Porphyrins. 20. Interaction of 2-formyl-5,10,15,20-tetraphenylporphyrin with ch acids

The reactions of 2-formyl-5,10,15-20-tetraphenylporphyrin (Ia) with nitromethane and of its Cu complex (Ib) with nitromethane, malonic acid, and its esters have been investigated. On interacting porphyrins (Ia,b) with nitromethane in AcOH/BuNH₂ the 2-(2-nitrovinyl)porphyrins (IIa,b) were formed, in liquid NH₃ the nitroalcohols (IIIa,b) were formed, and in DMF/BuNH₂ the dinitro derivatives (IVa,b) were formed. The interaction of porphyrin (Ib) with malonic acid and its esters led to the corresponding condensation products in high yield.For Communication 19 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 936–940, July, 1985.     

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 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.     

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.     

Pseudoesters and derivatives. XXV. 1,3-Dipolar cycloaddition of diazomethane to 5-methoxy-3-pyrrolin-2-ones

Cycloaddition of diazomethane to pyrrolinones 1a,b,d,e affords only one regioisomer as a mixture of the epimeric pyrrolopyrazolines 2 and 2 ′,4-Halo derivatives 1f,g react with diazomethane to give the two possible regioisomers 2 and 3. The regio- and stereochemistry of the adducts is evidenced by the ¹H-nmr data. The primary adducts originated from the halopyrrolinones suffer dehydrohalogenation to give aromatized products, which by further methylation give derivatives of type 7, 8, 10 and 11.     

Diazo carbonyl derivatives of heterocycles. 2. Reaction of anhydrides of pyridine- and quinolinedicarboxylic acids with diazomethane

The reaction of anhydrides of cinchomeronic, quinolinic, and acridinic acids with diazomethane was studied. The reaction pathway that they have in common is acylation of diazomethane with opening of the anhydride ring, accompanied by the formation of the corresponding diazo ketones. It is shown that the nature of the heterocyclic part of the anhydride molecule has a substantial effect on the character of the parallel reactions.See [1] for communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1103–1107, August, 1983.     

聚2-对丙烯酰氧苯基-5,10,15,20-四苯基卟啉镍的合成

2－对羟基苯基－5，10，15，20－四苯基卟啉镍（Ⅰ)和2－邻羟基苯基－5，10，15，20－四苯基卟啉镍（Ⅰ′）分别与丙烯酰氯反应，生成了2－对丙烯酰氧苯基－5，10，15，20－四苯基卟啉镍（Ⅱ）和2－邻丙烯酰氧苯基－5，10，15，20－四苯基卟啉镍（Ⅱ′），在引发剂作用下，前者聚合生成了聚2－对丙烯酰氧苯基－5，10，15，20－四苯基卟啉镍（Ⅲ）。通过元素分析、红外光谱、紫外－可见光谱、核磁共振谱和质谱对单体和聚合物的结构进行了表征。     

Reaction of (+)-usninic acid and several of its derivatives with diazomethane

New derivatives of (+)-usninic acid including products of ring expansion, methylation of enol and phenol hydroxyls, and formation of an oxirane ring in addition to products with pyran and furan rings annelated to ring A of (+)-usninic acid were prepared by reaction of (+)-usninic acid and its pyrazole derivatives with diazomethane.     

Reaction of 2-perfluoroalkanoylcyclohexane-1,3-diones with diazomethane

Treatment of 2-perfluoroalkanoyl-5.5-dimethylcyclohexane-1,3-diones with a solution of diazomethane in diethyl ether led to the formation of the corresponding enol ethers and 3-hydroxy-6,6-dimethyl-3-perfluoroalkyl-2,3,6,7-tetrahydrobenzofuran-4(5H)-ones. The latter underwent dehydration on heating in boiling benzene in the presence of a catalytic amount of p-toluenesulfonic acid to give 6,6-dimethyl-3-perfluoroalkyl-6,7-dihydrobenzofuran-4(5H)-ones.     

Reaction of 2-formyl-1,3-cyclohexanediones with cyanoacetamide

Chemistry of Heterocyclic Compounds -     

Monomeric and Trimeric Manganese(III) Complexes of 2-Hydroxy-5,10,15,20-tetraphenylporphyrin. Synthesis and Characterization

