5,5'-bis-benzyloxycarbonyl-3,3',4,4'-tetramethyl-2,2'-dipyrromethane | 915-74-2

• 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: 5,5'-bis-benzyloxycarbonyl-3,3',4,4'-tetramethyl-2,2'-dipyrromethane
• 英文别名: dibenzyl 3,3',4,4'-tetramethylpyrromethane-5,5'-dicarboxylate；dibenzyl 3,3',4,4'-tetramethylpyrromethane-5-5'-dicarboxylate；Dibenzyl 2,3,7,8-tetramethyldipyrromethane-1,9-dicarboxylate；3,4,3',4'-tetramethyl-1H,1'H-5,5'-methanediyl-bis-pyrrole-2-carboxylic acid dibenzyl ester；Di-(3,4-dimethyl-pyrrol-2-yl)-methan-5,5'-dicarbonsaeure-dibenzylester；3,3',4,4'-Tetramethyl-pyrromethan-5,5'-dicarbonsaeuredibenzylester；Benzyl 5,5'-methylenebis(3,4-dimethyl-1H-pyrrole-2-carboxylate)；benzyl 5-[(3,4-dimethyl-5-phenylmethoxycarbonyl-1H-pyrrol-2-yl)methyl]-3,4-dimethyl-1H-pyrrole-2-carboxylate
• CAS: 915-74-2
• 化学式: C₂₉H₃₀N₂O₄
• 分子量: 470.568
• InChiKey: CYNZLUUUTZXXHF-UHFFFAOYSA-N

物化性质

• 熔点：
  182-184 °C
• 沸点：
  671.1±55.0 °C(Predicted)
• 密度：
  1.213±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 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：

  5,5'-bis-benzyloxycarbonyl-3,3',4,4'-tetramethyl-2,2'-dipyrromethane 在 palladium on activated charcoal 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 生成 1,19-Bis(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-a,c-biladiene dihydrobromide
  参考文献：
  名称：

  Novel macrocycles from metal-catalyzed oxidative cyclizations of a,c-biladiene salts

  摘要：

  From the metal-promoted oxidative cyclization of several 1,19-disubstituted a,c-biladiene dihydrobromide salts, a number of novel macrocycles were prepared. For example, the cyclization of 1,-19-bis(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-a,c-biladiene dihydrobromide salt (10) with copper(II) acetate afforded copper(II) 20-((methoxycarbonyl)methyl)-1-(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-1,20-dihydroporphyrin (13) (39% yield), which, upon demetalation, yielded the metal-free 20-((methoxycarbonyl)methyl)-1-(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-1,20-dihydroporphyrin (14) (48% yield). With the substrate 19-((ethoxycarbonyl)methyl)-1-(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-a,c-biladiene dihydrobromide (15), the metal-catalyzed cyclization process produced copper(II) 20-(ethoxycarbonyl)-1-(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-1,20-dihydroporphyrin (18) (27 % yield) and copper(II) 20-(ethoxycarbonyl)-2-(2-(methoxycarbonyl)ethyl)-2,7,8,12,13,17,18-heptamethyl-3-methylidene-2,3-dihydroporphyrin (23) (19 % yield). Upon demetalation of the copper dihydroporphyrin 18, 20'-(ethoxycarbonyl)-20-(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-20'-homoporphyrin (28) (16.5 % yield) was isolated; demetalation of copper(II) 20-(ethoxycarbonyl)-2-(2-(methoxycarbonyl)ethyl)-2,7,8,12,13,17,18-heptamethyl-3-methylidene-2,3-dihydroporphyrin (23) yielded the free base 20-(ethoxycarbonyl)-2-(2-(methoxycarbonyl)ethyl)-2,7,8,12,13,17,18-heptamethyl-3-methylidene-2,3-dihydroporphyrin (25) (24% yield). Using chromium(III) hydroxy acetate as the oxidant (in place of copper(II)), 1,2,3,7,8,12,13,17,18-nonamethyl-1,20-dihydroporphyrin (5) (55-62%) was obtained from the 1,2,3,7,8,12,13,17,18,19-decamethyl-a,c-biladiene salt 3. Mechanisms of macrocycle formation from a,c-biladiene salts, promoted by either copper(II) or chromium(III), appear to proceed via pathways closely resembling the electrochemical cyclization reaction of 1,19-dimethyl-a,c-biladiene salts.

  DOI：

  10.1021/jo00076a030
• 作为产物：
  描述：

  2-((benzyloxy)carbonyl)-3,4,5-trimethylpyrrole 在 溴 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 5.5h， 生成 5,5'-bis-benzyloxycarbonyl-3,3',4,4'-tetramethyl-2,2'-dipyrromethane
  参考文献：
  名称：

  1'，8'-二取代-a ，c-二丁烯盐的电化学环化反应产生的四吡咯产物

  摘要：

  1'，8'-二甲基-和其他1'，8'-二取代的ac -biladiene盐的阳极氧化可提供新颖的环化产物。除卟啉外，还分离，结构鉴定并鉴定了在卟啉合成过程中由氧化环环吡唑酮产生的未结合的大环中间产物，并对其光谱学，电化学行为和化学反应性进行了表征。还简要讨论了由1'-乙氧基羰基甲基-8'-（2-甲氧基羰基乙基）-a ，c-二苯二胺盐形成新的高卟啉的过程。

  DOI：

  10.1016/s0040-4020(01)87058-7

文献信息

• Process For Preparing Prophyrin Derivatives, Such As Protoprophyrin (IX) And Synthesis Intermediates
  申请人：Martin Pierre

  公开号：US20110306761A1

  公开（公告）日：2011-12-15

  The present invention relates to a process for preparing a porphyrin of formula (I), optionally in the form of a salt with an alkali metal and/or in the form of a metal complex: in which: R and R′ are as defined in claim 1, comprising: a step of condensation, in an acidic medium, between a dipyrromethane of formula (II): in which R′b is as defined above for (I), and a dipyrromethane of formula (III): in which R″ is as defined in claim 1 , and also the compounds of formula (III).

  本发明涉及制备公式(I)的卟啉的方法，可以是与碱金属盐和/或金属配合物形式的盐。其中：R和R'如权利要求书所定义，包括以下步骤：在酸性介质中，通过公式(II)的二吡咯甲烷和公式(III)的二吡咯甲烷进行缩合反应。其中，公式(II)的R'b如上所述，公式(III)的R"如权利要求书所定义，还包括公式(III)的化合物。
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  作者：Ben Y. Liu、Christian Brückner、David Dolphin

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