WO2012161313A1 - Composé 1-(phényl substitué par 2-amino)-2-halo-2,2-difluoroéthanone et procédé de fabrication d'un composé 1-(phényl substitué)-2-halo-2,2-difluoroéthanone - Google Patents

Composé 1-(phényl substitué par 2-amino)-2-halo-2,2-difluoroéthanone et procédé de fabrication d'un composé 1-(phényl substitué)-2-halo-2,2-difluoroéthanone Download PDF

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WO2012161313A1
WO2012161313A1 PCT/JP2012/063488 JP2012063488W WO2012161313A1 WO 2012161313 A1 WO2012161313 A1 WO 2012161313A1 JP 2012063488 W JP2012063488 W JP 2012063488W WO 2012161313 A1 WO2012161313 A1 WO 2012161313A1
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atom
acid
group
compound
haloalkyl
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PCT/JP2012/063488
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Japanese (ja)
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前田　兼成
紘久 齋藤
水越　隆司
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日産化学工業株式会社
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Priority to JP2013516457A priority Critical patent/JP6124012B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups

Definitions

  • the present invention relates to a method for producing a 1- (substituted phenyl) -2-halo-2,2-difluoroethanone compound useful as a production intermediate for pharmaceuticals, agricultural chemicals, electronic materials, etc. (2-Amino-substituted phenyl) -2-halo-2,2-difluoroethanone compounds.
  • substituted isoxazoline compounds are harmful to N- (2,2,2-trifluoroethyl) -4- (5-substituted-5-substituted phenyl-4,5-dihydroisoxazol-3-yl) benzamide and the like. It is known to be used as a biocontrol agent, particularly an insecticide / miticide, or an internal or ectoparasite control agent for mammals and birds (see, for example, Patent Documents 1 and 2).
  • 1- (Substituted phenyl) -2-halo-2,2-difluoroethanone compounds are known to be used as production intermediates for substituted isoxazoline compounds (see, for example, Patent Documents 3 to 6).
  • 1- (2-amino-substituted phenyl) -2-halo-2,2-difluoroethanone compounds 1- (2-amino-5-chlorophenyl) -2,2,2-trifluoroethanone is As a synthesis intermediate of a benzoxazinone compound having HIV reverse transcriptase inhibitory activity (see, for example, Patent Document 9), as a synthesis intermediate of an inflammatory disease drug indole compound (see, for example, Patent Document 10) or a T-type calcium channel It is known as a synthetic intermediate of a quinazolinone compound having inhibitory activity (see, for example, Patent Document 11).
  • Pest control agents for harmful arthropods in the fields of agriculture, horticulture and livestock / hygiene (agricultural and horticultural insecticides, acaricides, mammals as domestic animals and pets, and insects inside or outside parasites) , Household and commercial hygiene pests and unpleasant pest control agents), which is effective against a wide range of pest species and has acquired resistance to existing insecticides and acaricides
  • Substituted isoxazoline compounds exhibiting excellent control effects exhibit control effects at extremely low doses, have low persistence and light environmental impact, and are adversely affected by non-target organisms such as mammals, fish and beneficial insects It is an excellent pest control agent that has little effect on water.
  • the development of more efficient production methods and the development of useful production intermediates used therefor are always required.
  • 1- (2-) represented by the following general formula (2) which can be used as an intermediate for the production of a specific substituted isoxazoline compound.
  • Amino-substituted phenyl) -2-halo-2,2-difluoroethanone compound and method for producing 1- (substituted phenyl) -2-halo-2,2-difluoroethanone compound represented by general formula (1) The present invention has been completed.
  • the present invention relates to the following [1] to [17].
  • X 1 represents a hydrogen atom
  • X 2 is a halogen atom, cyano, nitro, —SF 5 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 8 cyclo
  • X 1 is a halogen atom, cyano, nitro, —SF 5 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 8 cyclo Represents alkyl or C 3 -C 8 halocycloalkyl
  • X 2 represents a hydrogen atom, a halogen atom, cyano, nitro, —SF 5 , C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy, C 1 to C 6 haloalkoxy, C 3 to The process for producing a compound according to [1], which represents C 8 cycloalkyl or C 3 -C 8 halocycloalkyl.
  • X 1 and X 2 each independently represent a halogen atom, C 1 -C 6 haloalkyl or C 1 -C 6 haloalkoxy
  • X 3 represents a hydrogen atom or a halogen atom
  • Y represents the fluorine atom
  • X 1 represents a chlorine atom or C 1 -C 6 haloalkyl
  • X 2 represents a hydrogen atom, a halogen atom, cyano, nitro, C 1 -C 6 haloalkyl or C 1 -C 6 haloalkoxy
  • X 3 represents a hydrogen atom, a halogen atom or a C 1 -C 6 haloalkyl
  • Y is a compound or a salt thereof according to [8], which represents a fluorine atom.
  • X 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a C 1 -C 6 haloalkyl
  • X 3 represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, or a compound or a salt thereof according to [9].
  • X 1 represents a chlorine atom
  • X 2 represents a hydrogen atom, a chlorine atom, a bromine atom or a trifluoromethyl group
  • X 3 represents a hydrogen atom, a fluorine atom or a chlorine atom, the compound or a salt thereof according to [10].
  • X 2 represents a hydrogen atom, a fluorine atom, a bromine atom, cyano, nitro, C 1 -C 6 haloalkyl or C 1 -C 6 haloalkoxy
  • X 3 represents a hydrogen atom, a halogen atom or a C 1 -C 6 haloalkyl
  • Y represents a fluorine atom, or the compound or salt thereof according to [12].
  • X 2 represents a hydrogen atom, a fluorine atom, a bromine atom or a C 1 -C 6 haloalkyl
  • X 3 represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, or a compound or a salt thereof according to [13].
