WO2010018868A1 - Pest control agent containing triazolopyrimidine derivative or salt thereof - Google Patents

Pest control agent containing triazolopyrimidine derivative or salt thereof Download PDF

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Publication number
WO2010018868A1
WO2010018868A1 PCT/JP2009/064359 JP2009064359W WO2010018868A1 WO 2010018868 A1 WO2010018868 A1 WO 2010018868A1 JP 2009064359 W JP2009064359 W JP 2009064359W WO 2010018868 A1 WO2010018868 A1 WO 2010018868A1
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formula
alkyl
compound
reaction
optionally substituted
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PCT/JP2009/064359
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French (fr)
Japanese (ja)
Inventor
一浩 山元
剛 上田
寿彦 植木
和久 桐山
幸太郎 吉田
久樹 田中
哲也 小玉
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石原産業株式会社
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/02—Antiprotozoals, e.g. for leishmaniasis, trichomoniasis, toxoplasmosis
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/02—Antiprotozoals, e.g. for leishmaniasis, trichomoniasis, toxoplasmosis
    • A61P33/06—Antimalarials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/10—Anthelmintics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/10—Anthelmintics
    • A61P33/12—Schistosomicides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the present invention relates to a novel pest control agent containing a triazolopyrimidine derivative or a salt thereof as an active ingredient.
  • Patent Documents 1 and 2 describe triazolopyrimidine derivatives used for the production of dyes. Non-Patent Documents 1 and 2 also describe that triazolopyrimidine derivatives have herbicidal activity. However, these documents do not describe the use of triazolopyrimidine derivatives as insecticides, acaricides, nematicides or soil insecticides or animal parasite control agents. Furthermore, there is no specific description of the triazolopyrimidine derivative represented by the following formula (I- ⁇ ).
  • An object of the present invention is to provide a pest control agent that can control various pests that cause problems in the field of agriculture and horticulture and pests that parasitize animals without any disadvantages such as limited use.
  • the present inventors have made various studies on triazolopyrimidine derivatives in order to find better pest control agents. As a result, the present inventors have found that the triazolopyrimidine derivative represented by the following formula (I) has a very high control effect against pests with a low dose, and completed the present invention.
  • the present invention has the formula (I):
  • R 1 is a hydrogen atom, alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano , Aryl optionally substituted with halogen, heterocyclic group optionally substituted with alkyl, C ⁇ NOR 2 , C ⁇ NNR 4 R 5 , COR 2 , COOR 2 , OR 2 , S (O) n R 3 , NR 4 R 5 , N 3 or CONR 4 R 5 ;
  • X is alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, NR 4 R 5 , S (O) n R 3 , OR 2 , COR 2 , COOR 2 or CONR 4 R 5 ;
  • Y is a hydrogen atom or a fluorine atom;
  • Z is CH,
  • R 1 ⁇ is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano, halogen Aryl which may be substituted, heterocyclic group which may be substituted with alkyl, C ⁇ NOR 2 , C ⁇ NNR 4 R 5 , COR 2 , COOR 2 , OR 2 , S (O) n R 3 or CONR 4 R It is 5;
  • X is an alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, NR 4 R 5, S ( O) n R 3, oR 2, COR 2, COOR 2 or CONR 4 R It is 5;
  • Y is a hydrogen atom or a fluorine atom;
  • Z is CH, CX or n;
  • A is a halogen, oR
  • M is an integer from 1 to 4; n is an integer from 0 to 2; provided that (1) when R 1 ⁇ is methyl, X is 4-methoxy, and Z is CH, (2 ) R 1 ⁇ is methyl, X is 3,4-dimethoxy, Z is CH, and (3) R 1 ⁇ is methyl, X is 4-methyl, and Z is CH.
  • New It relates rear triazolopyrimidine derivative or a salt thereof.
  • the pest control agent comprising the triazolopyrimidine derivative of the formula (I) or a salt thereof as an active ingredient has a very high control effect against pests at a low dose.
  • each X may be the same or different.
  • halogen in formula (I) or the halogen as a substituent examples include each atom of fluorine, chlorine, bromine or iodine.
  • the number of halogens as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen may be the same or different. Further, the halogen substitution position may be any position.
  • the alkyl in the formula (I) may be linear or branched, for example, C 1-6 such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, etc. Can be mentioned.
  • cycloalkyl in formula (I) examples include C 3-6 such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • the alkenyl in the formula (I) may be linear or branched, such as vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1,3-butadienyl, 1-hexenyl and the like. C 2-6 may be mentioned.
  • the alkynyl in the formula (I) may be linear or branched.
  • Examples of the aryl in the formula (I) include C 6-10 aryl such as phenyl and naphthyl.
  • the heterocyclic group in the formula (I) includes a condensed heterocyclic group in addition to a monocyclic heterocyclic group.
  • Monocyclic heterocyclic groups include, for example, 3-membered heterocyclic groups such as oxiranyl; furyl, tetrahydrofuryl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, dioxolanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl 5-membered heterocyclic groups such as pyrazolinyl, pyrazolidinyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl; 6-membered heterocyclic groups such as pyranyl, pyridyl, piperidinyl, dioxanyl,
  • a 5- or 6-membered heterocyclic group containing 1 to 4 atoms of at least one atom selected from the group consisting of O, S and N is desirable.
  • the condensed heterocyclic group include benzofuranyl, isobenzofuranyl, dihydrobenzofuranyl, dihydroisobenzofuranyl, benzothienyl, isobenzothienyl, dihydrobenzothienyl, dihydroisobenzothienyl, tetrahydrobenzothienyl, indolyl, isoindolyl, Benzoxazolyl, benzothiazolyl, indazolyl, benzimidazolyl, benzodioxolanyl, benzodioxanyl, chromenyl, chromanyl, isochromanyl, chromonyl, chromanonyl, quinolyl, isoquinolyl, cin
  • Examples of the salt of the triazolopyrimidine derivative of the formula (I) include any agriculturally acceptable salt, for example, ammonium salts such as dimethylammonium salt and triethylammonium salt; Examples thereof include inorganic acid salts such as acid salts, sulfates and nitrates; organic acid salts such as acetates and methanesulfonates.
  • the present invention includes both isomers and isomer mixtures.
  • isomers are described as a mixture unless otherwise specified.
  • the present invention also includes various isomers other than those described above within the scope of technical common sense in the technical field.
  • the chemical structure may be different from that of the formula (I).
  • the scope of the present invention It is clear that it is within.
  • the triazolopyrimidine derivative of the formula (I) or a salt thereof can be produced according to the following production methods [1] to [19] and usual salt production methods. The reaction flow will be described in detail below for each production method. Manufacturing method [1]
  • R 1a is a hydrogen atom, alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen
  • R 6 and R 7 are each independently alkyl; A, X, Z and m are as defined above.
  • the production method [1] comprises the reaction steps of the above [1] -1 and [1] -2. From the compound of the formula (II), [1,2,4] triazolo [1,5 of the formula (I-1) -A] Pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
  • an ⁇ , ⁇ -unsaturated ketone derivative of the formula (IV) can be produced by condensing the compound of the formula (II) and the compound of the formula (III).
  • the compound of formula (III) can be used at a ratio of 1 to 5 equivalents, preferably 1 to 3 equivalents, per 1 mol of the compound of formula (II).
  • This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • alcohols such as methanol, ethanol, propanol and butanol
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • pentane and hexane Aliphatic hydrocarbons such as petroleum ether, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; esters such as methyl acetate and ethyl acetate; acetonitrile Nitriles such as propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; Heki Phosphoric acid amides such as methyl phosphoramide; chloroform, dich
  • the compound of formula (I-1) can be produced by condensing the compound of formula (IV) and the compound of formula (V).
  • the compound of the formula (V) can be used in a ratio of 1 to 10 equivalents, desirably 1 to 2.5 equivalents, per 1 mol of the compound of the formula (IV).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely affect the reaction.
  • carboxylic acids such as acetic acid and propionic acid
  • alcohols such as methanol, ethanol, propanol and butanol
  • benzene, toluene and xylene for example, carboxylic acids such as acetic acid and propionic acid; alcohols such as methanol, ethanol, propanol and butanol; benzene, toluene and xylene.
  • Aromatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; methyl acetate Esters such as ethyl acetate; nitriles such as acetonitrile and propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; and dimethyl sulfoxide Sulfoxy Sulfones such as sulfolane; phosphoric acid amides such as hexamethylphosphoramide; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane; and mixed solvents thereof Among them, carboxylic
  • R 1b is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, and halogen substituted.
  • R 8 is alkyl;
  • A, X, Z and m are as described above.
  • the production method [2] comprises the reaction steps of the above [2] -1 and [2] -2. From the compound of formula (II), [1,2,4] triazolo [1,5 of formula (I-2) -A] Pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
  • the compound of formula (VII) can be produced by reacting the compound of formula (II) with the compound of formula (VI).
  • the compound of the formula (VI) can be used in an amount of 1 equivalent to a large excess, desirably 1 to 3 equivalents, relative to 1 mol of the compound of the formula (II). This reaction can usually be performed in the presence of a base and a solvent.
  • the base examples include metal hydrides such as sodium hydride and potassium hydride; metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as sodium and potassium; sodium methoxide and sodium ethoxide And alkali metal alkoxides such as potassium tertiary butoxide;
  • the base can be used in an amount of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of formula (II).
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • aromatic hydrocarbons such as benzene, toluene, xylene; pentane, hexane, heptane, petroleum ether, ligroin, petroleum benzine Aliphatic hydrocarbons; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone; Examples thereof include sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane; and mixed solvents thereof. Ethers are desirable.
  • the reaction temperature is usually 0 to 70 ° C., preferably 10 to 50 ° C.
  • the reaction time is usually
  • the compound of formula (I-2) can be produced by condensing the compound of formula (VII) with the compound of formula (V).
  • the compound of the formula (V) can be used at a ratio of 1 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of the formula (VII).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • carboxylic acids such as acetic acid and propionic acid
  • alcohols such as methanol, ethanol, propanol and butanol
  • aromatic carbonization such as benzene, toluene and xylene Hydrogen: aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; esters such as methyl acetate and ethyl acetate Nitriles such as acetonitrile and propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfolane and the like Examples include sulfones; phosphoric acid amide
  • R 9 is alkyl; R 1b , X, Z and m are as described above.
  • the production method [3] comprises the reaction steps of the above [3] -1 and [3] -2. From the compound of the formula (VIII), [1,2,4] triazolo [1,5] of the formula (I-2) -A] Pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
  • the compound of formula (VII) can be produced by reacting the compound of formula (VIII) with the compound of formula (IX).
  • the compound of the formula (IX) can be used in a proportion of 0.8 equivalent to a large excess, desirably 1 to 10 equivalent, relative to 1 mol of the compound of the formula (VIII).
  • This reaction can usually be performed in the presence of a base and a solvent.
  • the base include those similar to the reaction step [2] -1 in the above production method [2].
  • the base can be used in a proportion of usually 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of the formula (VIII).
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • the same solvents as those in the reaction step [2] -1 of the above production method [2] can be exemplified, and among these, ethers are desirable.
  • the reaction temperature is usually 0 to 70 ° C., preferably 10 to 50 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • This reaction step can be carried out in the same manner as in the reaction step [2] -2 of the production method [2]. Manufacturing method [4]
  • R 1c is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, cyano or halogen.
  • R 10 is alkyl;
  • R 11 is OH, alkyl, cycloalkyl P is 2 when R 11 is alkyl, cycloalkyl or alkoxy, and 3 when R 11 is a fluorine atom;
  • alkyl or alkoxy of R 11 is an adjacent boron atom May be bonded to each other to form a ring;
  • hal is a halogen;
  • R 2 , R 3 , R 4 , R 5 , A, X, Z and m are as described above. Examples of the halogen represented by hal include fluorine, chlorine, bromine or iodine atoms.
  • Production method [4] comprises the reaction steps of [4] -1, [4] -2, [4] -3 and [4] -4, and from the compound of formula (X) to formula (I-4) [1,2,4] Triazolo [1,5-a] pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
  • This reaction step is a reaction step for halogenating the compound of the formula (XI), (A) reacting a compound of formula (XI) with a chlorinating agent or brominating agent to produce a compound of formula (XII) wherein hal is a chlorine or bromine atom; (B) If necessary, the compound of the formula (XII) formed in (a) and a fluorinating agent are reacted to give a compound of the formula (XII) (wherein hal is a fluorine atom) Manufacturing; and (C) If necessary, the compound of formula (XII) formed in (a) is reacted with ammonia and then reacted with an iodinating agent in the presence of a diazotizing agent to give a compound of formula (XII) ( Wherein at least one hal is an iodine atom).
  • the methods (a) to (c) will be described in detail below.
  • Examples of the chlorinating agent include phosphorus oxychloride, phosphorus trichloride, and phosphorus pentachloride.
  • Examples of the brominating agent include phosphorus oxybromide, phosphorus tribromide, and phosphorus pentabromide.
  • the chlorinating agent or brominating agent can be used usually in a proportion of 1 equivalent to a large excess with respect to 1 mol of the compound of the formula (XI). This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include halogenated hydrocarbons such as dichloromethane.
  • the reaction temperature is usually 0 ° C. to the reflux temperature of the reaction mixture, preferably 20 ° C. to the reflux temperature of the reaction mixture.
  • the reaction time is usually 1 to 48 hours.
  • Examples of the fluorinating agent include fluorides of alkali metals, particularly potassium fluoride, antimony pentafluoride and diethylaminosulfur trifluoride.
  • the fluorinating agent can be used in an amount of 1 to 5 equivalents, preferably 1.5 to 3 equivalents, per mole of the compound of formula (XII) (wherein hal is a chlorine atom or a bromine atom).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile and propionitrile; sulfones such as sulfolane; And acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; and mixed solvents thereof.
