Pyrrolo[3,4-e][2,1,3]benzothiadiazole | 155656-89-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻二唑类
• 英文名称: Pyrrolo[3,4-e][2,1,3]benzothiadiazole
• 英文别名: thiadiazolobenzo<3,4-c>pyrrole
• CAS: 155656-89-6
• 化学式: C₈H₅N₃S
• 分子量: 175.214
• InChiKey: GDEGMBYJRUNSBU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.17
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  41.57
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  Pyrrolo[3,4-e][2,1,3]benzothiadiazole 在 溶剂黄146 作用下， 以 乙醇 为溶剂， 生成 7,18-bis-(2-methoxycarbonylethyl)-8,17-dimethylthiadiazolobenzo<3,4-b>phenanthro<9,10-l>porphyrin
  参考文献：
  名称：

  Porphyrins with Exocyclic Rings. 13.¹ Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings

  摘要：

  As part of a survey on the influence of fused aromatic rings on the porphyrin chromophore, a series of novel structures with fused acenaphthylene or benzothiadiazole rings have been synthesized. Base-catalyzed condensation of 1-nitroacenaphthylene or 4-nitrobenzothiadiazole with esters of isocyanoacetic acid afforded good yields of the annelated pyrroles 5 and 28. Cleavage of the ester moieties with KOH in refluxing ethylene glycol gave the unsubstituted heterocycles, and subsequent condensation with 2 equiv of acetoxymethylpyrroles 9 in acetic acid/ethanol produced the modified tripyrranes 12 and 31. Tripyrranes with terminal tert-butyl ester units were treated with TFA and condensed with 3,4-diethyl-2,5-pyrroledicarboxaldehyde 13 in dichloromethane to give, following oxidation with DDQ, the corresponding pi-extended porphyrins 14 and 32. Acenaphthoporphyrins 14 showed unique UV-vis spectra with a triply split Soret band region and a relatively strong band near 660 nm. Strongly red-shifted absorptions were also noted for the dications and the nickel(II), copper(II), and zinc chelates for this system. Thiadiazoloporphyrins 32 gave two broadened Soret bands, but the Q-band region was unexceptional. However, the nickel(II), copper(II), and zinc complexes all showed abnormally strong absorptions between 600 and 612 nm. Porphyrins with two antipodal fused aromatic rings were easily prepared by condensing c-annelated pyrroledialdehydes 17 with tripyrranes 12 and 31, and the spectroscopic properties of the resulting porphyrins showed that the observed ring-fusion effects were essentially additive. Porphyrins with two adjacent acenaphthylene rings were also prepared by the MacDonald "2 + 2" condensation, although this chemistrry gave poor results in the synthesis of a porphyrin with two fused benzothiadiazole rings. The spectroscopic properties of these new highly conjugated porphyrin structures show that ring fusion can profoundly modify the porphyrin chromophore.

  DOI：

  10.1021/jo9815655
• 作为产物：
  描述：

  2,1,3-苯并噻二唑 在 氢氧化钾 、 硫酸 、 硝酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 乙二醇 、 甲苯 为溶剂， 反应 7.0h， 生成 Pyrrolo[3,4-e][2,1,3]benzothiadiazole
  参考文献：
  名称：

  Synthesis and coplanarity-dependent HOMO–LUMO separation of π-conjugated dimers

  摘要：

  通过应用钯催化的铃木偶联反应，制备了包含吡咯并[3,4-e][2,1,3]苯并噻二唑单元的三系列二聚体。通过电子吸收光谱和循环伏安法评估了HOMO-LUMO能级间隔对共平面性的依赖性。吡咯二聚体5c因其固有的平面结构展现出狭窄的HOMO-LUMO能级间隔，这一点已通过1H NMR得到证实。

  DOI：

  10.1039/b003211p

文献信息

• Synthesis of novel porphyrin chromophores from nitroarenes: Further applications of the Barton-Zard pyrrole condensation
  作者：Timothy D. Lash、Chaminda Wijesinghe、Augustine T. Osuma、Jyoti R. Patel

  DOI：10.1016/s0040-4039(97)00287-6

  日期：1997.3

  Porphyrins with fused nitronaphthalene and benzothiadiazole subunits have been synthesized by the “2 + 2” and “3 + 1” methodologies; the key pyrrolic intermediates were prepared by the base catalyzed condensation of dinitronaphthalenes or 4-nitro-2,1,3-benzothiadiazole with isocyanoacetates.

