- Supported Ni catalyst for liquid phase hydrogenation of adiponitrile to 6-Aminocapronitrile and hexamethyenediamine
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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.
- Wang, Chengqiang,Jia, Zekun,Zhen, Bin,Han, Minghan
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Read Online
- Method for preparing 1, 6-hexamethylenediamine from 5-hydroxymethylfurfural
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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.
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Paragraph 140; 0146; 0148
(2021/06/06)
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- METHOD FOR PRODUCING HEXAMETHYLENE DIAMINE
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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
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Paragraph 0033-0055
(2021/02/13)
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- Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
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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.
- Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
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p. 2059 - 2067
(2021/09/02)
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- Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
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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.
- Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
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p. 3943 - 3957
(2021/04/12)
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- PROCESS FOR THE PREPARATION OF HEXAMETHYLENEDIAMINE BY HYDROGENATION OF ADIPONITRILE WITH REDUCED FORMATION OF DIAMINOCYCLOHEXANE
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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.
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Page/Page column 6; 7
(2021/10/02)
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- Method for preparing organic diamine from amino nitrile organic matter
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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.
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Paragraph 0240-0285
(2021/10/02)
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- Method for synthesizing 1,6-hexamethylenediamine by catalyzing hydrogenation ring opening of 2,5-dicyanofuran
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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.
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Paragraph 0070-0126
(2021/06/22)
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- Industrial preparation method of hexamethylenediamine
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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.
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Paragraph 0029; 0031-0033; 0035-0037; 0039-0040; 0044-0045
(2021/06/13)
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- Method for preparing aliphatic amine compound
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The invention discloses a method for preparing an aliphatic amine compound, comprising the following steps: using furfuryl amine or a furfuryl amine derivative as a raw material, and carrying out hydrogenolysis in the presence of a supported metal catalyst to obtain the aliphatic amine compound. According to the method disclosed by the invention, the aliphatic amine compound is prepared by catalyzing hydrogenolysis of the biomass-based furfuryl amine and the derivative thereof for the first time. The catalyst has high activity and high product selectivity. According to the method, a biomass-based compound is used as a raw material to prepare the aliphatic amine compound, and the requirements of sustainable development and green chemistry are met. The aliphatic amine compound prepared by the method has high selectivity, and is convenient for separation and purification of products. After the reaction of the method is finished, the catalyst is easy to separate and can be recycled, so that the method has a good application prospect.
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Paragraph 0074-0076
(2020/05/14)
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- Method for preparing hexamethylene diamine by catalytically hydrogenating adiponitrile
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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%.
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Paragraph 0038-0048
(2020/10/20)
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- Modulating: Trans -imination and hydrogenation towards the highly selective production of primary diamines from dialdehydes
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Bio-based primary diamines are important building blocks for sustainable bio-polymers, but their synthesis remains challenging due to the high susceptibility to polymerization. Herein, we have developed a new strategy to suppress the polymerization by employing a more nucleophilic alkylamine to scavenge the dialdehyde and a Co/ZrO2 catalyst to regulate the trans-imination and hydrogenation activity. With this strategy, 2,5-bis(aminomethyl)furan (BAMF), a promising monomer for the production of new polyamides and polyureas, is successfully synthesized via the reductive amination of biomass-derived 2,5-diformylfuran (DFF) under a H2 and NH3 atmosphere with an unprecedentedly high selectivity up to 95%. This strategy is applicable to the reductive amination of other biomass-derived dialdehydes, thus paving a new way to bio-based diamine monomers. This journal is
- Hao, Rui,Li, Lin,Liu, Fei,Qi, Haifeng,Su, Yang,Wang, Aiqin,Yang, Jingyi,Zhang, Leilei,Zhang, Tao
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p. 6897 - 6901
(2020/11/09)
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- Method for synthesizing hexanediamine by taking caprolactam as raw material
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The invention discloses a method for synthesizing hexanediamine by taking caprolactam as a raw material. The method comprises the following steps that (1) after the hexanediamine, alkali and water aremixed, heating reflux is conducted, and thus 6-amino-caproate is obtained; (2) the 6-amino-hexanoate obtained in the step (1) is introduced into an amino protecting group to protect an amino end group, then acid is added for neutralization to generate aminocaproic acid with the amino protecting group; (3) after a product obtained in the step (2) is dried, a dehydration catalyst for amide is added, a heating reaction is conducted in the presence of an ammonia source to convert a carboxylic acid group into a cyano group, and thus product nitrile is obtained; and (4) after the product nitrile obtained in the step (3) is extracted and purified, catalytic hydrogenation is conducted to generate corresponding amine, then the protecting group is removed, and thus a target product can be obtained.
