5,21-Dibromo-7,9,11,13,15,17,19-heptathiaheptacyclo[12.9.0.02,12.03,10.04,8.016,23.018,22]tricosa-1(14),2(12),3(10),4(8),5,16(23),18(22),20-octaene | 798570-58-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩并噻吩类
• 英文名称: 5,21-Dibromo-7,9,11,13,15,17,19-heptathiaheptacyclo[12.9.0.02,12.03,10.04,8.016,23.018,22]tricosa-1(14),2(12),3(10),4(8),5,16(23),18(22),20-octaene
• 英文别名: 5,21-dibromo-7,9,11,13,15,17,19-heptathiaheptacyclo[12.9.0.02,12.03,10.04,8.016,23.018,22]tricosa-1(14),2(12),3(10),4(8),5,16(23),18(22),20-octaene
• CAS: 798570-58-8
• 化学式: C₁₆H₂Br₂S₇
• 分子量: 578.462
• InChiKey: SDDWOFBJHVDWQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.1
• 重原子数：
  25
• 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：
  198
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5,21-Dibromo-7,9,11,13,15,17,19-heptathiaheptacyclo[12.9.0.02,12.03,10.04,8.016,23.018,22]tricosa-1(14),2(12),3(10),4(8),5,16(23),18(22),20-octaene 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以81%的产率得到quasi[8]circulene
  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：

  (5,21-dibromo-20-trimethylsilyl-7,9,11,13,15,17,19-heptathiaheptacyclo[12.9.0.02,12.03,10.04,8.016,23.018,22]tricosa-1(14),2(12),3(10),4(8),5,16(23),18(22),20-octaen-6-yl)-trimethylsilane 在 三氟乙酸 、 lithium diisopropyl amide 作用下， 以 乙醚 、 正己烷 、 氯仿 、 氘代苯 为溶剂， 反应 1.0h， 生成 5,21-Dibromo-7,9,11,13,15,17,19-heptathiaheptacyclo[12.9.0.02,12.03,10.04,8.016,23.018,22]tricosa-1(14),2(12),3(10),4(8),5,16(23),18(22),20-octaene
  参考文献：
  名称：

  螺旋退火和交叉共轭低聚噻吩：碳-硫 [7] 螺旋的不对称合成、拆分和表征

  摘要：

  描述了一种新型低聚噻吩的合成和表征，其中噻吩环退火成具有交叉共轭 pi 系统的 [7] 螺旋。这种 [7] 螺旋可以被视为前所未有的碳硫 (C(2)S)(n)() 螺旋的碎片，拥有富含硫的分子外围。[7] helicene 的外消旋合成基于两个步骤的迭代交替：噻吩的 β 位之间的 CC 键同源偶联和噻吩的 α 位之间的退火。使用 (-)-sparteine 介导的轴向手性双（芳基锂）与亲电子硫等价物的退火进行不对称合成。或者，[7]螺旋烯的对映异构体通过使用基于薄荷醇的手性硅氧烷拆分获得。外消旋 [7] helicene 和退火的其他四种大环产物通过 X 射线晶体学表征。[7] helicene 的一种溶剂多晶型物具有相反对映异构体的 pi 堆积柱和多个短分子间接触，包括同手性和异手性短 S...S 接触，表明在二维中存在有效的分子间电子耦合。[7]螺旋烯在室温下构型稳定，在 199 摄氏度时外消旋，半衰期约为

  DOI：

  10.1021/ja0462530

文献信息

• Helically Annelated and Cross-Conjugated Oligothiophenes:  Asymmetric Synthesis, Resolution, and Characterization of a Carbon−Sulfur [7]Helicene
  作者：Andrzej Rajca、Makoto Miyasaka、Maren Pink、Hua Wang、Suchada Rajca

  DOI：10.1021/ja0462530

  日期：2004.11.1

  alpha-positions of thiophenes. Asymmetric synthesis is carried out using (-)-sparteine-mediated annelation of the axially chiral bis(aryllithium) with electrophilic sulfur equivalent. Alternatively, enantiomers of the [7]helicene are obtained via resolution using menthol-based chiral siloxanes. Racemic [7]helicene and four other macrocyclic products of the annelation are characterized by X-ray crystallography

  描述了一种新型低聚噻吩的合成和表征，其中噻吩环退火成具有交叉共轭 pi 系统的 [7] 螺旋。这种 [7] 螺旋可以被视为前所未有的碳硫 (C(2)S)(n)() 螺旋的碎片，拥有富含硫的分子外围。[7] helicene 的外消旋合成基于两个步骤的迭代交替：噻吩的 β 位之间的 CC 键同源偶联和噻吩的 α 位之间的退火。使用 (-)-sparteine 介导的轴向手性双（芳基锂）与亲电子硫等价物的退火进行不对称合成。或者，[7]螺旋烯的对映异构体通过使用基于薄荷醇的手性硅氧烷拆分获得。外消旋 [7] helicene 和退火的其他四种大环产物通过 X 射线晶体学表征。[7] helicene 的一种溶剂多晶型物具有相反对映异构体的 pi 堆积柱和多个短分子间接触，包括同手性和异手性短 S...S 接触，表明在二维中存在有效的分子间电子耦合。[7]螺旋烯在室温下构型稳定，在 199 摄氏度时外消旋，半衰期约为
• 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.