  • X 2 represents an iodine atom, nitro or C 1 -C 6 haloalkoxy
  • X 3 represents a hydrogen atom, a halogen atom or a C 1 -C 6 haloalkyl
  • Y is a compound or a salt thereof according to [16], which represents a fluorine atom.
  • the present invention has excellent insecticidal / miticidal activity against many agricultural insect pests, spider mites, mammals or birds, or acquired resistance to existing insecticides / miticides.
  • New production method of 1- (substituted phenyl) -2-halo-2,2-difluoroethanone compound which is a production intermediate of substituted isoxazoline compounds exhibiting sufficient control effect against pests, and production intermediates thereof
  • the present invention provides novel 1- (2-amino-substituted phenyl) -2-halo-2,2-difluoroethanone compounds useful as: In the process of the present invention, no harmful waste derived from the catalyst or transition metal is substantially produced.
  • the method of the present invention does not require an expensive reagent, has little decomposition of raw materials and products, and has a high industrial utility value.
  • the 1- (2-amino-substituted phenyl) -2-halo-2,2-difluoroethanone compound according to the present invention exhibits excellent pest control activity, particularly insecticidal / miticidal activity, and is a mammal. It is extremely useful as a novel intermediate for the production of substituted isoxazoline compounds with less adverse effects on non-target organisms such as animals, fish and beneficial insects.
  • n- represents normal
  • i- represents iso
  • s- represents secondary
  • t- represents tertiary
  • Ph represents phenyl
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the notation “halo” also represents these halogen atoms.
  • C a -C b alkyl in the present specification represents a linear or branched hydrocarbon group comprising a to b carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, neopentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1 -Ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethyl
  • C a -C b haloalkyl in this specification is a linear or branched chain consisting of a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom.
  • fluoromethyl group chloromethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, chlorodifluoromethyl group, trichloromethyl group, bromodifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl Group, 2,2-difluoroethyl group, 2-chloro-2-fluoroethyl group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2-bromo-2-chloroethyl group, 2,2 , 2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2-fluoroethyl group, 2,2,2-trichloroethyl group, 2-bromo-2,2- Difluoroethyl group, 2-bromo-2-chloro-2-fluoro
  • C a -C b cycloalkyl represents a cyclic hydrocarbon group having a to b carbon atoms, and forms a monocyclic or complex ring structure having 3 to 6 members. I can do it. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms.
  • cyclopropyl group 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2- Specific examples include methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo [2.2.1] heptan-2-yl group, etc. , Each selected range of carbon atoms.
  • C a -C b halocycloalkyl represents a cyclic hydrocarbon group having a carbon number of a to b in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. And can form monocyclic or complex ring structures from 3 to 6-membered rings. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, It may be both, and when it is substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other.
  • Specific examples include a cyclohexyl group, a 4-trifluoromethylcyclohexyl group, and the like, and each is selected within the range of the designated number of carbon atoms.
  • C a -C b alkoxy in the present specification represents an alkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, for example, methoxy group, ethoxy group, n-propyloxy group, Specific examples include i-propyloxy group, n-butyloxy group, s-butyloxy group, i-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, etc. It is selected in the range of the number of atoms.
  • C a -C b haloalkoxy in the present specification represents a haloalkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as a difluoromethoxy group, a trifluoromethoxy group, a chlorodifluoro Methoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2-chloro-1 1,2-trifluoroethoxy group, 2-bromo-1,1,2-trifluoroethoxy group, 2,2-dichloro-1,1,2-trifluoroethoxy group, pentafluoroethoxy group, 2,2 , 2-trichloro-1,1-difluoroethoxy group, 2-bromo-1,1,2,2-tetrafluoroethoxy group
  • general formula (2) [wherein X 1 , X 2 , X 3 and Y each have the same meaning as described above.
  • the presence of an acid a compound represented by, general formula is reacted with nitrous acid compound (3) [wherein X 1, X 2, X 3 and Y each represent the same meaning as above, X - is Chloride ion, bromide ion, fluoride ion, nitrate ion, phosphate ion, perchlorate ion, acetate ion, methanesulfonate ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, hexafluorophosphate ion or sulfuric acid Represents hydrogen ion.
  • the diazonium salt represented by the general formula (1) is prepared and then reacted with a reducing agent, wherein X 1 , X 2 , X 3 and Y each have the same meaning as described above.
  • Acids used in the preparation of the diazonium salt represented by the general formula (3) are hydrochloric acid, hydrobromic acid, hydrofluoric acid, nitric acid, phosphoric acid, perchloric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, Tetrafluoroboric acid, hexafluorophosphoric acid or sulfuric acid may be mentioned, preferably hydrochloric acid, hydrobromic acid, nitric acid, perchloric acid, methanesulfonic acid, trifluoromethanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid or A sulfuric acid is mentioned, More preferably, hydrochloric acid or a sulfuric acid is mentioned. This acid can be used alone, as an aqueous solution, or as a mixture having an arbitrary mixing ratio.
  • the amount of the acid used may be any amount as long as the reaction proceeds sufficiently, but is 1.0 to 100 equivalents, preferably 1 with respect to 1 equivalent of the compound represented by the general formula (2) (raw material compound). A range of 0.5 to 50 equivalents, more preferably 1.5 to 20 equivalents can be exemplified.
  • nitrite compound used examples include nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, barium nitrite, silver nitrate, and C 1 -C 6 alkyl nitrite, preferably sodium nitrite and potassium nitrite. Can be mentioned.
  • the amount of the nitrous acid compound used may be any amount as long as the reaction proceeds sufficiently, but is preferably 1.0 to 20 equivalents, preferably 1 to 20 equivalents relative to 1 equivalent of the compound (raw material compound) represented by the general formula (2). Is 1.0 to 10 equivalents, more preferably 1.5 to 3.0 equivalents.