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- Imprinted Apportionment of Functional Groups in Multivariate Metal-Organic Frameworks
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Sophisticated chemical processes widely observed in biological cells require precise apportionment regulation of building units, which inspires researchers to develop tailorable architectures with controllable heterogeneity for replication, recognition and information storage. However, it remains a substantial challenge to endow multivariate materials with internal sequences and controllable apportionments. Herein, we introduce a novel strategy to manipulate the apportionment of functional groups in multivariate metal-organic frameworks (MTV-MOFs) by preincorporating interlocked linkers into framework materials. As a proof of concept, the imprinted apportionment of functional groups within ZIF-8 was achieved by exchanging imine-based linker templates with original linkers initially. The removal of linker fragments by hydrolysis can be achieved via postsynthetic labilization, leading to the formation of architectures with controlled heterogeneity. The distributions of functional groups in the resulting imprinted MOFs can be tuned by judicious control of the interlocked chain length, which was further analyzed by computational methods. This work provides synthetic tools for precise control of pore environment and functionality sequences inside multicomponent materials.
- Feng, Liang,Wang, Kun-Yu,Lv, Xiu-Liang,Powell, Joshua A.,Yan, Tian-Hao,Willman, Jeremy,Zhou, Hong-Cai
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supporting information
p. 14524 - 14529
(2019/10/02)
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- Functionalized multi-walled carbon nanotubes supported Ni-based catalysts for adiponitrile selective hydrogenation to 6-aminohexanenitrile and 1,6-hexanediamine: Switching selectivity with [Bmim]OH
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Functionalized multi-walled carbon nanotubes supported nickel-based catalysts were prepared and applied in adiponitrile (ADN) hydrogenation. The characterization results show that different functional groups such as NH2– COOH– OH– on MWCNTs surface can effectively act on metal ions by electrostatic attractions and chemical interactions so as to provide nucleation sites, and N species in MWCNTs can act as active sites for Ni deposition due to the strong electronic interactions between N species and Ni so as to promote ultra-small Ni nanoparticles formation, decrease NiO reduction activation energy, increase zero-valent Ni amounts as well as Ni nanoparticles dispersion. Furthermore, the doped N increases the lewis basicity, which favors the formation of primary amine of 6-aminohexanenitrile (ACN) and 1,6-hexanediamine (HDA). Moreover, the basic ionic liquid [Bmim]OH may switch the selectivity by inhibiting nucleophilic addition of the primary amine to the α-carbon of aldimine via the stabilization of –NH2 groups in the amino-imine intermediates so as to impede by-products formation. In addition, the mechanism for ADN hydrogenation in [Bmim]OH was studied by density functional theory calculations. Under optimized conditions, it gives 97.80% total selectivity to ACN and HDA at 95.34% ADN conversion over Ni/N-MWCNTs-800 in the presence of [Bmim]OH.
