7,8-bis(4-methylphenyl)bicyclo<4.2.1>nona-2,4,7-triene | 138054-67-8

• 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-bis(4-methylphenyl)bicyclo<4.2.1>nona-2,4,7-triene
• 英文别名: 7,8-Bis(4-methylphenyl)bicyclo[4.2.1]nona-2,4,7-triene
• CAS: 138054-67-8
• 化学式: C₂₃H₂₂
• 分子量: 298.428
• InChiKey: QNPCHSGWGJTGIY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 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38%的产率得到7,8-bis(4-methylphenyl)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

• Photoinduced [6 + 2] cycloadditions of alkynes to tricarbonylcycloheptatrienechromium(0)
  作者：Karen Chaffee、John B. Sheridan、Arnis Aistars

  DOI：10.1021/om00037a010

  日期：1992.1

  Photolysis of [(eta(6)-C7H8)Cr(CO)3] (1) and RC = CR (2a, R = Ph; 2b, R = Tol) in toluene or n-hexane results in the formation of [(eta(2): eta(4)-C9H8R2)Cr(CO)3] (3a,b) in 70-85% isolated yield via a [6 + 2] cycloaddition reaction. Heating 3a,b in toluene gives the bicyclo [4.2.1]-nona-2,4,7-trienes 4a,b and [(eta-C6H6Me)Cr(CO)3]. Photolysis of 1 and excess DMAD (dimethyl acetylenedicarboxylate, 5) in toluene at 0-degrees-C yields the bicyclotriene 4c as the major product and small amounts of the arene C6(CO2Me)6 and the [4 + 2] cycloadduct between 4c and 5.
• Metal-Mediated [6 + 2] Cycloadditions of Alkynes to Cycloheptatriene and N-Carbethoxyazepine
  作者：Karen Chaffee、Pei Huo、John B. Sheridan、Anthony Barbieri、Arnis Aistars、Roger A. Lalancette、Robert L. Ostrander、Arnold L. Rheingold

  DOI：10.1021/ja00112a005

  日期：1995.2

  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.