33 results about "Aryl halide" patented technology

The invention relates to the field of organic chemical synthesis, in particular to a quinazolinone compound synthesized by carbon dioxide and a preparation method of the quinazolinone compound. According to the preparation method for synthesizing the quinazolinone compound from carbon dioxide, carbon dioxide, a 2-aminobenzamide compound and aryl halide are taken as raw materials, and are subjected to a heating reaction in the presence of a palladium metal catalyst, a ligand, a reducing agent, alkali and an organic solvent to generate the quinazolinone compound. The mechanism is as follows: carbon dioxide forms an intermediate A under the conditions of alkali and a reducing agent, aryl halide and the intermediate A form a carbonyl metal compound B under the action of a palladium metal catalyst, and then the carbonyl metal compound B reacts with a 2-aminobenzamide compound under the action of the alkali and the reducing agent to obtain the quinazolinone compound. The catalyst system has universality to various types of 2-aminobenzamide and derivatives and aryl halides thereof, the raw materials are wide in source, cheap and easy to obtain, and the reaction process is simple and controllable.

The invention discloses a method for dehalogenation reduction of electron-rich aryl halide, which comprises the following step: by taking aryl halide as a raw material, carrying out heating reaction in the presence of phosphorous acid, elemental iodine and a solvent to prepare a corresponding aromatic compound. According to the method, the defect that expensive transition metal catalysts and equivalent metal reagents need to be used for participation in current mainstream methods is directly avoided, the electron-rich aryl halide is subjected to one-step dehalogenation reduction to obtain the corresponding aromatic hydrocarbon by taking low-cost, low-toxicity and relatively stable phosphorous acid as a reducing agent and taking the iodine elementary substance as a catalyst, and the method has the advantages of no metal participation, simple operation, low cost and the like. The method has the advantages of simple operation, low cost, environmental protection and the like, avoids the use of a metal reagent and the limitation that special equipment is not easy to amplify production, after the phosphorous acid reaction is finished, byproducts are generally phosphoric acid and corresponding phosphorus salts thereof and can be quickly removed by washing, the post-treatment is simple, and the method is beneficial to industrial production.

The application discloses a kind of using cobalt catalyst by unreported double migration coupling strategy, realizes migration asymmetric nitrogen hetero Nozaki-Hiyama-Kishi (aza-NHK) reaction, and the selective preparation α-chiral (E)-allyl amine starting from simple and easy to obtain ortho halogen phenyl ethylene or corresponding E / Z-alkyl bromide or its mixture belongs to the field of organic chemistry and medicinal chemistry.The application under the action of metal cobalt source, ligand, organic additive, inorganic additive etc., makes cyclic sulfonamide and ortho alkenyl substituted aryl halide or alkenyl halide react in organic solvent, to obtain a series of polysubstituted olefins with excellent regioselectivity, stereoselectivity and good yield, which can be used as active drug molecules and important synthetic intermediates.The application uses cheap transition metal cobalt as catalyst, and uses ortho alkenyl substituted aryl iodine and cyclic sulfonamide as raw material, and the reaction condition is warm, simple operation, and good functional group compatibility.

This invention discloses a migration C(sp²)-H / C(sp³)-H cross-coupling reaction achieved using metal / photoredox catalysis, belonging to the fields of organic chemistry and medicinal chemistry. Under the action of a nickel source, photocatalyst, ligands, base, and additives, this invention enables the reaction of alkanes with ortho-alkenyl-substituted aryl halides or ortho-pyridine-substituted aryl halides in an organic solvent under light irradiation, yielding a series of polysubstituted olefins or polysubstituted aromatic compounds with excellent regioselectivity, stereoselectivity, and good yields, which can serve as active pharmaceutical molecules. This invention uses inexpensive transition metal nickel as a catalyst, readily available alkanes and haloaromatics as raw materials, and features mild and simple conditions, good functional group compatibility, and easy operation.

