- One-step Synthesis of Adiponitrile by Catalytic Ammoxidation over Antimony-Vanadium Phosphorus Oxide/γ-Alumina Catalyst
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The selective synthesis of adiponitrile from cyclohexanol, cyclohexanone,cyclohexane and n-hexane in a single step by vapour-phase ammoxidation over an antimony-promoted vanadium phosphorus oxide catalyst supported on alumina is reported.
- Reddy, B. Mahipal,Manohar, B.
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- Stable fluorophosphines: Predicted and realized ligands for catalysis
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Ligand maps lead to treasure! The activity of complexes of fluorophosphines (R2PF) in catalytic hydroformylation and hydrocyanation is predicted from a ligand map. However, the instability of R2PF to disproportionation is well-documented. Examples of R2PF ligands (see scheme) are described that are stabilized to such an extent that they can be used in catalysis and are shown to be highly effective.
- Fey, Natalie,Garland, Michael,Hopewell, Jonathan P.,McMullin, Claire L.,Mastroianni, Sergio,Orpen, A. Guy,Pringle, Paul G.
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- Electrochemical synthesis of adiponitrile from the renewable raw material glutamic acid
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Current affairs: Adiponitrile, used to produce nylon 6.6, is prepared from the renewable compound glutamic acid by an electrochemical route, involving electro-oxidative decarboxylation and Kolbe coupling reactions. The new route is an example of the use of glutamic acid as a versatile substrate in the transformation of biomass into chemicals. Also, it highlights the use of electrochemical methods in biomass conversion.
- Dai, Jian-Jun,Huang, Yao-Bing,Fang, Chi,Guo, Qing-Xiang,Fu, Yao
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- A new simple method for the synthesis of cyclobutyl cyanide
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A clean and efficient intramolecular cyclization of δ- halovaleronitrile to cyclobutyl cyanide was achieved using NaOH and phase- transfer catalysts in a solid-liquid system at 70°C.
- Cohen, Shlomo,Rothenberg, Gadi,Sasson, Yoel
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- Backbone diversity analysis in catalyst design
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We present a computer-based heuristic framework for designing libraries of homogeneous catalysts. In this approach, a set of given bidentate ligand-metal complexes is disassembled into key substructures ("building blocks"). These include metal atoms, ligating groups, backbone groups, and residue groups. The computer then rearranges these building blocks into a new library of virtual catalysts. We then tackle the practical problem of choosing a diverse subset of catalysts from this library for actual synthesis and testing. This is not trivial, since 'catalyst diversity' itself is a vague concept. Thus, we first define and quantify this diversity as the difference between key structural parameters (descriptors) of the catalysts, for the specific reaction at hand. Subsequently, we propose a method for choosing diverse sets of catalysts based on catalyst backbone selection, using weighted D-optimal design. The computer selects catalysts with different backbones, where the difference is measured as a distance in the descriptors space. We show that choosing such a D-optimal subset of backbones gives more diversity than a simple random sampling. The results are demonstrated experimentally in the nickel-catalysed hydrocyanation of 3-pentenenitrile to adiponitrile. Finally, the connection between backbone diversity and catalyst diversity, and the implications towards in silico catalysis design are discussed.
- Maldonado, Ana G.,Hageman, Jos A.,Mastroianni, Sergio,Rothenberg, Gadi
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- Linear relationship between activity of a new Ru-catalyst and acidity of substituted benzoic acids in the dimerization of acrylonitrile
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A new type of catalyst system using ruthenium and carboxylic acid is useful for the tail-to-tail dimerization of acrylonitrile, proceeding without the formation of undesired by-product propionitrile. Carboxylic acids having pK a 3.5-5 are suitable as co-catalysts for the dimerization of acrylonitrile. The relationship between the logarithm of the relative rate in the dimer formation and the pKa of m- and p-substituted benzoic acids (Bronsted plot) was linear (R2 = 0.946) with a slope of -0.199. The role of the carboxylic acids can be considered to be effective protonation in the protonolysis of the carbon-ruthenium bond of an intermediate Ru complex. Copyright
- Kashiwagi, Kohichi,Sugise, Ryoji,Shimakawa, Toshihiro,Matuura, Tunao,Shirai, Masashi
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- 1,4-DICYANOBUTENE-BRIDGED BINUCLEAR RHODIUM(I) COMPLEXES AND THEIR CATALYTIC ACTIVITIES
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Reactions of Rh(ClO4)(CO)(PPh3)2 with dicyano olefins, cis-NCCH=CHCH2CH2CN (c-DC1B), trans-NCCH=CHCH2CH2CN (t-DC1B), trans-NCCH2CH=CHCH2CN (t-DC2B), and NCCH2CH2CH2CN (DCB) produce the binuclear dicationic rhodium(I) complexes, (ClO4)2 (NC-A-CN=c-DC1B (1), t-DC1B (2), t-DC2B (3), DCB (4)).Complexes 1 and 2 are catalytically active for the hydrogenation of c-DC1B and t-DC1B, respectively, to give DCB, while complex 3 catalyzes the isomerization of t-DC2B to give c-DC1B and t-DC1B, and the hydrogenation of t-DC2B to DCB at 100 deg C.
