5,23-Dibromo-9,10,18,19-tetraheptyl-7,12,14,16,21-pentathiaheptacyclo[13.10.0.02,13.03,11.04,8.017,25.020,24]pentacosa-1(15),2(13),3(11),4(8),5,9,17(25),18,20(24),22-decaene | 1186084-03-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻吩类
• 英文名称: 5,23-Dibromo-9,10,18,19-tetraheptyl-7,12,14,16,21-pentathiaheptacyclo[13.10.0.02,13.03,11.04,8.017,25.020,24]pentacosa-1(15),2(13),3(11),4(8),5,9,17(25),18,20(24),22-decaene
• CAS: 1186084-03-6
• 化学式: C₄₈H₆₂Br₂S₅
• 分子量: 959.158
• InChiKey: UXHQLHXMSXZUGX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  24.4
• 重原子数：
  55
• 可旋转键数：
  24
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  141
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5,23-Dibromo-9,10,18,19-tetraheptyl-7,12,14,16,21-pentathiaheptacyclo[13.10.0.02,13.03,11.04,8.017,25.020,24]pentacosa-1(15),2(13),3(11),4(8),5,9,17(25),18,20(24),22-decaene 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以93%的产率得到9,10,18,19-Tetraheptyl-7,12,14,16,21-pentathiaoctacyclo[13.10.0.02,13.03,11.04,8.05,23.017,25.020,24]pentacosa-1(15),2(13),3(11),4(8),5,9,17(25),18,20(24),22-decaene
  参考文献：
  名称：

  Intramolecular Cyclization of Thiophene-Based [7]Helicenes to Quasi-[8]Circulenes

  摘要：

  Intramolecular cyclization in a series of thiophene-based dibromo[7]helicenes (4-6) with different helix Structures is investigated by vacuum pyrolysis, tin- and palladium-mediated C-C bond forming reactions. The product With the cyclic structure of the annelated aromatic rings, which resembles [S]circulene devoid of an atom linkage, is referred to as quasi-[8]circulene. Vacuum pyrolysis of 4 gives insoluble, unidentified products, while 5 and 6 yield the corresponding quasi-[8]circulenes Under similar conditions. Thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses for 4 indicate complex reaction pathways, while those for 5 and 6 show a single process corresponding to a loss of 1 equiv of Br-2 at about 330 degrees C. Pd-mediated reductive cyclization provides quasi-[8]circulenes for all three [7]helicenes, though only 4 gives a good isolated yield. Tributyltin hydride-mediated radical cyclization of 4-6 provides quasi-[8]circulenes In excellent yields, and it is practically insensitive to the helix Structure. Experimental and calculated UV-vis absorption spectra for quasi-[8]circulenes and [8]circulenes are reported. The results suggest that the lack of atom linkage in quasi-[8]circulene does not significantly affect properties and conformation, compared to those for the corresponding [8]circulenes.

  DOI：

  10.1021/jo902030u
• 作为产物：
  描述：

  (5,23-Dibromo-9,10,18,19-tetraheptyl-22-trimethylsilyl-7,12,14,16,21-pentathiaheptacyclo[13.10.0.02,13.03,11.04,8.017,25.020,24]pentacosa-1(15),2(13),3(11),4(8),5,9,17(25),18,20(24),22-decaen-6-yl)-trimethylsilane 在 四丁基氟化铵 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 0.13h， 以85%的产率得到5,23-Dibromo-9,10,18,19-tetraheptyl-7,12,14,16,21-pentathiaheptacyclo[13.10.0.02,13.03,11.04,8.017,25.020,24]pentacosa-1(15),2(13),3(11),4(8),5,9,17(25),18,20(24),22-decaene
  参考文献：
  名称：

  Functionalized Thiophene-Based [7]Helicene: Chirooptical Properties versus Electron Delocalization

