methyl 3-formyl-3-devinylpheophorbide-a | 143986-11-2

• 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: methyl 3-formyl-3-devinylpheophorbide-a
• 英文别名: methyl-3-formyl-3-devinylpheophorbide-a；pheophorbide d methyl ester；methyl pheophorbide-d；methylpheophorbide d；3-formyl-3-devinyl-pheophorbide-a-methyl ester；3-Formyl-3-desvinyl-phaeophorbid-a-methylester
• CAS: 143986-11-2
• 化学式: C₃₅H₃₆N₄O₆
• 分子量: 608.694
• InChiKey: COKAKCHPSAVUFE-QTDPBJQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.38
• 重原子数：
  45.0
• 可旋转键数：
  6.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  144.1
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  methyl 3-formyl-3-devinylpheophorbide-a 在 重氧水 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 [3¹-18O]-methyl pheophorbide-d
  参考文献：
  名称：

  Synthesis of regioselectively 18O-labelled chlorophyll derivatives at the 31- and/or 131-positions through one-pot exchange of carbonyl oxygen atoms

  摘要：

  3(1)- and/or 13(1)-O-18-oxo-labelled methyl pyropheophorbides (84-90% O-18 atoms at each position) were prepared by exchanging carbonyl oxygen atoms under biphasic conditions of acidic (H2O)-O-18. 95% O-18) and dichloromethane. The (un)labelling occurred more rapidly at less sterically hindered (13-C O possessing 13 2 -COOCH3 > 13-C O lacking it) or more reactive carbonyl groups (formyl > keto group), and not at any hydroxy groups. Reduction of a carbonyl to carbinol group was useful for preparation of regioselectively O-18-labelled chlorophyll derivatives. Following the labelling procedure, 13(1)-O-18-pheophytin-a and 3(1)-O-18-pheophytin-d were obtained. All the synthetic O-18-labelled compounds were characterized by their FAB-mass, C-13 NMR and IR spectra. Especially, O-18-labelling induced 0.02 (C-13-O) and 0.04-0.05 ppm high field shifts (C-13=O) in O-18-attached carbon resonances and about 30 cm(-1) down-shifts in O-18-labelled carbonyl stretching vibrational bands. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.04.012
• 作为产物：
  描述：

  (5Z,10Z,14Z,19Z)-(17S,18S)-7-Ethyl-12-formyl-18-(2-methoxycarbonyl-ethyl)-20-methoxycarbonylmethyl-3,8,13,17-tetramethyl-17,18,21,23-tetrahydro-porphine-2-carboxylic acid methyl ester 在 氢氧化钾 作用下， 生成 methyl 3-formyl-3-devinylpheophorbide-a
  参考文献：
  名称：

  Fischer; Walter, Justus Liebigs Annalen der Chemie, 1941, vol. 549, p. 44,74

  摘要：

  DOI：

文献信息

• Reaction of methylpheophorbides d and b with amines
  作者：D. V. Belykh、E. V. Buravlev、M. V. Malˈshakova、N. N. Parshukova、E. A. Kopylov、I. V. Gruzdev、A. V. Kuchin

  DOI：10.1007/s10600-011-9836-1

  日期：2011.3

  A series of formyl analogs of chlorin e6 13-amides were synthesized in high yields by reaction under mild conditions of primary and secondary amines with methylpheophorides b and d. In contrast with the secondary 13-amides, tertiary 13-amides were found as two isomers differing in the orientation of the amide plane relative to the plane of the chlorin ring. Methylpheophorbides b and d were more reactive toward the amines than methylpheophorbide a.

  一系列氯氨C6 13-酰胺的甲酰类似物在温和条件下通过初级和次级胺与甲基酯的b和d反应合成，产率高。与次级13-酰胺相比，发现三级13-酰胺以两种异构体的形式存在，这两种异构体在酰胺平面相对于氯因环平面的方位上存在差异。甲基酯b和d对胺的反应性比甲基酯a更强。
• Synthesis of conjugates of isobornylphenols and natural chlorins
  作者：E. V. Buravlev、I. Yu. Chukicheva、D. V. Belykh、A. V. Kuchin

  DOI：10.1007/s10600-008-9137-5

  日期：2008.9

  A series of terpenophenol—chlorin conjugates containing terpenophenol and porphyrin fragments of various structure was synthesized. The terpenophenol fragment was added to the chlorin macrocycle using reactions of the exocyclic ester and the propionate substituent in the 17-position of methylpheophorbide a analogs.

