(Z)-1,3,4,5-Tetrahydro-3,3,3',4'-tetramethyl-5-oxo-2,2'-pyrromethen-5'-carbonsaeure-tert-butylester | 100923-21-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (Z)-1,3,4,5-Tetrahydro-3,3,3',4'-tetramethyl-5-oxo-2,2'-pyrromethen-5'-carbonsaeure-tert-butylester
• CAS: 100923-21-5
• 化学式: C₁₈H₂₆N₂O₃
• 分子量: 318.416
• InChiKey: HXMKTGOEZOAIHR-JYRVWZFOSA-N

物化性质

• 沸点：
  445.8±45.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  67.76
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (Z)-4-Ethyl-3-methyl-5-(3,4-dimethyl-5-formyl-2-pyrrolyl-methylen)-3-pyrrolin-2-on 、 (Z)-1,3,4,5-Tetrahydro-3,3,3',4'-tetramethyl-5-oxo-2,2'-pyrromethen-5'-carbonsaeure-tert-butylester 以83%的产率得到(Z,Z,Z)-1,19-Dioxo-3,3,7,8,12,13,18-heptamethyl-17-ethyl-1,2,3,19,23,24-hexahydro-21H-bilin
  参考文献：
  名称：

  Beiträge zur Chemie der Pyrrolpigmente, 51. Mitt.: Phytochrommodellstudien: Zur Deprotonierung von 3,4-Dihydropyrromethenonen und 2,3-Dihydrobilatrienen-abc

  摘要：

  DOI：

  10.1007/bf00799035

文献信息

• Protonated 2,3-Dihydrobilindiones—Models for the Chromophores of Phycocyanin and the Red-Absorbing Form of Phytochrome
  作者：Michael Stanek、Karl Grubmayr

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

  日期：1998.9.4

  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.