WO2016119349A1 - Procédé de préparation de composés sulfonylurées et formate de sulfonamide - Google Patents

Procédé de préparation de composés sulfonylurées et formate de sulfonamide Download PDF

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WO2016119349A1
WO2016119349A1 PCT/CN2015/080090 CN2015080090W WO2016119349A1 WO 2016119349 A1 WO2016119349 A1 WO 2016119349A1 CN 2015080090 W CN2015080090 W CN 2015080090W WO 2016119349 A1 WO2016119349 A1 WO 2016119349A1
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group
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palladium
compound
substituents
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张振华
赵晋
李宗洋
傅滨
王明安
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中国农业大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/53—X and Y not being nitrogen atoms, e.g. N-sulfonylcarbamic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
    • C07C311/55—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
    • C07C311/57—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/58—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings having nitrogen atoms of the sulfonylurea groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
    • C07C311/57—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/60—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings having nitrogen atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/34—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds

Definitions

  • the invention belongs to the field of organic synthesis, and in particular relates to a preparation method of a sulfonylurea and a sulfonamide compound.
  • Sulfonylureas and sulfonamide compounds are a class of very important organic compounds and are widely used in the fields of medicines, pesticides and polymer functional materials.
  • sulfonylurea compounds are effective for the treatment of type 2 diabetes, which inhibits the release of potassium ions by binding K ATP channels on the membrane of the pancreas, thereby increasing insulin release.
  • sulfonylureas are an important class of herbicides that selectively inhibit acetolactate synthase (ALS)/acetate hydroxyacid synthase (AHAS), low toxicity, high efficiency and high selectivity for weeding.
  • a simple, efficient and low-cost method for synthesizing sulfonylureas and sulfonamide compounds has been sought.
  • the currently known synthesis methods are still very limited, mainly by the following methods: First, starting from a primary amine, and phosgene, etc., to prepare the corresponding isocyanate intermediate, and then react with the sulfonamide to obtain sulfonate An ureide compound (see Angew. Chem. 1971, 83, p. 407); 2. Starting from a sulfonamide, reacting with phosgene, etc., to prepare a corresponding sulfonyl isocyanate intermediate, and then reacting with an amine, an alcohol, etc.
  • sulfonylureas To obtain sulfonylureas, sulfonamide-based compounds (see WO 2003091228); third, starting from an amine, with phenyl chloroformate, etc., to prepare the corresponding phenoxy carboxamide, and then in the strong base The reaction with a sulfonamide gives a sulfonylurea compound (see JP 1989221366).
  • the disadvantages of the above methods are: (1) environmentally unfriendly, poor safety, the first two methods require the use of phosgene, and require relatively strict reaction conditions such as anhydrous; (2) poor substrate universality, sulfonamide group
  • the formate compound can only be prepared by the second method.
  • the first method can only prepare the sulfonylurea compound corresponding to the primary amine; (3) the third method has poor atomic economy and high cost, and the intermediate benzene Oxycarbamide is expensive compared to the starting amine and the effective molecular weight is not high.
  • the object of the present invention is to provide an inexpensive transition metal palladium-catalyzed preparation of a sulfonylurea or a sulfonamide-based compound by a one-pot reaction starting from a sulfonyl halide or a sulfonyl azide. method.
  • This method has a very wide range of substrate adaptability, by which a plurality of sulfonylureas and sulfonamide-based compounds having different substituents and aromatic heterocycles can be synthesized.
  • R 1 is selected from aryl, heteroaryl, alkyl, alkenyl or alkynyl;
  • R 2 is selected from aryl, heteroaryl, alkyl, alkenyl or alkynyl;
  • R 3 is selected from H, R 2 , or R 3 is bonded together with R 2 to form a ring;
  • R 4 is N 3 or a halogen atom, preferably fluorine or chlorine or bromine; when R 4 is a halogen atom, the system also includes sodium azide;
  • R 1 , R 2 , R 3 and X are as defined for formula (I).
  • R 1 is as defined in the formula (I).
  • the compound of the formula (V), the sodium azide and the compound of the formula (III) are reacted in a solvent under a carbon monoxide atmosphere under a catalysis of a palladium catalyst to obtain a compound of the formula (I). :
  • R 5 is a halogen atom, preferably fluorine or chlorine or bromine; and R 1 is as defined in the formula (I).
  • the aryl group may be a substituted or unsubstituted aryl group;
  • the heteroaryl group may be a substituted or unsubstituted aryl group bearing at least one nitrogen, oxygen or sulfur;
  • the aromatic group and the heterocyclic ring may have one or more substituents, and the position of the substituent is not particularly limited, and the ortho, meta and para positions may be used; the substituent is not limited in any way, and a common substituent such as an alkyl group , alkoxy group, disubstituted amine group, nitro group, cyano group, ester group, aldehyde group, ketone carbonyl group and halogen atom; etc.; when having a plurality of substituents, the plurality of substituents may be the same or different, and adjacent two The substituents may be independent or cyclic to each other.
  • the alkyl group may be a substituted or unsubstituted primary, secondary or tertiary alkyl group; the substituent is not defined in any way, and common substituents such as alkyl, alkoxy, disubstituted An amine group, a nitro group, a cyano group, an ester group, an aldehyde group, a ketone carbonyl group, a halogen atom and the like; when having a polysubstituent, the plurality of substituents may be the same or different, and two adjacent or adjacent substituents may be mutually Independent or looped.
