3',4'-butano-5'-(tert-butoxycarbonyl)-3-ethyl-4-methyl-2,2'-dipyrrylmethane-5-carboxylic acid | 143064-96-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 3',4'-butano-5'-(tert-butoxycarbonyl)-3-ethyl-4-methyl-2,2'-dipyrrylmethane-5-carboxylic acid
• 英文别名: 4-ethyl-3-methyl-5-[[3-[(2-methylpropan-2-yl)oxycarbonyl]-4,5,6,7-tetrahydro-2H-isoindol-1-yl]methyl]-1H-pyrrole-2-carboxylic acid
• CAS: 143064-96-4
• 化学式: C₂₂H₃₀N₂O₄
• 分子量: 386.491
• InChiKey: JMNUFZRRVDOVFP-UHFFFAOYSA-N

物化性质

• 沸点：
  605.8±55.0 °C(Predicted)
• 密度：
  1.202±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  95.2
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3',4'-butano-5'-(tert-butoxycarbonyl)-3-ethyl-4-methyl-2,2'-dipyrrylmethane-5-carboxylic acid 在 硫酸 、 氢溴酸 、 溶剂黄146 、 三氟乙酸 、 copper dichloride 作用下， 反应 5.42h， 生成 12,13-butano-3,8,17-triethyl-2,17,18-trimethylporphyrin
  参考文献：
  名称：

  Porphyrins with exocyclic rings. 2. Synthesis of geochemically significant tetrahydrobenzoporphyrins from 4,5,6,7-tetrahydro-2H-isoindoles

  摘要：

  Benzo- and tetrahydrobenzoporphyrins are widespread constituents of oil shales and petroleum. Although the origins of these materials are not known, a case is made for divinylchlorophyll a, a widespread pigment in marine algae, being the precursor to many of these geoporphyrins. Total syntheses of four tetrahydrobenzoporphyrins related to etioporphyrin III are described. Tetrahydroisoindoles were prepared by condensation of isocyanoacetates with 1-nitrocyclohexene in the presence of DBU or by reaction of aminomalonates with 2-formylcyclohexanone. Condensation of 3-unsubstituted 4,5,6,7-tetrahydro-2H-isoindoles 23c and 23d with (acetoxymethyl)pyrroles in the presence of Montmorillonite clay gave dipyrrylmethanes 28a and 36a in excellent yield. Hydrogenolysis of the benzyl esters and subsequent acid-catalyzed condensation with pyrrole aldehydes 37a and/or 37b gave a series of a,c-biladiene dihydrobromides. Copper(II) mediated cyclization of the a,c-biladienes 32, 33, 35, and 38, followed by demetallation with 15% sulfuric acid-trifluoroacetic acid, gave four isomeric tetrahydrobenzoporphyrins 10-13 in unusually high yield. This work provides a general route for the synthesis of these important porphyrin molecular fossils.

  DOI：

  10.1021/jo00044a013
• 作为产物：
  描述：

  异氰基乙酸叔丁酯 在 palladium on activated charcoal Montmorillonite clay K₁₀ 、 氢气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 异丙醇 、 丙酮 为溶剂， 25.0 ℃ 、206.84 kPa 条件下， 反应 19.0h， 生成 3',4'-butano-5'-(tert-butoxycarbonyl)-3-ethyl-4-methyl-2,2'-dipyrrylmethane-5-carboxylic acid
  参考文献：
  名称：

  Porphyrins with exocyclic rings. 2. Synthesis of geochemically significant tetrahydrobenzoporphyrins from 4,5,6,7-tetrahydro-2H-isoindoles

  摘要：

  Benzo- and tetrahydrobenzoporphyrins are widespread constituents of oil shales and petroleum. Although the origins of these materials are not known, a case is made for divinylchlorophyll a, a widespread pigment in marine algae, being the precursor to many of these geoporphyrins. Total syntheses of four tetrahydrobenzoporphyrins related to etioporphyrin III are described. Tetrahydroisoindoles were prepared by condensation of isocyanoacetates with 1-nitrocyclohexene in the presence of DBU or by reaction of aminomalonates with 2-formylcyclohexanone. Condensation of 3-unsubstituted 4,5,6,7-tetrahydro-2H-isoindoles 23c and 23d with (acetoxymethyl)pyrroles in the presence of Montmorillonite clay gave dipyrrylmethanes 28a and 36a in excellent yield. Hydrogenolysis of the benzyl esters and subsequent acid-catalyzed condensation with pyrrole aldehydes 37a and/or 37b gave a series of a,c-biladiene dihydrobromides. Copper(II) mediated cyclization of the a,c-biladienes 32, 33, 35, and 38, followed by demetallation with 15% sulfuric acid-trifluoroacetic acid, gave four isomeric tetrahydrobenzoporphyrins 10-13 in unusually high yield. This work provides a general route for the synthesis of these important porphyrin molecular fossils.

  DOI：

  10.1021/jo00044a013

文献信息

• Porphyrins with exocyclic rings. 2. Synthesis of geochemically significant tetrahydrobenzoporphyrins from 4,5,6,7-tetrahydro-2H-isoindoles
  作者：Donald A. May、Timothy D. Lash

  DOI：10.1021/jo00044a013

  日期：1992.8

  Benzo- and tetrahydrobenzoporphyrins are widespread constituents of oil shales and petroleum. Although the origins of these materials are not known, a case is made for divinylchlorophyll a, a widespread pigment in marine algae, being the precursor to many of these geoporphyrins. Total syntheses of four tetrahydrobenzoporphyrins related to etioporphyrin III are described. Tetrahydroisoindoles were prepared by condensation of isocyanoacetates with 1-nitrocyclohexene in the presence of DBU or by reaction of aminomalonates with 2-formylcyclohexanone. Condensation of 3-unsubstituted 4,5,6,7-tetrahydro-2H-isoindoles 23c and 23d with (acetoxymethyl)pyrroles in the presence of Montmorillonite clay gave dipyrrylmethanes 28a and 36a in excellent yield. Hydrogenolysis of the benzyl esters and subsequent acid-catalyzed condensation with pyrrole aldehydes 37a and/or 37b gave a series of a,c-biladiene dihydrobromides. Copper(II) mediated cyclization of the a,c-biladienes 32, 33, 35, and 38, followed by demetallation with 15% sulfuric acid-trifluoroacetic acid, gave four isomeric tetrahydrobenzoporphyrins 10-13 in unusually high yield. This work provides a general route for the synthesis of these important porphyrin molecular fossils.