β(S)-methylxanthobilirubic acid | 148616-08-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: β(S)-methylxanthobilirubic acid
• 英文别名: (3S)-3-[5-[(Z)-(3-ethyl-4-methyl-5-oxopyrrol-2-ylidene)methyl]-2,4-dimethyl-1H-pyrrol-3-yl]butanoic acid
• CAS: 148616-08-4
• 化学式: C₁₈H₂₄N₂O₃
• 分子量: 316.4
• InChiKey: DZXIGVFASHREKL-AVPSXBMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  82.2
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  β(S)-methylxanthobilirubic acid 在 三乙胺 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 7.5h， 生成 (S)-8-[2-(N-{[(benzyloxy)carbonyl]methyl}carbamoyl)-1-methylethyl]-3-ethyl-2,7,9-trimethyl-(10H)-dipyrrin-1-one
  参考文献：
  名称：

  On the Conformation of Glycobilirubin

  摘要：

  从（S）-β-甲基黄绿胆红素酸甘氨酸结合物8制备了第一个光学活性的甘氨酸结合物1。后者是通过对苄基甘氨酸对甲苯磺酸酯与在（S）-β-甲基黄绿胆红素酸6与异丁基氯甲酸酯反应中形成的混合酸酐反应合成的。对1在各种溶剂中（包括水相缓冲液）的圆二色谱光谱进行了光谱分析，表明其对M-螺旋脊瓦结构具有构象偏好，从而为糖胆红素的构象提供了第一个光谱学证据。

  DOI：

  10.1135/cccc20031007
• 作为产物：
  描述：

  在 sodium hydroxide 作用下， 反应 7.0h， 生成 β(S)-methylxanthobilirubic acid
  参考文献：
  名称：

  Boiadjiev, Stefan E.; Anstine, D. Timothy; Lightner, David A., Journal of the American Chemical Society, 1995, vol. 117, # 34, p. 8727 - 8736

  摘要：

  DOI：

文献信息

• Steric Size in Conformational Analysis. Steric Compression Analyzed by Circular Dichroism Spectroscopy
  作者：Stefan E. Boiadjiev、David A. Lightner

  DOI：10.1021/ja002069c

  日期：2000.11.22

  methyl, ethyl, isopropyl, tert-butyl, phenyl, and benzyl groups has been determined from a sensitive tetrapyrrole model and exciton coupling circular dichroism (CD) measurements. Unlike the classical cyclohexane model, from which the relative steric demand of functional groups has been assessed quantitatively (A-values) and is based on the preference for equatorial vs axial orientations, the bilirubin

  甲基、乙基、异丙基、叔丁基、苯基和苄基的相对空间尺寸已通过灵敏的四吡咯模型和激子耦合圆二色性 (CD) 测量确定。与经典的环己烷模型不同，后者定量评估了官能团的相对空间需求（A 值）并基于对赤道方向与轴向方向的偏好，胆红素模型从头对头空间压缩评估取代基大小. 因此，一组敏感的抗手性 α(R/S)-取代的-β'(S)-甲基中胆红素-XIIIα (1−6) 的激子 CD 振幅表明明显的相对空间大小：叔丁基 ∼ 异丙基 > 苯基∼ 乙基 > 苄基 > 甲基。
• Hydrogen bonding and π-stacking in dipyrrinone acid dimers of xanthobilirubic acid and chiral analogs
  作者：Stefan E. Boiadjiev、D.Timothy Anstine、Emily Maverick、David A. Lightner

  DOI：10.1016/0957-4166(95)00301-5

  日期：1995.9

  Xanthobilirubic acid and its analogs self-associate strongly through intermolecular hydrogen bonding between their carboxylic acid and dipyrrinone components, forming π-stacked dimers. In contrast, their methyl esters form planar dimers conjoined by dipyrrinone to dipyrrinone intermolecular hydrogen bonding. When a stereogenic center is present in the propionic side acid chain, unusually large optical

  黄胆红酸及其类似物通过其羧酸和二吡啶酮组分之间的分子间氢键强烈自缔合，形成π堆积的二聚体。相反，它们的甲酯形成平面二聚体，该二聚体由二吡啶酮连接至二吡啶酮分子间氢键。当一个立体异构中心存在于丙酸侧酸链，异常大的旋光和激子耦合圆二色性可为光学活性的酸可以观察到：βS -methylxanthobilirubic酸（1）具有[ α ] d 20 = -314°和Δ ∈ 434最大= -10.9，Δ ∈ 388最大= 5.7（氯仿3）。相比之下，甲基酯显示较弱的旋转和微乎其微CD：的（甲基酯1）具有[ α ] d 20 + 62°和Δ＆Element; 435 ⪡0.5，Δ＆Element;⪡0.5。
• Synthesis, intramolecular hydrogen bonding and conformation of optically active bilirubin amides. Analysis by circular dichroism and NMR
  作者：Stefan E. Boiadjiev、Richard V. Person、David A. Lightner

  DOI：10.1016/s0957-4166(00)86092-9

  日期：1993.3

  diamide and the bis-N-methylamide of an optically active analog of bilirubin (βS,β′S-dimethylmesobilirubin-XIIIα) is stabilized in a ridge-tile shape by intramolecular hydrogen bonding, as detected by 1H-NMR and CD spectroscopy. The matrix of intramolecular hydrogen bonds resists disruption even in (CH3)2SO solvent, where very strong exciton coupling CD is evident: Δϵmax427 −417, Δϵmax383 +234 (diamide)

  二酰胺的构象和胆红素的光学活性的类似物的双-N-甲基酰胺（β小号，β'小号-dimethylmesobilirubin-XIIIα）被稳定在由分子内氢键的脊瓦片形状，通过所检测的1 H- NMR和CD光谱。分子内氢键的基质甚至在（CH 3）2 SO溶剂中也能抵抗破坏，在这种情况下，很强的激子耦合CD很明显：Δϵ max 427 -417，Δϵ max 383 +234（二酰胺）。
• Intramolecular hydrogen bonding and its influence on conformation. Circular dichroism of chiral bilirubin analogs
  作者：Stefan E. Boiadjiev、David A. Lightner

  DOI：10.1016/s0957-4166(99)00254-2

  日期：1999.7

  Enantiopure synthetic bilirubin analogs with variously modified (e.g. alkyl for natural propionic acid or ester) C(8) and C(12) side chains and with but a single chiral center in either or both, exhibited exciton coupled circular dichroism (CD) spectra. The CD intensity is greater when the stereogenic center is in a propionic acid side chain than in an alkyl side chain. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Conformational analysis of an optically active bilirubin dimethyl ester and bis-N,N-dimethyl amide by circular dichroism, NMR and molecular dynamics
  作者：Stefan E. Boiadjiev、D.Timothy Anstine、David A. Lightner

  DOI：10.1016/s0957-4166(00)86270-9

  日期：1994.10

  The dimethyl ester and bis-N,N-dimethylamide of an optically active analog of bilirubin (beta S,beta'S-dimethylmesobilirubin-XIII alpha) is stabilized in a ridge-tile conformation by intramolecular hydrogen bonding, as detected by H-1-NMR and CD spectroscopy. The ridge-tile shape is most evident in nonpolar solvents, where very strong exciton coupling CD is evident: e.g., in benzene, Delta epsilon(412)(max) -199, Delta epsilon(372)(max)+87 for the dimethyl ester and Delta epsilon(421)(max)-165, Delta epsilon(384)(max)+46 for the bis-N,N-dimethylamide.