(Z,Z,Z)-1,19-dioxo-3,3,7,8,12,13,17,18-octamethyl-1,2,3,19,23,24-hexahydro-21H-bilin | 93233-13-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: (Z,Z,Z)-1,19-dioxo-3,3,7,8,12,13,17,18-octamethyl-1,2,3,19,23,24-hexahydro-21H-bilin
• CAS: 93233-13-7
• 化学式: C₂₇H₃₂N₄O₂
• 分子量: 444.577
• InChiKey: CPUMFNKETIFRNG-OAASHTDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.0
• 重原子数：
  33.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  86.35
• 氢给体数：
  3.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1,5,7-三氮杂双环[4.4.0]癸-5-烯 、 (Z,Z,Z)-1,19-dioxo-3,3,7,8,12,13,17,18-octamethyl-1,2,3,19,23,24-hexahydro-21H-bilin 以 氘代二甲亚砜 为溶剂， 生成
  参考文献：
  名称：

  Deprotonated 2,3‐Dihydrobilindiones—Models for the Chromophore of the Far‐Red‐Absorbing Form of Phytochrome

  摘要：

  Chromophore anions of synthetic 2,3-dihydrobilindiones can serve as models for the chromophore of the far-red-absorbing form of phytochrome because of the strong resemblance of their UV/Vis spectra, Significant red shifts of their long-wavelength maxima result from the elongation of the chromophores by deprotonation and the donor-acceptor reversal upon the conversion of the ring A lactam (N-->C=O) into the lactim anion (N=C <-- O-). The best resemblance was observed in the case of a 15-E configured chromophore anion. C-13 NMR spectroscopic investigations demonstrated that changes in chromophore structure are caused not only by regioselective deprotonation of the 2,3-dihydrolactam moiety of ring A, but also by the subsequent dipyrrin tautomerization within rings B and C. Generally, the chromophore structure can be interpreted in terms of an oxygen-donor/oxygen-acceptor-substituted polyene. The remarkable red shift of the long wavelength maximum results from the strong donor power of the oxygen atom on ring A, where the negative charge is localized, A simple model can be proposed for the interconversion of the structurally different chromophores of the red-absorbing form (Pr) and the far-red-absorbing form (Pfr) of phytochrome, based on oppositely charged chromophore ions of different geometry and stability: a stable 15Z-configured cation for physiologically inactive Pr and a labile 15E-configured anion for physiologically active Pfr, Interconversion requires only two types of reactions, namely Z/E photoisomerization and proton transfer.

  DOI：

  10.1002/(sici)1521-3765(19980904)4:9<1660::aid-chem1660>3.0.co;2-#
• 作为产物：
  描述：

  (Z)-3,4-Dimethyl-5-(3,4-dimethyl-5-formyl-2-pyrrolylmethylen)-3-pyrrolin-2-on 、 (Z)-1,3,4,5-Tetrahydro-3,3,3',4'-tetramethyl-5-oxo-2,2'-pyrromethen-5'-carbonsaeure-tert-butylester 在 三氟乙酸 作用下， 生成 (Z,Z,Z)-1,19-dioxo-3,3,7,8,12,13,17,18-octamethyl-1,2,3,19,23,24-hexahydro-21H-bilin 、
  参考文献：
  名称：

  Protonated 2,3-Dihydrobilindiones—Models for the Chromophores of Phycocyanin and the Red-Absorbing Form of Phytochrome

  摘要：

  New structural and thermodynamic data on the protonation of 2,3-dihydrobilindiones are presented with respect to the ionic aspects of the chromophore-protein interactions in biliproteins. When intermolecular protonation with stoichiometric quantities of strong (sulfonic) acids was investigated by NMR spectroscopy, it was found that the positive charge is localized at the nitrogen atom of the azafulvenic ring B moiety. Complete protonation by weaker (carboxylic) acids can be achieved only intramolecularly at low temperature. The (2R,3R,3'R,CysR)-cysteine adduct of phycocyanobilin dimethyl ester was synthesized to mimic the acid-base chemistry between protein and chromophore. Thermodynamic data for the equilibrium between its neutral form 1 and zwitterion 1(+/-) were calculated from the temperature dependence of the visible spectra (Delta H degrees = -20.8 kJ mol(-1) Delta S degrees = -71 J mol(-1) K-1). These data are in accord. with others from intramolecular proton transfers, explaining the perfect order of highly conserved consensus sequences necessary for the effective protonation of the chromophores in various light-harvesting biliproteins such as phycocyanin. On the other hand, the highly negative value of Delta S degrees indicates the possibility of the reprotonation of the protein in case of steric interference. The geometrical changes of the protonated Pr chromophore of phytochrome as a result of the Z-->E photoisomerization may trigger proton transfer back to the protein and thus initiate the sequence of dark reactions that lead to the physiologically active Pfr form of phytochrome.

  DOI：

  10.1002/(sici)1521-3765(19980904)4:9<1653::aid-chem1653>3.0.co;2-k