101-60-0Relevant academic research and scientific papers
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
Protonation salt derivative with heavy-atom effect on phthalocyanine for enhanced in vitro photodynamic therapy
Chen, Xianglan,Li, Yejing,Wang, Ao,Zhou, Lin,Lu, Shan,Zhou, Jiahong,Lin, Yun,Wei, Shaohua
, p. 93 - 104 (2015)
In order to improve water-solubility and photodynamic activity of 2(3), 9(10), 16(17), 23(24)-tetra-((amino)methyl)phenoxy)phthalocyaninato-zinc (ZnPc) simultaneously, here, we present the first attempt to introduce heavy atoms (Br and I) to ZnPc though a simple method by synthesizing the hydrobromide and hydriodate protonation salt derivatives of ZnPc. Researches indicated that these protonation salt derivatives of ZnPc can stably disperse in aqueous system for a long time. Furthermore, the internal heavy atom effect from hydriodate in the ZnPc molecules enhances the intersystem crossing (ISC) efficiency of ZnPc during its photo-exciting process. Therefore, the generation of reactive oxygen species (ROSs), especially singlet oxygen (1O2), is significantly improved, which leads to an improved in vitro photodynamic therapy (PDT).
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.
Direct synthesis of magnesium porphine via 1-formyldipyrromethane
Dogutan, Dilek Kiper,Ptaszek, Marcin,Lindsey, Jonathan S.
, p. 5008 - 5011 (2007)
(Chemical Equation Presented) The reaction of 1-formyldipyrromethane (100 mM) in toluene at 115°C containing DBU (10 mol equiv) and MgBr2 (3 mol equiv) in the presence of air affords the magnesium chelate Mg(II) porphine in 30-40% yield. The advantages of the new method include simplicity, high concentration, chromatography-free purification, gram-scale synthesis, and avoidance of the poorly soluble free base porphine. Mg(II) porphine exhibits good solubility in common organic solvents and is a valuable core scaffold for derivatization.
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.
Porphine and pyrrole-substituted porphyrin from cyclocondensation of tripyrrane with mono-substituted pyrroles
Saltsman, Irena,Goldberg, Israel,Balasz, Yael,Gross, Zeev
, p. 239 - 244 (2007)
The condensation of non-substituted tripyrrane with mono-substituted pyrroles did not lead to corrole, but to porphine and 5-pyrrolyl-porphyrin. Both compounds were fully characterized by a combination of spectroscopic methods and X-ray crystallography.
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.
The facile synthesis of 5-formylporphyrin
Liu, Peng Peng,Feng, Ya Qing,Gu, Cheng Zhi,Meng, Shu Xian,Zhang, Bao
, p. 505 - 508 (2012)
A facile synthetic route of 5-formylporphyrin (2) has been developed. Using pyrrole and pivaldehyde as the starting materials, 2 was obtained through several facile reactions. The synthetic route is easy to perform and can be scaled up, which gives the compound a better application perspective.
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.
