3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene | 135888-05-0

• 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: 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene
• 英文别名: 7,7,8,8-Tetraethyl-7,8-disilabicyclo[4.2.0]octa-1,3,5-triene
• CAS: 135888-05-0
• 化学式: C₁₄H₂₄Si₂
• 分子量: 248.516
• InChiKey: MUJZRFTVKPNRTG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene 在 tetrakis(triethylphosphine)nickel(0) 、 2,3-benzo-1,1,2,2-tetramethyl-1,2-disilacyclopent-3-ene 作用下， 反应 48.0h， 生成 1-phenyldimethylsilyl-2-(trimethylsilyl)phenylethene
  参考文献：
  名称：

  硅碳不饱和化合物LIV：3,4-苯并-1,1,2,2-四乙基-1,2-二硅环丁-3-烯与炔烃的镍催化反应

  摘要：

  研究了3,4-苯并-1,1,2,2-四乙基-1,2-二硅环丁-3-烯（1）与二取代乙炔的镍催化反应。在150°C下用3-己炔和二苯乙炔处理1得到两种加合物：5,6-苯并-1,4-二硅环六-2,5-二烯和5,6-苯并1,2-二硅环六-3 ，5-二烯，以及少量其他异构体。1与苯基（三甲基甲硅烷基）乙炔的反应生成5,6-苯并-1,1,4,4-四乙基-3-苯基-2-三甲基甲硅烷基-1,4-二硅环己-2,5-二烯和4,5 -苯并-1,1,3,3-四乙基-2- [苯基（三甲基甲硅烷基）亚甲基] -1,3-二硅环戊-4-烯（10）。1的相似反应与1-（三甲基甲硅烷基）己炔还提供了5,6-苯并-3-丁基-1,1,4,4-四乙基-2-三甲基甲硅烷基-1,4-二硅环己-2,5-二烯和4,5-苯并-2- [丁基（三甲基甲硅烷基）亚甲基] -1,1,3,3-四乙基-1,3-二硅环戊-4-烯（12）。提出了一种亚乙

  DOI：

  10.1016/0022-328x(95)00329-o
• 作为产物：
  描述：

  1,2-bis(diethylsilanyl)benzene 在 sodium 、 palladium dichloride 作用下， 以 四氯化碳 、 甲苯 为溶剂， 反应 51.0h， 生成 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene
  参考文献：
  名称：

  A Strained Disilane-Promoted Carboxylation of Organic Halides with CO₂ under Transition-Metal-Free Conditions

  摘要：

  By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency.

  DOI：

  10.1021/acs.orglett.5b02645
• 作为试剂：
  描述：

  4-碘代苯乙酮 、 二氧化碳 在 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene 、 cesium fluoride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 2.0h， 以76%的产率得到4-乙酰基苯甲酸
  参考文献：
  名称：

  A Strained Disilane-Promoted Carboxylation of Organic Halides with CO₂ under Transition-Metal-Free Conditions

  摘要：

  By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency.

  DOI：

  10.1021/acs.orglett.5b02645

文献信息

• Palladium-catalyzed reactions of 1,1,2,2-tetraethyl- and 1,1,2,2-tetra(isopropyl)-3,4-benzo-1,2-disilacyclobut-3-ene with alkynes
  作者：Akinobu Naka、Taiichi Okada、Mitsuo Ishikawa

  DOI：10.1016/0022-328x(96)06160-8

  日期：1996.8

  The reactions of 3,4-benzo-1,1,2,2-tetra(isopropyl)-1,2-disilacyclobut-3-ene (2) with acetylene, phenylacetylene, 1-hexyne, and o-tolylacetylene in the presence of tetrakis(triphenylphosphine)palladium gave the respective 5,6-benzo-1,4-disilacyclohexa-2,5-dienes 3-6. Similar reactions of 2 with mesitylacetylene, trimethylsilylacetylene, and dimethylphenylsilylacetylene afforded 1-alkynyl(diisopropylsilyl)-2-(diisopropylsilyl)benzenes 7-9 arising from sp-hybridized C-H bond activation of acetylenes. The reactions of 3,4-benzo-1,1 ,2,2-tetraethyl-1,2-disilacyclobut-3-ene with mesitylacetylene, trimethylsilylacetylene, and dimethylphenylsilylacetylene produced 5,6-benzo-1,4-disilacyclohexa-2,5-dienes 10-12 as the sole product. The stoichiometric reaction of 2 with tetrakis(triphenylphosphine)palladium gave a yield of 3,4-benzo-2,2,5,5-tetra(isopropyl)-1-pallada-2,5-disilacyclopent-3-ene (A), arising from insertion of a palladium species into a silicon-silicon bond in 2.
• Silicon-carbon unsaturated compounds
  作者：Hiromu Sakamoto、Mitsuo Ishikawa

