Xn:Harmful;111-92-2Relevant articles and documents
General Cleavage of N-N and N-O Bonds Using Nickel/Aluminum Alloy
Lunn, George,Sansone, Eric B.,Keefer, Larry K.
, p. 1104 - 1108 (1985)
Addition of nickel/aluminum alloy to alkaline solutions of compounds containing N-N or N-O bonds appears to offer a general and convenient means for reducing such compounds to the corresponding amines.The method has been successfully applied to the reduction of nitrosamines, hydrazines, hydroxylamines, hydroxylamine ethers, triazenes, nitramines, N-oxides, tetrazenes, and nitroso, azo, and azoxy compounds.
One-pot reductive amination of carboxylic acids: a sustainable method for primary amine synthesis
Coeck, Robin,De Vos, Dirk E.
supporting information, p. 5105 - 5114 (2020/08/25)
The reductive amination of carboxylic acids is a very green, efficient and sustainable method for the production of (bio-based) amines. However, with current technology, this reaction requires two to three reaction steps. Here, we report the first (heterogeneous) catalytic system for the one-pot reductive amination of carboxylic acids to amines, with solely H2 and NH3 as the reactants. This reaction can be performed with relatively cheap ruthenium-tungsten bimetallic catalysts in the green and benign solvent cyclopentyl methyl ether (CPME). Selectivities of up to 99% for the primary amine could be achieved at high conversions. Additionally, the catalyst is recyclable and tolerant for common impurities such as water and cations (e.g. sodium carboxylate).
Effect of the catalyst preparation method on the performance of Ni-supported catalysts for the synthesis of saturated amines from nitrile hydrogenation
Segobia,Trasarti,Apesteguía
, p. 1693 - 1703 (2019/11/11)
The liquid-phase hydrogenation of butyronitrile to saturated amines was studied on silica-supported Ni catalysts prepared by either incipient-wetness impregnation (Ni/SiO2-I) or ammonia (Ni/SiO2-A) methods. A Ni/SiO2-Al2O3-I sample was also used. Ni/SiO2-I was a non-acidic catalyst containing large Ni0 particles of low interaction with the support, while Ni/SiO2-A was an acidic catalyst due to the presence of Ni2+ species in Ni phyllosilicates of low reducibility. Ni/SiO2-I formed essentially butylamine (80%), and dibutylamine as the only byproduct. In contrast, Ni/SiO2-A yielded a mixture of dibutylamine (49%) and tributylamine (45%), being the formation of butylamine almost completely suppressed. The selective formation of secondary and tertiary amines on Ni/SiO2-A was explained by considering that butylamine is not release to the liquid phase during the reaction because it is strongly adsorbed on surface acid sites contiguous to Ni0 atoms, thereby favoring the butylimine/butylamine condensation to higher amines between adsorbed species.
Selective Synthesis of Secondary and Tertiary Amines by Reductive N-Alkylation of Nitriles and N-Alkylation of Amines and Ammonium Formate Catalyzed by Ruthenium Complex
Alshakova, Iryna D.,Nikonov, Georgii I.
, p. 5370 - 5378 (2019/06/14)
A new ruthenium catalytic system for the syntheses of secondary and tertiary amines via reductive N-alkylation of nitriles and N-alkylation of primary amines is proposed. Isomeric complexes 8 catalyze transfer hydrogenation and N-alkylation of nitriles in ethanol to give secondary amines. Unsymmetrical secondary amines can be produced by N-alkylation of primary amines with alcohols via the borrowing hydrogen methodology. Aliphatic amines were obtained with excellent yields, while only moderate conversions were observed for anilines. Based on kinetic and mechanistic studies, it is suggested that the rate determining step is the hydrogenation of intermediate imine to amine. Finally, ammonium formate was applied as the amination reagent for alcohols in the presence of ruthenium catalyst 8. Secondary amines were obtained from primary alcohols within 24 hours at 100 °C, and tertiary amines can be produced after prolonged heating. Secondary alcohols can only be converted to secondary amines with moderate yield. Based on mechanistic studies, the process is suggested to proceed through an ammonium alkoxy carbonate intermediate, where carbonate acts as an efficient leaving group.