- Lv, Yang,Cui, Haishuai,Liu, Pingle,Hao, Fang,Xiong, Wei,Luo, He′an
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p. 330 - 351
(2019/03/28)
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- Highly efficient nitrobenzene and alkyl/aryl azide reduction in stainless steel jars without catalyst addition
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The mechanochemical and selective reduction of aryl nitro and aryl/alkyl azide derivatives, with either formate salts or hydrazine, to the corresponding, synthetically useful amines occurs in excellent yields in a planetary ball mill without the addition of a catalyst. This newly developed and solvent-free protocol is efficient, fast and does not require the addition of a metal hydrogenation catalyst as the stainless steel jar itself fulfils that role. The method has been applied to a broad range of compounds and excellent yields have been obtained. The formylation of alkyl amines has been successfully performed, by means of mechanochemical activation, in the presence of ammonium formate alone.
- Martina, Katia,Baricco, Francesca,Tagliapietra, Silvia,Moran, Maria Jesus,Cravotto, Giancarlo,Cintas, Pedro
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supporting information
p. 18881 - 18888
(2018/11/26)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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- Corresponding amine nitrile and method of manufacturing thereof (by machine translation)
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The present invention relates to a nitrile manufacturing method, which has characteristics of significantly-reduced ammonia source consumption, low environmental pressure, low energy consumption, low production cost, high nitrile purity, high nitrile yield and the like compared with the method in the prior art, wherein nitrile having a complicated structure can be obtained through the method. The present invention further relates to a method for producing a corresponding amine from the nitrile.
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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- Preparation method of hexamethylenediamine
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The invention discloses a preparation method of hexamethylenediamine. Hexane dinitrile is used as a raw material, and a nano-nickel and magnesium oxide composite material is used as a catalyst to prepare the hexamethylenediamine through liquid phase hydrogenation. The preparation method of the hexamethylenediamine comprises the following steps: dipping a porous carrier by using nickel acetate andmagnesium nitrate aqueous solutions at different concentrations at first, and carrying out in-situ reduction to obtain an immobilized nickel and magnesium oxide based composite catalyst under different conditions; adding raw materials, the catalyst and a solvent in a reaction kettle in proportion, sealing the reaction kettle, removing air in the kettle by a hydrogen substitution method, starting aheating power supply, applying set pressure to hydrogen after the temperature in the kettle is raised to the set reaction temperature, then starting a magnetic stirrer, and beginning to time reaction; and after the reaction is finished, filtering out the catalyst, and distilling and separating under reduced pressure. The yield of a target product is high, the yield of the hexamethylenediamine isgreater than 70%, and the solvent and the catalyst are recyclable.
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Paragraph 0026-0027
(2018/05/01)
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- Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
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The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Alshammari, Ahmad S.,Pohl, Marga-Martina,Beller, Matthias,Jagadeesh, Rajenahally V.
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p. 8553 - 8560
(2018/11/30)
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- Method for preparing hexamethylene diamine by direct hydrogenation of adiponitrile under alkali-free conditions
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The invention discloses a method for preparing hexamethylene diamine by direct hydrogenation of adiponitrile under alkali-free conditions. The method comprises the steps of using an alkaline earth metal oxide or rare earth metal oxide prepared by a coprecipitation method for modifying an aluminium trioxide-supported metallic nickel catalyst under a condition of no need of adding alkali or ammoniawater, directly hydrogenating an adiponitrile ethanol solution at a temperature of 60 to 200 DEG C, under pressure of 3 to 8 MPa, and obtaining high-qualityhexamethylene diamine through vacuum distillation of a resulting product. The method is suitable for using in batch tank reactors and also in continuous fixed bed reactors.
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Paragraph 0022; 0024; 0025; 0026; 0028
(2018/08/04)
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- Design, synthesis, and conformational analysis of 3-: Cyclo -butylcarbamoyl hydantoins as novel hydrogen bond driven universal peptidomimetics
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A collection of systematically substituted 3-cyclo-butylcarbamoyl hydantoins was synthesized by a regioselective multicomponent domino process followed by easy coupling reactions. Calculations, NMR studies and X-ray analysis show that these scaffolds are able to project their side chains similar to common secondary structures, such as the α-helix and β-turn, with favourable enthalpic and entropic profiles.