  • sulfones or acid amides are used as a solvent, it is advantageous to use toluene as a co-solvent to assist dehydration of the fluorinating agent.
  • the reaction temperature is usually 15 ° C. to the reflux temperature of the reaction mixture, preferably 40 ° C. to the reflux temperature of the reaction mixture.
  • the reaction time is usually 2 to 48 hours.
  • the reaction temperature is from 20 ° C. to the reflux temperature of the reaction mixture, preferably from 40 ° C. to the reflux temperature of the reaction mixture.
  • the reaction time is usually 2 to 48 hours.
  • the reaction is then carried out with an iodinating agent in the presence of a diazotizing agent.
  • a diazotizing agent include any alkyl ester of nitrous acid, and isopentyl nitrite is particularly preferable.
  • the diazotizing agent can be used usually in a ratio of 1 equivalent to 5 equivalents per 1 mol of the compound of the formula (XII) (wherein hal is a chlorine or bromine atom).
  • the iodinating agent include iodine and diiodomethane.
  • the iodinating agent can be used in an amount of 1 to 5 equivalents, preferably 1.5 to 3 equivalents, per mole of the compound of formula (XII) (wherein hal is a chlorine atom or a bromine atom).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, ligroin, petroleum benzine; diethyl ether, dipropyl ether, diethylene
  • ethers such as butyl ether, tetrahydrofuran and dioxane
  • esters such as methyl acetate and ethyl acetate
  • nitriles such as acetonitrile and propionitrile
  • the reaction of (c) can be carried out as a one-pot synthesis, and when an alkyl ester of nitrous acid is used as a diazotizing agent, diiodomethane can be used as a cosolvent as an iodinating agent. .
  • the reaction temperature is usually 60 ° C. to 120 ° C., desirably 70 ° C. to 110 ° C.
  • the reaction time is usually 1 to 48 hours.
  • R 11 is a fluorine atom
  • p is 3. Since the —BF 3 group is negatively charged, Forms trifluoroborate salts with alkali metals.
  • Examples of the substituted boron represented by B (R 11 ) p in formula (XIII) include hydroxyboron, alkylboron, alkoxyboron, and trifluoroborate potassium salt.
  • the boron compound of the formula (XIII) can be used at a ratio of 0.5 to 1 equivalent per 1 mol of the compound of the formula (XII).
  • the transition metal catalyst used in this reaction means a transition metal compound or a complex of a transition metal compound and an arbitrary ligand.
  • a transition metal compound or a complex of a transition metal compound and an arbitrary ligand for example, palladium-carbon (Pd / C), tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), tetrakis (dibenzylideneacetone) dipalladium (0), palladium (II)- Examples thereof include triphenylphosphine and palladium (II) acetate-tricyclohexylphosphine. .
  • transition metal catalyst can be used in a proportion of 0.001 to 0.2 equivalent, preferably 0.01 to 0.1 equivalent, relative to 1 mol of the compound of formula (XII).
  • This reaction can usually be performed in the presence of a base.
  • the base include alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate; sodium hydroxide , Alkali metal hydroxides such as potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; inorganic salts such as cesium fluoride and potassium fluoride, triethylamine, pyridine, 4- (N, N -Amines such as (dimethylamino) pyridine;
  • the base can be used usually in a proportion of 0.9 to 20 equivalents per 1 mol of the compound of the formula (XII).
  • this reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • water alcohols such as methanol, ethanol, propanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; pentane Aliphatic hydrocarbons such as hexane, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether; acetonitrile, propionitrile Nitriles such as: halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane; and mixed solvents thereof.
  • the reaction temperature is usually 15 ° C. to the reflux temperature of the reaction mixture, preferably 40 ° C. to the reflux temperature of the reaction mixture.
  • the reaction time is not constant depending on the reaction temperature, reaction amount, reaction pressure and the like, but is usually 1 to 96 hours.
  • the boron compound of formula (XIII) is commercially available or can be synthesized by a conventional method.
  • it can be synthesized from the corresponding halogen, preferably a bromine derivative, by the action of trimethyl borate in the presence of a base such as tert-butyllithium.
  • the compound of formula (I-4) can be produced by reacting the compound of formula (I-3) with a nucleophile.
  • nucleophile examples include amines represented by the general formula HNR 4 R 5 (wherein R 4 and R 5 are as described above); the general formula HOR 2 (wherein R 2 is the same as that described above).
  • alkali metal salts such as sodium cyanide and sodium azide; heterocyclic amines such as morpholine or alkali metal salts thereof; organometallic reagents such as methylmagnesium bromide, ethylmagnesium bromide and phenylmagnesium bromide; Can do. More specific examples include methylamine, dimethylamine, piperidine; sodium methoxide, sodium ethoxide; sodium mercaptan and the like.
  • the nucleophile can be used at a ratio of 1 to 30 equivalents per 1 mol of the compound of the formula (I-3).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • alcohols such as methanol, ethanol and propanol
  • ethers such as diethyl ether, butyl ethyl ether, tetrahydrofuran, dioxane and dimethoxyethane
  • Halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatics such as pentane and hexane Hydrocarbons
  • Esters such as methyl acetate and ethyl acetate
  • Nitriles such as acetonitrile and propiononitrile
  • R 1d is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, and halogen substituted.
  • R 12 is alkyl; R 11 , A, X, Y, Z, hal, m and p are as described above.
  • Production method [5] comprises the reaction steps of [5] -1, [5] -2 and [5] -3 above, and the compound of formula (XIV) is converted to [1,2,4 of formula (I-5). ] A triazolo [1,5-a] pyrimidine derivative can be produced.
  • the compound of formula (XV) can be produced by condensing the compound of formula (XIV) with the compound of formula (V).
  • the compound of the formula (V) can be used in a proportion of usually 0.8 to 10 equivalents, desirably 0.8 to 3 equivalents, relative to 1 mol of the compound of the formula (XIV).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • carboxylic acids such as acetic acid and propionic acid
  • alcohols such as methanol, ethanol, propanol, and butanol
  • methyl acetate, ethyl acetate and the like are examples of carboxylic acids such as acetic acid and propionic acid, alcohols such as methanol, ethanol, propanol, and butanol; methyl acetate, ethyl acetate and the like.
  • Nitriles such as acetonitrile and propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfolane Examples thereof include sulfones such as: phosphoric acid amides such as hexamethylphosphoramide; and mixed solvents thereof, among which carboxylic acids are preferable.
  • the reaction temperature is usually 50 to 150 ° C., desirably 80 to 120 ° C.
  • the reaction time is usually 0.5 to 100 hours.
  • R 3 , X, Z, hal and m are as described above.
  • the production method [6] comprises the reaction steps of the above [6] -1 and [6] -2. From the compound of formula (II), [1,2,4] triazolo [1,5 of formula (I-6) -A] Pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
  • an ⁇ , ⁇ -unsaturated ketone derivative of formula (XVIII) can be produced by reacting a compound of formula (II) with carbon disulfide and a compound of formula (XVII).
  • Carbon disulfide and the compound of formula (XVII) can be used in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents, per 1 mol of the compound of formula (II).
  • This reaction can usually be performed in the presence of a base and a solvent.
  • the base include metal hydrides such as sodium hydride and potassium hydride; metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as sodium and potassium; sodium methoxide and sodium ethoxide. And alkali metal alkoxides such as potassium tertiary butoxide; and the like.
  • the base can be used in an amount of 1 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of formula (II).
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • the same solvents as those in the reaction step [1] -1 of the above production method [1] can be exemplified, and among these, ethers are desirable.
  • the reaction temperature is usually 0 to 100 ° C., preferably 10 to 50 ° C.
  • the reaction time is usually 6 to 48 hours.
  • [6] -2 In this reaction step, the compound of the formula (I-6) can be produced by condensing the compound of the formula (XVIII) and the compound of the formula (V).
  • the compound of the formula (V) can be used in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of the formula (XVIII).
  • This reaction can usually be performed in the presence of a base and a solvent.
  • the base include metal hydrides such as sodium hydride and potassium hydride; metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as sodium and potassium; sodium methoxide and sodium ethoxide Alkali metal alkoxides such as potassium tertiary butoxide; carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate; organic bases such as triethylamine and pyridine; Can do.
  • the base can be used in a proportion of 1 to 5 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of formula (V).
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include the same as those in the reaction step [1] -1 of the above production method [1]. desirable.
  • the reaction temperature is usually 100 to 200 ° C.
  • the reaction time is usually 0.1 to 10 hours. Manufacturing method [7]
  • R 3 , X, Z, m and n are as described above.
  • a [1,2,4] triazolo [1,5-a] pyrimidine derivative of the formula (I-7) is produced by reacting the compound of the formula (I-6) with an oxidizing agent. it can.
  • oxidizing agent used in this reaction examples include hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid, and the like.
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely affect the reaction.
  • halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and 1,2-dichloroethane, and ketones such as acetone and methyl ethyl ketone.
  • ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and dioxane; carboxylic acids such as acetic acid and propionic acid; and mixed solvents thereof.
  • the reaction temperature is usually 15 ° C. to reflux temperature.
  • the reaction time is usually 1 to 24 hours.
  • R 1e is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano, Aryl optionally substituted with halogen, heterocyclic group optionally substituted with alkyl, OR 2 , NR 4 R 5 or N 3 ; R 2 , R 4 , R 5 , A, X, Z and m are As described above.
  • a [1,2,4] triazolo [1,5-a] pyrimidine derivative of the formula (I-8) is reacted by reacting a compound of the formula (I-7) with a nucleophile.
  • a nucleophile include amines represented by the general formula HNR 4 R 5 (wherein R 4 and R 5 are as described above); the general formula HOR 2 (wherein R 2 is the same as that described above).
  • Alkali metal salts (metal alkoxides) of alcohols represented by the following formulas; various alkali metal salts such as sodium cyanide and sodium azide; heterocyclic amines such as morpholine or alkali metal salts thereof; And organic metal reagents such as ethylmagnesium bromide and phenylmagnesium bromide; fluorinating agents such as potassium fluoride, cesium fluoride and tetraammonium fluoride; More specific examples include methylamine, dimethylamine, piperidine; sodium methoxide, sodium ethoxide; and the like.
  • the nucleophilic agent can be used in an amount of 1 to 10 equivalents, preferably 1.5 to 3 equivalents, relative to 1 mol of the compound of formula (I-7).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • alcohols such as methanol, ethanol, propanol and butanol
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • pentane and hexane Aliphatic hydrocarbons such as benzene, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride
  • Halogenated hydrocarbons such as chloroethane, dichloroethane, trichloroethane, dichloroethylene
  • esters such as methyl acetate and ethyl acetate
  • R 13 is alkyl; R 9 , X, Z, hal and m are as described above.
  • the production method [9] comprises the reaction steps of the above [9] -1 to [9] -5, and from the compound of the formula (VIII), the compound of the formula (I-9) or the formula (I-3) [1, 2, 4] A triazolo [1,5-a] pyrimidine derivative can be produced. Each reaction step will be described in detail below.
  • the compound of formula (XX) can be produced by reacting the compound of formula (VIII) with the compound of formula (XIX) in the presence of a base.
  • the compound of the formula (XIX) can be used in a proportion of 0.8 equivalent to large excess, desirably 1 to 30 equivalents, relative to 1 mol of the compound of the formula (VIII).
  • Examples of the base include those similar to the reaction in the reaction step [6] -1 of the production method [6].
  • the base can be used at a ratio of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of the formula (VIII). This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include the same reaction as in the reaction step [2] -1 in the above production method [2]. desirable.
  • the reaction temperature is usually 0 to 70 ° C., preferably 10 to 50 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • the compound of the formula (XXI) can be produced by hydrolyzing the compound of the formula (XX) in the presence of a base and water.
  • the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • the base can be used in an amount of 1 equivalent to large excess, desirably 2 to 10 equivalents, relative to 1 mol of the compound of formula (XX).
  • the reaction temperature is usually 0 to 70 ° C., preferably 10 to 50 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • the compound of the formula (XXII) can be produced by reacting the compound of the formula (XXI) with a halogenating agent.
  • a halogenating agent include thionyl chloride and oxalyl dichloride.
  • the halogenating agent can be used in a proportion of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of formula (XXI). This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane.
  • the reaction temperature is usually 0 to 100 ° C., preferably 10 to 50 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • the same solvent as in the reaction step [2] -1 in the above production method [2] can be mentioned, and among them, acid amides are preferable.
  • the reaction temperature is usually 0 to 150 ° C., preferably 20 to 100 ° C.
  • the reaction time is usually 0.5 to 100 hours.
  • the compound of compound (I-9) is reacted with a halogenating agent to react with 5-halo [1,2,4] triazolo [1, 5-a] pyrimidine derivatives can be produced.
  • a halogenating agent include thionyl chloride, phosphorus oxychloride, phosphorus oxybromide and the like.
  • the halogenating agent can be used in a proportion of 1 to 20 equivalents, preferably 1 to 8 equivalents, relative to 1 mol of the compound of formula (I-9). This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane.
  • the reaction temperature is usually 0 to 150 ° C., preferably 20 to 100 ° C.
  • the reaction time is usually 0.1 to 24 hours. Manufacturing method [10]
  • Production method [10] is a production example of a [1,2,4] triazolo [1,5-a] pyrimidine derivative of the formula (I-12), for example, the above [10] -1 to [10] -3
  • the compound of the formula (I-12) can be produced by any reaction. Each reaction is described in detail below.
  • the compound of the formula (I-12) can be produced by reacting the compound of the formula (I-10) with an oxidizing agent.
  • the oxidizing agent include sodium periodate, selenium dioxide, potassium permanganate and the like.
  • the oxidizing agent can be used in a proportion of 0.8 equivalent to large excess, preferably 1 to 30 equivalents, relative to 1 mol of the compound of formula (I-10).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction. Examples thereof include water; amides such as N, N-dimethylformamide; and the like.
