2,7-二甲基-5-硅杂螺[4.4]壬-2,7-二烯 | 54767-28-1

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 中文名称: 2,7-二甲基-5-硅杂螺[4.4]壬-2,7-二烯
• 英文名称: 2,7-Dimethyl-5-silaspiro<4.4>nona-2,7-diene
• 英文别名: 2,7-dimethyl-5-sila-spiro[4.4]nona-2,7-diene；2,7-Dimethyl-5-silaspiro <4.4>nona-2,7-dien；2,7-Dimethyl-5-silaspiro[4.4]nona-2,7-diene；3,8-dimethyl-5-silaspiro[4.4]nona-2,7-diene
• CAS: 54767-28-1
• 化学式: C₁₀H₁₆Si
• mdl: MFCD00192089
• 分子量: 164.323
• InChiKey: PCTZDZCYAPUYIY-UHFFFAOYSA-N

物化性质

• 沸点：
  140 °C105 mm Hg(lit.)
• 密度：
  0.939 g/mL at 25 °C(lit.)
• 闪点：
  163 °F
• 稳定性/保质期：
  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• WGK Germany：
  3
• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  2,7-二甲基-5-硅杂螺[4.4]壬-2,7-二烯 生成 3,8-dimethyl-5-sila-spiro[4.4]nonane-2,7-diol
  参考文献：
  名称：

  2,7-Dimethyl-5-silaspiro[4.4]nona-2,7-diene的一步合成及其衍生物的合成

  摘要：

  研究了二烷氧基二氯硅烷（例如二甲氧基-、二乙氧基-、二丙氧基-、二丁氧基-和二异丁氧基二氯硅烷）与异戊二烯和镁在四氢呋喃 (THF) 中的原位反应。发现双退火产物，即 2,7-二甲基-5-silaspiro[4.4]nona-2,7-diene (1)，是由二乙氧基-、二丙氧基-和二丁氧基二氯硅烷在 87.0、65.2、和 66.5% 的收益率。另一方面，二甲氧基和二乙氧基二氯硅烷与丁二烯和镁在 THF 中的反应分别以 20.7% 和 35.4% 的产率得到 5-silaspiro[4.4]nona-2,7-diene (7)。几种硅螺酮衍生物由 1 合成。

  DOI：

  10.1246/bcsj.50.1545
• 作为产物：
  描述：

  天然橡胶 在 四氯化硅 、 magnesium 作用下， 生成 2,7-二甲基-5-硅杂螺[4.4]壬-2,7-二烯
  参考文献：
  名称：

  Chemistry of substituted (2-butene-1,4-diyl)magnesium: a facile approach to complex carbocycles, functionalized ketones and alcohols, and silicon-containing heterocycles

  摘要：

  Highly reactive magnesium reacts with a wide variety of substituted 1,3-dienes to give the corresponding substituted (2-butene-1,4-diyl)magnesium complexes. Reactions of symmetrical (2-butene-1,4-diyl)magnesium with alpha,omega-alkylene dihalides form three-, four-, five-, and six-membered carbocycles. Significantly, the cyclizations are always stereospecific and completely regioselective. Depending on the initial 1,3-diene and specific electrophiles, uncyclized products can be obtained. Stepwise reactions of (2,3-dimethyl-2-butene-1,4-diyl)magnesium with two different electrophiles afford polyfunctionalized ketones with the generation of a quaternary center. Formal 1,2-additions can be effected in this manner. Substituted five- and six-membered cyclic ketones can also be synthesized in one step by this approach. Treatment of unsymmetrical (2-butene-1,4-diyl)magnesium complexes with triorganosilyl chlorides followed by cyclohexanone results in additions across a terminal double bond with high regioselectivity. Silicon-containing heterocycles or spiro compounds can be readily synthesized by using the bis-Grignard reagents.