  摘要：

  The functionalized, enantiomerically pure [7]helicene 1 derived from bis(benzodithiophene) functionalized with four heptyl groups is prepared from 1,8-dibromo-4,5-diheptylbenzo[1,2-b:4,3-b']dithiophene building block 2. Such [7]helicene structure, functionalized with bromines at the terminal positions of the helicene inner rim and multiple solubilizing alkyl groups, is an attractive building block for long [n]helicenes and oligo[7]helicenes. Chirooptical properties and the degree of electron delocalization are determined and compared to those of analogous carbon-sulfur [7]helicene and [7]helicenes derived from benzodithiophene to provide a correlation between chirooptical properties and the degree of electron delocalization. [7]Helicene 1 possesses a moderately increased electron delocalization, but its chirooptical properties are similar to those for analogous [7]helicenes with relatively lower electron delocalization, indicating that chirooptical properties are not significantly affected by electron delocalization for this series of [7]helicenes. Molecular structures of racemic [7]helicene 1 and its benzodithiophene building block 2 are confirmed by single-crystal X-ray analysis. Crystals of 2 are chiral and adopt the shape of long, flexible, flat needles that can be readily bent.

  DOI：

  10.1021/jo901769c

文献信息

• Functionalized Thiophene-Based [7]Helicene: Chirooptical Properties versus Electron Delocalization
  作者：Andrzej Rajca、Maren Pink、Shuzhang Xiao、Makoto Miyasaka、Suchada Rajca、Kausik Das、Kristin Plessel

  DOI：10.1021/jo901769c

  日期：2009.10.2

  The functionalized, enantiomerically pure [7]helicene 1 derived from bis(benzodithiophene) functionalized with four heptyl groups is prepared from 1,8-dibromo-4,5-diheptylbenzo[1,2-b:4,3-b']dithiophene building block 2. Such [7]helicene structure, functionalized with bromines at the terminal positions of the helicene inner rim and multiple solubilizing alkyl groups, is an attractive building block for long [n]helicenes and oligo[7]helicenes. Chirooptical properties and the degree of electron delocalization are determined and compared to those of analogous carbon-sulfur [7]helicene and [7]helicenes derived from benzodithiophene to provide a correlation between chirooptical properties and the degree of electron delocalization. [7]Helicene 1 possesses a moderately increased electron delocalization, but its chirooptical properties are similar to those for analogous [7]helicenes with relatively lower electron delocalization, indicating that chirooptical properties are not significantly affected by electron delocalization for this series of [7]helicenes. Molecular structures of racemic [7]helicene 1 and its benzodithiophene building block 2 are confirmed by single-crystal X-ray analysis. Crystals of 2 are chiral and adopt the shape of long, flexible, flat needles that can be readily bent.
• Intramolecular Cyclization of Thiophene-Based [7]Helicenes to Quasi-[8]Circulenes
  作者：Andrzej Rajca、Makoto Miyasaka、Shuzhang Xiao、Przemysław J. Boratyński、Maren Pink、Suchada Rajca

  DOI：10.1021/jo902030u

  日期：2009.12.4

  Intramolecular cyclization in a series of thiophene-based dibromo[7]helicenes (4-6) with different helix Structures is investigated by vacuum pyrolysis, tin- and palladium-mediated C-C bond forming reactions. The product With the cyclic structure of the annelated aromatic rings, which resembles [S]circulene devoid of an atom linkage, is referred to as quasi-[8]circulene. Vacuum pyrolysis of 4 gives insoluble, unidentified products, while 5 and 6 yield the corresponding quasi-[8]circulenes Under similar conditions. Thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses for 4 indicate complex reaction pathways, while those for 5 and 6 show a single process corresponding to a loss of 1 equiv of Br-2 at about 330 degrees C. Pd-mediated reductive cyclization provides quasi-[8]circulenes for all three [7]helicenes, though only 4 gives a good isolated yield. Tributyltin hydride-mediated radical cyclization of 4-6 provides quasi-[8]circulenes In excellent yields, and it is practically insensitive to the helix Structure. Experimental and calculated UV-vis absorption spectra for quasi-[8]circulenes and [8]circulenes are reported. The results suggest that the lack of atom linkage in quasi-[8]circulene does not significantly affect properties and conformation, compared to those for the corresponding [8]circulenes.