57 results about "Aryl halide" patented technology

The invention relates to the technical field of water treatment, in particular to a method for treating degradation-resistant organic pollution underground water based on a micro-interface strengthening technology. According to the technical scheme, the method comprises the steps that an underground water sample is collected and subjected to pollution characteristic analysis, composite material slurry is injected into a water-containing layer to construct an interface-enhanced in-situ reaction system, and the slurry is composed of nanoscale iron-based metal particles, graphene oxide derivatives, modified biochar, a surfactant and the like; meanwhile, a low-pressure gas injection system is arranged to form a micro-aerobic environment so as to improve the interface reaction efficiency, dominant microbial communities are synchronously injected, a slow-release carbon source carrier is added so as to strengthen the biological synergistic degradation effect, and the operation state of the system is regulated and controlled through multi-parameter monitoring. According to the method, a micro-interface synergistic system integrating physical adsorption, chemical reduction and biological metabolism is constructed, refractory organic pollutants such as aryl halide and polycyclic aromatic hydrocarbon in underground water can be efficiently and stably removed, and the method has the advantages of being high in remediation efficiency, high in operation stability and wide in environmental adaptability.

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.

Gold(I) complexes capable of absorbing light in the near-UV and / or visible region, and methods of making and using the same, are described. These gold(I) complexes have photochemical reactivity, such as strong absorption of near-UV and / or visible light, quenching rate constants of > 3.5 x 10 5 s ‑1 This enables them to catalyze photoredox reactions under near-UV and / or visible light, such as homocoupling of organic halides (e.g., alkyl halides and aryl halides), alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinolines, cyclization of indoles, reductive dehalogenation of aryl halides, and / or C-H bond cleavage, among others. The yields of products of photo-induced organic reactions catalyzed by the gold(I) complexes described herein can be higher than the yields of the same products formed from the same reactions under the same reaction conditions using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3] at the same or higher loading than the loading of the one or more gold(I) complexes.

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 application discloses a preparation method of aryl trimethyl tin alkylate, which comprises the following steps: uniformly mixing aryl halide, 2,4,5,6-tetrakis(9-carbazolyl)-m-dinitrile, N,N-diisopropylethylamine, hexamethyldistannane and a solvent, carrying out reaction, and removing the solvent after the reaction is completed; then carrying out column chromatography to obtain pure aryl trimethyl tin alkylate; the reaction method of tin alkylation has good tolerance and universality to functional groups, the yield of the prepared aryl trimethyl tin alkylate is high, and the highest yield can reach 95%. The raw material adopted is cheap, stable, environment-friendly, low-toxic and the like, and is widely available, cheap and easy to obtain, and has low production cost.

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 invention discloses a method for catalyzing a coupling reaction of aryl halide and Hanus ester by light / cobalt redox, which comprises the following steps: adding a photocatalyst and cobalt salt into a solvent containing organic amine and zinc salt, and catalyzing the coupling reaction of aryl halide and Hanus ester to synthesize diphenylmethane compounds and derivatives thereof under the irradiation of visible light. According to the method disclosed by the invention, the Hanus ester is used as a mild free radical precursor to replace a traditional metal reagent to carry out coupling reaction with the aryl halide, so that the substrate compatibility and the reaction operability are improved, and the product yield can be up to 93%.

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 discloses a method for synthesizing aryl amide by light / nickel concerted catalysis of aryl halide. Compared with the prior art, after the phenyl aryl benzoate product is obtained, treatment is not needed, and amine is directly added to obtain amide. The preparation method provided by the invention has the advantages of simple operation steps, good substrate universality, coverage of polycyclic and heterocyclic substituted aryl phenyl benzoate, wide functionality tolerance, mild reaction conditions and high yield, and is a green chemical synthesis method with good application prospects.

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 provides a method for photocatalysis of aryl acetic acid and aryl halide through boron-carbon-nitrogen-nickel, and the method comprises the following steps: taking an aromatic acetic acid compound and aryl halide as raw materials, boron-carbon-nitrogen (h-BCN) as a non-metal photocatalyst and NiCl2 as a cocatalyst, and carrying out synergistic catalysis on aryl acetic acid and aryl halide by the aromatic acetic acid compound and aryl halide. Under inert gas protection and visible light irradiation, a reaction is carried out at room temperature, and a C (sp2)-C (sp3) cross-coupling product is efficiently synthesized. An expensive, toxic and scarce iridium-based photocatalyst is replaced with a boron-carbon-nitrogen-nickel catalytic system, the adopted boron-carbon-nitrogen photocatalyst can be simply and conveniently prepared by calcining boric acid, urea and glucose precursors at high temperature, operation is easy, conditions are mild, precious metal is completely avoided, selectivity and high efficiency are both achieved, the actual production requirement is met, and the method is suitable for industrial production. The method has great application potential.

