49results about How to "The hydrogenation reaction conditions are mild" patented technology

The invention relates to a method for synthesizing chiral indoline through palladium-catalyzed asymmetric hydrogenation, which is characterized in that Bronsted acid is used as the activator and the used catalysis system is a palladium chiral diphosphine complex. The reaction can be carried out under the following conditions: the reaction temperature is 20-50 DEG C; the solvent used in the reaction is a mixed solvent of dichloromethane and 2,2,2-trifluoroethanol (the DCM / TFE volume ratio is 1:1); the hydrogen pressure is 13-45 atmospheres; the substrate-catalyst ratio is 50 / 1; the used metal precursor is palladium trifluoroacetate (Pd(OCOCF3)2); the used chiral ligand is a chiral diphosphine ligand; the used activator is L-camphorsulfonic acid (L-CSA); and unprotected simple 2-substituted indole and 2,3-disubstituted indole can be hydrogenated to obtain the corresponding chiral indoline product, and the enantiomeric excess can be up to 96%. The method has the advantages of convenient operation process, high practicality, easy acquisition of raw materials, good enantioselectivity and high yield.

The invention relates to a method for synthesizing chiral dihydro-5H-pyrrolo[2,1-c][1,4]-benzodiazepino-5-one by iridium-catalyzed asymmetric hydrogenation. The reaction conditions are as follows: the temperature is 20-50 DEG C; the solvent is a dichloromethane-toluene mixed solvent (V / V=1:2); the pressure is 13-50 atmospheric pressures; the ratio of the substrate to the catalyst is 50 / 1; the catalyst is a complex of (1,5-cyclooctadiene)iridium chloride dimer and diphosphine ligand; and the additive is morpholine trifluoroacetate or piperidine hydrochloride. Seven-element cyclic pyrrolo[2,1-c][1,4]-benzodiazepino-5-one is hydrogenated to obtain the corresponding chiral dihydro product, and the enantiomeric excess can reach 96%. The invention is simple and practical to operate, and has the advantages of accessible raw materials, favorable selectivity for antipode, high yield, atomic economical efficiency for reaction, and environment friendliness.

In an iridium catalytic method for asymmetric hydrogenation to synthesize piperazine derivatives, an iridium chiral diphosphine complex is used as a catalyst. The reaction is carried out in the following condition that the temperature is in a range of -20 to 70 DEG C, the solvent is toluene, tetrahydrofuran and ethyl acetate, the pressure is 10-80 times of atmospheric pressure, the ratio of a substrate to the catalyst is 50 / 1, and the catalyst is a complex of (1,5-cyclo-octadiene) iridium chloride dimer and chiral diphosphine. 3-substitued, 3,5-disubstitued, and 2,3-disubstitued pyrazine salt can all be well hydrogenated to obtain corresponding chiral piperazine derivatives, with the highest enantiomeric excess reaching 96%. The method is simple to operate, available in raw materials, high in enantioselectivity, and good in yield, and an atom-economic eco-friendly route is provided for synthesizing 3-substitued, 3,5-disubstitued, and 2,3-disubstitued piperazine derivatives.

The invention discloses a hydrogenation catalyst and application thereof. The hydrogenation catalyst is prepared from a carrier as well as main active element(s) and additive elements which are loadedon the carrier, wherein the main active element(s) is / are Rh or / and Ru, the additive elements are selected from Sm, Eu and Yb, and the carrier is selected from activated carbon, Al2O3 and SiO2. The invention also discloses a method for preparing cyclohexane-1, 2-diformylic acid dibasic ester by using the hydrogenation catalyst. The hydrogenation catalyst provided by the invention has higher hydrogenation catalytic activity, also shows higher catalytic activity even at the lower reaction temperature when being used as the catalyst for preparing the cyclohexane-1, 2-diformylic acid dibasic ester by carrying out hydrogenation on diisonoyl phthalate dibasic ester, and has higher raw material conversion rate and product selectivity.

