725 results about "Rearrangement reaction" patented technology

The invention discloses a green synthesis method for high-content carvacrol capable of replacing natural oregano. The method comprises the steps of taking food-grade L-carvone as raw material, adopting organic acid or inorganic acid as a main catalyst, taking PEG-400 or PEG-600 as an auxiliary catalyst and preparing the high-content carvacrol through intramolecular rearrangement reaction. The method adopts one step to synthesize a target product, and has the advantages of mild reaction conditions and convenient operation. The product is high in yield and good in quality, and can replace natural carvacrol. As no solvent harmful to human body and environment is added in reaction, the method is safe and friendly to environment.

A process for producing epsi-caprolactam is provided which comprises the steps of subjecting cyclohexanone oxime to a gaseous phase Beckmann rearrangement reaction in a fluidized bed system using a solid catalyst and re-generating the catalyst, wherein said process comprises a step of treating the catalyst with an oxygen-containing gas at an elevated temperature in a re-generation step so that the nitrogen content of the catalyst falls within a range of 10 ppm to 2,500 ppm on its way to the reaction step from the re-generating step. According to the present invention, epsi-caprolactam is produced with a high conversion or a high selectivity without interrupting the rearrangement reaction or the re-generation step.

The invention relates to a method for synthesizing trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine which is an intermediate for preparing an anticoagulation medicine Ticagrelor. The method provided by the invention mainly comprises the following steps of: synthesizing the trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine protected by tertiarybutoxy carbonyl through carrying out a rearrangement reaction of DPPA (Diphenylphosphoryl Azide); then removing the protective group of the trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine protected by the tertiarybutoxy carbonyl and then alkalifying to obtain the product. The whole reaction can be finished through a one-pot boiling synthetic method so that synthesizing steps and synthesizing time are greatly saved, the cost is effectively reduced and the yield is improved; and the method for synthesizing the trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine has the very active meaning in the industrial production.

The invention discloses a method for synthesizing 4-(3-chloro-4-fluorophenylamino)-7-methoxy -6-[3-(4-morpholinyl)-propoxy] quinoline. The method comprises the following steps: 1) 3-hydroxide radical-4-methoxybenzaldehyde is used as a raw material to prepare 3-hydroxide radical-4-methoxy-benzonitrile; 2) the 3-hydroxide radical-4-methoxy-benzonitrile and 3- chloropropy morpholinehydrochloride are heated to have reflux reaction to obtain 4- methoxy-3-[3-(4- morpholinyl) propoxy] benzonitrile; 3) the 4- methoxy-3-[3-(4-morpholinyl) propoxy] benzonitrile is subjected to nitration to obtain 2- nitryl-4- methoxy -5-[3-(4-morpholinyl) propoxy] benzonitrile; 4) the 2- nitryl-4- methoxy -5-[3-(4-morpholinyl) propoxy] benzonitrile is subjected to reduction to obtain 2-amido-4- methoxy-5-[3-(4-morpholinyl) propoxy] benzonitrile; and 5) the 2-amido-4- methoxy-5-[3-(4-morpholinyl) propoxy] benzonitrile and an azomethine intermediate of 3-chloro-4-fluoroaniline have rearrangement reaction to obtain 4-(3-chloro-4-fluorophenylamino)-7-methoxy-6-[3-(4-morpholinyl)-propoxy] quinoline. The method has characteristics of environmental protection and high production rate.

A subject for the invention is to provide a branched aromatic polycarbonate which is excellent in hue and in melt characteristics such as melt strength.

The invention provides a branched aromatic polycarbonate having a viscosity-average molecular weight of 16,000 or higher obtained by the transesterification method, characterized in that the ratio of the weight-average molecular weight (Mw) to number-average molecular weight (Mn) as measured by gel permeation chromatography and calculated for standard polystyrene (Mw/Mn) is in the range of from 2.8 to 4.5 and that the proportion of the number of moles of all structural units yielded by a rearrangement reaction in the course of melt polymerization reaction to 1 mol of structural units having the framework of an aromatic dihydroxy compound used as a starting material is higher than 0.3 mol % and not higher than 0.95 mol.

