42 results about "Cyclopropanation" patented technology

The application discloses a chiral fluorocyclopropane carboxylate and a preparation method thereof. Under the catalysis of divalent rhodium, ethyl aryl diazoacetate and fluorostyrene are reacted through an asymmetric cyclopropanation reaction to generate a chiral fluorocyclopropane compound. Different substitution types of substrates in the system are expanded, and good universality is shown. Various types of substituted substrates can smoothly participate in the reaction to synthesize 12 fluorocyclopropane ester substrates with a yield of 56-89%, 82-99% ee and a highest >20.0:1.0 dr. The application efficiently realizes the introduction of a fluorine atom to a cyclopropane skeleton, and efficiently constructs the fluorocyclopropane compound under mild conditions, thereby providing a new strategy which is simple, efficient and has strong universality for the synthesis of the important compound.

The application discloses a preparation method of a cyclopropane compound and application of the cyclopropane compound in nematode killing activity. The application uses an electrochemical method to quickly cyclopropanate a methylene compound by using a cheap and easily available sulfide. The synthesis method is simple, clean, efficient, short in reaction time, low in energy consumption, and cheap and easily available in raw materials, and is suitable for mass production and better research. Through activity testing, the cyclopropane compound has strong activity against pine wood nematode disease, and relevant research provides a good basis for strong biological activity, anticancer activity, antibacterial activity and anti-inflammatory activity.

The invention provides a cyclopropane skeleton monophosphine ligand, an adduct, a palladium complex and a preparation method and application thereof, and belongs to the technical field of monophosphine ligand preparation. The monophosphine ligand (cyclopropane skeleton monophosphine ligand) with a gem-diaryl cyclopropane structure is finally obtained through a series of reaction steps of cyclopropanation, debromination, substitution and the like by taking 1, 1-stilbene as an initial raw material. The synthesized monophosphine ligand can be subjected to coordination reaction with palladium salt to form a palladium complex with a specific structure and properties. According to the present invention, the synthesized gem-diaryl cyclopropane skeleton monophosphine ligand has excellent catalytic activity in the Buchwald-Harwig and Suzuki-Miyaura organic synthesis reaction, can significantly improve the efficiency and the selectivity of the reaction, and has good application potential and broad market prospects.

The present invention relates to cyclopropane skeleton monophosphine ligands and preparation methods for palladium complexes thereof and an application. Specifically, trans-diaryl substituted cyclopropane skeleton monophosphine ligands are synthesized after trans-1,2-diaryl ethylene undergoing the steps of cyclopropanation reaction, debromination reaction, substitution reaction, and the like. Palladium complexes prepared by coordinating the cyclopropane skeleton monophosphine ligands with a palladium salt show very high activity in catalyzing C—N bond coupling reactions, and have good application prospects.

The present invention is in the field of perfumery and relates to novel perfume compounds according to general formula (I) derived from campholenic aldehyde, having a sandalwood-based fragrance note and improved acid stability. Furthermore, the present invention also relates to perfume compositions comprising one or more compounds of the present invention. Moreover, the present invention relates to the use of these compounds or perfume compositions as flavor enhancers or for improving the odor fixation of perfume compounds or perfume compositions and for the preparation of perfumed products. In addition, the present invention also relates to the use of the compounds or compositions for the preparation of perfumed products and to the perfumed products themselves.

The invention belongs to the field of organic chemical synthesis, and relates to a method for synthesizing a natural product Pyrroloazocine indole alkaloid skeleton. According to the method, a commercially available compound 1 and phenylhydrazine are taken as synthesis starting points, and a [2.2. 2] bridge ring system is constructed through key Fischer indole synthesis, Stille coupling reaction and intermolecular Diels-Alder reaction. The preparation method comprises the following steps: carrying out a cyclopropanation reaction mediated by carbene, carrying out a Ley-Griffith oxidation reaction, and carrying out a Beckmann rearrangement and an intramolecular SN2 cyclization cascade reaction so as to realize the construction of the core skeleton of the Pyrroloazocine indole alkaloid. According to the method, a material basis can be provided for activity testing of the Pyrroloazocine indole alkaloid and the analogue thereof, and a thought is provided for synthesis route design of more complex cage-shaped indole alkaloid basic frameworks.

