31 results about "Hydroamination" patented technology

The present invention belongs to the technical field of petrochemical catalysis, and relates to a preparation method for improving the stability of a Cu-Beta zeolite catalyst for preparing caprolactam from caprolactone, and the use thereof. In the present invention, a cavity-modified dealuminated Beta zeolite is used as a carrier, and copper is loaded in pore channels of the zeolite carrier by means of an improved ammonia distillation method. The cavity modification refers to subjecting the dealuminated Beta zeolite carrier to a desiliconization technique controlled by the use of a weak organic base so as to enlarge silanol nests generated by dealumination of the dealuminated Beta zeolite carrier, thereby better accommodating and stabilizing the nano and sub-nano copper particles. The core of the improved ammonia distillation method involves impregnating a zeolite carrier with an equal volume of a copper-ammonia complex solution, such that the copper-ammonia complex mainly undergoes, during ammonia distillation, a reaction of depositing copper hydroxide in zeolite pore channels, thereby improving the sintering resistance. The Cu-Beta catalyst prepared using the method provided by the present invention exhibits high activity, selectivity and stability when applied to the reaction of caprolactam prepared from caprolactone via gas-solid phase hydroamination.

The application provides a reverse Markovnikov hydroamination reaction of trifluoromethyl enone under catalyst-free and base-free conditions, uses a sulfonhydrazide compound with good functional group tolerance as a nitrogen source, realizes the introduction of a nitrogen-containing functional group in a green and environment-friendly manner, and synthesizes a series of alpha-sulfonhydrazine-alpha-hexafluoroisopropyl-substituted carbonyl compounds. The method has the characteristics of no transition metal participation, mild conditions, wide substrate universality and the like.

The invention discloses a gram-level synthesis method of Dactyllactone A. The gram-level synthesis method of Dactyllactone A is shown in the description. The method comprises the following steps: with simple and easily available aryl iodide, aziridine and triisopropyl silylacetylene as starting materials, stirring and reacting in an organic solvent at 60-70 DEG C under the action of a palladium catalyst, a phosphine ligand, a norbornene derivative and alkali to obtain a key intermediate; the key intermediate is condensed with iodo gem-dimethyl ester furanone prepared from propiolic acid and dimethyl malonate iodine ylide, and then the condensation product is subjected to an Au / Ag catalyzed intramolecular hydroamination reaction, photocatalytic 6-pi electro-cyclization and two-step conversion, so that the natural product Dactyllactone A can be obtained, wherein the iodo gem-dimethyl ester furanone and iodo gem-dimethyl ester furanone are prepared from propiolic acid and dimethyl malonate iodine ylide. The method has the advantages of cheap and easily available raw materials, short reaction steps, high reaction efficiency, large preparation scale, simple preparation process and the like, has great application potential, and lays a good foundation for industrial production.

The invention discloses a method for preparing primary amine chemicals by hydrogenation amination of aldehyde and ketone through a platinum group monatomic doped nickel-based layered hydroxide catalyst, and belongs to the technical field of heterogeneous catalysis preparation of high-quality chemicals. The method comprises the following steps: by taking aldehyde and ketone chemicals as raw materials and ammonia gas as a gas source, carrying out hydrogenation amination reaction in a reaction solvent under the action of a platinum group monatomic doped nickel-based layered hydroxide catalyst and a hydrogen atmosphere to prepare a primary amine chemical; the platinum group single atom is any one of palladium, platinum, ruthenium, iridium or rhodium; wherein the effective active components on the nickel-based layered hydroxide carrier are composed of nickel metal and other metals, and the other metals are one or more of zinc, magnesium, aluminum, cerium, manganese, zirconium, iron, niobium or copper. The primary amine chemical prepared by the method has very high economic value.

A preparation method and use of a novel pure inorganic solid silicon-based sulfonic acid and / or phosphoric acid catalytic material are disclosed. The surface hydroxyl-rich metasilicic acid is used as the raw material, and by using a sulfonating reagent and / or phosphoric acid, the sulfonic acid group and / or the phosphoric acid group are bonded to the inorganic silicon material by chemical bonding to obtain a pure inorganic solid silicon-based sulfonic acid and / or phosphoric acid catalytic material. The catalytic material can be widely used in many acid-catalyzed organic reactions such as isomerization, esterification, alkylation, hydroamination of olefins, condensation, nitration, etherification, multi-component reactions and oxidation reactions. The inorganic solid silicon-based sulfonic acid and / or phosphoric acid catalytic material of the present invention has the advantages of high acid amount, high activity, good hydrothermal stability, no swelling, simple preparation, low cost, no pollution, no corrosion, easy separation and reusability.