  • the alkenyl group may be a substituted or unsubstituted alkenyl group, and the position and the number of the substituent are not particularly limited, and one, two, and three may be used, and both cis and trans may be used.
  • the substituent is not limited in any way, and common substituents such as an alkyl group, an alkoxy group, a disubstituted amine group, a nitro group, a cyano group, an ester group, an aldehyde group, a ketone carbonyl group, a halogen atom, etc.;
  • the plurality of substituents may be the same or different, and the adjacent or adjacent two substituents may be independent or cyclic.
  • the alkynyl group may be a substituted or unsubstituted alkynyl group; the substituent is not limited in any way, and common substituents such as an alkyl group, an alkoxy group, a disubstituted amine group, a nitro group, a cyano group And an ester group, an aldehyde group, a ketone carbonyl group, a halogen atom or the like; when having a polysubstituent, the plurality of substituents may be the same or different, and two adjacent or adjacent substituents may be independent or cyclic.
  • the alkyl group preferably means an alkyl group having 1 to 10 carbon atoms
  • the substituent on the alkyl group is preferably an alkoxy group, a nitro group, a cyano group, an ester group, an aldehyde group, a ketone carbonyl group and a halogen atom, more preferably a halogen atom such as fluorine, chlorine or bromine, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl Base, neopentyl, halogenated C 1-10 alkyl, more preferably trifluoromethyl.
  • the alkoxy group preferably means an alkoxy group having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, Tert-butoxy, sec-butoxy.
  • the alkenyl group preferably means an alkenyl group having 2 to 10 carbon atoms
  • the substituent on the alkenyl group is preferably an alkoxy group, a nitro group, a cyano group, an ester group, an aldehyde group, a ketone carbonyl group,
  • a halogen atom more preferably a halogen atom such as fluorine, chlorine or bromine, such as a vinyl group, a propenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, a halogenated C 2-10 alkenyl group.
  • the alkynyl group preferably means an alkynyl group having 2 to 10 carbon atoms
  • the substituent on the alkynyl group is preferably an alkoxy group, a nitro group, a cyano group, an ester group, an aldehyde group, a ketone carbonyl group and a halogen atom, more preferably a halogen atom such as fluorine, chlorine or bromine, said alkynyl group such as ethynyl, propynyl, butynyl, pentynyl, isopentynyl, hexynyl, halogenated C 2-10 Alkynyl.
  • the aryl group is preferably a monocyclic or bicyclic aryl group, more preferably an aryl group of 6 to 14 carbon atoms, such as a phenyl or naphthyl group.
  • the substituent on the aryl group is preferably an alkyl group, an alkoxy group, a nitro group, a cyano group, an ester group, an aldehyde group, a ketone carbonyl group and a halogen atom, more preferably a halogenated alkyl group such as a trifluoromethyl group.
  • the heteroatoms in the heteroaryl group may be one, two, three or four.
  • the heteroaryl group preferably contains 5 to 30 atoms, more preferably 6 to 20 atoms, such as thiophene, furan, pyrrole, pyrazole, imidazole, oxazole, thiazole, isoxazole, isothiazole, oxazoline, Thiazoline, pyridine, pyran, thiopyran, pyrimidine, pyridazine, pyrazine, piperazine, azepine, oxazepine, thiazolidine, hydrazine, benzimidazole, benzothiophene, benzofuran, benzene Thiazole, benzoxazole, benzisoxazole, phenylisoisothiazole, quinoline, isoquinoline, quinazoline, carbazole, pteridine, anthracene,
  • the substituent on the heteroaryl group is preferably an alkyl group, an alkoxy group, a nitro group, a cyano group, an ester group, an aldehyde group, a ketone carbonyl group and a halogen atom, more preferably a halogenated alkyl group such as a trifluoromethyl group.
  • the substituents of the disubstituted amino group may be the same or different and are independently selected from an alkyl group or an aryl group, for example, N,N-dimethylamino group, N,N-diphenylamino group, N-methyl-N-phenylamino group and the like.
  • the amide group is, for example, an acetamide group, a propionamide group, a butyramide group or the like.
  • the ester group is, for example, a formate group, an acetate group, a propionate group, a butyrate group or the like.
  • the halogen atom means a fluorine, chlorine, bromine or iodine atom or the like.
  • the sodium azide can be used as a commercial reagent without special treatment.
  • the palladium catalyst may be a commercially available reagent, which may be a palladium, palladium or palladium complex with a phosphine-containing ligand, a nitrogen-containing ligand, an oxygen-containing ligand, a sulfur-containing ligand or an alkenyl ligand.
  • a complex preferably but not limited to one of the following: palladium carbon, palladium oxide, palladium hydroxide, palladium sulfate, palladium acetate, palladium trifluoroacetate, tris(dibenzylideneacetone) dipalladium, two (two Phenylacetone)palladium, bis(acetylacetonate)palladium, palladium trifluoroacetylacetonate, palladium (1,5-cyclooctadiene), palladium allyl chloride, ditriphenylphosphine dichloride Palladium, tetrakis(triphenylphosphino)palladium, bis(benzonitrile)palladium chloride, di(acetonitrile)palladium chloride.
  • the catalytic amount thereof is preferably 0.001 to 2% based on the compound of the formula (II) Within the range of the equivalent amount, it is more preferably in the range of 0.01 to 1% by equivalent, and still more preferably in the range of 0.05 to 0.1% by equivalent.
  • the solvent is water or an organic solvent, preferably but not limited to one or a mixture of the following: water, dichloromethane, 1,2-dichloroethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl n-butyl ether, methanol, ethanol, isopropanol, benzene, toluene, acetonitrile, nitromethane, pentane, hexane, and the like.
  • organic solvent preferably but not limited to one or a mixture of the following: water, dichloromethane, 1,2-dichloroethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl n-butyl ether, methanol, ethanol, isopropanol, benzene, toluene, acetonitrile, nitromethane, pent
