101-60-0Relevant articles and documents
Convenient synthesis of porphine from β-tetra(tert-butyl)porphyrin
Neya, Saburo,Quan, Jingshun,Hoshino, Tyuji,Hata, Masayuki,Funasaki, Noriaki
, p. 8629 - 8630 (2004)
β-Tetra(tert-butyl)porphyrin was prepared from 2-dimethylaminomethyl- 4-tert-butylpyrrole and converted into porphine, the mother compound of porphyrins, in 64% yield. The dealkylation smoothly proceeded in aqueous sulfuric acid over 15 min at 190°C under
Inducing Open-Shell Character in Porphyrins through Surface-Assisted Phenalenyl π-Extension
Bottari, Giovanni,Fasel, Roman,Lorente, Nicolas,Mateo, Luis M.,Robles, Roberto,Ruffieux, Pascal,Sun, Qiang,Torres, Tomás
, p. 18109 - 18117 (2020)
Organic open-shell compounds are extraordinarily attractive materials for their use in molecular spintronics thanks to their long spin-relaxation times and structural flexibility. Porphyrins (Pors) have widely been used as molecular platforms to craft persistent open-shell structures through solution-based redox chemistry. However, very few examples of inherently open-shell Pors have been reported, which are typically obtained through the fusion of non-Kekulé polyaromatic hydrocarbon moieties to the Por core. The inherent instability and low solubility of these radical species, however, requires the use of bulky substituents and multistep synthetic approaches. On-surface synthesis has emerged as a powerful tool to overcome such limitations, giving access to structures that cannot be obtained through classical methods. Herein, we present a simple and straightforward method for the on-surface synthesis of phenalenyl-fused Pors using readily available molecular precursors. In a systematic study, we examine the structural and electronic properties of three surface-supported Pors, bearing zero, two (PorA2), and four (PorA4) meso-fused phenalenyl moieties. Through atomically resolved real-space imaging by scanning probe microscopy and high-resolution scanning tunneling spectroscopy combined with density functional theory calculations, we unambiguously demonstrate a triplet ground state for PorA2 and a charge-transfer-induced open-shell character for the intrinsically closed-shell PorA4.
meso-tetra(tert-butyl)porphyrin as a precursor of porphine
Neya, Saburo,Funasaki, Noriaki
, p. 1057 - 1058 (2002)
Treatment of meso-tetra(tert-butyl)porphyrin with sulfuric acid/1-butanol at 90°C over 15 min afforded porphine in an isolated yield of 74%. De-tert-butylation of the substituted porphyrin provides a rational access to porphine.
A facile route to tripyrrane from 2,5-bis(hydroxymethyl)pyrrole and the improved synthesis of porphine by the '3+1' approach
Taniguchi, Shozo,Hasegawa, Hikaru,Nishimura, Masato,Takahashi, Masahiko
, p. 73 - 74 (1999)
The treatment of 2,5-bis(hydroxymethyl)pyrrole with pyrrole in the presence of hydrochloric acid gave tripyrrane in 61% yield, which afforded porphine in an improved 31% yield by the '3+1' approach.
A novel and efficient synthesis of porphine
Neya, Saburo,Quan, Jingshun,Hata, Masayuki,Hoshino, Tyuji,Funasaki, Noriaki
, p. 8731 - 8732 (2006)
meso-Tetra(n-hexyloxycarbonyl)porphyrin was found to be converted into porphine, the mother compound of porphyrins, in a 77% yield when heated in aqueous sulfuric acid at 180 °C over 30 min under an inert atmosphere. The observation demonstrates that the substituted porphyrin serves as a novel and useful precursor for porphine.
High-Resolution Solid-State 13C NMR Spectra of Porphine and 5,10,15,20-Tetraalkylporphyrins: Implications for the N-H Tautomerization Process
Frydman, Lucio,Olivieri, Alejandro C.,Diaz, Luis E.,Frydman, Benjamin,Morin, Frederick G.,et al.
