(E,Z)-6-trimethylsilyl-4-hexenal | 119554-29-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E,Z)-6-trimethylsilyl-4-hexenal
• 英文别名: 6-trimethylsilylhex-4-enal
• CAS: 119554-29-9
• 化学式: C₉H₁₈OSi
• 分子量: 170.327
• InChiKey: KBQGCJGFHIUJOT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  11.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (E,Z)-6-trimethylsilyl-4-hexenal 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 cis,cis-1,1'-Oxybis(2-vinylcyclobutane) 、 cis,trans-1,1'-Oxybis(2-vinylcyclobutane)
  参考文献：
  名称：

  About the Stereoelectronics of the Intramolecular Addition of Allylsilanes to Aldehydes

  摘要：

  (Z)-omega -Trimethylsilyl-(omega -2)-alken-1-ols are readily accessible by consecutive superbase metalation and silylation of (omega -1)-alken-1-ols. These versatile intermediates may be oxidized to give the corresponding (Z)-omega -trimethylsilyl-(omega -2)-alkenals which, in the presence of trifluoroacetic acid, can be converted into 2-vinylcycloalkanols such as 2-vinylcyclohexanol (2), isopulegol (4), and bis(2 vinylcyclobutyl) ether (8). The stereochemical outcome of these cyclization reactions suggests the interference of a novel electrodynamic effect.

  DOI：

  10.1002/1521-3765(20010504)7:9<1909::aid-chem1909>3.3.co;2-8
• 作为产物：
  描述：

  N-cyclohexyl-N-cyclopentylidenamine 在 草酸 、 lithium diisopropyl amide 作用下， 以 环己烷 为溶剂， 反应 7.0h， 生成 (E,Z)-6-trimethylsilyl-4-hexenal
  参考文献：
  名称：

  Intramolecular Ene and Related Reactions, Part 9. Photochemically Induced Synthesis of Allylsilane Carbaldehydes

  摘要：

  烯丙基硅烷羰基醛是串联 Knoevenagel 烯丙基硅烷和亚胺环化反应的重要底物。烯丙基硅烷羰基醛是串联 Knoevenagel 烯丙基硅烷和亚胺环化反应的重要底物，可以通过对δ位带有三甲基硅甲基的环酮进行光化学δ-裂解（Norrish I 型裂解）而轻松制备。硅能稳定 δ 位上的自由基，从而促进了光解过程。辐照酮 15a-d 主要生成醛 16a-d。此外，辐照 19a 主要得到醛 20。

  DOI：

  10.1055/s-1990-27070

文献信息

• Silicon-directed Norrish type I cleavage of β-trimethylsilyl cycloalkanones
  作者：Jih Ru Hwu、Bryant A. Gilbert、Lung Ching Lin、Ben Ruey Liaw

  DOI：10.1039/c39900000161

  日期：——

  The Me3Si group in β-trimethylsilyl cycloalkanones was able to direct the Norrish type I cleavage by providing regioselectivity in the C-1-C-2 bond cleavage and by increasing the quantum yield and the reaction rate.

  β-三甲基甲硅烷基环烷酮中的Me 3 Si基团能够通过在C-1-C-2键断裂中提供区域选择性并增加量子产率和反应速率来指导Norrish I型断裂。
• About the Stereoelectronics of the Intramolecular Addition of Allylsilanes to Aldehydes
  作者：Manfred Schlosser、Livia Franzini、Carsten Bauer、Frédéric Leroux

  DOI：10.1002/1521-3765(20010504)7:9<1909::aid-chem1909>3.3.co;2-8

  日期：2001.5.4

  (Z)-omega -Trimethylsilyl-(omega -2)-alken-1-ols are readily accessible by consecutive superbase metalation and silylation of (omega -1)-alken-1-ols. These versatile intermediates may be oxidized to give the corresponding (Z)-omega -trimethylsilyl-(omega -2)-alkenals which, in the presence of trifluoroacetic acid, can be converted into 2-vinylcycloalkanols such as 2-vinylcyclohexanol (2), isopulegol (4), and bis(2 vinylcyclobutyl) ether (8). The stereochemical outcome of these cyclization reactions suggests the interference of a novel electrodynamic effect.
• Intramolecular Ene and Related Reactions, Part 9. Photochemically Induced Synthesis of Allylsilane Carbaldehydes
  作者：Lutz F. Tietze、Josef R. Wünsch

  DOI：10.1055/s-1990-27070

  日期：——

  Allylsilane carbaldehydes are valuable substrates for the tandem Knoevenagel allylsilane and iminium cyclization. They can easily be prepared by a photochemical α-cleavage of cyclic ketones bearing a trimethylsilylmethyl group in the α-position (Norrish Type I cleavage). The photolytic process is facilitated by the silicon due to its stabilization of a radical in the β-position. Irradiation of the ketones 15a-d leads mainly to the aldehydes 16a-d. In addition irradiation of 19a gives mostly the aldehyde 20.

  烯丙基硅烷羰基醛是串联 Knoevenagel 烯丙基硅烷和亚胺环化反应的重要底物。烯丙基硅烷羰基醛是串联 Knoevenagel 烯丙基硅烷和亚胺环化反应的重要底物，可以通过对δ位带有三甲基硅甲基的环酮进行光化学δ-裂解（Norrish I 型裂解）而轻松制备。硅能稳定 δ 位上的自由基，从而促进了光解过程。辐照酮 15a-d 主要生成醛 16a-d。此外，辐照 19a 主要得到醛 20。