1,3-bis-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-thiadiazolobenzo<3,4-c>pyrrole | 189124-76-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1,3-bis-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-thiadiazolobenzo<3,4-c>pyrrole
• CAS: 189124-76-3
• 化学式: C₃₄H₄₃N₅O₄S
• 分子量: 617.813
• InChiKey: XNNUGKANVSNOEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.66
• 重原子数：
  44.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  125.75
• 氢给体数：
  3.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  1,3-bis-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-thiadiazolobenzo<3,4-c>pyrrole 在 三乙胺 、 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 反应 3.17h， 生成 8,12,13,17-tetraethyl-7,18-dimethylthiadiazolobenzo<3,4-b>porphyrin
  参考文献：
  名称：

  由硝基芳烃合成新型卟啉发色团：Barton-Zard吡咯缩合反应的进一步应用

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(97)00287-6
• 作为产物：
  描述：

  Ethyl pyrrolo[3,4-e][2,1,3]benzothiadiazole-6-carboxylate 在 氢氧化钾 作用下， 以 乙二醇 、 溶剂黄146 、 异丙醇 为溶剂， 反应 16.0h， 生成 1,3-bis-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-thiadiazolobenzo<3,4-c>pyrrole
  参考文献：
  名称：

  由硝基芳烃合成新型卟啉发色团：Barton-Zard吡咯缩合反应的进一步应用

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(97)00287-6

文献信息

• 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.