  • the carbon monoxide can be used as a commercial gas without special treatment, and the purity of the gas is preferably, but not limited to, >98%.
  • the pressure of the gas during the reaction is usually from 0 to 10 atm, preferably from 0 to 2 atm.
  • the preferred feed molar ratio of the reactants is:
  • the reaction temperature and reaction time of the reaction are slightly different depending on the starting materials, and the reaction temperature is usually -10 ° C to 100 ° C, preferably 25 ° C to 35 ° C, and the reaction time is usually 2 to 24 hours. If heating is required, an oil bath (such as silicone oil, paraffin oil, etc.) or other heating means may be used.
  • an oil bath such as silicone oil, paraffin oil, etc.
  • the method further comprises a concentration step.
  • the concentration process may employ a method such as atmospheric distillation, vacuum distillation, or the like.
  • the method further comprises a purification step.
  • the purification process is a pure product obtained by column chromatography, vacuum distillation, and/or recrystallization. More preferably, the purification process is followed by column chromatography followed by vacuum distillation or recrystallization to obtain a purified product.
  • the solubility of the compound of the formula (III) when the solubility of the compound of the formula (III) is low, it is preferred to add a substance selected from a phenol, an alcohol or a tertiary amine to the system.
  • a substance selected from a phenol, an alcohol or a tertiary amine to the system.
  • the phenol is a substituted or unsubstituted phenol such as phenol.
  • the above-mentioned substance selected from a phenol, an alcohol or a tertiary amine is added before the addition of the compound of the formula (III).
  • the method of the invention realizes starting from a sulfonyl azide (compound of the formula (IV)) or a sulfonyl halide (compound of the formula (V)), directly using an unactivated amine, an alcohol (compound of the formula (III)) as a raw material,
  • a sulfonyl azide compound of the formula (IV)
  • a sulfonyl halide compound of the formula (V)
  • the reaction environment involved in the present invention is relatively friendly, and the reaction itself or in the synthesis process of the raw materials is not It is necessary to use phosgene, and the reaction starts from a sulfonyl azide or a sulfonyl halide, and directly uses an unactivated amine or an alcohol as a raw material to obtain a corresponding sulfonylurea or sulfonamide compound by a one-pot method;
  • the reaction involved in the method of the invention has very good tolerance and universality to the functional group, and may be a substituted or unsubstituted aromatic ring, an aromatic heterocyclic ring, an alkyl group, an alkenyl group or an alkynyl group, and the substituent may be an alkane.
  • a base, an alkoxy group, a secondary amine group, a nitro group, a cyano group, an ester group, an aldehyde group, a ketone carbonyl group, and a halogen atom (F, Cl, Br, I), etc. can be used for preparing various sulfonyl-containing medicines, Pesticide and polymer functional materials;
  • the reaction of the present invention does not require strict anhydrous anaerobic conditions, does not require high temperature reaction, does not require a high pressure carbon monoxide reaction atmosphere, and is very simple to handle.
  • the amount of catalyst can be reduced to less than 1% equivalent and the reaction is very efficient.
  • the amount of the catalyst is very small, and since the unactivated amine and the alcohol can be directly used as raw materials, the reaction cost is low.
  • Figure 8 is a schematic diagram showing the reaction of palladium acetate with a sulfonylurea.
  • HOAc represents acetic acid
  • Pd(OAc) 2 represents palladium acetate
  • PdCl 2 represents palladium chloride
  • the present invention discloses a method of preparing a compound of the formula (I),
  • R 1 is selected from aryl, heteroaryl, alkyl, alkenyl or alkynyl
  • R 2 is selected from aryl, heteroaryl, alkyl, alkenyl or alkynyl
  • R 3 is selected from H, R 2 , or R 3 and R 2 are bonded together to form a ring; taking the compound of the formula (IV) as an example, the reaction formula is as follows:
  • reaction of the present invention is very tolerant to functional groups.
  • Palladium acetate can smoothly catalyze the reaction of a sulfonyl azide with an amine to form a sulfonylurea under the conditions of a room temperature and a normal pressure of carbon monoxide atmosphere, with a yield of 93%.
  • the solubility of the compound of formula (III) when the solubility of the compound of formula (III) is low, it is preferred to add to the system a material selected from the group consisting of phenols, alcohols or tertiary amines.
  • the phenol is a substituted or unsubstituted phenol such as phenol.
  • the above-mentioned substance selected from the group consisting of a phenol, an alcohol or a tertiary amine is added before the addition of the compound of the formula (III).
  • a 25 ml two-necked bottle was sequentially added with Pd(OAc) 2 (1 mg, 0.004 mmol), p-toluenesulfonyl azide (79 mg, 0.40 mmol), morpholine (42 mg, 0.48 mmol), 4 ml of acetonitrile, and the system was evacuated to 20 mmHg. Then, the CO gas was charged to normal pressure, and this was repeated three times. After the reaction was vigorously stirred at room temperature for 12 hours, the solvent was evaporated to dryness crystals crystals crystals crystals %.
  • the 25 ml two-necked bottle was first charged with p-toluenesulfonyl chloride (76 mg, 0.40 mmol), sodium azide (34 mg, 0.52 mmol), acetonitrile 4 ml, water 0.036 ml (2.0 mmol), stirred vigorously, and then added Pd (OAc). 2 (1 mg, 0.004 mmol), morpholine (42 mg, 0.48 mmol), the system was evacuated to 20 mmHg, and then charged with CO gas to normal pressure, and this was repeated three times. After the reaction was vigorously stirred at room temperature for 12 hours, the solvent was evaporated to dryness crystals crystals crystals crystals %.
  • Examples 2-36 were prepared in the same manner as in Example 1. The specific raw material ratios are shown in Tables 1 and 2.

