24 results about "Oxidative cyclization" patented technology

The invention relates to a non-natural cannabinoid synthase comprising at least one amino acid variation as compared to a wild type cannabinoid synthase Δ9-tetrahydrocannabinolic acid synthase (THCAS), comprising three alpha helices (αA, αB and αC) where a disulfide bond is not formed between alpha helix αA and alpha helix αC, wherein the non-natural cannabinoid synthase catalyzes the oxidative cyclization of cannabigerolic acid (CBGA) into a cannabinoid. The invention further relates to a non-natural Δ9-tetrahydrocannabinolic acid synthase (THCAS), a non-natural cannabidiolic acid synthase (CBDAS), and a non-natural cannabichromenic acid synthase (CBCAS) comprising at least one amino acid variation as compared to a wild type THCAS, CBDAS, or CBCAS, respectively, comprising three alpha helices (αA, αB and αC) and wherein a disulfide bond is not formed between alpha helix αA and alpha helix αC. The invention also relates to a nucleic acid, expression construct, and engineered cell for making the non-natural THCAS, CBDAS, and / or CBCAS. Also provided are compositions comprising the non-natural THCAS, CBDAS, and / or CBCAS; isolated non-natural THCAS, CBDAS, and / or CBCAS enzymes; methods of making the isolated enzymes; cell extracts comprising cannabinoids; and methods of making cannabinoids.

This invention relates to the field of oilfield chemical additives technology, and discloses a method for preparing a 1-benzyl-10-phenylpyrrolo[1,2-a:3,4-b']dipyrazine-1-onium type quaternary ammonium salt high-temperature acidizing corrosion inhibitor. The method uses 2,2'-piperazine as the starting material, which undergoes a quaternization reaction with benzyl bromide to obtain a quaternary ammonium salt intermediate. The obtained intermediate undergoes an oxidative cyclization reaction with benzaldehyde and manganese dioxide in a dichloromethane system. After separation, drying, and purification, the target product is obtained. The preparation process of this invention is simple and easy to control, the product is easy to purify, and it is suitable for industrial production. It exhibits good synergistic effects with additives, excellent water solubility and compatibility, can stabilize and protect steel, reduce construction risks, and is suitable for various high-temperature acidizing operations.

This application discloses a method for synthesizing chiral cyano-containing full-carbon quaternary cyclic compounds, characterized by the following steps: mixing a solvent, an oxidant, an alkynyl malononitrile compound, a carboxylic acid compound, a palladium salt, and a chiral dinitrogen ligand; reacting the mixture; drying; and separating to obtain the chiral cyano-containing full-carbon quaternary cyclic compound. This method can achieve a palladium-catalyzed tandem reaction of alkynyl malononitrile with a carboxylic acid involving asymmetric acyl oxidative cyclization / acyl migration, yielding cyano-containing full-carbon quaternary cyclic compounds with optical purity in good yields (enantiomer ratios up to 96.5:3.5). This invention features a broad substrate range, readily available raw materials, simple and practical operation, and mild reaction conditions.

The application belongs to the field of organic chemistry and particularly relates to a synthesis method of berberine hydrochloride. The method comprises the following steps: taking 3,4-dimethoxyphenethylamine hydrochloride and 3,4-methylenedioxybenzaldehyde as starting materials, sequentially undergoing oxidative cyclization, selective reduction and quaternary ammonium ring closure through three-step reactions, and finally directly obtaining the target product berberine hydrochloride through acid treatment. The technical scheme has the characteristics of high efficiency, simplicity, and high industrial cost ratio in the synthesis of berberine hydrochloride, the overall reaction is more green and safe, the reaction condition is more mild, the reaction process has high selectivity, and the berberine hydrochloride product with higher purity can be obtained.