  • the reaction temperature is 0 to 200 ° C., desirably 0 to 150 ° C.
  • the reaction time is 1 to 30 hours.
  • [10] -2 This reaction includes the above two reactions of (1) metalation and (2) formylation. That is, the compound of the formula (I-12) can be produced by metallizing the compound of the formula (I-3), reacting it with a formylating agent and then hydrolyzing it.
  • the reactions (1) and (2) can usually be carried out continuously.
  • the metalation in (1) means preparation of a lithium reagent by a halogen-lithium exchange reaction with a lithium reagent such as n-butyllithium or tert-butyllithium, or a Grignard reagent by a halogen-magnesium exchange reaction with a Grignard reagent.
  • the preparation of a Grignard reagent by reaction with metallic magnesium and the lithium reagent, Grignard reagent and magnesium used in this case are metallizing agents.
  • the metallizing agent can be used in a proportion of 1 equivalent to 1.5 equivalents relative to the compound of formula (I-3).
  • the reaction temperature is usually ⁇ 100 to 70 ° C., desirably ⁇ 30 to 50 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • Examples of the formylating agent in (2) include methyl formate, N, N-dimethylformamide, 4-formylmorpholine and the like.
  • the formylating agent can be used at a ratio of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of formula (I-3).
  • the reaction temperature is usually ⁇ 20 to 50 ° C., desirably ⁇ 10 to 30 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • the compound of formula (I-12) can be produced by hydrolyzing the reaction product in the presence of an acid and water.
  • the acid include inorganic acids such as hydrochloric acid and sulfuric acid.
  • the acid can be used in an amount of 1 equivalent to a large excess, desirably 2 to 10 equivalents, relative to the metallizing agent.
  • the reaction temperature is usually ⁇ 10 to 30 ° C., preferably 0 to 20 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely affect the reaction.
  • the same solvent as in reaction step [2] -1 of the above production method [2] can be mentioned, and among these, ethers are desirable.
  • the compound of the formula (I-12) can be produced by reacting the compound of the formula (I-11) with a reducing agent.
  • a reducing agent examples include diisobutylaluminum hydride (DIBAL), sodium bis (2-methoxyethoxy) aluminum hydride (SBMEA), and the like.
  • DIBAL diisobutylaluminum hydride
  • SBMEA sodium bis (2-methoxyethoxy) aluminum hydride
  • the reducing agent can be used in a proportion of 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to 1 mol of the compound of formula (I-11). This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene.
  • the reaction temperature is usually ⁇ 80 ° C. to 100 ° C., desirably ⁇ 30 to 50 ° C.
  • the reaction time is usually 0.1 to 24 hours. Manufacturing method [11]
  • R 14 represents alkyl or cycloalkyl, and X, Z and m are as described above.
  • the compound of the formula (I-11) is reacted with a nucleophile and then hydrolyzed to thereby react the [1,2,4] triazolo [1,5- (5) of the formula (I-13).
  • a] Pyrimidine derivatives can be produced.
  • the nucleophilic agent include Grignard reagents such as methylmagnesium bromide and cyclopropylmagnesium chloride.
  • the nucleophilic agent can be used in an amount of 1 to 2 equivalents, preferably 1 to 1.3 equivalents, relative to 1 mol of the compound of the formula (I-11). This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include ethers such as tetrahydrofuran; aliphatic hydrocarbons such as pentane hexane; and the like.
  • the reaction temperature is usually ⁇ 80 ° C. to 100 ° C., desirably ⁇ 30 to 50 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • the compound of formula (I-13) can be obtained by hydrolyzing the reaction product in the presence of an acid and water.
  • the acid include inorganic acids such as hydrochloric acid and sulfuric acid.
  • the acid can be used in an amount of 1 equivalent to a large excess relative to the nucleophile, preferably 2 to 10 equivalents.
  • the reaction temperature is usually ⁇ 20 to 30 ° C., preferably 0 to 20 ° C.
  • the reaction time is usually 0.1 to 24 hours.
  • R 1f is an alkyl which may be substituted with A or a heterocyclic group which may be substituted with alkyl; R 14 , X, Z and m are as described above. Examples of R 1f include dimethoxymethyl, diethoxymethyl, 1,3-dioxolan-2-yl and the like.
  • Examples of the alcohol include methanol, ethanol, and ethylene glycol.
  • the alcohol can be used in a proportion of 1 equivalent to a large excess with respect to 1 mol of the compound of the formula (I-12) or the formula (I-13).
  • This reaction can be performed in the presence of an acid catalyst, if necessary.
  • the acid catalyst include inorganic acids such as concentrated hydrochloric acid and concentrated sulfuric acid; organic acids such as acetic acid and p-toluenesulfonic acid.
  • the acid catalyst can be used in a proportion of 0.001 to 0.3 equivalent, desirably 0.01 to 0.2 equivalent, relative to 1 mol of the compound of formula (I-12) or formula (I-13).
  • This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include aromatic hydrocarbons such as benzene and toluene.
  • the reaction temperature is usually 0 ° C. to 200 ° C., preferably 10 to 100 ° C.
  • the reaction time is usually 0.1 to 24 hours. Manufacturing method [13]
  • Production method [13] is an example of production of a [1,2,4] triazolo [1,5-a] pyrimidine derivative of formula (I-15).
  • the production methods [13] -1 to [13] -3 The compound of the formula (I-15) can be produced by any reaction. Each reaction is described in detail below.
  • the compound of formula (I-15) can be produced by hydrolyzing the compound of formula (I-11).
  • This reaction can be carried out according to a conventional method. For example, it can be carried out according to the method described in Org. Synth., III, 557 (1955).
  • As a kind of hydrolysis any of acid hydrolysis, alkali hydrolysis, and oxidative hydrolysis may be used.
  • the compound of formula (I-15) can be produced by oxidizing the compound of formula (I-12) with an oxidizing agent.
  • the oxidizing agent include manganese dioxide, potassium permanganate, sodium periodate, Jones reagent, pyridium dichromate, and the like.
  • the oxidizing agent can be used in an amount of 1 to 3 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of the formula (I-12).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include water, acetone, acetonitrile, methanol and the like.
  • the reaction temperature is usually 0 to 50 ° C.
  • the reaction time is usually 0 to 24 hours. Manufacturing method [14]
  • R 15 is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, cyano or halogen.
  • the production method [14] comprises the reaction steps of the above [14] -1 and [14] -2. From the compound of the formula (I-15), the [1,2,4] triazolo [1] of the formula (I-17) , 5-a] pyrimidine derivatives can be prepared. Each reaction step will be described in detail below.
  • the compound of the formula (I-16) can be produced by reacting the formula (I-15) with a halogenating agent.
  • a halogenating agent examples include thionyl chloride and oxalyl chloride.
  • the halogenating agent can be used in an amount of usually 1 equivalent to a large excess, desirably 1 to 5 equivalents, relative to 1 mol of the compound of the formula (I-15).
  • This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction.
  • the same solvent as in reaction step [9] -3 of the above production method [9] can be mentioned.
  • the reaction temperature is usually 0 to 100 ° C., preferably 0 to 50 ° C.
  • the reaction time is usually 1 to 24 hours.
  • the compound of formula (I-17) can be produced by reacting the compound of formula (I-16) with a nucleophile. This reaction can be carried out according to the reaction step [4] -4 in the above production method [4]. Manufacturing method [15]
  • Production method [15] is a production example of a [1,2,4] triazolo [1,5-a] pyrimidine derivative of formula (I-19), for example, in the above [15] -1 or [15] -2
  • the compound of formula (I-19) can be produced by any method. Each reaction is described in detail below.
  • the compound of formula (I-19) can be produced by the rearrangement reaction of the compound of formula (I-15).
  • the compound of formula (I-15) and diphenyl phosphate azide are reacted by heating under reflux in the presence of triethylamine in a mixed solution of tert-butanol and toluene to obtain a tert-butyl carbamate derivative.
  • the compound of formula (I-19) can be produced by heating with a carbamate derivative and trifluoroacetic acid.
  • the compound of formula (I-19) can be produced by reacting the compound of formula (I-18) with a reducing agent.
  • the reducing agent include sodium borohydride.
  • the reducing agent can be used at a ratio of 1 to 2 equivalents relative to 1 mole of the formula (I-18).
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include alcohols; ethers.
  • the reaction temperature is usually 0 to 50 ° C.
  • the reaction time is usually 1 to 24 hours. Manufacturing method [16]
  • Q is a leaving group such as halogen, alkylcarbonyloxy, haloalkylcarbonyloxy, triflate or mesylate; R 4 , R 5 , X, Z and m are as described above.
  • the compound of the formula (XXIII) can be used usually in a proportion of 1 equivalent to a large excess, desirably 1 to 20 equivalents, relative to 1 mol of the compound of the formula (I-20).
  • This reaction can be performed in the presence of a base, if necessary.
  • the base include amines such as triethylamine and pyridine; inorganic bases such as potassium carbonate and sodium carbonate;
  • the base can be generally used in a proportion of 1 to 10 equivalents, preferably 1 to 5 equivalents, relative to 1 mol of the compound of formula (I-20).
  • This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include acetones; ethers; nitriles;
  • the reaction temperature is 0 to 50 ° C., desirably 0 to 30 ° C.
  • the reaction time is usually 1 to 24 hours. In this reaction, the reaction rate may be accelerated by using a catalytic amount of dimethylaminopyridine.
  • R 16 is OR 2 or NR 4 R 5 ;
  • R 2 , R 4 , R 5 , X, Z and m are as described above.
  • the compound of the formula (XXIV) can be used in an amount of 1 equivalent to a large excess, desirably 1 to 20 equivalents, relative to 1 mole of the compound of the formula (I-12).
  • This reaction can be performed in the presence of an acid catalyst, if necessary.
  • the acid catalyst include those similar to the above production method [12].
  • the acid catalyst can be used in a proportion of 0.001 to 0.3 equivalent, preferably 0.01 to 0.2 equivalent, relative to 1 mol of the compound of formula (I-12).
  • This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include the same as in the above production method [12].
  • the reaction temperature is usually 0 to 150 ° C., preferably 10 to 100 ° C.
  • the reaction time is usually 0.1 to 24 hours. Manufacturing method [18]
  • R 16 , X, Z and m are as described above.
  • the compound of the formula (I-23) can be produced by reacting the compound of the formula (I-15) with the compound of the formula (XXV) in the presence of a catalyst or a condensing agent.
  • Examples of the compound of the formula (XXV) include alcohols such as methanol and ethanol; amines such as methylamine and dimethylamine; The compound of the formula (XXV) can be used usually in a proportion of 1 to 30 equivalents relative to 1 mol of the compound of the formula (I-15).
  • examples of the catalyst include inorganic acids and organic acids.
  • This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent include alcohols; aromatic hydrocarbons; halogenated hydrocarbons;
  • the reaction temperature is usually 10 to 150 ° C., preferably 20 to 100 ° C.
  • the reaction time is usually 1 to 24 hours.
  • the condensing agent examples include dicyclohexylcarbodiimide, 1,1-carbonyldiimidazole, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide.
  • the condensing agent can be used in a proportion of usually 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the formula (I-15).
  • This reaction can be performed in the presence of a solvent, if necessary.
  • the solvent include alcohols; aromatic hydrocarbons; halogenated hydrocarbons;
  • the reaction temperature is usually 0 to 100 ° C., preferably 0 to 50 ° C.
  • the reaction time is usually 1 to 24 hours. Manufacturing method [19]
  • R 17 is a hydrogen atom, OR 2 or NR 4 R 5 ; R 2 , R 4 , R 5 , X, Z, hal and m are as described above.
  • a compound of the formula (I-3) is reacted with a compound of the formula (XXVI) and carbon monoxide in the presence of a transition metal catalyst, a phosphine ligand and a base, thereby producing a compound of the formula (I -24) [1,2,4] triazolo [1,5-a] pyrimidine derivatives can be produced.
  • Examples of the compound of the formula (XXVI) include water; hydrogen; alcohols such as methanol and ethanol; amines such as methylamine and dimethylamine; The compound of the formula (XXVI) can be generally used at a ratio of 1 to 5 equivalents per 1 mol of the compound of the formula (I-3).
  • Carbon monoxide can be used in an amount of usually 1 to 10 equivalents, preferably 1 to 5 equivalents, relative to 1 mol of the compound of formula (I-3).
  • the transition metal catalyst include a palladium or cobalt catalyst.
  • the phosphine ligand can be selected according to the reaction system such as the type of transition metal catalyst. Examples of the combination of the transition catalyst and the ligand include palladium acetate and diphenylphosphinopropane.
  • the base examples include inorganic salts such as sodium carbonate and cesium carbonate; trimethylamine, triethylamine, triisopropylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine, 4-pyrrolidinopyridine, N -Methylmorpholine, N, N-dimethylaniline, N, N-diethylaniline, N-ethyl-N-methylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [ 2.2.2] amines such as octane;
  • This reaction can usually be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include polar aprotic solvents such as N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
  • the reaction temperature is usually 25 to 120 ° C., preferably 50 to 70 ° C.
  • the reaction time is usually about 1 to 24 hours, preferably 3 to 7 hours. If necessary, the reaction can be carried out under pressure.
  • production method [1], production method [3], production method [4], production method [5], production method [9], production method [10], production method [12], production method [15] or production method [ 16] is a particularly desirable embodiment.
  • the pest control agent of the present invention includes, for example, various pest control agents that are problematic in the field of agriculture and horticulture, that is, agricultural and horticultural pest control agents, and pest control agents that parasitize animals, that is, animal parasite control agents. As particularly useful.
  • the pest control agent of the present invention is particularly useful for controlling pests among various pests, and the pest control agent is one of desirable embodiments.
  • Pesticides for agricultural and horticultural use are useful, for example, as insecticides, acaricides, nematicides or soil insecticides.