- Bellucci,Frigerio,Castellano,Meneghetti,Sacchetti,Volonterio
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p. 521 - 525
(2018/02/07)
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- Cobalt complex, preparation method thereof, and application thereof in selective catalysis of transfer hydrogenation reaction of cyano group
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The invention discloses a cobalt complex, a preparation method thereof, and an application thereof in the selective catalysis of a transfer hydrogenation reaction of a cyano group. The structural formula of the cobalt complex is represented by formula I. The cobalt complex is prepared through a reaction of a cobalt salt and an NNP ligand or a PNP ligand under the protection of an inert atmosphere;and the chemical formula of the cobalt salt is CoX12, wherein X1 represents halogen, a sulfate radical, a perchlorate radical, a hexafluorophosphate radical, a hexafluoroantimonate radical, a tetrafluoroborate radical, a trifluoromethanesulfonate radical or a tetra(pentafluorophenyl)borate radical. The cobalt complex can be used in the selective catalysis of the transfer hydrogenation reaction ofthe cyano group to obtain a primary amine compound, a secondary amine compound and a tertiary amine compound, the primary amine compound, the secondary amine compound and the tertiary amine compoundare important intermediates in a series of subsequent functionalizing reactions, and the cobalt complex has a very high catalysis activity, and has great research values and a great application prospect.
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Paragraph 0157-0159; 0162
(2018/05/07)
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- SHAPED POROUS CARBON PRODUCTS
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Shaped porous carbon products and processes for preparing these products are provided. The shaped porous carbon products can be used, for example, as catalyst supports and adsorbents. Catalyst compositions including these shaped porous carbon products, processes of preparing the catalyst compositions, and various processes of using the shaped porous carbon products and catalyst compositions are also provided.
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Paragraph 0399-0400
(2017/05/21)
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- A new route to α,ω-diamines from hydrogenation of dicarboxylic acids and their derivatives in the presence of amines
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A new and selective route for the synthesis of polymer precursors, primary diamines or N-substituted diamines, from dicarboxylic acids, diesters, diamides and diols using a Ru/triphos catalyst is reported. Excellent conversions and yields are obtained under optimised reaction conditions. The reactions worked very well using 1,4-dioxane as solvent, but the greener solvent, 2-methyl tetrahydrofuran, also gave very similar results. This method provides a potential route to converting waste biomass to value added materials. The reaction is proposed to go through both amide and aldehyde pathways.
- Shi, Yiping,Kamer, Paul C. J.,Cole-Hamilton, David J.
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supporting information
p. 5460 - 5466
(2017/11/22)
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- Reductive amination of 1,6-hexanediol with Ru/Al2O3 catalyst in supercritical ammonia
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Hexamethylenediamine (HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an environmental friendly route to produce HMDA via catalytic reductive amination of 1,6-hexanediol (HDO) in the presence of hydrogen. The activities of several heterogeneous metal catalysts such as supported Ni, Co, Ru, Pt, Pd catalysts were screened for the present reaction in supercritical ammonia without any additives. Among the catalysts examined, Ru/Al2O3 presented a high catalytic activity and highest selectivity for the desired product of HMDA. The high performance of Ru/Al2O3 was discussed based on the Ru dispersion and the surface properties like the acid-basicity. In addition, the reaction parameters such as reaction temperature, time, H2 and NH3 pressure were examined, and the reaction processes were discussed in detail.
