zinc(II) 2,3-bis(phenylethynyl)-5,10,15,20-tetraphenylporphyrin | 842125-57-9

• 分子结构分类: 有机化合物
• 英文名称: zinc(II) 2,3-bis(phenylethynyl)-5,10,15,20-tetraphenylporphyrin
• CAS: 842125-57-9
• 化学式: C₆₀H₃₆N₄Zn
• 分子量: 878.363
• InChiKey: LSBMYDCEFYPUBO-MQNLLRMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.42
• 重原子数：
  65.0
• 可旋转键数：
  4.0
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  zinc(II) 2,3-bis(phenylethynyl)-5,10,15,20-tetraphenylporphyrin 以 further solvent(s) 为溶剂， 以30%的产率得到
  参考文献：
  名称：

  Controlling Both Ground- and Excited-State Thermal Barriers to Bergman Cyclization with Alkyne Termini Substitution

  摘要：

  The cross-coupling reaction of 2,3-dibromo-5,10,15,20-tetraphenylporphyrin with corresponding organostannanes in the presence of a Pd0 catalyst in THF at reflux temperature yields free base 2,3-dialkynylporphyrins 1a,c-e. The subsequent deprotection of trimethylsilyl group of 1a with TBAF in THF under aqueous conditions produces the 2,3-diethynyl-5,10,15,20-tetraphenylporphyrins 1b in 87% yield. Compounds 1a-d undergo zinc insertion upon treatment with Zn(OAc)2.2H2O in CHCl3/MeOH to give zinc(II) 2,3-dialkynyl-5,10,15,20-tetraphenylporphyrins (2a-d) in 70-92% yields. Thermal Bergman cyclization of 1a-e and 2a-d was studied in chlorobenzene and approximately 35-fold 1,4-cyclohexadiene at 120-210 degrees C. Compounds 1b and 2b with R = H react at lower temperature (120 degrees C) and produce cyclized products 3b and 4b in higher yields (65-70%) than their propyl, isopropyl, and phenyl analogues, with R = Ph being the most stable. Continuing in this trend, the -TMS derivatives 1a and 2a exhibit no reactivity even after heating at 190 degrees C in chlorobenzene/CHD for 24 h. Photolysis (at lambda >/= 395 nm) of 1b and 2b at 10 degrees C leads the formation of isolable picenoporphyrin products in 15 and 35% yields, respectively, in 72 h, whereas these compounds are stable in solution under same reaction conditions at 25 degrees C in the dark. Unlike thermolysis at 125 degrees C, which did not yield Bergman cyclized product for R = Ph, photolysis generated very small amounts of picenoporphyrin products (3c: 5%; 4c: 8% based on 1H NMR) as well as a mixture of reduced porphyrin products that were not separable. Thus, trends in the barrier to Bergman cyclization in the excited state exhibit the same trend as those observed in the ground state as a function of R-group. Finally, photolysis of 2b at 10 degrees C with lambda >/= 515 or 590 nm in benzene/iPrOH (4:1, 72 h) produces 4b in 15 and 6% isolated yields, indicating that conjugation of the enediyne unit into the porphyrin electronic transitions leads to sufficient distortion to generate photoproduct even with long wavelength excitation.

  DOI：

  10.1021/ja045979t
• 作为产物：
  描述：

  2,3-bis(phenylethynyl)-5,10,15,20-tetraphenylporphyrin 、 zinc(II) acetate dihydrate 以 甲醇 、 氯仿 为溶剂， 生成 zinc(II) 2,3-bis(phenylethynyl)-5,10,15,20-tetraphenylporphyrin
  参考文献：
  名称：

  Controlling Both Ground- and Excited-State Thermal Barriers to Bergman Cyclization with Alkyne Termini Substitution