  • Plant parasitic mites such as rustic mites, mites, aphids such as peach aphids and cotton aphids; diamondback moths, weevil, scallops, codling moths, ball worms, tobacco worms, mai moths, yellow moths, prickly winged clams, Colorado Agricultural pests such as leaf beetle, cucumber beetle, ball weevil, planthoppers, leafhoppers, scale insects, stink bugs, whitefly, thrips, grasshoppers, fly flies, scarab beetles, Tamanayaga, Kaburayaga, ants, etc .; Parasitic nematodes such as mosquitoes, cyst nematodes, nesting nematodes, rice scented nematodes, strawberry nema
  • the agricultural and horticultural pest control agent of the present invention is particularly effective for controlling plant parasitic mites, agricultural pests, plant parasitic nematodes and the like. Among them, it is most useful as an insecticidal or acaricidal agent because it exhibits a further excellent effect in controlling plant parasitic mites and agricultural pests.
  • the agricultural and horticultural pest control agent of the present invention is also effective in controlling various resistant pests against drugs such as organic phosphorus agents, carbamate agents, and synthetic pyrethroid agents.
  • the compound of the formula (I) has an excellent osmotic transfer property
  • soil harmful insects, mites, nematodes It is possible to control pests in the foliage at the same time as the control of mosses, gastropods, and isopods.
  • pest control agent of the present invention there are agricultural and horticultural harmful substances that comprehensively control the above-mentioned plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods, soil pests, etc. Biological control agents are mentioned.
  • the agricultural and horticultural pest control agent of the present invention is usually a powder, granule, granule wettable powder, wettable powder, aqueous suspension, oily suspension by mixing the compound and various agricultural adjuvants.
  • a powder, granule, granule wettable powder, wettable powder, aqueous suspension, oily suspension by mixing the compound and various agricultural adjuvants.
  • Used in various forms, such as an agent, an aqueous solvent, an emulsion, a liquid, a paste, an aerosol, and a microdispersion but is generally used in the art as long as it meets the purpose of the present invention. Any formulation can be used.
  • Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch; water , Toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, alcohol, etc.
  • solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite,
  • Solvent fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, al Sulfuric acid ester salt, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester salt, alkyl aryl phosphate, Styryl aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl
  • each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention.
  • it can be used by appropriately selecting from those known in the art.
  • a bulking agent for example, a bulking agent, a thickening agent, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a phytotoxicity reduction.
  • Various commonly used adjuvants such as agents, antifungal agents and the like can also be used.
  • the compounding ratio (weight ratio) of the compound of the formula (I) and various adjuvants is 0.001: 99.999 to 95: 5, preferably 0.005: 99.995 to 90:10. In actual use of these preparations, use them as they are, or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.
  • the application of the agricultural and horticultural pest control agent of the present invention cannot be defined unconditionally due to differences in weather conditions, formulation form, application time, application location, type of pests and occurrence status, but generally 0.05 to 800,000 ppm, preferably 0.5
  • the active ingredient concentration is ⁇ 500,000 ppm
  • the application amount per unit area is 0.05 to 50,000 g, preferably 1 to 30,000 g, of the compound of formula (I) per hectare.
  • application of the agricultural and horticultural pest control agent which is another desirable embodiment of the pest control agent of the present invention, is performed according to the application of the pest control agent.
  • the present invention includes a method for controlling pests by such an application method, particularly a method for controlling plant parasitic mites, agricultural pests, and plant parasitic nematodes.
  • the various formulations of the pesticide for agricultural and horticultural use according to the present invention, or the dilutions thereof are usually applied by a commonly used application method, that is, spraying (for example, spraying, spraying, misting, atomizing, dusting, Water surface application, etc.), soil application (mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.), immersion poison bait, etc.
  • spraying for example, spraying, spraying, misting, atomizing, dusting, Water surface application, etc.
  • soil application mixtureing, irrigation, etc.
  • surface application application, powder coating, coating, etc.
  • immersion poison bait etc.
  • the agricultural and horticultural pest control agent of the present invention can be used in combination or in combination with other agricultural chemicals, fertilizers, safeners, etc., and in this case, more excellent effects and activities may be exhibited.
  • Other agrochemicals include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. It is done.
  • a composition for controlling mixed pests in which a compound of formula (I) and one or more active ingredient compounds of other agricultural chemicals are mixed or used in combination is applicable range, timing of chemical treatment, control activity, etc. Can be improved in a preferred direction.
  • the compound of formula (I) and the active ingredient compound of other agricultural chemicals may be used by mixing separately formulated ones at the time of spraying, or by formulating both together.
  • the present invention includes such a composition for controlling mixed pests.
  • the mixing ratio (weight ratio) between the compound of formula (I) and the active ingredient compound of other pesticides cannot be specified unconditionally due to differences in weather conditions, formulation form, application time, application location, pest type or occurrence status. However, it is generally 1: 300 to 300: 1, preferably 1: 100 to 100: 1.
  • the appropriate amount to be applied is 0.1 to 50000 g, preferably 1 to 30000 g as the total amount of active ingredient compounds per hectare.
  • the present invention also includes a method for controlling pests by a method for applying such a composition for controlling mixed pests.
  • active ingredient compounds of insecticides, acaricides, nematicides or soil pesticides in the above other pesticides
  • active ingredient compounds include, for example, profenofos , Dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiofos, fothiaz , Cadusafos, dislufoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate, sulfophos ( sulprofos), thiometon, bamidithione (vamidot) hion), pyraclofos, pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion
  • Organometallic compounds such as fenbutatin oxide and cyhexatin; Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprox, flufenprox, cyfluthrin , Fenpropathrin, flucytrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrin, esfenvalerate, Tetramethrin, resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypermethri n), allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin
  • Pyridine compounds such as pyridalyl, flonicamid and the like; Tetronic acid compounds such as spirodiclofen; Strobilurin-based compounds such as fluacrypyrim; Pyridinamine compounds such as flufenerim; Dinitro compounds; organic sulfur compounds; urea compounds; triazine compounds; hydrazone compounds; and other compounds such as buprofezin, hexythiazox, amitraz, chlordimeform, silafluofen ), Triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, cyromazine, 1,3-dichloropropene (1,3-dichloropropene), diafenthiuron, benclothiaz, bifenazate, spiromesifen, spirotetramat, propargi Propargite, clofentezine, metaflum
  • Bacillus thuringienses aizawai, Bacillus thuringienses kurstaki, Bacillus thuringienses israelensis, Bacillus thuringienses japonensis, Bacillus thuringienses tenebrionis, crystalline protein toxins produced by Bacillus thuringienses, entomopathogenic fungi, nematode pathogenic fungi, etc.
  • Microbial pesticides such as: avermectin, emamectin-benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin and antibiotics such as abamectin and emamectin; semi-synthetic antibiotics; natural products such as azadirachtin and rotenone; repellents such as deet;
  • the bactericidal active ingredient compound includes, for example, mepanipyrim, pyrimethanil, cyprodinil ( cyprodinil) and anilinopyrimidine compounds such as ferimzone; Tria such as 5-chloro-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidin-1-yl) [1,2,4] triazolo [1,5-a] pyrimidine Zolopyrimidine compounds; Pyridinamine compounds such as fluazinam; Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz
  • Quinoxaline compounds such as quinomethionate; Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram; Organochlorine compounds such as fthalide, chlorothalonil, quintozene; Imidazole compounds such as benomyl, thiophanate-methyl, carbendazim, thiabendazole, fuberiazole, cyazofamid; Cyanoacetamide compounds such as cymoxanil; Metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, offurace, benalaxyl, benalaxyl-M, also known as kiralaxyl, chiax ), Phenylamide compounds such as furalaxyl, cyprofuram;
  • Sulfenic acid compounds such as dichlofluanid; Copper-based compounds such as cupric hydroxide and oxine copper; isoxazole-based compounds such as hymexazol; Fosetyl aluminum (fosetyl-Al), tolclofos-methyl, edifenphos, iprobenfos, S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum Organophosphorus compounds such as ethyl hydrogen phosphonate; N-halogenothioalkyl compounds such as captan, captafol, folpet; Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
  • Benzanilide compounds such as flutolanil, mepronil, zoxamid, tiadinil; Carboxin (carboxin), oxycarboxin, thifluzamide, penthiopyrad, boscalid, isothianil, bixafen, 3- (difluoromethyl) -1-methyl-N- [(1RS, 4SR, 9RS) -1,2,3,4-Tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl] pyrazole-4-carboxamide and 3- (difluoromethyl) -1-methyl- Of a mixture of N-[(1RS, 4SR, 9SR) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl] pyrazole-4-carboxamide (isopyrazam) Such anilide compounds; Piperazine compounds such as triforine; Pyridine compounds such as pyrif
  • Organotin compounds such as fentin hydroxide and fentin acetate; Urea-based compounds such as pencycuron; Synamic acid compounds such as dimethomorph and flumorph; Phenyl carbamate compounds such as dietofencarb; Cyanopyrrole compounds such as fludioxonil and fenpiclonil; Azoxystrobin, kresoxim-methyl, metominofen, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin Strobilurin compounds such as pyraclostrobin, fluoxastrobin, fluacrypyrim;
  • Oxazolidinone compounds such as famoxadone; Thiazole carboxamide compounds such as ethaboxam; Silylamide compounds such as silthiopham; Iprovalicarb, Benthiavalicarb-isopropyl, methyl [S- (R, S)]-[3- (N-isopropoxycarbonylvalinyl) -amino] -3- (4-chloro Aminoacid amide carbamate compounds such as -phenyl) propionate (valiphenal); Imidazolidine compounds such as fenamidone; Hydroxyanilide compounds such as fenhexamid; Benzenesulfonamide compounds such as flusulfamide; Oxime ether compounds such as cyflufenamid; Phenoxyamide compounds such as fenoxanil; Antibiotics such as validamycin, kasugamycin, polyoxins; Guanidine compounds such as iminoctadine and dodine
  • animal parasite control agents include ectoparasites that parasitize on the body surface of the host animal (back, armpit, lower abdomen, inner thigh, etc.) and the host animal body (stomach, intestinal tract, lung, heart, liver). , Vascular, subcutaneous, lymphoid tissue, etc.) are effective in controlling endoparasites, and in particular, are effective in controlling ectoparasites.
  • ectoparasites examples include animal parasitic mites and fleas. There are so many of these types that it is difficult to list them all.
  • the animal parasitic mites for example Boophilus microplus (Boophilus microplus), Rhipicephalus sanguineus (Rhipicephalus sanguineus), Haemaphysalis longicornis (Haemaphysalis longicornis), Haemaphysalis flava (Haemaphysalis flava), Adenophora chima tick (Haemaphysalis campanulata), Isukachimadani (Haemaphysalis concinna), Yamatochimadani (Haemaphysalis japonica), H.
  • kitaokai Haemaphysalis kitaokai
  • Iyasuchimadani Haemaphysalis ias
  • Ixodes ovatus Ixodes ovatus
  • I. nipponensis Ixodes nipponensis
  • Schulze ticks Ixodes persulcatus
  • Takasago testudinarium Amblyomma testudinarium
  • Ootogechimadani Haemaphysalis megaspinosa
  • tick such as Dermacentor reticulatus , Dermacentor taiwanesis ; duck ( Dermanyssus gallinae ); Shidani (Ornithonyssus sylviarum), Torisashidani, such as Southern tri sand mite (Ornithonyssus bursa); Nan iodine tsutsugamushi (Eutromb
  • chiggers such as Miyagawa Tama chiggers (Helenicula miyagawai); Inutsumedani (Cheyletiella yasguri), rabbit Tsumedani (Cheyletiella parasitivorax), Nekotsumedani (Cheyletiella blakei) Tsumedani, such as; rabbits 9,000 mite (Psoroptes cuniculi), Ushishokuhidani (Chorioptes bovis), dog ear mites (Otodectes cynotis), mange mites (Sar coptes scabiei ), mite mites like Notoedres
  • fleas examples include ectoparasite worms belonging to the order Flea ( Siphonaptera ), and more specifically fleas belonging to the family Flea family ( Pulicidae ), Nagano family ( Ceratephyllus ) and the like.
  • fleas belonging to the family flea family include, for example, dog fleas ( Ctenocephalides canis ), cat fleas ( Ctenocephalides felis ), human fleas ( Purex irritans ), elephant fleas ( Echidnophaga gallinacea ), keops mouse fleas ( Xenopsylla cheopis ) Leptopsylla segnis ), European mud minnow ( Nosopsyllus fasciatus ), and Yamato mud mink ( Monopsyllus anisus ).
  • the animal parasite control agent containing the compound of the formula (I) is effective for controlling fleas belonging to the family flea family, especially dog fleas, cat fleas and the like.
  • ectoparasites include, for example, lice such as bovine lice, foal lice, sheep lice, bovine white lice, head lice; lice such as dog lice; blood-sucking dipterous pests such as bovine abs, quail sharks, .
  • endoparasites include nematodes such as lungworms, benthic worms, tuberous worms, gastric parasites, roundworms, and filamentous worms; Tapeworms such as real tapeworms, multi-headed tapeworms, single-banded tapeworms, multi-banded tapeworms; Japanese schistosomiasis, fluke like liver fluke; coccidium, malaria parasite, intestinal granulocyst, toxoplasma, chestnut Protozoa such as Ptosporidium, and the like.
  • nematodes such as lungworms, benthic worms, tuberous worms, gastric parasites, roundworms, and filamentous worms
  • Tapeworms such as real tapeworms, multi-headed tapeworms, single-banded tapeworms, multi-banded tapeworms
  • Japanese schistosomiasis fluke like liver fluke
  • Examples of host animals include various pet animals, livestock, poultry, etc., and more specifically dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (eg, pigeons, parrots, (E.g., nine-bird, bird, parakeet, juvenile pine, canary, etc.), cattle, horses, pigs, sheep, ducks, chickens, etc.