- Park, Hwa-Kun,Kim, In Bum,Chin, Chong Shik
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- Improvement of catalyst activity in the Ru-catalyzed dimerization of acrylonitrile by using diphenyl ether as a solvent
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For the catalyst system of ruthenium and carboxylic acid, which is useful for the efficient tail-to-tail dimerization of acrylonitrile, the TON increases as the ruthenium catalyst concentration is decreased. Furthermore, the addition of aromatic solvents of equal volume to that of acrylonitrile improves the catalyst activity. Especially, the use of diphenyl ether leads to a 1.7 time improvement of the TON. Copyright
- Kashiwagi, Kohichi,Sugise, Ryoji,Shimakawa, Toshihiro,Matuura, Tunao
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- Ligand descriptor analysis in nickel-catalysed hydrocyanation: A combined experimental and theoretical study
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The problem of choosing the 'right chelating ligand' for a homogeneously catalysed reaction is outlined. A model is introduced that combines mechanistic information and ligand descriptors. This model is used together with automated synthesis tools to study the structure-activity relationship in a diverse set of forty-two ligands, and extract information on active regions in the catalyst space. The concept is demonstrated on nickel-catalysed hydrocyanation, using bidentate phosphine and phosphite ligands. The charge at the ligating atoms, the rigidity of the molecules, the steric crowding around the Ni atom, and the bite angle are found to be the most important descriptors. A comparison is made with literature hydrocyanation data and approaches for designing new homogeneous catalysts are discussed.
- Burello, Enrico,Marion, Philippe,Galland, Jean-Christophe,Chamard, Alex,Rothenberg, Gadi
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- STUDIES OF A COBALT-PROMOTED ACRYLONITRILE COUPLING REACTION
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A stoichiometric cobalt-promoted acrylonitrile (AN) coupling reaction leading to adiponitrile (ADN) formation was reinvestigated.The active catalyst appears to involve cobalt(0) species.Cobalt hydride complexes are either inactive or give only low yields of ADN .Intermediate Co(AN)2 species can be reduced to give ADN using H2S or using H2 and Pt on C.Choice of ligand is a factor in determination of ADN yield, such yields decreasing in the order (CH3)2NCHOPPh3>P(OPh)3>P(CH3)3>P(OC2H5)3.Formation of stoichiometric ADN yields from Co(N2)(PPh3)3 and AN indicate that co-promoters, such as ZnCl2 and CoCl2, are not required.Different ADN/c,t-1,4-dicyanobutene-1 product ratios, obtained by H2S treatment of Co(AN)2 species and a known complex, suggest that the intermediate Co(AN)2 species consist mainly of polymeric structures rather than monomeric metallacyclic complexes.
- Druliner, J. D.,Blackstone, R. C.
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- Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
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The synthesis of nitrile under mild conditions was achieved via dehydration of primary amide using lead salts as catalyst. The reaction processes were intensified by not only adding surfactant but also continuously removing the only by-product, water from the system. Both aliphatic and aromatic nitriles can be prepared in this manner with moderate to excellent yields. The reaction mechanisms were obtained with high-level quantum chemical calculations, and the crucial role the anionic ligand plays in the transformations were revealed.
- Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
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- METHOD FOR PRODUCING NITRILE
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The present invention provides a method of producing a nitrile from a primary amide, characterized in that the primary amide is subjected to a dehydration reaction in a supercritical fluid in the presence of an acid catalyst. The present invention achieves the object of reducing the corrosion of a reactor and the thermal decomposition of raw materials, as well as provides the effect of improving the reaction rate and nitrile selectivity.
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Paragraph 0080; 0084
(2021/02/05)
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- Production of adiponitrile
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The invention relates to production of adiponitrile. The present invention provides a process for producing a nitrile product, the method comprising: reacting a nitrile product in a reaction zone in the presence of a Bronsted acid catalyst, a carboxylic acid or amide, in particular adipic acid, cyanovaleric acid, adipamide or cyanovaleramide is contacted with a feedstock nitrile selected from a group consisting of acetonitrile and branched C5-C 12 nitriles under conditions effective to maintain the carboxylic acids and/or amides in the liquid phase and to convert at least a portion of the carboxylic acids and amides into a nitrile product different from the feedstock nitrile, in particular adiponitrile; a reaction effluent containing the nitrile product is then recovered from a reaction zone.
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Paragraph 0057-0058
(2021/08/19)
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- Method for continuous preparation of nitriles in a pipelined reactor (by machine translation)
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The method comprises the following steps that a tin catalyst is coated on the inner wall of the pipeline reactor; and the method comprises the following steps: coating a tin catalyst on the inner wall of the pipeline reactor. The amide solution and the catalytic auxiliary agent are mixed and then sent to a pipeline reactor, and the amide is dehydrated to generate nitrile at the reaction pressure of 0.1 - 2.0 mpa and 100 - 200 °C reaction temperature. The resulting reaction product was separated to give the crude product of the nitrile to which the amide corresponded. In the pipeline reactor, the corresponding nitrile is continuously prepared under the action of the tin catalyst, a dehydrating agent is not needed, byproducts only are water, and three wastes are reduced. (by machine translation)
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Paragraph 0036-0047; 0056; 0058
(2020/12/14)
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- Synthetic method of adiponitrile
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The invention provides a synthetic method of adiponitrile. The target product adiponitrile can be obtained by taking 1, 3-butadiene which is relatively easy to obtain as an initial raw material, carrying out a hydroaminocarbonylation reaction on terminal olefin of 1, 3-butadiene and then dehydrating, and the whole preparation process is mild in condition, good in reaction selectivity, high in yield, clean and non-toxic in reaction raw material and catalyst and small in environmental pollution.