This application relates to the field of organic chemical synthesis, specifically to a method for synthesizing quinazolinone compounds from carbon dioxide and its preparation. The method uses carbon dioxide, 2-aminobenzamide compounds, and aryl halides as raw materials, and reacts under heating in the presence of a palladium metal catalyst, a ligand, a reducing agent, a base, and an organic solvent to generate quinazolinone compounds. The mechanism is as follows: carbon dioxide forms intermediate A under alkaline and reducing conditions; the aryl halide reacts with intermediate A under the action of a palladium metal catalyst to form a carbonyl metal compound B, which then reacts with the 2-aminobenzamide compound under the action of an alkaline and reducing agent to obtain the quinazolinone compound. This catalyst system is universally applicable to various types of 2-aminobenzamides and their derivatives, as well as aryl halides; the raw materials are widely available, inexpensive, and readily available; and the reaction process is simple and controllable.

The application discloses a method for dehalogenation reduction of electron-rich aryl halide. The aryl halide is used as raw material, and is heated to react in the presence of phosphorous acid, iodine and a solvent, so that the corresponding aromatic hydrocarbon compound is prepared. The method directly avoids the defects of the current mainstream method, i.e. the need of using expensive transition metal catalyst and equivalent metal reagent. The electron-rich aryl halide is reduced to the corresponding aromatic hydrocarbon by one step through using the cheap, low-toxic and stable phosphorous acid as a reducing agent and iodine as a catalyst. The method has the advantages of no need of metal participation, simple operation, low cost, green environmental protection and the like, avoids the use of metal reagent and the limitation of special equipment which is not easy to be enlarged for production. After the reaction of the phosphorous acid is completed, the by-product is generally phosphoric acid and the corresponding phosphorus salt, which can be quickly removed through water washing, and the post-treatment is simple, so that the industrialized production is facilitated.

The present invention provides the process for the preparation of substituted aryl halide compound of Formula (I) from substituted aryl amine compound of Formula (II) in the absence of catalyst wherein, X, n and R1 are as defined herein.

The present application provides a class of hydroxyl-substituted pyridine-2-carboxylic acid amide ligands and their use in copper-catalyzed aryl halide coupling reactions. Specifically, the present application provides a class of hydroxyl-substituted pyridine-2-carboxylic acid amide ligands and their use; wherein the definitions of each group are as described in the specification. The ligands are used in a catalytic system for copper-catalyzed cross-coupling reactions of aryl halides (particularly aryl chlorides) with aromatic amine compounds.

The invention discloses a conjugated microporous polymer material as well as a preparation method and application thereof in photocatalysis, and belongs to the technical field of organic photoelectric materials and photocatalysis. According to the preparation method of the conjugated microporous polymer material, 1, 3, 5-trivinyl benzene and aryl halide ligands (such as 1, 4-dibromobenzene, 1, 3, 5-tribromobenzene and the like) are used as raw materials, palladium acetate is used as a catalyst, and the conjugated microporous polymer material is synthesized through a Heck coupling reaction by a hydrothermal method. The prepared conjugated microporous polymer material can generate photo-generated charges under an illumination condition, shows semiconductor-like characteristics and a two-dimensional plane structure, and is suitable for photocatalytic degradation of organic pollutants in water and reduction of carbon dioxide. The photocatalyst has a remarkable degradation effect on tetracycline hydrochloride under visible light and can be used for photocatalytic reduction of carbon dioxide to generate useful products. The material is stable in structure, large in specific surface area and reasonable in pore size distribution, and has a good application prospect.

The application discloses a kind of dihydrotriazole aromatization precursor, preparation method and the dihydrotriazole aromatization precursor in the deacyl arylation of ketone, and the application includes: (1) ketone and 2-pyridyl hydrazine amide are dissolved in solvent, then active additive is added, and heating activation reaction is carried out under inert gas atmosphere, to obtain dihydrotriazole aromatization precursor;(2) the product of step (1) is mixed with aryl halide after or without purification, and is carried out under the conditions of photocatalyst, nickel catalyst, base, solvent and light irradiation photocatalytic reaction, to obtain the deacyl arylation product of ketone.The deacyl arylation reaction method of ketone of the application has the advantages that raw material is simple and easy to obtain, reaction condition is mild, substrate applicability is wide, etc., meets the requirements of developing green environment-friendly chemistry.

