82 results about "Hydroamination" patented technology

The invention relates to a method for preparing propane diamine by taking propylene glycol and liquid ammonia as raw materials. Propylene glycol and liquid ammonia are mixed in a certain ratio and are pumped into a reactor by virtue of a pump, and reaction is carried out in presence of a catalyst and hydrogen. The method for preparing the propane diamine by taking the propylene glycol and liquid ammonia as the raw materials has the advantages that a novel catalyst is adopted, catalytic performance is excellent, and long-time operation can be easily carried out; propylene glycol is subjected to hydroamination for producing a propane diamine product at lower reaction pressure, and reaction conditions are adjusted and changed, so that composition of the product can be flexibly adjusted and changed, selectivity of a target product is improved, a reaction process is simple, one-time investment of a production unit and production cost are reduced, a reaction product and a catalyst can be simply separated, and large-scale continuous industrial production can be easily realized.

The invention relates to a method of preparing 1,2-diaminopropane from isopropanolamine and liquid ammonia. The method includes mixing the isopropanolamine and the liquid ammonia according to a certain ratio, pumping the mixture into a reactor and reacting under existence of a catalyst and hydrogen. The method adopts the novel catalyst which is excellent in catalytic performance and prone to long-term operation. The method allows production of a diaminopropane product by hydroamination of the isopropanolamine to be achieved under a low reaction pressure. By adjustment of reaction conditions, composition of products can be regulated flexibly and selectivity of a target product is improved. A reaction process is simple. One-time investment of production devices and a production cost are reduced. Separation of a reaction product from the catalyst is simple. The method is prone to large-scale continuous industrial production.

The invention relates to a Schiff-base ligand-based rare-earth metal complex, a preparation method and applications. The complex is prepared by reacting a Schiff-base ligand with a rare-earth metal amino compound. When the complex is used as a catalyst, hydrogen-alkane oxidation reaction and hydroamination can be directly and efficiently catalyzed without the assistance of any activating agents or cocatalysts, and moreover, the complex can be recycled in catalytic reaction. The structural general formula of the rare-earth supported catalyst is shown as follows in the specification.

The invention discloses a continuous preparation method of amine-terminated polyether, and the method comprises the following steps of: taking polyether polyol, H2 and NH3 as raw materials, executing critical hydroamination in a fixed bed reactor under a critical hydroamination catalyst, executing gas-liquid separation in a gas-liquid separator to feed liquid from the fixed bed reactor, reusing NH3 and H2 without being reacted after being dried and pressurized; accessing the liquid material into a vacuum chamber, removing H2O and other small-molecule materials in vacuum, continuously discharging to prepare amine-terminated polyether. The method is continuous in operating processes and more steady in a product quality batch method; in preparation, the gas can be reused to prevent environmental pollution; the method can effectively solve the problems of decreased conversion and weak selectivity caused by poorly contacting the gas and the catalyst during large-molecular polyether reaction; the method has the advantages of higher reaction conversion ratio and primary amine selectivity.

This invention relates to phosphoramidite compounds and catalyst complexes which can be used to provide enantioselective reactions including hydroamination reactions, etherification reactions and conjugate addition reactions and allylic substitution reactions, among others. In a first aspect, the present invention is directed to phosphoramidite and related compounds according to general structure (I), where Z is absent or is a group containing O, N or S, preferably O; R1 and R2 are independently an optionally substituted C1-12 alkyl group, an optionally substituted (CH2)n-aromatic group or (CH2)n-heteroaromatic group, or are linked together to form an optionally substituted aliphatic or (CH2)n-aromatic dianion of a diol, diamine, dithiol, aminoalcohol, aminohiolate or a alcoholthiol group; R3′ and R3 are each independently H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group with the proviso that R3′ and R3 are not both H, or together R3′ and R3 form an optionally substituted C5-C15 saturated or unsaturated carbocyclic ring; R4 is H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group; R5 is absent, H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic or (CH2)n-heteroaromatic group; Ra and Ra′ are each independently H or a C1-C3 alkyl group, or Ra and Ra′ together with the carbon to which they are attached form a optionally substituted C5-C15 saturated or unsaturated carbocyclic or heterocyclic ring, or an aromatic or heteroaromatic ring; R6 and R7 are each independently H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group, with the proviso that R5, R6 and R7 cannot simultaneously be H, and when Ra and Ra′, together with the carbon to which they are attached, form a carbocyclic ring, heterocyclic ring or an aromatic or heteroaromatic ring, R5 is absent or is preferably H; R6 and R7 are preferably H or CH3; and each n is independently 0, 1, 2, 3, 4, 5 or 6 and wherein at least one of the carbon atoms attached to the nitrogen of the phosphoramidite group is a chiral center.

