3-methyl-3-triethylsilyldioxybutyl benzoate | 124081-35-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-methyl-3-triethylsilyldioxybutyl benzoate
• 英文别名: (3-Methyl-3-triethylsilylperoxybutyl) benzoate
• CAS: 124081-35-2
• 化学式: C₁₈H₃₀O₄Si
• 分子量: 338.519
• InChiKey: KRLSGKOQSQLFHM-UHFFFAOYSA-N

物化性质

• 沸点：
  379.4±25.0 °C(Predicted)
• 密度：
  0.992±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.97
• 重原子数：
  23
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-methyl-3-triethylsilyldioxybutyl benzoate 在 盐酸 、 甲醇 作用下， 反应 0.08h， 以340 mg的产率得到3-hydroperoxy-3-methylbutyl benzoate
  参考文献：
  名称：

  Co(III)−Alkyl Complex- and Co(III)−Alkylperoxo Complex-Catalyzed Triethylsilylperoxidation of Alkenes with Molecular Oxygen and Triethylsilane

  摘要：

  [GRAPHICS]Both a Co(III)-alkyl complex and a Co(III)-alkylperoxo complex were found to catalyze triethylsilylperoxidation of alkenes with O-2 and Et3SiH. On this basis, together with the nonstereoselectivity in the Co(II)-catalyzed peroxidation of 3-phenylindene and the formation of the corresponding 1,2-dioxolane from 2-phenyl-1-vinylcyclopropane (a radical clock), we propose a reasonable mechanism for the Co(II)-catalyzed novel autoxidation of alkenes with Et3SiH discovered by Isayama and Mukaiyama.

  DOI：

  10.1021/ol0201299
• 作为产物：
  描述：

  3-甲基-3-丁烯-1-醇 在 [5,5-dimethyl-1-(morpholin-4-yl)hexane-1,2,4-trionato]2Co 氧气 、 三乙胺 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 5.33h， 生成 3-methyl-3-triethylsilyldioxybutyl benzoate
  参考文献：
  名称：

  Co(II)/O2/Et3SiH 通过二烯的化学和区域选择性过氧化合成环状过氧化物

  摘要：

  在两种烯烃与 Co(II)/O 2 /Et 3 SiH的混合物的竞争性过氧化反应中，发现烯烃底物的相对反应性受三个主要因素的影响：(1) 烯烃与 HCo(III) 络合物反应形成的中间碳中心自由基的相对稳定性，(2) C C 双键周围的空间效应，以及 (3) 与 C 相关的电子因素C 双键。与简单烯烃的结果一致，还实现了二烯的化学和区域选择性过氧化。根据二烯结构，产物不仅包括预期的无环不饱和三乙基甲硅烷基过氧化物，还包括 1,2-二氧戊环和 1,2-二氧六环衍生物，通过不饱和过氧自由基中间体的分子内环化。

  DOI：

  10.1021/jo048359j

文献信息

• Syntheses of New {Tetrakis(1-pyrazolyl)borato}samarium(III) Complexes and Their Temperature-Dependent Exchange Motions of All Pyrazolyl Groups
  作者：Masayoshi Onishi、Hitoshi Yamaguchi、Hirokazu Shimotsuma、Katsuma Hiraki、Junko Nagaoka、Hiroyuki Kawano

  DOI：10.1246/cl.1999.573

  日期：1999.7

  As the first unambiguous syntheses and characterization of the tetrakis(1-pyrazolyl)borato}lanthanide(III) complexes, stable eight-coordinate (β-ketoenolato)samariums [Smη3-B(pz)4}2(β-ketoenolato)] (pz = 1-pyrazolyl group) were prepared, and novel stereochemically non-rigid temperature-dependent motions of the B(pz)4 ligands were observed on their solution-state 1H-NMR spectra, showing the spectroscopic