- Li, Yan,Cheng, Haiyang,Zhang, Chao,Zhang, Bin,Liu, Tong,Wu, Qifan,Su, Xinluona,Lin, Weiwei,Zhao, Fengyu
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p. 920 - 926
(2017/07/05)
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- Improved catalytic performance of acid-activated sepiolite supported nickel and potassium bimetallic catalysts for liquid phase hydrogenation of 1,6-hexanedinitrile
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Different inorganic acids were used to activate sepiolite, and the acid-activated sepiolites supported nickel and potassium bimetallic catalysts were prepared. Nitrogen adsorption-desorption, hydrogen chemisorption, ammonia temperature programmed desorption (NH3-TPD), temperature programmed reduction (TPR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR) and energy dispersive X-ray (EDX) were used to characterize the catalysts. The catalytic performance of the acid-activated sepiolite supported K-Ni bimetallic catalysts were investigated in 1,6-hexanedinitrile (HDN) hydrogenation in liquid phase. It was revealed that the potassium could increase the alkalinity of the catalyst with the aim of inhibiting the formation of the 1-azacycloheptane (ACH). And the addition of potassium reduces the particle size of nickel and improves its dispersion. Compared with hydrochloric acid and sulfuric acid, nitric acid treatment increases more silanol groups (Si[sbnd]OH) on the sepiolite surface, which is helpful to nickel particles adsorption and dispersion. Nitric acid activated sepiolite supported nickel and potassium bimetallic catalysts (K-Ni/NASEP) present the best catalytic performance, the conversion of HDN comes up to 92.0% under moderate conditions of lower temperature and pressure, the selectivity to 6-aminocapronitrile (ACN) and 1,6-hexanediamine (HDA) is up to 95.2%.
- Lv, Yang,Hao, Fang,Liu, Pingle,Xiong, Shaofeng,Luo, He'an
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- A preparation method of the hexamethylene diamine
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The invention discloses a preparation method of hexamethylenediamine. The method is used for preparing 1, 6-hexamethylenediamine by virtue of carrying out ammoniation and catalytic hydrogenation on 1, 6-adipaldehyde. The method is simple in process, low in cost, high in yield, low in energy consumption and free from industrial three wastes.
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- PROMOTER FOR SELECTIVE NITRILE HYDROGENATION
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Disclosed is a process for hydrogenating a dinitrile comprising contacting the dinitrile with hydrogen over catalyst comprising at least 90 wt.% iron in the presence of promoter comprising at least one selected from alkali metal and alkaline earth metal promoters.
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Paragraph 0084-0088
(2017/09/08)
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- Is water a suitable solvent for the catalytic amination of alcohols?
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The catalytic conversion of biomass and biogenic platform chemicals typically requires the use of solvents. Water is present already in the raw materials and in most cases a suitable solvent for the typically highly polar substrates. Hence, the development of novel catalytic routes for further processing would profit from the optimization of the reaction conditions in the aqueous phase mainly for energetic reasons by avoiding the initial water separation. Herein, we report the amination of biogenic alcohols in aqueous solutions using solid Ru-based catalysts and ammonia as a reactant. The influence of different support materials and bimetallic catalysts is investigated for the amination of isomannide as a biogenic diol. Most importantly, the transferability of the reaction conditions to various other primary and secondary alcohols is successfully proved. Hence, water appears to be a suitable solvent for the sustainable production of biogenic amines and offers great potential for further process development.
- Niemeier, Johannes,Engel, Rebecca V.,Rose, Marcus
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supporting information
p. 2839 - 2845
(2017/07/24)
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- Synthesis of Adipic Acid, 1,6-Hexanediamine, and 1,6-Hexanediol via Double-n-Selective Hydroformylation of 1,3-Butadiene
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A method for the synthesis of the industrially relevant monomers adipic acid, 1,6-hexanediol (HDO), and 1,6-hexanediamine (HMD) via isomerizing hydroformylation of 1,3-butadiene is described. The aldehyde intermediates are protected in situ as acetals to avoid hydrogenation to pentanal. Adipic aldehyde diacetal is obtained in good yields, and the first examples for the conversion toward adipic acid, 1,6-hexanediol, and 1,6-hexanediamine are shown.
- Mormul, Jaroslaw,Breitenfeld, Jan,Trapp, Oliver,Paciello, Rocco,Schaub, Thomas,Hofmann, Peter
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p. 2802 - 2810
(2016/07/06)
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- METHODS OF PRODUCING COMPOUNDS FROM 5-(HALOMETHYL)FURFURAL
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Provided herein are methods of producing compounds, such as cyclohexanone, hexanediamine, hexanediol, hexamethylenediamine, caprolactam and nylon, from 5-(halomethyl)furfural.
