<5>Helicene-5,6,9,10-tetracarboxylic 5,6:9,10-dianhydride | 163271-52-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: <5>Helicene-5,6,9,10-tetracarboxylic 5,6:9,10-dianhydride
• 英文别名: Dibenzanthracene-5,6,12,13-tetracarboxylic 5,6:12,13-dianhydride；11,20-Dioxaheptacyclo[15.11.0.02,14.03,8.09,13.018,22.023,28]octacosa-1(17),2(14),3,5,7,9(13),15,18(22),23,25,27-undecaene-10,12,19,21-tetrone
• CAS: 163271-52-1
• 化学式: C₂₆H₁₀O₆
• 分子量: 418.362
• InChiKey: ISBRSZJFMAFCNB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  32
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  甲醇 、 <5>Helicene-5,6,9,10-tetracarboxylic 5,6:9,10-dianhydride 反应 168.0h， 生成 10-Methoxycarbonyl-16,18-dioxo-17-oxahexacyclo[12.11.0.02,11.03,8.015,19.020,25]pentacosa-1(14),2(11),3,5,7,9,12,15(19),20,22,24-undecaene-9-carboxylic acid 、 10,16-Bis(methoxycarbonyl)pentacyclo[12.8.0.02,11.03,8.017,22]docosa-1(14),2(11),3,5,7,9,12,15,17,19,21-undecaene-9,15-dicarboxylic acid 、 、
  参考文献：
  名称：

  Reinvestigation of the Photocyclization of 1,4-Phenylenebis[phenylmaleic anhydride]: Preparation and Structure of [5]Helicene 5,6:9,10-Dianhydride

  摘要：

  The I-2-catalyzed photooxidative cyclization of 1,4-phenylene bis(phenylmaleic anhydride) [PPMA] yields two products in an overall yield approaching 80%. Contrary to a previous report, the major product has been identified by X-ray crystallography as the novel [5]helicene-5,6,9,10-tetracarboxylic 5,6:9,10-dianhydride [HLDA], while the minor product (<5% yield) is the isomeric dibenz[ah]anthracene-5,6,12,13-tetracarboxylic 5,6:12,13-dianhydride [DBAA]. Partial irradiation permits the isolation of the monocyclization intermediate PMPA, which under the photolysis conditions generates the observed dicyclization products. Unlike HLDA, DBAA resists prolonged methanolysis to the corresponding acid esters. This confirms molecular modeling predictions that the 1,6-interaction between the H-4, H-7, H-11, and H-14 aromatic hydrogens and the corresponding neighboring carbonyl oxygens in DBAA inhibit opening of the resulting O-CO anhydride bond. Noteworthy as well is that HLDA, unlike the parent [5]helicene, resists further photocyclization under the reaction conditions to the:corresponding benzo[ghi]perylene. AM1 semiempirical calculations indicate that, contrary to [5]helicene, there is no buildup of bonding interaction between the designated bonding carbons (C-1 and C-14) as one goes from the HOMO to the corresponding LUMO.

  DOI：

  10.1021/jo00111a026
• 作为产物：
  描述：

  1,4-Phenylene bis(phenylmaleic anhydride) 在 碘 、 氧气 作用下， 以 丙酮 为溶剂， 反应 16.0h， 以26%的产率得到<5>Helicene-5,6,9,10-tetracarboxylic 5,6:9,10-dianhydride
  参考文献：
  名称：

  Diaryl-substituted maleic anhydrides

  摘要：

  DOI：

  10.1021/jo00304a034

文献信息

• Syntheses of polycyclic aromatic diimides via intramolecular cyclization of maleic acid derivatives
  作者：Ranran Wang、Ke Shi、Kang Cai、Yikun Guo、Xiao Yang、Jie-Yu Wang、Jian Pei、Dahui Zhao

  DOI：10.1039/c5nj01849h

  日期：——

  series of polycyclic aromatic molecules bearing two phthalimide functional groups are synthesized via Perkin condensation followed by intramolecular cyclization reactions. Two different cyclization methods, photo-oxidation and Heck cross-coupling, are employed, both of which effectively accomplish the transformations from diaryl maleic anhydride or maleimide to polycyclic aromatic phthalimide functionality

  使用现成的芳基乙醛酸和亚芳基二乙酸作为原料，通过以下方法合成一系列带有两个邻苯二甲酰亚胺官能团的多环芳族分子珀金缩合，然后进行分子内环化反应。使用了两种不同的环化方法，即光氧化法和Heck交叉偶联法，两者均有效地完成了从二芳基马来酸酐或马来酰亚胺到多环芳族邻苯二甲酰亚胺官能团的转化。通过光环化方案，可以方便地将由马来酸酐基团连接的两个简单的芳族CH杂位进行直接桥连，并唯一地产生更多扭曲的多环骨架作为主要产物，而Heck偶联方法通常可以提供更多扩展的多环骨架。然后使用劳氏试剂对所得的多环二酰亚胺分子进行亚硫酰化反应。对于所有分离的稳定产物，都会发生部分硫磺化。制备的多环二酰亚胺化合物的LUMO含量相对较低，硫代化进一步降低了分子的LUMO能量0.2-0.3 eV。通过使用溶液处理的OFET器件来表征电子传输性能，电子迁移率为0.054 cm通过选择的化合物证明2 V -1 s -1。这种半导
• Diaryl-substituted maleic anhydrides
  作者：Ellis K. Fields、S. J. Behrend、S. Meyerson、M. L. Winzenburg、B. R. Ortega、H. K. Hall

  DOI：10.1021/jo00304a034

  日期：1990.8
• Reinvestigation of the Photocyclization of 1,4-Phenylenebis[phenylmaleic anhydride]: Preparation and Structure of [5]Helicene 5,6:9,10-Dianhydride
  作者：Aryeh A. Frimer、James D. Kinder、Wiley J. Youngs、Mary Ann B. Meador

  DOI：10.1021/jo00111a026

  日期：1995.3

  The I-2-catalyzed photooxidative cyclization of 1,4-phenylene bis(phenylmaleic anhydride) [PPMA] yields two products in an overall yield approaching 80%. Contrary to a previous report, the major product has been identified by X-ray crystallography as the novel [5]helicene-5,6,9,10-tetracarboxylic 5,6:9,10-dianhydride [HLDA], while the minor product (<5% yield) is the isomeric dibenz[ah]anthracene-5,6,12,13-tetracarboxylic 5,6:12,13-dianhydride [DBAA]. Partial irradiation permits the isolation of the monocyclization intermediate PMPA, which under the photolysis conditions generates the observed dicyclization products. Unlike HLDA, DBAA resists prolonged methanolysis to the corresponding acid esters. This confirms molecular modeling predictions that the 1,6-interaction between the H-4, H-7, H-11, and H-14 aromatic hydrogens and the corresponding neighboring carbonyl oxygens in DBAA inhibit opening of the resulting O-CO anhydride bond. Noteworthy as well is that HLDA, unlike the parent [5]helicene, resists further photocyclization under the reaction conditions to the:corresponding benzo[ghi]perylene. AM1 semiempirical calculations indicate that, contrary to [5]helicene, there is no buildup of bonding interaction between the designated bonding carbons (C-1 and C-14) as one goes from the HOMO to the corresponding LUMO.