  • the solvent used for the preparation of the diazonium salt represented by the general formula (3) is not particularly limited as long as it does not inhibit the progress of the reaction.
  • water methanol, ethanol, 1-propanol, 2-propanol Alcohols such as 1-butanol and 2-butanol; aliphatic hydrocarbons such as heptane and hexane; aromatic hydrocarbons such as toluene and xylene; halogenated aliphatics such as dichloromethane, chloroform and 1,2-dichloroethane Hydrocarbons; aprotic polar solvents such as acetonitrile and N, N-dimethylformamide.
  • solvents can be used alone or as a mixed solvent having an arbitrary mixing ratio.
  • preferred solvents are water, alcohols, mixed solvents of alcohols and water, aprotic polar solvents, mixed solvents of aprotic polar solvents and water, halogenated fats.
  • More preferable solvents include water, methanol, ethanol, a mixed solvent of ethanol and water, a mixed solvent of 1-propanol and water, a mixed solvent of 2-propanol and water, a mixed solvent of acetonitrile and water, and a mixed solvent of dichloromethane and water. 1, 2-dichloroethane and water mixed solvent, toluene, toluene and water mixed solvent.
  • the amount of the solvent may be an amount that can sufficiently stir the reaction system, but is usually 0.05 to 10 L (liter), preferably 1 mol per 1 mol of the compound represented by the general formula (2) (raw material compound). May be in the range of 0.5 to 2L.
  • the reaction temperature in the preparation of the diazonium salt represented by the general formula (3) can be set to an arbitrary temperature of ⁇ 20 to 80 ° C., preferably ⁇ 10 to 60 ° C., particularly ⁇ 5 to It is preferable to set to 50 ° C.
  • the reaction time in the preparation of the diazonium salt represented by the general formula (3) varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set in the range of 0.1 to 48 hours, preferably The time can be set to 0.1 to 24 hours, and more preferably 0.5 to 10 hours.
  • the reaction mixture after the preparation of the diazonium salt represented by the general formula (3) can be processed as it is, concentrated, liquid-separated, or precipitated and taken out with a salt.
  • the reaction mixture is used in the next step as it is or after being separated.
  • the diazonium salt represented by the general formula (3) is reacted with a reducing agent to produce the general formula (1).
  • the reducing agent used herein include hypophosphites such as hypophosphorous acid, sodium hypophosphite and calcium hypophosphite, hexamethylphosphoric triamide, methanol, ethanol, 1-propanol, 2-propanol, 1-propanol Alcohols such as butanol, 2-butanol, formic acid esters such as formic acid, methyl formate, ethyl formate, phenol, N, N-dimethylformamide, sodium stannate, tributyltin hydride, triethylsilane, sodium borohydride, etc.
  • Preferred examples include hypophosphorous acid, methanol, ethanol, 1-propanol, 2-propanol, formic acid, methyl formate, ethyl formate, and N, N-dimethylformamide.
  • the reducing agent may be used in any amount as long as the reaction proceeds sufficiently. If necessary, the reducing agent can also be used as a solvent, and 1 equivalent of the compound represented by the general formula (2) (raw material compound). On the other hand, a range of 1.0 to 100 equivalents, preferably 1.5 to 50 equivalents, more preferably 1.5 to 20 equivalents can be exemplified.
  • a catalyst can be used.
  • the catalyst used include anhydrous copper sulfate (II), copper sulfate (II) pentahydrate, copper (I) oxide, copper (II) oxide, copper chloride (I), anhydrous copper chloride (II), and chloride.
  • examples thereof include copper (II) dihydrate, anhydrous iron (II) sulfate, iron (II) sulfate heptahydrate and the like.
  • the amount of catalyst used can be 0.001 to 1 equivalent added to 1 equivalent of the compound (raw material compound) represented by the general formula (2).
  • the method for producing the compound represented by the general formula (1) by reaction with a reducing agent may be performed in the presence of a solvent, if necessary.
  • the solvent used in the production method is not particularly limited as long as it does not inhibit the progress of the reaction.
  • water, methanol, ethanol, 1-propanol, 2-propanol, acetonitrile, N, N-dimethylformamide examples include dichloromethane, 1,2-dichloroethane, toluene, xylene, hexane, heptane, diethyl ether, tetrahydrofuran, 1,4-dioxane, and ethyl acetate.
  • solvents can be used alone or as a mixed solvent of any mixing ratio, but preferably water, methanol, ethanol, acetonitrile, dichloromethane, 1,2-dichloroethane, toluene, xylene, hexane, heptane Or a mixed solvent of any mixing ratio, and more preferably water, methanol, ethanol, dichloromethane, toluene, heptane alone or a mixed solvent of any mixing ratio.
  • the amount of the solvent may be an amount that can sufficiently stir the reaction system, but is usually 0.05 to 10 L (liter), preferably 1 mol per 1 mol of the compound represented by the general formula (2) (raw material compound). May be in the range of 0.5 to 2L.
  • the reaction temperature of this production method can be set to any temperature in the range of ⁇ 20 ° C. to the reflux temperature of the reaction mixture, preferably 0 to 100 ° C., and particularly preferably 20 to 70 ° C. preferable.
  • reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, it can usually be arbitrarily set in the range of 0.1 to 48 hours, preferably 0.1 to 24 hours, and particularly preferably 0.2. It is preferable to set 5 to 10 hours
  • the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, washed with water, concentrated in ice water or poured into ice water, concentrated after extraction with an organic solvent, and then subjected to usual post-treatment to give the desired compound of the present invention.
  • it can be separated and purified by any purification method such as distillation, back extraction, recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.
  • This production method is carried out in the presence of an acid.
