28 results about "Transfer hydrogenation" patented technology

The invention discloses a high-efficiency transfer hydrogenation method of non-activated olefin, which comprises the following steps: adding a non-activated alkenyl amide compound, nickel acetylacetonate dihydrate, phenylsilane, water and cesium pivalate into an organic solvent 1, 4-dioxane, reacting at room temperature under a nitrogen condition for 12 hours, and after the reaction is completed, filtering to obtain a filtrate, namely the high-efficiency transfer hydrogenation method of the non-activated olefin. And performing post-treatment (extraction and column chromatography separation) to obtain the corresponding alkyl chloride compound. According to the method, phenylsilane and water are directly used as hydrogen sources, direct use of hydrogen can be avoided, operation is easy and convenient, and efficient construction of C (sp3)-C (sp3) bonds can be achieved through transfer hydrogenation of non-activated olefin. The conversion reaction conditions are extremely mild, and the reaction activity is high; the method has the advantages of excellent atom economy and step economy, wide substrate application range, good functional group compatibility and the like. It is worthy that the synthesis method is also suitable for later-stage modification of medicine molecules, and the druggability of the molecules is expected to be further improved.

The application belongs to the technical field of catalysts, and discloses a supported ruthenium nanocluster catalyst Ru / CNT@CN, a preparation method and application thereof. The catalyst takes carboxylated carbon nanotubes as a carrier, has a carbon nitride shell outside the carrier, and has ruthenium nanoclusters inlaid on the surface of the carbon nitride shell in situ. The preparation steps are as follows: (1) a mixed acid solution composed of concentrated nitric acid and concentrated sulfuric acid is used to perform oxidation treatment on multi-walled carbon nanotubes, and the carbon nanotubes are washed and dried to obtain carboxylated carbon nanotubes, denoted as CNT; (2) first, the CNT, DCD, Ru metal salt and water are stirred at 50-100 DEG C for 2-12 h to obtain a dispersion liquid; then, the dispersion liquid is frozen with liquid nitrogen and subjected to freeze-drying treatment to obtain a catalyst precursor CNT@DCD-Ru; finally, the CNT@DCD-Ru is annealed at 500-700 DEG C for 2-8 h in a hydrogen-inert gas mixed atmosphere to obtain the target catalyst Ru / CNT@CN. The catalyst is applied in the hydrogen production by ammonia borane hydrolysis or the transfer hydrogenation reaction of nitroaromatic compounds. The catalyst prepared by the application has excellent catalytic activity and stability.

The present application relates to the field of drug synthesis, in particular to a novel intermediate, a method for preparing the same and application thereof. The structural formula of the novel intermediate provided by the present application is as expressed by formula I:where R is a secondary amine protection group. Based on the possible biogenic pathway of morphine derivatives, the present application realizes the efficient synthesis of morphine derivatives through the strategy of biomimetic synthesis, taking the asymmetric transfer hydrogenation reaction and the intramolecular oxidative dearomatization Heck reaction in the process of preparing the intermediate as the key reactions of total synthesis. Using the novel intermediate provided by the present application to synthesize morphine derivatives has the characteristics of significantly reducing the synthesis steps, improving the yield, reducing the discharge of three wastes and reducing the production cost.

The application discloses a method for preparing furfuryl alcohol by furfural transfer hydrogenation. The active components Zr and Mg of the magnetic catalyst come from corresponding non-noble metal salt solution, and Fe is selected from oxides. The catalyst is prepared by a coprecipitation method. The method takes furfuryl alcohol as raw material, commercial isopropyl alcohol as hydrogen source and solvent, and carries out a closed reaction at 160-210 DEG C for 3-7 h under the stirring rate of 500 rpm, and then is cooled to room temperature to obtain the furfuryl alcohol. Under the optimal conditions, the conversion rate of furfuryl alcohol is 99.13%, and the yield of furfuryl alcohol is 92.50%. The catalyst preparation method is simple, low in price and good in cycle stability, the catalytic system is green and efficient, and has a wide application prospect.

