2-Acetyldeuteroporphyrindimethylester | 15295-27-9

• 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: 2-Acetyldeuteroporphyrindimethylester
• CAS: 15295-27-9
• 化学式: C₃₄H₃₆N₄O₅
• 分子量: 580.684
• InChiKey: IARMSTLDMBLSJD-YFDVIUBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.68
• 重原子数：
  43.0
• 可旋转键数：
  7.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  127.03
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  2-Acetyldeuteroporphyrindimethylester 在 吡啶 、 盐酸 、 sodium tetrahydroborate 、 对甲苯磺酸 、 thallium(III) nitrate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 邻二氯苯 为溶剂， 反应 21.29h， 生成 2-(2-acetoxyethyl)-6,7-bis(2-methoxycarbonylethyl)-1,3,5,8-tetramethylporphyrin
  参考文献：
  名称：

  Manipulation of vinyl groups in protoporphyrin IX: introduction of deuterium and carbon-13 labels for spectroscopic studies

  摘要：

  DOI：

  10.1021/ja00360a015
• 作为产物：
  描述：

  3,3'-<8-<(RS)-1-Hydroxyethyl>-2,7,12,18-tetramethyl-21H,23H-porphyrin-13,17-diyl>dipropionsaeure-dimethylester 、 2-(1-Hydroxyethyl)deuteroporphyrin-IX dimethyl ester 在 吡啶 、 sodium dichromate 作用下， 生成 3,3'-<8-Acetyl-2,7,12,18-tetramethyl-21H,23H-porphyrin-13,17-diyl>dipropionsaeure-dimethylester 、 2-Acetyldeuteroporphyrindimethylester
  参考文献：
  名称：

  Fischer; Wecker, Hoppe-Seyler's Zeitschrift fur Physiologische Chemie, 1942, vol. 272, p. 1,11, 18

  摘要：

  DOI：

文献信息

• Substituent effects in tetrapyrrole subunit reactivity and pinacol-pinacolone rearrangements: Vic-dihydroxychlorins and vic-dihydroxybacteriochlorins
  作者：Ravindra K. Pandey、Fuu-Yau Shiau、Meden Isaac、S. Ramaprasad、Thomas J. Dougherty、Kevin M. Smith

  DOI：10.1016/s0040-4039(00)74751-4

  日期：1992.12

  presence of electron-withdrawing groups on the macrocycle, the oxidation taking place at the subunit in the quadrant opposite to the electronegative group. Migratory aptitudes in subsequent pinacol-pinacolone rearrangements of porphyrin and pheophorbide vic-dihydroxy systems are likewise dependent upon the presence of electron-withdrawing functionalities.

  卟啉中吡咯亚基OsO 4氧化的区域专一性受到大环上吸电子基团的显着影响，氧化发生在与负电基团相反的象限中的亚基上。在卟啉和脱镁叶绿的后续频哪醇-频哪酮重排洄游性向VIC -二羟基系统同样是依赖于吸电子官能团的存在。
• Protiodeacetylation of porphyrins and pyrroles: a new partial synthesis of dehydrocoproporphyrin (S411-porphyrin)
  作者：Kevin M. Smith、Kevin C. Langry

  DOI：10.1039/c39810000283

  日期：——

  complexes of acetyl-porphyrins with ethanedithiol and boron trifluoride–ether in acetic acid efficiently accomplishes deacetylation of the porphyrin system, and this reaction is demonstrated in a new partial synthesis of dehydrocoproporphyrin (S411-porphyrin); acetylpyrroles are also quantitatively deacetylated under these conditions.

  用乙二硫醇和三氟化硼-乙醚在乙酸中处理乙酰基卟啉的铜（II）配合物可有效地完成卟啉体系的脱乙酰作用，该反应在脱氢卟啉的新的部分合成中得到了证实（S411-卟啉）；在这些条件下，乙酰基吡咯也被定量脱乙酰。
• Regioselective syntheses of ether-linked porphyrin dimers and trimers related to photofrin-II®
  作者：Ravindra K. Pandey、Fuu-Yau Shiau、Thomas J. Dougherty、Kevin M. Smiths

  DOI：10.1016/s0040-4020(01)91025-7

  日期：1991.11

  Using isomerically pure 4-(1-hydroxyethyl)deuteroporphyrin-IX dimethyl ester 10, 2-(1-hydroxyethyl)deuteroporphyrin-IX dimethyl ester 11, 2-acetyl-4-(1-hydroxyethyl)deuteroporphyrin-IX dimethyl ester 12 and 4-acetyl-2-(1-hydroxyethyl)deuteroporphyrin-IX dimethyl ester 13 as starting materials, a series of regiochemically pure ether-linked porphyrin dimers 25–41 and trimers 42–47 related to an anticancer