The invention provides a high-allene phosphine oxide as well as a preparation method and application thereof. The preparation method of the high-allene phosphine oxide comprises the following steps: in a solvent A, under the promotion of alkali, an eneyne ketone compound II and a phosphine oxide compound III are subjected to a conjugated phosphine hydrogenation reaction, and the high-allene phosphine oxide I is obtained. According to the method, the high-allene phosphine oxide is prepared by starting from simple and easily available starting raw materials and adopting an alkali-promoted conjugated phosphine hydrogenation reaction, the atom utilization rate is 100%, and the method is a reaction meeting atom economy and green chemistry, and is mild in condition, easy to implement, simple and convenient to operate, easy in product separation and purification and high in yield. The high-allene phosphine oxide synthesized by the method is excellent in diastereoselectivity and novel in structure, has various active functional groups, and has potential synthesis application value. The high-allene phosphine oxide disclosed by the invention can be used as a catalyst and is applied to a reaction for catalyzing dehydration between carboxyl groups to generate anhydride.

The invention discloses a catalyst for synthesizing tetrahydropyrrole through hydroamination of furan as well as a preparation method and application of the catalyst, and belongs to the technical field of catalysis. According to the catalyst, an acidic amination catalyst is taken as a core, a composite oxide doped with hydrogenation active metal and an auxiliary agent is taken as a shell, an equivalent-volume impregnation method and a coprecipitation method are respectively adopted to prepare a core material and a shell layer material, then the shell layer is coated on the surface of the core through a rolling ball forming process, and the bifunctional catalyst with an eggshell-shaped structure is formed. According to the catalyst, tetrahydrofuran can be generated through hydrogenation of furan in a shell layer in a single reactor, then tetrahydrofuran is diffused to an inner core to be subjected to an amination reaction to generate tetrahydropyrrole, the problem of furan polymerization coking caused by coexistence of an acid center and hydrogenation activity on a traditional catalyst is effectively solved, the stability of the catalyst is remarkably improved, and the service life of the catalyst is remarkably prolonged. Meanwhile, the catalyst integrates two-step reaction, simplifies the process flow, and has the comprehensive advantages of high activity, high selectivity and good stability.

The method comprises the following steps: filling a high-pressure fixed bed reactor with a certain amount of a catalyst, reducing the catalyst by hydrogen in advance, enabling raw materials 1, 6-hexanediol, a solvent, liquid ammonia and hydrogen to pass through a bed layer filled with the catalyst, controlling the temperature of the catalyst bed layer, the reaction pressure and the weight hourly space velocity of the materials, and carrying out direct hydrogenation ammoniation on the raw materials to synthesize cycloheximine. Carrying out selective hydrogen ammonification on 1, 6-hexanediol to continuously prepare cycloheximine; the cheap transition metal supported catalyst comprises a main catalytic active component and a carrier. The method has the advantages of production process simplification, wide raw material source, production and separation cost reduction, resource utilization rate improvement, and solving of the problems of catalyst deactivation, reactant intermolecular condensation, and the like. And the technical problems that the yield of hexamethyleneimine is low, the process flow is complicated, the product quality is not high, the catalyst is easy to inactivate, and environmental pollution is easy to generate after-treatment of the product in China at present can be solved.

The application discloses a method for preparing primary amine chemicals by hydrogenation amination of aldehyde and ketone through a platinum group single-atom doped nickel-based layered hydroxide catalyst, and belongs to the technical field of heterogeneous catalysis for preparing high-quality chemicals. The method uses aldehyde and ketone chemicals as raw materials, ammonia gas as a gas source, and under the action of the platinum group single-atom doped nickel-based layered hydroxide catalyst, hydrogenation amination reaction is carried out in a reaction solvent under a hydrogen atmosphere to prepare primary amine chemicals; the platinum group single atom is any one of palladium, platinum, ruthenium, iridium or rhodium; wherein the effective active components on the nickel-based layered hydroxide carrier are composed of nickel metal and other metals, and the other metals are one or more of zinc, magnesium, aluminum, cerium, manganese, zirconium, iron, niobium or copper. The primary amine chemicals prepared by the method have very high economic value.

