phycocyanobilin dimethyl ester | 135682-79-0

• 英文名称: phycocyanobilin dimethyl ester
• CAS: 135682-79-0
• 化学式: C₃₅H₄₂N₄O₆
• 分子量: 614.742
• InChiKey: TWODAMFYKHNLPP-FRFNWOMISA-N

物化性质

• 沸点：
  824.9±65.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.29
• 重原子数：
  45.0
• 可旋转键数：
  10.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  138.95
• 氢给体数：
  3.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  tert-butyl 5-((Z)-2-(tert-butoxy)-1-((E)-3-ethylidene-4-methyl-5-oxopyrrolidin-2-ylidene)-2-oxoethyl)-3-(3-methoxy-3-oxopropyl)-4-methyl-1H-pyrrole-2-carboxylate 在 氢溴酸 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 23.84h， 生成 phycocyanobilin dimethyl ester
  参考文献：
  名称：

  Diastereoselective synthesis of phycocyanobilin-cysteine adducts

  摘要：

  Methodology is presented for the synthesis of two diastereomers of a cysteine-linked phycocyanobilin derivative. The crucial reaction is a diastereoselective 1,6-Michael addition of cysteine methyl ester to an appropriate dihydropyrromethenone educt. The diastereomers so generated were then elaborated to two phycocyanobilin trimethyl esters. Definitive assignments of relative stereochemistry, double bond geometry, and solution conformation are accomplished by application of ROESY NMR experiments, while absolute stereochemical assignments are based on degradation to compounds of known chirality.

  DOI：

  10.1021/ja00021a032