(p-methoxybenzyl)triisopropylsilane | 123621-30-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (p-methoxybenzyl)triisopropylsilane
• 英文别名: 4-methoxybenzyltriisopropylsilane；[(4-Methoxyphenyl)methyl]tri(propan-2-yl)silane；(4-methoxyphenyl)methyl-tri(propan-2-yl)silane
• CAS: 123621-30-7
• 化学式: C₁₇H₃₀OSi
• 分子量: 278.51
• InChiKey: VGYFOHTYAFEUGW-UHFFFAOYSA-N

物化性质

• 沸点：
  328.6±17.0 °C(Predicted)
• 密度：
  0.883±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.46
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 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：

  (p-methoxybenzyl)triisopropylsilane 在 联苯 、 9,10-二氰基蒽 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  亲核试剂辅助裂解硅烷阳离子自由基

  摘要：

  La scission des radicaux cationiques（苄基三烷基）硅烷 dans l'acetonitrile est en faveur d'un mecanisme mettant en jeu une 参与亲核试剂杜溶剂

  DOI：

  10.1021/ja00206a061

文献信息

• A kinetic study of the electron-transfer-initiated carbon-silicon bond cleavage reactions of benzyltrialkylsilanes promoted by dodecatungstocobalt(III)ate ion
  作者：Enrico Baciocchi、Manuela Crescenzi、Elisabetta Fasella、Mario Mattioli

  DOI：10.1021/jo00043a028

  日期：1992.8

  The reactions of some ring-substituted benzyltrimethylsilanes (1Z), (p-methylbenzyl)triethylsilane (2), (p-methylbenzyl)triisopropylsilane (3), and (p-methoxybenzyl)triisopropylsilane (4) with potassium 12-tungstocobalt(III)ate, K5[CoIIIW12O40] (CO(III)W), have been studied in AcOH-H2O. In all cases desilylated products, benzyl acetates, and benzyl alcohols have been obtained, with a 2:1 oxidant to substrate stoichiometry. A kinetic investigation has shown that the reactions of 1Z and 2 are strictly first order in Co(III)W and first order in the substrate. Added salts (NaClO4, NaOAc) decrease the rate, whereas no retarding effect by Co(II)W has been noted. In contrast, the reaction of 4 is no longer first order in Co(III)W and the rate is significantly decreased by added Co(II)W. These data have been interpreted in terms of an electron-transfer mechanism, in which a benzyltrialkylsilane radical cation is formed and then undergoes a C-Si bond cleavage to form a benzyl radical. Reaction of this radical with Co(III)W leads to the products. In the reactions of 1Z and 2 the rate-determining step is the transfer of the electron from the substrate to Co(III)W, whereas in the reaction of 4 the slow step is the one where the C-Si bond cleavage takes place. The mechanistic changeover is probably related to the much lower rate of C-Si bond cleavage in 4+. than in 1Z+. and 2+., due to the fact that in the former cation radical nucleophilic attack at silicon is made difficult by the bulky isopropyl groups. The kinetic data for the reactions of 1Z and 2 fit the Marcus equation for a reorganization energy lambda of 43 +/- 1 kcal mol-1. From this value a lambda-value of 61 kcal mol-1 for the couple ArCH2SiMe3+./ArCH2SiMe3 has been evaluated, which is somewhat higher than that found for a number of ArCH3+./ArCH3 Systems. The possible reasons for this difference are discussed on the basis of ab initio calculations (STO-3G) concerning bond distances and angles in PhCH3+. and PhCH2SiH3+..
• DINNOCENZO, J. P.;FARID, S.;GOODMAN, J. L.;GOULD, I. R.;TODD, W. P.;MATTE+, J. AMER. CHEM. SOC., 111,(1989) N4, C. 8973-8975
  作者：DINNOCENZO, J. P.、FARID, S.、GOODMAN, J. L.、GOULD, I. R.、TODD, W. P.、MATTE+

  DOI：——

  日期：——