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Paragraph 0030; 0033-0034; 0035; 0038; 0042; 0046; 0050
(2020/05/30)
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- METHOD FOR PRODUCING epsilon-CAPROLACTAM
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The present invention is a method of producing ε-caprolactam through adipamide as an intermediate, and characteristically includes a lactamization step of reacting adipamide, formed from a material compound, with hydrogen and ammonia in the presence of a catalyst containing: a metal oxide mainly containing an oxide(s) of one or more metallic elements selected from the group consisting of metallic elements of group 5 and groups 7 to 14 in the 4th to 6th periods of the periodic table; and a metal and/or a metal compound having a hydrogenation ability. The method can increase the selectivity of ε-caprolactam.
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Paragraph 0142; 0155; 0161
(2020/03/09)
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- Method for continuous preparation of nitriles by amides (by machine translation)
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The method comprises the following steps: preparing a lead salt supported by a molecular sieve by a lead salt and a molecular sieve through an impregnation method; and filling a molecular sieve-loaded lead catalyst into a fixed bed reactor. The amide or amide solution is sent into a fixed bed reactor from the top of the fixed bed to be subjected to catalytic dehydration, and the obtained reaction product is led out from the bottom of the fixed bed. The reaction product is separated to obtain the crude product of the nitrile corresponding to the amide. A fixed bed continuous production process is adopted, the reaction process is simple, the production efficiency is high, the product post-treatment is simple, and industrial production is easy to realize. (by machine translation)
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Paragraph 0033-0054; 0061-0066
(2020/12/15)
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- Ni-Catalyzed hydrocyanation of alkenes with formamide as the cyano source
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CN generation from formamide dehydration! A novel Ni-catalyzed hydrocyanation of various alkenes to provide aliphatic nitriles is developed by generating hydrocyanic acid in situ from safe and readily available formamide. Excellent linear or branched regio-selectivity, wide substrate scope, cheap and stable nickel salt as a pre-catalyst, a safe cyano source, slow generation of CN to obviate catalyst deactivation and convenient experimental operation would render this hydrocyanation attactive for laboratory synthesis of aliphatic nitriles.
- Shu, Xiao,Jiang, Yuan-Yuan,Kang, Lei,Yang, Luo
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supporting information
p. 2734 - 2738
(2020/06/17)
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- Method for preparing nitrile by reacting acetone cyanohydrin with haloalkane
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The invention provides a method for preparing nitrile by reacting acetone cyanohydrin with haloalkane. According to the invention, by using acetone cyanohydrin as a cyaniding reagent, the problems, such as long reaction time, low yield, strict reaction conditions and the like enchanted in an existing preparation method in which highly toxic sodium cyanide or potassium cyanide or expensive trimethylsilyl cyanide is used as a cyanogen source, are solved. The method comprises the following steps: dissolving acetone cyanohydrin in a mixed solvent of a high boiling point dipolar aprotic solvent anda low boiling point aprotic solvent, adding a catalyst lithium hydroxide, stirring at 25-50 DEG C for one hour and then adding a haloalkane for continuous reaction for 2-3 hours; next, adding saturated saline water for washing twice, separating out an organic layer, and boiling off the solvent after drying, thereby obtaining a nitrile compound. The method for preparing a nitrile compound disclosed in the invention is characterized by low reaction toxicity, simple process, easy of operation, low production cost, and a yield of more than 95%.
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Paragraph 0043-0049; 0051-0057; 0065
(2019/08/20)
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- Hydrosilane Reduction of Nitriles to Primary Amines by Cobalt-Isocyanide Catalysts
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Reduction of nitriles to silylated primary amines was achieved by combination of 1,1,3,3-tetramethyldisiloxane (TMDS) as the hydrosilane and a catalytic amount of Co(OPIV)2 (PIV = COtBu) associated with isocyanide ligands. The resulting silylated amines were subjected to acid hydrolysis or treatment with acid chlorides to give the corresponding primary amines or imides in good yields. One-pot synthesis of primary amides to primary amines with hydrosilanes was also achieved by iron-cobalt dual catalyst systems.
- Sanagawa, Atsushi,Nagashima, Hideo
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supporting information
p. 287 - 291
(2019/01/10)
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- Method for one-step synthesis of adiponitrile from hexadialdehyde and ionic liquid hydroxylamine salt (by machine translation)
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The invention discloses a method for one-step synthesis of adiponitrile from hexadialdehyde and ionic liquid hydroxylamine salt. The method comprises the following steps: adding an organic solvent, stirring, refluxing and condensing, adding an organic solvent, stirring, refluxing and condensing to obtain a product adiponitrile 50~90 °C 20~100min 1 - 1 . The organic solvent is bromobenzene, toluene, p-xylene, benzene, ethylbenzene, o-dichlorobenzene or acetonitrile. The method realizes one-step clean synthesis of adiponitrile. (by machine translation)
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Paragraph 0025-0078
(2019/11/29)
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- Method for preparing adiponitrile by catalytic ammonia oxidation cracking of cyclohexanol
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The invention relates to a method for preparing adiponitrile by the catalytic ammonia oxidation cracking of cyclohexanol. In the method, ammonia gas is used as the nitrogen source, air and/or oxygen is used as the oxygen source, and cyclohexanol is subjected to the ammonia oxidation cracking to prepare adiponitrile under the catalytic action. According to the method, the ammonia oxidation efficiency is high, and the product yield is high; the air is used as the oxygen source, so that the method is economic and environment-friendly; and the product and the catalyst are easy to separate, and thepost-treatment is simple, so that the method has good application prospect.