, p. 336 - 342 (1988)
The solid-state high-resolution 13C nuclear magnetic resonance spectra of porphine and of 5,10,15,20-tetraalkylporphyrins were recorded with use of the CP/MAS technique.The solution kinetics of the hydogen migration between the two tautomers of porphine, meso-tetrapropyl- and meso-tetrahexylporphyrins, were also studied, and the activation parameters were found to be similar to those reported in the literature for tetraarylporphyrins.Porphine showed the same dynamical behavior in the solid state as in solution, while in the solid state the tetraalkylporphyrins showed doubling of the pyrrole carbon resonances at room temperature.The results obtained with the tetraalkylporphyrins can be explained assuming either a proton-transfer reaction slow on the NMR time scale or a fast exchange between two unequally populated tautomers.Three hypotheses are discussed with regard to the kinetic solid-state effects involved: (a) a quenching of the tunneling contribution to the proton-migration process; (b) a fixed geometry adopted by the four nitrogen atoms in the crystal that controls the migration; (c) a coupling between the proton-exchange process and the deformation of the porphyrin skeleton, the latter being hindered by neighboring molecules.
Concerning the Crystal Structure of Porphine: A Proton Pulsed and 13C CPMAS NMR Study
Frydman, Lucio,Olivieri, Alejandro C.,Diaz, Luis E.,Frydman, Benjamin,Kustanovich, Irina,Vega, Shimon
, p. 7001 - 7005 (1989)
Solid-state NMR techniques were employed in order to study the structure and the dynamics of prophine.The changes observed in the line width of the 1H NMR signal between 173 and 443 K suggest that the porphine macrocycles rotate in the crystals.This was confirmed by recording the 13C CPMAS NMR spectra at different temperatures which showed, in addition to expected coalescence of signals due to the central hydrogens tautomerism, a broadening of the resonances due to overall molecular rotation.These studies, coupled to measurements at different temperatures and fieldsof the relaxation times of the 1H magnetization in the rotating frame, allowed us to obtain activation parametres for the motion which are, within experimental error, equal to those made available by CPMAS NMR for the tautomerism of the central hydrogens.These results suggest an explanation for what seems to be a contradiction between the structure of phorphine observed by X-ray, according to which the central hydrogens are localized in opposite pairs of nitrogens, and the structure observed by CPMAS in which the hydrogen migrate between the four central nitrogens.If it is assumed that the migration of the central hydrogens is coupled to a 90 deg rotation of the molecules, the translational symmetry of the crystal will not be changed by the tautomerism, and an X-ray analysis would always detect a single tautomer.
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Krol
, p. 2065 (1959)
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Soluble porphyrin polymers
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Page/Page column, (2015/07/15)
Porphyrin polymers of Structure 1, where n is an integer (e.g., 1, 2, 3, 4, 5, or greater) are synthesized by the method shown in FIGS. 2A and 2B. The porphyrin polymers of Structure 1 are soluble in organic solvents such as 2-MeTHF and the like, and can be synthesized in bulk (i.e., in processes other than electropolymerization). These porphyrin polymers have long excited state lifetimes, making the material suitable as an organic semiconductor for organic electronic devices including transistors and memories, as well as solar cells, sensors, light-emitting devices, and other opto-electronic devices.
Synthesis and evaluation of analgesic, anti-inflammatory and anti-bacterial activity of synthetic porphyrin derivatives
Naveed Umar, Muhammad,Ur. Rashid, Haroon,Gul Sayed, Mian,Karim, Nasiara,Ghaffar, Rukhsana,Antonio Utrera Martines, Marco,Shoaib, Mohammad
, p. 861 - 866 (2015/11/24)
In this work porphyrins compounds (N1-N4) were synthesized from monohydroxy tetraphenylporphyrin, and then characterized on the basis of their chemical properties and spectral data. They were further tested for their potential analgesic and anti-inflammatory activities in acetic acid induced writhing test in mice and carrageenan induced paw edema in rats. The compounds were also evaluated for antibacterial activity in disc diffusion method. Compounds N1, N2 and N4 showed significant analgesic and anti-inflammatory activity at 10 and 30 mg/kg (b.w), comparable to the standard reference drugs. Furthermore, all the tested compounds possessed significant anti-bacterial activity against both gram positive and gram negative bacteria. The analgesic, anti-inflammatory and anti-bacterial activities of the tested compounds were found comparable to reference drugs. These compounds can serve as precursors for the development of clinically useful analgesics, anti-inflammatory and anti-bacterial agents.
