2-[(trimethylsilyl)oxy]acetophenone | 26205-41-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-[(trimethylsilyl)oxy]acetophenone
• 英文别名: 1-Phenyl-2-trimethylsiloxy-ethanon；1-Phenyl-2-trimethylsilyloxy-ethanon；Ethanone, 1-phenyl-2-[(trimethylsilyl)oxy]-；1-phenyl-2-trimethylsilyloxyethanone
• CAS: 26205-41-4
• 化学式: C₁₁H₁₆O₂Si
• 分子量: 208.332
• InChiKey: ZRLFPEKFTDGLJS-UHFFFAOYSA-N

物化性质

• 沸点：
  115 °C(Press: 4 Torr)
• 密度：
  0.979±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[(trimethylsilyl)oxy]acetophenone 、 甲基溴化镁 以 乙醚 为溶剂， 生成 2-苯基-1,2-丙二醇
  参考文献：
  名称：

  A Convenient Synthesis of 2-Phenylglycerol

  摘要：

  1,3-Dihydroxyacetone dimer is treated with trimethylsilyl chloride and triethylamine in dichloromethane to provide monomeric ketone having both of its alcohols protected as their di-TMS ethers. The latter is added to phenylmagnesium bromide in ether at -78 degrees C. Work-up by treatment with aqueous ammonium chloride followed by 2 N HCl provides 2-phenylglycerol in 70% yield.

  DOI：

  10.1080/00397910008087018
• 作为产物：
  描述：

  2-溴苯乙酮 在 甲醇 、 potassium formate 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 2-[(trimethylsilyl)oxy]acetophenone
  参考文献：
  名称：

  使用手性改性的硼氢化物的不对称合成。第3部分。用硼烷和手性氨基醇制备的试剂对酮和肟醚进行对映选择性还原

  摘要：

  研究了由硼烷和手性氨基醇制得的试剂对芳香族和脂肪族酮，卤代酮，羟基酮，酮酯和酮肟醚的不对称还原。当使用（2 S，3 R）-（–）-2-氨基-3-甲基-1,1-二苯基戊醇（2d）等α，α-二苯基β-氨基醇作为手性助剂时在还原各种酮和肟醚时，具有很高的对映选择性（约90％ee）。

  DOI：

  10.1039/p19850002039

文献信息

• Preparation of silyl enol ethers from acyloin derivatives using silyllithium reagents
  作者：Bradley D. Robertson、Aaron M. Hartel

  DOI：10.1016/j.tetlet.2008.01.133

  日期：2008.3

  A new method for the regioselective preparation of silyl enol ethers from acyloin derivatives using silyllithium reagents has been developed. Both dimethylphenyl- and methyldiphenylsilyllithium were found to be effective, the latter providing greater stereocontrol. The reaction is believed to proceed via Brook rearrangement assisted by expulsion of the adjacent leaving group. A number of acyclic acyloin

  已经开发出一种新的方法，用于使用硅烷基锂试剂从酰基糖苷衍生物区域选择性地制备甲硅烷基烯醇醚。发现二甲基苯基-和甲基二苯基甲硅烷基锂都是有效的，后者提供更大的立体控制。据信该反应是通过布鲁克重排而进行的，其中布鲁克被重排，相邻的离去基团被驱逐。使许多无环的酰氯衍生物以良好至优异的产率反应形成相应的甲硅烷基烯醇醚。
• Macrae,D.M.; Brook,A.G., Journal of Organometallic Chemistry, 1974, vol. 77, p. C19 - C21
  作者：Macrae,D.M.、Brook,A.G.

  DOI：——

  日期：——
• Takai, Toshihiro; Yamada, Tohru; Rhode, Oliver, Chemistry Letters, 1991, # 2, p. 281 - 284
  作者：Takai, Toshihiro、Yamada, Tohru、Rhode, Oliver、Mukaiyama, Teruaki

  DOI：——

  日期：——
• Reaktivität und Selektivität bei der Oxidation von Styrolderivaten. V. Untersuchungen zur Oxidation vonα-substituierten Styrolen
  作者：W.Ya. Suprun

  DOI：10.1002/(sici)1521-3897(199901)341:1<52::aid-prac52>3.0.co;2-d

  日期：1999.1

  The liquid phase oxidation of alpha-phenyl-1a, alpha-trimethylsilyloxy Ib, alpha-cyclopropyl-1c, alpha-trifluoromethyl-1d styrene, and styrene le with oxygen in chlorobenzene and cumene solution in the temperature range 55-125 degrees C was investigated. The product yields were determined gaschromatographically. The epoxide selectivity increases up to 90 degrees C with increasing temperature. The epoxides of la and Ic rearrange at higher temperatures, therefore their yield decreases. The relative chain propagation constants (k(p)C=C) were determined by competitive oxidations of cumene.
• Dehomologation of Aldehydes via Oxidative Cleavage of Silyl Enol Ethers with Aqueous Hydrogen Peroxide Catalyzed by Cetylpyridinium Peroxotungstophosphate under Two-Phase Conditions
  作者：Satoshi Sakaguchi、Yumiko Yamamoto、Takuma Sugimoto、Hiroyo Yamamoto、Yasutaka Ishii

  DOI：10.1021/jo990477x

  日期：1999.8.1

  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.