The invention relates to a novel tridentate nitrogen ligand, rare earth metal complexes thereof and the application of the rare earth metal complexes in the olefin hydroamination reaction and the polyester synthesis. The ligand of the kind can be obtained from corresponding beta diketone and amine by two-step condensation reaction; the rare earth complexes can be obtained by the reaction between the ligand and rare earth metal alkyl and amidine compounds. The rare earth complexes can effectively catalyze the olefin hydroamination reaction and the ring-opening polymerization of lactones. The structural general formulas of the tridentate nitrogen and the corresponding rare earth complexes are shown as above.

This invention relates to a polyolefin composition comprising one or more of the following formulae:wherein the PO is the residual portion of a vinyl terminated macromonomer (VTM) having had a terminal unsaturated carbon of an allylic chain and a vinyl carbon adjacent to the terminal unsaturated carbon; R1 is a hydrogen atom, an aryl group, or an alkyl group, wherein the aryl group or alkyl group can include one or more heteroatoms, an alkyl or aryl amino group, a polyalkylamino group; wherein the VTM is a vinyl terminated macromonomer.

The invention discloses a synthetic method of sitagliptin and a salt thereof. The synthetic method comprises the steps: carrying out an esterification reaction, a reduction reaction, an oxidizing reaction and a witting reaction on 2,4,5-trifluorophenylacetic acid as a starting raw material to obtain 4-(2,4,5-trifluorophenyl)-2-ethyl crotonate; then carrying out a hydroamination reaction on 4-(2,4,5-trifluorophenyl)-2-ethyl crotonate and chiral amine in the presence of butyl lithium or hexamethyldisilazane sodium to form a chiral hydroamination product; carrying out an esterolysis reaction, a condensation reaction and a hydrogenation reaction to obtain sitagliptin. The raw materials used in the synthetic method of sitagliptin are low in price and easy to obtain; the synthetic method of sitagliptin is less in step, easy to operate and capable of effectively reducing cost. By the use of the method, high-purity sitagliptin can be obtained, a sitgliptin phosphate obtained through salifying has an HPLC (High Performance Liquid Chromatography) and an ee (enantiomeric excess) value of more than 99% and can be applied to the field of medicine.

Alkylamine production by reaction of olefins with ammonia or primary or secondary amines under hydroamination conditions with a calcined zeolitic catalyst is such that at most 24 hours before the reaction the catalyst is heat- activated at 100-550degreesC in a gas stream of air, nitrogen and / or other inert gases.

The invention belongs to the technical field of synthetic chemistry, and in particular relates to a trivalent iridium imine complex containing iridium nitrogen double bonds, a preparation method and an application of the trivalent iridium imine complex. A binuclear iridium compound cyclooctadiene iridium chloride dimer [ (COD) IrCl ]2 is taken as a raw material, and the binuclear iridium compoundiridium(I) cyclooctadiene chloride, dimer [ (COD) IrCl ]2 reacts with phenyl dipyrrole compounds under an alkaline condition to obtain a precursor containing a monovalent iridium complex, and the precursor is oxidized into the trivalent iridium imine compound containing the iridium nitrogen double bonds by using an azide oxidation method. The synthesis process is simple and green, and has excellent selectivity and higher yield. The trivalent iridium imine complex has the characteristics of stable physical and chemical properties, thermal stability and the like, and shows excellent activity andregioselectivity (anti-Markovnikov's rule) in hydroamination of olefins.

