pyropheophorbide-d methyl ester | 58326-67-3

• 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: pyropheophorbide-d methyl ester
• 英文别名: methyl pyropheophorbide-d；methyl 3-devinyl-3-formyl-13²-demethoxycarbonylpheophorbide a；MPP d
• CAS: 58326-67-3
• 化学式: C₃₃H₃₄N₄O₄
• 分子量: 550.657
• InChiKey: YHGDONPNNAEGQY-DACWROEISA-N

物化性质

• 熔点：
  174-176 °C
• 沸点：
  969.1±65.0 °C(Predicted)
• 密度：
  1.263±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.66
• 重原子数：
  41.0
• 可旋转键数：
  5.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  117.8
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  pyropheophorbide-d methyl ester 在 吡啶 、 magnesium(II) perchlorate 作用下， 生成 zinc methyl pyropheophorbide d
  参考文献：
  名称：

  In vitro demetalation of central magnesium in various chlorophyll derivatives using Mg-dechelatase homolog from the chloroflexi Anaerolineae

  摘要：

  In the metabolic pathway of chlorophylls (Chls), an enzyme called STAY-GREEN or SGR catalyzes the removal of the central magnesium ion of Chls and their derivatives to their corresponding free bases, including pheophytins. The substrate specificity of SGR has been investigated through in vitro reactions using Chl-related molecules. However, information about the biochemical properties and reaction mechanisms of SGR and its substrate specificity remains elusive. In this study, we synthesized various Chl derivatives and investigated their in vitro dechelations using an SGR enzyme. Chl-a derivatives with the C3-vinyl group on the A-ring, which is commonly found as a substituent in natural substrates, and their analogs with ethyl, hydroxymethyl, formyl, and styryl groups at the C3-position were prepared as substrates. In vitro dechelatase reactions of these substrates were performed using an SGR enzyme derived from an Anaerolineae bacterium, allowing us to investigate their specificity. Reactivity was reduced for substrates with an electron-withdrawing formyl or sterically demanding styryl group at the C3-position. Furthermore, the Chl derivative with the C8-styryl group on the B-ring was less reactive for SGR dechelation than the C3-styryl substrate. These results indicate that the SGR enzyme recognizes substituents on the B-ring of substrates more than those on the A-ring.

  DOI：

  10.1007/s11120-024-01088-4
• 作为产物：
  描述：

  methyl 3-(1-hydroxyethyl)-3-deacetyl-bacteriopyrropheophorbide-a 在 sodium periodate 、 四氧化锇 、 silica gel 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 12.0h， 生成 pyropheophorbide-d methyl ester
  参考文献：
  名称：

  Synthesis and Optical Properties of Bacteriochlorophyll-a Derivatives Having Various C3 Substituents on the Bacteriochlorin π-System

  摘要：

  Methyl bacteriopyropheophorbide-a derivatives having a series of substituents at the C3 position were prepared and their optical properties were compared with the corresponding chlorin analogues. Two kinds of oxidation reaction (C3-vinyl -> formyl -> carboxy group) were found to be applicable with a little alteration of the free-base bacteriochlorin macrocycles. The Q(x) and Q(y) electronic absorption peak positions of synthetic bacteriochlorins in CH2Cl2 were affected by the C3 substituents and found to be more sensitive than those of the chlorins. The observed Q(x)/Q(y) peaks in their monomeric states were shifted to a longer wavelength in the order of 1-hydroxyethyl < hydroxymethyl < acetoxymethyl < vinyl < acetyl < carboxy < formyl < 2,2-dicyanoethynyl group. Zinc complex with the C3-hydroxymethyl group formed self-aggregates in a nonpolar organic solvent, which showed the largest red-shift of the Q(y) band (2380 cm(-1), 726 nm in THF to 878 nm in 1% THF-cyclohexane) among those of the synthetic self-aggregative (bacterio)chlorins examined.

  DOI：

  10.1021/jo0523969

文献信息

• Synthesis of chlorophyll-a derivatives possessing the 3-(2-acylethenyl) group by cross-aldol condensation and their optical properties
  作者：Kota Ohashi、Yusuke Kinoshita、Hitoshi Tamiaki

  DOI：10.1016/j.tet.2018.04.018

  日期：2018.5

  possessing a trans-2-acylethenyl group at the C3-position were prepared by cross-aldol (Claisen-Schmidt) condensation of methyl pyropheophorbide-d having the C3-formyl group with ketones bearing α-hydrogen atoms including (un)substituted acetophenones, acetylarenes, and alkanones under basic conditions. The Qy absorption and fluorescence emission bands of the synthetic chalcone analogs in dichloromethane

  叶绿素一个衍生物具有一个反式在C3位上-2- acylethenyl组通过交叉醛醇缩合制备（克莱森-施密特）甲基pyropheophorbide-的缩合d与酮轴承α氢原子，包括未具有C3-甲酰基（ ）在碱性条件下取代的苯乙酮，乙酰芳烃和链烷酮。合成查耳酮类似物在二氯甲烷中的Qy吸收带和荧光发射带在很大程度上取决于C3 3-取代基。特别地，将给电子和吸电子基团引入C 3 3-苯环分别导致最大值的红移和蓝移。此外，通过用C 3 3-苯基环上的硝基取代，极大地抑制了荧光量子产率和寿命。
• Synthesis of methyl pyropheophorbide-d derivatives possessing the 3-acyl groups and their electronic absorption spectra
  作者：Hitoshi Tamiaki、Yuki Kimura、Hiroaki Watanabe、Tomohiro Miyatake