The invention relates to asymmetric catalyst systems and uses thereof. The asymmetric catalyst system comprises a copper catalyst, a ligand and a solvent, the solvent comprises a solvent of which the molecular structure contains a benzene ring; the ligand comprises at least one compound with the structure shown as the formula IV and the formula V. According to the preparation method, an asymmetric catalyst system with a specific structure and composition is selected, so that the problem of three-dimensional control caused by small energy difference of a cis / trans path in fluorocyclopropanation is solved, and high enantioselectivity and diastereoselectivity of the product are realized. Formula IV and formula V

The invention discloses a preparation method of irisone, which comprises the following steps of: performing condensation reaction on citral (compound II) serving as a raw material and acetone to obtain pseudoionone (compound III); the preparation method comprises the following steps: carrying out a cyclopropanation reaction with diethyl zinc and diiodomethane under the action of a catalyst to obtain a compound IV, carrying out an intramolecular cyclization reaction on the compound IV under the action of the catalyst, and carrying out post-treatment to obtain a compound I. The route is mild in reaction condition, simple and convenient to operate, stable in process and good in reaction selectivity; the proportion of alpha-irisone in the crude product of the compound I is high, the total yield can reach 78%, and the method is suitable for large-scale industrial production.

The invention discloses a method for synthesizing a polysubstituted furan compound through ring opening of gem-difluorocyclopropane, and belongs to the technical field of compound synthesis. The preparation method comprises the following steps: carrying out ring-opening defluorination-nucleophilic addition reaction on a gem-difluorocyclopropane compound, a carbonyl compound and a ligand in a solvent, and sequentially carrying out filtration, rotary evaporation and column chromatography after the reaction to obtain the polysubstituted furan compound. The method is simple and convenient to operate, the raw materials are easy to obtain, the reaction conditions are mild, the furan ring is efficiently constructed through the one-pot cascade reaction, and an efficient and practical new way is provided for synthesis of the polysubstituted furan compound.

The invention discloses a continuous preparation method for carrying out cyclopropanation reaction by using a microreactor. According to the method, a three-stage series bottom splashing microreactor system is adopted, and efficient and safe cyclopropanation reaction is realized through gradient catalysis design and accurate temperature control. A reaction system comprises olefin, a diazomethane precursor, alkali liquor and a solvent, wherein a catalyst adopts a gradient distribution design of SBA-15 and CeO2 loaded monatomic palladium. And the three-stage series bottom splashing microreactors are respectively controlled at different temperatures. The process is simple, high conversion rate and high safety are realized, and the cost is reduced.

The invention discloses a PNN ligand, a cobalt complex of the PNN ligand, a preparation method of the cobalt complex and application of the cobalt complex. The invention specifically provides a compound as shown in a formula 1. The PNN ligand and the metal complex thereof disclosed by the invention have excellent catalytic activity in a diastereoselective cyclopropanation reaction of alpha-olefin; the reaction selectivity and diastereoselectivity are excellent; the reaction yield is high; the reaction conditions are mild; the preparation method of the PNN ligand and the cobalt complex thereof is simple; raw materials are cheap and easily available; the post-treatment is simple; the method is relatively environment-friendly; the method is suitable for large-scale industrial production.

The application discloses a preparation method of 1,4-diazocane, which comprises the following steps: reacting an imidazoline compound with a cyclopropane compound in the presence of a Lewis acid catalyst and an organic solvent to obtain a compound with a structure shown in formula I: wherein R1 is selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaromatic group, substituted or unsubstituted C 2‑10 alkenyl, substituted or unsubstituted C 2‑10 alkynyl and substituted or unsubstituted C 1～6 alkyl; R2 is selected from C 2～10 ester group and nitrile group; and R3 is selected from substituted or unsubstituted phenyl. According to the application, the 1,4-diazocane is prepared through [5+3] cyclization of the imidazoline compound and the cyclopropane compound under the action of the Lewis acid catalyst, the raw material is cheap and easy to obtain, the operation is convenient, and the yield is high.

The present invention belongs to the technical field of organic synthesis, and relates to a method for preparing a geminal bis(boryl)cyclopropane compound. The present invention forms a γ-iodine-substituted geminal di(boryl) ester compound intermediate by an intermolecular halogen atom transfer radical addition reaction, and then the γ-iodine-substituted geminal di(boryl) ester compound intermediate is deprotonated and alkylated in the presence of a base to produce a cyclization product, a geminal bis(boryl)cyclopropane compound. The method provided by the present invention can synthesize a geminal bis(boryl)cyclopropane compound by a one-pot method from an olefin combined with (diborylmethyl) iodide under visible light irradiation, is simple to operate, and provides a rapid way to synthesize highly functionalized compound molecules.