The invention discloses an environmental-friendly and efficient preparation method of a quinolone compound. According to the adopted technical scheme, the environmental-friendly and efficient preparation method comprises the following steps: putting an intermediate 1 (I) in a reactor, dropwise adding an intermediate 2 (II) at a room temperature, and mixing and stirring uniformly under the condition without solvent to carry out solvent-free hydroamination; after a detection reaction is completed, carrying out chromatography on reaction liquid through a silicagel column, concentrating through reduced pressure distillation to obtain a yellow oily intermediate 3 (III); then putting the intermediate 3 (III) in the reactor, directly adding a catalyst, heating for dissolution while stirring to carry out an intramolecular cyclization reaction; after the detection reaction is completed, quenching the reaction by using ice water, extracting, concentrating and recrystallizing to obtain a target compound 4 (IV). The preparation method of the quinolone compound disclosed by the invention is environmental-friendly, efficient, simple, convenient and safe to operate, and the produced quinolone compound is low in cost.

Methods are provided for the catalytic hydroamination of compounds having an alkyne or allene functional group, in which the compound is contacted with ammonia or an amine in the presence of a catalytic amount of a gold complex under conditions sufficient for hydroamination to occur.

The invention provides a large-steric-hindrance trivalent rhodium imide complex containing a rhodium-nitrogen dual-key structure. The large-steric-hindrance trivalent rhodium imide complex is characterized by including the following structure shown in the description. A synthesis technology is simple and green, and has excellent selectivity and a high yield. The large-steric-hindrance trivalent rhodium imide complex has the features of stable physical and chemical properties and thermal stability, and has excellent activity and regional selectivity in an anti-Markovnikov hydroamination reaction of olefins.

The present invention relates to a method for the enzymatic hydroamination of C—C double bonds catalyzed by enzymes structurally and / or functionally related to phenylalanine ammonia lyase (PAL) isolated from microorganisms of Petroselinum crispum, Rhodoturula glutinis and / or functional active derivatives thereof.

The invention discloses a method for preparing cyclohexane dimethylamine. The method comprises the following steps: (1) carrying out a dehydrogenation reaction on cyclohexane dimethanol under the catalysis of a dehydrogenation catalyst to obtain cyclohexanediformaldehyde; and (2) carrying out a hydroamination reaction on the cyclohexane dicarboxaldehyde obtained in the step (1), liquid ammonia andhydrogen under the action of an amination catalyst to obtain cyclohexane dimethylamine. According to the method, by adopting different types of catalysts and different reaction control conditions insections, the reaction processes of dehydrogenation of cyclohexane dimethanol, imidization and hydrogenation are controlled, and the generation of secondary amine and high polymer byproducts in the amination process is inhibited, so that the selectivity and the yield of the cyclohexane dimethylamine product are greatly improved.

A preparing method of 2,2,6,6-tetramethyl-4-piperidylamine by a catalytic amination method is disclosed. The preparing method includes following steps of: (1) adding 2,2,6,6-tetramethyl-4-piperidone, sodium hydroxide, ammonia water and a skeleton nickel catalyst into a high-pressure kettle having a condenser, a pressure gage, a stirrer and a thermocouple, feeding nitrogen to replace air in the kettle, feeding hydrogen until the pressure is 2.5 MPa, stirring, heating to 110 DEG C, and reacting for 30 min; and (2) after the reaction is completed, cooling to room temperature, stopping stirring, venting, taking reaction materials out, filtering, subjecting filtrate to distillation under atmospheric pressure to distill ammonia gas and water, subjecting the residue in the kettle to vacuum distillation, and collecting a fraction that is the 2,2,6,6-tetramethyl-4-piperidylamine. The preparing method adopts the skeleton nickel as the catalyst, synthesizes the 2,2,6,6-tetramethyl-4-piperidylamine by hydrogenation and amination, and is high in yield and purity of products.