The hydrolysis of the monomeric five-coordinate (2-BzO-TPP)Mn(III)Cl complex has been investigated.(1) Evidence for the formation of the cyclic trimeric complex [(2-O-TPP)Mn(III)](3) is presented. The (1)H NMR spectroscopic evidence indicates that the trimeric manganese(III) complex has a head-to-tail cyclic trimeric structure with the pyrrolic alkoxide groups forming bridges from one macrocycle to the manganese(III) ion in the adjacent macrocycle PMn-O-PMn-O-PMn-O. The three manganese(III) porphyrin subunits are not equivalent. The characteristic upfield shift of the 3-H pyrrole resonance (-111.5 ppm at 291 K) was determined and considered as the diagnostic feature for the high-spin d(4) manganese(III)-pyrrole alkoxide coordination. The strong upfield shift of the 3-H resonance has been accounted for by the donation of the electron density from the filled orbital of the 2-O atom on the half-occupied d(z)()()2 orbital of the external manganese(III) ion. The other pyrrole resonances produce the complex multiplet at the typical -5 to -40 ppm region. The (1)H NMR spectra of the series of monomeric 2-substituted manganese(III) 5,10,15,20-tetraphenylporphyrin complexes (2-X-TPP)Mn(III)Cl have been obtained and analyzed. The pattern of the assigned seven pyrrole resonances reflects the asymmetry imposed by 2-substitution and has been used as a (1)H NMR spectroscopic probe to map the spin density distribution. The electronic effect is strongly localized at the beta-substituted pyrrole. The upfield shift of the 3-H resonance increases in the order (2-NO(2)-TPP)Mn(III)Cl < (2-BzO-TPP)Mn(III)Cl < (2-OCH(3)-TPP)Mn(III)Cl < (2-OH-TPP)Mn(III)Cl < (2-NH(2)-TPP)Mn(III)Cl < [(2-O-TPP)Mn(III)(OH)](-) following the increasing electron-donating properties of the beta-substituent.     

Reaction of alkylidenemalononitriles with diazomethane

At –15° C isopropylidenemalononitrile (5) reacts with anequimolar amount of diazomethane to yield the pyrazoline8, which loses nitrogen upon heating, to give 2,2-dimethyl-1,1-cyclopropanedicarbonitrile (9), and 2-butylidenemalononitrile (6). At room temperature with anexcess of diazomethane5 gives a number of homologous 2-methyl-2-n-alkyl-1,1-cyclopropane-dicarbonitriles9–13 via the corresponding homologous alkylidenemalononitriles, as supported by the similarity of products obtained from the reaction of 2-pentylidenemalononitrile (7) and diazomethane.

---

Zusammenfassung Bei –15° C reagiert Isopropylidenmalonitril (5) mit Diazomethan in mol. Verhältnis 11 zu dem Pyrazolin8, welches beim Erwärmen Stickstoff verliert und zu 2,2-Dimethyl-1,1-cyclopropandicarbonitril cyclopropandicarbonitril (9) und 2-Butylidenmalonnitril (6) umgesetzt wird.Wird die Reaktion bei Zimmertemp. mit überschüss. CH₂N₂ ausgeführt, so erhält man ein Gemisch von homologen 2-Methyl-2-n-alkyl-1,1-cyclopropandicarbonitrilen9–13. Die Reaktion verläuft wahrscheinlich über die homologen Alkylidenmalonitrile, weil 2-Pentylidenmalonitril (7) und Diazomethan ein Gemisch von gleichartigen Produkten liefern.

---

---

Herrn Prof. Dr.F. Wessely zum 70. Geburtstag in Hochachtung gewidmet.     

Reaction of thioxanthylium perchlorate with diazomethane

The reaction of thioxanthylium perchlorate with diazomethane was investigated. Depending on the reaction conditions, seven compounds (II, III, V, VI, VIII, IX, and X) are formed which were identified on the basis of spectral data (mainly mass spectra) and chemical reactions. A synthesis was worked out (reaction of compound VII with boron trifluoride) in which dibenzo[b,f]thiepine (VIII) is formed as major product (55%).     

Reaction of diazomethane with p-quinolide compounds

Conclusions The reaction of diazomethane with bromoquinolide compounds leads to the insertion products of the CH₂ group at the C-Br bond, whereas other p-quinolide compounds proved to be inert in this reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp.1889–1891, August, 1976.     

Basicity of 3-formyl-4,7-diaminocoumarins and their azomethine derivatives

The basicity of a series of 3-formyl-4,7-diaminocoumarins and their azomethine derivatives was studied. By using PMR data, it was determined that primary protonation of most aldehydes affects the nitrogen atom in the 7 position and, in the case of azomethines, the nitrogen atom of the azomethine group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 349–352, March, 1993.     

An insight into the vicarious nucleophilic substitution reaction of 2-nitro-5,10,15,20-tetraphenylporphyrin with p-chlorophenoxyacetonitrile: Synthesis and gas-phase fragmentation studies

Meso-tetraarylporphyrins bearing nitro groups are considered as excellent templates to introduce new functionalities in the porphyrin core, namely through reactions with nucleophiles. Here the reaction of 2-nitro-5,10,15,20-tetraphenylporphyrin with p-chlorophenoxyacetonitrile was revisited and it was found that the reaction profile was strongly dependent on the presence or absence of a metal ion in the porphyrinic inner core and on the solvent used. Under the studied synthetic conditions several porphyrins modified at neighbouring β-positions with nitro, amino, ether, ester, nitrile, methylcyano and formyl functionalities were isolated. Most of them are suitable for further modifications and/or conjugation to other substrates or materials. The gas-phase fragmentation studies corroborated the proposed structures. In general, the formation of the main fragment ions involves intramolecular cyclization processes with the formation of five or six-membered rings between the β-pyrrolic and the ortho position of the adjacent meso-phenyl group.