The invention provides a method for synthesizing chiral 3,4-dihydroquinazolinone through asymmetric hydrogenation of a quinazolinone compound under the catalysis of iridium, wherein in the formula defined in the specification, R is C1-6 alkyl or aryl containing a substituent group, R' is at least one selected from hydrogen, C1 alkyl, alkoxy and chlorine, and the substituent group is at least one selected from F, Cl, CF3, Ph, Me and MeO. According to the invention, with the method, the substrate range is wide, the synthesis of chiral 3,4-dihydroquinazolinone is diverse, and the enantiomeric excess can achieve 98%; and the method has characteristics of simple, convenient, practical and easily-performing operation, high yield, environmental protection, commercially available catalyst, mild reaction conditions and practical application value.

The invention provides a method for synthesizing chiral amine. Catalyzed pyrrole / indol [1,2-a] quinoxaline is prepared through asymmetric hydrogenation reaction, a catalyst is the complex of a metal precursor and chiral bisphosphine ligand of iridium, reaction activity and enantioselectivity are high, two kinds of hydrogenation products, i.e., an in situ protected hydrogenation product and a direct hydrogenation product, can be respectively or simultaneously obtained through regulating and controlling the added quantity and reaction time of acetic anhydride, a corresponding chiral tertiary amine compound is obtained, one or two kinds of high enantiomeric excess pure products can be obtained, and the enantiomeric excess of the pure products can be up to 97% at most. The method is simple, convenient, practical and easy in operation, high in yield and friendly to the environment, the catalyst can be commercially obtained, the reaction conditions are mild, and therefore, the method has a potential practical application value.

The invention discloses a method for synthesizing chiral tertiary amine by asymmetric hydrogenation of a 9-amide phenanthrene compound under catalysis of a ruthenium-diphosphine ligand. The method includes: adopting 2-5mol% of a ruthenium catalyst, and adding 4-10mol% of fluoboric acid for asymmetric hydrogenation of the 9-amide phenanthrene compound to obtain a corresponding chiral tertiary aminecompound, wherein the enantiomeric excess reaches 98%. The method is simple, convenient, practical and feasible in operation, high in yield, environmentally friendly and mild in reaction condition, the catalyst is commercially acquirable, and a potential practical application value is achieved.

The invention provides a palladium-catalyzed method for asymmetric hydrogenation of 2-hydroxypyrazine compounds to synthesize chiral lactams, wherein: R is C 1‑6 Alkyl or aryl containing substituents, the substituents are F, Cl, Br, CF 3 , Me, MeO, Et, n At least one of Pr. The invention has easy-to-obtain raw materials, high product enantioselectivity and good yield, and its enantiomeric excess can reach 90%. The catalyst is cheap and easy to obtain, and has good air stability, and provides an atom-economical and environmentally friendly route for the asymmetric hydrogenation of 2-hydroxypyrazine compounds to synthesize chiral lactams. At the same time, the present invention is simple and practical to operate, high in yield, environmentally friendly and green, mild in reaction conditions, and has potential practical application value.

The invention discloses a method for synthesizing chiral fluoroamine by palladium catalytic asymmetric hydrogenation, wherein, the used catalysis system comprises a palladium chiral diphosphite complex. The reaction is carried out under the following conditions that: the temperature is 0-50 DEG C, the solvent is a 2,2,2-trifluoroethyl alcohol, the pressure is 1-42 atm, the ratio of the substrate to the catalyst is 50 : 1, the used metal precursor is palladium trifluoroacetate, the used chiral ligand is a chiral diphosphite ligand. The catalyst is prepared by stirring the palladium metal precursor and the chiral diphosphite ligand in acetone at room temperature, and then carrying out vacuum condensation. According to the invention, by the hydrogenation of imine containing trifluoromethyl, corresponding chiral amine containing trifluoromethyl is obtained, the enantiomeric excess can reach to 94 %; by the hydrogenation of imine containing perfluoroalkyl, corresponding chiral amine containing perfluoroalkyl is obtained, and the enantiomeric excess can reach to 86 %. The present invention has the advantages of simple and practical operation, high enantioselectivitiy, good yield, green atom economy of the reaction, and no environmental pollution.