The invention discloses a preparation method of a deuterated alkyl (hetero) aryl ether compound (deuterated medicine), and belongs to the technical field of deuterated compound synthesis. The preparation method comprises the following steps: adding a (hetero) aryl halide, deuterated alcohol, a nickel catalyst, organic alkali and a silane reagent into an organic solvent, and reacting in an inert gas atmosphere to obtain the deuterated alkyl (hetero) aryl ether compound and the deuterated drug. The compound can be applied to later modification of drug molecules and synthesis of deuterated drugs such as agomelatine and phenacetin. The method has the advantages of mild reaction conditions, simple operation and low cost, and has good application prospects in the field of deuterated drug synthesis.

The invention discloses a synthesis method of a copper-catalyzed aryl nitrile compound. Specifically, the method comprises the following steps: cuprous cyanide, aryl halide, ligand and alkali are placed in an organic solvent, heating and stirring reaction are performed to obtain the aryl nitrile compound, the reaction process is shown in the specification, and the definition of each group is shown in the specification. The synthesis method has the advantages of cheap and easily available raw materials, low catalyst cost, mild reaction conditions, low production cost, high raw material conversion rate, good selectivity, good product purity, stability, high efficiency, simple operation, compatibility with almost all common functional groups, and good industrial production prospect.

The invention discloses a broad-spectrum alkyne metathesis catalyst and a preparation method of a ligand of the broad-spectrum alkyne metathesis catalyst. In an inert gas atmosphere, in the presence of a palladium catalyst and alkali, pinacol borate substituted triphenylmethane and aryl halide are subjected to a heating reaction in a mixed solvent of an organic solvent and water, and the tridentate ligand is obtained. The method comprises the following steps: mixing a tridentate ligand and a molybdenum carbine precursor in an organic solvent, stirring and reacting to obtain a tridentate ligand metal catalyst, then adding a metathesis substrate, and catalyzing alkyne metathesis reaction at 25-110 DEG C. The invention provides a simple, convenient and efficient preparation process, synthesis of various ligands can be realized, and a new technical approach is provided for expansion of a ligand library. The catalyst prepared by using the ligand has high solvent and substrate applicability, overcomes the dependence of a known catalyst system on a high-toxicity solvent carbon tetrachloride, and can realize efficient conversion of a substrate which is generally difficult to carry out alkyne double decomposition reaction.

The invention relates to a catalyst for synthesizing aryl silane by photo-nickel co-catalysis of aryl halide and a synthesis method. The invention discloses a catalyst for synthesizing aryl silane by photo-nickel co-catalysis of aryl halide. The catalyst comprises tetrabutylammonium decatungstate, a nickel catalyst, a ligand, an alkali additive and an organic solvent. The invention also discloses a synthesis method for synthesizing aryl silane from aryl halide through photo-nickel co-catalysis. According to the catalyst for synthesizing aryl silane from aryl halide through photo-nickel co-catalysis and the synthesis method, complex aryl silane can be directly synthesized from existing silane under mild conditions, the defect that precious metal such as platinum participates in a traditional free radical silylation reaction is overcome, the cost is low, and synthesis steps are simple and convenient.

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 relates to a synthesis method of (S)-2-(2-isopropyl phenyl) pyrrolidine. The method comprises the following steps: firstly, converting aryl halide into a Grignard reagent, and carrying out ring opening reaction on the Grignard reagent and an N-protected 4-6-membered ring lactam compound to obtain an intermediate; and then removing a protecting group, and carrying out asymmetric hydrogenation under the condition of a chiral catalytic system to finally obtain (S)-2-(2-isopropyl phenyl) pyrrolidine with high optical purity. The method has good stereoselectivity, simplicity and convenience in operation and industrial adaptability, and is suitable for efficient synthesis of chiral amine compounds, especially chiral drug intermediates.