  使用异构体纯的4-（1-羟乙基）次卟-IX二甲酯10，2-（1-羟乙基）次卟-IX二甲酯11 2-乙酰基-4-（1-羟乙基）次卟-IX二甲酯12和4 -乙酰基-2-（1-羟乙基）氘卟啉-IX二甲酯13作为起始原料，一系列区域化学纯的醚连接卟啉二聚体25-41和三聚体42-47合成了与一种称为Photofrin-II®的抗癌药物有关的药物。质子NMR核Overhauser增强实验和可变温度质子NMR光谱用于表征异构体。测试了其中某些化合物相对于Photofrin-II的体内光敏能力，并简要描述了初步结果。
• Synthesis of Fluorine Analogs of Protoporphyrin Potentially Useful for Diagnosis and Therapy of Cancer. IV. Synthesis of (Trifluorovinyl)vinyl- and (1-Chloro-2,2-difluorovinyl)vinyldeuteroporphyrins.
  作者：Tsuyoshi SHIGEOKA、Yasuhisa KUWAHARA、Kiyoko WATANABE、Kasuyuki SATO、Masaaki OMOTE、Akira ANDO、Itsumaro KUMADAKI

  DOI：10.1248/cpb.47.1326

  日期：——

  Trifluoro or Chlorodifluoro analogs lf protoporphyrin, the compounds in the title, were synthesized for use in the diagnosis and therapy of cancer. 3-Or 8-acetyldeuteroporphyrin dimethyl esters (2 and 3) were iodinated with iodine in the presence of potassium carbonate to the corresponding iodo compounds (5 and 6). The iodo compounds (5 and 6) were treated with bis(trifluorovinyl)zinc in the presence of tetrakis(triphenylphosphine)-palladium to give trifluorovinyl derivatives (7 and 8) in good yields.Reduction of the acetyl group of 7 and 8 with sodium borohydride afforded the corresponding hydroxyethyl derivatives (9 and 10). Compounds (9 and 10) were dehydrated with methanesulfonyl chloride and triethylamine to give (trifluorovinyl)vinyldeuteroporphyrin dimethyl esters (11 and 12).Treatment of 5 and 6 with bis(1-chloro-2, 2-difluorovinyl)zinc in the presence of tetrakis(triphenylphosphine)palladium, followed by similar reactions as above gave (1-chloro-2, 2-difluorovinyl)-vinyldeuteroporphyrin dimethyl esters (17 and 18).

  三氟或二氟氯原卟啉类似物（即标题中的化合物）被合成用于癌症的诊断和治疗。在碳酸钾存在下，3-或8-乙酰基二氢卟啉二甲酯（2和3）被碘化，得到相应的碘化合物（5和6）。在四（三苯基膦）钯存在下，碘化合物（5和6）与双（三氟乙烯基）锌反应，得到三氟乙烯基衍生物（7和8），收率较高。用硼氢化钠还原7和8的乙酰基，得到相应的羟乙基衍生物（9和10）。用甲磺酰氯和三乙胺使化合物（9和10）脱水，得到（三氟乙烯基）乙烯基二氢卟啉二甲酯（11和12）。在四（三苯基膦）钯存在下，用双（1-氯-2,2-二氟乙烯基）锌处理5和6，然后进行与上述类似的反应，得到（1-氯-2,2-二氟乙烯基）乙烯基二氢卟啉二甲酯（17和18）。
• Pinacol−Pinacolone Rearrangements in <i>vic-</i>Dihydroxychlorins and Bacteriochlorins:  Effect of Substituents at the Peripheral Positions
  作者：Ravindra K. Pandey、Meden Isaac、Craig J. Medforth、Mathias O. Senge、Thomas J. Dougherty、Kevin M. Smith

  DOI：10.1021/jo960720h

  日期：1997.3.1

  Upon reaction with osmium tetraoxide a series of porphyrins and chlorins were converted into the corresponding vic-dihydroxychlorins and bacteriochlorins. The presence of an electron-withdrawing substituent at a peripheral position on the porphyrins or chlorins deactivated that particular pyrrole unit toward oxidation, and also directed the oxidation regioselectively to the pyrrole ring opposite to the one bearing the electronegative group. The vic-dihydroxychlorins and bacteriochlorins were converted into the corresponding oxochlorins and dioxobacteriochlorins under pinacol-pinacolone reaction conditions. The migratory behavior of the various substituents were found to be quite complex, since distant conjugated peripheral substituents were able to affect the stability of the carbocation intermediates during the process; the ability to rearrange was affected not only by the intrinsic nature of the migratory group but also by steric and electronic factors operative elsewhere on the porphyrin and chlorin macrocycles. Preferential migration of the propionic ester over the methyl substituent in dioxobacteriochlorins obtained from 2,3,12,13-tetrahydroxycoproporphyrin II tetramethyl ester (IUPAC nomenclature) under pinacol-pinacolone conditions was confirmed by a single crystal X-ray study. The dioxobacteriochlorins obtained from mesoporphyrin III dimethyl ester and coproporphyrin II tetramethyl ester were converted into the corresponding dithioanalogues using Lawesson's reagent; this caused a red shift of 62 nm (compared with the dioxo compounds) affording long wavelength absorption at lambda(max) 746 nm.