3,13-diacetyl-17,18-dihydro-18,18-dimethyl-10-mesitylporphyrin | 892861-76-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 3,13-diacetyl-17,18-dihydro-18,18-dimethyl-10-mesitylporphyrin
• CAS: 892861-76-6
• 化学式: C₃₅H₃₂N₄O₂Zn
• 分子量: 606.055
• InChiKey: IHYPZOIPAIAYQA-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  三丁基(1-乙氧基乙烯)锡 、 zinc(II)-3,13-dibromo-17,18-dihydro-10-mesityl-18,18-dimethylporphyrin 在 三氟乙酸 、 bis-triphenylphosphine-palladium(II) chloride 、 盐酸 作用下， 以 二氯甲烷 、 四氢呋喃 、 水 为溶剂， 反应 22.0h， 以74%的产率得到3,13-diacetyl-17,18-dihydro-18,18-dimethyl-10-mesitylporphyrin
  参考文献：
  名称：

  Effects of Substituents on Synthetic Analogs of Chlorophylls. Part 3: The Distinctive Impact of Auxochromes at the 7- versus 3-Positions

  摘要：

  AbstractAssessing the effects of substituents on the spectra of chlorophylls is essential for gaining a deep understanding of photosynthetic processes. Chlorophyll a and b differ solely in the nature of the 7‐substituent (methyl versus formyl), whereas chlorophyll a and d differ solely in the 3‐substituent (vinyl versus formyl), yet have distinct long‐wavelength absorption maxima: 665 (a) 646 (b) and 692 nm (d). Herein, the spectra, singlet excited‐state decay characteristics, and results from DFT calculations are examined for synthetic chlorins and 131‐oxophorbines that contain ethynyl, acetyl, formyl and other groups at the 3‐, 7‐ and/or 13‐positions. Substituent effects on the absorption spectra are well accounted for using Gouterman’s four‐orbital model. Key findings are that (1) the dramatic difference in auxochromic effects of a given substituent at the 7‐ versus3‐ or 13‐positions primarily derives from relative effects on the LUMO+1 and LUMO; (2) formyl at the 7‐ or 8‐position effectively “porphyrinizes” the chlorin and (3) the substituent effect increases in the order of vinyl < ethynyl < acetyl < formyl. Thus, the spectral properties are governed by an intricate interplay of electronic effects of substituents at particular sites on the four frontier MOs of the chlorin macrocycle.

  DOI：

  10.1111/j.1751-1097.2012.01083.x