Nucleophilic substitution of <i>meso</i>-nitrooctaethylporphyrins

Gong, Liang-Chu; Dolphin, David

doi:10.1139/v85-067

Cited by 36 publications

(21 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Strong nitration reagents such as NO2 in acetone, and nitronium tetrafluoroborate, have been used for the nitration of 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) (17,18) and fuming nitric acid has been used for the nitration of TetPhP (13a). These reagents are strong oxidants and the low nitration yields probably result from destruction of the porphyrin ring structure.…”

Section: Synthesis Of the Porphyrins I Dmentioning

confidence: 99%

Porphyrin chemistry pertaining to the design of anti-cancer drugs; part 1, the synthesis of porphyrins containing meso-pyridyl and meso-substituted phenyl functional groups

Meng¹,

James²,

Skov³

1994

Can. J. Chem.

View full text Add to dashboard Cite

Condensation of pyrrole with a benzaldehyde and 4-pyridinecarboxaldehyde mixture yields the six possible meso-substituted phenyl or pyridyl porphyrins. Nitration of four of these has yielded 13 other porphyrins containing one to four 4-nitrophenyl moieties, and SnCl2 reduction of eight of these nitrophenylporphyrins gives the corresponding 4-aminophenyl(phenyl)- or 4-aminophenyl(phenyl)(4-pyridyl)-porphyrins. Twelve of the porphyrins are new, but all 27 are fully characterized by 1H NMR; resonances for every proton within each of the phenyl, pyridyl, and pyrrole rings are assigned. Trends in UV–VIS data are discussed, while IR and mass spectral data are noted for selected porphyrins.

show abstract

Section: Synthesis Of the Porphyrins I Dmentioning

confidence: 99%

Porphyrin chemistry pertaining to the design of anti-cancer drugs; part 1, the synthesis of porphyrins containing meso-pyridyl and meso-substituted phenyl functional groups

Meng¹,

James²,

Skov³

1994

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…The incorporation of electron donor groups in the nitroporphyrins offers a valuable tool to investigate the photophysical properties. Several interesting studies of β-octaalkyl and tetraphenyl/tetratolylporphyrins endowed with nitro groups either directly attached at the β-pyrrole position(s) [3][4][5] or at the meso-carbon atom(s) 6,7 or on the meso-aryl ring(s) [8][9][10][11] have been reported in the literature. Porphyrins substituted with electron withdrawing nitro group(s) have been studied for tuning redox 12 and photophysical properties 13 and for further functionalization of the macrocycle.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic, Redox and Biological Studies of Push-Pull Porphyrins and Their Metal Complexes

Rajesh¹,

Rahiman²,

Bharathi³

et al. 2010

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

We have synthesized a series of push-pull porphyrins containing both donor and acceptor substituents at the mesopositions and have examined their spectral and biological properties. The push-pull porphyrins containing both strong donor NH2 and acceptor NO2 at meso-positions, in which donor group condensed with the ligand, (2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formlyphenol (L) to form imine linkages with porphyrin. The Schiff base ligand 5-[4-(2,6-bis(4-methylpiperazine-1-yl-methyl)-4-iminomethylphenol)phenyl]-10,15,20-tris(4-nitrophenyl) porphyrin [an3(TPP)L] can be synthesized from 2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formylphenol (L) and 5-(4-aminophenyl)-10, 15,20-tris(4-nitrophenyl)porphyrin. The push-pull porphyrin [an3(TPP)L] was metallated to get copper, nickel and zinc complexes. The spectral, electrochemical, antibacterial, antifungal and cytotoxicity properties of all the donor-acceptor push-pull porphyrins and their complexes were characterized and studied.

show abstract

“…Care must be taken during demetallation since acid catalyzed tzucleophilic substitution of the nitro groups can readily occur (24).…”

mentioning

confidence: 99%

Nitrooctaethylporphyrins: synthesis, optical and redox properties

Gong¹,

Dolphin²

1985

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

LIANG-CHU GONG and DAVID DOLPHIN. Can. J. Chem. 63, 401 ( 1 985). The reaction of zinc octaethylporphyrin with N z 0 4 in dichloromethane gives, in a stepwise reaction, the zinc complexes of mono-, di-, tri-, and tetra-nitrooctaethylporphyrins. Demetallation, under acidic conditions, gives the corresponding free base porphyrins. The meso-nitro groups exert both steric and electronic effects on the porphyrin macrocycle. Thus N-protonation of the nitrated species causes a distortion of the ring and gives an optical spectrum similar to that of protonated meso-arylsubstituted porphyrins. In addition, the nitro groups make the oxidation of the porphyrin ring more difficult and at the same time facilitate the ring reductions.LIANG-CHU GONG et DAVID DOLPHIN. Can. J. Chem. 63, 401 ( I 985). La rkaction du sel de zinc de I'octaCthylporphyrine avec le N204 dans le dichloromCthane conduit, par I'intermCdiaire d'une sCrie de rCactions, aux complexes de zinc des mono-, di-, tri-et tCtra-nitrooctaCthylporphyrines. La dCmCtalation, en utilisant des conditions acides, conduit aux porphyrines correspondantes qui existent sous forme de bases libres. Les groupes nitro en positions mPso exercent des effets la fois stCriques et Clectroniques sur le macrocycle de porphyrine. La N-protonation des espkces nitrCes provoque donc une distortion du cycle et fournit un spectre optique semblable a celui des porphyrines protontes portant des substituants aryles en position meso. De plus, les groupes nitro rendent le cycle porphyrine moins susceptible a I'oxydation et ils facilitent les reductions des cycles.[Traduit par le journal]Porphyrins, like most other aromatic systems, undergo electrophilic substitution. However, as with all heteroaromatic systems, the competition between the basicity of the heteroatom and the nucleophilicity of the aromatic a-system can prevent many substitution reactions from occurring. A striking example of this is the faster rate of meso-substitution of octaethylporphyrin (OEP) in CH3COzD compared to CF3C02D (I)! ~, Electrophilic substitution at the porphyrin periphery has been recently reviewed (2) and, while a wide variety of reactions have been described, few high-yield reactions have been reported. The usually large effort that must be expended to prepare any porphyrin, other than the trivially easy reactions to generate tneso-arylporphyrins (3), requires that further manipulations should be as efficient as possible. We report here on the convenient preparation of the nitrooctaethylporphyrins and the effect the electron-withdrawing groups have on the redox properties of the free bases and some metal complexes.The direct nitration of OEP in fuming nitric acidlacetic acid gives good yields of 5-nitrooctaethylporphyrin (5-(N02)OEP (1)) with considerably diminished yields of the dinitroporphyrins 5,10-(N0)z0EP (2) and 5,15-(NOz)OEP (3). Under more forcing conditions (HN03/H2S04), 20% of the 5,10,15-trinitrooctaethylporphyrin (4) can be formed but isolable amounts of the 5,10,15,20-tetranitroporphyrin (5) are not ob...

show abstract

Nucleophilic substitution of meso-nitrooctaethylporphyrins

Cited by 36 publications

References 4 publications

Porphyrin chemistry pertaining to the design of anti-cancer drugs; part 1, the synthesis of porphyrins containing meso-pyridyl and meso-substituted phenyl functional groups

Porphyrin chemistry pertaining to the design of anti-cancer drugs; part 1, the synthesis of porphyrins containing meso-pyridyl and meso-substituted phenyl functional groups

Spectroscopic, Redox and Biological Studies of Push-Pull Porphyrins and Their Metal Complexes

Nitrooctaethylporphyrins: synthesis, optical and redox properties

Contact Info

Product

Resources

About