20 results about "Cyclobutanone" patented technology

The invention discloses a synthesis method of a silicon-substituted benzo-bicyclo [3.1. 1] heptane compound, which comprises the following steps: under the action of a copper catalyst, alkali and a silicon reagent, putting o-alkynyl phenyl cyclobutanone in a solvent for reaction, and carrying out post-treatment to obtain the silicon-substituted benzo-bicyclo [3.1. 1] heptane compound, the silicon source is (dimethylphenylsilyl) boronic acid pinacol ester. The silicon-substituted benzo-bicyclo [3.1. 1] heptane compound is prepared by combining a cheap metal copper catalyst with a silicon reagent. The reaction system is good in selectivity and mild in condition, the highest yield can reach 68%, and the method has wide application prospects.

The invention discloses a synthesis method of a polysubstituted cyclopropyl carbonyl derivative, and belongs to the technical field of organic synthesis and the technical field of medicine synthesis. The method comprises the following steps: (1) taking substituted olefin as a raw material, and obtaining alpha-chlorocyclobutanone through [2 + 2] cycloaddition and reduction reaction; and (2) carrying out rearrangement reaction on the alpha-chlorocyclobutanone and different types of Grignard reagents or organic lithium reagents to obtain the polysubstituted cyclopropyl carbonyl derivative. The synthesis method provided by the invention has the advantages of wide substrate range, good functional group compatibility, mild reaction conditions, no need of preparation of active intermediates or use of expensive transition metal catalysts, simple operation, capability of obtaining various types of cyclopropyl carbonyl compounds, and the like. The practicability of the method is further shown through later-stage functional group modification of complex bioactive molecules and abundant derivatization of polysubstituted cyclopropyl carbonyl products of the complex bioactive molecules.

The invention discloses a polysubstituted cyclopropyl carbonyl compound with calcium ion channel regulation activity as well as a pharmaceutical composition and application thereof, and belongs to the technical field of medicines. An alpha-chlorocyclobutanone compound is used as a raw material and reacts with aryl magnesium bromide with different substituent groups in an organic solvent, and the polysubstituted cyclopropyl carbonyl compound is obtained in one step. The polysubstituted cyclopropyl carbonyl compound is novel in structure, the preparation method has the advantages of being low in cost, simple and convenient to operate, mild in condition and the like, and the polysubstituted cyclopropyl carbonyl compound novel in structure can be rapidly obtained. The prepared cyclopropyl carbonyl compound has T-type calcium channel regulation activity and has an analgesic effect.

The application discloses a kind of Baeyer-Villiger monooxygenase and its mutant in synthesis optical pure 3-substituted chiral butyrolactone Application, the application with the Baeyer-Villiger monooxygenase ArBVMO of Acinetobacter radioresistens (CGMCC No.25186) source of resistance to radiation Acinetobacter (Acinetobacter radioresistens) and its mutant as biocatalyst, can catalyze the asymmetric oxidation of series latent chiral 3-substituted cyclobutanone, preparation corresponding optical pure chiral butyrolactone.Compared with prior art, the application has the advantages of high enzyme reaction substrate concentration, mild reaction condition, environment-friendly, high space-time yield, high product optical purity, and has good application prospect.

The invention discloses a synthesis method of limidoterol, and belongs to the technical field of medicine synthesis. The method comprises the following steps: coupling cyclobutanone oxime and a caffeic acid derivative under the catalysis of ferrous acetylacetonate, a chlorobenzene solvent and the protection of nitrogen to obtain a decarboxylated cyanogen alkylation intermediate; oxidizing the intermediate with m-chloroperoxybenzoic acid in dichloromethane in the presence of sodium carbonate to obtain a vicinal diol monoester intermediate; catalyzing by cobalt chloride in methanol, reducing by sodium borohydride, and protecting by Boc2O to obtain a cyclized precursor; cyclizing the precursor in tetrahydrofuran by using sodium hydride to obtain a cyclized intermediate; and performing deprotection to obtain the limiterol. According to the method, dangerous reagents and processes are not used, the safety is high, and no heavy metal residues exist; the cost is low, precious metals are not needed, the post-treatment operation is simple and convenient, a complex purification process is not needed, and the total yield reaches 21%; process conditions are mild, normal pressure and conventional heating modes are adopted, and industrial production is easy to realize.