The invention provides a synthetic method of cyclopropyl alcohol, which comprises the following steps: firstly, by taking vinyl acetate as a substrate, carrying out diazomethane catalytic cyclopropanation reaction to obtain cyclopropyl acetate; and secondly, carrying out hydrolysis reaction on the cyclopropyl acetate to obtain cyclopropyl alcohol. The synthetic method for preparing cyclopropyl alcohol has the advantages of simple process, convenient post-treatment, no obvious by-product or waste water, yield of more than 95%, and substantial cost reduction, and is more suitable for industrial large-scale production.

The application relates to the field of drug synthesis, and particularly discloses a high-efficiency asymmetric synthesis method of a sitafloxacin intermediate (1S, 2S)-2-fluorocyclopropane carboxylic acid, which comprises the following steps: S1. reacting a compound SM1 with a chiral compound SM2 in a solvent under the action of an alkali to obtain an epoxide ring-opening chiral compound 1; S2. introducing a group into a hydroxyl group in the compound 1 to obtain a compound 2; S3. obtaining an absolute chiral configuration cyclopropane compound 3 from the compound 2 under the action of an alkali; S4. obtaining an absolute chiral configuration compound 4 from the compound 3 after a deprotection group; S5. generating an absolute chiral configuration compound 5 by oxidizing the compound 4 with an oxidizing agent; and S5. removing a benzene (sulfo) sulfonyl group from the compound 5 to obtain the absolute chiral configuration (1S, 2S)-2-fluorocyclopropane carboxylic acid. The preparation method has the advantages that starting materials are easy to obtain, each step in the synthesis process is simple in operation and separation and extraction, the reaction conditions are mild, the cis-trans selectivity is special, the enantioselectivity is high, the total yield and production capacity are high, and the method is suitable for large-scale industrial production.

The invention belongs to the technical field of organic synthetic chemistry, and particularly relates to a synthetic method of a dideuterated cyclopropane compound. In a nitrogen environment, a cyclopropene compound is taken as a raw material, potassium carbonate is added in a 450-465nm blue photoreactor under the condition that 2, 4, 5, 6-tetra (9-carbazolyl)-isophthalonitrile is taken as a catalyst, the mixture and deuterium water are subjected to a deuteration reaction, a reaction product is subjected to quenching, extraction, filtration and column chromatography, and the dideuterated cyclopropane compound can be obtained. The catalytic system comprises a catalyst, an alkaline substance and a solvent N-methyl pyrrolidone. According to the method, deuteration of the cyclopropene compound can be realized by using a relatively low catalyst dosage, the deuteration degree is high, the operation process and the separation process are simple, and the method has relatively good safety.

The present invention relates to an improved process for the preparation of cyclopropyl compounds from olefins, in particular to an improved process for the preparation of cyclopropyl compounds from olefins by reaction (cyclopropanation reaction) of olefins in the presence of bromochloromethane, elemental zinc and elemental copper or copper compounds.

The invention discloses a boron-based compound, a preparation method thereof and an application of the boron-based compound in synthesis of bororidine, and the boron-based compound is prepared by taking a hydroborane derivative as a boron source and a specific diphosphine compound as a ligand through a mild deprotonation process. According to the preparation method, a strong reducing agent does not need to be used, the reaction condition is mild, and the boron-based compound modified by different space electric substituent groups can be prepared. More importantly, the boron-based compound provided by the invention is different from the traditional nucleophilic boron-based, has amphiphilic reactivity, and can be used as a boron transfer reagent to efficiently react with an olefin compound at room temperature to construct a boron heterocyclic propane compound, and the phosphine ligand in the prepared boron heterocyclic propane compound is easy to leave, so that the boron heterocyclic propane compound can be used for preparing the boron heterocyclic propane compound. The compound can be used as a reagent for further conversion, and has a good application prospect in the fields of organic chemistry and medicinal chemistry.

The present invention relates to novel compounds of formula (1), pharmaceutical compositions comprising such compounds and their use for treating, alleviating or preventing diseases or disorders relating to cancer, as well as their use for treatment or prevention of NF-kB-related diseases or disorders.

The present disclosure provides methods of preparing substituted cyclopropane compounds.

The invention provides a method for preparing a dicyclopropane-based high-energy fuel through catalytic olefination of C1-C2 organic carboxylic acid, which is used for solving the problems of low conversion rate, low dicycloproduct selectivity, high catalytic reaction cost and inapplicability to industrial production in preparation of the dicyclopropane-based high-energy fuel from dicyclopentadiene. The preparation method mainly comprises the following steps: mixing and stirring an organic solvent, olefin, C1-C2 organic carboxylic acid, Zn powder and CH2Br2 to react, and then filtering and separating to obtain the dicyclopropane high-energy fuel. The method is characterized in that formic acid or acetic acid is used as a catalyst, CH2Br2 is used as a carbene precursor to carry out olefin cyclopropanation reaction, and the reaction cost is greatly reduced; the experimental process is relatively safe, the catalyst efficiency is high, the olefin conversion rate is high (gt, 99.9%), and the product selectivity is high (gt, 90%); and the experiment operation is simple, the reaction is rapid, the atom economy is high, and the industrial production is expected to be realized.