  • the animal parasite control agent containing the compound of the formula (I) is effective for controlling pests parasitic on pet animals or livestock, particularly ectoparasites.
  • pet animals or domestic animals it is particularly effective for dogs, cats, cows or horses.
  • the compound of the formula (I) when used as an animal parasite control agent, it may be used as it is, and together with suitable adjuvants, powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions. It can also be formulated and used in various forms such as a suspending agent and an oily suspension. In addition to the above-mentioned preparation forms, any preparation forms used in the normal field can be used as long as the object of the present invention is met.
  • adjuvant used in the preparation examples include anionic surfactants and nonionic surfactants exemplified as the above-mentioned preparation adjuvants for agricultural and horticultural pest control agents; positive agents such as cetyltrimethylammonium bromide.
  • Ionic surfactants water, acetone, acetonitrile, N-methylacetamide, N, N-dimethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, kerosene, triacetin, methanol, Ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl Solvents such as ether, diethylene glycol normal butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol normal butyl ether; oxidations such as butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium metabisulfite, propyl gallate, sodium thiosulfate Inhibitors; Film
  • each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention.
  • it can be used by appropriately selecting from those known in the field, and further, selected from various adjuvants used in the above-mentioned agricultural and horticultural fields. You can also
  • the compounding ratio (weight ratio) of the compound of formula (I) and various adjuvants is usually about 0.1: 99.9 to 90:10. In actual use of these preparations, use them as they are, or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.
  • Administration of the compound of formula (I) to the host animal is performed orally or parenterally.
  • the oral administration method include a method of administering tablets, liquid agents, capsules, wafers, biscuits, minced meat, and other feeds containing the compound of formula (I).
  • a parenteral administration method for example, a compound of formula (I) is prepared into an appropriate formulation and then taken into the body by intravenous administration, intramuscular administration, intradermal administration, subcutaneous administration, etc .; spot-on (spot -on) treatment, pour-on treatment, spray treatment, and the like; and a method of embedding a resin piece containing the compound of formula (I) under the skin of a host animal.
  • the dose of the compound of formula (I) to the host animal varies depending on the administration method, administration purpose, disease symptoms, etc., but is usually 0.01 mg to 100 g, preferably 0.1 mg to 1 kg body weight of the host animal. It is appropriate to administer at a rate of 10 g.
  • the present invention includes a method for controlling pests according to the administration method or dosage as described above, particularly a method for controlling ectoparasites or endoparasites.
  • the present invention includes a prophylactic or therapeutic agent for parasite-derived animal diseases containing the compound of formula (I) as an active ingredient, and a method for preventing or treating parasite-derived animal diseases.
  • the present invention includes a composition for controlling mixed pests in which various components as described above are mixed or used together, and a method for controlling pests using the composition, particularly a method for controlling ectoparasites or endoparasites. Is also included.
  • R 1 is a hydrogen atom, alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, optionally substituted with A Alkynyl, halogen, cyano, aryl optionally substituted with halogen, heterocyclic group optionally substituted with alkyl, C ⁇ NOR 2 , C ⁇ NNR 4 R 5 , COR 2 , COOR 2 , OR 2 , S (O ) n R 3 , NR 4 R 5 , N 3 or CONR 4 R 5 ;
  • X is alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, NR 4 R 5 , S (O) n R 3 , OR 2 , COR 2 or COOR 2 ;
  • Y is
  • R 1 is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen , Cyano, OR 2 , S (O) n R 3 or NR 4 R 5 ;
  • X is alkyl, alkenyl, alkynyl, halogen, haloalkyl, cyano or nitro;
  • A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5 , cyano, cycloalkyl, aryl or a heterocyclic group;
  • R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl or aryl, a triazolopyrimidine derivative or a salt thereof as an active ingredient Contains pest control agents.
  • R 3 , R 4 , R 5 , Y, Z, m, and n have
  • R 1 ⁇ is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A , Halogen, cyano, OR 2 or S (O) n R 3 ;
  • X is alkyl, alkenyl, alkynyl, halogen, haloalkyl, cyano or nitro;
  • A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5 , cyano, cycloalkyl, aryl or heterocyclic group;
  • R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl or aryl; and
  • m is an integer of 2 to 4, a triazolopyrimidine derivative Or its salt.
  • R 3 , R 4 , R 5 , Y, Z, and n are as defined in (1) above.
  • Synthesis example 1 Synthesis of 7- [2-chloro-5- (trifluoromethyl) phenyl] -5-methyl [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 18)
  • 2-Chloro A mixed solution of 1.19 g of methyl -5-trifluoromethylbenzoate, 2 ml of acetone and 10 ml of tetrahydrofuran was ice-cooled, and 432 mg of solid sodium ethoxide was added little by little.
  • Synthesis example 2 Synthesis of 5-chloro-7- [2-chloro-4- (trifluoromethyl) phenyl] [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 21) (1) 5,7 A suspension of 919 mg of dihydroxy [1,2,4] triazolo [1,5-a] pyrimidine and 3 ml of phosphorus oxychloride was refluxed for 3 hours. After completion of the reaction, excess phosphorus oxychloride was distilled off from the obtained transparent reaction solution, 10 ml of ice water was carefully added, and the mixture was extracted with ethyl acetate.
  • Synthesis example 4 Synthesis of 7- [2-chloro-6- (trifluoromethyl) pyridin-3-yl] -5-methyl [1,2,4] troazolo [1,5-a] pyrimidine (Compound No. 29) ) 1.18 g of 3-acetyl-2-chloro-6- (trifluoromethyl) pyridine and 843 mg of N, N-dimethylacetamide dimethylacetal were reacted overnight at 100 ° C. in 11 ml of toluene.
  • Synthesis example 5 Synthesis of 7- [2-chloro-4- (trifluoromethyl) phenyl] -6-fluoro-5-methyl [1,2,4] troazolo [1,5-a] pyrimidine (Compound No. 34) ) 4.2 g of ethyl 2-fluoro-3-oxobutanoate was dissolved in 8 mL of acetic acid, and 2 g of 3-amino-1H-1,2,4-triazole was added and reacted at 100 ° C. for 2 hours.
  • reaction solution is returned to room temperature, the precipitated solid is filtered, washed with methanol, and washed with 6-fluoro-7-hydroxy-5-methyl [1,2,4] troazolo [1,5-a] pyrimidine (intermediate No. XV- 4) 407 mg was obtained as white crystals.
  • Table 3 lists representative examples of the compound of the formula (IV) in the above production method [1]. These compounds can be synthesized based on the above synthesis examples or the various production methods described above.
  • No. represents intermediate No.
  • Me represents methyl
  • i-Bu represents isobutyl.
  • 1 H-NMR is shown in Table 4 for the compounds described in Table 3.
  • Table 5 shows representative examples of the compound of formula (XV) in the production method [5]. These compounds can be synthesized based on the above synthesis examples or the various production methods described above.
  • No. represents intermediate No.
  • Me represents methyl
  • Et represents ethyl
  • i-Pr represents isopropyl
  • Table 1 shows the 1 H-NMR for the compounds whose physical properties in Table 5 are amorphous.
  • Table 7 lists representative examples of the compound of formula (XVI) in the above production method [5]. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 7, No. represents intermediate No., Me represents methyl, Et represents ethyl, i-Pr represents isopropyl, and the temperatures shown as physical properties are melting points. Table 8 shows the 1 H-NMR for the compounds whose physical properties in Table 7 are solid or oil.
  • Table 9 shows representative examples of the compound of formula (VII) in the above production method [2]. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 9, No. indicates intermediate No. Further, 1 H-NMR is shown in Table 10 for the compounds described in Table 9.
  • Test Example 1 Effect test on peach aphid Japanese radish leaves were inserted into a test tube containing water, and about 20 first-instar larvae were released on the leaves. The next day, after counting the number of larvae parasitic on radish leaves, the parasitic radish leaves were immersed in a chemical solution adjusted to a concentration of 200 ppm of the compound of formula (I) for about 10 seconds. After the chemical solution was air-dried, it was left in a constant temperature room at 25 ° C. with illumination. Five days after the treatment, the viability of the peach aphid was determined, and the mortality rate was determined by the following formula. The detached insects and abnormal insects were regarded as dead insects. When the compound Nos. 13, 20, 32, 33, 48, 49 and 53 were tested, all the compounds showed a death rate of 90% or more.
  • Test Example 2 Effect test on green planthopper Rice seedlings were immersed for about 10 seconds in a chemical solution adjusted so that the concentration of the compound of formula (I) was 200 ppm. After the chemical solution was air-dried, the root was wrapped with wet absorbent cotton and placed in a test tube. Ten 10-year-old larvae of the green planthopper were released into this, and the tube mouth was covered with gauze and left in a constant temperature room at 25 ° C. Five days after the insect release, the dead planthopper was judged to be alive or dead, and the mortality rate was determined by the following formula. Compound Nos.
  • Death rate (%) (Number of dead insects / Number of dead insects) ⁇ 100
  • Test example 3 Effect test on silver leaf whitefly Silver leaf whitefly 1-2 years old infested cucumber seedlings infested with a chemical solution adjusted so that the concentration of the compound of formula (I) is 200 ppm using a hand spray Processed. After the chemical solution was air-dried, it was left in a constant temperature room at 25 ° C. with illumination. Seven days after the treatment, the number of old larvae was examined, and the control efficiency (%) was determined by the following formula. When the compound Nos. 1, 5, 7, 13, 18, 29, 32, 33, 48 and 49 were tested, all the compounds showed a control efficiency of 80% or more.
  • Control efficiency (%) (1 ⁇ (Ta ⁇ Cb) / (Tb ⁇ Ca)) ⁇ 100
  • Ta old larvae after treatment in treated cucumber seedlings
  • Tb Number of 1-2 instar larvae before treatment in treated cucumber seedlings
  • Ca number of old larvae after treatment in untreated cucumber seedlings
  • Cb Number of 1-2 instar larvae before treatment in untreated cucumber seedlings
  • Test Example 4 Medicinal Efficacy Test Using Dogs against Phytophyllum Tick
  • a dog (beagle, 8 months old) was administered a gelatin capsule containing 10 mg / kg body weight of the compound of formula (I), and immediately after that about 50 young mite mites were collected. Release to the pinna of the dog and let it artificially infest. After the treatment, observe the number of infestations, the number of drops, and the life and death of the fallen spider mites. As a result, the compound of formula (I) drops or kills the parasitic spider mite.
  • Test Example 5 Medicinal Efficacy Test Using Dogs for Cat Fleas A dog (beagle, 8 months old) was administered a gelatin capsule containing 10 mg / kg body weight of the compound of formula (I), and immediately after that about 100 cat flea non-blood-sucking adults were administered. Let go on the back coat and let it artificially infest. The compound of the formula (I) exhibits a hatching-inhibiting effect on the treated laying eggs of adults.
  • Formulation Example 1 (1) Compound of formula (I) 20 parts by weight (2) Clay 70 parts by weight (3) White carbon 5 parts by weight (4) Sodium polycarboxylate 3 parts by weight (5) Sodium alkylnaphthalenesulfonate 2 parts by weight or more Mix things uniformly to make a wettable powder.
  • Formulation Example 2 (1) Compound of formula (I) 5 parts by weight (2) Talc 60 parts by weight (3) Calcium carbonate 34.5 parts by weight (4) Liquid paraffin To do.
  • Formulation Example 3 (1) Compound of formula (I) 20 parts by weight (2) N, N-dimethylacetamide 20 parts by weight (3) Polyoxyethylene tristyryl phenyl ether 10 parts by weight (4) Calcium dodecylbenzenesulfonate 2 parts by weight (5 ) Xylene 48 parts by weight or more are uniformly mixed and dissolved to prepare an emulsion.
  • Formulation Example 4 (1) Clay 68 parts by weight (2) Sodium lignin sulfonate 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) White carbon 25 parts by weight A mixture of each component and formula (I) The compound is mixed at a weight ratio of 4: 1 to obtain a wettable powder.
  • Formulation Example 5 (1) Compound of formula (I) 50 parts by weight (2) Sodium alkylnaphthalenesulfonate formaldehyde condensate 2 parts by weight (3) Silicone oil 0.2 part by weight (4) Water 47.8 parts by weight or more uniform (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are added to the stock solution mixed and pulverized, and mixed uniformly, granulated, and dried to obtain a granulated wettable powder.
  • Formulation Example 6 (1) Compound of formula (I) 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene alkyl ether phosphate 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight Parts (1) to (3) are mixed uniformly in advance, diluted with an appropriate amount of acetone, sprayed onto (4), and acetone is removed to form granules.
  • Formulation Example 7 (1) Compound of formula (I) 2.5 parts by weight (2) N, N-dimethylacetamide 2.5 parts by weight (3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to form a trace amount Use as an ultra low volume formulation.
  • Formulation Example 8 (1) Compound of formula (I) 40 parts by weight (2) Polyoxyethylene tristyryl phenyl ether potassium phosphate 4 parts by weight (3) Silicone oil 0.2 parts by weight (4) Xanthan gum 0.1 parts by weight (5) Ethylene glycol 5 parts by weight (6) Water 50.7 parts by weight or more are uniformly mixed and ground to obtain an aqueous suspension.
  • Formulation Example 9 (1) Compound of formula (I) 10 parts by weight (2) Diethylene glycol monoethyl ether 80 parts by weight (3) Polyoxyethylene alkyl ether 10 parts by weight or more of ingredients are mixed uniformly to obtain an aqueous solution.
  • the pest control agent containing the triazolopyrimidine derivative or salt thereof of the present invention as an active ingredient is sufficiently effective at a low dose, and is used as a control agent for various pests in the field of agriculture and horticulture, and is harmful to animals. It is useful as an animal parasite control agent that is a biological control agent.

