18 results about "Oxidative addition" patented technology

The invention relates to the technical field of organic chemistry, in particular to a method for synthesizing a benzothiophene coupling product through a non-metal-participated anchoring-migration strategy. The method comprises the following steps: taking a benzothiophene compound or a benzothiophene sulfoxide compound as a reaction substrate, mixing the reaction substrate with an aryl nucleophilic reagent in the presence of an anhydride activator and a solvent, and carrying out nucleophilic substitution reaction to obtain benzothiophene sulfonium salt; the preparation method comprises the following steps: mixing benzothiophene sulfonium salt with an organic solvent, and carrying out metal-catalysis-free intramolecular migration reaction to form a carbon-carbon bond at the C2 site of benzothiophene, thereby obtaining the benzothiophene coupling product. The preparation conditions are mild, the operation is simple and convenient, a traditional oxidation addition-reduction elimination process is replaced by an anchoring-migration strategy, protection of a noble metal catalyst, a complex ligand, strong base or inert gas is not needed, and the problems of high cost, metal residues, harsh reaction conditions and limited substrate applicability in the prior art are fundamentally solved.

The application relates to a method for synthesizing 1,1-bisaryl compounds by using non-activated alkenes, and belongs to the fields of organic synthesis methods and electrochemical catalysis. The application solves the technical problem that the existing reaction technology cannot realize efficient coupling of non-activated alkenes and halogenated arenes to generate 1,1-bisaryl compound products. In the application, a nickel catalyst is reduced on a cathode by a constant current under an inert gas atmosphere, then a secondary oxidative addition is carried out with another halogenated arene, and finally a 1,1-bisaryl compound product is generated through a reductive elimination step. The nickel catalyst circulates in the reaction by maintaining its valence state under electrochemical conditions, effectively avoiding the use of an additional chemical reducing agent, simplifying the operation and reducing the environmental burden. The reaction system of the application has high efficiency and universality, and can be applied to various halogenated arenes and non-activated alkenes under mild conditions, and has significant application value in the modification and synthesis of natural products and drug molecules.

This invention discloses a method for synthesizing a full-carbon quaternary carbocyclic ketone-spirocyclic pseudoindole derivative. This method uses a metal carbonyl compound as a safe carbonyl source and involves a catalytic cycle from zero-valent palladium to divalent palladium. Specifically, it involves the oxidative addition of palladium(O) via a carbon-halogen bond, the coordination and migration insertion of CO to form a carbonyl palladium species, followed by nucleophilic attack of the indole C3 ring to achieve dearomatization of the indole ring, and then reductive elimination to obtain the full-carbon quaternary carbocyclic ketone-spirocyclic pseudoindole derivative. Specifically, compound 1 and the metal carbonyl compound Co2(CO)8 are reacted under heating conditions with palladium as a catalyst, organophosphine as a ligand, and sodium salt as a base to obtain the full-carbon quaternary carbocyclic ketone-spirocyclic pseudoindole molecule. This method is a novel synthetic method for full-carbon quaternary carbocyclic ketone-spirocyclic pseudoindole derivatives, solving the problems of existing technologies such as the need for multiple reaction steps, harsh reaction conditions, narrow substrate range, and high toxicity of starting materials.

The invention discloses a preparation method and application of phenyluracil, and belongs to the technical field of organic synthesis. The technical problems to be solved are to avoid the influence of amido bond dimethylation impurities on the product purity, reduce the production cost and improve the yield and the purity of the final product. The key point of the technical scheme is that a compound I-1 and a compound I-2 are subjected to a coupling reaction to obtain a compound I; the compound I-1 is shown in the specification; the compound I-2 is shown in the specification; the compound I is shown in the specification; the R1 group is selected from a group which can be subjected to oxidative addition with a palladium catalyst; and the R2 group is selected from hydrogen and methyl.

