4,4-dichloro-3-neopentyl-1-trimethylsilyl-4-silahexa-5-ene-1-yne

• 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: 4,4-dichloro-3-neopentyl-1-trimethylsilyl-4-silahexa-5-ene-1-yne
• 英文别名: dichloro-(5,5-dimethyl-1-trimethylsilylhex-1-yn-3-yl)-ethenylsilane
• 化学式: C₁₃H₂₄Cl₂Si₂
• 分子量: 307.411
• InChiKey: BKCQOJGHNDMJJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.32
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  乙烯基三氯硅烷 、 2-甲基-4-三甲基硅基-1-丁烯-3-炔 、 叔丁基锂 生成 4,4-dichloro-3-neopentyl-1-trimethylsilyl-4-silahexa-5-ene-1-yne
  参考文献：
  名称：

  Silaheterocyclen XXXVII.

  摘要：

  A series of differently substituted alkeneinylhalogensilanes R2Si(X)-C drop CC(Me)=CH2 (X = Cl: R = Me (2), Cl (3), Ph (4); X = F: R = Me (5), Mes (6), Tip (7)) is reacted with t-BuLi in solvents of different polarity to give mainly E/Z-isomeric 2.4-bispentenylidene-1,3-disilacyclobutanes (11, 23 and 31) and E/Z-isomeric 2.4,6-trispentenylidene-1,3.5-trisilacydohexanes (12 and 24) competitively. Obviously the four- and six-membered silacycles are formed stepwise by intermolecular coupling reactions of the lithiated precursors R2Si(X)C(Li)=C=C(Me)-t-Bu which preliminary result from the 1,4-addition of the lithium organyle to the alkeneinylhalogensilanes. Alternatively, silacumulene formation (R2Si=C=C=C(Me)CH2-t-Bu) might be discussed, but the isolation of Cl3Si-C(=C=C(Me)CH2-t-Bu)-C-C-C(Me)=CH2 (22) as coupling product starting from trichlorosilane 3 and t-BuLi and high molecular multistep coupling products starting from the fluorinated precursors 5 and 7 strongly favour the the coupling reactions over silacumulene formation. Consequently, all attempts to isolate a stable silacumulene from the silicon sterically overcrowded starting compounds 6 and 7 failed. (C) 2001 Published by Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00855-x

文献信息

• Silaheterocycles 36 (1). Trichlorovinylsilane, lithium-<i>tert</i>-butyl, and 1,3-enynes: A versatile combination for the competitive formation of silacyclobutanes and silacyclobutenes
  作者：N Auner、M Grasmann、B Herrschaft、M Hummer

  DOI：10.1139/v99-247

  日期：2000.11.1

  Equimolar amounts of trichlorovinylsilane (9), lithium-tert-butyl, and 1,3-enynes were reacted to yield the corresponding isomeric silacyclobutanes and silacyclobutenes competitively. As reaction pathway the mixture 9/^tBuLi is discussed to give a silene equivalent, Cl₂Si=CHCH₂^tBu (10), yielding the four-membered ring silacycles by formal [2 + 2] cycloaddition reactions of 10 with the C=C double or the C=C triple bond of the 1,3-enyne. The relative ratio of the products formed depends on the polarity of the multiple bonds in the enyne, which is mainly determined by the substituent pattern. Thus, from the organosubstituted 1,3-enynes R¹ C=C-C(R²)=CR³R⁴ (R¹ = Me, Et, SiMe₃, Ph; R² = H, Me, Ph; R³=Me, OMe, Ph; R⁴=H; and R¹C=C-R' (R' = 1-cyclohexenyl, cyclohexanevinylidyne)) and 9/^tBuLi the silacyclobutanes 12, 13, and 15 and the silacyclobutenes 14,16-24, and 27 (from 10 and 3-hexyne) are prepared in a one-step synthesis and isolated from the reaction mixtures. The silacyclobutanes and -butenes are thermally stable and can be distilled under vacuo up to temperatures of about 150°C without decomposition. The experimental results are confirmed qualitatively by semiempiric calculations at the AM-1 level and their analysis using FMO theory. The solid state structure of the silacyclobutene 19 (C₁₇H₃₀Cl₂Si₂) has been determined by single crystal X-ray diffractometry. 19 is orthorhombic, space group P2₁2₁2₁, a = 1030.94(2) pm, b = 1244.6(2) pm, c = 1605.5(3) pm, Z = 4.Key words: neopentylsilene, dichloroneopentylsilene, silacyclobutenes, silacyclobutanes, 1,3-enynes.