  带有稠合的硝基萘和苯并噻二唑亚基的卟啉已通过“ 2 + 2”和“ 3 +1”方法合成。关键的吡咯中间体是通过二硝基萘或4-硝基-2,1,3-苯并噻二唑与异氰基乙酸酯的碱催化缩合制备的。
• Synthesis of pyrroles annulated with polycyclic aromatic compounds; precursor molecules for low band gap polymers
  作者：Noboru Ono、Hideo Hironaga、Kazuhiro Simizu、Kazuo Ono、Kayoko Kuwano、Takuji Ogawa

  DOI：10.1039/c39940001019

  日期：——

  Pyrroles annulated with polycyclic aromatic compounds, which are expected to be good precursor molecules for low band gap polymers, are prepared by the reaction of aromatic nitro compounds with ethyl isocyanoacetate and the subsequent deethoxycarbonylation.

  通过芳族硝基化合物与异氰基乙酸乙酯反应，然后进行脱乙氧基羰基化反应，可以制备与多环芳族化合物环合的吡咯，这些环对于低带隙聚合物而言是很好的前体分子。
• Synthesis and coplanarity-dependent HOMO–LUMO separation of π-conjugated dimers
  作者：Takashi Murashima、Daiki Shiga、Keiji Nishi、Hidemitsu Uno、Noboru Ono

  DOI：10.1039/b003211p

  日期：——

  Three series of dimers containing pyrrolo[3,4-e][2,1,3]benzothiadiazole units have been prepared by application of the Pd-catalyzed Suzuki coupling. The dependence of the HOMO–LUMO separation on coplanarity has been evaluated by means of electronic absorption spectra and cyclic voltammetry. The pyrrole dimer 5c shows a narrow HOMO–LUMO separation owing to its intrinsically planar structure, as confirmed by 1H NMR.

  通过应用钯催化的铃木偶联反应，制备了包含吡咯并[3,4-e][2,1,3]苯并噻二唑单元的三系列二聚体。通过电子吸收光谱和循环伏安法评估了HOMO-LUMO能级间隔对共平面性的依赖性。吡咯二聚体5c因其固有的平面结构展现出狭窄的HOMO-LUMO能级间隔，这一点已通过1H NMR得到证实。
• Porphyrins with Exocyclic Rings. 13.¹ Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings
  作者：Timothy D. Lash、Pushpa Chandrasekar、Augustine T. Osuma、Sun T. Chaney、John D. Spence

  DOI：10.1021/jo9815655

  日期：1998.11.1

  As part of a survey on the influence of fused aromatic rings on the porphyrin chromophore, a series of novel structures with fused acenaphthylene or benzothiadiazole rings have been synthesized. Base-catalyzed condensation of 1-nitroacenaphthylene or 4-nitrobenzothiadiazole with esters of isocyanoacetic acid afforded good yields of the annelated pyrroles 5 and 28. Cleavage of the ester moieties with KOH in refluxing ethylene glycol gave the unsubstituted heterocycles, and subsequent condensation with 2 equiv of acetoxymethylpyrroles 9 in acetic acid/ethanol produced the modified tripyrranes 12 and 31. Tripyrranes with terminal tert-butyl ester units were treated with TFA and condensed with 3,4-diethyl-2,5-pyrroledicarboxaldehyde 13 in dichloromethane to give, following oxidation with DDQ, the corresponding pi-extended porphyrins 14 and 32. Acenaphthoporphyrins 14 showed unique UV-vis spectra with a triply split Soret band region and a relatively strong band near 660 nm. Strongly red-shifted absorptions were also noted for the dications and the nickel(II), copper(II), and zinc chelates for this system. Thiadiazoloporphyrins 32 gave two broadened Soret bands, but the Q-band region was unexceptional. However, the nickel(II), copper(II), and zinc complexes all showed abnormally strong absorptions between 600 and 612 nm. Porphyrins with two antipodal fused aromatic rings were easily prepared by condensing c-annelated pyrroledialdehydes 17 with tripyrranes 12 and 31, and the spectroscopic properties of the resulting porphyrins showed that the observed ring-fusion effects were essentially additive. Porphyrins with two adjacent acenaphthylene rings were also prepared by the MacDonald "2 + 2" condensation, although this chemistrry gave poor results in the synthesis of a porphyrin with two fused benzothiadiazole rings. The spectroscopic properties of these new highly conjugated porphyrin structures show that ring fusion can profoundly modify the porphyrin chromophore.