The application discloses a preparation method of a photoinitiator TPO and belongs to the field of photoinitiators. The preparation method of the photoinitiator TPO comprises the following steps: carrying out chlorination reaction on diphenyl phosphoric acid and a chlorinating agent to generate diphenyl phosphinic chloride; carrying out condensation reaction on the diphenyl phosphinic chloride and 2,4,6-trimethylbenzyl magnesium chloride to obtain (2,4,6-trimethylbenzyl) diphenyl phosphine oxide; and carrying out oxidation addition reaction on the (2,4,6-trimethylbenzyl) diphenyl phosphine oxide and an oxidizing agent to obtain the photoinitiator TPO. The diphenyl phosphoric acid originally as solid waste is fully utilized, waste is turned into treasure, energy is fully utilized, environmental protection pressure is reduced, the synthesis mode of the photoinitiator TPO is expanded, and the production cost of the photoinitiator TPO is reduced, and the economic and environmental friendliness of the photoinitiator TPO makes the preparation method convenient for large-scale popularization and application.

The invention discloses a homogeneous electro-catalysis chain type low-temperature methanol preparation method for biological natural gas. The method comprises the following steps: S1, constructing a PtII / PtIV redox cycle system, and forming a homogeneous electro-catalysis system by using acidic solution coordination ions as a reaction medium; s2, the biogas is introduced into a homogeneous electro-catalysis system, and a Pt II complex is adopted to generate a Pt II-methyl intermediate through an oxidative addition reaction; s3, oxidizing the Pt II-methyl intermediate into a PtIV-CH3 compound through a Pt IV complex, and reducing, eliminating and releasing methanol to regenerate a Pt II complex; s4, PtII species accumulated in the reaction are regenerated into PtIV through electrochemical cathode reduction, methanol is prepared through closed-loop circulation of the catalyst, and unreacted biogas is combusted to supply heat to other steps in the system while the unreacted biogas is subjected to circular reaction. The concentration of the methanol product obtained by the method provided by the invention is as high as 99.8%, and the method has the advantages of simple and convenient process, low cost, cleanness, high efficiency and wide application prospect.

The application provides a preparation method and application of a pre-activated Pd (II)-P catalyst, and belongs to the technical field of chemical catalysis. In the structure of the pre-activated Pd (II)-P catalyst, N and C are respectively coordinated with Pd (II) to construct a stable five-membered ring chelate system, ppy, X and PR3 jointly maintain the stability of the Pd (II) center in a "dormant state", and R-C-Pd-X bonds constitute the core site of the oxidative addition step in a coupling reaction, so that the oxidative addition energy barrier that needs to be overcome in the activation process of a catalytic precursor is avoided, and the activation of a new (PR3) n -Pd (0) is a key structural unit; the introduction of PR3 with large steric hindrance can enhance the "dormant state" stability of the Pd (II) center through the steric hindrance effect of ppy ligands, and can also prevent the Pd (0) generated by the reduction and activation of Pd (II) from agglomerating into palladium black, and improve the yield of a catalytic synthesis product.

The present application relates to a synthesis method of On-DNA 2-thioxoquinazolinone compounds, and belongs to the technical field of DNA coded compound library. The synthesis method comprises the following steps: firstly, On-DNA amine compounds are converted into On-DNA isothiocyanate compounds under the action of 1,1'-thiocarbonyldiimidazole; then the obtained On-DNA isothiocyanate compounds are subjected to oxidative addition reaction with isatoic anhydride compounds and tert-butyl hydroperoxide in an aqueous solvent system, so that On-DNA 2-thioxoquinazolinone compounds are obtained. The synthesis method has small damage to DNA, good substrate universality, high yield and low cost, is suitable for the construction of DNA coded compound library, and is conducive to promoting the development of On-DNA 2-thioxoquinazolinone drugs.

The invention relates to the technical field of organic synthesis, and provides an asymmetric carbon-hydrogen bond boronation reaction catalyst and a preparation method of chiral dicyclobutane. A catalyst composed of a chiral boron-based ligand and an iridium salt is adopted to catalyze an asymmetric carbon-hydrogen bond boronation reaction of prochiral dicyclobutane, in a reaction system, the iridium salt and the chiral boron-based ligand are combined to form a complex, the complex reacts with B2pin2 to form an active intermediate, and the active intermediate is separated from the chiral boron-based ligand to form the chiral dicyclobutane. Then the iridium center and a carbon-hydrogen bond of a 3-substituted dicyclobutane-1-formamide compound are subjected to an asymmetric oxidative addition reaction to form an iridium-carbon bond, then reduction elimination is carried out, and the target product chiral dicyclobutane is generated. The reaction condition for constructing the chiral dicyclobutane is mild, the selectivity is high, the enantioselectivity is 95% or above, the substrate universality is wide, and chiral dicyclobutane compounds of different structures can be synthesized.

