23 results about "Heck reaction" patented technology

The invention discloses a synthesis method of a mono / dibromo pyridine derivative, which comprises the following steps: reacting a pyridine derivative with dimethyl butynedioate and methyl pyruvate at room temperature by using acetonitrile as a solvent to generate a dearomatized heteroaromatic compound; in an oxygen environment, copper bromide is used for brominating the dearomatized heteroaromatic compound to realize dibromination, and if potassium carbonate is additionally added in the reaction, monobromination is realized; and finally, respectively generating mono / dibromopyridine derivatives under hydrochloric acid hydrolysis. A carbon halogen bond of bromopyridine has very high activity, and various reactions such as Suzuki coupling, Sonogashira coupling, Heck reaction, amination reaction and the like can be carried out. On the basis, the polysubstituted bromopyridine can be subjected to selective reaction, and many new ideas can be provided for organic synthesis. The method disclosed by the invention is simple and safe to operate and environment-friendly, the cost is lower by using the copper bromide, and the required reaction conditions are simple.

The invention discloses a tetrazine probe synthon and a preparation method and application thereof.The preparation method comprises the following steps that under the inert atmosphere, diethyl cyanomethylphosphonate, 3-hydroxypropionitrile, 3-mercaptopropionic acid and hydrazine hydrate are mixed and then react at the room temperature, a sodium nitrite solution is added after the reaction is finished, then acid is continuously added till the reaction system reaches acidity, and a tetrazine probe synthon product is obtained; continuously reacting to obtain an intermediate; and dissolving the intermediate in a solvent in an inert atmosphere, adding triethylamine, slowly adding methanesulfonyl chloride, and reacting at room temperature to obtain the tetrazine probe synthon shown in the formula I. The invention further discloses a preparation method of the tetrazine probe synthon. The tetrazine probe synthon provided by the invention can perform series Heck reaction and HWE reaction, so that controllable combination of functional groups on two sides of a tetrazine coupling probe is realized under mild reaction conditions, and the functional groups on two sides are designed according to actual requirements to regulate and control photophysical properties of the probe. A brand new way is provided for developing a high-performance biological orthogonal fluorescent probe.

The invention relates to the technical field of high-frequency and high-speed substrate resin and packaging materials of microelectronic devices, and particularly discloses hydrocarbon resin of dibenzocyclobutene fluorene and derivatives thereof and a preparation method of the hydrocarbon resin, and the hydrocarbon resin is prepared by mixing 9, 9-disubstituent-9H-fluorene and / or the dibenzocyclobutene fluorene derivatives according to a specific proportion, adding a solvent, and stirring to obtain the hydrocarbon resin of the dibenzocyclobutene fluorene and the derivatives of the dibenzocyclobutene fluorene and the derivatives of the dibenzocyclobutene fluorene. And carrying out a thermocuring reaction to obtain the product. The dibenzocyclobutene fluorene derivative is prepared by carrying out Heck reaction on 9, 9-disubstituent-9H-fluorene and halogenated benzocyclobutene under the catalysis of a base catalyst and a modified palladium catalyst, the prepared hydrocarbon resin has very low dielectric constant and dielectric loss and higher softening point and peel strength, and can better meet market requirements.

The application discloses a five-membered ring containing alkynyl or triazole functional group P The chiral phosphine oxide compound is obtained through Domino Heck-Sonogashira cascade reaction by taking a prochiral tertiary phosphine oxide compound containing a double ethylene group and phenylacetylene as raw materials, transition metal palladium catalyst and chiral TADDOL phosphoramidite ligand under the protection of inert gas P The chiral phosphine oxide compound has a product yield of 96% and an enantioselectivity ee value of 99%, and a diastereoselectivity dr value of greater than 20:1. The application adopts an asymmetric desymmetrization strategy, uses a Heck reaction to start and a Sonogashira reaction to end a cascade reaction, simultaneously constructs P The chiral and quaternary carbon chiral center has mild reaction conditions, simple operation and good substrate universality, provides a compound skeleton with diversity, and is successfully applied to a palladium-catalyzed asymmetric allyl substitution reaction as a chiral ligand.

The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing a chiral allene compound from aromatic hydrocarbon and alkyne. A simple aromatic hydrocarbon compound and thianthrene-S-oxide are designed to construct an aryl thianthrene salt in situ under the action of an electrophilic activation reagent, then the aryl thianthrene salt constructed in situ under catalysis of a palladium catalyst and a chiral ligand is subjected to an asymmetric Heck reaction with alkyne, and the tri-substituted chiral allene compound is rapidly and efficiently constructed. The method is mild in condition, wide in substrate range and excellent in enantioselectivity and yield, and meanwhile, chiral allene fragments can be introduced into salicin and indometacin which have anti-inflammatory and analgesic activities.