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Abstract

La présente invention concerne un procédé de préparation d'un composé représenté par la formule (I). Le composé représenté par la formule (I) est préparé par la réaction d'un composé représenté par la formule (II) avec un composé représenté par la formule (III) sous la catalyse d'un catalyseur au palladium et sous une atmosphère de monoxyde de carbone et un solvant. La réaction associée au procédé de la présente invention ne nécessite pas de conditions anhydres et anaérobies strictes ni d'atmosphère de monoxyde de carbone à haute pression, le fonctionnement est pratique et simple, et la réaction présente de très bonnes tolérance et universalité vis-à-vis des groupes fonctionnels; en même temps, la dose de catalyseur est extrêmement faible, le coût de la réaction est très bas, et le procédé peut être largement appliqué à la préparation de composés sulfonylurées.
PCT/CN2015/080090 2015-01-29 2015-05-28 Procédé de préparation de composés sulfonylurées et formate de sulfonamide WO2016119349A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10538487B2 (en) 2015-02-16 2020-01-21 The University Of Queensland Sulfonylureas and related compounds and use of same
WO2021107037A1 (fr) * 2019-11-28 2021-06-03 三菱ケミカル株式会社 Révélateur et matériau d'enregistrement thermosensible
CN113372319A (zh) * 2021-05-17 2021-09-10 东北师范大学 一种含有胺基的δ-内酯类化合物及其制备方法
WO2022115417A1 (fr) * 2020-11-25 2022-06-02 VenatoRx Pharmaceuticals, Inc. Inhibiteurs d'inflammasome de nlrp3 sulfonylurée
US11465992B2 (en) 2017-07-07 2022-10-11 Inflazome Limited Sulfonamide carboxamide compounds

Citations (5)

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