Methods for preparing 3-azabicyclo[3.1.0]hexane-6-carboxamide derivatives, which can be useful as SSTR4 agonist compounds. Methods for preparing 3-azabicyclo[3.1.0]hexane-6-carboxamide derivatives through a rhodium catalyzed cyclopropanation reaction with alkyl diazoacetate under low catalyst loadings. Methods for preparing 3-azabicyclo[3.1.0]hexane-6-carboxamide derivatives including a isomerization step and / or a selective hydrolysis step. Methods for preparing an intermediate compound through a rhodium catalyzed cyclopropanation reaction with alkyl diazoacetate under low catalyst loadings, which can be useful in the preparation of a variety of 3-azabicyclo[3.1.0]hexane-6-carboxamide derivatives.

The present invention provides a process for preparing (R)-6-(tert-butoxycarbonyl)-6-azaspiro[2.5]octane-5-carboxylic acid (SM1), said process comprising the step of: iv) converting a compound of formula (VII) into a compound of formula (VIII) using a Wittig reagent in a suitable solvent; v) reacting through the Makosza reaction the compound of Formula (VIII) using bromoform and a suitable base to obtain cyclopropane compound of Formula (IX); and vi) removing bromine atoms in the presence of a reducing agent and a base in an alcoholic solvent thus obtaining (SM1). The invention relates also to a process for the conversion of the compound (SM1) for preparing (R)-4-(1-(6-(4-(trifluoromethyl)benzyl)-6-azaspiro[2.5]octane-5-carboxamido)cyclopropyl) benzoic acid (IV) or a salt thereof. The salt is preferably the sodium salt, more preferably the polymorphic form A of sodium (R)-4-(1-(6-(4-(trifluoromethyl)benzyl)-6-azaspiro[2.5]octane-5-carboxamido)-cyclopropyl) benzoate characterized by a powder XRD spectrum with peaks at values of the angle 2θ+0.2° of 4.3, 5.0, 5.8, 6.4, 7.1, 8.3, 8.7, 12.8, 15.3, 15.9.

The present invention discloses a monoterpene cyclopropanated derivative and a preparation method thereof, belonging to the field of biosynthesis. In the present invention, perillyl alcohol, carveol, carvone or perillartine is used as a substrate, and the trifluoromethyl cyclopropanation modification is carried out by catalysis with the artificial metalloenzyme BM3I357AL86G-Fe(TPP)Cl to obtain the monoterpene cyclopropanated derivative; wherein, the artificial metalloenzyme BM3I357AL86G-Fe(TPP)Cl is prepared by titration reaction of the synthase BM3I357AL86G and Fe(TPP)Cl and then purified. The present invention realizes the trifluoromethyl cyclopropanation modification of four natural monoterpenes, namely L-carveol, carvone, perillyl alcohol and perillartine, by enzymatic catalysis under green and mild conditions, and obtains four natural monoterpene derivatives with new structures. Compared with chemical catalysis, the yield selectivity is improved, and the yield is significantly increased, and the monoterpene derivative 3b is increased by nearly 28 times.

Disclosed are methods for forming a cyclopropyl or cyclopropenyl ring in a compound by, for example, contacting an unsaturated hydrocarbon and an active methylene compound with an oxidant and a catalytically effective amount of a photocatalyst; and irradiating the photocatalyst with a light source to form a cyclopropyl or cyclopropenyl-containing product. Also described herein are methods for forming a cyclopropyl or cyclopropenyl ring in a compound by contacting an unsaturated hydrocarbon and an active methylene compound with an oxidant under conditions effective to form a cyclopropyl or cyclopropenyl ring. Additionally disclosed herein are compounds comprising a cyclopropyl or cyclopropenyl ring formed by the methods disclosed herewith.