The invention relates to the medicine chemical synthesis field, and especially discloses a preparation method of a Ticagrelor intermediate. The preparation method comprises the following steps: 1) taking 3,4-difluorobenzaldehyde (I) as an initial raw material, reacting with a phosphorus ylide material liquid to obtain (E)-3-(3,4-difluorophenyl)-2-acrylic acid ester (II); 2) performing a Simons-Smith asymmetric cyproteronethe reaction on the (E)-3-(3,4-difluorophenyl)-2-acrylic acid ester (II) to obtain trans-(1R,2R)-2-(3,4-difluorophenyl) cyclopropanecarboxylic acid ester (III); 3) performing aminolysis on the trans-(1R,2R)-2-(3,4-difluorophenyl) cyclopropanecarboxylic acid ester to obtain trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxamide (IV); and 4) performing a Huffman rearrangement reaction on the trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxamide (IV) to obatain the Ticagrelor intermediate (V). The method of the invention has the advantages of simple process, convenient operation, mild reaction condition and easy control, low cost and easy acquisition of raw material, high product yield and product purity, and is adapted to large scale industrial production.

The invention belongs to the technical field of biomass conversion utilization, and concretely relates to a method for preparing cyclopentanone by taking biomass resource as a raw material. The method comprises taking furfural coming from biomass as the raw material, taking a hydrogen-containing gas as a reducing agent, and in the presence of a metal supported type catalyst, performing hydrogenation rearrangement reaction in a high-pressure reaction kettle or a fixed bed reactor, so as to obtain cyclopentanone in one step, wherein the carrier of the metal supported type catalyst is selected from Nb2O5, H-ZSM-5 molecular sieve, HY molecular sieve, Fe2O3, ZrO2, Al2O3, SiO2, CeO2, MgO, active carbon, and TiO2 in various crystal forms, the active composition is selected from Au, Pt, Ru, Rh, Pd, Ir, Ni and Cu, and the active composition load capacity is 0.1-5% of the catalyst. The method is mild in reaction technological conditions, and cheap and easily-available in raw materials, is capable of realizing quantitative conversion of furfural to cyclopentanone, and belongs to an environment-friendly green chemical technology.

The invention relates to a method for preparing compound palbociclib (shown as the formula I). A compound D (shown as the formula II) serves as a raw material, and a compound E (shown as the formula III) is obtained through a rearrangement reaction of alkenyl ether; then the compound E is subjected to t-butyloxycarboryl protection group removal under the acidic condition, and target product palbociclib is obtained; an R group in a compound D is selected from any one of a C1-C6 alkyl group, a C1-C6 halogenate alkyl group, C1-C6 hydroxyalkyl and a C1-C6 naphthenic base. The process procedure and operation steps are easy and convenient, prepared palbociclib is high in purity, and good popularization prospects are achieved.

The invention relates to an ethyl maltol synthetic method, which includes an alpha-furans propanol chlorination rearrangement reaction and a hydrolysis reaction to the product of the alpha-furans chlorination rearrangement reaction. Wherein, the hydrolysis reaction comprises: hydrolyzing the mixture obtained in the chlorination rearrangement reaction under the temperature of 95-140 degrees centigrade and the pressure of 1.9-8.5Mpa for 1.5-5.5 hours; cooling to below 100 degrees centigrade; separating out the by-product: chloromethanes gas; and obtaining the hydrolysis mixed liquor containing the product: ethyl maltol. The invention can achieves the synthesized ethyl maltol yield of 60% which is improved by 4-6% compared with conventional methods; enables the hydrogen chloride generated in the reaction process to react with solvent methanol to generate a large amount of recyclable by-product: chloromethanes; reduces the hydrochloric acid concentration in the hydrolysate by 75-80%; reduces the sodium hydroxide used amount in the subsequent ethyl maltol separating and refining process; and reduces the sodium chloride content in the technique waste water; thereby, reduces environmental pollution and production cost.

The invention discloses a method for synthesizing a gamma, delta-nonsaturated ketones compound. The method comprises the following steps: under protection of inert gas, nonsaturated alcohol and 2-alkyloxy propylene are taken as the raw materials, Bronsted acid functional ionic liquid is dissolved in a high boiling solvent as a catalyst, a rearrangement reaction is carried out, after the reaction is complete, the materials is subjected to post-treatment to obtain the gamma, delta-nonsaturated ketones compound and a catalyst solution. The used Bronsted acid functional ionic liquid catalyst has a plurality of physical and chemical properties which are similar with the conventional ionic liquid, the acid functional group is introduced, so that the catalyst has the advantages of high acid site density, adjustable acidity, uniform acidity distribution and difficult loss of acidity. An autoclave series mode is used for realizing the continuous synthesis of nonsaturated ketone and continuous recycling of the catalyst.

