dibenzyl 2,3,7,8-tetramethyl-5-(dichloromethyl)dipyrromethane-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 2,3,7,8-tetramethyl-5-(dichloromethyl)dipyrromethane-1,9-dicarboxylate
• 英文别名: benzyl 5-[2,2-dichloro-1-(3,4-dimethyl-5-phenylmethoxycarbonyl-1H-pyrrol-2-yl)ethyl]-3,4-dimethyl-1H-pyrrole-2-carboxylate
• 化学式: C₃₀H₃₀Cl₂N₂O₄
• 分子量: 553.485
• InChiKey: HQQAAYKIWDXZLE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.27
• 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 2,3,7,8-tetramethyl-5-(dichloromethyl)dipyrromethane-1,9-dicarboxylate 在 palladium on activated charcoal 氢气 作用下， 以 四氢呋喃 为溶剂， 生成 5-[1-(5-carboxy-3,4-dimethyl-1H-pyrrol-2-yl)-2,2-dichloroethyl]-3,4-dimethyl-1H-pyrrole-2-carboxylic acid
  参考文献：
  名称：

  Functionalization of Corroles:  Formylcorroles

  摘要：

  Porphyrins and metalloporphyrins can be readily functionalized at the meso-(5,10,15,20)-positions by using a variety of reagents, the Vilsmeier formylation reaction being universally regarded as the prototypical example. On the other hand, the literature shows that corroles and metallocorroles are unusually resistant to most functionalization procedures which are common to porphyrins. The first example of peripheral functionalization of the corrole ring is now reported. Octamethylcorrole 1 readily reacts with the Vilsmeier reagent (POCl3/DMF), but the product is the 10-dimethylaminomethene derivative 2, and not the expected meso-formyl derivatives 3 or 4, as confirmed by a single crystal X-ray crystallographic study. Corrole 5, where the 10-meso-position is substituted, affords the similar product 6. When the reaction is extended to corrole 7 two different products, 8 and 9, are obtained wherein the substitution is performed at both 5- and 10-meso-positions. Unlike the case of porphyrins, no reaction occurs at the beta-unsubstituted pyrrolic positions. Coordination of cobalt to the dimethylaminomethenylcorroles 2 and 5 causes both metalation and tautomerization/hydrolysis to afford the originally targeted meso-formylcorrolato complexes in almost quantitative yields. Attempts to formylate cobalt complex 14 using TFA/trimethylorthoformate affords the corresponding beta-formyl complexes 15 and 16, the ratio of which depends on the reaction time. meso-Formylcorroles are also obtained by way of a new direct synthesis, described herein, using a prefunctionalized a,c-biladiene 22.

  DOI：

  10.1021/jo9706739
• 作为产物：
  描述：

  2,2-二氯-1,1-二乙氧基乙烷 、 3,4-dimethyl-pyrrole-2-carboxylic acid benzyl ester 在 Montmorillonite K₁₀ clay 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以76%的产率得到dibenzyl 2,3,7,8-tetramethyl-5-(dichloromethyl)dipyrromethane-1,9-dicarboxylate
  参考文献：
  名称：

  Functionalization of Corroles:  Formylcorroles

  摘要：

  Porphyrins and metalloporphyrins can be readily functionalized at the meso-(5,10,15,20)-positions by using a variety of reagents, the Vilsmeier formylation reaction being universally regarded as the prototypical example. On the other hand, the literature shows that corroles and metallocorroles are unusually resistant to most functionalization procedures which are common to porphyrins. The first example of peripheral functionalization of the corrole ring is now reported. Octamethylcorrole 1 readily reacts with the Vilsmeier reagent (POCl3/DMF), but the product is the 10-dimethylaminomethene derivative 2, and not the expected meso-formyl derivatives 3 or 4, as confirmed by a single crystal X-ray crystallographic study. Corrole 5, where the 10-meso-position is substituted, affords the similar product 6. When the reaction is extended to corrole 7 two different products, 8 and 9, are obtained wherein the substitution is performed at both 5- and 10-meso-positions. Unlike the case of porphyrins, no reaction occurs at the beta-unsubstituted pyrrolic positions. Coordination of cobalt to the dimethylaminomethenylcorroles 2 and 5 causes both metalation and tautomerization/hydrolysis to afford the originally targeted meso-formylcorrolato complexes in almost quantitative yields. Attempts to formylate cobalt complex 14 using TFA/trimethylorthoformate affords the corresponding beta-formyl complexes 15 and 16, the ratio of which depends on the reaction time. meso-Formylcorroles are also obtained by way of a new direct synthesis, described herein, using a prefunctionalized a,c-biladiene 22.

  DOI：

  10.1021/jo9706739

文献信息

• Functionalization of Corroles:  Formylcorroles
  作者：Roberto Paolesse、Laurent Jaquinod、Mathias O. Senge、Kevin M. Smith

  DOI：10.1021/jo9706739

  日期：1997.9.1

  Porphyrins and metalloporphyrins can be readily functionalized at the meso-(5,10,15,20)-positions by using a variety of reagents, the Vilsmeier formylation reaction being universally regarded as the prototypical example. On the other hand, the literature shows that corroles and metallocorroles are unusually resistant to most functionalization procedures which are common to porphyrins. The first example of peripheral functionalization of the corrole ring is now reported. Octamethylcorrole 1 readily reacts with the Vilsmeier reagent (POCl3/DMF), but the product is the 10-dimethylaminomethene derivative 2, and not the expected meso-formyl derivatives 3 or 4, as confirmed by a single crystal X-ray crystallographic study. Corrole 5, where the 10-meso-position is substituted, affords the similar product 6. When the reaction is extended to corrole 7 two different products, 8 and 9, are obtained wherein the substitution is performed at both 5- and 10-meso-positions. Unlike the case of porphyrins, no reaction occurs at the beta-unsubstituted pyrrolic positions. Coordination of cobalt to the dimethylaminomethenylcorroles 2 and 5 causes both metalation and tautomerization/hydrolysis to afford the originally targeted meso-formylcorrolato complexes in almost quantitative yields. Attempts to formylate cobalt complex 14 using TFA/trimethylorthoformate affords the corresponding beta-formyl complexes 15 and 16, the ratio of which depends on the reaction time. meso-Formylcorroles are also obtained by way of a new direct synthesis, described herein, using a prefunctionalized a,c-biladiene 22.