The present invention discloses a biomass spirocyclic hydrocarbon fuel and a preparation method thereof. Cyclopentanone / cyclohexanone dissolved in a solvent is added dropwise to a low-valent titanium reagent, and then transferred to an oil bath to undergo a McMurry reaction to generate an olefin with an intercyclic double bond, with a product yield of not less than 95%; (2) a homogeneous / heterogeneous acid-catalyzed cyclopropanation reaction: an olefin with an intercyclic double bond dissolved in a solvent is slowly added to a reaction system containing a carbene body, a cyclopropanation reaction occurs, and the reaction is terminated to obtain a novel biomass spirocyclic hydrocarbon fuel, with a product yield of not less than 95%. The present invention uses biomass as raw material to prepare liquid hydrocarbon fuel, which can not only expand the source of raw materials and ensure energy supply security, but also achieve efficient utilization of biomass and improve economic benefits. The calorific value is increased by about 25% compared to traditional fuels (35MJ / L), and under the same other conditions, the endurance or load of an aircraft can be increased by about 25%. The freezing point is not higher than -70°C, which can ensure the safety of aircraft in high-altitude and low-temperature flight.

The invention provides a heterogeneous catalytic reaction rectification synthesis method of a cyclopropane compound, belongs to the technical field of aerospace industrial fuel, and aims to solve the technical problems of low process integration level, difficulty in serialization, low production capacity and the like due to the fact that alkaline hydroxide is used as a catalyst in the prior art. A catalytic reaction rectifying tower is used as a reaction device, and a pyrazoline derivative is used as a reaction raw material to prepare the cyclopropane compound. The catalytic reaction rectifying tower comprises an upper rectifying section, a middle reaction section and a lower stripping section; the reaction section is filled with a catalyst, the pyrazoline derivative is fed from the upper part of the reaction section and is in contact with the catalyst to perform denitrification reaction, the cyclopropane compound is extracted from the top of the tower, and the unreacted pyrazoline derivative and ketazine compound are collected at the bottom of the tower. According to the invention, pyrazoline derivatives are continuously fed from the upper part of the reaction section and are in contact with a catalyst, products are continuously removed, reactants are left for continuous reaction, and the reaction is continuously carried out towards the direction of generating cyclopropane compounds; the coupling integration of reaction and rectification is realized, and the production capacity of products is improved on the whole.

The invention relates to research on an arylation amination reaction of aryl cyclopropane. An aryl cyclopropane compound is reacted with terephthalonitrile and pyrazole through electro-catalysis. The preparation method comprises the following steps: 1, adding aryl cyclopropane, terephthalonitrile, a pyrazole compound, cesium carbonate, tris (4-bromobenzene) amine and tetraethylammonium tetrafluoroborate into a three-mouth reaction bottle with magnetons; step 2, slowly adding ultrapure acetonitrile and graphite as positive and negative electrode materials in a nitrogen atmosphere, reacting at room temperature under the condition of constant current of 5mA, stirring and reacting at room temperature, monitoring the reaction through TLC (Thin Layer Chromatography), and stopping the reaction after the arylcyclopropane is completely reacted; and 3, transferring the mixture obtained in the step 2 into a reaction bottle, concentrating the solvent by using a rotary evaporator, and separating and purifying the obtained crude product by using a silica gel column to obtain a corresponding arylated aminated product. Compared with a traditional synthesis method, the method has the advantages that the reaction condition is mild, the reaction can be carried out under the room temperature condition, the yield and the chemical selectivity are good, indirect electrochemical oxidation is used in the reaction, the reaction is transferred from an electrode to a solution, and the coupling effect of anodic oxidation and cathode reduction is utilized at the same time.

The application discloses a kind of double sulfur ylide compounds, its preparation method and application.The application discloses a kind of compound as shown in formula I: Wherein, m and n are independently 0, 1, 2, 3, 4 or 5;R 7 And R 8 Independently be C1~C6Alkyl, C1~C6Alkoxy, nitro or halogen;E is CO2R 9 ;R 9 C1~C6Alkyl.This double sulfur ylide compound can be used as the difluorocarbene precursor of photo initiation, can release difluorocarbene under room temperature and neutral blue light condition, can realize the gem difluorocyclopropanation reaction of olefin under photocatalysis and the difluoromethylation reaction of alcohol, provides important methodological support for the post modification of functional molecule in medicine, material and the like.

The application discloses a series of compounds with various cyclopropyl spirocyclohexanedione skeletons synthesized by base-assisted p / ortho-bromophenol and active olefin (methylene malonate) [2+1] de-aromatic reaction. With bromonaphthol and methylene malonate as raw materials, de-aromatic Michael addition occurs in the presence of a base, followed by intramolecular free radical SRN1 dehalogenation cyclopropanation, and then derivatization and ring closure to obtain (±)‑cycloclavine analogues. The method has the advantages of good chemical selectivity and high yield, and the product contains a chiral quaternary carbon center.