The present invention relates to a method for coupling aryl halides with N-nucleophilic reagent compounds, characterized in that the coupling is carried out in the presence of a binuclear copper (II) complex with a substituted salbed-type ligand of formula (I). Also described are novel binuclear copper (II) complexes with a substituted salbed-type ligand within the scope of Formula (I).

The application discloses a method for preparing fluorine-containing aromatic hydrocarbon by using a high gravity reactor and belongs to the technical field of organic fluorine chemical industry. The method comprises the following steps: dissolving aryl halide in a polar aprotic solvent to obtain an aryl halide solution; dispersing alkali metal fluoride in the polar aprotic solvent to obtain an alkali metal fluoride suspension; feeding the prepared aryl halide solution as one feed and the prepared alkali metal fluoride suspension as another feed into a high gravity reactor continuously, fully mixing the two feeds in a high gravity field at a reaction temperature and making the two feeds undergo halogen exchange fluorination, and after the reaction liquid flows out of the high gravity reactor, the target fluorine-containing aromatic hydrocarbon product is obtained through separation and purification. The method has the advantages of high mass transfer efficiency, short reaction time, few by-products, low energy consumption and high intrinsic safety.

The invention relates to a mechanically driven synthesis method of a hydroarylation product in the technical field of mechanochemical synthesis, which comprises the following steps: taking aryl or alkyl acrylamide as shown in a formula 1a and aryl halide as shown in a formula 2a as substrates, and taking a piezoelectric material as a catalyst; a hydroarylation product as shown in a formula 3 is synthesized in a mechanical driving mode under the conditions of a liquid auxiliary grinding agent (LAG) and an alkaline substance, and the synthesis route is as shown in the specification. The synthesis method provided by the invention has the advantages of high efficiency and greenness.

The invention discloses an aryl halide ligand and application of the aryl halide ligand in a trans-Martensite hydrogenation arylation reaction of palladium-catalyzed terminal alkyne and arylboronic acid. According to the method, arylboronic acid and terminal alkyne are taken as raw materials, in the presence of a palladium catalyst, an aryl halide ligand, alkali, a solvent and a proton source, the anti-Markov hydrogenation arylation reaction of alkyne is realized, and E-type 1, 2-disubstituted olefin is efficiently prepared. The method has the advantages of strong originality, mild conditions, simplicity and convenience in operation, short reaction time, few byproducts and the like, meets the requirement of green synthesis, and is suitable for large-scale preparation of E-type 1, 2-disubstituted olefin.

The invention relates to novel iminoamides of general formula (I) and to the use thereof as ligands in copper-catalyzed coupling reactions in which (hetero) aryl halides form C-C, C-N, C-S, C-O, C-P-bonds and other bonds, in particular to the use of compounds of formula (I) as ligands in copper-catalyzed coupling reactions in which aryl halides form C-O-bonds.

The application is suitable for the technical field of coupling reaction, and provides a method and device for column flow continuous coupling reaction based on Pickering emulsion, wherein the method comprises the following steps: performing wetting activation treatment on graphene oxide under alkaline condition through an activation agent; under high-speed stirring condition, performing sufficient mixing of the obtained graphene oxide with interface activity and a catalyst under the action of an organic solvent; loading the obtained Pickering emulsion of the solid-supported catalyst into a column reactor, continuously feeding aryl halide and boric acid compound from the lower part of the column reactor, and continuously feeding carbonate from the upper part of the column reactor to perform coupling reaction. The application provides a new method for column flow continuous coupling reaction of the solid-supported catalyst, the reaction system is stable, the problems such as the collection of products by demulsification / emulsification are not needed, the operation is simple and easy to implement, the conditions are mild, the method is suitable for most coupling reactions, and is easy to implement large-scale production.

