A metal-free catalytic system with N,N',N″-trihydroxyisocyanuric acid (THICA) as the catalyst for the oxidation of nitrotoluenes is introduced, and a novel Pd-free approach for the synthesis of THICA was developed. In a solution of acetic acid, THICA and concentrated nitric acid, nitrotoluenes especially polynitrotoluenes such as 2,4,6-trinitrotoluene (TNT), were converted into the desired carboxylic acids under 0.2 MPa of O(2) at 100°C with yields up to 99%. THICA was synthesized from N-hydroxyphtalimide through a four-step synthesis in a total yield of 46%. A possible mechanism of this catalytic process was proposed where NO(2) and nitric acid first induced a radical of THICA, which then abstracts a hydrogen atom from the methyl on the aromatic ring to form a benzyl radical. This radical then initiates subsequent reactions. The production of the benzyl radical was supported by ESR measurements.
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Theoretical design of multi-nitroxyl organocatalysts with enhanced reactivity for aerobic oxidation.
Chemphyschem
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Department of Chemistry, ZJU-NHU United R&D Center, Zhejiang University, Hangzhou 310027 (China); State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027 (China).
Higher catalytic performances of N,N',N''-trihydroxyisocyanuric acid (THICA), N,N-dihydroxypyromellitimide (NDHPI), and N-hydroxynaphthalimide (NHNI) than that of N-hydroxyphthalimide (NHPI) have been demonstrated recently in aerobic oxidation. Herein, the rational design of reactive multi-nitroxyl organocatalysts has been addressed theoretically by using systematic analysis of some important properties and catalytic activities of yet-to-be-synthesized catalysts. Our results show that 1) NHNI and its analogue, similar to THICA, unlike NHPI and others, are unsuitable for solvent- or mediator-free catalysis due to their strong intramolecular hydrogen-bonding interactions; 2) increasing the reactive hydroxyimide groups on the same aromatic ring, or doped N atoms or ionic-pair groups onto the aromatic ring, can improve catalytic reactivity, whereas appropriate enlargement of conjugated aromatic systems results in unchanged activity; 3) the newly designed catalysts are more active than NHPI and NHNI and have catalytic activities comparable to NDHPI and THICA; 4) the ionic-pair supported case is suggested to be a very active catalyst, even towards inert propane, and can be used as a novel model catalyst for further improvements.
View Article and Find Full Text PDFTheoretical studies on muti-hydroxyimides as highly efficient catalysts for aerobic oxidation.
Chemphyschem
January 2013
Department of Chemistry, Zhejiang University, Hangzhou 310027, PR China.
N,N-dihydroxypyromellitimide (NDHPI) and N,N',N''-trihydroxyisocyanuric acid (THICA) have been recently demonstrated to act as better carbon-radical-producing catalysts than the popular N-hydroxyphthalimide (NHPI). To gain a mature understanding of these particular catalysts, herein their geometrical, electronic, and thermochemical properties, as well as their catalytic activities, have been systemically investigated by a theoretical analysis. It appears that THICA, unlike NDHPI and NHPI, is unsuitable for solvent-free catalysis or catalysis in aprotic solvents due to its favorable coexistent planar conformer.
View Article and Find Full Text PDFA metal-free aerobic oxidation of nitrotoluenes catalyzed by N,N',N″-trihydroxyisocyanuric acid (THICA) and a novel approach to the catalyst.
J Hazard Mater
December 2010
School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, China.
A metal-free catalytic system with N,N',N″-trihydroxyisocyanuric acid (THICA) as the catalyst for the oxidation of nitrotoluenes is introduced, and a novel Pd-free approach for the synthesis of THICA was developed. In a solution of acetic acid, THICA and concentrated nitric acid, nitrotoluenes especially polynitrotoluenes such as 2,4,6-trinitrotoluene (TNT), were converted into the desired carboxylic acids under 0.2 MPa of O(2) at 100°C with yields up to 99%.
View Article and Find Full Text PDFOxidation of substituted toluenes with molecular oxygen in the presence of N,N',N' '-trihydroxyisocyanuric acid as a key catalyst.
J Org Chem
August 2003
Daicel Chemical Industry, Ltd., Shinzaike, Aboshi-ku, Himeji Hyogo 671-1283, Japan.
N,N',N' '-Trihydroxyisocianuric acid (THICA) was found to be a very efficient catalyst for the oxidation of alkylbenzenes with dioxygen. Thus, a variety of meta- and para-substituted toluenes bearing an electron-withdrawing substituent such as cyanotoluene, chlorotoluene, and toluic acid under O(2) (1 atm) in the presence of THICA (5 mol %) and Co(OAc)(2) (0.5 mol %) at 100 degrees C were smoothly oxidized to the corresponding benzoic acids in almost quantitative yields.
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