  摘要：

  The cross-coupling reaction of 2,3-dibromo-5,10,15,20-tetraphenylporphyrin with corresponding organostannanes in the presence of a Pd0 catalyst in THF at reflux temperature yields free base 2,3-dialkynylporphyrins 1a,c-e. The subsequent deprotection of trimethylsilyl group of 1a with TBAF in THF under aqueous conditions produces the 2,3-diethynyl-5,10,15,20-tetraphenylporphyrins 1b in 87% yield. Compounds 1a-d undergo zinc insertion upon treatment with Zn(OAc)2.2H2O in CHCl3/MeOH to give zinc(II) 2,3-dialkynyl-5,10,15,20-tetraphenylporphyrins (2a-d) in 70-92% yields. Thermal Bergman cyclization of 1a-e and 2a-d was studied in chlorobenzene and approximately 35-fold 1,4-cyclohexadiene at 120-210 degrees C. Compounds 1b and 2b with R = H react at lower temperature (120 degrees C) and produce cyclized products 3b and 4b in higher yields (65-70%) than their propyl, isopropyl, and phenyl analogues, with R = Ph being the most stable. Continuing in this trend, the -TMS derivatives 1a and 2a exhibit no reactivity even after heating at 190 degrees C in chlorobenzene/CHD for 24 h. Photolysis (at lambda >/= 395 nm) of 1b and 2b at 10 degrees C leads the formation of isolable picenoporphyrin products in 15 and 35% yields, respectively, in 72 h, whereas these compounds are stable in solution under same reaction conditions at 25 degrees C in the dark. Unlike thermolysis at 125 degrees C, which did not yield Bergman cyclized product for R = Ph, photolysis generated very small amounts of picenoporphyrin products (3c: 5%; 4c: 8% based on 1H NMR) as well as a mixture of reduced porphyrin products that were not separable. Thus, trends in the barrier to Bergman cyclization in the excited state exhibit the same trend as those observed in the ground state as a function of R-group. Finally, photolysis of 2b at 10 degrees C with lambda >/= 515 or 590 nm in benzene/iPrOH (4:1, 72 h) produces 4b in 15 and 6% isolated yields, indicating that conjugation of the enediyne unit into the porphyrin electronic transitions leads to sufficient distortion to generate photoproduct even with long wavelength excitation.

  DOI：

  10.1021/ja045979t

文献信息

• Regioselective 2,3-disubstituted porphyrins: synthesis, spectral, structural and electrochemical properties
  作者：Waseem Arif、Ravi Kumar

  DOI：10.1039/d3nj01288c

  日期：——

  withdrawing nature and follows the sequence of H2TPP(PE)2 > H2TPP(Br)2 > H2TPP(Ph)2 > H2TPP(CH3)2. A reduction in the HOMO–LUMO gap was observed in these porphyrins compared with the unsubstituted metal complexes (MTPPs), and thus redox tunability was achieved upon β-disubstitution. Single-crystal X-ray structure analysis of H2TPP(CH3)2 and CuTPP(PE)2 revealed quasi-planar and ruffled conformations of the

  一系列区域选择性 β-二取代内消旋-四苯基卟啉 H 2 TPP(X) 2（其中 X = 甲基 (CH 3 )、苯基 (Ph)、溴 (Br) 和苯乙炔基 (PE)），以及它们的金属络合物 (合成了Cu( II )、Co( II )、Ni( II ) 和 Zn( II ))，并使用各种光谱技术对其进行了表征。苯乙炔基取代的卟啉 H 2 TPP(PE) 2的吸收带在 Soret 带中表现出相当大的红移 6-18 nm，在 Q x (0,0) 带中表现出 10-25 nm 与甲基-和苯基-二取代的卟啉，即。H 2 TPP(CH 3 ) 2和H 2 TPP(Ph) 2。这种红移归因于卟啉 π 骨架上存在的苯基和苯乙炔基的感应和共振效应，并遵循 H 2 TPP(CH 3 ) 2 < H 2 TPP(Ph) 2 < H 2 TPP( PE) 2。在这些区域选择性 β-二取代游离碱基卟啉中发生两个连续的单