2,3,5,7,8-pentamethyldipyrromethane-1,9-dicarboxylic acid | 1094-58-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 2,3,5,7,8-pentamethyldipyrromethane-1,9-dicarboxylic acid
• 英文别名: 3,4,3',4'-tetramethyl-1H,1'H-5,5'-ethane-1,1-diyl-bis-pyrrole-2-carboxylic acid；Meso-3,3',4,4'-pentamethyl-dipyrromethan-5,5'-dicarbonsaeure；meso,3,4,3',4'-Pentamethyl-dipyrromethan-5,5'-dicarbonsaeure；5-[1-(5-carboxy-3,4-dimethyl-1H-pyrrol-2-yl)ethyl]-3,4-dimethyl-1H-pyrrole-2-carboxylic acid
• CAS: 1094-58-2
• 化学式: C₁₆H₂₀N₂O₄
• 分子量: 304.346
• InChiKey: GNQNCXRZLRUXHV-UHFFFAOYSA-N

物化性质

• 熔点：
  151-153 °C
• 沸点：
  583.5±50.0 °C(Predicted)
• 密度：
  1.306±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  106
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,3,5,7,8-pentamethyldipyrromethane-1,9-dicarboxylic acid 、 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 在 氧气 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 42.0h， 生成 13,17-bis(2-(methoxycarbonyl)ethyl)-2,3,5,7,8,12,18-heptamethylporphyrin
  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：

  3,4-dimethyl-pyrrole-2-carboxylic acid benzyl ester 在 palladium on activated charcoal 氢气 、 四氯化锡 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.67h， 生成 2,3,5,7,8-pentamethyldipyrromethane-1,9-dicarboxylic acid
  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

文献信息

• Syntheses and Some Chemistry of 1,2- and 1,1-Bis(2-pyrrolyl)ethenes
  作者：Hong Xie、David A. Lee、David M. Wallace、Mathias O. Senge、Kevin M. Smith

  DOI：10.1021/jo961582z

  日期：1996.1.1

  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.