Porphyrins 31. Synthesis and properties of 2-dimethylaminomethyl-5,10,15,20-tetraphenylporphyrin

2-Dimethylaininometkvl-5,10,15, 20-tetraphenylporphyrin has been synthesized for the first time. Its conversion into the previously unknown 2-iodomethyl-5,10,15, 20-tetraphenylporphyrin has been discovered and the facile solvolysis of the latter has been shown.For part 30 see [1].Institute of Biomedical Chemistry, Russian Academy of Medical Sciences, Moscow 119832. Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 7, pp. 906–909, July, 1995. Original article submitted May 24, 1995.     

Porphyrins. 14. Synthesis and properties of 1-substituted derivatives of 5,10,15,20-tetraphenylporphyrin

The Vilsmeier formylatlon of the cobalt complex of 5,10,15,20-tetraphenylporphyrin was realized, and its intermediate salt with the dimethylformamide-POC1₃ complex was isolated; demetallation of the latter gave 1-formyl-5,10,15,20-tetraphenylporphyrin. Formyltetraphenylporphyrin oxime and its 0-acetyl derivative and 1-cyano-5,10,15, 20-tetraphenylporphyrin were synthesized. The Wittig reaction with formylporphyrin and its copper and cobalt complexes with methoxycarbonylmethinyltriphenylphosphorane and diethylamidocarbonylmethinylhexamethyltriamidophosphorane was realized, and conditions that affect the ratios of the Z and E isomers of the acrylic derivatives obtained were studied.See [1] for Communication 13.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 59–64, January, 1982.The authors sincerely thank L. B. Lazukova and A. M. Shul'ge for recording the PMR spectra, V. P. Suboch for recording the mass spectra, and I. I. Mizrakhfor providing us with a sample of phosphorane B.     

Synthesis of Octasubstituted Porphyrins

The synthesis of porphyrins having high solubility in organic solvents requires the presence of long chain aliphatic substituents. Such substituted porphyrins are readily prepared in good yields by extension of our general procedure¹ which involves the synthesis of α,β-unsaturated ketones, conversion of these to 3,4-disubstituted pyrroles followed by acid catalyzed condensations of these pyrroles with formaldehyde in the presence of air.     

键联环糊精、糖苷的卟啉及金属卟啉的合成

全甲基化-6-羟基-β-环糊精(PMβ-CD-CH₂OH)在N₂气流下与三氟甲基磺酸酐反应得到全甲基化-6-三氟甲基磺酸酯-β-环糊精(PMβ-CD-CH₂OTf)(6).6分别与5-(p-氨基苯基)-10,15,20-三苯基镍(钌羰基)卟啉[NiTP_NH2P](2)和[Ru(CO)TP_NH2P](3)缩合得到化合物7和8.1-溴-2,3,4,6-O-乙酰基-α-D-葡萄糖(4)和1-溴-2,3,5-O-乙酰-β-D-呋喃糖(5)分别与H₂TP_NH2P(1)反应得到化合物9和10.新化合物6-10经IR,UV-Vis,¹HNMR和元素分析确证,其中化合物6由MS谱进一步确定.     

Synthesis and Characterization of Push-Pull Porphyrins

A series of “push-pull” porphyrins with 4-nitrophenyl and 4-aminophenyl substituents were synthesized and separated by flash column chromatographic techniques. They were fully characterized by elemental analysis, FAB-MS, FTIR, UV-visible, and ¹H NMR spectroscopies. The unsymmetrical π-electron distribution of the porphyrins caused by the donor (amino) and acceptor (nitro) substituents were investigated by ¹H NMR technique. The pyrrole-H resonance positions can be correlated to the Hammett σ constants of the substituents. Although with strong donor and acceptor substituents, UV-visible spectra show the push-pull porphyrins have rather weak solvatochromism and hence limited intramolecular charge-transfer character.     

