hexadecahydrotetrabenzo{b,g,l,q}porphyrin | 20413-13-2

• 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: hexadecahydrotetrabenzo{b,g,l,q}porphyrin
• 英文别名: 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-Hexadecahydro-29H,31H-tetrabenzoporphyrin；1,2:3,4:5,6:7,8-Tetrakis(tetramethylene)porphyrin；2,3:7,8:12,13:17,18-tetrabutanoporphyrin；tetrabutanoporphyrin
• CAS: 20413-13-2
• 化学式: C₃₆H₃₈N₄
• 分子量: 526.725
• InChiKey: UBFCASQCYPQFRM-MUZKIALCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.04
• 重原子数：
  40.0
• 可旋转键数：
  0.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  57.36
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  hexadecahydrotetrabenzo{b,g,l,q}porphyrin 在 2,6-二甲基吡啶 、 manganese(ll) chloride 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 1.0h， 以89%的产率得到
  参考文献：
  名称：

  Retooling Manganese(III) Porphyrin-Based Peroxynitrite Decomposition Catalysts for Selectivity and Oral Activity: A Potential New Strategy for Treating Chronic Pain

  摘要：

  Redox-active metalloporphyrins represent the most well-characterized class of catalysts capable of attenuating oxidative stress in vivo through the direct interception and decomposition of superoxide and peroxynitrite. While many interesting pharmacological probes have emerged from these studies, few catalysts have been developed with pharmaceutical properties in mind. Herein, we describe our efforts to identify new Mn(III) porphyrin systems with enhanced membrane solubilizing properties. To this end, seven new Mn(III)-tetracyclohexenylporphyin (TCHP) analogues, 7, 10, 12, 15, and 16a-c, have been prepared in which the beta-fused cyclohexenyl rings provide a means to shield the charged metal center from the membrane during passive transport. Compounds 7, 15, and 16a-c have been shown to be orally active and potent analgesics in a model of carrageenan-induced thermal hyperalgesia. In addition, oral administration of compound 7 (10 100 mg/kg, n = 5) has been shown to dose dependently reverse mechano-allodynia in the CCI model of chronic neuropathic pain.

  DOI：

  10.1021/jm201233r
• 作为产物：
  描述：

  butyl 4,5,6,7-tetrahydro-2H-isoindole-1-carboxylate 在 吡啶 、 lithium aluminium tetrahydride 、 溶剂黄146 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 hexadecahydrotetrabenzo{b,g,l,q}porphyrin
  参考文献：
  名称：

  带有环外环的卟啉。第8部分†。氮15和碳13标记的2,3：7,8：12,13：17,18-四丁氧基卟啉的合成‡ §

  摘要：

  通过异氰基乙酸丁酯从15 N-甘氨酸制备氮15标记的4,5,6,7-四氢-2 H-异二烯基-1-羧酸丁酯，总产率为46％。该双环中间体被转化为氮15和碳13标记的2,3：7,8：12,13：17,18-四丁烷卟啉，这是用于沉积四氢苯并卟啉的有用模型系统。

  DOI：

  10.1002/jhet.5570340141

文献信息

• Synthesis of Octaalkyl- and Octaarylporphyrins from Nitroalkenes
  作者：Noboru Ono、Kazuhiro Maruyama

  DOI：10.1246/cl.1988.1511

  日期：1988.9.5

  Symmetrically substituted octaalkyl- and octaarylporphyrins are readily prepared by the reduction of 2-ethoxycarbonyl-3,4-diarkyl (or diaryl)pyrroles with LiAlH4 followed by treatment with acetic acid and oxidizing agents.

  对称取代的八烷基和八芳基卟啉可以通过用LiAlH4还原2-乙氧基羧基-3,4-二烷基（或二芳基）吡咯，随后用醋酸和氧化剂处理来容易地制备。
• Synthesis of nonplanar <i>meso</i>-trifluoromethyl-substituted tetrabenzoporphyrins <i>via</i> oxidation of tetrabutanoporphyrins
  作者：Koji Okinaga、Masaaki Suzuki

  DOI：10.1142/s1088424619500664

  日期：2020.1

  Simultaneous synthesis of meso-trifluoromethyl-substituted tetrabutanoporphyrins having one or two trifluoromethyl groups at their 5-, 5,10-, and 5,15-positions has been achieved. The products can be converted into the corresponding meso-trifluoromethyl-substituted tetrabenzoporphyrins by oxidative treatment with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone under reflux. Their crystal structures reveal

  同时合成中观已经获得了在它们的5-、5,10-和5,15-位具有一个或两个三氟甲基的-三氟甲基取代的四丁卟啉。产品可以转换成相应的中观-三氟甲基取代的四苯并卟啉，在回流下用 2,3-二氯-5,6-二氰基-1,4-苯醌氧化处理。它们的晶体结构揭示了由外围取代基的空间排斥引起的非平面畸变，这可以提高四苯并卟啉骨架在普通溶剂中的溶解度，而不会损失延伸的π共轭。
• Metal Complexes with Tetrapyrrole Ligands. 47. Yttrium(III) Bis(octaalkylporphyrinate)s: Synthesis and Electron Spin Resonance Spectra of Earth Metal Porphyrin Sandwich Compounds
  作者：Johann Walter Buchler、Jürgen Hüttermann、Jürgen Löffler