This invention discloses a method for synthesizing ferrocene-isoquinoline and ferrocene-dihydroisoquinoline planar chiral compounds, belonging to the field of asymmetric catalysis technology. Using chiral phosphoric acid (CPA) as a catalyst, 1,4-dihydropyridine compound (HEH) as a hydrogen source, and racemic ferrocene-isoquinoline derivative (+ / -)-1 and ditert-butyl dicarbonate as substrates, two types of planar chiral ferrocene compounds are synthesized through asymmetric transfer hydrogenation resolution. The enantiomeric excess of the ferrocene-isoquinoline planar chiral compounds can reach 95%, while the enantiomeric excess of the ferrocene-dihydroisoquinoline carboxylic acid tert-butyl ester planar chiral compounds can reach 89%, with a resolution coefficient (S value) reaching 50. This invention achieves the hydrogenation kinetic resolution of ferrocene-isoquinoline compounds, is simple to operate, uses commercially available catalysts, operates under mild reaction conditions, and exhibits good resolution effects, showing excellent application prospects.

The invention discloses a non-activated olefin transfer hydrogenation method driven by a light / cobalt / mercaptan triple catalytic system. Olefin compounds and derivatives thereof are used as raw materials, bio-based gamma-terpinene is used as a hydrogen source, and catalytic circulation is realized through a hydrogen atom transfer (HAT) relay mechanism under the mild condition of visible light irradiation. The method is characterized in that (1) a dual-function activation mode of gamma-terpinene is created for the first time, wherein weak bonding diallyl C-H bonds (BDE = 76kcal / mol) synchronously provide hydrogen atoms and aromatization driving force; and (2) a three-catalyst synergistic system: an organic photosensitizer / cobalt-based catalyst / thiol reagent forms a cascade HAT pathway. (3) normal-temperature normal-pressure operation: high-pressure equipment is not needed, and the reaction time is less than 24 hours; the method breaks through the dependence of traditional hydrogenation on precious metal, high-pressure hydrogen and an oxidizing agent, realizes efficient hydrogenation of non-activated olefin, and provides a new way for synthesis of drug molecule intermediates.

Disclosed in the present invention are a polymeric diamine ligand, a diamine ligand, a preparation method therefor, and the use in catalytic synthesis of a chiral alcohol. Specifically provided in the present invention is a polymeric diamine compound, the polymeric diamine compound having a structural framework shown as formula I. A polymeric diamine metal chelate prepared from the polymeric diamine compound may be used as a catalyst in a transfer hydrogenation reaction to obtain chiral alcohol compounds having a plurality of substituents with a low catalyst loading and a high yield. Moreover, said reaction involves mild conditions, no alkali participation and simple operation and does not need special reactors.

A process for preparing 2,2,4,4-tetramethylcyclobutane-1,3-diol by reacting 2,2,4,4-tetramethylcyclobutanedione with isobutanol in the presence of a tandem transfer hydrogenation and Tischenko reaction catalyst.

Disclosed is a process for preparing 2,2,4,4-tetramethylcyclobutane-1,3-diol by reacting 2,2,4,4-tetramethylcyclobutanedione with a secondary alcohol in the presence of a transfer hydrogenation catalyst.

The invention discloses a preparation method of chiral aryloxy substituted chiral diol, which comprises the following step: in the presence of a chiral catalyst and a transfer hydrogenation reagent, carrying out selective transfer hydrogenation reaction on aryloxy substituted asymmetric diketone to generate the chiral aryloxy substituted chiral diol. According to the method provided by the invention, the raw materials and the catalyst are cheap and easy to obtain, the reaction condition is mild, the operation is simple, and the reaction is efficient; through asymmetric transfer hydrogenation of aryloxy-substituted asymmetric diketone, the chiral aryloxy-substituted chiral diol core skeleton is prepared with high selectivity, the synthesis route is direct, and the atom economy is high.

