17 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 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 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 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 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.

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.