dibenzyl 5-(chloromethyl)-3,7-diethyl-2,8-dimethyldipyrromethane-1,9-dicarboxylate

• 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: dibenzyl 5-(chloromethyl)-3,7-diethyl-2,8-dimethyldipyrromethane-1,9-dicarboxylate
• 英文别名: benzyl 5-[2-chloro-1-(3-ethyl-4-methyl-5-phenylmethoxycarbonyl-1H-pyrrol-2-yl)ethyl]-4-ethyl-3-methyl-1H-pyrrole-2-carboxylate
• 化学式: C₃₂H₃₅ClN₂O₄
• 分子量: 547.094
• InChiKey: GFOYQLNKXYLDDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  39
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  84.2
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dibenzyl 5-(chloromethyl)-3,7-diethyl-2,8-dimethyldipyrromethane-1,9-dicarboxylate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 以19%的产率得到trans-1,2-bis(5-(benzyloxycarbonyl)-3-ethyl-4-methyl-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-氯乙醛缩二甲醇 、 benzyl 4-ethyl-3-methyl-1H-pyrrole-2-carboxylate 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 0.67h， 以91%的产率得到dibenzyl 5-(chloromethyl)-3,7-diethyl-2,8-dimethyldipyrromethane-1,9-dicarboxylate
  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.