The invention belongs to the field of total synthesis of natural products, and relates to a method for asymmetrically synthesizing a natural product (+)-Tronanocarpine. According to the method, a known compound S1 and commercially available 4-cyclohexanone carboxylic acid are taken as synthesis starting points, and manganese-mediated oxidative cyclization is utilized to construct a key indolo-azabicyclo [3.3. 1] bridged ring system. The preparation method comprises the following steps: introducing an exocyclic aldehyde group through a recarburization reaction, and further carrying out a nucleophilic addition reaction and deprotection spontaneous cyclization to obtain seven-membered ring lactam to obtain a basic skeleton precursor of (+)-Tronanocarpine. Finally, the asymmetric total synthesis of the (+)-Tronanocarpine is realized through a series of functional group conversion such as lithium triethylborohydride selective reduction amide, Dess-Martin oxidation reaction and the like. The method lays a material foundation for subsequent research on pharmacological values of the natural products and development of anticancer innovative drugs for reversing multidrug resistance.

The invention provides a method for preparing a pyrrolo [2, 3-b] indole derivative, and relates to the technical field of indole compound preparation, tryptophan derivative is used as a substrate, in an unseparated electrolytic tank, in the presence of a solvent, an additive and an electrolyte, constant current is introduced into the electrolytic tank for electrolytic reaction, intramolecular oxidation cyclization is realized, and the pyrrolo [2, 3-b] indole derivative is constructed. According to the invention, electrons are used as a unique oxidant, reaction driving can be realized under the condition that no additional chemical oxidant or metal catalyst is needed, and element impurities and post-treatment difficulty are obviously reduced; on the other hand, the additive plays roles of electron transfer and stable reaction proceeding and reaction trend, so that efficient ring-merging conversion is realized on the premise of simple reaction conditions; and on the other hand, the reaction conditions are mild, and good compatibility is shown for various protecting groups and functional groups, so that the application range of the substrate is wide.

The application discloses a method for synthesizing alpha-tertiary carbon hyperallylic amine from non-activated olefin by nickel catalysis, which comprises the following steps: in an organic solvent, using metal nickel as a catalyst and metal manganese as a reducing agent, making imine and non-activated olefin to generate alpha-tertiary carbon hyperallylic primary amine through oxidative cyclization coupling. The application has the advantages of simple preparation of raw materials, cheap and easy purchase of catalyst and reducing agent, mild reaction condition, non-toxic and harmless, high reaction selectivity and yield, good compatibility of substrate functional groups and wide application range. The application can well realize the oxidative cyclization reaction of olefin and imine. Under the optimized reaction condition, the yield of the target product can be up to 92% after separation.

The present disclosure relates to a non-natural flavin-dependent oxidase that does not comprise a disulfide bond and that is capable of oxidative cyclization of a prenylated aromatic compound into a cannabinoid. In some embodiments, the non-natural flavin-dependent oxidase comprises: (i) at least 70% sequence identity to SEQ ID NO: 3; and (ii) substitutions at amino acid positions Q275, C285, V323, E370, V372, N400, D404, and T438, wherein the amino acid positions correspond to SEQ ID NO:3. The present disclosure further relates to a polynucleotide, an expression construct, and an engineered cell for making the non-natural flavin-dependent oxidase. Also provided are a composition comprising the non-natural flavin-dependent oxidase; an isolated non-natural flavin-dependent oxidase and methods of making the same; a cell extract or cell culture medium comprising the non-natural flavin-dependent oxidase; and methods of making a cannabinoid.

This invention discloses an N-N axial chiral phase-transfer catalyst, its synthesis method, and its applications, belonging to the field of asymmetric catalytic synthesis technology. Using chiral 2,4-pentanediol and N-Boc-indolephenol as starting materials, this invention efficiently constructs an N-N axial chiral biscarbazole cyclic ether skeleton through a five-step reaction involving Mitsunobu etherification, deBoc protection, PIDA oxidative cyclization, radical bromoxymethylation, and intramolecular quaternization. This method eliminates the need for complex chiral resolution and noble metal coupling, employs mild reaction conditions, uses readily available and inexpensive starting materials, achieves high overall yield, and yields a product with an axial chirality ee value ≥98%. The resulting catalyst possesses excellent conformational rigidity, chiral induction ability, and phase-transfer performance, exhibiting broad substrate applicability. It also possesses bisindole ring bioactivity, making it widely applicable in asymmetric catalytic synthesis in pharmaceuticals, fine chemicals, and other fields, and providing new directions for the development of antibacterial and antitumor biomaterials.