A method for synthesizing chiral exocyclic amine by iridium-catalyzed asymmetric hydrogenation of quinoline-3-amine, the catalytic system used is chiral diphosphorus complex of iridium. The reaction can be carried out under the following conditions, temperature: 25-70°C; solvent: a mixed solvent of toluene / tetrahydrofuran (V / V=3:1); pressure: 2-14 atmospheres; the ratio of substrate to catalyst is 25 / l; The catalyst is a complex of (1,5-cyclooctadiene) iridium chloride dimer and a chiral bisphosphine ligand. For quinoline-3-amine, the corresponding chiral exocyclic amine derivative can be obtained, and its enantiomeric excess value can reach 94%. The invention has the advantages of simple and practical operation, readily available raw materials, high enantioselectivity and good yield, and the reaction has green atom economy and is environmentally friendly.

The invention provides a method for synthesizing chiral cyclic urea by asymmetric hydrogenation of 2-hydroxy pyrimidine compounds catalyzed by iridium. In the formula described below, R refers to alkyl or aryl of C1-C6; R' refers to aryl, heteroaryl or alkyl containing substituents, and the substituent contains at least one of F, Cl, CF3, Me and MeO, and the enantiomeric excess of the synthesizedchiral cyclic urea can reach 96%. The method is simple to operate and practical and easy to implement, high in the yield, environmental friendly, commercially available for catalysts and moderate in reaction condition and has potential practical application value.

The invention relates to diphenylalkyl halide or diphenyl carboxylic acid and a simple and convenient synthesis method thereof. The method comprises the following steps of: after a bromobenzene derivative and magnesium form a Grignard reagent, reacting the Grignard reagent and lactone, and opening loop to obtain 1,1-diphenyl-diol; reacting the 1,1-diphenyl-diol under the condition of a mixed solvent of an organic solvent and an acid to form diphenylenol; reacting the diphenylenol, a halogen or a halide and triphenylphosphine in the organic solvent to form diphenylalkenyl halogen; and reacting the diphenylalkenyl halogen and hydrogen to form diphenylalkyl halide, or reacting the diphenylenol and hydrogen to form diphenyl alcohol; and reacting the diphenyl alcohol and CrO3 under the action of the organic solvent and the acid to form diphenyl carboxylic acid. The reaction raw materials are cheap; the reaction conditions are mild; and substitutional diphenylalkyl halide or diphenyl carboxylic acid compounds with different benzene rings can be synthesized.

The invention relates to the field of catalytic hydrogenation reaction, and discloses a hydrogenation catalyst, a preparation method and application thereof, and a method for hydrogenation reaction of phenols. The hydrogenation catalyst comprises a modified carrier and an active component loaded on the modified carrier, the active component is selected from at least one of Pd, Rh and Ru, and the modified carrier is obtained by containing an amino group The organosilylating agent is used to functionalize the carrier. The hydrogenation catalyst of the present invention has relatively high catalytic activity, and in the hydrogenation reaction of phenolic compounds, the hydrogenation catalyst can still be used at low temperature, low pressure and low hydrogen phenol mole Ratio of mild conditions to achieve high conversion of raw materials and product selectivity.

The invention discloses a method for synthesizing chiral benzosultam via palladium-catalytic asymmetric hydrogenation, comprising the following reaction conditions that: the temperature is 25-70DEG C; a solvent is 2,2,2-trifluoroethanol; the pressure is 28-40atm; the proportion of a substrate to a catalyst is 50 / 1; the catalyst is a complex of palladium trifluoroacetate and diphosphine ligand; the benzo six-membered ring shaped sulfonyl enamine of the benzo is hydrogenated to obtain the corresponding chiral benzo six-membered sultam with an enantiomeric excess up to 98%; and the benzo five-membered ring shaped sulfonyl enamine is hydrogenated to obtain the corresponding chiral benzo five-membered sultam with an enantiomeric excess up to 94%. The method disclosed by the invention is simple, convenient and practical for operation, high in enantioselectivity, good in yield and environmentally friendly, and has green atom economy for the reaction.