The invention discloses a technological method for continuously preparing pyrrolidine, and belongs to the technical field of organic chemical industry. A fixed bed reactor is filled with a nickel and yttrium loaded solid-phase catalyst, a hydroamination reaction of 1, 4-butanediol and ammonia is continuously catalyzed, no solvent participates, nickel valence distribution and carrier acid sites are optimized through the synergistic effect of double metals, and carbon deposition is inhibited. According to the method, the 100% conversion rate of 1, 4-butanediol and the pyrrolidine selectivity larger than or equal to 93.7% are achieved under the mesoporous confinement effect, and the method is simple in technological process, low in cost and easy to operate; the catalyst is easy to prepare and low in price; the method has the advantages of high raw material conversion rate and good product selectivity, is suitable for continuous preparation of industrial production, and provides a new thought for the design of a heterogeneous catalytic system.

The invention discloses a catalyst, a preparation method and a method for preparing triethylamine through hydroamination of coal-based ethanol. The catalyst comprises a carrier and an active component loaded on the carrier, the active component comprises an active element; the active elements are cobalt and rhenium; the carrier is rod-like aluminum oxide; and the length-diameter ratio of the rod-like aluminum oxide is 5-30. Compared with a CoRe / Al2O3 (irregular morphology) catalyst, the selectivity of triethylamine in the catalyst prepared by the method disclosed by the invention can be obviously improved.

The present invention belongs to the field of fine chemical engineering and provides a synthetic process for continuously preparing 1,2-cyclohexanediamine from cyclohexene oxide. The raw material cyclohexene oxide and ammonia water are passed through a No. 1 reactor equipped with a solid acid catalyst in a certain proportion, and a hydrolysis reaction is carried out under certain reaction process conditions; the mixed liquid obtained from the reaction enters a static mixer and is mixed with hydrogen in a certain proportion, and after being uniformly mixed, it enters a No. 2 reactor equipped with a nickel-based catalyst, and a hydroamination reaction is carried out under certain reaction process conditions; finally, the product enters a gas-liquid separator, and 1,2-cyclohexanediamine is separated. The present invention innovatively realizes the one-step reaction of cyclohexene oxide to obtain 1,2-cyclohexanediamine by connecting the hydrolysis reactor and the hydroamination reactor in series.

The present invention relates to a method for preparing 1,6-hexanediamine, wherein the method of the present invention is that 1,6-hexanediol or 6-amino-1-hexanol or cyclohexylimine synthesizes 1,6-hexanediamine through hydroamination in the presence of a catalyst, and the catalyst is composed of three parts: an active metal, an auxiliary element, and a porous carrier. The present invention is characterized in that the catalyst is a non-uniform catalyst, wherein the non-uniform catalyst particles are composed of a core and an outer layer, and the core and the outer layer are composed of a carrier and an active metal (one or more of Co, Ni, Cu) and an auxiliary (one or more of metals or oxides such as Ru, Pd, Fe, B, Zn, Re, W, Y) limiting the amount of loading, and the thickness of the outer layer of the catalyst particles or the proportion of the catalyst volume occupied have special requirements. The catalyst of the present invention is used for preparing 1,6-hexanediamine by hydroamination, and has the advantages of significantly reducing the generation of oligomers in the product, long life, and high yield of 1,6-hexanediamine.

The invention discloses a method for preparing an ionic enamine compound from a pyridinium-alkyne monomer and application of the ionic enamine compound, belongs to the technical field of organic synthesis, and particularly relates to a method for preparing the ionic enamine compound by taking the pyridinium-alkyne monomer and an amine monomer as raw materials and carrying out alkyne-amine hydroamination reaction. The method can be carried out at room temperature without the action of a catalyst, the reaction efficiency is high, excellent regioselectivity and stereoselectivity are achieved, no by-product is generated in the reaction process, the atom economy is high, and the prepared ionic enamine compound contains ionic groups, is good in water solubility, contains heteroatoms and benzene rings in the structure, and can be used for preparing the ionic enamine compound. The compound has rich electrons, has a good application prospect in preparation of photodynamic drugs, photosensitizers, photodynamic antibacterial agents or biological imaging reagents, and can also be used as an effective synthon, that is, a nucleophilic reaction is further carried out, and compounds with more diversified structures are synthesized.

