- Synthesis of Secondary Aldimines from the Hydrogenative Cross-Coupling of Nitriles and Amines over Al2O3-Supported Ni Catalysts
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A heterogeneous Ni catalyst was discovered to be active in the synthesis of secondary cross-imines via hydrogenative coupling of nitriles and amines. The mesoporous Al2O3-supported Ni nanoparticles (abbreviated as Ni/m-Al2O3-600, where 600 represents the reduction temperature) were active in hydrogenative coupling of nitriles and amines reaction at 80 °C and 1 bar H2, affording corresponding cross-imines with yields in the range 64.1-98.1%. Density functional theory calculations reveal the hydrogenation of benzonitrile (PhCN) to benzylamine (PhCH2NH2) has higher activation energy than that for hydrogenative cross-coupling of PhCN and RNH2 on the Ni/m-Al2O3-600 catalyst, suggesting the latter reaction is more favorable. The theoretical calculations are in good agreement with our experimental results.
- Zhou, Peng,Jiang, Liang,Wang, Shuguo,Hu, Xun,Wang, Hongming,Yuan, Ziliang,Zhang, Zehui
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p. 8413 - 8423
(2019/09/07)
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- Divalent osmium complex and preparation method and application thereof
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The invention discloses divalent osmium complex and a preparation method and application thereof. The chemical formula of the divalent osmium complex is M2OsL2 or M2OsLCO, wherein m is 3-trifluoromethyl-5-(2-puridyl)-1,2,4-triazole, and L is triphenylphosphine, pyridine or dimethylphenylphosphine. The preparation method includes adding triosmium dodecacarbonyl and ligand Min a high-pressure reactor for reacting at 180-200 DEG C for 24-48 hours, and purifying after reaction; adding ethylene glycol monethyl ether, decarbonylation agent Me3NO to react at 100-120 DEG C for 1-2 hours in the protection of nitrogen gas, and adding ligand L to react at 180-190 DEG C for 10-16 hours, and purifying reactants to obtain products. The divalent osmium complex has visible response and is catalyst capable of quickly oxidizing and coupling benzyl amine compound quickly under light irradiation.
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Paragraph 0027; 0029
(2016/10/09)
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- Nucleophilic addition to carbonyl compounds, competition between hard (amine) and soft (phosphite) nucleophile
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In the Kabachnik Fields reaction mixture, two nucleophiles: dialkyl phosphite and the amine compete for the electrophilic carbonyl compound. Reaction mixture composition studies, kinetic studies as well as theoretical calculations, indicate that the softe
- Gancarz, Roman
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p. 10627 - 10632
(2007/10/02)
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