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Abstract

Disclosed is a novel pest control agent. The pest control agent contains a triazolopyrimidine derivative represented by formula (I) or a salt thereof as an active ingredient. (In the formula, R1 represents a hydrogen atom, an alkyl which may be substituted by A, a cycloalkyl which may be substituted by A, an alkenyl which may be substituted by A, an alkynyl which may be substituted by A, or the like; X represents an alkyl, a hydroxyalkyl, an alkenyl, an alkynyl, an aryl or the like; Y represents a hydrogen or fluorine atom; Z represents CH, CX or N; A represents a halogen, a cyano, a nitro or the like; and m represents an integer of 1-4.)

Description

トリアゾロピリミジン誘導体又はその塩を含有する有害生物防除剤Pest control agent containing triazolopyrimidine derivative or salt thereof
　本発明は、トリアゾロピリミジン誘導体又はその塩を有効成分として含有する新規な有害生物防除剤に関する。 The present invention relates to a novel pest control agent containing a triazolopyrimidine derivative or a salt thereof as an active ingredient.
　特許文献１及び２には、染料の製造に利用されるトリアゾロピリミジン誘導体が記載されている。また、非特許文献１及び２には、トリアゾロピリミジン誘導体に除草活性があることについての記載がある。しかしながら、これらの文献にはトリアゾロピリミジン誘導体を殺虫、殺ダニ、殺線虫又は殺土壌害虫剤や、動物寄生生物防除剤として使用することの記載はない。さらに、後記式（I－α）で表されるトリアゾロピリミジン誘導体について具体的な記載はない。 Patent Documents 1 and 2 describe triazolopyrimidine derivatives used for the production of dyes. Non-Patent Documents 1 and 2 also describe that triazolopyrimidine derivatives have herbicidal activity. However, these documents do not describe the use of triazolopyrimidine derivatives as insecticides, acaricides, nematicides or soil insecticides or animal parasite control agents. Furthermore, there is no specific description of the triazolopyrimidine derivative represented by the following formula (I-α).
米国特許第2,439,210号U.S. Pat.No. 2,439,210 米国特許第2,443,136号U.S. Pat.No. 2,443,136
　長年にわたり、多数の有害生物防除剤が使用されているが、効力が不十分、有害生物が抵抗性を獲得し、その使用が制限される等、種々の課題を有するものが少なくない。従って、かかる欠点の少ない新規な有害生物防除剤、例えば、農園芸分野で問題となる各種有害生物や、動物に寄生する有害生物を防除できる有害生物防除剤の開発が望まれている。
　本発明は、使用が制限されるなどの欠点がなく、農園芸分野で問題となる各種有害生物や、動物に寄生する有害生物を防除できる有害生物防除剤を提供することを目的とする。 Many pest control agents have been used for many years, but many have various problems such as insufficient efficacy, pests gaining resistance, and their use is restricted. Therefore, development of a novel pest control agent with few drawbacks, for example, a pest control agent capable of controlling various pests that are problematic in the field of agriculture and horticulture and pests parasitic on animals is desired.
An object of the present invention is to provide a pest control agent that can control various pests that cause problems in the field of agriculture and horticulture and pests that parasitize animals without any disadvantages such as limited use.
　本発明者らは、より優れた有害生物防除剤を見出すべく、トリアゾロピリミジン誘導体について種々検討した。その結果、後記式（I）で表されるトリアゾロピリミジン誘導体が、低薬量で有害生物に対して極めて高い防除効果を有することを見出し、本発明を完成した。 The present inventors have made various studies on triazolopyrimidine derivatives in order to find better pest control agents. As a result, the present inventors have found that the triazolopyrimidine derivative represented by the following formula (I) has a very high control effect against pests with a low dose, and completed the present invention.
　すなわち本発明は、式（I）： That is, the present invention has the formula (I):
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔式中、Ｒ1は水素原子、Ａで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、Ｃ＝ＮＯＲ２、Ｃ＝ＮＮＲ4Ｒ5、ＣＯＲ２、ＣＯＯＲ２、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、Ｎ３又はＣＯＮＲ4Ｒ5であり；Ｘはアルキル、ヒドロキシアルキル、アルケニル、アルキニル、アリール、ハロゲン、ハロアルキル、シアノ、ニトロ、ＮＲ4Ｒ5、Ｓ(Ｏ)nＲ3、ＯＲ2、ＣＯＲ２、ＣＯＯＲ２又はＣＯＮＲ4Ｒ5であり；Ｙは水素原子又はフッ素原子であり；ＺはＣＨ、ＣＸ又はＮであり；Ａはハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、アルキル、シクロアルキル、アリール、複素環基、ＳＣＨ２ＣＯＯＲ２ 、ＮＨＮＲ4Ｒ5 、ＣＯＯＲ２、ニトロ又は－ＣＨ（ＣＮ）2であり；Ｒ2は水素原子、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシアルキル、アセチル又はアリールであり；Ｒ3はアルキル又はアセチルであり；Ｒ4は水素原子又はアルキルであり；Ｒ5は水素原子、アルキル、ハロアルキル、ＣＯＲ２、ＣＯＯＲ２、ＣＨ２ＣＨ２ＯＲ2又はシアノアルキルであり；ｍは１～４の整数であり；ｎは０～２の整数である〕で表されるトリアゾロピリミジン誘導体又はその塩を有効成分として含有する有害生物防除剤、当該トリアゾロピリミジン誘導体又はその塩の有効量を施用して有害生物を防除する方法に関する。
　さらに本発明は、式（I）のトリアゾロピリミジン誘導体の中で、従来、具体的に知られていなかった式（I－α）： [Wherein, R 1 is a hydrogen atom, alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano , Aryl optionally substituted with halogen, heterocyclic group optionally substituted with alkyl, C═NOR 2 , C═NNR 4 R 5 , COR 2 , COOR 2 , OR 2 , S (O) n R 3 , NR 4 R 5 , N 3 or CONR 4 R 5 ; X is alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, NR 4 R 5 , S (O) n R 3 , OR 2 , COR 2 , COOR 2 or CONR 4 R 5 ; Y is a hydrogen atom or a fluorine atom; Z is CH, CX or N; A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5 , shear , Alkyl, cycloalkyl, aryl, heterocyclic group, SCH 2 COOR 2 , NHNR 4 R 5 , COOR 2 , nitro or —CH (CN) 2 ; R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl R 3 is alkyl or acetyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl, haloalkyl, COR 2 , COOR 2 , CH 2 CH 2 OR 2 or cyanoalkyl; m is an integer of 1 to 4; n is an integer of 0 to 2], and a pesticide containing the triazolopyrimidine derivative or a salt thereof as an active ingredient, The present invention relates to a method for controlling pests by applying an effective amount of a triazolopyrimidine derivative or a salt thereof.
Furthermore, the present invention relates to a triazolopyrimidine derivative of the formula (I), which has not been specifically known conventionally (I-α):
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
〔式中、Ｒ1αはＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、Ｃ＝ＮＯＲ２、Ｃ＝ＮＮＲ4Ｒ5、ＣＯＲ２、ＣＯＯＲ２、ＯＲ2、Ｓ(Ｏ)nＲ3又はＣＯＮＲ4Ｒ5であり；Ｘはアルキル、ヒドロキシアルキル、アルケニル、アルキニル、アリール、ハロゲン、ハロアルキル、シアノ、ニトロ、ＮＲ4Ｒ5、Ｓ(Ｏ)nＲ3、ＯＲ2、ＣＯＲ２、ＣＯＯＲ２又はＣＯＮＲ4Ｒ5であり；Ｙは水素原子又はフッ素原子であり；ＺはＣＨ、ＣＸ又はＮであり；Ａはハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、アルキル、シクロアルキル、アリール、複素環基、ＳＣＨ２ＣＯＯＲ２ 、ＮＨＮＲ4Ｒ5 、ＣＯＯＲ２、ニトロ又は－ＣＨ（ＣＮ）2であり；Ｒ2は水素原子、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシアルキル、アセチル又はアリールであり；Ｒ3はアルキル又はアセチルであり；Ｒ4は水素原子又はアルキルであり；Ｒ5は水素原子、アルキル、ハロアルキル、ＣＯＲ２、ＣＯＯＲ２、ＣＨ２ＣＨ２ＯＲ2又はシアノアルキルであり；ｍは１～４の整数であり；ｎは０～２の整数である；但し、(1)Ｒ1αがメチルであり、Ｘが4-メトキシであり、ＺがＣＨである場合、(2)Ｒ1αがメチルであり、Ｘが3，4-ジメトキシであり、ＺがＣＨである場合及び(3)Ｒ1αがメチルであり、Ｘが4-メチルであり、ＺがＣＨである場合を除く〕で表される新規トリアゾロピリミジン誘導体又はその塩に関する。 Wherein R 1α is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano, halogen Aryl which may be substituted, heterocyclic group which may be substituted with alkyl, C═NOR 2 , C═NNR 4 R 5 , COR 2 , COOR 2 , OR 2 , S (O) n R 3 or CONR 4 R It is 5; X is an alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, NR 4 R 5, S ( O) n R 3, oR 2, COR 2, COOR 2 or CONR 4 R It is 5; Y is a hydrogen atom or a fluorine atom; Z is CH, CX or n; A is a halogen, oR 2, S (O) n R 3, NR 4 R 5, cyano, alkyl, cycloalkyl , Aryl, heterocyclic group, SCH 2 COOR 2 , NHNR 4 R 5 , COOR 2 , nitro or —CH (CN) 2 ; R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, acetyl or R 3 is alkyl or acetyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl, haloalkyl, COR 2 , COOR 2 , CH 2 CH 2 OR 2 or cyanoalkyl. M is an integer from 1 to 4; n is an integer from 0 to 2; provided that (1) when R 1α is methyl, X is 4-methoxy, and Z is CH, (2 ) R 1α is methyl, X is 3,4-dimethoxy, Z is CH, and (3) R 1α is methyl, X is 4-methyl, and Z is CH. New It relates rear triazolopyrimidine derivative or a salt thereof.
　式（I）のトリアゾロピリミジン誘導体又はその塩を有効成分とする有害生物防除剤は、低薬量で有害生物に対して極めて高い防除効果を有する。 The pest control agent comprising the triazolopyrimidine derivative of the formula (I) or a salt thereof as an active ingredient has a very high control effect against pests at a low dose.
Figure JPOXMLDOC01-appb-I000005
　式（I）中のｍが２以上の場合、各Ｘは同一であっても相異なってもよい。
Figure JPOXMLDOC01-appb-I000005
When m in the formula (I) is 2 or more, each X may be the same or different.
　式（I）中のハロゲン又は置換基としてのハロゲンとしては、フッ素、塩素、臭素又はヨウ素の各原子が挙げられる。置換基としてのハロゲンの数は１又は２以上であってよく、２以上の場合、各ハロゲンは同一でも相異なってもよい。また、ハロゲンの置換位置はいずれの位置でもよい。 Examples of the halogen in formula (I) or the halogen as a substituent include each atom of fluorine, chlorine, bromine or iodine. The number of halogens as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen may be the same or different. Further, the halogen substitution position may be any position.
　式（I）中のアルキルとしては、直鎖状又は分枝状のいずれでもよく、例えばメチル、エチル、プロピル、イソプロピル、ブチル、tert－ブチル、ペンチル、ヘキシルのようなＣ１－６のものなどを挙げることができる。 The alkyl in the formula (I) may be linear or branched, for example, C 1-6 such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, etc. Can be mentioned.
　式（I）中のシクロアルキルとしては、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシルのようなＣ３－６のものなどを挙げることができる。 Examples of cycloalkyl in formula (I) include C 3-6 such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
　式（I）中のアルケニルとしては、直鎖状又は分枝状のいずれでもよく、例えばビニル、１－プロペニル、アリル、イソプロペニル、１－ブテニル、１,３－ブタジエニル、１－ヘキセニルのようなＣ２－６のものなどを挙げることができる。 The alkenyl in the formula (I) may be linear or branched, such as vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1,3-butadienyl, 1-hexenyl and the like. C 2-6 may be mentioned.
　式（I）中のアルキニルとしては、直鎖状又は分枝状のいずれでもよく、例えばエチニル、２－ブチニル、２－ペンチニル、３－メチル－１－ブチニル、２－ペンテン－４－イニル、３－ヘキシニルのようなＣ２－６のものなどを挙げることができる。 The alkynyl in the formula (I) may be linear or branched. For example, ethynyl, 2-butynyl, 2-pentynyl, 3-methyl-1-butynyl, 2-penten-4-ynyl, 3 -C 2-6 such as hexynyl.
　式（I）中のアリールとしては、例えばフェニル、ナフチルのようなＣ6-10アリールなどを挙げることができる。 Examples of the aryl in the formula (I) include C 6-10 aryl such as phenyl and naphthyl.
