1,19-Bis(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-a,c-biladiene dihydrobromide | 125250-16-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 1,19-Bis(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-a,c-biladiene dihydrobromide
• 英文别名: 1,19-Bis[2-(methoxycarbonyl)ethyl]-2,3,7,8,12,13,17,18-octamethyl-a,c-biladiene dihydrobromide
• CAS: 125250-16-0
• 化学式: 2Br*C₃₅H₄₆N₄O₄
• 分子量: 746.583
• InChiKey: YWRIMQHAYICCHU-YPUDFGKRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.72
• 重原子数：
  44.0
• 可旋转键数：
  10.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  108.9
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1,19-Bis(2-(methoxycarbonyl)ethyl)-2,3,7,8,12,13,17,18-octamethyl-a,c-biladiene dihydrobromide 在 Cu(II)-salt 、 硫酸 作用下， 生成 1-(2-(Methoxycarbonyl)ethyl)-20-((methoxycarbonyl)methyl)-2,3,7,8,12,13,17,18-octamethyl-1,20-dihydroporphyrin
  参考文献：
  名称：

  四吡咯大环中的新型外围取代基迁移反应

  摘要：

  带有大末端（1'，8'）取代基的铜（II）促进a，c-胆二烯盐的环化提供了中间体，这些中间体分阶段经历了各种裂解和环化反应，以生成单-间位取代的卟啉，二氢卟酚，和二内消旋取代的卟啉通过容易的迁移反应。

  DOI：

  10.1016/s0040-4039(00)94672-0
• 作为产物：
  描述：

  在 三氯氧磷 作用下， 反应 0.08h， 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

文献信息

• Porphyrin synthesis from a,c-biladienes. Evidence for a common mechanistic pathway in the electrochemical and chemical routes: formation of novel macrocycles possessing the homoporphyrin carbon skeleton
  作者：Paul A. Liddell、Marilyn M. Olmstead、Kevin M. Smith

  DOI：10.1021/ja00161a081

  日期：1990.2

  RESEARCHERS' APPROACH The key step in the proposed pathway of the electrocyclization (Scheme 2) is the attack of a nucleophile on the angular methyl group of the cyclized intermediate 3. A similar intermediate has not hitherto been isolated from chemical cyclization. The cupric salt-catalyzed cyclization was therefore carried out on biladienes (1) that could produce corresponding intermediates (5)

  研究人员的方法 所提议的电环化途径（方案 2）中的关键步骤是亲核试剂对环化中间体 3 的角甲基的攻击。迄今为止，尚未从化学环化中分离出类似的中间体。因此，铜盐催化的环化反应是在可产生相应中间体 (5) 的双二烯 (1) 上进行的。但由于空间和/或电子原因，它不会发生亲核反应。研究人员的成就