2-ethyl-3,7,13-trimethyl-8,12-bis(carbomethoxyethyl)-14-formyltripyrrin-1(15H)-one | 82094-20-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 2-ethyl-3,7,13-trimethyl-8,12-bis(carbomethoxyethyl)-14-formyltripyrrin-1(15H)-one
• CAS: 82094-20-0
• 化学式: C₂₈H₃₃N₃O₆
• 分子量: 507.587
• InChiKey: PTMCPGYNUJWWJC-YFBGDSSHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  37.0
• 可旋转键数：
  10.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  126.92
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为产物：
  描述：

  phycocyanobilin dimethyl ester 在 氧气 作用下， 反应 23.0h， 生成 2-ethyl-3,7,13-trimethyl-8,12-bis(carbomethoxyethyl)-14-formyltripyrrin-1(15H)-one
  参考文献：
  名称：

  Phytochrome models. 11. Photophysics and photochemistry of phycocyanobilin dimethyl ester

  摘要：

  Phycocyanobilin dimethyl ester (3) undergoes a self-sensitized oxidation by a singlet oxygen [O2(1-DELTA-g)] mechanism with a quantum yield of 10(-5)-10(-6), depending on the solvent, excitation wavelength, and concentration. The main photooxidation products are a tripyrrolic aldehyde (7) and three stereoisomeric peroxides (8-10) formed from two units of 3. Near-IR emission of O2(1-DELTA-g)-formed upon sensitization by 3 under both steady-state irradiation and pulsed excitation-constitutes the first direct evidence for the intersystem crossing of a bilatriene. The low photooxidation yield results from a low intersystem crossing yield from 3, PHI-isc < 10(-4), estimated by the energy-transfer method in flash photolysis. A total rate constant of k(q) = (3.4 +/- 0.3) X 10(8) M-1 s-1 was determined for the quenching of O2(1-DELTA-g) by 3. Possible relations between these findings and the photophobic movement of Anabaena variabilis are discussed. In analogy to biliverdin dimethyl ester, two types of conformations (a helical form and a family of stretched forms) for 3 [and for its 3,3'-dihydro-3'-thioethoxy derivatives (3'S*)-5] were detected in methanol at room temperature by stationary fluorescence and excitation spectra. The wavelength dependence of the self-sensitized photooxidation of 3 is due to the selective reaction of the helical conformer, while a selective photoisomerization of the stretched forms of 3 and 5 was observed by time-resolved laser-induced optoacoustic spectroscopy. For 3 the latter process takes place with a quantum yield > 0.5, and the resulting isomer (probably a C-10 stereoisomer of the parent compound) reverts to the ground state with a lifetime of around 200 ns.

  DOI：

  10.1021/ja00019a033

文献信息

• Phytochrome models. 11. Photophysics and photochemistry of phycocyanobilin dimethyl ester
  作者：Silvia E. Braslavsky、Dagmar Schneider、Klaus Heihoff、Santiago Nonell、Pedro F. Aramendia、Kurt Schaffner

  DOI：10.1021/ja00019a033

  日期：1991.9

  Phycocyanobilin dimethyl ester (3) undergoes a self-sensitized oxidation by a singlet oxygen [O2(1-DELTA-g)] mechanism with a quantum yield of 10(-5)-10(-6), depending on the solvent, excitation wavelength, and concentration. The main photooxidation products are a tripyrrolic aldehyde (7) and three stereoisomeric peroxides (8-10) formed from two units of 3. Near-IR emission of O2(1-DELTA-g)-formed upon sensitization by 3 under both steady-state irradiation and pulsed excitation-constitutes the first direct evidence for the intersystem crossing of a bilatriene. The low photooxidation yield results from a low intersystem crossing yield from 3, PHI-isc < 10(-4), estimated by the energy-transfer method in flash photolysis. A total rate constant of k(q) = (3.4 +/- 0.3) X 10(8) M-1 s-1 was determined for the quenching of O2(1-DELTA-g) by 3. Possible relations between these findings and the photophobic movement of Anabaena variabilis are discussed. In analogy to biliverdin dimethyl ester, two types of conformations (a helical form and a family of stretched forms) for 3 [and for its 3,3'-dihydro-3'-thioethoxy derivatives (3'S*)-5] were detected in methanol at room temperature by stationary fluorescence and excitation spectra. The wavelength dependence of the self-sensitized photooxidation of 3 is due to the selective reaction of the helical conformer, while a selective photoisomerization of the stretched forms of 3 and 5 was observed by time-resolved laser-induced optoacoustic spectroscopy. For 3 the latter process takes place with a quantum yield > 0.5, and the resulting isomer (probably a C-10 stereoisomer of the parent compound) reverts to the ground state with a lifetime of around 200 ns.