23 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 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 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 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 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 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 three-dimensional divergence method for synthesizing chiral amine through asymmetric hydroamination of nickel-catalyzed trisubstituted olefin and application of the three-dimensional divergence method in pharmaceutical molecule synthesis. The preparation method comprises the following steps: sequentially adding ethylene glycol dimethyl ether nickel dibromide, a direct-linked imidazole chiral ligand, a trisubstituted olefin compound, lithium hydroxide, potassium iodide, benzoyl hydroxylamine and tert-butyl alcohol into a dry glass reaction bottle, reacting at 30 DEG C by taking methyldiethoxysilane as a hydrogen source, and carrying out a reaction for 2-4 hours at the temperature of 30 DEG C; the fatty amine compound which is constructed by trisubstituted olefin and benzoyl hydroxylamine and has a continuous double chiral center is obtained. The continuous double-chiral central amine compound with various structures can be efficiently constructed by utilizing the method disclosed by the invention, and can be directly applied to later-stage modification of drug molecules. Meanwhile, the preparation method is efficient and convenient, and has excellent enantioselectivity, diastereoselectivity and regioselectivity; the synthesis route is safe and easy to implement, the cost is low, and the reaction operation and post-treatment process are simple. More importantly, the method has been successfully applied to construction of drug molecular skeleton derivatives with Moclobemide, Acecainide and the like, provides an efficient strategy for rapidly obtaining chiral amine compound libraries with various structures, and shows important application potential in the field of later modification and screening of drugs.