The application provides a polyquinamine organic positive electrode material and a preparation method thereof. The polyquinamine organic positive electrode material is hardly soluble in an electrolyte, can effectively inhibit active material loss when applied to an ion battery, has a stable configuration structure of embedding multivalent ions, and is suitable for a multivalent ion battery. The polyquinamine organic positive electrode material is prepared by the following two methods: method one: 1,4-benzoquinone and 1,2-cyclohexanediamine are used as reaction raw materials, dissolved in a reaction solvent, and subjected to an oxidative addition reaction for preparation; and method two: 2,5-dichloro-1,4-benzoquinone and 1,2-cyclohexanediamine are used as reaction raw materials, dissolved in a reaction solvent, and subjected to a condensation reaction under inert gas protection for preparation. The polyquinamine organic positive electrode material exhibits good capacity performance and cycle performance in a zinc ion battery, and the highest discharge specific capacity can reach 138 mAh g ‑1 -1 under a current density of 0.02 Ag ‑1 -1, and the discharge specific capacity can be maintained at 78 mAh g ‑1 -1 after 200 charge-discharge cycles.

This invention relates to a method for synthesizing phenylhydrazine hydrochloride, belonging to the field of pharmaceutical synthesis technology. Using palladium chloride as a catalyst and sodium ethoxide as a basic agent, under conditions of 50-55°C, an oxidative addition reaction first occurs with the bromine atom on a haloaromatic compound with a bromine atom at the para position, increasing the oxidation state of palladium and forming a highly reactive palladium intermediate. Sodium ethoxide neutralizes the generated hydrogen bromide, driving the reaction forward. The lone pair electrons on the nitrogen atom in hydrazine hydrate attack the palladium intermediate, undergoing a nucleophilic substitution reaction, attaching the nitrogen atom to the carbon atom bonded to the bromine atom. The palladium intermediate then undergoes a reduction reaction, restoring the oxidation state of palladium and generating phenylhydrazine compounds. Simultaneously, palladium chloride is regenerated and can continue to participate in the catalytic cycle. Ethanol serves as the reaction solvent, providing a homogeneous environment for the reaction. Hydrochloric acid is then added to the reaction system, where hydrogen ions combine with the nitrogen atom in the phenylhydrazine molecule to form a stable salt.

The invention discloses a preparation method of chiral propargyl substituted aldehyde compounds in the technical field of organic synthesis, which comprises the following steps: reacting propargyl acetate with aldehyde in a catalytic system of alkali, a palladium catalyst and a chiral ligand, and preparing a series of chiral propargyl substituted aldehyde compounds in a sealed tube in an inert argon environment; in the preparation method disclosed by the invention, the raw materials used in the reaction system, such as propargyl acetate and aldehyde, can be prepared by a simple method. According to the reaction, through continuous palladium catalytic oxidation addition, olefin migration insertion and reduction elimination, the chiral propargyl substituted aldehyde compound can be obtained through one-step conversion. The preparation method has the advantages of mild reaction conditions, wide substrate expansion range, simple preparation operation and the like; the chiral thiourea small-molecule catalyst can be converted into a series of important heterocyclic compounds and has important significance, and the chiral thiourea small-molecule catalyst can be further applied to asymmetric catalytic reaction and has excellent enantioselectivity.

The invention relates to the technical field of organic catalytic synthesis, and particularly discloses synthesis of an upatinib base fragment, through a catalytic system composed of palladium and phosphine ligands, the catalytic efficiency is remarkably improved, the production cost is greatly reduced, the palladium center is greatly activated through the unique electronic effect and steric hindrance characteristics of the ligands, and the yield of the upatinib base fragment is improved. Compared with the prior art, the method has the advantages that the rate of oxidative addition and reduction elimination is remarkably increased, the dosage of the catalyst is reduced to 0.05 mol%, the consumption of expensive noble metal is greatly reduced, the cost of raw materials is remarkably reduced, the treatment pressure of metal residues is relieved, the excellent yield of 95% or above can still be obtained under the condition of low palladium catalyst loading capacity, the reaction selectivity is extremely high, the reaction conditions are mild, and the method is suitable for industrial production. The method is simple in operation, friendly to operators and suitable for coupling of tert-butyl carbamate and coupling of ethyl carbamate, and a flexible and efficient universal solution is provided for different synthesis process routes of upatinib.