The present application relates to the field of drug synthesis, in particular to a novel intermediate, a method for preparing the same and application thereof. The structural formula of the novel intermediate provided by the present application is as expressed by formula I:where R is a secondary amine protection group. Based on the possible biogenic pathway of morphine derivatives, the present application realizes the efficient synthesis of morphine derivatives through the strategy of biomimetic synthesis, taking the asymmetric transfer hydrogenation reaction and the intramolecular oxidative dearomatization Heck reaction in the process of preparing the intermediate as the key reactions of total synthesis. Using the novel intermediate provided by the present application to synthesize morphine derivatives has the characteristics of significantly reducing the synthesis steps, improving the yield, reducing the discharge of three wastes and reducing the production cost.

The application discloses a method for constructing a cycloalkene-quinolinone axial chiral compound through a Heck reaction. The method uses a quinolinone compound containing central chirality as a substrate, uses palladium acetate (Pd(OAc)2) and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (Xantphos) as a catalyst, uses silver phosphate (Ag3PO4) as an alkali, and uses toluene as a solvent to prepare a cycloalkene-quinolinone axial chiral compound. The compound can be reacted with diisobutylaluminum hydride to realize conversion of a functional group. The method has mild reaction conditions, raw materials are easy to obtain, the product has excellent enantioselectivity, and has excellent yield, and thus provides a new method for synthesizing a cycloalkene-quinolinone axial chiral compound.

The invention relates to a nitrogen-rich acylhydrazone covalent organic framework material as well as a preparation method and application thereof, 5 '-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3, 3'-dimethoxy-[1, 1 ': 3', 1 '-terphenyl]-4, 4'-dicarboxylic acid dihydrazide, 1, 3, 5-tri (2-formyl pyridine-5-yl) benzene and 4, 4 ', 4' '-(1, 3, 5-triazine-2, 4, 6-triyl) tribenzaldehyde are used as construction units, and the nitrogen-rich acylhydrazone covalent organic framework material is prepared by a one-step method. The compound is synthesized by Schiff base reaction. The nitrogen-rich acylhydrazone covalent organic framework material disclosed by the invention has good chemical stability and can be used as a carrier to load palladium nanoparticles through metal coordination to obtain a composite material, and the composite material shows excellent catalytic activity and substrate universality in catalysis of Heck reaction; the method has potential application value in the fields of biological medicine, green chemistry and the like.

The invention discloses a preparation method of 2, 6-dimethyl-2, 3-dihydro-1-indanone, which comprises the following steps: carrying out a heck reaction on p-bromotoluene and methacrylic acid under the action of a catalyst to generate 2-methyl-3-(4-methylphenyl)-2-acrylic acid, and then carrying out hydrogenation, acylating chlorination and Friedel-Crafts acylation cyclization to synthesize the 2, 6-dimethyl-2, 3-dihydro-1-indanone. The method is mild in reaction condition, high in total yield, clean and environment-friendly in whole route, small in environmental pollution and suitable for industrial production.

This invention provides a ( E This invention relates to the field of pharmaceutical synthesis technology and provides a method for synthesizing 3,5-dihydroxy-4-isopropylstilbene. The method comprises three steps: starting with 3,5-dimethoxy-bromobenzene as a starting material, isopropylation is carried out under acidic conditions to obtain 3,5-dimethoxy-4-isopropylstilbene; further, a Heck reaction is performed with styrene under palladium catalysis to obtain (…). E )-3,5-dimethoxy-4-isopropylstilbene; demethylation reaction yields the ( E 3,5-Dihydroxy-4-isopropylstilbene. Compared to existing synthetic routes, the synthetic method of this invention significantly shortens the synthetic path, has higher atom utilization, higher product yield, and is environmentally friendly.

The invention discloses a chiral benzoxazine diphosphine ligand and a complex and application thereof. The structure of the chiral benzoxadiphosphine ligand is shown as a formula (I), and in the formula (I), R1 is alkyl or aryl, R2 is alkyl or aryl, and R3 is at least one of fluorine, carbazolyl and 2, 6-dimethoxyphenyl. The chiral benzoxazine diphosphine ligand disclosed by the invention can be applied to two asymmetric reactions, namely cross dehydrogenation coupling of disilane hydrogen and benzyl alcohol under catalysis of rhodium and axial chiral Heck reaction of aryl trifluoromethanesulfonate and alkenyl ether under catalysis of palladium, and has excellent activity and relatively high enantioselectivity in the two asymmetric reactions; moreover, the chiral benzoxadiphosphine ligand can be directly synthesized from simple and easily available chiral aldehyde, and the preparation method is simple and easy to operate.