The invention discloses a preparation method of a phosphorus and oxygen co-doped nitrogen-doped carbon core-shell structure catalyst and a method for preparing aromatic amine through transfer hydrogenation reduction of nitro-aromatic hydrocarbon, and the preparation method of the catalyst comprises the following steps: step (1), respectively dissolving heteroatom salt, zinc salt and dimethylimidazole in deionized water to obtain respective solutions, the preparation method comprises the following steps: adding organic amine into a dimethylimidazole solution, stirring, then adding a heteroatom salt solution, finally adding a zinc salt solution to obtain a mixed solution, reacting the mixed solution for a set time, centrifugally filtering and washing a reaction product, and carrying out vacuum drying to obtain a ZIF-8 precursor compound; and (2) calcining the ZIF-8 precursor compound at a high temperature in an inert atmosphere to obtain the phosphorus and oxygen co-doped nitrogen-doped carbon core-shell structure catalyst. According to the preparation method of the phosphorus and oxygen co-doped nitrogen-doped carbon core-shell structure catalyst disclosed by the embodiment of the invention, the prepared catalyst is low in cost, not easy to inactivate and high in catalytic reaction activity.

The application discloses a kind of defective type UiO-66 (Zr) nanometer catalyst and its preparation method and application, it is related to biomass catalytic conversion and metal organic framework material technical field, specifically includes: zirconium chloride, terephthalic acid and acid adjusting agent are added in N,N-dimethylformamide, solvent thermal reaction is carried out under the condition of 120-160 ℃ 3-5h, after centrifugation, washing and drying, defective precursor material is obtained;Defective precursor material is dispersed in organic solution and reflux elution is carried out, after centrifugation, washing and drying, defective type UiO-66 (Zr) nanometer catalyst is obtained.The application solves the problem that the material of UiO-66 (Zr) prepared by traditional method is poor in acid-base site synergy in furfural transfer hydrogenation reaction, low in catalytic efficiency and difficult to realize gram preparation, realizes 100% furfural conversion rate and 99.5% furfuryl alcohol selectivity.

The present disclosure relates to novel intermediates in the synthesis of elacestrant and methods of making the same. The chiral compound N-(2-((1R,2S)-6-(benzyloxy)-1-hydroxy-1,2,3,4- tetrahydronaphthalen-2-yl)-5-methoxyphenyl)acetamide (Compound (I-1)), is prepared in two steps: (1) a Pd-catalyzed α-arylation of a ketone precursor, 6-(benzyloxy)-3,4-dihydronaphthalen- 1(2H)-one, (Compound (a-1)), with N-(2-bromo-5-methoxyphenyl)acetamide (Compound (b- 1)); and (2) the asymmetric transfer hydrogenation of the product from Step 1, N-(2-(6- (benzyloxy)-1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)-5-methoxyphenyl)acetamide (Compound (c-1)), to produce N-(2-((1R,2S)-6-(benzyloxy)-1-hydroxy-1,2,3,4-tetrahydronaphthalen-2-yl)-5- methoxyphenyl)acetamide (Compound (I-1)). The chiral compound (R)-6-(2-amino-4- methoxyphenyl)-5,6,7,8-tetrahydronaphtalen-2-ol (Compound (d)) is produced from Compound (I-1) by two additional steps: 3) dehydroxylation and debenzylation of N-(2-((1R,2S)-6- (benzyloxy)-1-hydroxy-1,2,3,4-tetrahydronaphtalen-2-yl)-5-methoxyphenyl)acetamide (Compound (I-1)) to produce N-(2-(6-hydroxy)-1,2,3,4-tetrahydronaphtalen-2-yl)-5- methoxyphenyl)acetamide (Compound (III-1)); and 4) hydrolysis of N-(2-(6-hydroxy)-1,2,3,4- tetrahydronaphtalen-2-yl)-5-methoxyphenyl)acetamide (Compound (III-1)) to produce (R)-6-(2- amino-4-methoxyphenyl)-5,6,7,8-tetrahydronaphtalen-2-ol (Compound (d)).