The invention discloses a synthesis method of a cyclohexene-containing liquid crystal monomer, which comprises the following steps: step 1, hydrazone reaction: reacting an alkyl cyclohexanone compound with a hydrazine compound to generate a corresponding hydrazone compound intermediate; step 2, coupling reaction: mixing the hydrazone compound intermediate obtained in the step 1 with aryl halide, alkali and a composite catalyst, and carrying out coupling reaction to obtain a liquid crystal monomer compound containing a cyclohexene structure; wherein the composite catalyst comprises a palladium catalyst and a phosphine ligand. According to the invention, the keto group of alkyl cyclohexanone is converted into hydrazone, then the hydrazone is used as a key intermediate and is subjected to cross coupling with aryl halide through transition metal catalysis, beta-hydrogen elimination of the hydrazone is realized, cyclohexene double bonds are directly constructed from a ketone precursor, the whole reaction can be completed by a one-step method, intermediate post-treatment and purification are not needed, and the method is suitable for industrial production. The synthesis steps are reduced, and the reaction efficiency is improved while the reaction conversion rate and yield are ensured.

The application belongs to the technical field of organic phosphine ligands, and particularly relates to a fluorenyl biphosphine ligand and a preparation method and application thereof. The fluorenyl biphosphine ligand is prepared by using an easily available aryl halide as a starting material, constructing a phosphine-containing intermediate, and further converting the phosphine-containing intermediate to realize efficient construction of a fluorene skeleton biphosphine structure. The method has a clear reaction route, the raw materials are widely available, the reaction can be completed under mild conditions, is suitable for synthesis of different biphosphine substitution systems, and the prepared fluorenyl biphosphine ligand exhibits excellent catalytic performance in a Sonogashira coupling reaction, and has good practicability and promotional value.

The invention discloses ammonium fluoride etched micron zero-valent iron-nickel particles based on mechanical ball milling as well as a preparation method and application of the ammonium fluoride etched micron zero-valent iron-nickel particles. The micron zero-valent iron-nickel particles are mainly prepared by mixing micron zero-valent iron, ammonium fluoride and a transition metal nickel compound through a mechanical ball-milling etching-loading process, the transition metal nickel compound is mainly composed of nickel chloride hexahydrate, and the mass ratio of the micron zero-valent iron to the ammonium fluoride to the nickel chloride hexahydrate is 1: (0.01-0.04): (0.02-0.08). Ammonium fluoride is added for modifying and improving the dehalogenation performance of the iron-nickel particles. The reductive dehalogenation reaction activity of the particles on halogenated organic matters is remarkably improved, and the particles still keep stable performance after being recycled for more than 20 times and are not obviously attenuated; meanwhile, halogen functional groups in aliphatic halides and aryl halides can be efficiently reduced and removed, and excellent water treatment application potential is shown.

The invention provides alpha-hydroxyamide and acylhydrazine ligands and an application of the alpha-hydroxyamide and acylhydrazine ligands in a copper catalytic coupling reaction. Specifically, the invention provides a compound as shown in a formula I. The definition of each group is as shown in the specification, and the compound is used as a ligand for a copper-catalyzed aryl halide coupling reaction. The ligand provided by the invention can be carried out at lower catalyst dosage and reaction temperature, and the substrate is wide in universality.

The invention provides an norcamphane skeleton monophosphine ligand L modified palladium complex as well as a preparation method and application thereof. The palladium complex has a structure represented by the formula wherein L is an norcamphane skeleton monophosphine ligand having the structure represented by the formula, and Ar, R1, and R2 are as defined herein. The palladium complex may be prepared by reacting halogenated norbornene or an analog thereof with an aryl halide or an aryl sulfonate in the presence of an organic solvent and a palladium catalyst; reacting the obtained intermediate with R1R2PCl; and reacting the obtained ligand L with a palladium precursor and 2-(trimethylsilyl) ethyl-4-bromophenylmethyl ester. The palladium complex disclosed by the invention not only can be used as a catalyst for promoting a C-N coupling reaction in the synthesis of an organic compound containing a C-N structural unit, but also can reduce the dosage of the catalyst and expand the application range of efficient catalytic reaction due to the unique rigid skeleton and remarkable three-dimensional space characteristics of norcamphane molecules.