The invention relates to a large Stokes shift cholinesterase near-infrared fluorescent probe and a construction method thereof.Quinoline is used as a core skeleton, and a conjugated system is constructed through a D-pi-A electronic regulation strategy: aryl, alkenyl or amido is introduced to the 4th site / 6th site to regulate the emission wavelength; the construction method comprises the following steps: synthesizing a fluorophore main skeleton through a Wittig reaction / Heck reaction, connecting a recognition unit through a substitution reaction, and introducing the electron-withdrawing group through a Najing condensation reaction. Stokes shift breaks through 100 nm, and excitation light interference can be inhibited. According to the probe, a recognition unit simulating acetylcholine / butyrylcholine'dumbbell-shaped 'conformation is covalently connected to a quinoline nitrogen atom through a benzyl bromide group, the recognition unit comprises an aromatic cavity adaptive to AChE / BChE substrate pocket hydrophobicity and an active site for catalyzing ester bond hydrolysis, an enzymatic reaction triggers intramolecular electron rearrangement and C-N bond breakage, a fluorescence quenching state is relieved, and the quinoline nitrogen atom can be detected. And "off-on" type signal conversion is realized.

This invention discloses a process for synthesizing rosuvastatin acetone tert-butyl ester, comprising the following steps: First, compound I is dissolved in an organic solvent, compound II is added, and the reaction is stirred at room temperature. The reaction is monitored by HPLC. After the reaction is complete, the product is separated to obtain compound III. Second, a palladium catalyst is added to the organic solvent, stirred and mixed evenly, and then compound III and compound IV are added and stirred under the action of the palladium catalyst to obtain compound V. The advantages of this invention are: mild reaction conditions, the entire process is carried out at room temperature, eliminating the need for harsh conditions such as high temperature and high pressure, reducing energy consumption and equipment requirements, and making it suitable for industrial-scale production; excellent stereoselectivity, using a palladium-catalyzed reselective Heck reaction to replace the traditional Witting and Julia olefin reactions, avoiding stereoisomer byproducts, and resulting in higher purity of the target product; fewer byproducts and simpler separation.

The application relates to a novel structure of a bidentate nitrogen ligand palladium complex and a preparation method and application thereof, and the bidentate nitrogen ligand palladium complex is obtained by heating reaction of 2-acetylpyridine, palladium chloride and a substituted aniline in an organic acid. Compared with the prior art, the novel structure of the palladium complex prepared by the application has the advantages of simple synthesis process, high catalytic activity, excellent reaction activity in a Heck reaction for synthesizing a key intermediate of montelukast, obvious reduction of the cost of the montelukast bulk drug, and good industrialization prospect.

The invention belongs to the technical field of high polymer materials and electrochromism, and provides a preparation method and application of a column [5] arene conjugated polymer containing a D-A-D structure. The preparation method comprises the following steps: derivatizing column [5] arene, and synthesizing column [5] arene with thienyl on a side chain through Suzuki coupling reaction; and further taking the column [5] arene conjugated polymer as a polymeric monomer, and polymerizing with a triphenylamine derivative containing a donor-acceptor structure through a Heck reaction to obtain the column [5] arene conjugated polymer with an electrochromic function. A D-A-D structure is introduced into a column [5] arene electrochromic system for the first time, and an electrochromic device manufactured based on the column [5] arene electrochromic system is yellow in a neutral state and green in an oxidation state, and is short in response time, high in optical contrast, good in cycling stability, simple and convenient in synthesis process, low in cost and easy for industrial production; wide application prospects are shown in the fields of dimming glass, intelligent portholes and the like.

The application provides a carbonyl-modified imidazo[1,2-alpha]pyridine fluorescent probe molecule and a preparation method and application thereof, and belongs to the technical field of fluorescent probes, and aims to solve the technical problem of low sensitivity of organic small-molecule fluorescent dyes in pesticide detection. The fluorescent probe molecule has good solvatochromic properties and viscosity-dependent fluorescence emission behavior, and is applied to detection of organic pesticide DCN. The preparation process is as follows: 2-aminopyridine is used as a starting material to synthesize two compounds with different conjugation degrees through a Claisen-Schmidt reaction, an iodine-catalyzed cyclization reaction and a Heck reaction, and the structural formulae are as follows: in the formula, R 1 =F, Cl, Br, I, CF3, COOMe, CN, H, Me or OMe; R 2 =Cl, Br, CF3, COOMe, H, Me or OMe; R 3 =F, Cl, Br, I, CF3, H, Me or OMe; n is a positive integer between 0 and 11. The two compounds have good light-emitting properties in tetrahydrofuran solution, and can selectively recognize organic pesticide DCN, and are expected to become probe molecules for detecting DCN residues in actual samples.