The application discloses a synthesis method of a trivalent rhodium covalent organic framework catalyst. The method comprises the following steps: uniformly mixing 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 2,2'-bipyridine-5,5'-diformaldehyde in an organic solvent, and then sequentially undergoing an acetic acid catalyzed Schiff base condensation reaction, an oxidative cyclization reaction and a trivalent rhodium metallization process, and finally obtaining a trivalent rhodium covalent organic framework. The pi-conjugated system based on the covalent organic framework has good chemical stability, thermal stability and atomically dispersed trivalent rhodium active centers, and the covalent organic framework can be used for heat-driven or light-driven trivalent rhodium catalytic region-selective C(sp 2 )‑H bond functionalization, and realizes effective recycling of the trivalent rhodium in the region-selective C(sp 2 )‑H bond functionalization.

INVENTION NAME: Preparation method of 3-(pyridine-2-yl)imidazo[1,5-a]pyridine Abstract: The application discloses a one-step oxidative cyclization reaction for preparing 3-(pyridine-2-yl)imidazo[1,5-a]pyridine product by taking dimethylpyridine amine as raw material and using cheap copper catalyst. The new method has the advantages of mild reaction condition, wide raw material source, low cost, clean catalytic process, no need of noble metal catalyst and no need of complex and expensive ligand. The method can provide an effective way for green and clean preparation of important "Lego building block molecule" 3-(pyridine-2-yl)imidazo[1,5-a]pyridine product.

The invention belongs to the technical field of medicine synthesis, and particularly relates to a brand-new efficient furosemide-D5 synthesis method which comprises the following steps: starting from a simple raw material trans-2, 3-dibromo-2-butene-1, 4-diol and the like, performing oxidative cyclization, low-temperature metallization-carboxylation, lewis acid catalytic bromination, catalytic deuteration, LiAlD4 reduction and the like to obtain furosemide-D5. And the furosemide-D5 molecule is efficiently synthesized by a relatively short linear step. The synthesis reaction raw materials are easy to obtain, the operation is simple and safe, less waste is generated, the isotope raw material utilization rate is high, and the deuterium atoms are subjected to precise fixed-point substitution reaction.

The application discloses a kind of overcharge-preventing lithium battery electrolyte and its preparation method in the technical field of lithium ion battery, the electrolyte uses the composite system of carbonate solvent and fluorine-containing solvent, cooperates mixed lithium salt and two new additives: difluorocyclohexyl benzothiazolium hexafluorophosphate and 2,4,6-tri (cyanoacetic acid methyl ester group) -1,3,5-triazine.The preparation process includes solvent mixing, lithium salt dissolving, additive adding and multi-step purification process.Two additives are prepared by oxidation cyclization, quaternary ammonium and esterification, condensation reaction.The electrolyte has high conductivity and lithium ion transference number, high oxidation potential, good thermal stability, can effectively inhibit electrolyte decomposition and metal ion dissolution under overcharge condition, significantly improves the high-voltage stability and safety of lithium battery, and is suitable for high-voltage lithium battery, electric vehicle power battery and large-scale energy storage system and other fields.

The invention discloses an anti-overcharge lithium battery electrolyte and a preparation method thereof in the technical field of lithium ion batteries, the electrolyte adopts a composite system of a carbonic ester solvent and a fluorine-containing solvent, and is matched and mixed with a lithium salt and two novel additives: difluorocyclohexyl benzothiazolium hexafluorophosphate and 2, 4, 6-tri (methyl cyanoacetate)-1, 3, 4-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1 and 2, 3, 5-triazine is obtained. The preparation method comprises the steps of solvent mixing, lithium salt dissolving, additive adding and multi-step purifying. The two additives are respectively prepared through oxidative cyclization, quaternization, esterification and condensation reaction. The electrolyte has high conductivity and lithium ion transference number, high oxidation potential and good thermal stability, electrolyte decomposition and metal ion dissolution under the overcharge condition can be effectively inhibited, the high-voltage stability and safety of the lithium battery are remarkably improved, and the electrolyte is suitable for the fields of high-voltage lithium batteries, electric vehicle power batteries, large-scale energy storage systems and the like.