  • the acid to be used include mineral acids such as hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, phosphoric acid and nitric acid, and organic acids such as acetic acid and methanesulfonic acid, preferably hydrochloric acid and sulfuric acid. .
  • This acid can be used alone or as a mixture in any mixing ratio.
  • the acid may be used in any amount as long as the reaction proceeds sufficiently, and is 1.0 to 100 equivalents, preferably 1.100 equivalents relative to 1 equivalent of the compound (raw material compound) represented by the general formula (2).
  • a range of 5 to 50 equivalents, more preferably 1.5 to 30 equivalents can be exemplified.
  • Examples of reducing agents used include hypophosphites such as hypophosphorous acid, sodium hypophosphite and calcium hypophosphite, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol.
  • Formic acid esters such as formic acid, methyl formate, ethyl formate, and N, N-dimethylformamide, preferably hypophosphorous acid, methanol, ethanol, 1-propanol, 2-propanol, formic acid, methyl formate
  • Examples include ethyl formate.
  • the reducing agent may be used in any amount as long as the reaction proceeds sufficiently. If necessary, the reducing agent can also be used as a solvent, and 1 equivalent of the compound represented by the general formula (2) (raw material compound). On the other hand, a range of 1.0 to 200 equivalents, preferably 1.5 to 100 equivalents, more preferably 1.5 to 30 equivalents can be exemplified.
  • a catalyst can be used.
  • the catalyst used include anhydrous copper sulfate (II), copper sulfate (II) pentahydrate, copper (I) oxide, copper (II) oxide, copper chloride (I), anhydrous copper chloride (II), and chloride.
  • examples thereof include copper (II) dihydrate, anhydrous iron (II) sulfate, iron (II) sulfate heptahydrate and the like.
  • the amount of catalyst used can be 0.001 to 1 equivalent added to 1 equivalent of the compound (raw material compound) represented by the general formula (2).
  • nitrite compound used examples include nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, barium nitrite, silver nitrate, and C 1 -C 6 alkyl nitrite, preferably sodium nitrite and potassium nitrite. Can be mentioned.
  • the amount of the nitrous acid compound used may be any amount as long as the reaction proceeds sufficiently, but is preferably 1.0 to 20 equivalents, preferably 1 to 20 equivalents relative to 1 equivalent of the compound (raw material compound) represented by the general formula (2). Is 1.0 to 10 equivalents, more preferably 1.5 to 3.0 equivalents.
  • This production method may be performed in the presence of a solvent, if necessary.
  • the solvent used in the production method is not particularly limited as long as it does not inhibit the progress of the reaction.
  • water, methanol, ethanol, 1-propanol, 2-propanol, acetonitrile, N, N-dimethylformamide examples include dichloromethane, 1,2-dichloroethane, toluene, xylene, hexane, heptane, diethyl ether, tetrahydrofuran, 1,4-dioxane, and ethyl acetate.
  • These solvents can be used alone or as a mixed solvent having an arbitrary mixing ratio.
  • nitrite compound preferably water, methanol, ethanol, 1-propanol, 2-propanol, acetonitrile, toluene, xylene, hexane and heptane are used alone or in any mixing ratio. It is preferable to use water, methanol, ethanol, 1-propanol, 2-propanol alone or as a mixed solvent of any mixing ratio.
  • the amount of the solvent may be an amount that can sufficiently stir the reaction system, but is usually 0.05 to 10 L (liter), preferably 1 mol per 1 mol of the compound represented by the general formula (2) (raw material compound). May be in the range of 0.5 to 2L.
  • the reaction temperature of this production method can be set at an arbitrary temperature within the range of ⁇ 20 ° C. to the reflux temperature of the reaction mixture, preferably ⁇ 10 to 100 ° C., particularly set at ⁇ 5 to 80 ° C. It is preferable.
  • reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, it can usually be arbitrarily set in the range of 0.1 to 48 hours, preferably 0.1 to 24 hours, and particularly preferably 0.2. It is preferable to set 5 to 10 hours.
  • the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, washed with water, concentrated in ice water or poured into ice water, concentrated after extraction with an organic solvent, and then subjected to usual post-treatment to give the desired compound of the present invention.
  • it can be separated and purified by any purification method such as distillation, back extraction, recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.
  • the compound represented by General formula (2) is demonstrated.
  • the compound represented by the general formula (2) can be produced, for example, by the following method. Manufacturing method A
  • Examples of the acid to be used include hydrochloric acid, hydrobromic acid, sulfuric acid, trifluoroacetic acid and the like, and 1 to 120 equivalents can be used with respect to 1 equivalent of the compound represented by the general formula (4).
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • acetic acid water, methanol, ethanol, 1,4-dioxane, dichloromethane, chloroform, carbon tetrachloride, 1 , 2-dichloroethane, toluene and chlorobenzene.
  • solvents may be used alone or as a mixture of two or more thereof.
  • the reaction temperature can be set to an arbitrary temperature from ⁇ 10 to 150 ° C., and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily in the range of 0.5 to 48 hours. Can be set.
  • the compound represented by the general formula (2-1) in which X 1 represents a halogen atom can be produced, for example, by the following method. Manufacturing method B
  • general formula (2-2) [wherein X 2 represents the same meaning as described above excluding a hydrogen atom, and X 3 and Y represent the same meaning as described above.
  • the compound represented by the above formula is halogenated using a halogenating agent in a solvent inert to the reaction if necessary, in the presence of a catalyst if necessary, and in the presence of an oxidizing agent if necessary.
  • general formula (2-1) [wherein X 1 represents a chlorine atom, a bromine atom or an iodine atom, and X 2 , X 3 and Y represent a compound represented by general formula (2-2) It represents the same meaning. The compound represented by this can be obtained.