  合成了一系列包含萜烯酚和不同结构的卟啉片段的萜烯酚—氯素结合物。通过对环外酯和甲基叶绿素a类似物17位的丙酸酯取代基的反应，将萜烯酚片段添加到氯素大环中。
• The synthesis of chlorophyll-a skeleton homologs bearing linear six-carbon chain from methyl pheophorbide-a
  作者：J. J. Wang、G. F. Han、Y. K. Shim

  DOI：10.1007/bf03246552

  日期：2011.12

  The synthesis of chlorins bearing 6C-straight chain was accomplished from methyl pheophorbide-a. A series of chemical modifications were employed for the construction of active functional groups, such as bromine atom or aldehyde group, on the periphery of chlorins. These functionalized chlorins further reacted with the reagent containing straight carbon-chain by common chemical reactions to produce

  二氢卟酚轴承6C-直链的从甲基被完成的合成pheophorbide-一个。一系列化学修饰被用于在二氢卟酚的外围上构建活性官能团，例如溴原子或醛基。这些官能化的二氢卟酚还通过通常的化学反应与含有直碳链的试剂反应，生成目标化合物。所有新二氢卟酚的结构均通过元素分析，IR，UV-Vis和1 H NMR光谱进行了表征。
• Synthesis of Chlorophylla Labeled at C(32) from Pheophorbidea Methyl Ester
  作者：Rolf Fischer、Norbert Engel、Arthur Henseler、Albert Gossauer

  DOI：10.1002/hlca.19940770417

  日期：1994.6.29

  [32-14C]Chlorophyll a (10b) was synthesized from pheophorbide a methyl ester (5a) in a seven-step partial synthesis. The key intermediate pheophorbide d methyl ester (6) was obtained by ozonolysis of the vinyl group of 5a in 91% yield. Selective reduction of the CHO group of 6 gave the corresponding alcohol 7, and conversion of the latter to the phosphonium bromide 8 yielded after Wittig reaction with

  [3 2 - 14 C]叶绿素一个（10B）从脱镁叶绿合成一甲酯（5A）在七步部分合成。通过对5a的乙烯基进行臭氧分解，可以以91％的收率获得关键的中间体脱镁叶绿酸d甲酯（6）。的CHO基团的选择性还原6，得到相应的醇7，而后者的转化为溴化鏻8后得到维悌希与[反应14 C]的多聚甲醛，[3 2 - 14C]脱镁叶绿一甲酯（图5b）。最终转化为标题化合物通过酸水解来实现图5b，酯化的天然植醇〜[3 2 - 14 C]脱镁叶绿素一个（9B），以及镁的最终插入2+离子。
• Ene-thiol reaction of <font>C</font>3-vinylated chlorophyll derivatives in the presence of oxygen: synthesis of <font>C</font>3-formyl-chlorins under mild conditions
  作者：Takanori Fukusumi、Natsuki Takei、Yubi Tateno、Takuya Aoki、Ai Ando、Kouhei Kozakai、Hiroko Shima、Tadashi Mizoguchi、Satoshi Ito、Tsukasa Ikeda、Hitoshi Tamiaki、Toru Oba

  DOI：10.1142/s1088424613500983

  日期：2013.12

  Reactions of thiol with the C 3-vinyl group of various chlorophyll (Chl) derivatives were examined. The reactions resemble thiol-olefin co-oxidation, except that the vinyl C = C double bond was cleaved to afford a formyl group without any transition metal catalyst, and that the simple anti-Markovnikov adduct of thiol to olefin was obtained as a minor product. Peripheral substituents of Chl derivatives little affected the reaction, while the central metal atom of the chlorin macrocycle influenced the composition of the products. Oxygen and acid dissolved in the reaction mixture can facilitate the oxidation. Sufficiently mild conditions in this regioselective oxidation at the C 3¹-position are significant in bioorganic chemistry.

  研究了硫醇与各种叶绿素（Chl）衍生物的 C 3-乙烯基的反应。这些反应类似于硫醇与烯烃的共氧化反应，只是乙烯基 C = C 双键在没有任何过渡金属催化剂的情况下被裂解以产生甲酰基，而且硫醇与烯烃的简单反马尔科夫尼科夫加合物作为次要产物被获得。Chl 衍生物的外围取代基对反应的影响很小，而氯素大环的中心金属原子则会影响产物的组成。溶解在反应混合物中的氧气和酸可促进氧化。在这种 C 31 位的区域选择性氧化反应中，足够温和的条件在生物有机化学中具有重要意义。