The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of piperidine hexamethylenediamine, an efficient catalytic system composed of 4-CzIPN and a supported catalyst is constructed, the activation potential energy of an olefin hydroamination reaction system can be effectively reduced, the hydroamination reaction between olefin and amine molecules is promoted, the reaction condition is mild, the yield and purity are high, and the method is suitable for industrial production. Use of dangerous gases such as hydrogen is avoided, safety is good, and the method can be suitable for large-scale industrial production.

The invention discloses a preparation method of a chiral cyclic amine compound. Specifically, the method comprises the following steps: in a solvent, in the presence of a palladium catalyst, an oxazoline ligand, an oxidizing agent and a reducing agent, carrying out a ring closing reaction on a compound as shown in a formula II to obtain a compound as shown in a formula I. According to the preparation method disclosed by the invention, the intramolecular hydroamination reaction of the non-activated internal olefin is efficiently realized under a mild condition, good functional group compatibility and general substrate applicability are realized, the operation is simple, and a chiral amine center can be constructed in one step.

The invention provides a method for preparing high-carbon diamine from high-carbon dihydric alcohol through hydroamination, which comprises the following steps: dissolving high-carbon dihydric alcohol in an inert solution, then mixing with liquid ammonia to obtain a mixed solution, heating a fixed bed reactor filled with a modified noble metal catalyst to a reaction temperature, introducing hydrogen at the same time, and reacting to obtain high-carbon diamine. The active components of the modified noble metal catalyst comprise a palladium element, a chromium element and / or a cobalt element, the carrier is alumina, then adding the mixed solution into a fixed bed reactor, reacting under reaction pressure, and purifying to obtain the high-carbon diamine. According to the method for preparing the high-carbon diamine, multi-step reaction is not needed, the reaction process is greatly simplified, continuous production is facilitated, no toxic intermediate product is generated in the preparation process, atom economy is high, and the method is green and environmentally friendly.

The invention belongs to the technical field of fine chemical engineering, and discloses a method for preparing 2, 2-bis (4-aminocyclohexyl) propane through hydroamination, which comprises the following steps: taking ruthenium as an active component, combining with a ligand to synthesize a ruthenium homogeneous catalyst, and under the condition of the ruthenium homogeneous catalyst, catalytically hydrogenating a bisphenol A solution and liquid ammonia to generate hydroamination reaction to prepare the 2, 2-bis (4-aminocyclohexyl) propane. The catalyst is 1, 2-bis (4-aminocyclohexyl) propane. According to the method provided by the invention, the activity of the catalyst and the selectivity of primary amine can be effectively improved, and the proportion of isomers in the product can be adjusted by adjusting the type of the Ru ligand.

The invention belongs to the technical field of catalysts, and discloses a preparation method of a water-resistant multi-metal composite catalyst and application of the water-resistant multi-metal composite catalyst in preparation of polyether amine. The preparation method comprises the following steps: (1) mixing a nickel source, a lanthanum source, a chromium source and an aluminum source, adding a precipitant to carry out a co-precipitation reaction, and then aging and granulating to prepare metal hydroxide precipitation particles; and (2) dipping the metal hydroxide precipitation particles into a noble metal precursor solution, then roasting, processing and forming, and finally reducing to obtain the multi-metal composite catalyst. By optimizing the preparation process, high-dispersion noble metal active sites are formed, the catalytic activity and water resistance of the catalyst in hydroamination reaction can be effectively improved, and the cost is reduced. When being applied to synthesis of polyether amine, the catalyst can effectively resist the influence of water generated in synthesis reaction of polyether amine on the catalyst, prolong the service life of the catalyst and ensure long-term stable operation of the catalyst in actual production.