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Paragraph 0021-0022; 0023-0024; 0025-0026; 0027-0050
(2019/07/16)
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- Boosting Hydrogen Production by Anodic Oxidation of Primary Amines over a NiSe Nanorod Electrode
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For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts the cathodic hydrogen evolution reaction (HER). Therefore, developing an alternative anodic reaction with accelerating kinetics to produce value-added chemicals, especially coupled with HER, is of great importance. Now, a thermodynamically more favorable primary amine (?CH2?NH2) electrooxidation catalyzed by NiSe nanorod arrays in water is reported to replace OER for enhancing HER. The increased H2 production can be obtained at cathode; meanwhile, a variety of aromatic and aliphatic primary amines are selectively electrooxidized to nitriles with good yields at the anode. Mechanistic investigations suggest that NiII/NiIII may serve as the redox active species for the primary amines transformation. Hydrophobic nitrile products can readily escape from aqueous electrolyte/electrode interface, avoiding the deactivation of the catalyst and thus contributing to continuous gram-scale synthesis.
- Chong, Xiaodan,Huang, Yi,Liang, Yu,Liu, Cuibo,Zhang, Bin
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supporting information
p. 13163 - 13166
(2018/09/21)
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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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Paragraph 0136; 0137; 0140
(2018/07/15)
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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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Paragraph 0136; 0137; 0140
(2018/05/24)
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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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Paragraph 0137; 0138; 0139; 0140; 0141
(2018/07/15)
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- Synthetic method for organically compounding intermediate cyanogen
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Provided is a synthetic method for organically compounding intermediate cyanogen. The method mainly comprises the following steps that 5 moles of 1,4-diiodobutane dissolves in 5 liters of acetone solution, the stirring speed is controlled at 110-150 revolutions per minute, 6-7 moles of 4-methyl-benzonitrile is added into, the temperature of the solution is heated to 60-70 DEG C, circulation refluxis carried out for 90-110 minutes, the temperature of the solution is reduced to 10-15 DEG C, filtering is carried out, a filter mass is washed by a methylamine solution, and then poured into a potassium iodide solution, stratification occurs, an oil layer is washed by a sodium chloride solution, pentane solution and ethyl acetate solution in sequence, reduced pressure distillation is carried out, cut fraction of 50-55 DEG C is collected, dehydration is carried out by using a dehydrating agent, and finished cyanogen is obtained.
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Paragraph 0011; 0013; 0014; 0015
(2018/07/30)
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- Method for preparing organophosphorus ligand and further preparing adiponitrile by using mixed phenol
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The invention provides a method for preparing an organophosphorus ligand and further preparing adiponitrile by using mixed phenol. The method includes the steps of preparation of a first catalyst, primary hydrocyanation, preparation of a second catalyst, isomerization, preparation of a third catalyst, and secondary hydrocyanation. The monodentate phosphorus ligand is prepared by the mixed phenol, the production cost is obviously reduced, and a better catalytic effect is achieved; effects of the primary hydrocyanation and the isomerization reaction are slightly better to those of a monodentate phosphorus ligand prepared by single phenol; during the isomerization reaction, a ligand synthesized by phenol B and the prepared catalysts have the activity higher than that of catalysts prepared by phenol A and phenol C, at the time, the isomerization reaction can be carried out without a Lewis acid auxiliary agent, and the conversion rate, selectivity and other reaction indexes have no obvious change; during secondary hydrocyanation, the poisoning of the catalyst and degradation of the organophosphorus ligand can be effectively inhibited, secondary hydrocyanation consumption is reduced, and the raw material cost is decreased.
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Paragraph 0030; 0032
(2017/08/27)
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- Synthesis of nitriles from amines using nanoscale Co3O4-based catalysts via sustainable aerobic oxidation
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The selective oxidation of amines for the benign synthesis of nitriles under mild conditions is described. Key to success for this transformation is the application of reusable cobalt oxide-based nanocatalysts. The resulting nitriles constitute key precursors and central intermediates in organic synthesis.
- Natte, Kishore,Jagadeesh, Rajenahally V.,Sharif, Muhammad,Neumann, Helfried,Beller, Matthias
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supporting information
p. 3356 - 3359
(2016/04/09)
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- Nitrilation of carboxylic acids with acetonitrile catalyzed by molybdenum and vanadium complexes
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Various carbonitriles were synthesized by reaction of the corresponding carboxylic acids with acetonitrile in carbon tetrachloride in the presence of VO(acac)2and Mo(CO)6in 6 h at 150–170°C.
- Khusnutdinov,Shchadneva,Bayguzina,Mayakova, Yu. Yu.
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p. 1282 - 1286
(2016/10/26)
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- Method for producing adiponitrile with adipic acid liquid-phase method
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The invention discloses a method for producing adiponitrile with an adipic acid liquid-phase method. A solid phosphoric acid catalyst is adopted, adipic acid and a diluent are added into a reaction still, heating and raw material stirring are conducted during reaction, ammonia gas is supplied after temperature reaches a certain value, and the product is generated after reaction is conducted for a while. A novel environment-friendly adiponitrile synthesis method is adopted. By the adoption of the solid phosphoric acid catalyst, the defects of traditional catalysts are overcome, and catalysis effect is improved.