Disclosed is a process for preparing 2,2,4,4-tetramethylcyclobutane-1,3-diol by reacting 2,2,4,4-tetramethylcyclobutane dione with isobutanol in the presence of a tandem transfer hydrogenation and Tischenko reaction catalyst.

The application discloses a preparation process of bumetanide. 4-chloro-3-nitro-5-sulfamoylbenzoic acid is used as a starting material, and nucleophilic substitution is carried out with phenol in potassium hydroxide aqueous solution to obtain a compound with a structural formula Int01; in a methanol-water mixed solvent, palladium-carbon is used as a catalyst, and ammonium formate is used as a hydrogen source for transfer hydrogenation, so that the nitro group on the compound with the structural formula Int01 is reduced to an amino group, and a compound with a structural formula Int02 is obtained; the compound with the structural formula Int02 is subjected to reductive amination with n-butyl aldehyde and sodium triacetoxyborohydride to obtain a crude bumetanide product; after the crude bumetanide product is refined in an acetic acid and cyclohexane system, decolorization is carried out in methanol-water by using activated carbon, and crystallization is carried out to obtain a pure bumetanide product; and the pure bumetanide product is mixed with mannitol, an alkaline adjusting agent and taurine to obtain a finished product.

The invention discloses an N-heterocyclic carbene ligand complex as well as application, a preparation method and an intermediate thereof. The invention provides an application of a compound as shown in a formula I as a catalyst in a cis-transfer hydrogenation reaction of alkyne. The metal Ir complex of the CNHCCP ligand shows excellent catalytic activity in the cis-transfer hydrogenation reaction of dialkyl substituted alkyne taking alcohol as a hydrogen source, the cis-trans selectivity is excellent, the yield is high, and the reaction conditions are mild; the metal complex of the CNHCCP ligand also has obvious color change in the cis-transfer hydrogenation reaction of alkyne, and the reaction is stopped when the color of the reaction liquid is changed from purple to yellow, so that the cis-olefin with high yield and high conversion rate can be obtained. The preparation method of the CNHCCP ligand and the metal complex thereof has the advantages of simplicity, cheap and easily available raw materials, environmental friendliness, mild reaction conditions, high yield and simple post-treatment, and is suitable for industrial production.

The invention discloses a regulation and control method for catalyzing transfer hydrogenation and etherification of biomass-based aldehydes, which comprises the following steps: synthesizing a mesoporous molecular sieve carrier by a hydrothermal method, preparing a catalyst loading 5-20wt% of Zr by an equivalent-volume impregnation method, and regulating selective transfer hydrogenation and etherification of a biomass-based aldehyde compound in an alcohol solvent by controlling temperature programming, calcining and activating of the catalyst. And selective distribution of hydrogenation products and etherification products is realized. Taking furfural and cinnamyl aldehyde as examples, under the condition of reaction for 2-12 hours at 100-180 DEG C in an alcohol solvent, an unactivated catalyst can catalyze complete conversion of a substrate, and the selectivity of hydrogenated products furfuryl alcohol and cinnamyl alcohol can reach 94% and 85%; after the temperature of the catalyst is raised to 100-500 DEG C for activation, the main product is changed from alcohol to ether, and the selectivity of furfuryl ether and cinnamyl ether of etherification products can reach 65% and 60%; the selectivity of hydrogenation and etherification reactions can be further improved by regulating and controlling reaction conditions.