The application relates to a synthesis method of 2-hydroxy-2-methylcyclopentanone compounds and belongs to the technical field of organic synthesis. The 2-hydroxy-2-methylcyclopentanone compounds are prepared from cyclobutanone compounds through protection of carbonyl groups, deprotection and rearrangement reaction; the application does not need to use expensive metal catalysts, has mild reaction conditions, does not need high-pressure equipment, is high in safety and easy to be industrialized, is high in atomic economy, is simple in operation, avoids use of highly toxic or high-pollution reagents, and is low in mercury salt consumption.

The application provides a method for asymmetric hydrogenation of a single carbonyl group of a cyclobutanedione compound, which comprises: hydrogenating the cyclobutanedione compound under the action of a catalyst in the presence of hydrogen to obtain a 3-hydroxyl-cyclobutanone compound, wherein the catalyst comprises a complex of a group VIII metal and an amino acid. The method has the advantages of convenient ligand acquisition and good reaction selectivity without optical purification.

The invention discloses a peptide simulant and a preparation method thereof, 3-oxetanone and 3-methyl-1-nitrobutane are used as raw materials, and all reactions are carried out to obtain a target product. The peptide simulant is novel in structure and has potential biological activity, adopted protecting groups and functional groups are good in compatibility, and follow-up structural modification is facilitated; the designed synthesis route is simple, the reaction condition is mild, and amplification is easy; the yield of each step is high, and the product is easy to purify.

The invention relates to application of a rare earth-based catalyst. The application comprises the step of carrying out hydrogenation reaction on hydrogenation raw materials in the presence of the supported catalyst Ir / CeO2 to obtain alcohol, wherein the hydrogenation raw material is selected from one or more of furfural, 5-hydroxymethylfurfural, 5-methylfurfural, m-tolualdehyde, benzaldehyde, phenylacetaldehyde, phenylpropionaldehyde, p-fluorobenzaldehyde, cinnamyl aldehyde, cinnamyl alcohol, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, tetrahydropyran-4-ketone, tetrahydrothiapyran-4-ketone, crotonaldehyde and terephthalaldehyde; the catalyst is prepared by a method comprising the following steps: mixing a CeO2 carrier with a solution containing a metal Ir precursor, and reacting under heating and alkaline conditions to obtain a catalyst precursor; and calcining and reducing the catalyst precursor to obtain the supported catalyst Ir / CeO2. The rare earth-based catalyst is simple in preparation process, mild in condition, high in hydrogenation activity and good in stability.

The invention discloses a method for preparing a boron-substituted benzo-bicyclo [3.1. 1] heptane derivative. According to the method, the benzo-bicyclo [3.1. 1] heptane derivative can be obtained from reactants of different types of substrates at a good yield. The method comprises the following steps: by taking cyclobutanone as a raw material, adding a copper catalyst, alkali and a boron reagent, then adding an organic solvent under the protection of inert gas, and reacting at 80 DEG C for 24 hours. And after the reaction is finished, filtering with diatomite, spin-drying the reaction liquid, and carrying out silica gel column chromatography separation to obtain the target product. Wherein the organic solvent is toluene; the cyclobutanone is o-alkynyl aryl cyclobutanone. According to the method, the boron-substituted benzo-bicyclo [3.1. 1] heptane derivative is obtained by using the metal copper high in yield on the earth as the catalyst and combining with the boron reagent, all reactants are commercially available, the condition is mild, the yield is high, and compared with other methods of the same type, the boron-substituted benzo-bicyclo [3.1. 1] heptane derivative is excellent in performance and has a good application prospect.

The invention relates to a method for synthesizing squaric acid, which comprises the following steps of: (1) reacting alkyl vinyl ether, trichloroacetyl chloride and zinc to obtain 2, 2-dichloro-3-alkoxy cyclobutanone; (2) carrying out a chlorination reaction on the 2, 2-dichloro-3-alkoxy cyclobutanone and chlorine gas to obtain 2, 2, 4, 4-tetrachloro-3-alkoxy cyclobutanone, and carrying out a chlorination reaction on the 2, 2-dichloro-3-alkoxy cyclobutanone and chlorine gas to obtain 2, 2, 4, 4-tetrachloro-3-alkoxy cyclobutanone; (3) the 2, 2, 4, 4-tetrachloro-3-alkoxy cyclobutanone and alkali are subjected to an elimination reaction, and 2, 4, 4-trichloro-3-alkoxy cyclobutene-1-one is obtained; and (4) carrying out a hydrolysis reaction on the 2, 4, 4-trichloro-3-alkoxy cyclobutene-1-ketone, so as to obtain the squaric acid. The synthesis method provided by the invention can avoid the use of a forbidden raw material perchloro-1, 3 butadiene, also has lower energy consumption, and can meet the requirements of green and clean production.

