- Highly Selective Hydrogenative Conversion of Nitriles into Tertiary, Secondary, and Primary Amines under Flow Reaction Conditions
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Flow reaction methods have been developed to selectively synthesize tertiary, secondary, and primary amines depending on heterogeneous platinum-group metal species under catalytic hydrogenation conditions using nitriles as starting materials. A 10 % Pd/C-packed catalyst cartridge affords symmetrically substituted tertiary amines in good to excellent yields. A 10 % Rh/C-packed catalyst cartridge enables the divergent synthesis of secondary and primary amines, with either cyclohexane or acetic acid as a solvent, respectively. Reaction parameters, such as the metal catalyst, solvent, and reaction temperature, and continuous-flow conditions, such as flow direction and second support of the catalyst in a catalyst cartridge, are quite important for controlling the reaction between the hydrogenation of nitriles and nucleophilic attack of in situ-generated amines to imine intermediates. A wide variety of aliphatic and aromatic nitriles could be highly selectively transformed into the corresponding tertiary, secondary, and primary amines by simply changing the metal species of the catalyst or flow parameters. Furthermore, the selective continuous-flow methodologies are applied over at least 72 h to afford three different types of amines in 80–99 % yield without decrease in catalytic activities.
- Yamada, Tsuyoshi,Park, Kwihwan,Furugen, Chikara,Jiang, Jing,Shimizu, Eisho,Ito, Naoya,Sajiki, Hironao
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- Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co-Rh Heterobimetallic Nanocatalyst
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Symmetrical tertiary amines have been efficiently realized from amine and secondary amines via deaminated homocoupling with heterogeneous bimetallic Co2Rh2/C as catalyst (molar ratio Co:Rh=2:2). Unsymmetric secondary anilines were produced from the reaction of anilines with symmetric tertiary amines. The Co2Rh2/C catalyst exhibited very high catalytic activity towards a wide range of amines and could be conveniently recycled ten times without considerable leaching. (Figure presented.).
- Chung, Hyunho,Han, Seulgi,Chung, Young Keun,Park, Ji Hoon
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supporting information
p. 1267 - 1272
(2018/02/12)
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- Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines
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In the presence of palladium on carbon (Pd/C) as a catalyst, hydrogenation of aliphatic nitriles in cyclohexane efficiently proceeded at 25-60 °C under ordinary hydrogen gas pressure to afford the corresponding tertiary amines. However, the use of rhodium on carbon (Rh/C) led to the highly selective generation of secondary amines. Hydrogenation of aromatic nitriles and cyclohexanecarbonitrile selectively produced secondary amines in the presence of either Pd/C or Rh/C.
- Monguchi, Yasunari,Mizuno, Masahiro,Ichikawa, Tomohiro,Fujita, Yuki,Murakami, Eri,Hattori, Tomohiro,Maegawa, Tomohiro,Sawama, Yoshinari,Sajiki, Hironao
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p. 10939 - 10944
(2017/10/27)
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- A method of manufacturing a tertiary amine
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PROBLEM TO BE SOLVED: To provide a method for producing a tertiary amine selectively with a high yield by a reductive amination reaction in a batch system. SOLUTION: In this method for producing the tertiary amine, an aldehyde expressed by formula R-CHO (in the formula, R shows a 2-20C aliphatic hydrocarbon group, 3-20C alicyclic hydrocarbon group or 6-20C aromatic hydrocarbon group), ammonia and hydrogen are reacted together in a batch system in the presence of a hydrogenation catalyst, to thereby produce the tertiary amine expressed by formula (R-CH2)3N (in the formula, R is defined above), wherein a palladium catalyst is used as the hydrogenation catalyst, and the reaction is performed under the condition of a hydrogen pressure of 0.1-6.5 MPa. COPYRIGHT: (C)2012,JPOandINPIT
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Paragraph 0021; 0029-0030
(2016/12/16)
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- Preparation of organic compounds using as a reactant an adduct of isocyanic acid and a tertiary amine or an ether
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Process for the removal of isocyanic acid from a gaseous mixture of isocyanic acid and ammonia by introducing a tertiary amine or ether at 250° to 600° C. The gaseous reaction mixture is passed into an inert diluent and cooled, to condense an adduct of isocyanic acid and tertiary amine or ether, and the ammonia being removed as a gas.
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