The invention provides a method for preparing caprolactam through gas phase Beckmann rearrangement of cyclohexanone-oxime gas. According to the method, under the condition of rearrangement reaction, cyclohexanone-oxime is in contact with a catalyst, and the catalyst is obtained by the steps of forming a molecular screen with an aluminum-free MFI (Melt Flow Index) structure, and enabling the molecular screen to be in contact with an alkaline buffer solution of a nitrogen-containing compound. The method is high in cyclohexanone-oxime conversion rate, and is capable of realizing long-period and continuous production; the selectivity of caprolactam is capable of reaching 95.8 percent.

The invention relates to a preparation method of high-throughput graphene oxide/polyimide mixed matrix membrane material. The high-throughput graphene oxide/polyimide mixed matrix membrane material isprepared by the steps of introducing graphene oxide into a polyimide matrix subjected to thermotropic rearrangement reaction through an in-situ method to prepare a composite material membrane, and processing the composite material membrane for at least 0.1h under inert atmosphere. The prepared mixed matrix gas separation membrane material has the characteristics of excellent seepage separation performance and stable chemical structure and can solve the inadequate problems of limited separation performance, poor anti-plasticizing capability, poor temperature tolerance and the like of the existing polymer separation membrane material.

The present invention discloses oximation and rearrangement process of preparing amide with aliphatic and/or cyclic aliphatic ketone as material. The preparation process includes catalytic reaction of ketone, hydrogen peroxide solution and ammonia inside inert solvent to produce ketoxime solution, Beckmann rearrangement of the oil phase product under the action of fuming sulfuric acid, and hydrolysis to neutralize and produce amide. The present invention has shortened technological process, lowered cyclohexyl ketoxime rearranging reaction temperature, lowered sulfuric acid consumption and reduced side product.

The invention discloses a synthesis method of an SiC-containing ceramics precursor, which comprises the steps that: 1. low molecular weight polymer with main chain containing silicon is sent into a three-mouth flask, and is added with 0.5wt% - 20wt% of tantalum organic compounds or chloride; 2. under the protection of Ar or N2 or compound of the Ar or N2, the temperature of the three-mouth flask is raised to 350 to 500 DEG C, and the temperature of a cracking column is controlled within 450 DEG C to 550 DEG C; then thermal decomposition rearrangement reaction is carried out for 0.5 to 25 hours, and then cooling is done; 3. the obtained rough product is dissolved by xylene and filtered; the filtrate solution is distilled by reducing temperature to between 250 to 390 DEG C, then the obtained material is cooled. The invention has the advantages of wide raw material source, reaction process being easy to be controlled, simple equipment, high purity of product, good formability, and good performance of super-high temperature and absorbing property; in addition, the ceramics fiber produced in the method has good oxidation resistance performance and is easy to realize large-scale industrial production.

The invention discloses a composite method of triketone compound shown in the formula (I). In the formula (I), X is Cl or NO2. The composite method is as follows: enol ester shown in the formula (II) generates rearrangement reaction under the action of an alkaline reagent and a rearrangement catalyst in organic solvent; after reaction ends, the obtained reaction liquid is acidized and separated to obtain the triketone compound; the rearrangement catalyst is purine compound. The composite method of the triketone compound (sulcotrione and mesotrione) of the invention adopts the catalyst with small toxicity, protects environment, has high product yield and is suitable for industrial production.

The invention discloses a method for preparing halofuginone hydrobromide, which comprises the following steps: by using N-benzyl-3-piperidone or hydrochloride thereof, organic or inorganic base, halide of alkali metal and beta, gamma-dihaloalkene or allyl haloalkane as initial raw materials, performing Steven rearrangement reaction to obtain an intermediate VIII; performing Von Braun reaction on the intermediate VIII to obtain an intermediate VII; performing reduction reaction on the intermediate VII to obtain an intermediate VI; obtaining an intermediate V after reaction of the intermediate VI and NBS (N-bromosuccinimide); obtaining an intermediate IV after the reaction of the intermediate V and a compound 7-bromine-6-chlorine-4(3H) quinazolinone; performing deprotection on the intermediate IV to obtain an intermediate III; performing backflow processing on the intermediate III in ethanol to obtain an intermediate II; and obtaining the halofuginone hydrobromide after the salt forming reaction of intermediate II. The invention develops an efficient and simple method for synthesizing the halofuginone hydrobromide. The total yield can reach over 50 percent, cost is greatly reduced and the product has high purity.

