7,8-bis-(trimethylsilyl)bicyclo<4.2.1>nona-2,4,7-triene | 88061-83-0

• 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: 7,8-bis-(trimethylsilyl)bicyclo<4.2.1>nona-2,4,7-triene
• 英文别名: 7,8-bis(trimethylsilyl)bicyclo<4.2.1>nona-2,4,7-triene；7,8-bis(trimethylsilyl)bicyclo[4.2.1]nona-2,4,7-triene；trimethyl-(8-trimethylsilyl-7-bicyclo[4.2.1]nona-2,4,7-trienyl)silane
• CAS: 88061-83-0
• 化学式: C₁₅H₂₆Si₂
• 分子量: 262.542
• InChiKey: DSWXHMBQABMRSY-UHFFFAOYSA-N

物化性质

• 熔点：
  -3-0 °C
• 沸点：
  268.7±40.0 °C(Predicted)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  17
• 可旋转键数：
  2
• 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

反应信息

• 作为产物：
  描述：

  环庚三烯 、 二(三甲基甲硅烷基)乙炔 在 六羰基铬 作用下， 以 二丁醚 为溶剂， 反应 48.0h， 以65%的产率得到7,8-bis-(trimethylsilyl)bicyclo<4.2.1>nona-2,4,7-triene
  参考文献：
  名称：

  Metal-Mediated [6 + 2] Cycloadditions of Alkynes to Cycloheptatriene and N-Carbethoxyazepine

  摘要：

  UV photolysis of [(eta(6)-C(7)H(7)R)Cr(Co)(3)] (1, R = H, Ph, CH(CO(2)Me)(2)) and R'C = CR' (R' = Ph, Tol, SiMe(3), Et) in toluene or n-hexane gives the [6 + 2] cycloadducts [(eta(2:4)-C9H7(R)R'(2))Cr(CO)(3)] (2). Heating 2 in toluene releases the 7,8-disubstituted bicyclo[4.2.1]nona-2,4,7-trienes 3 and [(eta(6)-C(6)H(5)Me)Cr(CO)(3)]. Irradiation of solutions of 1 and dimethyl acetylenedicarboxylate at 0 degrees C yields the bicyclotriene as the major product but no organometallic complex. The diphenyl derivative 2a undergoes a reversible intramolecular metal migration to the eta(6)-aryl species 4. Irradiation of the azepine complex [(eta(6)-C6H6N(CO(2)Et))Cr(CO)(3)] (5) and R'C = CR' (R' = Ph, SiMe(3)) in toluene also forms [6 + 2] cycloadducts [(eta(2:4)-C8H6N(CO2Er)R'(2))Cr(CO)(3)] (6). The heterobicyclotrienes 7 are isolated from 6 by treatment with iodine (R' = SiMe(3)) or by hearing in toluene (R' = Ph). X-ray crystal structures are reported for 6b (R' = SiMe(3)) [orthorhombic, P2(1)2(1)2(1), a = 8.871(1), b = 10.148(1), and c = 26.017(4) Angstrom, R = 0.041 for 2500 independent reflections] and a byproduct (8) that results from the endo [6 + 4] cycloaddition of N-carbethoxyazepine to 5; monoclinic, P2(1)/c, a = 10.665(9), b = 14.976(7), and c = 13.004(7) Angstrom, beta = 100.05(7)degrees, R = 0.047 for 1044 independent reflections. Heating cycloheptatriene and alkynes R'C = CR' (R' = SiMe(3), Me, Et) in dibutyl ether with a catalytic amount of Cr(CO)(6) or Fe-2(CO)(9) also gives good yields of the [6 + 2] cycloadducts 3, whereas the thermal reaction with dimethyl acetylenedicarboxylate in the presence of Cr(CO)(6) gives the known norcaradiene [4 + 2] adduct 9.