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- Stable and Inert Cobalt Catalysts for Highly Selective and Practical Hydrogenation of C≡N and C=O Bonds
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Novel heterogeneous cobalt-based catalysts have been prepared by pyrolysis of cobalt complexes with nitrogen ligands on different inorganic supports. The activity and selectivity of the resulting materials in the hydrogenation of nitriles and carbonyl compounds is strongly influenced by the modification of the support and the nitrogen-containing ligand. The optimal catalyst system ([Co(OAc)2/Phenα-Al2O3]-800 = Cat. E) allows for efficient reduction of both aromatic and aliphatic nitriles including industrially relevant dinitriles to primary amines under mild conditions. The generality and practicability of this system is further demonstrated in the hydrogenation of diverse aliphatic, aromatic, and heterocyclic ketones as well as aldehydes, which are readily reduced to the corresponding alcohols.
- Chen, Feng,Topf, Christoph,Radnik, J?rg,Kreyenschulte, Carsten,Lund, Henrik,Schneider, Matthias,Surkus, Annette-Enrica,He, Lin,Junge, Kathrin,Beller, Matthias
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supporting information
p. 8781 - 8788
(2016/08/02)
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- Liquid phase hydrogenation of adiponitrile over directly reduced Ni/SiO2 catalyst
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Liquid phase hydrogenation of adiponitrile (ADN) to 6-aminocapronitrile (ACN) and hexamethylenediamine (HMD) was investigated on Ni/SiO2 catalysts prepared under different conditions. In this reaction, the highly reactive imine intermediate forms condensation byproducts by reacting with the primary amine products (ACN and HMD). A highly dispersed Ni/SiO2 catalyst prepared by the direct reduction of Ni(NO3)2/SiO2 was found to suppress the condensation reactions by promoting the hydrogenation of adsorbed imine, and it gave excellent hydrogenation activity and primary amine selectivity. Addition of NaOH increased the primary amine selectivity to 79% at the ADN conversion of 86%.
- Jia, Zekun,Zhen, Bin,Han, Minghan,Wang, Chengqiang
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- Catalytic properties of nickel/sepiolite promoted with potassium and lanthanum in adiponitrile hydrogenation under mild conditions
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Ni/sepiolite, potassium and (or) lanthanum doped Ni/sepiolite catalysts were prepared by the incipient impregnation method and characterized by N2 adsorption-desorption, temperature programmed reduction (TPR), hydrogen chemisorption, powder X-ray diffraction (XRD), ammonia temperature programmed desorption (NH3-TPD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). It was revealed that the potassium could inhibit the formation of the ACH by-product by neutralizing some acid sites on the catalyst, and the lanthanum could efficiently reduce the diameter and improve the dispersion of the active nickel particles. These catalysts were tested in liquid phase hydrogenation of adiponitrile (ADN). The products include 6-aminocapronitrile (ACN), hexamethylenediamine (HMDA), 1-azacycloheptane (ACH) and C12 compounds. It shows that the catalyst doped with potassium and lanthanum gives the best catalytic performance, the selectivity to ACN and HMDA reaches to 91.32% at 92.56% conversion of adiponitrile under 393 K and 2.0 MPa.
- Lv, Yang,Hao, Fang,Xiong, Shaofeng,Liu, Pingle,Luo, He'An
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p. 60933 - 60939
(2016/07/11)
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- Mild and Selective Cobalt-Catalyzed Chemodivergent Transfer Hydrogenation of Nitriles
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Herein, we describe a selective cobalt-catalyzed chemodivergent transfer hydrogenation of nitriles to synthesize primary, secondary, and tertiary amines. The solvent effect plays a key role for the selectivity control. The general applicability of this procedure was highlighted by the synthesis of more than 70 amine products bearing various functional groups in high chemoselectivity. Moreover, this mild system achieved >2000 TONs (turnover numbers) for the transfer hydrogenation of nitriles.