The application discloses a photochemical synthesis method of formanilide compounds. The method uses aryl halide compounds as raw materials, and performs selective C-X bond formamidation on the aryl halide compounds in the presence of formamide, a catalyst and an alkali, so that formanilide compounds are obtained with high selectivity. The method has the advantages of high efficiency, mild reaction condition, convenient operation, relatively short reaction time, less by-products and the like.

The invention provides thermocuring bending-resistant modified resin for an FPC (Flexible Printed Circuit) golden finger. The composition comprises modified polyimide, wherein polymeric monomers of the modified polyimide comprise an aromatic dianhydride component, a multi-benzene ring multi-ammonia structure aromatic diamine component and an ether bond-containing aromatic diamine component; the preparation method comprises the following steps: reacting a bisphenol aromatic compound with substituted nitro aryl halide under an alkaline condition, introducing a multi-benzene-ring structural unit, and converting nitro into amino through a hydrazine reduction reaction to prepare the aromatic diamine monomer with a multi-benzene-ring and multi-amino structure. The monomer is matched with an ether-bond-containing aromatic diamine component, the proportion is controlled, the monomer is compounded for preparing a polyimide material, the high temperature resistance, the bending fatigue resistance and the electrical property stability of the material can be remarkably improved, and the monomer is particularly suitable for a golden finger structure of a flexible printed circuit board.

The present invention relates to an improved process for preparing halophenols from haloaryl halides by copper-catalyzed hydroxylation reactions using suitable ligands. More specifically, the present invention relates to a method for preparing 3-chloro-2-fluorophenol from 3-chloro-2-fluoroiodobenzene, 1-bromo-3-chloro-2-fluorobenzene, or 1, 3-dichloro-2-fluorobenzene, by means of a copper catalyzed hydroxylation reaction using suitable ligands, to a process for preparing 3-chloro-2-fluorophenol from 3-chloro-2-fluoroiodobenzene, 1-bromo-3-chloro-2-fluorobenzene, or 1, 3-dichloro-2-fluorobenzene.

This invention proposes a method for photocatalyzing aryl acetic acid and aryl halides using a boron-carbon-nitrogen (h-BCN) system. The method comprises: using aromatic acetic acid compounds and aryl halides as raw materials, employing h-BCN as a non-metallic photocatalyst and NiCl2 as a co-catalyst, the two synergistically catalyze the reaction of aryl acetic acid and aryl halides at room temperature under inert gas protection and visible light irradiation, to efficiently synthesize C(sp2)-C(sp3) cross-coupled products. This invention replaces expensive, toxic, and scarce iridium-based photocatalysts with a h-BCN catalytic system. The h-BCN photocatalyst can be easily prepared by high-temperature calcination of boric acid, urea, and glucose precursors. The operation is simple, the conditions are mild, it completely avoids precious metals, and it combines selectivity and high efficiency, meeting practical production needs and possessing significant application potential.

This invention provides a method for copper-catalyzed Goldberg amination reactions involving piezoelectric materials driven by ball milling, belonging to the field of organic synthesis technology. The mechanical force of ball milling induces the formation of a piezoelectric potential on the surface of the piezoelectric material, which participates in the regulation of the oxidation state of the copper salt catalyst and the catalytic cycle, thereby activating aryl halides and nitrogen-containing nucleophiles. The entire reactant mixture reacts in a ball mill to obtain target products such as N-arylamines or N-arylamides. This invention combines piezoelectric materials with a copper catalytic system, enabling efficient C-N bond construction in copper-catalyzed Goldberg amination reactions under mechanical ball milling conditions without external heating and with little or no solvent. Experiments show that the reaction hardly occurs without the participation of piezoelectric materials, confirming the irreplaceable nature of piezoelectric materials. The method of this invention is mild, environmentally friendly, simple to operate, and has broad substrate applicability, making it suitable for the green construction of the skeletons of N-arylamines or N-arylamides in pharmaceutical, pesticide, and functional material molecules.

