benzyl 5-formyl-3,4-dimethylpyrrole-2-carboxylate | 59435-08-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzyl 5-formyl-3,4-dimethylpyrrole-2-carboxylate
• 英文别名: 5-formyl-3,4-dimethyl-pyrrole-2-carboxylic acid benzyl ester；5-Formyl-3,4-dimethyl-pyrrol-carbonsaeure-(2)-benzylester；2-Carbobenzyloxy-5-formyl-3,4-dimethylpyrrol；1H-Pyrrole-2-carboxylic acid, 5-formyl-3,4-dimethyl-, phenylmethyl ester；benzyl 5-formyl-3,4-dimethyl-1H-pyrrole-2-carboxylate
• CAS: 59435-08-4
• 化学式: C₁₅H₁₅NO₃
• 分子量: 257.289
• InChiKey: UOKPIJWFKFLVMD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  59.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  benzyl 5-formyl-3,4-dimethylpyrrole-2-carboxylate 在 TiCl₃-1,2-dimethoxyethane 、 铜 、 锌 作用下， 反应 8.0h， 以81%的产率得到trans-1,2-bis(5-(benzyloxycarbonyl)-3,4-dimethyl-2-pyrrolyl)ethene
  参考文献：
  名称：

  Syntheses and Some Chemistry of 1,2- and 1,1-Bis(2-pyrrolyl)ethenes

  摘要：

  trans-1,2-Bis(2-pyrrolyl)ethenes (e.g. 18-20) are prepared by McMurry-type reductive coupling of the corresponding 2-formylpyrroles. The isomeric 1,1-bis(2-pyrrolyl)ethenes (e.g. 24) are prepared as a minor byproduct in the reaction of 2-unsubstituted pyrroles (e.g. 22) with acetic anhydride under Friedel-Crafts conditions; the major product, as expected is the 2-acetylpyrrole 23. However, 5-(chloromethyl)dipyrromethanes (e.g. 35) can be obtained in high yield by reaction of 2-unsubstituted pyrroles 22 with chloroacetaldehyde diethyl acetal, Base-catalyzed elimination of HCl from 35 affords the 1,1-bis(2-pyrrolyl)ethene 24 along with the trans- and cis-1,2-bis(2-pyrrolyl)-ethenes 18 and 36, respectively. Conditions are optimized to afford a 66% yield of the 1,1-bis(2-pyrrolyl)ethene 24. In neutral organic solvents, 1,1-bis(2-pyrrolyl)ethenes exist in the ethene tautomeric form 2, rather than as the corresponding 5-methyldipyrromethene isomer 3; however, under acidic conditions, the 5-methyldipyrromethene salt 38 is observed, and the 5-methyl group undergoes acid-catalyzed exchange in deuterated solvents. 1,1-Bis(2-pyrrolyl)ethenes (e.g. 24) undergo standard chemistry, such as catalytic hydrogenation (Adams catalyst) of the alkene bond (to give 5-methyldipyrromethane 44), Vilsmeier formylation [to give 2-formyl-1,1-bis(2-pyrrolyl)ethene 57], and reaction with Eschenmoser's salt (N,N-dimethyl(methylene)ammonium iodide) [to give 2-((N,N-dimethylamino)methyl)-1,1-bis(2-pyrrolyl)ethene 59]. Both the 5-methyldipyrromethane-1,9-dicarboxylic acid 45 and the 1,1-bis(5-carboxy-3,4-dimethyl-2-pyrrolyl)ethene 53 react with the 1,9-diformyldipyrromethane 46, under standard MacDonald conditions, to give 3,5,8-trimethyl-deuteroporphyrin IX dimethyl ester 47.

  DOI：

  10.1021/jo961582z
• 作为产物：
  描述：

  2-((benzyloxy)carbonyl)-3,4,5-trimethylpyrrole 在 lead(IV) acetate 作用下， 生成 benzyl 5-formyl-3,4-dimethylpyrrole-2-carboxylate
  参考文献：
  名称：

  1,19-二溴-a，c-胆二烯的逐步合成及其转化为biliverdins，coroles和azaporphyrins

  摘要：

  通过不对称取代的1,19-二溴-a，c-胆二烯（例如3c）通过所谓的“三芳烃路线”进行第一步逐步合成，并将其轻松转化为biliverdins（比林-1,19-二酮），例如4c，描述；这种方法也适用于制备对称的biliverdins 4a以及corrols 5和azaporphyrins 6。

  DOI：

  10.1039/c39920000183

文献信息

• Preparation and characterization of myoglobin reconstituted with Fe(II) oxaporphyrin: The monoanionic macrocycle provides unique cyanide binding behavior for the ferrous species
  作者：Hiroyuki Meichin、Koji Oohora、Takashi Hayashi

  DOI：10.1016/j.ica.2017.06.054

  日期：2018.3

  μ-oxo bridged diiron structure. The Fe II /Fe III redox potential of FeOP dimethyl ester in acetonitrile is +310 mV vs an Ag|AgCl electrode as determined by cyclic voltammetry. The value is positively shifted by 710 mV from that of the native heme cofactor, indicating that the ferrous species is stabilized in the oxaporphyrin framework. Myoglobin reconstituted with Fe II OP was prepared in the presence

  摘要合成了具有两个丙酸酯侧链（FeOP）的铁氧卟啉作为肌红蛋白的人工辅因子。FeOP的自氧化提供了一个铁氧体桥联的二铁结构。通过循环伏安法测得，相对于Ag | AgCl电极，FeOP二甲基酯在乙腈中的Fe II / Fe III氧化还原电势为+310 mV。该值与天然血红素辅助因子的值正移710 mV，表明亚铁卟啉骨架中的亚铁种类稳定。Fe II OP重构的肌红蛋白是在连二亚硫酸盐存在下制备的，并通过紫外-可见光谱，ESI-TOF MS和尺寸排阻色谱进行了表征。有趣的是，发现重组蛋白的自氧化作用可从血红素袋中释放出辅因子，这表明Fe III OP对载脂蛋白的亲和力大大降低。此外，尽管天然的脱氧肌红蛋白对氰化物没有亲和力，但是氰化物以1.2×10 4 M -1的结合常数结合在肌红蛋白的血红素口袋中的Fe II OP上。这些发现表明，FeOP是一种新型的肌红蛋白人工辅因子，可为亚铁物种提供独特的特征。
• A meso-unsubstituted N-confused porphyrin prepared by rational synthesis
  作者：Ben Y. Liu、Christian Brückner、David Dolphin

  DOI：10.1039/cc9960002141

  日期：——
• Sapphyrins: novel aromatic pentapyrrolic macrocycles
  作者：Victor J. Bauer、Derrick L. J. Clive、David Dolphin、John B. Paine、Francis L. Harris、Michael M. King、John Loder、Shen Wei Chien Wang、Robert Burns Woodward

  DOI：10.1021/ja00359a012

  日期：1983.10
• Smith, Kevin M.; Kehres, Lisa A., Journal of the Chemical Society. Perkin transactions I, 1983, # 10, p. 2329 - 2335
  作者：Smith, Kevin M.、Kehres, Lisa A.

  DOI：——

  日期：——
• PAINE III J. B.; DOLPHIN D., CAN. J. CHEM. <CJCH-AG>, 1976, 54, NO 3, 411-414
  作者：PAINE III J. B.、 DOLPHIN D.

  DOI：——

  日期：——