  等摩尔量的三氯乙烯基硅烷(9)、叔丁基锂和1,3-烯烃反应，竞争性地产生相应的异构硅杂环丁烷和硅杂环丁烯。作为反应途径，讨论了混合物9/叔丁基锂生成硅烯等效物Cl2Si=CHCH2叔丁基(10)，通过10与1,3-烯烃的C=C双键或C=C三键的形式[2+2]环加成反应，生成四元环硅杂环。形成的产物相对比例取决于烯烃中多重键的极性，这主要由取代基模式决定。因此，从有机取代的1,3-烯烃R1C=C-C(R2)=CR3R4(R1=Me、Et、SiMe3、Ph；R2=H、Me、Ph；R3=Me、OMe、Ph；R4=H；和R1C=C-R' (R' = 1-环己烯基、环己烷乙烯基))和9/叔丁基锂中，制备了硅杂环丁烷12、13、15和硅杂环丁烯14、16-24和27(从10和3-己烯)的一步合成产物，并从反应混合物中分离出来。硅杂环丁烷和丁烯具有热稳定性，可以在真空下蒸馏到约150°C的温度而不分解。实验结果在AM-1水平上通过半经验计算进行了定性确认，并使用FMO理论进行了分析。硅杂环丁烯19(C17H30Cl2Si2)的固态结构已经通过单晶X射线衍射确定。19是正交晶系，空间群P212121，a = 1030.94(2) pm，b = 1244.6(2) pm，c = 1605.5(3) pm，Z = 4。关键词：新戊基硅烯，二氯新戊基硅烯，硅杂环丁烯，硅杂环丁烷，1,3-烯烃。
• Silaheterocyclen XXXVII.
  作者：Norbert Auner、Martin Grasmann

  DOI：10.1016/s0022-328x(00)00855-x

  日期：2001.3

  A series of differently substituted alkeneinylhalogensilanes R2Si(X)-C drop CC(Me)=CH2 (X = Cl: R = Me (2), Cl (3), Ph (4); X = F: R = Me (5), Mes (6), Tip (7)) is reacted with t-BuLi in solvents of different polarity to give mainly E/Z-isomeric 2.4-bispentenylidene-1,3-disilacyclobutanes (11, 23 and 31) and E/Z-isomeric 2.4,6-trispentenylidene-1,3.5-trisilacydohexanes (12 and 24) competitively. Obviously the four- and six-membered silacycles are formed stepwise by intermolecular coupling reactions of the lithiated precursors R2Si(X)C(Li)=C=C(Me)-t-Bu which preliminary result from the 1,4-addition of the lithium organyle to the alkeneinylhalogensilanes. Alternatively, silacumulene formation (R2Si=C=C=C(Me)CH2-t-Bu) might be discussed, but the isolation of Cl3Si-C(=C=C(Me)CH2-t-Bu)-C-C-C(Me)=CH2 (22) as coupling product starting from trichlorosilane 3 and t-BuLi and high molecular multistep coupling products starting from the fluorinated precursors 5 and 7 strongly favour the the coupling reactions over silacumulene formation. Consequently, all attempts to isolate a stable silacumulene from the silicon sterically overcrowded starting compounds 6 and 7 failed. (C) 2001 Published by Elsevier Science B.V. All rights reserved.