The application belongs to the technical field of medicine synthesis, and particularly relates to a preparation method of apalutamide. The preparation method comprises the following steps: 4-amino-2-fluoro-N-methyl benzamide is reacted with 1-bromocyclobutane-1-methyl carboxylate under the catalysis of silver oxide, the obtained product is reacted with 5-isothiocyanate-3-(trifluoromethyl) pyridine-2-cyan to obtain apalutamide; the starting material is cheap and easy to obtain, and the existing technology avoids the Strecker reaction of N-methyl-2-fluoro-4-amino benzamide, sodium cyanide (or trimethyl silyl cyanide) and cyclobutanone, which needs to use a toxic cyanide reagent; meanwhile, the Ullmann reaction needs high temperature and equivalent copper, and the application solves the problems, and is simple to operate, has a higher yield, and is more suitable for industrial mass production.

The present invention relates to a method for producing enantiomerically enriched cyclobutylamine of formula (I) from alpha-tert-cyclobutanone and reacting said enantiomerically enriched cyclobutylamine to obtain enantiomerically enriched cyclobutyramide. Such compounds are useful intermediates in the synthesis of microbicidal thiazole compounds. (I)

The invention discloses a synthesis method of a cobalt-catalyzed benzo-bicyclo [3.1. 1] heptane bridged ring compound, which comprises the following steps: by taking o-alkynyl aryl cyclobutanone as a reaction substrate and taking water and methanol as a hydrogen source synergistically, under the combined action of a cobalt catalyst, a ligand, alkali and a boron reagent, reacting for 8-48 hours at 85 DEG C under the protection of inert gas, thereby obtaining the cobalt-catalyzed benzo-bicyclo [3.1. 1] heptane bridged ring compound. And carrying out diatomite filtration, rotary evaporation concentration and silica gel column chromatography separation on the reaction liquid to obtain the target bridged ring compound. According to the method, metal cobalt which is high in yield on the earth is selected as a catalyst, all raw materials are commercially available chemicals which are easy to obtain, the method has the characteristics of mild reaction conditions and high target product yield, a bridge ring skeleton is constructed through a green hydrogen transfer path, the atom economy is excellent, and the method has a good industrial application prospect.

The present application relates to a kind of methods for synthesizing corresponding alcohol by electrocatalytic hydrogenation of carbonyl compound, using flow electrolytic cell or split H-type electrolytic cell, adding carbonyl compound in cathode electrolyte, collecting liquid phase alcohol product at reaction output end.The carbonyl compound includes formaldehyde, acetaldehyde, acetone, n-propyl aldehyde, n-butyl aldehyde, n-pentanal, 4-hydroxy-2-butanone, diacetone alcohol, 2-pentanone, cyclobutanone, furfural and other carbonyl-containing compounds.Different types of electrolytic cell are used, and the iron-based electrocatalyst constructed has the characteristics of low cost, high activity and high selectivity.Compared with traditional thermal catalytic technology, the electrocatalytic hydrogenation of carbonyl compound to synthesize corresponding alcohol technology is carried out at room temperature and normal pressure, using water as hydrogen source, which not only reduces energy consumption and production cost, but also is green, safe and efficient, in line with the requirements of green chemical industry.

The application discloses a method for preparing a full-carbon quaternary carbon center derivative through radical-initiated olefin and alkyne cross-coupling, which overcomes the problem that a tertiary carbon radical generated in situ has a large steric hindrance and is difficult to react with a cross-coupling reagent to construct a full-carbon quaternary carbon center by using the guiding effect of a guiding group. The method uses 1,1-disubstituted electron-deficient olefin, O-(tert-butyloxycarbonyl) cyclobutanone oxime compound and terminal alkyne as raw materials, and reacts at room temperature under the presence of a catalyst, a base and a solvent in an inert atmosphere. After the reaction is completed, N-(pyridine-2-yl)-6-cyano-2-aryl-2-alkynyl hexanamide derivatives are obtained through separation and purification. The method has good substrate adaptability and simple operation advantages.