The application discloses an application of a temperature-controlled phase transfer Pd nano catalyst in a Heck reaction and belongs to the technical field of nano catalysts. By introducing a functional group with both a polyether chain segment and a hydrogen bond function into a traditional aryl phosphine skeleton, the application realizes the reversible migration of the catalyst between an aqueous phase and an organic phase with the change of temperature, and meanwhile, the bulk group on the ligand enhances the electron density and stability of the palladium center. The temperature-controlled phase transfer Pd nano catalyst prepared by the application presents good catalytic activity for the Heck reaction under the condition of 85 DEG C, and the conversion rate is more than 75%. Moreover, the catalytic system has good stability in a water / organic two-phase system and can be repeatedly used for at least 4 times.

This invention discloses the application of a temperature-controlled phase-transfer Pd nanocatalyst in the Heck reaction, belonging to the field of nanocatalyst technology. This invention achieves reversible migration of the catalyst between the aqueous and organic phases with temperature changes by introducing functional groups with both polyether segments and hydrogen bonding on a traditional arylphosphine framework. Simultaneously, the large-volume groups on the ligands enhance the electron density and stability of the palladium center. The temperature-controlled phase-transfer Pd nanocatalyst prepared by this invention exhibits excellent catalytic activity in the Heck reaction at 85℃, with a conversion rate exceeding 75%; furthermore, this catalytic system shows good stability in the aqueous / organic two-phase system and can be reused at least four times.

The present application relates to a kind of nitrogen-rich acylhydrazone-based covalent organic framework material and its preparation method and application, to 5'-(4-(hydrazine carbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-tri phenyl]-4,4''-dicarboxylic dihydrazine, 1,3,5-tri (2-formylpyridine-5yl) Benzene and 4,4',4''-(1,3,5-triazine-2,4,6-triazyl) triphenyl formaldehyde as building unit, synthesis using Schiff base reaction.The nitrogen-rich acylhydrazone-based covalent organic framework material of the present application has good chemical stability, and can be used as carrier by metal coordination effect Palladium nanoparticles are loaded to obtain composite material, and the composite material shows excellent catalytic activity and substrate universality in catalyzing Heck reaction, has potential application value in the field of biological medicine and green chemistry.

The invention discloses a spirosilane-derived phosphine-phosphine oxide compound as well as a preparation method and application thereof. The invention specifically discloses a spirosilane-derived phosphine-phosphine oxide compound as shown in a formula I or a formula II, which can be used for catalyzing an asymmetric Heck reaction and an asymmetric Sonogashira reaction, and has one or more of the following advantages: the catalytic activity is high; the enantioselectivity of the product is high.

This application relates to the field of crosslinking agent technology, and in particular to an electronic crosslinking agent having two curing groups, its preparation method, and its application. The preparation method of the electronic crosslinking agent having two curing groups includes the following reaction steps: S1. Adding a solvent, fluorene, 4-vinylbenzyl chloride, a strong base, and a phase transfer catalyst to a reaction vessel, and reacting under an inert atmosphere, continuous stirring, and constant temperature conditions, sequentially performing descaling solvent removal, extraction, washing, and descaling solvent removal from the organic phase to obtain the target intermediate product; S2. Adding a solvent, the target intermediate product, 4-bromobenzocyclobutene, Heck reaction ligand, a weak base, and a phase transfer catalyst to a reaction vessel, adding a palladium catalyst under an inert atmosphere, and reacting under continuous stirring and constant temperature conditions, sequentially performing descaling solvent removal, extraction, washing, descaling solvent removal from the organic phase, and recrystallization to obtain the electronic crosslinking agent having two curing groups.

The application relates to the technical field of organic synthesis, and particularly relates to a method for synthesizing chiral diene compounds from aromatic hydrocarbons and alkynes. A simple aromatic hydrocarbon compound is designed to be in-situ constructed into an arylthianthrene onium salt under the action of an electrophilic activation reagent, then a palladium catalyst and a chiral ligand are used to catalyze the asymmetric Heck reaction of the arylthianthrene onium salt constructed in-situ and alkynes, so that a trisubstituted chiral diene compound is quickly and efficiently constructed. The method has mild conditions, a wide substrate range, excellent enantioselectivity and yield, and can introduce a chiral diene fragment into salicylate and indometacin which have anti-inflammatory and analgesic activities.

The invention discloses a preparation method of a siloxane-based fluorescent material for detecting trifluralin under sunlight, and particularly relates to the field of high polymer materials, vinyl siloxane and various brominated compounds are used as raw materials, and the siloxane-based fluorescent material is prepared based on a Heck reaction under the action of a catalyst; the siloxane-based material synthesized by the method disclosed by the invention has the fluorescence quantum yield up to 90%, and emits macroscopic blue-violet light under sunlight; according to the invention, trifluralin can be detected under sunlight, and the method has the characteristics of low detection limit, high sensitivity, good selectivity and rapid response.