38 results about "Baeyer–Villiger oxidation" patented technology

The invention discloses a synthetic method of ciprofibrate. The method comprises the following steps: taking styrene as a starting material; obtaining the ciprofibrate by the processes of cyclization, acylation, Baeyer-Villiger oxidation, alcoholysis, alkylation and hydrolysis, wherein an acylation reagent adopted in the acylation process is R1COCl; the R1 is C4-C12 alkyl. Fatty acyl chloride of which a hydrocarbyl structure is a long chain is adopted in acylation reaction, so that the steric hindrance is increased, the reaction activity of acyl chloride is reduced, the content of the produced ortho-position isomer is smaller than 0.2% and superior to that of acetyl chloride reaction (the content of the ortho-position isomer is 0.5-1%), the yield and the purity of the product are improved, and meanwhile, a room-temperature reaction condition is adopted, so that the energy consumption of production is reduced. Urea peroxide instead of hydrogen peroxide is used as an oxidant in the Baeyer-Villiger oxidation, and acetic acid is used instead of acetic anhydride, so that the reaction condition is milder, and the operation is more controllable.

Provided is a process of conducting a Baeyer-Villiger oxidation which comprises contacting a ketone and an oxidant in the presence of an Sn-DZ-1 catalyst to thereby oxidize the ketone to an ester. The Sn-DZ-1 catalyst comprises Sn heteroatoms on the external surface of the zeolitic material lattice framework, and B heteroatoms, or silanols created from boron hydrolysis, throughout the remainder of the lattice framework.

The invention discloses a carboxyl functionalized porous heteropoly acid polyionic liquid and a use thereof. A carboxyl functionalized polyquaternary ammonium salt with a long chain linear structure and a heteropoly acid as building units are self-assembled into a three-dimensional network porous structure under electrostatic interaction so that the polyionic liquid is obtained, or a carboxyl functionalized polyquaternary ammonium with a long chain cross-linked structure and a Dawson-type vanadium-doped heteropoly acid as building units are self-assembled into a three-dimensional network porous structure under electrostatic interaction. The carboxyl functionalized porous heteropoly acid polyionic liquid can be used as a heterogeneous catalyst. Industrial grade hydrogen peroxide is used asan oxidant. A cyclic ketone compound undergoes Baeyer-Villiger oxidation to produce a corresponding cyclic lactone under the solventless condition. The catalytic system has a novel structure, is usedfor a Baeyer-Villiger oxidation reaction, and has the characteristics of good selectivity, mild reaction condition, large operation flexibility and convenient recycling of the catalytic system.

The invention discloses a synthesis method of 1-pyrenol and intermediates thereof.The synthesis method includes firstly, preparing an intermediate, namely acetylpyrene by subjecting pyrene and acetyl chloride to Friedel-Crafts reaction; secondly, preparing an intermediate, namely acetoxypyrene by Baeyer-Villiger oxidation rearrangement; thirdly, preparing the 1-pyrenol by saponification.The synthesis method has the advantages that the 1-pyrenol and the intermediates thereof are prepared from the pyrene and the acetyl chloride, and accordingly the synthesis method is economic, easy to operate, little in environmental pollution, capable of saving production cost for enterprises and high in reaction yield rate of the 1-pyrenol and the intermediates thereof.

The invention discloses a method for synthesizing ciprofibrate intermediate. The method comprises: conducting cyclization reaction on styrene to obtain 2,2-dichloro-cyclopropylmethyl phenyl; conducting Friedel-Crafts acylation reaction on 2,2-dichloro-cyclopropylbenzene to obtain a compound (III), wherein an acylating agent is R1COCl, and R1 is C4-C12 alkyl group; and conducting Baeyer-Villiger oxidation reaction on the compound (III) to obtain a compound (IV). The invention employs fatty acyl chloride with long chain hydrocarbyl structure in the acylation reaction to increase steric hindrance and reduce the reaction activity of the acyl chloride; the content of the produced ortho isomer is less than 0.2%; and the method improves the yield and purity of the product, is superior to the reaction of acetyl chloride (the content of ortho isomer is 0.5-1%), and the utilization of room temperature conditions reduces energy consumption for production.

The present invention relates to a method for manufacturing an ester from a ketone or an aldehyde, which is a reactive substrate, by a Baeyer-Villiger oxidation reaction using hydrogen peroxide, and in this method, as a catalyst, M(BAr₄)_n, which is a metal borate, is used (M represents an alkali metal or an alkaline earth metal; Ar represents an aryl; and n is the same number as the valence of M). For example, when cyclohexanone was used as the reactive substrate, and Sr[B(3,5-CF₃C₆H₃)₄]₂ was used as the catalyst, ε-caprolactone was obtained at an isolated yield of 82%.

The invention belongs to the technical field of synthetic perfumes, and specifically relates to a continuous synthesis method of milk lactone perfume. The continuous synthesis method comprises the following steps: carrying out aldol reaction under the action of alkaline water, then carrying out hydrogenation reaction and Baeyer-Villiger oxidation, carrying out acidic continuous hydrolysis, and dehydrating the product to obtain the milk lactone perfume, wherein the aldol reaction comprises: uniformly mixing part of cyclohexanone serving as a base material with the alkaline water, heating the mixture, dropwise adding a mixture of the remaining cyclohexanone and n-butyraldehyde, stirring the materials while the mixture is dropwise added, continuously stirring after the dropwise adding is ended, and ending the heat-preserved reaction till the content of the n-butyraldehyde is less than 1 percent; allowing the solution to stand still, separating an oil layer, collecting a water layer for recycling and use; washing the collected oil layer with water, then transferring the oil layer into a distillation still for distillation to recycle excessive cyclohexanone for use; collecting a condensation product at the bottom of the distillation still. According to the continuous synthesis method, the yield of the aldol reaction is increased by adding the cyclohexanone in different ways; furthermore, under a reaction temperature condition of the continuous synthesis method, an aldol condensation product can be obtained in one step.