The present invention belongs to the technical field of organic polymer compound preparation and discloses a fatty alcohol polyetheramine polyether, a preparation method, and applications thereof. The method uses a fatty alcohol as an initiator, adds a first epoxy compound, and conducts a polymerization reaction to produce a fatty alcohol polyether. The fatty alcohol polyether is then subjected to a hydroamination reaction with liquid ammonia to produce a fatty alcohol polyetheramine. Finally, the fatty alcohol polyetheramine is subjected to a polymerization reaction with a second epoxy compound to produce a fatty alcohol polyetheramine polyether. The fatty alcohol polyetheramine polyether prepared by the present invention has the advantages of being safe, non-toxic, non-irritating to the skin, biodegradable, compatible, and environmentally friendly. It can be used to prepare quaternary ammonium salt intermediates and various industrial solvents. The fatty alcohol polyetheramine polyether prepared by the method has a high total amine value, conversion rate, and tertiary amine selectivity, with the tertiary amine rate exceeding 98.0% and as high as 99.5%. The raw materials are natural and readily available, the preparation process is simple, and the method is suitable for large-scale production and application.

The invention aims to provide a chiral bridged diimine group-containing trivalent rare earth metal alkylate as well as a preparation method and application thereof, and the chiral bridged diimine group-containing trivalent rare earth metal alkylate is characterized in that each central metal in the chiral bridged diimine group-containing trivalent rare earth metal alkylate is connected with four nitrogen atoms of a ligand to form a chelating structure taking rare earth metal as a center; in addition, the compound is sensitive to air and water, and has solubility in polar and non-polar organic solvents. The chiral bridged diimino-containing trivalent rare earth metal alkylate provided by the invention has strong stability on one hand, and can also be used as a catalyst for intramolecular hydroamination reaction on the other hand.

The invention discloses a catalyst and a method for hydrogenation amination of by-products containing benzene and cyclohexane. The catalyst carrier is diatomite, the active component is Ni, and the auxiliary agent is selected from one or more of platinum, palladium, cerium, molybdenum and zirconium. The catalyst prepared by the method is high in activity and good in selectivity, benzene and cyclohexane byproducts can be recycled to generate cyclohexylamine and dicyclohexylamine, and the method is mild in process condition, simple to operate, safe, environment-friendly and suitable for industrial large-scale production.

The present invention relates to the technical field of petrochemical catalysis, and relates to a method for preparing a Cu-Beta zeolite catalyst for the production of caprolactam from caprolactone, and a use. The main technical feature of the present invention is that by using dealuminated Beta zeolite as a carrier, copper is loaded in pore channels of the zeolite carrier by means of an improved ammonia evaporation method. The core of the improved ammonia evaporation method is to impregnate the zeolite carrier with a copper-ammonia complex solution in an equal volume, so that a copper-ammonia complex mainly undergoes, in the pore channels of the zeolite carrier and during ammonia evaporation, a reaction of depositing copper hydroxide. After roasting and hydrogen reduction treatment, the copper hydroxide deposited in the pore channels of the zeolite can directly form highly dispersed nano and sub-nano copper particles at lattice defect sites of hydroxyl nests in the pore channels, and the sub-nano copper particles obtain sintering resistance by means of tight interaction with the hydroxyl nests. When the Cu-Beta zeolite catalyst prepared by the method of the present invention is applied to the production of caprolactam from caprolactone via gas-solid phase hydroamination, high activity and selectivity and good stability are achieved.

The instant invention is directed to an efficient and scalable process for synthesizing Compound 5, (aminomethyl phenylalanine), or a salt thereof. The process utilizes an engineered PAL enzyme to prepare Compound 4 via an enantioselective hydroamination of readily accessible 3-cyanocinnamic acid, which is optimal for industrial scale manufacturing. In the instant invention, Compound 4 then undergoes a hydrogenation step to make Compound 5, or a salt thereof.

The invention provides a method for asymmetric hydroamination of olefin and aromatic amine through bimetallic catalysis. The structural general formula of the product chiral amine obtained through the method is shown in the specification. According to the chiral amine, unification of structural diversity, high stereoselectivity and synthesis efficiency is achieved through bi-metal concerted catalysis, a secondary amine structure of the chiral amine provides a rich molecular skeleton for drug design, a foundation is laid for biological activity optimization through precise stereo control, and the chiral amine has a wide application prospect. The method has the characteristics of academic innovation and industrial practicability, so that the method has wide application prospects in the fields of medicines, materials and the like.