　式（I）中の複素環基としては、単環式複素環基の他、縮合複素環基が含まれる。単環式複素環基としては、例えばオキシラニルのような３員複素環基；フリル、テトラヒドロフリル、チエニル、ピロリル、ピロリニル、ピロリジニル、ジオキソラニル、オキサゾリル、イソキサゾリル、チアゾリル、イソチアゾリル、イミダゾリル、イミダゾリニル、イミダゾリジニル、ピラゾリル、ピラゾリニル、ピラゾリジニル、トリアゾリル、オキサジアゾリル、チアジアゾリル、テトラゾリルなどの５員複素環基；ピラニル、ピリジル、ピペリジニル、ジオキサニル、オキサジニル、モルホリニル、チアジニル、ピリダジニル、ピリミジニル、ピラジニル、ピペラジニル、トリアジニルなどの６員複素環基が挙げられる。これら単環式複素環基の中では、Ｏ、Ｓ及びＮからなる群より選ばれる少なくとも１種の原子を１～４含有する５若しくは６員複素環基が望ましい。縮合複素環基としては、例えばベンゾフラニル、イソベンゾフラニル、ジヒドロベンゾフラニル、ジヒドロイソベンゾフラニル、ベンゾチエニル、イソベンゾチエニル、ジヒドロベンゾチエニル、ジヒドロイソベンゾチエニル、テトラヒドロベンゾチエニル、インドリル、イソインドリル、ベンゾオキサゾリル、ベンゾチアゾリル、インダゾリル、ベンズイミダゾリル、ベンゾジオキソラニル、ベンゾジオキサニル、クロメニル、クロマニル、イソクロマニル、クロモニル、クロマノニル、キノリル、イソキノリル、シンノリニル、フタラジニル、キナゾリニル、キノキサリニル、インドリジニル、キノリジニル、イミダゾピリジル、ナフチリジニル、プテリジニル、ジヒドロベンゾオキサジニル、ジヒドロベンゾオキサゾリノニル、ジヒドロベンゾオキサジノニル、ベンゾチオキサニルなどが挙げられる。これら縮合複素環基の中では、Ｏ、Ｓ及びＮからなる群より選ばれる少なくとも１種の原子を１～４含有する８～１０員縮合複素環基が望ましい。 The heterocyclic group in the formula (I) includes a condensed heterocyclic group in addition to a monocyclic heterocyclic group. Monocyclic heterocyclic groups include, for example, 3-membered heterocyclic groups such as oxiranyl; furyl, tetrahydrofuryl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, dioxolanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl 5-membered heterocyclic groups such as pyrazolinyl, pyrazolidinyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl; 6-membered heterocyclic groups such as pyranyl, pyridyl, piperidinyl, dioxanyl, oxazinyl, morpholinyl, thiazinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl Is mentioned. Among these monocyclic heterocyclic groups, a 5- or 6-membered heterocyclic group containing 1 to 4 atoms of at least one atom selected from the group consisting of O, S and N is desirable. Examples of the condensed heterocyclic group include benzofuranyl, isobenzofuranyl, dihydrobenzofuranyl, dihydroisobenzofuranyl, benzothienyl, isobenzothienyl, dihydrobenzothienyl, dihydroisobenzothienyl, tetrahydrobenzothienyl, indolyl, isoindolyl, Benzoxazolyl, benzothiazolyl, indazolyl, benzimidazolyl, benzodioxolanyl, benzodioxanyl, chromenyl, chromanyl, isochromanyl, chromonyl, chromanonyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolizinyl, quinolizylyl , Naphthyridinyl, pteridinyl, dihydrobenzoxazinyl, dihydrobenzoxazolinonyl, dihydride Benzoxadiazoles nonyl, benzothiadiazole oxa sulfonyl and the like. Among these condensed heterocyclic groups, 8- to 10-membered condensed heterocyclic groups containing 1 to 4 at least one atom selected from the group consisting of O, S and N are desirable.
　式（I）のトリアゾロピリミジン誘導体の塩としては、農業上許容されるものであればあらゆるものが含まれるが、例えば、ジメチルアンモニウム塩、トリエチルアンモニウム塩のようなアンモニウム塩；塩酸塩、過塩素酸塩、硫酸塩、硝酸塩のような無機酸塩；酢酸塩、メタンスルホン酸塩のような有機酸塩などを挙げることができる。 Examples of the salt of the triazolopyrimidine derivative of the formula (I) include any agriculturally acceptable salt, for example, ammonium salts such as dimethylammonium salt and triethylammonium salt; Examples thereof include inorganic acid salts such as acid salts, sulfates and nitrates; organic acid salts such as acetates and methanesulfonates.
　式（I）のトリアゾロピリミジン誘導体には、光学異性体、幾何異性体のような異性体が存在する場合があるが、本発明には各異性体及び異性体混合物の双方が含まれる。本発明の明細書においては、特に言及しない限り、異性体は混合物として記載する。尚、本発明には、当該技術分野における技術常識の範囲内において、前記したもの以外の各種異性体も含まれる。また、異性体の種類によっては、前記式（I）とは異なる化学構造となる場合があるが、当業者であればそれらが異性体の関係にあることが十分認識できる為、本発明の範囲内であることは明らかである。 In the triazolopyrimidine derivative of the formula (I), there may be isomers such as optical isomers and geometric isomers, but the present invention includes both isomers and isomer mixtures. In the specification of the present invention, isomers are described as a mixture unless otherwise specified. The present invention also includes various isomers other than those described above within the scope of technical common sense in the technical field. In addition, depending on the type of isomer, the chemical structure may be different from that of the formula (I). However, since those skilled in the art can sufficiently recognize that they are related to isomers, the scope of the present invention It is clear that it is within.
　式（I）のトリアゾロピリミジン誘導体又その塩は、下記の製法〔１〕～〔１９〕並びに、通常の塩の製造方法に従って製造することができる。以下に各製法について、反応フローを示し詳述する。
　製法〔１〕 The triazolopyrimidine derivative of the formula (I) or a salt thereof can be produced according to the following production methods [1] to [19] and usual salt production methods. The reaction flow will be described in detail below for each production method.
Manufacturing method [1]
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　製法〔１〕中、Ｒ1aは水素原子、Ａで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲンで置換されてもよいアリール又はアルキルで置換されてもよい複素環基であり；Ｒ６及びＲ７は各々独立にアルキルであり；Ａ、Ｘ、Ｚ及びｍは前述の通りである。 In the production process [1], R 1a is a hydrogen atom, alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen R 6 and R 7 are each independently alkyl; A, X, Z and m are as defined above.
　製法〔１〕は、上記〔１〕－１及び〔１〕－２の反応工程から成り、式（II）の化合物から式（I－１）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造することができる。各反応工程については、以下に詳述する。 The production method [1] comprises the reaction steps of the above [1] -1 and [1] -2. From the compound of the formula (II), [1,2,4] triazolo [1,5 of the formula (I-1) -A] Pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
　〔１〕－１；本反応工程では、式（II）の化合物と式（III）の化合物とを縮合させることによって式（IＶ）のα、β－不飽和ケトン誘導体を製造できる。 [1] -1; In this reaction step, an α, β-unsaturated ketone derivative of the formula (IV) can be produced by condensing the compound of the formula (II) and the compound of the formula (III).
　本反応工程において、式（III）の化合物は、式（II）の化合物１モルに対して１～５当量、望ましくは１～３当量の割合で使用できる。本反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばメタノール、エタノール、プロパノール、ブタノールのようなアルコール類；ベンゼン、トルエン、キシレンのような芳香族炭化水素類；ペンタン、ヘキサン、ヘプタン、石油エーテル、リグロイン、石油ベンジンのような脂肪族炭化水素類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサンのようなエーテル類；酢酸メチル、酢酸エチルのようなエステル類；アセトニトリル、プロピオニトリルのようなニトリル類；Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリジノンのような酸アミド類；ジメチルスルホキシドのようなスルホキシド類；スルホランのようなスルホン類；ヘキサメチルホスホルアミドのようなリン酸アミド類；クロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンのようなハロゲン化炭化水素類；及びこれらの混合溶媒などを挙げることができる。反応温度は通常８０～２００℃、望ましくは１００～１５０℃である。反応時間は通常６～４８時間である。 In this reaction step, the compound of formula (III) can be used at a ratio of 1 to 5 equivalents, preferably 1 to 3 equivalents, per 1 mol of the compound of formula (II). This reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, alcohols such as methanol, ethanol, propanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; pentane and hexane Aliphatic hydrocarbons such as petroleum ether, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; esters such as methyl acetate and ethyl acetate; acetonitrile Nitriles such as propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; Heki Phosphoric acid amides such as methyl phosphoramide; chloroform, dichloromethane, carbon tetrachloride, halogenated hydrocarbons such as 1,2-dichloroethane; and the like can be mentioned a mixture of these solvents. The reaction temperature is usually from 80 to 200 ° C, preferably from 100 to 150 ° C. The reaction time is usually 6 to 48 hours.
　〔１〕－２；本反応工程では、式（IＶ）の化合物と式（Ｖ）の化合物とを縮合させることによって式（I－１）の化合物を製造できる。 [1] -2; In this reaction step, the compound of formula (I-1) can be produced by condensing the compound of formula (IV) and the compound of formula (V).
　式（Ｖ）の化合物は、式（IＶ）の化合物１モルに対して、１～１０当量、望ましくは１～２．５当量の割合で使用できる。
　本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば酢酸、プロピオン酸のようなカルボン酸類；メタノール、エタノール、プロパノール、ブタノールのようなアルコール類；ベンゼン、トルエン、キシレンのような芳香族炭化水素類；ペンタン、ヘキサン、ヘプタン、石油エーテル、リグロイン、石油ベンジンのような脂肪族炭化水素類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサンのようなエーテル類；酢酸メチル、酢酸エチルのようなエステル類；アセトニトリル、プロピオニトリルのようなニトリル類；Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリジノンのような酸アミド類；ジメチルスルホキシドのようなスルホキシド類；スルホランのようなスルホン類；ヘキサメチルホスホルアミドのようなリン酸アミド類；クロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンのようなハロゲン化炭化水素類；及びこれらの混合溶媒などを挙げることができるが、中でもカルボン酸類が望ましい。反応温度は通常５０～１５０℃、望ましくは８０～１２０℃である。反応時間は通常０．５～１００時間である。
　製法〔２〕 The compound of the formula (V) can be used in a ratio of 1 to 10 equivalents, desirably 1 to 2.5 equivalents, per 1 mol of the compound of the formula (IV).
This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction. For example, carboxylic acids such as acetic acid and propionic acid; alcohols such as methanol, ethanol, propanol and butanol; benzene, toluene and xylene. Aromatic hydrocarbons; aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; methyl acetate Esters such as ethyl acetate; nitriles such as acetonitrile and propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; and dimethyl sulfoxide Sulfoxy Sulfones such as sulfolane; phosphoric acid amides such as hexamethylphosphoramide; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane; and mixed solvents thereof Among them, carboxylic acids are preferable. The reaction temperature is usually 50 to 150 ° C., desirably 80 to 120 ° C. The reaction time is usually 0.5 to 100 hours.
Manufacturing method [2]
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　製法〔２〕中、Ｒ1bはＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲンで置換されてもよいアリール又はアルキルで置換されてもよい複素環基であり；Ｒ８はアルキルであり；Ａ、Ｘ、Ｚ及びｍは前述の通りである。 In the production process [2], R 1b is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, and halogen substituted. A heterocyclic group optionally substituted with aryl or alkyl; R 8 is alkyl; A, X, Z and m are as described above.
　製法〔２〕は、上記〔２〕－１及び〔２〕－２の反応工程から成り、式（II）の化合物から式（I－２）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造することができる。各反応工程については、以下に詳述する。 The production method [2] comprises the reaction steps of the above [2] -1 and [2] -2. From the compound of formula (II), [1,2,4] triazolo [1,5 of formula (I-2) -A] Pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
　〔２〕－１；本反応工程では、式（II）の化合物と式（ＶI）の化合物とを反応させて式（ＶII）の化合物を製造できる。
　式（ＶI）の化合物は、式（II）の化合物１モルに対して１当量～大過剰量、望ましくは１～３当量の割合で使用できる。本反応は、通常、塩基及び溶媒の存在下で行うことができる。塩基としては、例えば水素化ナトリウム、水素化カリウムのような金属水素化物；水酸化ナトリウム、水酸化カリウムのような金属水酸化物；ナトリウム、カリウムのようなアルカリ金属；ナトリウムメトキシド、ナトリウムエトキシド、カリウム第３級ブトキシドのようなアルカリ金属アルコキシド；などを挙げることができる。塩基は、式（II）の化合物１モルに対して１～５当量、望ましくは１～２当量の割合で使用できる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばベンゼン、トルエン、キシレンのような芳香族炭化水素類；ペンタン、ヘキサン、ヘプタン、石油エーテル、リグロイン、石油ベンジンのような脂肪族炭化水素類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサンのようなエーテル類；Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリジノンのような酸アミド類；ジメチルスルホキシドなどのスルホキシド類；スルホランのようなスルホン類；クロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンのようなハロゲン化炭化水素類；及びこれらの混合溶媒などを挙げることができるが、中でもエーテル類が望ましい。反応温度は通常０～７０℃、望ましくは１０～５０℃である。反応時間は、通常０．１～２４時間である。 [2] -1; In this reaction step, the compound of formula (VII) can be produced by reacting the compound of formula (II) with the compound of formula (VI).
The compound of the formula (VI) can be used in an amount of 1 equivalent to a large excess, desirably 1 to 3 equivalents, relative to 1 mol of the compound of the formula (II). This reaction can usually be performed in the presence of a base and a solvent. Examples of the base include metal hydrides such as sodium hydride and potassium hydride; metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as sodium and potassium; sodium methoxide and sodium ethoxide And alkali metal alkoxides such as potassium tertiary butoxide; The base can be used in an amount of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of formula (II). The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene; pentane, hexane, heptane, petroleum ether, ligroin, petroleum benzine Aliphatic hydrocarbons; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone; Examples thereof include sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane; and mixed solvents thereof. Ethers are desirable. The reaction temperature is usually 0 to 70 ° C., preferably 10 to 50 ° C. The reaction time is usually 0.1 to 24 hours.
　〔２〕－２；本反応工程では、式（ＶII）の化合物と式（Ｖ）の化合物とを縮合させて式（I－２）の化合物を製造できる。
　本反応において、式（Ｖ）の化合物は、前記式（ＶII）の化合物１モルに対して１～１０当量、望ましくは１～３当量の割合で使用できる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては反応に悪影響を与えないものであれば特に限定はなく、例えば酢酸、プロピオン酸などのカルボン酸類；メタノール、エタノール、プロパノール、ブタノールなどのアルコール類；ベンゼン、トルエン、キシレンなどの芳香族炭化水素類；ペンタン、ヘキサン、ヘプタン、石油エーテル、リグロイン、石油ベンジンなどの脂肪族炭化水素類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサンなどのエーテル類；酢酸メチル、酢酸エチルなどのエステル類；アセトニトリル、プロピオニトリルなどのニトリル類；Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリジノンなどの酸アミド類；ジメチルスルホキシドなどのスルホキシド類；スルホランなどのスルホン類；ヘキサメチルホスホルアミドなどのリン酸アミド類；クロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンなどのハロゲン化炭化水素類；及びこれらの混合溶媒を挙げることができるが、中でもカルボン酸類が望ましい。反応温度は通常５０～１５０℃、望ましくは８０～１２０℃の反応温度で行われる。反応時間は、通常０．５～１００時間である。
　製法〔３〕 [2] -2; In this reaction step, the compound of formula (I-2) can be produced by condensing the compound of formula (VII) with the compound of formula (V).