  • halogenating agent examples include chlorine gas, sulfuryl chloride, sodium chlorate, sodium hypochlorite, t-butyl hypochlorite, N-chlorosuccinimide, N-chloroglutarimide, 1,3-dichloro Chlorinating agents such as 5,5-dimethylhydantoin, trichloroisocyanuric acid, hydrogen chloride, alkali metal bromates such as bromine, sodium bromate, potassium bromate, N-bromosuccinimide, 1,3-bromo- Brominating agents such as 5,5-dimethylhydantoin, N, N′-dibromoisocyanuric acid, iodine, iodine monochloride, potassium iodide, N-iodosuccinimide, 1,3-diiodo-5,5-dimethylhydantoin And 0.3 to 5.0 equivalents are used per 1 equivalent of the compound represented by the general formula (2-2). Door
  • examples of the catalyst used include Lewis acids such as aluminum chloride, iron (III) chloride, zinc chloride, etc., and 0.0001 to 1 with respect to 1 equivalent of the compound represented by the general formula (2-2). 0.0 equivalent can be used.
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • examples thereof include ethyl, acetonitrile, N, N-dimethylformamide, N-methyl-2-pyrrolidone, methanol, 2-propanol, acetic acid, hydrochloric acid, sulfuric acid and water.
  • These solvents may be used alone or as a mixture of two or more thereof.
  • the reaction temperature can be set to an arbitrary temperature from ⁇ 10 to 150 ° C., and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set within the range of 1 to 48 hours.
  • the compound represented by the general formula (2-3) in which X 1 and X 2 represent halogen atoms can be produced, for example, by the following method. Manufacturing method C
  • halogenating agent examples include chlorine gas, sulfuryl chloride, sodium chlorate, sodium hypochlorite, t-butyl hypochlorite, N-chlorosuccinimide, N-chloroglutarimide, 1,3-dichloro Chlorinating agents such as 5,5-dimethylhydantoin or trichloroisocyanuric acid, hydrogen chloride, alkali metal bromates such as bromine, sodium bromate, potassium bromate, N-bromosuccinimide, 1,3-bromo- Brominating agents such as 5,5-dimethylhydantoin, N, N′-dibromoisocyanuric acid, iodine, iodine monochloride, potassium iodide, N-iodosuccinimide, 1,3-diiodo-5,5-dimethylhydantoin And 0.6 to 5.0 equivalents of the compound represented by the general formula (2-4) are used. It is possible
  • examples of the catalyst used include Lewis acids such as aluminum chloride, iron (III) chloride, zinc chloride, etc., and 0.0001 to 1 with respect to 1 equivalent of the compound represented by the general formula (2-4). 0.0 equivalent can be used.
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • examples thereof include ethyl, acetonitrile, N, N-dimethylformamide, N-methyl-2-pyrrolidone, methanol, 2-propanol, acetic acid, hydrochloric acid, sulfuric acid and water.
  • These solvents may be used alone or as a mixture of two or more thereof.
  • the reaction temperature can be set to an arbitrary temperature from ⁇ 10 to 150 ° C., and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set within the range of 1 to 48 hours.
  • the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, washed with water, or concentrated in ice water, or subjected to usual post-treatment such as concentration after extraction with an organic solvent.
  • a compound represented by the formula (2) can be obtained. Further, when the necessity for purification arises, it can be separated and purified by any purification method such as recrystallization, back extraction, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.
  • the compound represented by the general formula (1) included in the present invention is reacted with an alcohol such as methanol, ethanol, 1-propanol, 2-propanol or water to give a compound represented by the general formula (1A) [wherein X 1 , X 2 , X 3 and Y have the same meaning as described above, and R represents a hydrogen atom or C 1 -C 4 alkyl. ] It can be set as the acetal compound represented by this.
  • the compound represented by the general formula (1A) may be present in a mixture containing the compound represented by the general formula (1) at an arbitrary ratio.
  • the compound represented by the general formula (2) included in the present invention is reacted with an alcohol such as methanol, ethanol, 1-propanol, 2-propanol or water to give a compound represented by the general formula (2A) [wherein X 1 , X 2 , X 3 , Y and R represent the same meaning as described above. ] It can be set as the acetal compound represented by this.
  • the compound represented by the general formula (2A) may be present in a mixture containing the compound represented by the general formula (2) at an arbitrary ratio.
  • the compound represented by the general formula (2-1) included in the present invention is reacted with an alcohol such as methanol, ethanol, 1-propanol, 2-propanol, or water to give a compound represented by the general formula (2-1A)
  • X 1 represents a chlorine atom, a bromine atom or an iodine atom
  • X 2 represents the same meaning as described above excluding a hydrogen atom
  • X 3 , Y and R represent the same meaning as described above.
  • the compound represented by the general formula (2-1A) may be present in a mixture containing the compound represented by the general formula (2-1) in an arbitrary ratio.
  • the compound represented by the general formula (2-2) included in the present invention is reacted with an alcohol such as methanol, ethanol, 1-propanol, 2-propanol, or water to give a compound represented by the general formula (2-2A)
  • an alcohol such as methanol, ethanol, 1-propanol, 2-propanol, or water
  • X 2 represents the same meaning as described above except for a hydrogen atom
  • X 3 , Y, and R represent the same meaning as described above.
  • the compound represented by the general formula (2-2A) may be present in a mixture containing the compound represented by the general formula (2-2) in an arbitrary ratio.
  • the compound represented by the general formula (2-3) included in the present invention is reacted with an alcohol such as methanol, ethanol, 1-propanol, 2-propanol, or water, so that the substituents X 1 and X 2 are changed.
  • General formula (2-3A) having the same meaning [wherein, X 1 and X 2 represent a chlorine atom, a bromine atom or an iodine atom, and X 3 , Y and R represent the same meaning as described above. ] It can be set as the acetal compound represented by this.