- Shao, Zhihui,Fu, Shaomin,Wei, Mufeng,Zhou, Shaolin,Liu, Qiang
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supporting information
p. 14653 - 14657
(2016/11/23)
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- Selective catalytic hydrogenation of nitriles to primary amines using iron pincer complexes
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The selective catalytic hydrogenation of nitriles to primary amines with the well-defined Fe(PNPCy) pincer complex 2 is reported. This iron pincer catalyst shows superior catalytic activity and selectivity in the reduction of various nitriles including industrially relevant adipodinitrile in high yields under relatively mild conditions.
- Lange,Elangovan,Cordes,Spannenberg,Jiao,Junge,Bachmann,Scalone,Topf,Junge,Beller
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p. 4768 - 4772
(2016/07/11)
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- The preparation obtained by homogeneous catalysis mellow amination method of the primary amine
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The invention relates to a method for producing primary amines comprising at least one functional group of formula (-CH2-NH2), by alcohol amination of educts which comprise at least one functional group of formula (-CH2-OH), using ammonia, and elimination of water. The homogeneously catalyzed alcohol amination is carried out in the presence of at least one complex catalyst which contains at least one element selected from the groups 8 and 9 of the periodic table and at least one phosphorus donor ligand of general formula (I).
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Paragraph 0207-0208; 0214
(2017/02/28)
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- METHOD FOR PRODUCING HEXAMETHYLENEDIAMINE
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The invention relates to a method for producing hexamethylenediamine, wherein a) a muconic acid starting material is provided, which is selected from among muconic acid, esters of muconic acid, lactones of muconic acid, and mixtures thereof, b) the muconic acid starting material is subjected to a reaction with hydrogen in the presence of at least one hydrogenation catalyst in order to form 1,6-hexanediol, and c) the 1,6-hexanediol obtained in step b) is subjected to amination in the presence of an amination catalyst in order to obtain hexamethylenediamine. The invention further relates to hexamethylenediamine which can be produced by means of said method.
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- METHOD FOR PRODUCING ALKANOL AMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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PROBLEM TO BE SOLVED: To provide a method for producing alkanol amines by alcohol amination of diols using ammonia under elimination of water. SOLUTION: The invention relates to a method for producing alkanol amines which comprise a primary amino group (-NH2) and a hydroxyl group (-OH), by alcohol amination of diols comprising two hydroxyl groups (-OH) using ammonia under elimination of water. The reaction is homogeneously catalyzed in the presence of at least one complex catalyst which contains at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0088; 0103
(2016/10/27)
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- · Uniform catalyst by using alcohol aminosilicone di-, tri-and a method of manufacturing a polyphenylenepolyamine
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The invention relates to a method for producing primary amines, which contain at least one functional group of the formula (-CH2-NH2) and at least one further primary amino group, by the alcohol amination of reactants, which contain at least one functional group of the formula (-CH2-OH) and at least one further functional group (-X), wherein (-X) is selected from hydroxyl groups and primary amino groups, using ammonia with removal of water, wherein the reaction is carried out in a homogeneously catalyzed manner in the presence of at least one complex catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand.
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Paragraph 0099; 0113
(2016/10/09)
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- METHODS OF PRODUCING COMPOUNDS FROM 5-(HALOMETHYL)FURFURAL
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Provided herein are methods of producing compounds, such as cyclohexanone, hexanediamine, hexanediol, hexamethylenediamine, caprolactam and nylon, from 5- (halomethyl)furfural.
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- METHOD FOR MAKING 2-METHYLPENTAMETHYLENEDIAMINE AND ADIPONITRILE WITH HOT AMMONIA SWEEP
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Disclosed is a process for extending the useful life of a hydrogenation catalyst for making diamines in which 2-methylglutaronitrile and adiponitrile are charged separately to the catalyst in sequence with an intervening step of contacting the catalyst with hydrogen and ammonia at elevated temperature.