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Paragraph 0076-0078
(2017/07/23)
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- A using 2-methyl-3-crotonization of a method of isomerizing hexanedinitrile;
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The invention discloses a method for synthesizing adiponitrile by isomerization liquid of 2-methyl-3-crotononitrile. The method comprises steps of (1) carrying out isomerization reaction on 2-methyl-3-crotononitrile in the presence of zero valent nickel catalyst, phosphorus-containing ligand and lewis acid so as to generate 3-pentenenitrile; (2) mixing the isomerization liquid obtained in step (1) with hydrocyanic acid for reaction so as to generate the product containing adiponitrile. In the presence of zero valent nickel catalyst, phosphorus-containing ligand and lewis acid, the 2-methyl-3-crotononitrile generates 3-pentenenitrile through isomerization reaction; as the composition of the isomerization liquid is relatively the same as the material for secondary hydrocyanic reaction, the method directly adopts the isomerization liquid and hydrocyanic acid for reaction so as to synthesize adiponitrile. Therefore, the method saves the step of separating and purifying 3-pentenenitrile from the isomerization liquid, thus greatly lowering equipment cost and production cost, and reducing poisoning caused by zero valent nickel catalyst and phosphorus-containing ligand.
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Paragraph 0022; 0024
(2017/02/24)
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- Synthetic hexanedinitrile pyprolylene law inhibiting phosphorus containing ligand degradation method
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The invention discloses a method for inhibiting degradation of phosphorus containing ligand in process of synthesizing adiponitrile via a butadiene method, and the method comprises the step of adding organic alkali in isomerization reaction and secondary hydrocyanation reaction, wherein the organic alkali comprises triethylamine, diethylamine, dimethylamine, hexamethylenediamine, pyridine, phenylamine, phenylamine and N,N-dimethylaniline or N,N-diethylaniline. According to the method, organic alkali is added in the isomerization reaction and secondary hydrocyanation reaction, then the degradation of the phosphorus containing ligand in the isomerization reaction and secondary hydrocyanation reaction is effectively inhibited, and the degradation rate of the phosphorus containing ligand is controlled within 5%, so that the magnitude of recruitment of the phosphorus containing ligand is decreased, the separation recovery rate of the zero-valence nickel catalyst and the phosphorus containing ligand is improved at the same time and the raw material cost for synthesizing the adiponitrile via the butadiene method is reduced; and the method provided by the invention does not influence the conversion rate and the selectivity of the isomerization reaction and secondary hydrocyanation reaction.
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Paragraph 0029-0030
(2017/04/03)
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- Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source
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An active nickel catalyst prepared in situ from a Ni(II) compound, phosphine ligand, and zinc powder was found to be an efficient catalyst system for the hydrocyanation of various alkenes using acetone cyanohydrin as a safer cyano source. The combination of NiCl2·6H2O and 1,3-bis(diphenylphosphino)propane was the most efficient catalyst precursor in DMF. Under the optimized conditions, various styrenes, heterocyclic alkenes, and aliphatic alkenes were converted to their corresponding nitriles in excellent yields.
- Nemoto, Koji,Nagafuchi, Tsuyoshi,Tominaga, Ken-ichi,Sato, Kazuhiko
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p. 3199 - 3203
(2016/07/06)
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- Palladium nanoparticles supported on fibrous-structured silica nanospheres (KCC-1): An efficient and selective catalyst for the transfer hydrogenation of alkenes
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An efficient palladium catalyst supported on fibrous silica nanospheres (KCC-1) has been developed for the hydrogenation of alkenes and α,β-unsaturated carbonyl compounds, providing excellent yields of the corresponding products with remarkable chemoselectivity. Comparison (high-resolution TEM, chemisorption) with analogous mesoporous (MCM-41, SBA-15) silica-supported Pd nanocatalysts prepared under identical conditions, demonstrates the advantage of employing the fibrous KCC-1 morphology versus traditional supports because it ensures superior accessibility of the catalytically active cores along with excellent Pd dispersion at high metal loading. This morphology ultimately leads to higher catalytic activity for the KCC-1-supported nanoparticles. The protocol developed for hydrogenation is advantageous and environmentally benign owing to the use of HCOOH as a source of hydrogen, water as a solvent, and because of efficient catalyst recyclability and durability. The recycled catalyst has been analyzed by XPS spectroscopy and TEM showing only minor changes in the oxidation state of Pd and in the morphology after the reaction, thus confirming the robustness of the catalyst.
- Qureshi, Ziyauddin S.,Sarawade, Pradip B.,Albert, Matthias,D'Elia, Valerio,Hedhili, Mohamed N.,K?hler, Klaus,Basset, Jean-Marie
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p. 635 - 642
(2015/03/05)
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- "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
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Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2O3)-based catalysts applying molecular oxygen.