  作为 tetrakis(1-pyrazolyl)borato}lanthanide(III) 络合物的第一个明确合成和表征，稳定的八配位 (β-ketoenolato) 钐 [Smη3-B(pz)4}2(β-ketoenolato) )] (pz = 1-吡唑基)，并在 B(pz)4 配体的溶液态 1H-NMR 谱上观察到新的立体化学非刚性温度依赖性运动，显示配位和高温下未配位的吡唑基。
• Co-catalyzed autoxidation of alkene in the presence of silane. The effect of the structure of silanes on the efficiency of the reaction and on the product distribution
  作者：Jin-Ming Wu、Shigeki Kunikawa、Takahiro Tokuyasu、Araki Masuyama、Masatomo Nojima、Hye-Sook Kim、Yusuke Wataya

  DOI：10.1016/j.tet.2005.08.025

  日期：2005.10

  A systematic investigation of the structural effect of silanes on the Co-catalyzed reductive oxygenation of alkene in the presence of silane (Mukaiyama-Isayama reaction) showed that the efficiency of the reaction decreases with the increase of the steric bulk of the silanes. A similar trend was observed for the metal-exchange reaction between Co(III)-alkylperoxo complex and silane, too. The peroxidation of (S)-limonene, followed by deprotection of the derived silyl peroxides, provides a mixture of the corresponding monocyclic hydroperoxide 24 and the bicyclic one 25, the ratio being a marked function of the steric bulk of silanes. (c) 2005 Elsevier Ltd. All rights reserved.
• ISAYAMA, SHIGERU;MUKAIYAMA, TERUAKI, CHEM. LETT.,(1989) N, C. 573-576
  作者：ISAYAMA, SHIGERU、MUKAIYAMA, TERUAKI

  DOI：——

  日期：——
• Co(III)−Alkyl Complex- and Co(III)−Alkylperoxo Complex-Catalyzed Triethylsilylperoxidation of Alkenes with Molecular Oxygen and Triethylsilane
  作者：Takahiro Tokuyasu、Shigeki Kunikawa、Araki Masuyama、Masatomo Nojima

  DOI：10.1021/ol0201299

  日期：2002.10.1

  [GRAPHICS]Both a Co(III)-alkyl complex and a Co(III)-alkylperoxo complex were found to catalyze triethylsilylperoxidation of alkenes with O-2 and Et3SiH. On this basis, together with the nonstereoselectivity in the Co(II)-catalyzed peroxidation of 3-phenylindene and the formation of the corresponding 1,2-dioxolane from 2-phenyl-1-vinylcyclopropane (a radical clock), we propose a reasonable mechanism for the Co(II)-catalyzed novel autoxidation of alkenes with Et3SiH discovered by Isayama and Mukaiyama.
• Synthesis of Cyclic Peroxides by Chemo- and Regioselective Peroxidation of Dienes with Co(II)/O₂/Et₃SiH
  作者：Takahiro Tokuyasu、Shigeki Kunikawa、Kevin J. McCullough、Araki Masuyama、Masatomo Nojima

  DOI：10.1021/jo048359j

  日期：2005.1.1

  Consistent with results from simple alkenes, the chemo- and regioselective peroxidation of dienes was also realized. Depending on the diene structure, the product included not only the expected acyclic unsaturated triethylsilyl peroxides but also 1,2-dioxolane and 1,2-dioxane derivatives via intramolecular cyclization of the unsaturated peroxy radical intermediates.

  在两种烯烃与 Co(II)/O 2 /Et 3 SiH的混合物的竞争性过氧化反应中，发现烯烃底物的相对反应性受三个主要因素的影响：(1) 烯烃与 HCo(III) 络合物反应形成的中间碳中心自由基的相对稳定性，(2) C C 双键周围的空间效应，以及 (3) 与 C 相关的电子因素C 双键。与简单烯烃的结果一致，还实现了二烯的化学和区域选择性过氧化。根据二烯结构，产物不仅包括预期的无环不饱和三乙基甲硅烷基过氧化物，还包括 1,2-二氧戊环和 1,2-二氧六环衍生物，通过不饱和过氧自由基中间体的分子内环化。