卟啉化合物的合成*

卟啉化合物在自然界中广泛存在,它作为辅基普遍存在于血色素、肌球素、细胞色素、接触酶素、过氧物酶、叶绿素和细胞叶绿素中。本文主要介绍吡咯与醛酮缩合环化合成卟啉化合物的两种方法：吡咯与醛酮直接缩合环化法和模块法,分别论述近年来四苯基卟啉型（meso-取代）和八乙基卟啉型（β-取代）合成方面的研究进展。对模块法中模块单体的合成制备给予较为详细的介绍。     

Synthesis of Unsymmetrically Substituted Porphyrins

Four new unsymmetrically substituted porphyrins have been synthesized using 10-aryl-a,c-biladiene dihydrobromide as key intermediate.     

Porphyrins. 39. Synthesis and Chemical Transformations of Porphyrins and Chlorins with 2-Acetyl-1-methyl-3-oxobutyl Substituents

Porphyrins and chlorins containing acetylacetone residues in the peripheral substituents [-CH(Me)CHAc₂] are converted under alkaline conditions into the corresponding deacetylated compounds with [-CH(Me)CH₂Ac] residues. Reduction of the latter as acids using sodium borohydride gives the corresponding alcohols and, after esterification, their acetates with branched peripheral [-CH(Me)CH₂CH(OAc)Me] substituents. Porphyrins and chlorins with such substituents in water-soluble form may hold interest as new photosensitizers in photodynamic cancer therapy.     

新型咔唑类卟啉的合成与性能

以咔唑、对氟苯甲醛和吡咯为原料制得meso-四（4-咔唑）苯基卟啉（TCPP）。以对硝基苯甲醛与吡咯为原料制得meso-四(4-硝基)苯基卟啉（TNPP）; TNPP经还原反应制得meso-四（4-氨基苯基）卟啉（TAPP）; TAPP与咔唑苯甲醛经缩合反应制得新型meso-四[对-（P-N-咔唑基亚苄基亚氨基）]苯基卟啉(TCIPP),其结构和性能经UV-Vis, ¹H NMR, ¹³C NMR, IR,元素分析和循环伏安法（CV）表征。结果表明：TCPP在270~300 nm处有新吸收峰;TCIPP的Q带和B带相比于TCPP有明显红移。TCPP和TCIPP的E_LUMO和E_HOMO分别为-3.18 eV, -5.17 eV和-3.49 eV, -5.08 eV,两者的能级结构与纳米TiO₂的导带能级相匹配。     

Porphyrins. 22. Synthesis of porphyrins with two cyclopentane rings

The Vilsmeier formylation of meso-methylporphyrins and a porphyrin with a cyclopentane ring was investigated. A meso substituent increases the ability of free meso positions to undergo electrophilic substitution reactions. Schiff bases of meso-formylporphyrins were subjected to thermolysis, and a porphyrin with two cyclopentane rings was synthesized for the first time.See [1] for communication 21.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 922–927, July, 1987.     

Porphyrins.

The synthesis of octaalkyl esters of 1,2-(meso-coproporphyrin-I-yl)ethane has been carried out from the corresponding copper complexes ofmeso-hydroxymethyl- and the nickel complexes ofmeso-dimethylaminomethylporphyrins. Their conversion into the correspondingtrans- andcis-ethylenebisporphyrins has been investigated. On boiling in AcOH or xylene, ethylenebisporphyrins form an equilibrium mixture ofcis andtrans isomers. The cis and trans isomers of 1,2-di(octaethylporphyrin-I-yl)ethylene and the octaethyl ester of 1,2-di(coproporphyrin-I-yl)ethylene have been isolated and their interconversions investigated. It was demonstrated by PMR that thecis isomers of ethylenebisporphyrins have a rigid structure in which there is no free rotation of the porphyrin rings. The presence of two atropisomers is also a characteristic of thecis isomer of the coproporphyrin-I derivative. The formation of metal complexes in combination with the preparation of complexes with additional ligands enables control of the conformation of ethanebisporphyrins in solution. A mechanism has been proposed for the oxidation of ethanebisporphyrins totrans-ethylenebisporphyrins in acetic and other lower aliphatic acids.For part 35 see [1]: for preliminary communications see [2, 3].Institute of Biomedicinal Chemistry, Russian Academy of Medical Sciences, Moscow 119832.Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki-shi, Osaka, 567, Japan. Queensland University of Technology. GPO Box 2434, Brisbane 4001, Australia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1627–1645, December, 1997.     