  • the compound represented by the general formula (2-3A) may be present in a mixture containing the compound represented by the general formula (2-3) in an arbitrary ratio.
  • the compound represented by the general formula (2-4) included in the present invention is reacted with an alcohol such as methanol, ethanol, 1-propanol, 2-propanol, or water, to give a compound represented by the general formula (2-4A) [
  • X 3 , Y and R represent the same meaning as described above. ] It can be set as the acetal compound represented by this.
  • the compound represented by the general formula (2-4A) may exist in a mixture containing the compound represented by the general formula (2-4) in an arbitrary ratio.
  • the compound represented by the general formula (3) included in the present invention is reacted with an alcohol such as methanol, ethanol, 1-propanol, 2-propanol or water to give a compound represented by the general formula (3A) [wherein X 1 , X 2 , X 3 and Y each have the same meaning as described above, and X ⁇ represents chloride ion, bromide ion, fluoride ion, nitrate ion, phosphate ion, perchlorate ion, acetate ion, methanesulfonic acid.
  • an alcohol such as methanol, ethanol, 1-propanol, 2-propanol or water
  • X ⁇ represents chloride ion, bromide ion, fluoride ion, nitrate ion, phosphate ion, perchlorate ion, acetate ion, methanesulfonic acid.
  • the compound represented by the general formula (3A) may be present in a mixture containing the compound represented by the general formula (3) at an arbitrary ratio.
  • the compound represented by formula (3) and the compound represented by formula (3A) can be converted to an acid addition salt according to a conventional method.
  • Examples of the acid used for forming the acid addition salt include hydrohalic acid salts such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, phosphoric acid, chloric acid, peroxygen, and the like.
  • Inorganic acids such as chloric acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, sulfonic acid such as p-toluenesulfonic acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid, Oxalic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, carboxylic acid such as lactic acid, gluconic acid and citric acid, or amino acid such as glutamic acid and aspartic acid can be used.
  • Inorganic acids such as chloric acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, sulfonic acid such as p-toluenesulfonic acid, formic acid
  • the compound represented by the general formula (1), the compound represented by the general formula (1A), the compound represented by the general formula (2), and the general formula (2A) included in the present invention Compound, compound represented by general formula (2-1), compound represented by general formula (2-1A), compound represented by general formula (2-2), represented by general formula (2-2A) A compound represented by formula (2-3), a compound represented by formula (2-3A), a compound represented by formula (2-4), a formula (2-4A)
  • the compound represented by general formula (3) and the compound represented by general formula (3A) can be converted into a metal salt according to a conventional method.
  • the base used for forming the metal salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as calcium, barium and magnesium, and aluminum.
  • the compound represented by the general formula (1) that can be produced according to the present invention is an intermediate of medical and agricultural chemicals, for example, agricultural pests, spider mites, mammals or birds described in WO2009 / 001942.
  • a substituted isoxazoline compound that has excellent insecticidal and acaricidal activity against internal or ectoparasites, and also exhibits a sufficient control effect against pests that have acquired resistance to existing insecticides and acaricides Useful as a production intermediate.
  • the proton nuclear magnetic resonance chemical shift value of the example was measured at 300 MHz using Me 4 Si (tetramethylsilane) as a reference substance. Moreover, the solvent used for the measurement is described in the following synthesis examples.
  • the solvent was distilled off from the obtained organic layer at normal pressure to obtain 0.37 g of a heptane solution containing the target product.
  • This heptane solution was found to contain 92 mg of the target product by an internal standard analysis method using high performance liquid chromatography (HPLC).
  • Synthesis example 2 Production of 1- (3,5-dichlorophenyl) -2,2,2-trifluoroethanone 1- (2-amino-3,5-dichlorophenyl) -2,2,2-trifluoroethanone 0.52 g, concentrated sulfuric acid A mixture of 2.0 and 0.5 g of water was dissolved with stirring at 50 ° C. After cooling to 5 ° C. or lower, 0.27 g of sodium nitrite was added over 5 minutes and stirred at the same temperature for 0.5 hour. The slurry solution was added over 30 minutes to a mixed solution of 1.5 ml of a 30-32 mass% hypophosphorous acid aqueous solution in a temperature range of 15-30 ° C.
  • reaction solution was added to a slurry of 0.22 g of iron sulfate heptahydrate and 0.40 g of N, N-dimethylformamide, and stirred at room temperature for 1 day. After completion of the stirring, an additional slurry of 0.22 g of iron sulfate heptahydrate and 0.60 g of N, N-dimethylformamide was added, and stirring was further continued at room temperature for 8 days.
  • Synthesis example 7 Preparation of 1- (3,5-dichlorophenyl) -2,2,2-trifluoroethanone 1- (2-amino-3,5-dichlorophenyl) -2,2,2-trifluoroethanone 0.50 g and toluene 1 0.5 g of the mixed solution was heated to 50 ° C., 1.32 g of 50 mass% sulfuric acid aqueous solution was added at the same temperature, and the mixture was stirred at the same temperature for 30 minutes.
  • heptane layer was separated from the reaction mixture, the aqueous layer was extracted with 1.5 g of heptane, and 3.3 g of a heptane solution containing the target product was obtained.
  • This heptane solution was found to contain 0.42 g of the desired product by an internal standard analysis method using gas chromatography (GC).
  • Synthesis example 8 Preparation of 1- (3,5-dichlorophenyl) -2,2,2-trifluoroethanone 1- (2-amino-3,5-dichlorophenyl) -2,2,2-trifluoroethanone 0.20 g, ethanol 1 A mixed solution of 0.000 g, concentrated sulfuric acid 0.27 g and copper (II) sulfate pentahydrate 19 mg was added dropwise over 5 minutes while stirring at 50 ° C. over a period of 5 minutes. Stirring was continued at temperature for an additional 13 hours.