The invention discloses a preparation method of a ketone nitrile compound, which comprises the following steps: carrying out reaction on cyclobutanone oxime ester, arylboronic acid, ethylene glycol dimethyl ether nickel chloride, 4, 4 '-di-tert-butyl-2, 2'-bipyridine, formic acid, acetic anhydride and triethylamine at 80 DEG C for 24 hours, and after the reaction is completed, carrying out post-treatment to obtain the ketone nitrile compound. According to the preparation method, cyclobutanone oxime ester and arylboronic acid are taken as reactants, formic acid is taken as a carbonyl source, the reaction condition is mild, the operation is simple, the tolerance range of substrate functional groups is wide, and the reaction efficiency is high. Various ketone nitrile compounds can be synthesized according to actual needs, so that the practicability of the method is widened while the operation is convenient.

The invention relates to a Papililone A tetracyclic diterpenoid analogue and a preparation method and application thereof, the Papililone A tetracyclic diterpenoid analogue has the following structural formula: R1, R2, R3, R4 and R5 are selected from hydrogen, alkyl and aryl, the Papililone A tetracyclic diterpenoid analogue is synthesized by carrying out diastereoselective 2 + 2 reaction on a cyanoalkene substrate to construct a cyclobutanone fragment, the other fragment is a constructed furan bromide, and the structural formula is shown in the specification. Performing bromine lithium exchange on furan bromide fragments, performing nucleophilic addition on the furan bromide fragments and cyclobutanone to connect the fragments, and performing photooxidation ring opening to construct an alkene-inserted alpha-hydroxy ketone rearrangement substrate. Under the alkaline condition, rearrangement is carried out, and the diquinane with two continuous quaternary carbon chiral centers is successfully constructed. The preparation method comprises the following steps: firstly, synthesizing tetracyclic diterpenoid, then selectively converting a substrate into trifluoromethanesulfonic acid alkenyl ester, and then carrying out carbonyl alpha-position alkenylation reaction and alkenyl insertion Michael reaction under the action of metal, so as to efficiently and concisely synthesize the tetracyclic diterpenoid natural product Papililone A for the first time. A series of Papililone A tetracyclic diterpenoid analogues are rapidly synthesized by adopting the synthesis method disclosed by the invention.

The invention discloses a cyclobutanone oxime ester compound, a preparation method thereof and application of the cyclobutanone oxime ester compound in a preparation method of an alkyl nitrile compound containing a quaternary carbon center. The cyclobutanone oxime ester compound disclosed by the invention has a structure as shown in a formula I, wherein R1 and R2 are independently selected from C1-6 alkyl, naphthyl, phenyl, phenyl substituted by at least one of C1-6 alkyl, C1-6 alkoxy and phenyl, and C3-20 heteroaryl. According to the present invention, the cyclobutanone oxime ester compound and the aryl amine compound are adopted as the raw materials to prepare the quaternary carbon center-containing alkyl nitrile compound, such that the high yield is provided, the gram-level amplification experiment can be performed, and the method does not need the oxidizing agent or the high temperature and high pressure condition;

The invention belongs to the technical field of proton exchange membrane fuel cells, and provides catalyst slurry and a preparation method thereof, and a membrane electrode and a preparation method and application thereof. The catalyst slurry provided by the invention comprises a Nafion ionomer, a platinum carbon catalyst, naphthenone (including one or more of cyclobutanone, cyclohexanone and cyclooctanone), water and isopropanol. According to the invention, cycloalkanone is added, and cycloalkanone can form a stable structure with water and Pt in the platinum-carbon catalyst through specific adsorption, which is specifically embodied in that on one hand, cycloalkanone and water molecules form hydrogen bonds to capture water and participate in construction of a proton transmission channel; on the other hand, the naphthenone and Pt in the platinum-carbon catalyst interact to firmly fix water molecules around the Pt, so that when the overall temperature exceeds the vaporization temperature of the water, the naphthenone molecules cannot be lost due to vaporization of the water, the structural damage cannot be caused, and the constructed proton transmission channel is stabilized.