  DOI：10.1246/bcsj.61.71

  日期：1988.1

  octaethylporphyrinate, Li2(oep), formed in situ and Y(oep)(acac) in refluxing TCB. The constitution of the double-decker 3A is proved by UV/VIS, IR, 1H NMR, ESR, ENDOR, and mass spectra. The well-defined composition Y(oep)2 requires that one of the porphyrin rings is electron-deficient, i.e. the charge of the YIII ion is compensated by the normal porphyrinate dianion and a porphyrinate monoanion radical. The magnetic

  在回流的 1,2,4-三氯苯 (TCB) 中，三 (2,4-戊二酮) 钇 (III) 与八乙基卟啉 H2oep 反应生成痕量 (2%) 的双层 Y(oep)2 (3A) ) 除了主要量 (72%) 的单卟啉钇 (III) Y(oep)(acac) 之外，这些物质通过色谱法分离。从原位形成的八乙基卟啉二锂 Li2(oep)和回流 TCB 中的 Y(oep)(acac) 获得了可观的 Y(oep)2 (3A) (25%)。双层3A的构成通过UV/VIS、IR、1H NMR、ESR、ENDOR和质谱证实。明确定义的组成 Y(oep)2 要求卟啉环之一是缺电子的，即 YIII 离子的电荷由正常的卟啉二价阴离子和卟啉单阴离子自由基补偿。固态磁矩，μeff=1.5 BM (5–100 K)，也证明了 3A 的激进性质。在所用方法的时间分辨率下，未配对电子在两个卟啉环之间离域。的波数...
• Porphyrins with exocyclic rings. 2. Synthesis of geochemically significant tetrahydrobenzoporphyrins from 4,5,6,7-tetrahydro-2H-isoindoles
  作者：Donald A. May、Timothy D. Lash

  DOI：10.1021/jo00044a013

  日期：1992.8

  Benzo- and tetrahydrobenzoporphyrins are widespread constituents of oil shales and petroleum. Although the origins of these materials are not known, a case is made for divinylchlorophyll a, a widespread pigment in marine algae, being the precursor to many of these geoporphyrins. Total syntheses of four tetrahydrobenzoporphyrins related to etioporphyrin III are described. Tetrahydroisoindoles were prepared by condensation of isocyanoacetates with 1-nitrocyclohexene in the presence of DBU or by reaction of aminomalonates with 2-formylcyclohexanone. Condensation of 3-unsubstituted 4,5,6,7-tetrahydro-2H-isoindoles 23c and 23d with (acetoxymethyl)pyrroles in the presence of Montmorillonite clay gave dipyrrylmethanes 28a and 36a in excellent yield. Hydrogenolysis of the benzyl esters and subsequent acid-catalyzed condensation with pyrrole aldehydes 37a and/or 37b gave a series of a,c-biladiene dihydrobromides. Copper(II) mediated cyclization of the a,c-biladienes 32, 33, 35, and 38, followed by demetallation with 15% sulfuric acid-trifluoroacetic acid, gave four isomeric tetrahydrobenzoporphyrins 10-13 in unusually high yield. This work provides a general route for the synthesis of these important porphyrin molecular fossils.
• Synthesis of 5,15-Diaryltetrabenzoporphyrins
  作者：Mikhail A. Filatov、Artem Y. Lebedev、Sergei A. Vinogradov、Andrei V. Cheprakov

  DOI：10.1021/jo800509k

  日期：2008.6.1

  A general method of synthesis of 5,15-diaryltetrabenzoporphyrins (Ar(2)TBPs) has been developed, based on 2 + 2 condensation of dipyrromethanes followed by oxidative aromatization. Two pathways to Ar(2)TBPs were investigated: the tetrahydroisoindole pathway and the dihydroisoindole pathway. In the tetrahydroisoindole pathway, precursor 5,15-diaryltetracyclohexenoporphyrins (5,15-Ar(2)TCHPs) were assembled from cyclohexeno-fused meso-unsubstituted dipyrromethanes and aromatic aldehydes or, alternatively, by way of the classical MacDonald synthesis. In the first case, scrambling was observed. Aromatization by tetracyclone was more effective than aromatization by DDQ but failed in the cases of porphyrins with electron-withdrawing substituents in the meso-aryl rings. The dihydroisoindole pathway was found to be much superior to the tetrahydroisoindole pathway, and it was developed into a general preparative method, consisting of (1) the synthesis of 4,7-dihydroisoindole and its transformation into meso-unsubstituted dipyrromethanes, (2) the synthesis of 5,15-diaryloctahydrotetrabenzoporphyrins (5,15-Ar(2)OHTBPs), and (3) their subsequent aromatization by DDQ. Ar2TBP free bases exhibit optical absorption spectra similar to those of meso-unsubstituted tetrabenzoporphyrins and fluoresce with high quantum yields. Pd complex of Ph2TBP was found to be highly phosphorescent at room temperature.