124-09-4Relevant articles and documents
Supported Ni catalyst for liquid phase hydrogenation of adiponitrile to 6-Aminocapronitrile and hexamethyenediamine
Wang, Chengqiang,Jia, Zekun,Zhen, Bin,Han, Minghan
, (2018)
Supported Ni catalysts prepared under different conditions, for liquid phase hydrogenation of adiponitrile (ADN) to 6-aminocapronitrile (ACN) and hexamethyenediamine (HMD), were investigated. The highly reactive imine intermediate can form condensation byproducts with primary amine products (ACN and HMD), which decreased the yield coefficient of primary amines. The catalysts support, condition of catalyst preparation and dosage of additive were studied to improve the yield. A highly dispersed Ni/SiO2 catalyst prepared by the direct reduction of Ni(NO3)2/SiO2 suppressed the condensation reactions by promoting the hydrogenation of adsorbed imines, and it gave the improved hydrogenation activity of 0.63 mol·kgcat?1·min?1 and primary amine selectivity of 94% when NaOH was added into the reactor.
Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
, p. 3943 - 3957 (2021/04/12)
The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.
Method for preparing 1, 6-hexamethylenediamine from 5-hydroxymethylfurfural
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Paragraph 140; 0146; 0148, (2021/06/06)
The invention relates to a method for preparing 1, 6-hexamethylenediamine from 5-hydroxymethylfurfural, which is characterized in that the 5-hydroxymethylfurfural is used as a raw material, and the 1, 6-hexamethylenediamine is synthesized by a two-step method under the action of a catalyst. The method comprises the following steps: 1) in a hydrogen atmosphere, reacting the raw material 5-hydroxymethylfurfural with ammonia in the presence of a reductive amination catalyst to generate 2, 5-dimethylamine tetrahydrofuran; and 2) continuing the reaction, and carrying out a ring-opening reaction on the hydrodeoxygenation catalyst to produce the target product 1, 6-hexamethylenediamine. The method is characterized in that the reductive amination catalyst in the step 1) is an M1-M2 supported multi-metal component catalyst. The method is characterized in that the hydrodeoxygenation catalyst in the step 2) is a supported catalyst, and the metal active component is selected from one or more of transition metal elements Rh, Re, Pt, Ir, Pd and Ru. The 1, 6-hexamethylenediamine is produced by using the bio-based material monomer 5-hydroxymethylfurfural as the raw material, so that the method is green and clean, the process is easy to operate, the yield is high, and a wide application prospect is provided for biomass conversion.