5,5'-bis(tert-butoxycarbonyl)-4,4'-dimethyl-3,3'-bis-(methoxycarbonylethyl)-2,2'-dipyrrylmethane | 30103-05-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 5,5'-bis(tert-butoxycarbonyl)-4,4'-dimethyl-3,3'-bis-(methoxycarbonylethyl)-2,2'-dipyrrylmethane
• 英文别名: 5,5'-bis(tert-butoxycarbonyl)-4,4'-dimethyl-3,3-bis(2-(methoxycarbonyl)ethyl)-2,2'-dipyrrylmethane；di-tert-butyl 5,5'-methylenebis(4-(3-methoxy-3-oxopropyl)-3-methyl-1H-pyrrole-2-carboxylate)；tert-butyl 4-(3-methoxy-3-oxopropyl)-5-[[3-(3-methoxy-3-oxopropyl)-4-methyl-5-[(2-methylpropan-2-yl)oxycarbonyl]-1H-pyrrol-2-yl]methyl]-3-methyl-1H-pyrrole-2-carboxylate
• CAS: 30103-05-0
• 化学式: C₂₉H₄₂N₂O₈
• 分子量: 546.661
• InChiKey: IYBSQZYREVZGEE-UHFFFAOYSA-N

物化性质

• 沸点：
  644.5±55.0 °C(Predicted)
• 密度：
  1.159±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  39
• 可旋转键数：
  16
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  137
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,5'-bis(tert-butoxycarbonyl)-4,4'-dimethyl-3,3'-bis-(methoxycarbonylethyl)-2,2'-dipyrrylmethane 在 三氟乙酸 作用下， 反应 0.08h， 生成 3-{5-Formyl-2-[5-formyl-3-(2-methoxycarbonyl-ethyl)-4-methyl-1H-pyrrol-2-ylmethyl]-4-methyl-1H-pyrrol-3-yl}-propionic acid methyl ester
  参考文献：
  名称：

  Synthesis of a 10-Oxo-Bilirubin:  Effects of the Oxo Group on Conformation, Transhepatic Transport, and Glucuronidation

  摘要：

  Bilirubin, the yellow pigment of jaundice, is a linear tetrapyrrole with a methylene group at its center, C(10), a position of crucial importance to its conformation and metabolism. The presence of the central methylene group allows the bilirubin to fold into an intramolecularly hydrogen-bonded conformation. This paper describes the first synthesis of a bilirubin analogue with an oxo group at C(10). The change from CH2 to C=O, from sp(3) to sp(2), is designed to stress the molecule at its hinge and relax its conformation. Such compounds have been suggested as potential oxidative metabolites of bilirubin in vivo. 10-Oxo-mesobilirubin-XIII alpha (1) is a red crystalline solid, unlike its parent, mesobilirubin-XIII alpha, which is a bright yellow solid. It is surprisingly polar, relative to the parent, yet it does not exhibit a significantly larger bicarbonate/chloroform partition coefficient. Like the parent, 1 appears to adopt an intramolecularly hydrogen-bonded ridge-tile-like conformation. In normal rats, 1 is metabolized to acylglucuronides, which are secreted into bile, but a portion of the administered dose is secreted into bile intact. In mutant rats (Gunn rats) lacking bilirubin glucuronyl transferase, 1 was excreted efficiently in bile in unchanged form, unlike the parent with a methylene group at C(10). Thus, introduction of the oxygen function at C(10) has little effect on hepatic uptake but a dramatic effect on canalicular secretion into bile.

  DOI：

  10.1021/ja991814m
• 作为产物：
  描述：

  5-乙酰氧基-4-硝基己酸甲酯 在 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 28.0h， 生成 5,5'-bis(tert-butoxycarbonyl)-4,4'-dimethyl-3,3'-bis-(methoxycarbonylethyl)-2,2'-dipyrrylmethane
  参考文献：
  名称：

  Porphyrin synthesis from nitrocompounds

  摘要：

  DOI：

  10.1016/s0040-4020(01)89062-1

文献信息

• The oxygen-independent coproporphyrinogen III oxidase HemN utilizes harderoporphyrinogen as a reaction intermediate during conversion of coproporphyrinogen III to protoporphyrinogen IX
  作者：Katrin Rand、Claudia Noll、Hans Martin Schiebel、Dorit Kemken、Thomas Dülcks、Markus Kalesse、Dirk W. Heinz、Gunhild Layer

  DOI：10.1515/bc.2010.006

  日期：2010.1.1

  Abstract During heme biosynthesis the oxygen-independent coproporphyrinogen III oxidase HemN catalyzes the oxidative decarboxylation of the two propionate side chains on rings A and B of coproporphyrinogen III to the corresponding vinyl groups to yield protoporphyrinogen IX. Here, the sequence of the two decarboxylation steps during HemN catalysis was investigated. A reaction intermediate of HemN activity

  摘要 在血红素生物合成过程中，不依赖氧的粪卟啉原 III 氧化酶 HemN 催化粪卟啉原 III 的 A 环和 B 环上的两个丙酸侧链氧化脱羧为相应的乙烯基，生成原卟啉原 IX。在这里，研究了 HemN 催化过程中两个脱羧步骤的顺序。通过HPLC分析分离出具有HemN活性的反应中间体，并通过质谱法鉴定为单乙烯基三丙酸卟啉。这种单乙烯基反应中间体在 HPLC 分析过程中表现出与硬卟啉（3-乙烯基-8,13,17-三丙酸-2,7,12,18-四甲基卟啉）相同的色谱行为。此外，HemN 能够利用化学合成的硬卟啉原作为底物并将其转化为原卟啉原 IX。
• Synthesis and properties of mesobilirubins XIIγ and XIIIγ and their mesobiliverdins
  作者：Portia Mahal G. Sabido、David A. Lightner

  DOI：10.1007/s00706-014-1160-6

  日期：2014.5

  The title pigments, with propionic acid groups displaced to the lactam end rings, were synthesized for the first time by the "1 + 2 + 1" approach, coupling two equivalents of a monopyrrole to a dipyrrylmethane (to give XII gamma), or the "2 + 2" approach, self-coupling two equivalents of a dipyrrinone (to give XIII gamma). Using the "1 + 2 + 1" approach, mesobilirubin III alpha was also prepared. Mesobilirubins XII gamma and XIII gamma are more polar than mesobilirubin III alpha and unlike III alpha cannot effectively engage the propionic acid groups in intramolecular hydrogen bonding to the dipyrrinone components. The new mesobilirubins give exciton coupled circular dichroism spectra in the presence of human serum albumin or quinine, with the XII gamma isomer exhibiting Cotton effect intensities nearly as strong as those from the III alpha isomer; whereas, the XIII gamma isomer exhibits far weaker intensities. Mesobilirubin III alpha requires glucuronidation for hepatobiliary elimination; whereas, XII gamma and XIII gamma do not, and they are excreted intact across the liver into bile. The corresponding biliverdins XII gamma and XIII gamma are reduced only slowly by biliverdin IX alpha reductase, in contrast to the fast reduction of the natural IX alpha isomer.