A method for synthesizing a pimozide intermediate, the present invention relates to the field of organic synthesis and electrochemical catalysis. The present invention solves the technical problem of efficiently coupling non-activated olefins with halogenated aromatics to generate 4,4,-bis(4-fluorobenzene)chlorobutane in the prior art. The present invention utilizes electrochemical catalysis means, and under an inert gas atmosphere, a nickel catalyst is reduced by a constant current, an oxidative addition reaction occurs with the halogenated aromatics, and then added to the non-activated olefin, a nickel migration reaction occurs, and an aromatic-displaced nickel compound intermediate is formed. The present invention greatly reduces the synthesis steps, improves the efficiency and selectivity of the reaction, and especially when synthesizing the pimozide intermediate, can significantly reduce production costs and reaction time, showing stronger industrial application potential. The pimozide intermediate prepared by the present invention is used to treat the field of chronic mental disorders.

The invention relates to a synthetic method of phenylhydrazine hydrochloride, which belongs to the technical field of drug synthesis, and comprises the following steps: by taking palladium chloride as a catalyst, carrying out oxidative addition reaction on the palladium chloride and bromine atoms on halogenated aromatic compounds of which the para-position is bromine atoms at 50-55 DEG C to increase the oxidation state of palladium so as to form a palladium intermediate with higher activity; lone pair electrons on a nitrogen atom in hydrazine hydrate attack the palladium intermediate, a nucleophilic substitution reaction is carried out, the nitrogen atom is connected to a carbon atom connected with a bromine atom, the palladium intermediate is subjected to a reduction reaction, the oxidation state of palladium is recovered, the phenylhydrazine compound is generated, meanwhile, palladium chloride is regenerated and can continue to participate in a catalytic cycle, and in the process, the palladium intermediate is subjected to a reduction reaction. Ethanol is used as a reaction solvent to provide a homogeneous environment for the reaction, promote effective collision among reactant molecules and play a role in promoting the reaction, then hydrochloric acid is added into the reaction system, and hydrogen ions in the hydrochloric acid are combined with nitrogen atoms in phenylhydrazine molecules to form stable salts.

The invention provides a low-valence metal complex with a stable N-heterocyclic germanium carbene ligand as well as a preparation method and application of the low-valence metal complex, and belongs to the technical field of metal organic chemistry. According to the low-valence metal complex, aza-germanium ring carbene is taken as a center, and a series of metal complexes are obtained by changing different substituent groups and different metals on a central ligand. The preparation method comprises the following steps: uniformly mixing an NHGe ligand, a metal precursor and DMA, and stirring and reacting at 60 DEG C for 24 hours to obtain the low-valence metal complex with the stable N-heterocyclic germanium carbene ligand. The preparation route is simple, the production efficiency is high, when a substituent group with large steric hindrance and strong electron donating is introduced to the ligand, the electron donating ability of the ligand can be improved, the oxidative addition ability of metal to inert bonds can be promoted, meanwhile, the reduction elimination ability of the metal can be promoted, the method can be used in cross coupling reaction, efficient activation of phenolic derivatives is achieved, and the method is suitable for industrial production. And the catalyst has higher catalytic efficiency.

The present invention discloses a method for synthesizing a carbonyl-containing, all-carbon, quaternary carbon spiroindoline. The method involves a zero-valent palladium catalytic cycle, i.e., oxidative addition of palladium (0) via a carbon-halogen bond, coordination of carbon monoxide and migration insertion to form a carbonyl palladium species, and then dearomatization of the indole ring via nucleophilic attack of indole C3, followed by reduction and elimination to obtain a carbonyl-containing, all-carbon, quaternary carbon spiroindoline derivative. Specifically, compound 1 and carbon monoxide gas are reacted under heating conditions using palladium as a catalyst, an organic phosphine as a ligand, and a sodium salt as an alkaline agent to obtain a carbonyl-containing, all-carbon, quaternary carbon spiroline molecule. The method is a novel method for synthesizing a carbonyl-containing, all-carbon, quaternary carbon spiroindoline, which solves the problems of the prior art, such as the need for multi-step reactions, harsh reaction conditions, a narrow substrate range, and high raw material toxicity.