A method for preparing nickel-based porous carbon catalysts from waste plastics includes the following steps: dissolving nickel salts and waste plastics in an alcohol solution, stirring at room temperature, impregnating, drying in a drying oven, evaporating the alcohol solvent to obtain nickel-containing plastic solids; placing the obtained nickel-containing plastic solids in a tube furnace, heating to the corresponding plastic pyrolysis temperature under an inert atmosphere, and completing the plastic pyrolysis to obtain the catalyst. The method for preparing nickel-based porous carbon catalysts from waste plastics provided by this invention requires no other additives, catalysts, or high-pressure conditions. The preparation process is simple, environmentally friendly, uses readily available raw materials, has strong versatility, and is easy to implement in batches. This invention applies the obtained nickel-based porous carbon catalyst to the transfer hydrogenation of ethyl levulinate to prepare γ-valerolactone without the need for external hydrogen gas, and under suitable reaction conditions, the yield of γ-valerolactone exceeds 90%.

The invention discloses a bidentate nitrogen-phosphorus-manganese complex, a preparation method of the bidentate nitrogen-phosphorus-manganese complex and application of the bidentate nitrogen-phosphorus-manganese complex in catalyzing transfer hydrogenation of indole compounds to prepare indoline compounds, and also relates to a related in-situ catalysis method. The bidentate nitrogen phosphorus manganese complex has high activity in transfer hydrogenation reaction of indole compounds, and has important application in preparation of indoline fine chemicals. The manganese complex is simple in preparation method, high in yield and good in stability. For the transfer hydrogenation reaction of indole compounds, the manganese-based catalytic system is high in catalytic activity, small in manganese loading amount, simple in method, small in environmental pollution and high in yield.

This invention discloses a copper-based catalyst doped with a single metal atom, its preparation method, and its application. The method uses a water-soluble metal salt as a precursor and prepares a series of copper-based catalysts by reduction with an aqueous sodium borohydride solution. The reaction process uses methanol or other alcohol solutions as the reaction medium and hydrogen source, and the reaction is carried out at 170-210 degrees Celsius, with the reaction product reaching a maximum yield of 99.9%. This method involves the interaction between the single metal atom and metallic copper to promote the efficient hydrogenation and deoxygenation of biomass-derived aldehydes without the addition of external hydrogen. This invention can prepare high-value-added liquid fuels from biomass-derived aldehydes, and features simple catalyst preparation, the ability to transfer hydrogenation in various solvents, high conversion efficiency, and high yield of the target product, showing promising prospects for industrial application.

The application discloses a synthesis method of lumerizine and intermediates thereof, and belongs to the technical field of medicine synthesis. The application takes 1-(4-fluorophenyl)-4-(4-piperidone-1-yl) butan-1-one with 2-(methylamino) phenylhydrazine as starting materials, and efficiently prepares medical-grade lumerizine p-toluenesulfonate through four core reactions of Fischer indole condensation, intramolecular double SN2 ring closure, normal-pressure metal-free asymmetric transfer hydrogenation and salt formation and refinement. Three kinds of key intermediates and preparation processes thereof are completely protected, a non-metal normal-pressure catalytic system is used throughout the process, and a noble metal high-pressure hydrogenation process is abandoned, so that metal residues are avoided, chiral selectivity is high, the process is simple, three-waste quantity is small, the problems of low yield, high cost, many impurities and difficulty in industrialization of the existing process are effectively solved, and the application has extremely high industrialization popularization value and patent protection value.

The invention discloses a method for preparing lignin oil by continuous hydrogenation depolymerization of lignin through microwave and microfluidics coupling, and belongs to the technical field of high-value utilization of biomass resources. The method comprises the following steps: adding water, mannitol, n-amyl alcohol and p-toluenesulfonic acid into a wood fiber raw material, performing in-situ extraction on lignin under microwaves, and performing capillary regulation to form a three-phase emulsion and a droplet microreactor; a Pd / carboxylated carbon nanotube-formic acid aqueous solution and n-amyl alcohol-lignin mixed flow form Pickering emulsion, microwave hydrogenation depolymerization is performed in a heart-shaped channel microreactor, a catalyst is cooled, separated and recycled, and an organic phase is distilled to obtain n-amyl alcohol and lignin oil. According to the invention, a series catalytic system for in-situ extraction of lignin and transfer hydrogenolysis is constructed, a micro-fluidic chip design is further combined, a complex one-pot reaction is divided into two characteristic reaction units, efficient preparation of high monophenol lignin oil is realized through continuous flow series connection, and the method is a novel simple, efficient and energy-saving lignin oil preparation strategy.

