3,3',3'',3'''-(3,7,13,17-tetramethyl-porphyrin-2,8,12,18-tetrayl)-tetra-propionic acid tetramethyl ester | 865-16-7

• 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: 3,3',3'',3'''-(3,7,13,17-tetramethyl-porphyrin-2,8,12,18-tetrayl)-tetra-propionic acid tetramethyl ester
• CAS: 865-16-7
• 化学式: C₄₀H₄₆N₄O₈
• 分子量: 710.827
• InChiKey: KIEMNPQCVHEDIL-PUQSVQPZSA-N

物化性质

• 熔点：
  287-289 °C
• 沸点：
  1058.9±65.0 °C(Predicted)
• 密度：
  1.224±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.91
• 重原子数：
  52.0
• 可旋转键数：
  12.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  162.56
• 氢给体数：
  2.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  3,3',3'',3'''-(3,7,13,17-tetramethyl-porphyrin-2,8,12,18-tetrayl)-tetra-propionic acid tetramethyl ester 在 劳森试剂 、 吡啶 、 四氧化锇 、 硫酸 作用下， 以 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Pinacol−Pinacolone Rearrangements in vic-Dihydroxychlorins and Bacteriochlorins:  Effect of Substituents at the Peripheral Positions

  摘要：

  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.

  DOI：

  10.1021/jo960720h
• 作为产物：
  描述：

  {4-(2-Ethoxycarbonyl-ethyl)-5-[3-(2-ethoxycarbonyl-ethyl)-4-methyl-1H-pyrrol-2-ylmethyl]-3-methyl-1H-pyrrol-2-ylmethylene}-dimethyl-ammonium; chloride 在 copper diacetate 、 硫酸 、 sodium carbonate 、 溶剂黄146 、 三氟乙酸 作用下， 以 甲醇 为溶剂， 反应 1.5h， 生成 3,3',3'',3'''-(3,7,13,17-tetramethyl-porphyrin-2,8,12,18-tetrayl)-tetra-propionic acid tetramethyl ester
  参考文献：
  名称：

  Magnetic circular dichroism studies. 66. Synthesis of demethyl monosubstituted porphyrins. The effect of substituent conformation on the magnetic circular dichroism spectra of ethoxycarbonyl porphyrins

  摘要：

  DOI：

  10.1021/jo00192a015

文献信息

• THE SYNTHESIS OF THE UROPORPHYRINS II AND IV
  作者：S. F. MacDonald、K. H. Michl

  DOI：10.1139/v56-230

  日期：1956.12.1

  Uroporphyrin II and uroporphyrin IV have been synthesized by rational methods. The former has also been separated from a mixture of uroporphyrins previously synthesized.

  尿卟啉II和尿卟啉IV已经通过合理的方法合成。前者还从先前合成的尿卟啉混合物中分离出来。
• 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。
• Biosynthesis of porphyrins and related macrocycles. Part 15. Chemical and enzymic formation of uroporphyrinogen isomers from unrearranged aminomethylpyrromethane: separation of isomeric coproporphyrin esters
  作者：Alan R. Battersby、Dennis G. Buckley、David W. Johnson、Lewis N. Mander、Edward McDonald、D. Clive Williams

  DOI：10.1039/p19810002779

  日期：——

  traces of uro'gen-III are formed. Uro'gen-I is produced via a tetrapyrrolic (bilane) intermediate and when the deaminase–cosynthetase enzyme system from Euglena gracilis is present, this intermediate is converted into uro'gen-III. The rearrangement step for this conversion has the same characteristics found earlier for the natural biosynthetic process from porphobilinogen. Pyrromethane (1) is not a direct

  未重排的吡咯甲烷（1）主要化学转化为具有少量uro'gen-IV的uro'gen-I，但仅形成了痕量的uro'gen-III。Uro'gen-I是通过四吡咯烷（乙撑）中间体生产的，当存在来自Euglena gracilis的脱氨基酶-合成酶体系时，该中间体会转化为uro'gen-III。该转化的重排步骤具有较早的从胆色素原的天然生物合成过程中发现的特征。吡咯甲烷（1）并不是uro'gen-III的直接生物合成前体，其原因尚可理解。
• A novel approach to the synthesis of symmetrical and unsymmetrical porphyrin dimers
  作者：Ravindra K. Pandey、Timothy P. Forsyth、Kevin R. Gerzevske、Jack J. Lin、Kevin M. Smith

  DOI：10.1016/s0040-4039(00)79081-2

  日期：1992.9

  Methodology for synthesis of symmetrical or unsymmetrical porphyrin dimers linked at the meso positions with phenyl or stilbene functionalities is reported; 5-porphyrinyl-dipyrromethanes are key intermediates in this approach.

  报道了在内消旋位置与苯基或二苯乙烯官能团连接的对称或不对称卟啉二聚体的合成方法；5-卟啉基-二吡咯甲烷是该方法中的关键中间体。
• Fischer, H.; Andersag, H., Liebigs Annalen der Chemie, 1927, vol. 458, p. 117 - 148
  作者：Fischer, H.、Andersag, H.

  DOI：——

  日期：——