The invention discloses a method for preparing progesterone and derivatives thereof. A compound 1 serves as a starting material, and through an oxidation reaction and a rearrangement reaction, the progesterone and derivatives thereof, namely, compounds 3 are obtained, wherein the reaction formula is defined in the description. By means of the method, the finished product progesterone and derivatives thereof are obtained with the total yield being 75wt% or above; the method is low in cost, environmentally friendly and suitable for industrial production.

The invention relates to a method and a device for preparing diphenylmethane series diamine and polyamine with low N-methyl impurity content and a catalyst. The method comprises the steps as follows:a) phenylamine and formaldehyde are subjected to a condensation reaction in the presence of an acid catalyst, and a reaction mixture containing polyamino benzylaniline salt is obtained; b) the reaction mixture from a) enters a fixed bed reactor loaded with the catalyst for a transposition rearrangement reaction, a mixture containing diphenylmethane series diamine salt and polyamine salt is obtained after the reaction, and active components of the transposition rearrangement reaction catalyst comprise one or more of vanadium phosphate oxide, a Nb2O5-La2O3 solid solution and a Pr2O3-Ce2O3 solidsolution. The reaction selectivity at the transposition rearrangement stage can be improved, so that the content of N-methyl MDA impurities in the product can be decreased, the product quality can besubstantially improved, and the N-methyl MDA content can be decreased to 0.01% or below.

The invention discloses a method for continuously preparing hexanolactam by using a cyclohexanone-oxime Beckmann rearrangement reaction. A circular reaction system consists of a recycle pump, a cooler, a mixing reactor and a curing reactor, and the circular reaction system is characterized in that heat instantly released from the rearrangement reaction is dissipated by combining heat storage of materials with heat absorption in solvent vaporization. The combination of the heat storage of the materials with the heat absorption in the thermal inertia solvent vaporization can control a micro-reaction temperature, and meanwhile, the heat absorption in the thermal inertia solvent vaporization can prevent over-high temperature of the partial reaction, so a reaction product with high yield and high quality can be obtained, the use amount of fuming sulphuric acid is small, the energy consumption is low and the operation is stable.

The invention relates to a method for separating Beckmann rearrangement reaction production from ion liquid, which comprises: selecting an organic dissolvant with the ion liquid used in cyclohexanone oxime Beckmann rearrangement reaction immiscible in the temperature of 10-60 Deg.C and miscible in the temperature of 50-150 Deg.C, mixing the organic dissolvant with the ion liquid with cyclohexanone oxime Beckmann rearrangement reaction production with the proportion in volume of 50 degree 1-1 degree 10 to form a immiscible two-phase system, stirring and lifting the temperature to 50-150 Deg.C to get the miscible mixture liquid of both organic dissolvents and ion liquid, holding 1-120 min in the temperature, then cooling the mixture liquid to 10-60 Deg.C to separate phase inactively.

The invention discloses a process for preparation of caprolactam from cyclic ketones through liquid phase rearrangement reaction in ionic liquid and at the presence of phosphorus-containing compounds as the catalyst, wherein the ionic liquid, organic solvent non-dissolving to the ionic liquids and acidic phosphorus-containing compound catalyst are mixed under stirring condition, dissolving the catalyst into the ionic liquid phase, heating the obtained two phase catalytic system to a rearrangement reaction temperature, charging the cyclic ketones or solution into the catalytic system for reaction, then subjecting to stewing and phase-splitting.

Disclosed is a method for industrially efficiently producing a lactam compound having 8 to 15 carbon atoms at low cost by allowing a rearrangement reaction of a cyclic oxime compound to proceed without causing large amounts of by-products such as ammonium sulfate.

[Solving Means] Disclosed is a method for producing a lactam compound, which includes the step of rearranging a cyclic oxime compound in a nonpolar solvent B in the presence of an aromatic compound A to give the lactam compound, in which the aromatic compound A has a leaving group bonded to a carbon atom constituting its aromatic ring and contains, as an atom constituting the aromatic ring, a heteroatom, or a carbon atom bonded with an electron-withdrawing group, the cyclic oxime compound is represented by following Formula (1):

wherein “m” denotes an integer of 7 to 14,

and the lactam compound is represented by following Formula (2):

wherein “m” is as defined above.