The application relates to the field of organic chemical synthesis, in particular to an unsymmetrical azobenzene compound, a synthesis method and application. The application discloses a C-N bond coupling of a palladium-catalyzed aryl (pseudo) halide and an aryl hydrazine compound in an air atmosphere, one-step efficient construction of a C-N=N structure, and realization of synthesis of unsymmetrical azobenzene derivatives. The aryl halide raw material and the aryl hydrazine reagent source are wide and commercially available; the reaction condition is mild, no inert gas protection is needed, the experimental operation is simple and safe, the functional group tolerance is good, and the reaction is easy to apply and expand. The substrate tolerance of the synthesis method is excellent, the site limitation of the traditional aromatic hydrocarbon diazo reaction is broken, the structural diversity of the product is greatly expanded, the synthesis method has very good application prospect in the fields of related azo dyes, drug development and photoswitching molecule synthesis, and has foreseeable market commercialization prospect.

This application relates to the field of organic chemical synthesis, specifically to a method for synthesizing benzoxazole compounds from carbon dioxide and its preparation. The method uses carbon dioxide, aminophenolic compounds, and aryl halides as raw materials, reacting them under heating in the presence of a copper catalyst, ligands, a reducing agent, a base, and an organic solvent to generate benzoxazole compounds. This method uses inexpensive, non-toxic, and renewable carbon dioxide as the carbonyl source, efficiently synthesizing benzoxazole compounds through a one-step carbonylation reaction. This route offers mild reaction conditions, high selectivity, and simple operation, avoiding the use of various high-pressure gases; the carbon source and catalyst are economical and widely applicable, and the raw materials are readily available and inexpensive, making it suitable for large-scale industrial production.

The invention belongs to the technical field of organic synthesis and photocatalysis, and relates to a light-mediated halogen exchange method from brominated aromatic hydrocarbon to chlorinated aromatic hydrocarbon by taking hydrochloric acid as a chlorine source. According to the method, hydrochloric acid (HCl) is used as a safe and cheap chlorine source, and under ultraviolet irradiation, efficient conversion from aryl bromide to aryl chloride is realized in an acetonitrile solvent by using vanadyl acetylacetonate [VO (acac) 2] as a catalyst and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline as a ligand. The reaction is carried out under a mild condition (0-30 DEG C), dangerous chlorinating agents such as chlorine, SOCl2 and the like are not needed, the operation is simple and convenient, and the method is safe and environment-friendly. According to the method, active chlorine species (Cl <. > or [VO]-Cl < + >) are generated through light-induced metal-halogen bond activation, C-Br bond breakage and chlorine substitution reaction are promoted, and high-selectivity conversion from Br to Cl is achieved. The reaction has the advantages of wide substrate applicability, high selectivity, few side reactions, recyclable catalytic system and the like, and is especially suitable for later modification and green synthesis of fine chemicals and drug intermediates. The invention provides a new halogen exchange strategy which is high in atom economy, environment-friendly and capable of being popularized on a large scale, and provides a new technical path and an industrial application prospect for efficient chlorination of aryl halide.

The invention discloses a method for preparing a diaryl ketone compound, and belongs to the field of organic synthesis. The preparation method comprises the following specific steps: dissolving aryl halide and aryl acetonitrile in a solvent, adding alkali in a protective atmosphere, carrying out heating reaction at 70-150 DEG C for 1-6 hours, placing the system in an air condition, and continuously carrying out heating reaction to obtain a product I; performing column chromatography separation on the product I to obtain the diaryl ketone compound, wherein the alkali is at least one of cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine and DBU; the molar ratio of the aryl halide to the aryl acetonitrile to the alkali is 1: (1-3): (1-6). The process is simple, and materials are easy to obtain. The method solves the problems of serious environmental pollution, complex post-treatment steps, high metal catalysis cost, more side reactions, poor substrate applicability and the like of a method for synthesizing the diaryl ketone compound in the prior art.