  • reaction mixture was allowed to cool to room temperature, diluted with 5 ml of water, and extracted with ethyl acetate (5 ml ⁇ 2) to obtain 13.50 g of an ethyl acetate solution containing the desired product.
  • This ethyl acetate solution was found to contain 107 mg of the target product by an internal standard analysis method using GC described in Synthesis Example 7.
  • reaction mixture was allowed to cool to room temperature, diluted with 5 ml of water and extracted with ethyl acetate (5 ml ⁇ 2) to obtain 13.23 g of an ethyl acetate solution containing the desired product.
  • This ethyl acetate solution was found to contain 183 mg of the desired product by an internal standard analysis method using GC described in Synthesis Example 7.
  • reaction mixture was allowed to cool to room temperature and extracted with heptane (2.2 ml ⁇ 2) to obtain 3.80 g of a heptane solution containing the target product.
  • This heptane solution was found to contain 451 mg of the desired product by an internal standard analysis method using GC described in Synthesis Example 7.
  • the whole toluene solution containing 1- (2-amino-5-chlorophenyl) -2,2,2-trifluoroethanone obtained was heated to 70 ° C., and a part of the toluene and water were distilled off at 24 to 25 kPa. did.
  • the toluene solution was cooled to room temperature, the internal pressure was returned to atmospheric pressure, and toluene was added so that the total amount became 50.7 g.
  • the obtained toluene solution was heated to 60 ° C., and 7.35 g of sulfuryl chloride was added dropwise over 1 hour and 30 minutes. After completion of dropping, the mixture was stirred at 60 ° C. for 5 hours.
  • the reaction solution was cooled to room temperature and then stirred overnight at room temperature. After completion of the stirring, the reaction solution was heated to 40 ° C., 20.3 g of water was added at the same temperature, and the mixture was stirred at the same temperature for 1 hour. After completion of the stirring, the aqueous layer was separated from the reaction mixture by a liquid separation operation to obtain 57.6 g of a toluene solution of 1- (2-amino-3,5-dichlorophenyl) -2,2,2-trifluoroethanone. .
  • the toluene solution contains 11.0 g of 1- (2-amino-3,5-dichlorophenyl) -2,2,2-trifluoroethanone by an internal standard analysis method using GC described in Synthesis Example 7. It has been found.
  • the aqueous layer was separated from the reaction mixture by a liquid separation operation, and the obtained aqueous layer was prepared in a separate solution in a mixed solution of 18.5 g of a 50 mass% hypophosphorous acid aqueous solution and 36.2 g of toluene. Was added dropwise at 50 ° C. over 30 minutes, and stirring was further continued at the same temperature for 2 hours.
  • the toluene layer was separated from the reaction mixture by a liquid separation operation.
  • the obtained toluene layer was washed with 11.0 g of water and 11.0 g of a 5% by mass aqueous sodium hydrogen carbonate solution to obtain 45.4 g of a toluene solution containing the target product.
  • the toluene solution was found to contain 9.71 g of 1- (3,5-dichlorophenyl) -2,2,2-trifluoroethanone by an internal standard analysis method using GC described in Synthesis Example 7. .
  • the organic layer was separated by liquid separation, 50 ml of water and 5 g of sodium bicarbonate were added to the obtained organic layer, and the mixture was stirred at room temperature for 30 minutes. After completion of the stirring, the organic layer was separated by liquid separation, and the obtained organic layer was dried over anhydrous sodium sulfate and evaporated under reduced pressure to obtain 11.48 g of the desired product as a yellow solid.
  • toluene layer A a toluene layer
  • aqueous layer by a liquid separation operation while maintaining 0 ° C.
  • the obtained aqueous layer was acidified by adding 2.86 ml of ice-cooled concentrated hydrochloric acid, and extracted three times with 20.1 g of toluene.
  • the toluene solution obtained by the extraction operation was concentrated under reduced pressure, and 3.032 g of 1- (2-amino-3,5-dichlorophenyl) -2,2,2-trifluoroethanone having a purity of 99.9% was yellow. Obtained as a solid.
  • the purity in this reference example was determined by analyzing the GC measurement conditions shown below and calculating the relative area percentage value excluding the solvent peak.
  • Process for producing 1- (substituted phenyl) -2-halo-2,2-difluoroethanone compound and 1- (2-amino-substituted phenyl) -2-halo-2,2-difluoroethanone compound according to the present invention Is extremely useful as a novel intermediate for the production of substituted isoxazoline compounds that exhibit excellent pest control activity, especially insecticidal / miticidal activity, and have little adverse effect on non-target organisms such as mammals, fish and beneficial insects. .

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Abstract

La présente invention a pour but de proposer un nouveau procédé pour produire un composé 1-(phényl substitué)-2-halo-2,2-difluoroéthanone. A cet effet, l'invention propose un procédé de fabrication de production d'un composé représenté par la formule générale (1) par une réaction d'un composé représenté par la formule générale (2) avec un composé acide nitreux. (Dans la formule générale (2), chacun parmi X1, X2 et X3 représente indépendamment un atome d'halogène, un groupe alkyle en C1-C6, un groupe haloalkyle en C1-C6, un groupe alcoxy en C1-C6, un groupe haloalcoxy en C1-C6 ou similaire, Y représente un atome d'halogène). (Dans la formule générale (1), X1, X2, X3 et Y sont tels que définis ci-dessus).