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Paragraph 0073; 0074
(2015/02/19)
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- HYDROGENATION OF DINITRILES FOR THE PREPARATION OF DIAMINES
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Disclosed is a method for hydrogenating a dinitrile to form a diamine. Also disclosed is a method for preparing a catalyst for this hydrogenation reaction by reducing iron oxide with hydrogen. The catalyst ages during the course of making the diamine. An aged catalyst is partially reactivated by abruptly interrupting the flow of feed to reactors.
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Paragraph 00258-00264
(2015/03/28)
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- HYDROGENATION OF DINITRILES FOR THE PREPARATION OF DIAMINES
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Disclosed is a method for hydrogenating a dinitrile to form a diamine. Also disclosed is a method for preparing a catalyst for this hydrogenation reaction by reducing iron oxide with hydrogen. The catalyst ages during the course of making the diamine. An aged catalyst is partially reactivated by interrupting the flow of dinitrile and ammonia feed to a reactor, while maintaining a flow of hydrogen to the reactor.
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Paragraph 00247-00255
(2015/03/28)
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- Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst
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Selective catalytic reductions of nitriles are presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including industrially important adipodinitrile are hydrogenated to the corresponding primary amines. Modelling suggests the reaction follows an outer sphere hydrogenation mechanism. An efficient and selective catalytic reduction of nitriles is presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including the industrially important adipodinitrile are hydrogenated to the corresponding primary amines. The reaction follows an outer-sphere mechanism.
- Neumann, Jacob,Bornschein, Christoph,Jiao, Haijun,Junge, Kathrin,Beller, Matthias
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supporting information
p. 5944 - 5948
(2015/09/22)
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- Applications of dynamic combinatorial chemistry for the determination of effective molarity
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A new strategy for determining thermodynamic effective molarities (EM) for macrocylisation reactions using dynamic combinatorial chemistry under dilute conditions is presented. At low concentrations, below the critical value, Dynamic Libraries (DLs) of bifunctional building blocks contain only cyclic species, so it is not possible to quantify the equilibria between linear and cyclic species. However, addition of a monofunctional chain stopper can be used to promote the formation of linear oligomers allowing measurement of EM for all cyclic species present in the DL. The effectiveness of this approach was demonstrated for DLs generated from mixtures of 1,3-diimine calix[4]arenes, linear diaminoalkanes and monoaminoalkanes. For macrocycles deriving from one bifunctional calixarene and one diamine, there is an alternating pattern of EM values with the number of methylene units in the diamine: odd numbers give significantly higher EMs than even numbers. For odd numbers of methylene units, the alkyl chain can adopt an extended all anti conformation, whereas for even numbers of methylene units, gauche conformations are required for cyclisation, and the associated strain reduces EM. The value of EM for the five-carbon linker indicates that this macrocycle is a strainless ring. This journal is
- Ciaccia, Maria,Tosi, Irene,Baldini, Laura,Cacciapaglia, Roberta,Mandolini, Luigi,Di Stefano, Stefano,Hunter, Christopher A.
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p. 144 - 151
(2015/02/19)
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- PROCESS FOR THE PRODUCTION OF HEXAMETHLENEDIAMINE
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It is described a process for the production of hexamethylenediamine by hydrogenation of adiponitrile, comprising an improved step of regeneration of the catalyst. Also described are an equipment for the production of hexamethylenediamine, and a washing apparatus (14) for implementing the catalyst regeneration step.
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Paragraph 0052; 0053; 0054; 0055
(2014/02/16)
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- PROCESS FOR PREPARING DI-, TRI- AND POLYAMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Process for preparing primary amines which have at least one functional group of the formula (—CH2—NH2) and at least one further primary amino group by alcohol amination of starting materials having at least one functional group of the formula (—CH2—OH) and at least one further functional group (—X), where (—X) is selected from among hydroxyl groups and primary amino groups, by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.
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Page/Page column 12; 16
(2012/09/22)
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