  DOI：10.1016/j.tet.2016.04.074

  日期：2016.6

  Methyl 3-acyl-pyropheophorbides-a were prepared by modification of naturally occurring chlorophyll-a through Grignard or Barbier reactions of the 3-formyl group and successive Ley–Griffith or Dess–Martin oxidations of the resulting secondary alcohols. The semi-synthetic 3-acyl-chlorins gave intense visible bands in dichloromethane and the absorption spectra were dependent on the 31-substituents. The

  3-酰基pyropheophorbides-一个被天然存在的叶绿素修饰制备一通过3-甲酰基团和所得到的仲醇的连续莱伊-格里菲斯或戴斯-马丁氧化剂氧化的格氏试剂或Barbier反应。半合成的3-酰基-二氢卟酚在二氯甲烷中产生很强的可见光带，吸收光谱取决于3 1-取代基。3-酰基与二氢卟酚部分的较大π共轭将可见光的吸收最大值移至更长的波长。
• 3¹-Substituent-dependent self-aggregation of bacteriochlorophyll-<i>d</i> analogs in aqueous micelle
  作者：Shunsuke Tani、Seiji Kanehisa、Hitoshi Tamiaki

  DOI：10.1246/cl.210312

  日期：——

  Zinc bacteriochlorophyll-d analogs possessing the 31-ethyl, vinyl, and ethynyl groups instead of the original 31-methyl group were prepared by chemically modifying chlorophyll-a. The 31-substituents affected their 31-diastereomerically controlled self-aggregation in an aqueous Triton X-100 micelle solution, where the (31R)-epimers of the ethylated and vinylated derivatives readily formed chlorosomal

  锌bacteriochlorophyll- d具有3类似物1，而不是原来的3 -乙基，乙烯基和乙炔基1 -甲基组通过化学修饰叶绿素制备一个。3 1 - 取代基影响了它们在 Triton X-100 胶束水溶液中的 3 1 - 非对映异构控制的自聚集，其中乙基化和乙烯基化衍生物的 (3 1 R )-差向异构体容易形成具有红移的染色体自聚集由于超分子中的激子偶联而产生了吸收带，但是相应的乙炔化差向异构体是单体。
• Chiral Alkyl Groups at Position 3(1′) of Pyropheophorbide-a Specify Uptake and Retention by Tumor Cells and Are Essential for Effective Photodynamic Therapy
  作者：Ravindra R. Cheruku、Erin C. Tracy、Walter Tabaczynski、Joseph R. Missert、Heinz Baumann、Ravindra K. Pandey

  DOI：10.1021/acs.jmedchem.0c02090

  日期：2021.4.22

  versus thioether side chain, and (d) methyl ester versus carboxylic acid group at position 172. The cellular uptake and specificity were defined in human lung and head/neck cancer cells. PSs without a chiral center and with an alkyl chain or thioether functionalities showed limited uptake and PDT efficacy. Replacing the methyl group at the chiral center with a propyl group or introducing an additional chiral

  为了研究焦脱镁叶绿素-a 3(1') 位的手性和精确结构对肿瘤细胞特异性和光动力治疗 (PDT) 的重要性，合成了一系列光敏剂 (PS)：位置 3(1')，(b) 具有可变数量的手性中心的烷基醚链，(c) 己基醚与硫醚侧链，和 (d) 甲酯与 17 位的羧酸基团2. 在人肺和头/颈癌细胞中定义了细胞摄取和特异性。没有手性中心和具有烷基链或硫醚官能团的 PS 显示出有限的吸收和 PDT 功效。用丙基取代手性中心的甲基或引入额外的手性中心可改善细胞保留和肿瘤细胞特异性。在 17 2位用甲酯取代羧酸降低了细胞摄取和 PDT 功效。确定了体外和体内 PS 摄取之间的直接相关性。
• Synthesis of chlorophyll- a derivatives methylated in the 3-vinyl group and their intrinsic site energy
  作者：Hitoshi Tamiaki、Kazuki Tsuji、Masaki Kuno、Yuki Kimura、Hiroaki Watanabe、Tomohiro Miyatake

  DOI：10.1016/j.bmcl.2016.05.008

  日期：2016.7

  Wittig reaction of methyl pyropheophorbide-d possessing the 3-formyl group gave readily methyl pyropheophorbides-a bearing a variety of 3-alkenyl groups as semi-synthetic models of chlorophyll-a. The 3-substituents rotated around the C3–C31 bond from the coplanar conformation with the chlorin π-system, moving the redmost visible absorption maxima to a shorter wavelength. The model experiments showed

  维蒂希的甲基pyropheophorbide-反应d具有3-甲酰基，得到容易甲基pyropheophorbides-一个轴承各种3-链烯基的如叶绿素的半合成模型一个。3-取代基从与二氢卟吩π系统共面构型绕C3–C3 1键旋转，从而将最红的可见光吸收最大值移至较短的波长。模型实验表明，带有3-乙烯基的天然叶绿素a将采用类似的旋转异构体来控制其固有位点能量。