- Jagadeesh, Rajenahally V.,Junge, Henrik,Beller, Matthias
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- INTEGRATED PROCESS FOR NITRILE MANUFACTURE WITH ENHANCED LIQUID-LIQUID EXTRACTION
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Phosphorus-containing ligands are recovered from mixtures comprising 3-pentenenitrile (3PN) and adiponitrile (ADN), using liquid-liquid extraction. ADN is produced by hydrocyanation of 3PN. The ADN is hydrogenated to produce a hexamethyiene diamine (HMD) and at Ieast one byproduct including bis-hexamethylene triamine (BHMT) or 1,2-diaminocyclohexane. At Ieast a portion of the HMD product or byproduct is used to enhance the liquid-liquid extraction to recover phosphorus-containing ligand.
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Paragraph 00101-00104
(2016/04/19)
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- METHOD FOR PRODUCING DINITRILE COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing a dinitrile compound from a nitrile compound which can use not only a highly toxic substance such as hydrogen cyanide or acrylonitrile but also a stable and safe substance such as acetonitrile as raw materials without requiring to use an expensive catalyst. SOLUTION: There is provided a method for producing a dinitrile compound by dimerization of a nitrile compound by a dielectric barrier discharge. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0047; 0050
(2017/07/11)
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- Copper nanoparticles from copper aluminum hydrotalcite: An efficient catalyst for acceptor- and oxidant-free dehydrogenation of amines and alcohols
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An efficient and simple process for the preparation of stable nanocopper(0) on alumina [Cu(0)/Al2O3] from the inorganic composite precursor copper aluminum hydrotalcite (Cu-AlHT) by a chemical reduction method is described. Cu(0)/ Al2O3 was employed as an efficient catalyst in the acceptor- and oxidant-free dehydrogenation of various amines and alcohols to their corresponding dehydrogenated products in good to excellent yields. The stability of Cu(0)/Al2O3 was assessed by studying its recoverability and reusability in the dehydrogenation of amines and alcohols for up to five cycles.
- Damodara, Dandu,Arundhathi, Racha,Likhar, Pravin R.
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supporting information
p. 189 - 198
(2014/03/21)
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- METHOD FOR PRODUCING NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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The present invention relates to a method for the hydrocyanation of organic ethylenically unsaturated compounds including at least one nitrile function. The invention specifically relates to a method for the hydrocyanation of a hydrocarbon compound including at least one ethylenic unsaturation by a reaction with hydrogen cyanide in a liquid medium and in the presence of a catalyst including a metal element selected from the transition metals and an organophosphorous ligand, the organophosphorous gaud including a compound of general formula (I), where R1 and R2, which are identical or different, are a linear or branched alkyl radical having 1-12 carbon atoms, which can include heteroatoms, or an optionally substituted aromatic or cycloaliphatic radical that can include heteroatoms, wherein the covalent bond between P and R1, and that between P and R2, are P—C bonds.
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Paragraph 0081-0088
(2014/09/16)
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- Iron nitrate/TEMPO: A superior homogeneous catalyst for oxidation of primary alcohols to nitriles in air
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A highly practical, one-step, facile synthesis of aromatic, heteroaromatic, allylic and aliphatic nitriles from primary alcohols catalyzed by ferric nitrate [Fe(NO3)3·9H2O] in the presence of TEMPO, aqueous ammonia and air at room temperature is described.
- Dighe, Shashikant U.,Chowdhury, Deepan,Batra, Sanjay
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p. 3892 - 3896
(2015/01/09)
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- PROCESS FOR THE PRODUCTION OF NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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A method is described for the hydrocyanation of organic ethylene-unsaturated compounds into compounds including at least one nitrile function. Also described, is a method for the hydrocyanation of a hydrocarbon compound including at least one ethylenic unsaturation by reaction in a liquid medium with hydrogen cyanide in the presence of a catalyst including a metal element selected from among the transition metals and an organophosphorous ligand including, in one embodiment of the invention, an organophosphorous compound. The described method can be used in particular for the synthesis of adiponitrile from butadiene.
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Paragraph 0117-0124
(2013/03/26)
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- ORGANOPHOSPHORUS COMPOUNDS, CATALYTIC SYSTEMS COMPRISING SAID COMPOUNDS AND METHOD OF HYDROCYANATION USING SAID CATALYTIC SYSTEMS
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The present invention relates to organophosphorus compounds belonging to the phosphinite-phosphite family, catalytic systems comprising a metallic element forming a complex with said phosphinite-phosphite compounds and methods of hydrocyanation employed in the presence of said catalytic systems.
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Paragraph 0104-0110
(2013/03/26)
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- Silver-catalyzed nitrogenation of alkynes: A direct approach to nitriles through C≡C bond cleavage
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Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry. Copyright
- Shen, Tao,Wang, Teng,Qin, Chong,Jiao, Ning
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supporting information
p. 6677 - 6680
(2013/07/25)
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- Molecular iodine in aqueous ammonia: Oxidative fragmentation of oxiranes to nitriles
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Oxiranes undergo oxidative fragmentation, when treated with iodine in aqueous ammonia, to give nitriles. The reaction goes via formation of 1,2-amino alcohols as intermediates followed by CC bond cleavage. Advantages of the method are use of off-the-shelf nonexplosive, unlike previously used potentially explosive o-iodoxybenzoic acid, reagents, mild reaction conditions, and easy work-up procedure.
- Jadhav, Ravindra R.,Akamanchi, Krishnacharya G.