Synthesis of Glucoside Bonded Metal Porphyrins

Enzyme catalyzed reaction often has high selectivity and efficiency under mild conditions. However, disadvantage of enzyme catalysts is the difficulty of recovery. Metalloporphyrin plays an important role in biological system such as redox reaction, electron transfer,oxygen transportation and charge separation etc.1,2 Metalloporphyrins as superoxide dismutase (SOD) mimics have showed the ability of catalyzing the redox reaction of some harmful radicals , such as O2·―, ·OH. Grove and co-…     

Synthesis of Highly Functionalized Fluorinated Porphyrins

Highly functionalized fluorinated porphyrins were synthesized by a convergent strategy. Nucleophilic substitution using fluorinated branched unit and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin afforded highly functionalized fluorinated porphyrin 8 containing 24 fluorinated chains in the peripheral region.     

Synthesis of b-Cyclodextrin Bonded Metal Porphyrins

6-Deoxy- 6-iodo-b -cyclodextrin (1) reacted with 5-(p-aminophenyl)-10,15,20-triphenyl porphyrin(2), 5-(p-aminophenyl)-10,15,20-triphenyl nickel(II) porphyrin [NiⅡTPPNH2P] (3), 5-(p-aminophenyl)-10,15,20-triphenyl manganese(Ⅲ) porphyrin [MnⅢTPPNH2P] (4) and 5-(p-aminophenyl)-10,15,20-triphenyl carbonyl ruthenium porphyrin [RuⅡ(CO)TPPNH2P] (5) to generate the compounds 6-9, respectively. Those new compound 5-9 have been identified by 1H NMR, IR, MS and UV-visible spectra and elemental analysis.     

7种中位—四取代苯基卟啉化合物的合成

卟啉是一类结构与生命物质(如血红素和维生素B_(12))相似的化合物,近年来曾被用于人体肿瘤的光动力学治疗;此外,在电化学、光物理学和光化学、放射医学、微量元素测定、纺织品漂洗等领域中的应用也相当广泛,已受到科技工作者的普遍关注和重视。本文按Rothemond法将相应的取代苯甲醛与新蒸吡咯在丙酸中缩合,制得具有酸性、中性和碱     

Porphyrins.

Substituted N-(meso-porphyrinylmethyl)amines have been synthesized for the first time by the transamination ofmeso-dimethylaminomethylporphyrins with various amines, including derivatives of amino acids and dipeptides, in the presence of methyl (or ethyl) iodide.For Communication 33, see [1].Institute of Biomedical Chemistry, Russian Academy of Medical Sciences, Moscow 119832. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 65–68, January, 1997.     

新型尾式组氨酸卟啉的合成及性质

设计并合成了新型尾式氨基酸卟啉5-(Trt-组氨酸酰胺基苯基)-10,15,20-三苯基卟啉(Trt-His-NH2-TPP,1)及其金属卟啉配合物(Zn,Co,Fe,Mn,分别标记为2～5).通过元素分析、核磁共振氨谱、质谱、紫外-可见光谱和红外光谱等对化合物进行了表征,研究了它们的荧光性质,并通过理论模拟研究了其最...     

Porphyrins and their derivatives: XXVI. Synthesis and properties of 2-(3-butenyl)-5,10,15,20-tetraphenylporphyrin

2-[2-(1,3-Dioxolan-2-yl)vinyl]-5,10,15,20-tetraphenylporphyrin and its copper complex were reduced into the corresponding ethyldioxolanes by diimide generated in the system hydrazine hydrate — air oxygen — pyridine. The hydrolysis of the obtained ethyldioxolanes results in the formylethyl derivatives that react with the methylenetriphenylphosphorane to form 2-(3-butenyl)-5,10,15,20-tetraphenyl porphyrin and its copper complex.     

几种对称镍卟啉配合物的合成、表征和电化学性质

卟啉试剂是一类重要的离子配位显色剂,在生物体中具有重要作用．作为自然界存在的金属卟啉之一,镍卟啉的电化学研究具有化学和生物学意义．四对羟基苯基卟啉合成已有不少报道［１,２］,但产率较低,只有１０％左右．Ｌｉｎｄｓｅｙ等发现用ＢＦ３作催化剂,在ＣＨ２Ｃ...