The invention belongs to the technical field of organic chemistry, and discloses a sequence-controllable linear / hyperbranched polymer prepared through metal-free catalyzed multi-component polymerization, and a preparation method and an application thereof. The method comprises the following steps: 1, adding alkyne and amine into a reaction container, and carrying out a hydroamination reaction with a polar solvent as a reaction medium to obtain an alkenyl ester intermediate, wherein the alkyne is a butyldiacetyl ester compound; 2, adding amine, aldehyde and a catalyst into the reaction container provided with the alkenyl ester intermediate, and carrying out a polymerization to obtain a polymer solution, wherein the catalyst is acid; and 3, adding the polymer solution to a settling agent in a dropwise manner under a stirring condition, allowing the obtained solution to stand, filtering the solution, washing the obtained material, and drying the washed material to obtain the sequence-controllable linear / hyperbranched polymer. The method has the advantages of simplicity, mild conditions, no metal catalysis, high yield of the polymer, controllable unit sequence of the polymer structure, realization of the preparation of linear and hyperbranched polymers, and potential application values in the field of biological and chemical luminescence detection.

The invention discloses a method for preparing polyether amine by hydroamination of polyether polyol, a catalyst in the method is mainly composed of a multi-metal active component, an auxiliary agent and a carrier, the multi-metal active component comprises M1-M2 (M1 is one or more than two of transition metals Ni, Co and Cu, and M2 is one or two of transition metals Re and Ru). The catalyst may also comprise an auxiliary agent, and the auxiliary agent is one or a combination of Fe, Cr, Mn, B, Mg, Ba, Pt and other metals or oxides. The catalyst disclosed by the invention is characterized in that in the preparation process of the catalyst, a complexing agent or a stabilizing agent needs to be added into the prepared precursor liquid of the multi-element metal active component and the auxiliary agent so as to improve the catalytic performance. When the catalyst is used for preparing polyether amine through polyether polyol hydroamination, the conversion rate is high, the catalytic performance is stable, the target product selectivity is high, the technological process is simple, the catalyst is suitable for a continuous or batch reactor, and the market prospect is wide.

The invention relates to a method for catalyzing intermolecular hydroamination reaction of alkyne and amine. The method comprises the following steps: reacting a terminal alkyne as shown in a formula (1) and a primary aromatic amine as shown in a formula (2) in an aprotic polar solvent at 25-100 DEG C for 6-24 hours under catalysis of tris(pentafluorophenyl)borane and under airtight conditions containing protective atmosphere, wherein structural formulae of the formula (1) and the formula (2) are as shown in the specification, wherein R1 is selected from C1-10 alkyl and aryl; and R2 is selected from hydrogen, C1-10 alkyl, alkoxy, cyano, trifluoromethyl, nitro, halogen and amino. The method is simple and available in raw material, simple in operation, relatively mild in reaction condition, relatively high in yield and relatively wide in application range of a substrate.

The invention provides a method for preparing an enamine compound by catalyzing phenylacetylene and utilizing the hydroamination reaction. The method is characterized by comprising the steps that thephenylacetylene and secondary amine are taken as raw materials, under the effect of a nickelous imine complex catalyst, the hydroamination reaction is conducted in a solvent, after finishing of the reaction and after-treatment, the enamine product is obtained, wherein the molecular formula of the nickelous imine complex catalyst is [R1R2C (C5H4N) 2] Ni=NPh, R1 and R2 are independently selected from H, CH3 and Ph, and arene is the solvent. The catalyst has extremely high catalytic activity and regioselectivity, the synthesizing technology is simple and green, good selectivity and high yield areachieved, the atom economy is good, and production of waste gas, waste water and industrial residues is reduced; the method protects the environment, and is simple in operation and suitable for industrial production.