The invention discloses a polymeric diamine ligand, a diamine ligand, a preparation method of the diamine ligand and application of the diamine ligand in catalytic synthesis of chiral alcohol. Specifically, the invention provides a polymeric diamine compound, and the polymeric diamine compound has a structural framework as shown in a formula I. The polymeric diamine compound and the prepared polymeric diamine metal chelate are used as a catalyst in a transfer hydrogenation reaction, chiral alcohol compounds with multiple substituent groups can be obtained with low catalyst loading capacity and high yield, the reaction condition is mild, alkali participation is not needed, operation is easy and convenient, and a special reactor is not needed.

The invention provides a preparation method of tofacitinib citrate, and belongs to the technical field of pharmaceutical chemicals. Formic acid and ammonium formate are used as hydrogen donors, transfer hydrogenation is carried out under catalysis of the noble metal catalyst, reaction safety is improved, use of high-pressure hydrogen and high-pressure operation risks are thoroughly avoided, special pressure-resistant equipment is not needed, only a conventional reaction kettle is needed, and equipment investment and safety control cost are greatly reduced.

The invention belongs to the technical field of organic synthesis, and provides a preparation method of heteroatom-containing chiral amine. The preparation method provided by the invention comprises the following steps: mixing imine containing heteroatoms, an ammonia borane compound, a chiral amino benzimidazole manganese catalyst and a solvent, and carrying out asymmetric transfer hydrogenation reaction to obtain the chiral amine containing heteroatoms. According to the preparation method disclosed by the invention, the optical activity of the heteroatom-containing chiral amine is improved, and data of the embodiment shows that the optical activity of the obtained heteroatom-containing chiral amine is 85-99% ee, and the separation yield is 65-99%; meanwhile, compared with an existing chiral phosphine ligand precious metal catalytic system, the preparation method has the advantages that the chiral amino benzimidazole manganese catalyst is used as the catalyst, so that the production cost and environmental pollution of the catalyst are reduced, and green preparation of key chiral drug intermediates can be realized.

Disclosed is a method for preparing 2,2,4,4-tetramethylcyclobutane-1,3-diol by reacting 2,2,4,4-tetramethylcyclobutanedione with a secondary alcohol in the presence of a transfer hydrogenation catalyst.

The invention discloses a method for preparing olefin by heterogeneous transfer hydrogenation of alkyne at room temperature, and relates to the technical field of selective catalytic hydrogenation of alkyne. The method comprises the following steps: preparing a catalyst carrier from a carrier source through a coprecipitation method, a solvothermal synthesis method or a sol-gel method; the preparation method comprises the following steps: uniformly dispersing a catalyst carrier into a mixed solvent, then adding a noble metal source solution, uniformly mixing, and sequentially carrying out vacuum drying, air calcination and hydrogen reduction treatment to obtain the catalyst, by adopting the functional design of the catalyst carrier and the construction of active sites, alkene is prepared by efficiently, stably and selectively hydrogenating alkyne.

The invention discloses a preparation method of chiral aryloxy substituted chiral alpha-hydroxy ketone, which comprises the following step: in the presence of a chiral catalyst and a transfer hydrogenation reagent, carrying out selective transfer hydrogenation reaction on aryloxy substituted asymmetric diketone to generate the chiral aryloxy substituted chiral alpha-hydroxy ketone. According to the method provided by the invention, the raw materials and the catalyst are cheap and easy to obtain, the reaction condition is mild, the operation is simple, and the reaction is efficient; through asymmetric transfer hydrogenation of aryloxy substituted asymmetric diketone, the chiral aryloxy substituted chiral alpha-hydroxy ketone core skeleton is prepared with high selectivity, the synthesis route is direct, and the atom economy is high.