  DOI：

  10.1021/ja00112a005

文献信息

• Nucleophilic addition reactions of bridged triene η⁶-chromiumtricarbonyl complexes
  作者：Rohan E. J. Beckwith、Michael B. Gravestock、Nigel S. Simpkins

  DOI：10.1039/b207708f

  日期：——

  The metal-mediated addition of a range of nucleophiles to several bridged η6-chromiumtricarbonyl complexes has been demonstrated for the first time. The reaction proceeds in regio- and stereoselective fashion and in fair to good yield. The new reaction was applied to the synthesis of an advanced intermediate towards anatoxin-a.

  首次证明了金属介导的一系列亲核物与几种桥接δ-6-铬三羰基络合物的加成反应。该反应以区域和立体选择性方式进行，收率相当高。新反应被用于合成锐毒毒素-a 的高级中间体。
• [_π6_s+_π2_s] Cycloadditions catalysed by the TiCl₄–Et₂AlCl system
  作者：Karel Mach、Helena Antropiusová、Petr Sedmera、Vladimír Hanuš、František Tureček

  DOI：10.1039/c39830000805

  日期：——

  The catalyst system TiCl4–Et2AlCl induces [π6s+π2s] cycloadditions of cycloheptatriene to buta-1,3-diene, norbornadiene, and acetylenes.

  催化剂体系TiCl4-Et2AlCl诱导环庚三烯与1,3-丁二烯、降冰片二烯和乙炔进行[α6s+α2s]环加成。
• [6+2]Cycloadditions catalyzed by titanium complexes
  作者：Karel Mach、Helena Antropiusová、Lidmila Petrusová、Vladimír Hanuš、Frantisek Tureček、Petr Sedmera

  DOI：10.1016/0040-4020(84)85014-0

  日期：1984.1

  The Ziegler catalyst TiCl4-Et2AlCl and the arenetitanium(II) complex (η6-C6H6)Ti(II)(AlCl4)2 induce [6 + 2]cycloaddition reactions of cycloheptatriene with dienes and acetylenes. Addition to 1,3-butadiene affords 7 - endo - vinyl - bicyclo[4.2.1]nona - 2,4 - diene (main product) and bicyclo[4.4.1]- undeca - 2,4,8 - triene, a product of [6+4]cycloaddition. Isoprene reacts similarly, yielding mainly

  齐格勒催化剂TiCl 4 -Et 2 AlCl和槟榔（II）配合物（η6- C6 H 6）Ti（II）（AlCl 4）2引发环庚三烯与二烯和乙炔的[6 + 2]环加成反应。除1，3-丁二烯外，得到7-内-乙烯基-双环[4.2.1]壬娜-2,4-二烯（主要产物）和双环[4.4.1]-十一烷-2,4,8-三烯，a [6 + 4]环加成的乘积。异戊二烯的反应类似，主要产生7-内-异丙烯基-双环[4.2.1]壬娜-2,4-二烯。2,3-二甲基-1,3-丁二烯生成8,9二甲基双环[4.4.1] undeca-2,4,8-三烯，是[6 + 4]环加成的产物，而[6 + 2]交叉加合物是次要产品。环庚三烯与降冰片二烯的反应主要产生六环[6.5.1.0 2,7 .0 3,12。通过[6 + 2]环加成反应生成6,10 .0 9,13 ]十四碳-4-烯，然后进行分子内Diels-Alder反应。作为副产物，五环[7
• Fischler, Ingrid; Grevels, Friedrich-Wilhelm; Leitich, Johannes, Chemische Berichte, 1991, vol. 124, # 12, p. 2857 - 2862
  作者：Fischler, Ingrid、Grevels, Friedrich-Wilhelm、Leitich, Johannes、Oezkar, Saim

  DOI：——

  日期：——
• Chaffee Karen, Huo Pei, Sheridan John B., Barbieri Anthony, Aistars Arnis+, J. Amer. Chem. Soc, 117 (1995) N 7, S 1900-1907
  作者：Chaffee Karen, Huo Pei, Sheridan John B., Barbieri Anthony, Aistars Arnis+

  DOI：——

  日期：——