PCT/JP2012/063488 2011-05-26 2012-05-25 Composé 1-(phényl substitué par 2-amino)-2-halo-2,2-difluoroéthanone et procédé de fabrication d'un composé 1-(phényl substitué)-2-halo-2,2-difluoroéthanone WO2012161313A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105801442A (zh) * 2015-10-16 2016-07-27 浙江沙星医药化工有限公司 4-氯-2-(三氟乙酰基)苯胺盐酸盐水合物的制备方法
CN106795080A (zh) * 2014-10-14 2017-05-31 先正达参股股份有限公司 用于制备卤代三氟苯乙酮的方法
CN106795093A (zh) * 2014-10-14 2017-05-31 先正达参股股份有限公司 用于制备1‑(3,5‑二氯苯基)‑2,2,2‑三氟乙酮及其衍生物的方法
CN113651707A (zh) * 2021-08-18 2021-11-16 杭州臻挚生物科技有限公司 邻位氨基三氟苯乙酮及其衍生物的制备方法
WO2022058916A1 (fr) 2020-09-17 2022-03-24 Pi Industries Limited Procédé de synthèse de composés acide/amide anthranilique et intermédiaires de ceux-ci
WO2022061920A1 (fr) * 2020-09-28 2022-03-31 台州臻挚生物科技有限公司 Procédé de préparation de 3',5'-dichloro-2,2,2-trifluoroacétophénone
WO2022061914A1 (fr) * 2020-09-28 2022-03-31 台州臻挚生物科技有限公司 Procédé de préparation de 3,5-dihalogénotrifluoroacétophénone et d'un dérivé correspondant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4577046A (en) * 1984-06-11 1986-03-18 University Of New Mexico Deamination of aromatic amines
JPH05286882A (ja) * 1992-04-03 1993-11-02 Seimi Chem Co Ltd ２，３−ジフルオロフェノール類の製造方法
JP2001505873A (ja) * 1996-10-02 2001-05-08 デュポン ファーマシューティカルズ カンパニー Ｈｉｖ逆転写酵素阻害剤として有用な４，４―二置換―１，４―ジヒドロ―２ｈ―３，１―ベンゾオキサジン―２―オン類、およびそれらを製造するための中間体および方法
JP2009530260A (ja) * 2006-03-17 2009-08-27 ミテーニ ソチエタ ペル アツィオーニ １−ブロモ−３−トリフルオロメトキシベンゼンの製法
WO2009116577A1 (fr) * 2008-03-18 2009-09-24 日産化学工業株式会社 Procédés de fabrication de 1-(phényl substitué)-1-(silyl substitué)-éthers, alcools ou cétones et intermédiaires correspondants

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4614746A (en) * 1985-03-21 1986-09-30 American Cyanamid Company 5-fluorobenzonitrile derivatives for increasing the lean meat to fat ratio and/or enhancing the growth rate of warm-blooded animals
JP2012051803A (ja) * 2008-12-25 2012-03-15 Kyorin Pharmaceutical Co Ltd 環状アミノ安息香酸エステル誘導体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4577046A (en) * 1984-06-11 1986-03-18 University Of New Mexico Deamination of aromatic amines
JPH05286882A (ja) * 1992-04-03 1993-11-02 Seimi Chem Co Ltd ２，３−ジフルオロフェノール類の製造方法
JP2001505873A (ja) * 1996-10-02 2001-05-08 デュポン ファーマシューティカルズ カンパニー Ｈｉｖ逆転写酵素阻害剤として有用な４，４―二置換―１，４―ジヒドロ―２ｈ―３，１―ベンゾオキサジン―２―オン類、およびそれらを製造するための中間体および方法
JP2009530260A (ja) * 2006-03-17 2009-08-27 ミテーニ ソチエタ ペル アツィオーニ １−ブロモ−３−トリフルオロメトキシベンゼンの製法
WO2009116577A1 (fr) * 2008-03-18 2009-09-24 日産化学工業株式会社 Procédés de fabrication de 1-(phényl substitué)-1-(silyl substitué)-éthers, alcools ou cétones et intermédiaires correspondants

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MARCH, JERRY: "Replacement of the Diazonium Group by Hydrongen", ADVANCED ORGANIC CHEMISTRY: REACTIONS, MECHANISMS, AND STRUCTURE, 1992, pages 721 - 722 *
XIE ET AL., ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 50, 11 October 2011 (2011-10-11), pages 11773 - 11776 *

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CN106795080A (zh) * 2014-10-14 2017-05-31 先正达参股股份有限公司 用于制备卤代三氟苯乙酮的方法
CN106795093A (zh) * 2014-10-14 2017-05-31 先正达参股股份有限公司 用于制备1‑(3,5‑二氯苯基)‑2,2,2‑三氟乙酮及其衍生物的方法
CN106795093B (zh) * 2014-10-14 2019-05-28 先正达参股股份有限公司 用于制备1-(3,5-二氯苯基)-2,2,2-三氟乙酮及其衍生物的方法
CN106795080B (zh) * 2014-10-14 2024-06-04 先正达参股股份有限公司 用于制备卤代三氟苯乙酮的方法
CN105801442A (zh) * 2015-10-16 2016-07-27 浙江沙星医药化工有限公司 4-氯-2-(三氟乙酰基)苯胺盐酸盐水合物的制备方法
WO2022058916A1 (fr) 2020-09-17 2022-03-24 Pi Industries Limited Procédé de synthèse de composés acide/amide anthranilique et intermédiaires de ceux-ci
WO2022061920A1 (fr) * 2020-09-28 2022-03-31 台州臻挚生物科技有限公司 Procédé de préparation de 3',5'-dichloro-2,2,2-trifluoroacétophénone
WO2022061914A1 (fr) * 2020-09-28 2022-03-31 台州臻挚生物科技有限公司 Procédé de préparation de 3,5-dihalogénotrifluoroacétophénone et d'un dérivé correspondant
CN113651707A (zh) * 2021-08-18 2021-11-16 杭州臻挚生物科技有限公司 邻位氨基三氟苯乙酮及其衍生物的制备方法

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