7,8-diphenylbicyclo<4.2.1>nona-2,4,7-triene | 54049-09-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 7,8-diphenylbicyclo<4.2.1>nona-2,4,7-triene
• 英文别名: 7,8-diphenyl-bicyclo[4.2.1]nona-2,4,7-triene；7,8-diphenylbicyclo[4.2.1]nona-2,4,7-triene；7,8-diphenylbicyclo{4.2.1}nona-2,4,7-triene；7,8-diphenyl-bicyclo(4.2.1)nona-2,4,7-triene
• CAS: 54049-09-1
• 化学式: C₂₁H₁₈
• 分子量: 270.374
• InChiKey: ABYAFVJYPMKGFI-UHFFFAOYSA-N

物化性质

• 熔点：
  53-55 °C
• 沸点：
  396.7±42.0 °C(Predicted)
• 密度：
  1.103±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  alkaline earth salt of/the/ methylsulfuric acid 以 甲苯 为溶剂， 反应 0.08h， 以29%的产率得到7,8-diphenylbicyclo<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

• [_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
• Cobalt-Catalysed [6+2] Cycloaddition of Internal Alkynes and Terminal ­Alkenes with Cycloheptatriene
  作者：Gerhard Hilt、Anna Paul、Christoph Hengst

  DOI：10.1055/s-0029-1216900

  日期：2009.10

  cobalt-catalysed [6+2] cycloaddition of cycloheptatriene with internal alkynes as well as with terminal alkenes is described. The cycloaddition process is most efficiently catalysed by cobalt dibromide[bis(triisopropylphosphite)] complexes in dichloromethane as the solvent of choice. In the cobalt-catalysed reaction of cycloheptatriene with norbornene an unexpected tricyclic [2+2] cycloaddition product was

  描述了钴与内部炔烃以及末端烯烃的环庚三烯的[6 + 2]环加成反应。环加成过程最有效地是由二氯甲烷中的二溴化钴[双（亚磷酸三异丙酯）]络合物作为选择的溶剂来催化的。在钴催化的环庚三烯与降冰片烯的反应中，分离出出乎意料的三环[2 + 2]环加成产物，收率很高。 炔烃-烯烃-钴-环加成反应-二烯
• Rhodium-Catalyzed [6 + 2] Cycloaddition of Internal Alkynes with Cycloheptatriene: Catalytic Study and DFT Calculations of the Reaction Mechanism
  作者：Xinrui Zhang、Jingjing Wang、Hui Zhao、Haitao Zhao、Jianhui Wang

  DOI：10.1021/om4003736

  日期：2013.6.24

  A rhodium-catalyzed [6 + 2] cycloaddition of internal alkynes with cycloheptatriene is described. A series of substituted alkynes were cycloadded to cycloheptatriene through a [6 + 2] addition to give a variety of substituted bicyclic compounds in excellent yields. The optimal catalytic system for these transformations was a [Rh(COD)Cl]2 (5.0 mol %) catalyst in combination with CuI (10 mol %) and PPh3

  描述了铑催化的内部炔烃与环庚三烯的[6 + 2]环加成反应。通过[6 + 2]加成反应将一系列取代的炔烃环加到环庚三烯中，从而以优异的收率得到各种取代的双环化合物。这些转化的最佳催化体系是[Rh（COD）Cl] 2（5.0 mol％）催化剂与CuI（10 mol％）和PPh 3的组合（10摩尔％）。该系统的拟议机理包括配位环庚三烯与内部炔烃之间的初始氧化偶联反应，然后Rh金属中心发生[1,3]位移，并从Rh（III）-烯丙基络合物还原为给出最终产品。还使用模型Rh（I）催化剂进行了计算，以进一步了解该机理。
• [2.pi. + 6.pi.] Cycloaddition reactions between ligands coordinated to an iron atom
  作者：Raymond E. Davis、Tom A. Dodds、T. H. Hseu、J. C. Wagnon、T. Devon、J. Tancrede、J. S. McKennis、R. Pettit

  DOI：10.1021/ja00831a034

  日期：1974.11

  Die Bestrahlung von THF-Losungen des Komplexes (II) und Acetylendicarbonsaureeste " in aquimolaren Mengen bei 0°C liefert die Verbindung (I), deren Kristallstruktur bestimmt wurde.

  Die Bestrahlung von THF-Losungen des Komplexes (II) 和 Acetylendicarbonsaureeste " in aquimolaren Mengen bei 0°C liefert die Verbindung (I), deren Kristallstruktur bestimmt wurde。