  DOI：10.1016/0022-328x(92)80080-h

  日期：1992.4

  Photolysis of 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene gives a silene which can be trapped by t-butyl alcohol and acetone in high yields.
• Nickel-catalyzed reactions of 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene
  作者：Mitsuo Ishikawa、Hiromu Sakamoto、Shougo Okazaki、Akinobu Naka

  DOI：10.1016/0022-328x(92)80049-4

  日期：1992.10

  The reaction of 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene (1) with benzene in the presence of a catalytic amount of Ni(PEt3)4 afforded 1-diethylphenylsilyl-2-(diethylsilyl)benzene, while reaction with diphenylacetylene and benzaldehyde gave the respective products arising from insertion of 1 into an Si-Si bond.
• Silicon-Carbon Unsaturated Compounds. 51. Nickel-Catalyzed Reactions of 3,4-Benzo-1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene with Alkenes and Dienes
  作者：Mitsuo Ishikawa、Shougo Okazaki、Akinobu Naka、Akitomo Tachibana、Susumu Kawauchi、Tokio Yamabe

  DOI：10.1021/om00001a020

  日期：1995.1

  The reactions of 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene (1) with alkenes in the presence of a catalytic amount of tetrakis(triethylphosphine)nickel(0) at 150 degrees C have been investigated. With 1,1-diphenylethylene, 1 afforded 1,2-bis(diethylsilyl)benzene (2), 4,5-benzo-1,1,3,3-tetraethyl-2-diphenylmethylene-1,3-disilacyclopent-4-ene, and 1-[diethyl(2, 2-diphenylethenyl)silyl]-2-diethylsilylbenzene in 4%, 55%, and 7% yields. The reaction of 1 with styrene gave 4,5-benzo-1,1,3,3-tetraethyl-2-phenylmethylene-1,3-disilacyclopent-4-ene and (E)-1-tetraethyl(2-phenyl)disilanyl-2-phenylethene in 12% and 47% yields, while with 1- and 2-hexene, 1 produced 4,5-benzo-1,1,3,3-tetraethyl-2-(n-pentylidene)-1,3-disilacyclopent-4-ene, together with a product arising from hydrosilation of 2 and 1-hexene. Similar treatment of 1 with ethylene in an autoclave afforded 4,5-benzo-1,1,3,3-tetraethyl-2-methylene-1 ,3-disilacyclopent-4-ene, tetraethyl-1-phenyl-2-vinyldisilane, and 2,3-benzo-1,1,4,4-tetraethyl-1,4-disilacyclohex-2-ene in 7%, 34%, and 10% yields. Similarly, the nickel-catalyzed reaction of 1 with 2,3-dimethylbutadiene yielded 4,5-benzo-1,1,3,3-tetraethyl-2-(1,2,2-trimethylethenyl)-1,3-disilacyclopent-4-ene and 2,3-benzo-1,1,4,4-tetraethyl-6,7-dimethyl-1 ,4-disilacycloocta-2,6-diene in 33% and 30% yields, while with 1,3- and 1,4-cyclohexadiene, 1 afforded 5,5,10,10-tetraethyl-8,9,13,14-tetrahydrosilanthrene, as the sole product. The results of MO calculations for 1-nickela-2,5-disilacydopent-3-ene are also reported.
• A Strained Disilane-Promoted Carboxylation of Organic Halides with CO₂ under Transition-Metal-Free Conditions
  作者：Tsuyoshi Mita、Kenta Suga、Kaori Sato、Yoshihiro Sato

  DOI：10.1021/acs.orglett.5b02645

  日期：2015.11.6

  By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency.