29116-33-4Relevant articles and documents
Realizing metalloporphyrin functionalization of 4-vinylpyridine copolymer via axial coordination reaction
Gao, Baojiao,Wang, Ruixin,Du, Ruikui
, p. 235 - 243 (2010)
Cobalt tetra(para-chlorophenyl)porphyrin (CoTCPP) and zinc tetraphenyl porphyrin (ZnTPP) were linked on the side chains of the copolymer of 4-vinylpyridine (4VP) and styrene (St), P(4VP-co-St), via axial coordination reactions, respectively, and the metalloporphyrin-functionalized macromolecules, CoTCPP-P(4VP-co-St) and ZnTPP-P(4VP-co-St), were prepared. Their chemical structures were characterized by FTIR and 1H NMR. The spectral properties of the two macromolecular axial coordination complexes were mainly studied, and their photophysical behavior were discussed in depth. The experimental results show that the metalloporphyrin-functionalized macromolecules, CoTCPP-P(4VP-co-St) and ZnTPP-P(4VP-co-St), can be prepared favorably through axial coordination reaction with the side pyridine groups of the copolymer P(4VP-co-St) as ligands. The two complexes have characteristic spectra similar to that of the small molecular metalloporphyrins, CoTCPP and ZnTPP, respectively. At the same time, they also display the characteristic spectroscopic property of axial coordination complexes: the electronic adsorption spectra of CoTCPP-P(4VP-co-St) and ZnTPP-P(4VP-co-St) red-shifted obviously as compared to that of CoTCPP and ZnTPP, and the fluorescence emission of ZnTPP-P(4VP-co-St) blue-shifted apparently with respect to that of ZnTPP. For CoTCPP-P(4VP-co-St) and ZnTPP-P(4VP-co-St), some polymer effects were found: (1) The bonding degree of the small molecular metalloporphyrin, CoTCPP or ZnTPP, on the side chains of the copolymer P(4VP-co-St) has a limit value because of the steric hindrance and there is a bonding degree difference between the actual value and the theoretical value; (2) For ZnTPP-P(4VP-co-St), slight energy transfer between adjacent ZnTPP units on an identical macromolecule occurs, leading to slight static quench of the fluorescence emission as the bonding density of ZnTPP units on the side chains of the copolymer P(4VP-co-St) reaches a certain value.
Efficient oxidation of cumene to cumene hydroperoxide with ambient O2 catalyzed by metalloporphyrins
Shen, Hai M.,Ye, Hong L.,Wang, Qin,Hu, Meng Y.,Liu, Lei,She, Yuan B.
, p. 314 - 322 (2021/04/09)
A novel and efficient protocol for oxidation of cumene to cumene hydroperoxide was presented using ambient O2 catalyzed by very simple metalloporphyrins. The selectivity toward cumene hydroperoxide reached 98.3% in the cumene conversion of 28.1% with T(4-COOH)PPCu as a catalyst at 80°C. The origin of the higher performance of T(4-COOH)PPCu was mainly ascribed to the low catalytic performance of copper(II) in the cumene hydroperoxide decomposition, and the ability of T(4-COOH)PP in stabilizing cumene hydroperoxide through hydrogen-bond interactions between them. Compared with current industrial processes and academic research in oxidation of cumene to cumene hydroperoxide with O2, the main superiorities of this protocol were the high selectivity, high conversion, simple catalysts, solvent-free, additive-free and mild conditions which made this work an appealing reference for the industrial oxidation of cumene to cumene hydroperoxide, as well as the oxidative functionalization of other C-H bonds in various hydrocarbons. 2021 World Scientific Publishing Company.
A preparing method of p-nitroacetophenone
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Paragraph 0051-0053, (2019/01/07)
A preparing method of p-nitroacetophenone is disclosed. The method includes reacting p-nitroethylbenzene, as a raw material, in an autoclave at 110-150 DGE C for 3-7 h under the function of a metalloporphyrin catalyst shown as a formula 1 or a formula 2 in an oxygen atmosphere having a pressure of 0.8-2 MPa under a condition of no solvent; and subjecting an obtained reaction liquid mixture to after-treatment to obtain the target product that is p-nitroacetophenone. The method includes reaction in the sealed autoclave, thus greatly reducing volatilization loss of the raw material, and avoidingemission of reaction waste gas so as to avoid environment pollution therefrom. The bionic metalloporphyrin catalyst which is naturally degradable is adopted as an auxiliary catalyst, is low in dosage,and can increase product selectivity. Consumption of an organic solvent and purification of the target product are avoided, thus reducing the cost.