Compositions and methods useful in facilitating or conducting a reaction at effective conditions, such as room temperature (e.g. about 70 degrees F.), utilize a compound including at least two different heteroatoms, and optionally a heterocycle, and a transition metal. The compound is effective in facilitating a variety of reactions including hydrolysis reactions, alcoholysis reactions, aminolysis reactions, carbon dioxide conversion reactions, hydroamination reactions, hydration reactions, and the like.

The invention belongs to the technical field of organic synthesis. A catalyst is a rare earth complex based on diimine ligands. The invention further provides application of the rare earth catalyst in aromatic amine hydroamination and alkylation reaction.

The invention relates to a nickelous imine complex with a nickel nitrogen double-bond structure and preparation and application of the nickelous imine complex. The preparation method of the nickelousimine complex comprises the following steps that 1, a phenyldipyridine ligand solution is added into a zero-valent nickel precursor solution for a reaction for 3-5 hours at room temperature; 2, azidobenzene is added for a reaction for 2-5 hours at room temperature, and through aftertreatment, the nickelous imine complex is obtained. The nickelous imine complex is used for catalyzing an anti-Markovnikov hydroamination reaction of styrene to prepare a linear-chain amine compound. Compared with the prior art, the synthesizing technology is simple and green, the selectivity and the yield are high,the nickelous imine complex prepared by using the method has the advantages of stable physicochemical properties, thermal stability and the like, and the nickelous imine complex can show excellent activity and regioselectivity in the reaction of catalyzing the anti-Markovnikov hydroamination reaction of the styrene.

The invention discloses a synthesis method of N, N, N'-trimethyl-N'-hydroxyethyl diaminoethyl ether. The synthesis method comprises the following steps of: in a solvent I, adopting dimethylaminoethoxyethanol as a raw material, and under a catalytic system of 2, 2, 6, 6-tetramethyl piperidinoxide-FeCl3-tertbutyl nitrite, utilizing oxygen gas to oxidize the dimethylaminoethoxyethanol into 2-[2-(dimethylamino)ethoxy]acetaldehyde; in a solvent II, mixing N-methylethanolamine with the 2-[2-(dimethylamino) ethoxy]acetaldehyde, adopting Raney Ni as a catalyst, adopting the above mixture as a reactionsystem to carry out hydrogenation and amination, and preparing the N, N, N'-trimethyl-N'-hydroxyethyl diaminoethyl ether. The N, N, N'-trimethyl-N'-hydroxyethyl diaminoethyl ether synthesized by adopting the synthesis method has the characteristics of simple process, low cost, high yield and less pollution.

The invention discloses a catalyst for synthesizing monoethylamine as well as a preparation method and application thereof. The catalyst comprises aluminum oxide particles and cobalt, palladium and rhenium deposited on the surfaces of the aluminum oxide particles. Cobalt accounts for 10%-40% of the total mass of the catalyst, palladium accounts for 0.5%-5% of the total mass of the catalyst, and rhenium accounts for 0.1%-1% of the total mass of the catalyst. The catalyst is prepared by adopting a spraying method. By adopting the catalyst provided by the invention, when monoethylamine is prepared through hydroamination of ethanol, the monoethylamine selectivity is greater than or equal to 86%(the conversion rate is greater than or equal to 61%, and the ethylamine selectivity is greater thanor equal to 99.9%), the advantages are obvious, and the catalyst has relatively high industrial application value.

The invention provides a synthesis method of trimetazidine hydrochloride, which comprises the following steps: carrying out hydroamination reaction by using 2,3,4-trimethoxybenzaldehyde and piperazineanhydrous as raw materials, and catalyzing by using a Lindlar catalyst. The trimetazidine hydrochloride produced by the method does not contains trimetazidine hydrochloride impurity B and has high purity.