The application belongs to the technical field of preparation of benzoxazine derivatives, and provides a method for preparing benzoxazine derivatives, which comprises adding 2-methylquinoline, o-aminobenzyl alcohol compounds and dimethyl sulfoxide into an electrolytic cell for reaction. The application realizes the oxidative cyclization conversion of related substrates in a high efficiency by synergistic effect of electrochemical promotion and thermal promotion, proposes a strategy taking electrons as clean reaction driving force, realizes the cyclization reaction of 2-methylquinoline and o-aminobenzyl alcohol in a high efficiency under mild conditions without additional chemical oxidants, significantly improves the synthesis efficiency and selectivity of target benzoxazine derivatives, and exhibits more prominent technical advantages and application potential compared with traditional methods.

The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a phenanthrene benzofuran compound. The phenanthrene benzofuran compound is obtained by taking a biphenyl benzofuran compound as a raw material, mixing the raw material, an oxidizing agent and a solvent and carrying out photooxidation cyclization reaction on the raw material under the condition of ultraviolet irradiation and the action of the oxidizing agent. The method does not need to use a transition metal catalyst or an acid-base catalyst, and is simple to operate, mild in reaction condition, easy to control and suitable for industrial production. In addition, the phenanthrene benzofuran compound synthesized by the method disclosed by the invention shows potential anti-tumor activity.

The application discloses a flavonol fluorescent probe for detecting biological amine, a preparation method thereof and a fluorescent spin coating film application thereof. The application takes 3'-hydroxy-4'-acetyl.[1,1'-biphenyl]-4-carboxylic acid as a starting material, and performs a hydroxy aldehyde condensation reaction with 2,4,6-trimethoxybenzaldehyde to prepare 3'-hydroxy-4'-(3-(2,4,6-trimethoxyphenyl) acryloyloxy)-[1,1'-biphenyl]-4-carboxylic acid (HTC); the HTC is subjected to oxidative cyclization under alkaline conditions to obtain 4-(2-(2,4,6-trimethoxyphenyl)-3-hydroxy-chromone-7-yl) benzoic acid (HTBA); the HTBA is further subjected to esterification with 4-cyanobenzoyl chloride to prepare 4-(2-(2,4,6-trimethoxyphenyl)-3-((4-cyanobenzoyl)oxy)-chromone-7-yl) benzoic acid (CTBA). Under the irradiation of 365nm ultraviolet light, after a DMF / 10mM PBS buffer (v / v=1 / 9) solution of the CTBA is added with biological amine cadaverine, the fluorescence color of the solution changes from light blue to bright yellow, and the detection limit of the biological amine reaches 3.6*10 ‑7 M, and the CTBA has a good application prospect as a fluorescent probe for detecting biological amine.

The invention discloses a polyacrylonitrile-based carbon fiber preparation method, which comprises: adding a modifier accounting for 2.5-8.0% of the total mass of a copolymer into a copolymer spinning solution composed of acrylonitrile and a carboxyl-containing monomer, uniformly mixing, spinning, post-treating, pre-oxidizing and carbonizing to prepare the polyacrylonitrile-based carbon fiber. Test results show that the modifier (guanidine compounds or salts thereof) is uniformly distributed in the fiber body and cooperates with carboxyl to catalyze a pre-oxidation cyclization reaction, so that the cyclization initial temperature is reduced by 8-15 DEG C, the exothermic enthalpy is improved by 15-35%, and the problem of'skin-core structure 'caused by traditional impregnation modification is effectively avoided. According to the method, the carbon yield can be finally increased to 52% or above, the tensile strength of the obtained carbon fiber monofilament is not lower than 4.6 GPa, and the performance uniformity is good.

The application discloses a chiral cis-hydrobenzofuran compound and a preparation method thereof. A mixture containing a compound shown in a formula I, a compound shown in a formula II, an oxidant and a catalyst is subjected to asymmetric acyloxylation cyclization reaction to obtain a chiral cis-hydrobenzofuran shown in a formula III. Through the method, the cis-hydrobenzofuran with optical purity (the enantiomer ratio can reach 98:2) can be obtained at a high yield. The application has high enantioselectivity, a wide substrate range, simple operation, mild reaction conditions, low energy consumption, environmental friendliness and good yield.

