C:Corrosive;
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.
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.
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.
PROCESS FOR THE PREPARATION OF HEXAMETHYLENEDIAMINE BY HYDROGENATION OF ADIPONITRILE WITH REDUCED FORMATION OF DIAMINOCYCLOHEXANE
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Page/Page column 6; 7, (2021/10/02)
The present invention relates to a process for the preparation of hexamethylenediamine by hydrogenation of adiponitrile in the presence of a Raney nickel catalyst, wherein a Raney nickel catalyst modified by treatment with carbon monoxide or carbon dioxide in a liquid medium is used.
METHOD FOR PRODUCING HEXAMETHYLENE DIAMINE
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Paragraph 0033-0055, (2021/02/13)
To provide a method for producing hexamethylene diamine from 1,6-hexanediol and ammonia, under easy-to-control mild conditions.SOLUTION: A method for producing hexamethylene diamine includes reacting 1,6-hexanediol with ammonia in the presence of a solvent by means of a noble metal-supporting catalyst.SELECTED DRAWING: None
Industrial preparation method of hexamethylenediamine
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Paragraph 0029; 0031-0033; 0035-0037; 0039-0040; 0044-0045, (2021/06/13)
The invention discloses an industrial preparation method of hexamethylenediamine, wherein the industrial preparation method comprises the following steps: 1) dissolving cyclohexene in a first organic solvent, carrying out electrocatalytic oxidation reaction in a reaction kettle, carrying out constant potential electrolysis to obtain a reaction solution, and carrying out reduced pressure distillation to obtain adipic dialdehyde; and 2) dissolving adipic dialdehyde in a second organic solvent, introducing ammonia gas and hydrogen, and carrying out reductive amination reaction under the action of a supported nickel catalyst to obtain the hexamethylenediamine. The reaction adopts an electrocatalytic oxidation mode, and the selectivity is controlled by utilizing electrode potential, so that the reaction is more accurate and sufficient, the product conversion rate is improved, and the product is easy to separate, clean and environment-friendly; according to the method, hexamethylenediamine can be prepared through rectification operation, the product conversion rate of the method reaches 98.70%, the total yield reaches 98.02%, the purity reaches 95.14%-98.13%, the requirements of industrial production are met, and the method has good application prospects in industry; in addition, raw materials and auxiliary materials are simple and easy to obtain, the price is low, the input cost is low, and the construction scale is not limited.
Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
, p. 2059 - 2067 (2021/09/02)
Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
Method for synthesizing 1,6-hexamethylenediamine by catalyzing hydrogenation ring opening of 2,5-dicyanofuran
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Paragraph 0070-0126, (2021/06/22)
The invention discloses a method for synthesizing 1,6-hexamethylenediamine by catalyzing hydrogenation ring opening of 2,5-dicyanofuran. The method comprises the following step: in a hydrogen source environment, subjecting a material containing 2,5-dicyanofuran to contacting and reacting with a catalyst so as to obtain 1,6-hexamethylenediamine, wherein the catalyst comprises an acidic carrier and a metal element; and the metal element is loaded on the acidic carrier. The method is a novel hydrogenation ring-opening technology which is high in yield, low in cost, easy in catalyst separation and low in pollution and uses hydrogen gas as a hydrogen source to prepare 1,6-hexamethylenediamine through ring-opening hydrogenation of 2,5-dicyanofuran. The method has wide application prospects.
Method for preparing organic diamine from amino nitrile organic matter
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Paragraph 0240-0285, (2021/10/02)
The invention provides a method for preparing organic diamine from an amino nitrile organic matter, which comprises the following steps: (1) reacting the amino nitrile organic matter with hydrogen in a solvent under the action of a catalyst to obtain a reacted material containing the organic diamine; (2) refining the reacted material to obtain crude organic diamine; and (3) adsorbing and purifying the crude organic diamine to obtain the purified organic diamine. According to the method, the amino nitrile organic matter reacts with hydrogen, the reaction selectivity and the conversion rate are high, and the high-purity organic diamine product can be obtained in the subsequent purification mode of combining refining and adsorption purification.
Method for preparing hexamethylene diamine by catalytically hydrogenating adiponitrile
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Paragraph 0038-0048, (2020/10/20)
The invention discloses a method for preparing hexamethylene diamine by catalytically hydrogenating adiponitrile, which comprises the step of contacting the adiponitrile with hydrogen in the presenceof a hydrogenation catalyst under the condition of preparing hexamethylene diamine by hydrogenation of the adiponitrile, and is characterized in that the hydrogenation catalyst contains dicyclopentadiene titanium dichloride. Compared with the intermittent heterogeneous catalytic hydrogenation in the prior art, the method has the defects of high hydrogenation pressure, low conversion rate and selectivity, complex separation of hydrogenation products, flammability and unsafety of Raney nickel catalysts and the like. According to the invention, the titanium dicyclopentadiene titanium dichloride catalyst is used for hydrogenation synthesis of adipamide from adiponitrile; compared with a Raney nickel catalytic hydrogenation preparation method, the hydrogenation reaction does not need high temperature and high pressure, and belongs to homogeneous catalytic hydrogenation, a high yield of converting adiponitrile into adipamine can be obtained by using a small amount of catalyst, the conversionrate is not less than 98.0%, the activity of the catalyst is high, and the selectivity is not less than 96%.