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p. 162 - 164
(2013/03/28)
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- PROCESS FOR PREPARING HEXAMETHYLENEDIAMINE AND POLYAMIDES THEREFROM
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Provided herein are processes for preparing hexamethylenediamine from one or more of the cis,cis-, cis,trans- and trans,trans- double-bond isomers of muconate diester. The muconate diester can contain carbon atoms derived from biomass containing detectable 14C content determined according to ASTM D6866 and optionally containing a 14C content up to 0.0000000001%. The process converts one or more of the cis,cis-, cis,trans- and trans,trans- double-bond isomers of muconate diester to the one or more of the cis,cis-, cis,trans- and trans,trans- double-bond isomers of muconamide. The isomer(s) of muconamide is then either: 1) directly converted by reduction to hexamethylenediamine; or 2) dehydrated to one or more of the cis,cis-, cis,trans- and trans,trans- double-bond isomers of mucononitrile which is then reduced to the hexamethylenediamine; or 3) reduced to adipamide, which is dehydrated to adiponitrile, and which is converted to hexamethylenediamine. Hexamethylenediamine so prepared can be used to make various polyamides.
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Page/Page column 44
(2012/11/06)
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- PROCESS FOR PRODUCING COMPOUNDS COMPRISING NITRILE FUNCTIONS
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The present invention relates to a process for producing compounds comprising at least one nitrile function by hydrocyanation of a compound comprising at least one non-conjugated unsaturation. The invention proposes a process for producing compounds comprising at least one nitrile function by hydrocyanation of an organic compound comprising at least one non-conjugated unsaturation, comprising from 2 to 20 carbon atoms, by reaction with hydrogen cyanide in the presence of a catalytic system comprising a complex of nickel having the oxidation state of zero with at least one organophosphorus ligand chosen from the group comprising organophosphites, organophosphonites, organophosphinites and organosphosphines and a cocatalyst of the Lewis acid type.
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Page/Page column 3
(2012/01/14)
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- ORGANOPHOSPHORUS COMPOUNDS, CATALYTIC SYSTEMS COMPRISING SAID COMPOUNDS AND METHOD OF HYDROCYANATION OR OF HYDROFORMYLATION USING SAID CATALYTIC SYSTEMS
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Organophosphorus compounds, catalytic systems comprising a metallic element forming a complex with the organophosphorus compounds and methods of hydrocyanation and of hydroformylation employed in the presence of the catalytic systems are described.
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Page/Page column 8
(2012/02/15)
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- ORGANOPHOSPHORUS COMPOUNDS BASED ON TETRAPHENOL (TP)-SUBSTITUTED STRUCTURES
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The invention relates to the synthesis of tetraphenol-substituted structures, in particular meta-substituted xylenes. Said tetraphenol-type structures are reacted to obtain organic phosphorus compounds, in particular organophosphites. The invention further relates to the production of catalytically active compositions which contain transition metals in addition to the aforementioned organic phosphorus compounds. According to another subject matter of the invention, said catalytically active compositions are used in chemical reactions with small molecules, e.g. HCN, CO, hydrogen, and amines.
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Page/Page column 14-15
(2012/08/08)
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- PROCESS FOR MAKING NITRILES
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Adiponitrile is made by reacting 3-pentenenitrile with hydrogen cyanide. The 3- pentenenitrile is made by reacting 1,3-butadiene with hydrogen cyanide. The catalyst for the reaction of 1,3-butadiene with hydrogen cyanide to make 3-pentenenitrile is recycled. At least a portion of the recycled catalyst is purified by an extraction process, which separates catalyst degradation products and reaction byproduct from the catalyst.
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Page/Page column 67; 93-94
(2012/02/01)
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- METHOD FOR MANUFACTURING COMPOUNDS INCLUDING NITRILE FUNCTIONS
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A process for the preparation of compounds containing nitrile functions and, more specifically, compounds containing two nitrile functions, such as succinonitrile and adiponitrile, is described. A process for preparing dintrile compounds obtained by reacting ammonia with an aqueous solution of a dicarboxyl compound in the presence of a silicon orthophosphate catalyst is also described.
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Page/Page column 3
(2011/12/12)
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- Cage phosphinites: Ligands for efficient nickel-catalyzed hydrocyanation of 3-pentenenitrile
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The cage monophosphinites CgPOR {where CgP = 6-phospha-2,4,8-trioxa- adamantane and R = C6H5 (La); 2-C 6H4CH3 (Lb); 2,4,6-C 6H2(CH3)3 (Lc); 2,4-C6H3tBu2 (Ld); CH3 (Le); CH2CF3 (Lf)} and diphosphinites CgPZPCg {where ZH2 = 2,2′-biphenol (L g) or 1,2-benzenedimethanol (Lh)} have been made from CgPBr and the corresponding alcohol or phenol. The cage phosphinites are remarkably stable to water. All the ligands La-h have been tested for nickel(0)-catalyzed hydrocyanation of 3-pentenenitrile in the presence of Lewis acids (ZnCl2, Ph2BOBPh2, or iBu2AlOAliBu2), and tentative structure-activity relationships are suggested. The hydrocyanation activities obtained with catalysts derived from monophosphinite Lf (with iBu2AlOAliBu2) and diphosphinite Lh (with ZnCl2) are comparable with the commercial catalyst based on P(OTol)3. The complexes trans-[PtCl 2(L)2] where L = La (1a), Le (1e), and Lf (1f) and the chelate cis-[PtCl2(Lh)] (1h) are reported. From the νCO values for the complexes trans-[RhCl(CO)(La-f)2] (2a-f), it is concluded that ligand Lf is the most phosphite-like of the monophosphinites. Treatment of [Ni(cod)2] (cod = 1,5-cyclo-octadiene) with L h leads to a mixture of products, one of which was characterized as the binuclear [Ni2(Lh)2(μ-cod)] (3h). The crystal structures of Lh, 1a, 1e, 1f, 1h?2CH2Cl 2, and 3h?3C6H5CH3 are reported.