This invention discloses a method for preparing 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, belonging to the field of organic synthesis technology. Using 1,3,5,7-cyclooctatetraene as a starting material, the method involves oxidative cyclization, ammonolytic cyclization, Boc protection and silane ether protection, secondary alcohol oxidation, deBoc acetylation, oximeization, geminitrohydration, and nitration to finally synthesize 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate. The synthesis method is simple, and the final product exhibits stable properties. This invention addresses the lack of research on "azaadamantanes" (alkanes with nitrogen and oxygen heteroatoms synergistically introduced onto the same adamantane skeleton) and the general lack of substituents available for in-depth functionalization in existing adamantane skeleton construction methods. Furthermore, it introduces six explosive groups into the synthesized skeleton, resulting in a product with high density and excellent detonation performance.

The invention belongs to the field of organic chemistry, and particularly relates to a synthetic method of berberine hydrochloride. The method comprises the following steps: taking 3, 4-dimethoxyphenylethylamine hydrochloride and 3, 4-methylenedioxybenzaldehyde as starting raw materials, carrying out three-step reaction in sequence, sequentially carrying out oxidative cyclization, selective reduction and quaternization ring closing, and finally directly obtaining the target product berberine hydrochloride through acid treatment. The technical scheme has the characteristics of high efficiency, simplicity and high industrial cost performance in synthesis of berberine hydrochloride, the whole reaction is green and safe, the reaction conditions are mild, the reaction process has extremely high selectivity, and a berberine hydrochloride product with higher purity can be obtained.

The application belongs to the technical field of medicine synthesis, and particularly relates to a novel and efficient furosemide-D5 synthesis method. The furosemide-D5 molecule is efficiently synthesized in a short linear step from simple raw materials such as trans-2,3-dibromo-2-butene-1,4-diol and the like through an oxidation cyclization, a low-temperature metallization-carboxylation, a Lewis acid catalysis bromination, a catalytic deuterium decomposition and a LiAlD4 reduction and the like. In the application, the synthesis reaction raw materials are easy to obtain, the operation is simple and safe, waste is less, the isotopic raw material utilization rate is high, and the precise site substitution reaction of deuterium atoms is realized.

The utility model discloses a production device of isothiazolinone, and relates to the technical field of isothiazolinone production, an inlet of a synthesis kettle is respectively communicated with a 2-methyl-2, 4-pentanediol tank, a carbon disulfide tank and a sodium hydroxide solution tank, an outlet of the synthesis kettle is communicated with a hydrolysis kettle, an inlet of the hydrolysis kettle is communicated with a hydrochloric acid solution tank, and an outlet of the hydrolysis kettle is communicated with a sodium hydroxide solution tank. An outlet of the hydrolysis kettle is communicated with a cyclization kettle, and an inlet of the cyclization kettle is communicated with a liquid chlorine tank; an outlet of the cyclization kettle is communicated with a distillation kettle, and a bottom outlet of the distillation kettle is communicated with a finished product tank. The method comprises the following steps: reacting 2-methyl-2, 4-pentanediol with carbon disulfide under an alkaline condition to generate dithiocarbonate, hydrolyzing with an acid to obtain an intermediate 2-methyl-2, 4-pentanedithiol, oxidizing and cyclizing with liquid chlorine at a low temperature, introducing chlorine atoms, and distilling and purifying the obtained reaction mixture to obtain an isothiazolinone product. The safety and the product yield are high, and the production cost is reduced.

The invention discloses a preparation method of eplerenone and an intermediate of eplerenone, and belongs to the technical field of chemical synthesis of medicines, and the preparation method comprises the following steps: by taking 9 alpha-hydroxy-4-androstene-3, 17-diketone which is low in price and easy to obtain as an initial raw material, firstly, constructing a delta9, 11-double bond with high selectivity through an acidic dehydration reaction; then, a gamma-lactone ring is efficiently constructed through 3-position carbonyl protection, 17-position propynylation and oxidative cyclization reaction, and an intermediate delta 9, 11-canrenone is obtained; further efficiently introducing carboxyl into the C7 site of the intermediate through a photocatalytic flow chemical technology, and finally preparing eplerenone through esterification and 9alpha, 11alpha-stereoselective epoxidation. The method is novel in route design, avoids the difficulty in selectivity and the use of toxic reagents in the traditional method, and is mild in condition in each step, high in yield, high in purity and suitable for industrial production.