dimethyl 4b,8b-dimethyl-4b,8b,8c,8d-tetrahydrodibenzocyclopropapentalene-8c,8d-dicarboxylate | 125903-01-7

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基四氢萘木脂素
• 英文名称: dimethyl 4b,8b-dimethyl-4b,8b,8c,8d-tetrahydrodibenzocyclopropapentalene-8c,8d-dicarboxylate
• 英文别名: 5,10,11-Methenodibenzo[a,d]cycloheptadiene,5,10-dimethyl-11,12-di(methoxycarbonyl)-；dimethyl 9,16-dimethylpentacyclo[7.7.0.02,16.03,8.010,15]hexadeca-3,5,7,10,12,14-hexaene-1,2-dicarboxylate
• CAS: 125903-01-7
• 化学式: C₂₂H₂₀O₄
• 分子量: 348.398
• InChiKey: QSSBDULZZHZPDX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  9,10-二甲基蒽 以 丙酮 为溶剂， 反应 1.42h， 生成 dimethyl 4b,8b-dimethyl-4b,8b,8c,8d-tetrahydrodibenzocyclopropapentalene-8c,8d-dicarboxylate
  参考文献：
  名称：

  Crystal structure correlations in the photochemistry of dimethyl 9,10-dimethyl-9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylate

  摘要：

  The photochemistry of the title 9,10-dimethlydi-benzobarrelene-11,12-diester (1) in solution and in the solid state exhibits unique differences as a function of reaction medium. In acetone the normal di-pi-methane reaction leads to a semibull-valene derivative, dimethyl 4b,8b-dimethy-4b,8b,8c,-8d-tetrahydrodibenzo[a,f]cyclopropa[calpentalene-gc,8d-dicarboxylate (2), while in acetonitrile an additional cyclooctatetraene (COT) photoproduct, dimethyl 5,11-dimethyldibenzo[a,e]cyclooctene-6,12-dicarboxylate (3), is obtained. In the solid state a new pentalene, dimethyl 5, 10-dimethyl-5, 10-dihydro-indeno[2,1-a]indene-5,10-dicarboxylate (4), is formed as the major product. Crystal data for (1), (3) and (4): T = 294 K, Cu Kalpha, lambda = 1.5418 angstrom, C22H20O4, M(r) = 348.40; (1), triclinic, P1BAR, a = 8.695 (1), b = 13.633 (1), c = 8.273 (1) angstrom, a = 98.51 (1), beta = 113.34(1), gamma = 80.97(1)-degrees, V = 885.2(1) angstrom3, Z = 2, D(x) = 1.307 g cm -3, mu = 6.9 cm -1, F(000) = 368, R = 0.057 for 3046 reflections; (3), monoclinic, P2(1)/n, a = 9.124 (2), b = 14.392 (2), c = 14.328 (1) angstrom, beta = 94.30 (1)-degrees, V = 1876.1 (5) angstrom3, Z = 4, D(x) = 1.233 g cm-3, mu = 6.5 cm-1, F(000) = 736, R = 0.048 for 2289 reflections; (4), monoclinic, I2/a, a = 19.020 (6), b = 11.963 (1), c = 17.083 (4) angstrom, beta = 105.15 (1)-degrees, V = 3752 (2) angstrom3, Z = 8 (two independent half-molecules per asymmetric unit), D(x) = 1.233 g cm-3, mu = 6.5 cm-1, F(000) = 1472, R = 0.072 for 1574 reflections. The structure of the solid-state photoproduct (4) provides an important clue in deriving a mechanism for its formation, involving a biradical intermediate with a pentalene-like skeleton. This mechanism also accounts for the formation of COT (3), whose structure is not that expected on the basis of previous mechanistic studies.

  DOI：

  10.1107/s0108768192006682

文献信息

• Novel photorearrangements of bridgehead-substituted dibenzobarrelene derivatives in solution and the solid state
  作者：Phani Raj Pokkuluri、John R. Scheffer、James Trotter

  DOI：10.1021/ja00165a072

  日期：1990.4
• Crystal structure correlations in the photochemistry of dimethyl 9,10-dimethyl-9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylate
  作者：P. R. Pokkuluri、J. R. Scheffer、J. Trotter

  DOI：10.1107/s0108768192006682

  日期：1993.2.1

  The photochemistry of the title 9,10-dimethlydi-benzobarrelene-11,12-diester (1) in solution and in the solid state exhibits unique differences as a function of reaction medium. In acetone the normal di-pi-methane reaction leads to a semibull-valene derivative, dimethyl 4b,8b-dimethy-4b,8b,8c,-8d-tetrahydrodibenzo[a,f]cyclopropa[calpentalene-gc,8d-dicarboxylate (2), while in acetonitrile an additional cyclooctatetraene (COT) photoproduct, dimethyl 5,11-dimethyldibenzo[a,e]cyclooctene-6,12-dicarboxylate (3), is obtained. In the solid state a new pentalene, dimethyl 5, 10-dimethyl-5, 10-dihydro-indeno[2,1-a]indene-5,10-dicarboxylate (4), is formed as the major product. Crystal data for (1), (3) and (4): T = 294 K, Cu Kalpha, lambda = 1.5418 angstrom, C22H20O4, M(r) = 348.40; (1), triclinic, P1BAR, a = 8.695 (1), b = 13.633 (1), c = 8.273 (1) angstrom, a = 98.51 (1), beta = 113.34(1), gamma = 80.97(1)-degrees, V = 885.2(1) angstrom3, Z = 2, D(x) = 1.307 g cm -3, mu = 6.9 cm -1, F(000) = 368, R = 0.057 for 3046 reflections; (3), monoclinic, P2(1)/n, a = 9.124 (2), b = 14.392 (2), c = 14.328 (1) angstrom, beta = 94.30 (1)-degrees, V = 1876.1 (5) angstrom3, Z = 4, D(x) = 1.233 g cm-3, mu = 6.5 cm-1, F(000) = 736, R = 0.048 for 2289 reflections; (4), monoclinic, I2/a, a = 19.020 (6), b = 11.963 (1), c = 17.083 (4) angstrom, beta = 105.15 (1)-degrees, V = 3752 (2) angstrom3, Z = 8 (two independent half-molecules per asymmetric unit), D(x) = 1.233 g cm-3, mu = 6.5 cm-1, F(000) = 1472, R = 0.072 for 1574 reflections. The structure of the solid-state photoproduct (4) provides an important clue in deriving a mechanism for its formation, involving a biradical intermediate with a pentalene-like skeleton. This mechanism also accounts for the formation of COT (3), whose structure is not that expected on the basis of previous mechanistic studies.