- Mikhel, Igor S.,Garland, Michael,Hopewell, Jonathan,Mastroianni, Sergio,McMullin, Claire L.,Orpen, A. Guy,Pringle, Paul G.
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experimental part
p. 974 - 985
(2011/05/04)
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- PREPARATION OF NITRILES FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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A process for the hydrocyanation of a hydrocarbon-based compound having at least one site of ethylenic unsaturation into a nitrile compound includes reaction thereof, in a liquid medium, with hydrogen cyanide in the presence of a catalyst containing a metal element selected from among the transition metals and an organophosphorus ligand, wherein the organophosphorus ligand is a mixture of at least one monodentate organophosphite compound and at least one monodentate organophosphine compound; the subject process is especially useful for the synthesis of adiponitrile from butadiene.
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Page/Page column 4-5
(2011/07/29)
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- PRODUCTION OF COMPOUNDS COMPRISING NITRILE FUNCTIONAL GROUPS
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The present invention relates to a process for producing compounds comprising at least one nitrile function by hydrocyanation of a compound comprising at least one non-conjugated unsaturation. The invention proposes a process for producing compounds comprising at least one nitrile function by hydrocyanation of an organic compound comprising at least one non-conjugated unsaturation, comprising from 2 to 20 carbon atoms, by reaction with hydrogen cyanide in the presence of a catalytic system comprising a complex of nickel having the oxidation state of zero with at least one organophosphorus ligand chosen from the group comprising organophosphites, organophosphonites, organophosphinites and organosphosphines and a cocatalyst of the Lewis acid type of formula in which M1 and M2 represent elements chosen from the group comprising zinc, boron, aluminium, cadmium, gallium, indium and tin.
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Page/Page column 3
(2011/02/18)
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- PREPARATION OF NITRILES FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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A process for the hydrocyanation of a hydrocarbon-based compound having at least one site of ethylenic unsaturation into a nitrile compound includes reaction thereof, in a liquid medium, with hydrogen cyanide in the presence of a catalyst containing a metal element selected from among the transition metals and an organophosphorus ligand, wherein the organophosphorus ligand is a compound of formula (I): The subject process is particularly useful for the synthesis of adiponitrile from butadiene.
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Page/Page column 5
(2011/06/10)
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- NICKEL METAL COMPOSITIONS AND NICKEL COMPLEXES DERIVED FROM BASIC NICKEL CARBONATES
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Nickel-metal-containing solids for use in manufacturing nickel metal complexes are disclosed. The nickel-metal-containing solids are made by reducing basic nickel carbonates. By varying the molar ratios of carbonates and bicarbonates to nickel salts, the methods provide basic nickel carbonates that produce superior nickel metal-containing solids that react more effectively with phosphorous-containing ligands. The phosphorous containing ligands can be both monodentate and bidentate phosphorous-containing ligands.
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Page/Page column 9
(2011/08/22)
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- Direct oxidative conversion of alcohols, aldehydes and amines into nitriles using hypervalent iodine(III) reagent
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An efficient, facile, and high-yielding procedure for the direct oxidative conversion of alcohols, aldehydes, and primary, secondary, and tertiary amines into the corresponding nitriles using the hypervalent iodine(III) reagent hydroxy(tosyloxy)iodobenzene in combination with ammonium acetate as a nitrogen source is reported. The oxidation proceeded in mixed solvent to afford nitriles in excellent yields and high selectivity even at room temperature. Selective oxidation of primary amines in the presence of secondary amines and tertiary amines was also achieved. A possible mechanism for the oxidation is proposed.
- Zhu, Chenjie,Sun, Chengguo,Wei, Yunyang
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supporting information; experimental part
p. 4235 - 4241
(2011/02/25)
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- Oxidation of amines over alumina based catalysts
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Amines were oxidized by molecular oxygen in the vapor phase at atmospheric pressure over alumina and silicotungstic acid/alumina catalysts. The study is focused on the influence of structure of amine and catalyst properties on the composition of the main reaction products and byproducts. Coating of γ-Al2O3 with silicotungstic acid or its semisalt can significantly enhance its catalytic activity in amine oxidation. The adsorption of amine on weak acidic sites of catalyst is essential for its oxidation to main reaction products. Cycloalkylamines are oxidized mainly to cyclic oximes (selectivity up to 64%) and Schiff bases of appropriate cycloalkanone and cycloalkylamine (selectivity up to 38%). Mainly nitriles (selectivity up to 55%) and appropriate Schiff bases (selectivity up to 54%) were observed in the oxidation products of primary alkylamines. Their molar ratio depends on the catalyst acidity and reaction conditions. 1,6-Hexanediamine is oxidized mainly to caprolactam (yield 48%) and other cyclic lactames and Schiff bases as well as to dinitrile (yield 13%).
- Rakottyay, Karol,Kaszonyi, Alexander,Vají?ek, Stanislav
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experimental part
p. 33 - 41
(2010/08/22)
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