The invention discloses a method for preparing testolactone by microbial transformation, which mainly comprises the following steps: dissolving dehydroepiandrosterone in a solubilizer, adding the mixture in a transformation solution to prepare a transformation substrate solution; adding the transformation substrate solution into a transformation reaction device, adding fusarium oxysporum, transforming to obtain an intermediate of 3beta-hydroxy-17alpha-oxo-D-hexocyclo-androst-5-ene-17-ketone under the fusarium oxysporum resting cell transformation action through a Baeyer-Villiger oxidation reaction, adding gordonia after the transformation reaction is completed, performing a transformation reaction of the intermediate under the gordonia resting cell action to obtain testolactone. The method for preparing testolactone of the invention has the advantages of simple process route, easily available raw materials, cheap auxiliary materials, high substrate transformation rate, few by products, low production cost, and the like, overcomes the deficiencies of original production technology, and is suitable for industrial production.

The invention discloses a synthetic method of 4-(2,2-dichloro cyclopropyl)phenol acetate. The synthetic method comprises the following steps: taking 2,2-dichloro cyclopropyl benzene as a starting rawmaterial and carrying out electrophilic substitution reaction and baeyer-villiger oxidation reaction to synthesize the 4-(2,2-dichloro cyclopropyl)phenol acetate. According to the preparation method disclosed by the invention, an iodine element-containing co-catalyst is added into the electrophilic substitution reaction to reduce the temperature of the electrophilic substitution reaction, so thatthe selectivity of the electrophilic substitution reaction is improved; the content of an ortho-isomer is reduced within 0.3 percent by adopting relatively-inexpensive acetyl chloride as an electrophilic reagent; the activity of oxidation reaction is improved by adding an iron salt catalyst in the baeyer-villiger oxidation reaction, so that the reaction can be successfully carried out under the condition of taking acetic anhydride as an oxidizing medium, the yield of oxidation reaction is improved and potential safety hazards of a post-treatment process are reduced.

The invention is an industrialized preparation method of 1,4,5,8-naphthalene tetracarboxylic acid. The invention uses cheap and easy-to-obtain naphthalene as a starting material, and undergoes Friedel-Crafts acylation reaction, Baeyer-Villiger oxidation-hydrolysis "one 1,4,5,8-naphthalene tetracarboxylic acid is obtained after the pot method "reaction. Wherein the Friedel-Crafts acylation reaction yield is 87%, the Baeyer-Villiger oxidation-hydrolysis yield is 91%, and the total reaction yield is 79%. The present invention emphasizes the characteristics of short steps, simple reaction, high yield, simple purification method, easy operation and the like from the chemical point of view.

The invention discloses a method for preparing epsilon-caprolactone by using in-situ peroxide. The method efficiently utilizes an in-situ peroxide obtained in a process of oxidizing alcohol by oxygento oxidize cyclohexanone into epsilon-caprolactone, i.e., under the catalysis of a catalyst, an alcohol is oxidized into the corresponding ketone while substances such as peroxy hydroxyl or hydrogen peroxide and the like generated in the process are fully utilized, so that the Baeyer Villiger oxidation reaction from cyclohexanone to epsilon-caprolactone is realized. Compared with a previous epsilon-caprolactone synthesis method, the method of the invention has the advantages that the product yield is remarkably increased, the use efficiency of alcohol is further improved, raw materials and reagents are cheap and easy to obtain, operation is easy, reaction conditions are mild, and the method is clean and environmentally friendly.

The invention relates to the field of chemical synthesis and discloses a preparation method for 3,4,5-trialkoxy phenol. According to the method, 3,4,5-trialkoxy benzaldehyde or 3,4,5-trialkoxy phenyl alkyl ketone and hydrogen peroxide are used as raw materials and are subjected to Baeyer-Villiger oxidation rearrangement reaction in a mixed solvent of dimethyl carbonate and methanol under the catalysis of a strong acid and then to basic hydrolysis, and 3,4,5-trialkoxy phenol is obtained after the strong acid is neutralized. The method provided in the invention has simple process steps, a yield of more than 50% and a remarkable application value in industrial production.

The coupling of aryl, heteroaryl, and vinyl halides with α,α-difluoroketones or silyl ethers or siylenol ethers of α,α-difluoroketones and α,α-difluoroamides and esters are described. Further derivatization of the coupling products (such as ketone cleavage and Baeyer-Villiger oxidation) is also described.

The present invention belongs to the field of organic chemistry and drug synthesis, and relates to a synthetic method of 2-methoxyestradiol. The present invention adopts estradiol as the original raw material, which undergoes six reactions including acylation with acetic anhydride and acetate as the reagents, and a mixture of petroleum benzene and acetone with the ratio of 20:1 which is used as the TLC developer to trace the recomposition, a phase-transference benzyl ether protection, Baeyer-Villiger oxidation, one-step 2-,17-diacetoxylide hydrolysis -2-methylation, concentrated and hydrochloride acid 3- protection to product the intended product of 2-methoxyestradiol. The present invention has mild reaction condition, simple operation, the reagent which is easily accessible with low cost, thorough reaction, shortened reaction duration, simple post treatment, raised recovery rate and raised purity of the product, economized reagent and the decreased cost, as well as the prospect of industrialized production.