The application provides an asymmetric total synthesis method of alkaloid martinellic acid. Compared with the prior art, the asymmetric total synthesis method provided by the application constructs a pyrroloquinoline skeleton through a transition metal catalyst catalyzed tandem asymmetric cyclization reaction, and realizes carbon chain growth and amine group introduction through an olefin hydroamination carbonylation reaction, raw materials are simple and easy to obtain, the synthesis route is simple, and the conversion efficiency is high, so that the application provides a new idea and platform for drug molecule design and modification.

The invention discloses a preparation method of polyether amine for an emulsifier, and belongs to the technical field of synthesis of organic high-molecular compounds. The preparation method comprises the following steps: firstly, by taking methanol as an initiator and sodium methoxide as a catalyst, introducing epoxide in sections to obtain methanol polyether; liquid ammonia, hydrogen and the prepared methanol polyether are introduced into a tubular reactor with a reductive amination catalyst for a hydrogenation amination reaction, and methanol polyether amine is prepared. Wherein the segmented introduction of the epoxide is as follows: ethylene oxide is introduced in the first stage, a mixture of ethylene oxide and epoxypropane is introduced in the second stage, and epoxypropane is introduced in the third stage for blocking. The polyether structure with excellent emulsifying performance is obtained by designing different addition modes and sequences of EO and PO, the emulsifying performance of polyether amine is greatly improved, and the process is simple and easy to operate.

The application discloses a new type of organic aluminum catalyst catalyzed implementation of unactivated aromatic olefin anti-Markovnikov hydroamination addition, belongs to the field of organic chemistry. The aluminum catalyst is synthesized by using existing ligand and commercially available aluminum alkyl compound, and the synthesis step is simple and easy to operate. Under the action of the aluminum catalyst and the additive, aromatic olefin and different amines are reacted in an organic solvent, and a series of amine compounds are obtained with good regioselectivity and high yield. The application uses cheap and easily available main group metal aluminum catalyst, and synthesizes olefin anti-Markovnikov hydroamination addition product with excellent regioselectivity under relatively mild and simple reaction conditions.

Disclosed in the present invention are an efficient and stable catalyst, and a preparation method therefor and a use thereof. The catalyst comprises a metal oxide support having a three-dimensional porous structure, and a polyoxometalate dispersed in a monomolecular state and attached to the metal oxide support, wherein the polyoxometalate is a proton-type polyoxometalate capable of providing hydrogen ions. Further, the catalyst also comprises an active metal component dispersed in a monatomic state and attached to one or both of the polyoxometalate and the metal oxide support. The present invention overcomes the problem in the prior art of inability to fully use the active sites of a polyoxometalate and a metal, has excellent catalytic activity and good stability, and is suitable for being used in reactions such as alkylation, esterification, hydrogenation, and amination.

The invention discloses a method for hydrogenation of aliphatic olefins by nickel catalysis. The reaction process is as follows: in a nitrogen atmosphere, a compound 2, a nickel catalyst, an aromatic boronic acid, a base, a solvent, an additive, a phosphine ligand and a compound 1 are sequentially mixed, stirred at 80-120°C for reaction for 18-36 hours, cooled to room temperature, decompressed to remove the solvent, and separated by column chromatography to obtain a target product. When the phosphine ligand is tri-tert-butyl phosphine, the target product is compound 3, and when the phosphine ligand is diphenylethyl phosphine, the target product is compound 4. The molar ratio of the compound 2, the phosphine ligand, the nickel catalyst, the aromatic boronic acid, the base and the additive is 1:(0.1-0.4):(0.05-0.2):(0.2-1.2):(0.4-1.2):(0.05-0.2), the equivalent ratio of the compound 1 to the compound 2 is 1:(1-3), R 1 is an alkyl group or a silicon group, R 2 is an alkyl, aryl or heteroaryl group, R 3 The present invention can selectively synthesize branched or chain alkylamine compounds only by regulating the ligand in the nickel catalyst.