  DOI：

  10.1021/jo00009a034

文献信息

• Hypotheses sur la formation par pyrolyse du premier intermediaire a silicium digonal
  作者：G. Bertrand、G. Manuel、P. Mazerolles

  DOI：10.1016/0040-4020(78)80102-1

  日期：1978.1

  formed by the reaction of this product with methyl acetylene dicarboxylate is studied. From the characterization of the copyrolysis products, two possible mechanisms are proposed which imply the formation of digonal silicon such as 2-silaallene and 2-silaketene.

  描述了2,8-二甲基3,9-二氯6-sila [5.5]螺不连续的2.4,8,10-烯的合成。研究了该产物与乙炔二甲酸甲酯反应生成的加合物的热分解。通过对共分解产物的表征，提出了两种可能的机制，这些机制暗示了诸如2-硅氮丙烯和2-硅氧乙烯烯的对角硅的形成。
• MANUEL, G.;BERTRAND, G.;WEBER, W. P.;KAZOURA, SAMIH, A., ORGANOMETALLICS, 1984, 3, N 9, 1340-1343
  作者：MANUEL, G.、BERTRAND, G.、WEBER, W. P.、KAZOURA, SAMIH, A.

  DOI：——

  日期：——
• A One-step Synthesis of 2,7-Dimethyl-5-silaspiro[4.4]nona-2,7-diene and the Synthesis of Its Derivatives
  作者：Daiyo Terunuma、Satoshi Hatta、Tsunao Araki、Tadashi Ueki、Tsutomu Okazaki、Yasutaka Suzuki

  DOI：10.1246/bcsj.50.1545

  日期：1977.6

  the double annelation product, i.e., 2,7-dimethyl-5-silaspiro[4.4]nona-2,7-diene (1), was obtained from diethoxy-, dipropoxy-, and dibutoxydichlorosilane in 87.0, 65.2, and 66.5% yields respectively. On the other hand, the reaction of dimethoxy- and diethoxydichlorosilane with butadiene and magnesium in THF gave 5-silaspiro[4.4]nona-2,7-diene (7) in 20.7 and 35.4% yields respectively. Several silaspirononane

  研究了二烷氧基二氯硅烷（例如二甲氧基-、二乙氧基-、二丙氧基-、二丁氧基-和二异丁氧基二氯硅烷）与异戊二烯和镁在四氢呋喃 (THF) 中的原位反应。发现双退火产物，即 2,7-二甲基-5-silaspiro[4.4]nona-2,7-diene (1)，是由二乙氧基-、二丙氧基-和二丁氧基二氯硅烷在 87.0、65.2、和 66.5% 的收益率。另一方面，二甲氧基和二乙氧基二氯硅烷与丁二烯和镁在 THF 中的反应分别以 20.7% 和 35.4% 的产率得到 5-silaspiro[4.4]nona-2,7-diene (7)。几种硅螺酮衍生物由 1 合成。
• Chemistry of substituted (2-butene-1,4-diyl)magnesium: a facile approach to complex carbocycles, functionalized ketones and alcohols, and silicon-containing heterocycles
  作者：Reuben D. Rieke、Heping Xiong

  DOI：10.1021/jo00009a034

  日期：1991.4

  Highly reactive magnesium reacts with a wide variety of substituted 1,3-dienes to give the corresponding substituted (2-butene-1,4-diyl)magnesium complexes. Reactions of symmetrical (2-butene-1,4-diyl)magnesium with alpha,omega-alkylene dihalides form three-, four-, five-, and six-membered carbocycles. Significantly, the cyclizations are always stereospecific and completely regioselective. Depending on the initial 1,3-diene and specific electrophiles, uncyclized products can be obtained. Stepwise reactions of (2,3-dimethyl-2-butene-1,4-diyl)magnesium with two different electrophiles afford polyfunctionalized ketones with the generation of a quaternary center. Formal 1,2-additions can be effected in this manner. Substituted five- and six-membered cyclic ketones can also be synthesized in one step by this approach. Treatment of unsymmetrical (2-butene-1,4-diyl)magnesium complexes with triorganosilyl chlorides followed by cyclohexanone results in additions across a terminal double bond with high regioselectivity. Silicon-containing heterocycles or spiro compounds can be readily synthesized by using the bis-Grignard reagents.

表征谱图