成庚醛，产率为71％。
• HUDRLIK P. F.; SCHWARTZ R. H.; KULKARNI A. K., TETRAHEDRON LETT., 1979, NO 24, 2233-2236
  作者：HUDRLIK P. F.、 SCHWARTZ R. H.、 KULKARNI A. K.

  DOI：——

  日期：——
• GARST M. E., J. ORG. CHEM., 1979, NO 9, 1578-1580
  作者：GARST M. E.

  DOI：——

  日期：——
• MILLER R. D.; MCKEAN D. R., SYNTHESIS, 1979, NO 9, 730-732
  作者：MILLER R. D.、 MCKEAN D. R.

  DOI：——

  日期：——