In this reaction, the compound of the formula (V) can be used at a ratio of 1 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of the formula (VII). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, carboxylic acids such as acetic acid and propionic acid; alcohols such as methanol, ethanol, propanol and butanol; aromatic carbonization such as benzene, toluene and xylene Hydrogen: aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; esters such as methyl acetate and ethyl acetate Nitriles such as acetonitrile and propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfolane and the like Examples include sulfones; phosphoric acid amides such as hexamethylphosphoramide; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane; and mixed solvents thereof. Acids are desirable. The reaction temperature is usually 50 to 150 ° C., preferably 80 to 120 ° C. The reaction time is usually 0.5 to 100 hours.
Manufacturing method [3]
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　製法〔３〕中、Ｒ9はアルキルであり；Ｒ1b、Ｘ、Ｚ及びｍは前述の通りである。 In the production process [3], R 9 is alkyl; R 1b , X, Z and m are as described above.
　製法〔３〕は、上記〔３〕－１及び〔３〕－２の反応工程から成り、式（ＶIII）の化合物から式（I－２）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造することができる。各反応工程については、以下に詳述する。 The production method [3] comprises the reaction steps of the above [3] -1 and [3] -2. From the compound of the formula (VIII), [1,2,4] triazolo [1,5] of the formula (I-2) -A] Pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
　〔３〕－１；本反応工程では、式（ＶIII）の化合物と式（IＸ）の化合物とを反応させて式（ＶII）の化合物を製造できる。 [3] -1; In this reaction step, the compound of formula (VII) can be produced by reacting the compound of formula (VIII) with the compound of formula (IX).
　式（IＸ）の化合物は、式（ＶIII）の化合物１モルに対して０．８当量～大過剰量、望ましくは１～１０当量の割合で使用できる。本反応は、通常、塩基及び溶媒の存在下で行うことができる。塩基としては、例えば前記製法〔２〕の反応工程〔２〕－１と同様のものなどを挙げることができる。塩基は、式（ＶIII）の化合物１モルに対して通常１～５当量、望ましくは１～２当量の割合で使用できる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば前記製法〔２〕の反応工程〔２〕－１と同様のものを挙げることができるが、中でもエーテル類が望ましい。反応温度は通常０～７０℃、望ましくは１０～５０℃である。反応時間は、通常０．１～２４時間である。
　〔３〕－２；本反応工程では、式（ＶII）の化合物と式（Ｖ）の化合物とを縮合させて式（I－２）の化合物を製造できる。 The compound of the formula (IX) can be used in a proportion of 0.8 equivalent to a large excess, desirably 1 to 10 equivalent, relative to 1 mol of the compound of the formula (VIII). This reaction can usually be performed in the presence of a base and a solvent. Examples of the base include those similar to the reaction step [2] -1 in the above production method [2]. The base can be used in a proportion of usually 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of the formula (VIII). The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, the same solvents as those in the reaction step [2] -1 of the above production method [2] can be exemplified, and among these, ethers are desirable. The reaction temperature is usually 0 to 70 ° C., preferably 10 to 50 ° C. The reaction time is usually 0.1 to 24 hours.
[3] -2: In this reaction step, the compound of formula (I-2) can be produced by condensing the compound of formula (VII) with the compound of formula (V).
　本反応工程は、前記製法〔２〕の反応工程〔２〕－２と同様に実施することができる。
　製法〔４〕 This reaction step can be carried out in the same manner as in the reaction step [2] -2 of the production method [2].
Manufacturing method [4]
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　製法〔４〕中、Ｒ1cはＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、ＯＲ2、ＳＲ3、ＮＲ4Ｒ5又はＮ３であり；Ｒ10はアルキルであり；Ｒ11はＯＨ、アルキル、シクロアルキル、アルコキシ又はフッ素原子であり；ｐはＲ11がアルキル、シクロアルキル又はアルコキシである場合２であり、Ｒ11がフッ素原子である場合３であり；Ｒ11のアルキル又はアルコキシは、隣接するホウ素原子と相互に結合して環を形成してもよく；ｈａｌはハロゲンであり；Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ａ、Ｘ、Ｚ及びｍは前述の通りである。ｈａｌで表されるハロゲンとしては、フッ素、塩素、臭素又はヨウ素の各原子を挙げることができる。 In the production method [4], R 1c is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, cyano or halogen. Aryl which may be substituted, heterocyclic group which may be substituted with alkyl, OR 2 , SR 3 , NR 4 R 5 or N 3 ; R 10 is alkyl; R 11 is OH, alkyl, cycloalkyl P is 2 when R 11 is alkyl, cycloalkyl or alkoxy, and 3 when R 11 is a fluorine atom; alkyl or alkoxy of R 11 is an adjacent boron atom May be bonded to each other to form a ring; hal is a halogen; R 2 , R 3 , R 4 , R 5 , A, X, Z and m are as described above. Examples of the halogen represented by hal include fluorine, chlorine, bromine or iodine atoms.
　製法〔４〕は、上記〔４〕－１、〔４〕－２、〔４〕－３及び〔４〕－４の反応工程から成り、式（X）の化合物から式（I－４）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造することができる。各反応工程については、以下に詳述する。 Production method [4] comprises the reaction steps of [4] -1, [4] -2, [4] -3 and [4] -4, and from the compound of formula (X) to formula (I-4) [1,2,4] Triazolo [1,5-a] pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
　〔４〕－１；本反応工程では、公知の方法（例えばChem．Pharm．Bull、Volume 9、801（1961）など）に準じて、式（Ｘ）のマロン酸エステルと式（Ｖ）の化合物とをアルカリ性条件下で縮合させることにより式（ＸI）の５,７-ジヒドロキシ［１,２,４］トリアゾロ［１,５－ａ］ピリミジンを製造できる。 [4] -1; In this reaction step, a malonic acid ester of the formula (X) and a compound of the formula (V) according to a known method (for example, Chem. Pharm. Bull, Volume 9, 9, 801 (1961), etc.) And 5,7-dihydroxy [1,2,4] triazolo [1,5-a] pyrimidine of the formula (XI) can be prepared by condensing the above with alkaline conditions.
　〔４〕－２；本反応工程は、式（ＸI）の化合物をハロゲン化する反応工程であり、
　（ａ）式（ＸI）の化合物と塩素化剤又は臭素化剤とを反応させ、式（ＸII）の化合物（式中、ｈａｌは塩素又は臭素原子である）を製造すること；
　（ｂ）必要であれば、（ａ）で形成した式（ＸII）の化合物とフッ素化剤とを反応させ、式（ＸII）の化合物（式中、ｈａｌはフッ素原子である）で示される化合物を製造すること；及び、
　（ｃ）必要であれば、（ａ）で形成した式（ＸII）の化合物とアンモニアとを反応させ、次いでジアゾ化剤の存在下でヨウ素化剤と反応させて、式（ＸII）の化合物（式中、少なくとも一方のｈａｌはヨウ素原子である）を製造すること；からなる。
　以下に（ａ）～（ｃ）の各方法について詳述する。 [4] -2; This reaction step is a reaction step for halogenating the compound of the formula (XI),
(A) reacting a compound of formula (XI) with a chlorinating agent or brominating agent to produce a compound of formula (XII) wherein hal is a chlorine or bromine atom;
(B) If necessary, the compound of the formula (XII) formed in (a) and a fluorinating agent are reacted to give a compound of the formula (XII) (wherein hal is a fluorine atom) Manufacturing; and
(C) If necessary, the compound of formula (XII) formed in (a) is reacted with ammonia and then reacted with an iodinating agent in the presence of a diazotizing agent to give a compound of formula (XII) ( Wherein at least one hal is an iodine atom).
The methods (a) to (c) will be described in detail below.
　（ａ）塩素化剤としては、例えばオキシ塩化リン、三塩化リン及び五塩化リンなどを挙げることができる。臭素化剤としては、例えばオキシ臭化リン、三臭化リン及び五臭化リンなどを挙げることができる。塩素化剤又は臭素化剤は、式（ＸI）の化合物１モルに対して通常１当量～大過剰量の割合で使用できる。本反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばジクロロメタンのようなハロゲン化炭化水素類を挙げることができる。反応温度は通常０℃～反応混合物の還流温度、望ましくは２０℃～反応混合物の還流温度である。反応時間は通常１～４８時間である。 (A) Examples of the chlorinating agent include phosphorus oxychloride, phosphorus trichloride, and phosphorus pentachloride. Examples of the brominating agent include phosphorus oxybromide, phosphorus tribromide, and phosphorus pentabromide. The chlorinating agent or brominating agent can be used usually in a proportion of 1 equivalent to a large excess with respect to 1 mol of the compound of the formula (XI). This reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include halogenated hydrocarbons such as dichloromethane. The reaction temperature is usually 0 ° C. to the reflux temperature of the reaction mixture, preferably 20 ° C. to the reflux temperature of the reaction mixture. The reaction time is usually 1 to 48 hours.
　（ｂ）フッ素化剤としては、アルカリ金属のフッ化物、特にフッ化カリウム、五フッ化アンチモン及び三フッ化ジエチルアミノ硫黄などを挙げることができる。フッ素化剤は、式（ＸII）の化合物（式中、ｈａｌは塩素原子又は臭素原子である）１モルに対して１当量～５当量、望ましくは１．５～３当量の割合で使用できる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばトルエン、キシレンのような芳香族炭化水素類；アセトニトリル、プロピオニトリルのようなニトリル類；スルホランのようなスルホン類、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリジノンのような酸アミド類；及びこれらの混合溶媒などを挙げることができる。スルホン類または酸アミド類を溶媒として用いる場合には、フッ素化剤の脱水を助けるためにトルエンを共溶媒として用いるのが有利である。反応温度は、通常１５℃～反応混合物の還流温度、望ましくは４０℃～反応混合物の還流温度である。反応時間は、通常２～４８時間である。 (B) Examples of the fluorinating agent include fluorides of alkali metals, particularly potassium fluoride, antimony pentafluoride and diethylaminosulfur trifluoride. The fluorinating agent can be used in an amount of 1 to 5 equivalents, preferably 1.5 to 3 equivalents, per mole of the compound of formula (XII) (wherein hal is a chlorine atom or a bromine atom). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile and propionitrile; sulfones such as sulfolane; And acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; and mixed solvents thereof. When sulfones or acid amides are used as a solvent, it is advantageous to use toluene as a co-solvent to assist dehydration of the fluorinating agent. The reaction temperature is usually 15 ° C. to the reflux temperature of the reaction mixture, preferably 40 ° C. to the reflux temperature of the reaction mixture. The reaction time is usually 2 to 48 hours.
　（ｃ）式（ＸII）の化合物（式中、ｈａｌは塩素原子又は臭素原子である）とアンモニアとの反応は、通常、塩基の存在下で行うことができるが、中でも過剰のアンモニアを用い、塩基と兼ねることが望ましい。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては反応に悪影響を与えないものであれば特に限定はなく、例えばベンゼン、トルエン、キシレンのような芳香族炭化水素類；ペンタン、ヘキサン、ヘプタン、石油エーテル、リグロイン、石油ベンジンのような脂肪族炭化水素類；クロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンのようなハロゲン化炭化水素類；及びこれらの混合溶媒などを挙げることができる。反応温度は、２０℃～反応混合物の還流温度、望ましくは４０℃～反応混合物の還流温度である。反応時間は、通常２～４８時間である。 (C) The reaction of the compound of the formula (XII) (wherein hal is a chlorine atom or a bromine atom) and ammonia can usually be carried out in the presence of a base, but among them, excess ammonia is used. It is desirable to double as a base. This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; fats such as pentane, hexane, heptane, petroleum ether, ligroin and petroleum benzine. Group hydrocarbons; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane; and mixed solvents thereof. The reaction temperature is from 20 ° C. to the reflux temperature of the reaction mixture, preferably from 40 ° C. to the reflux temperature of the reaction mixture. The reaction time is usually 2 to 48 hours.
　アンモニアとの反応終了後、次いでジアゾ化剤の存在下でヨウ素化剤と反応を行う。ジアゾ化剤としては、例えば亜硝酸の任意のアルキルエステルを挙げることができるが、中でも亜硝酸イソペンチルが望ましい。ジアゾ化剤は、式（ＸII）の化合物（式中、ｈａｌは塩素又は臭素原子である）１モルに対して、通常１当量～５当量の割合で使用できる。ヨウ素化剤としては、例えばヨウ素、ジヨードメタンなどを挙げることができる。
　ヨウ素化剤は、式（ＸII）の化合物（式中、ｈａｌは塩素原子又は臭素原子である）１モルに対して１当量～５当量、望ましくは１．５～３当量の割合で使用できる。
　本反応は、通常、溶媒の存在下で行うことができる。溶媒としては反応に悪影響を与えないものであれば特に限定はなく、例えば、ペンタン、ヘキサン、ヘプタン、石油エーテル、リグロイン、石油ベンジンのような脂肪族炭化水素類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサンのようなエーテル類；酢酸メチル、酢酸エチルのようなエステル類；アセトニトリル、プロピオニトリルのようなニトリル類；及びこれらの混合溶媒などを挙げることができる。 After completion of the reaction with ammonia, the reaction is then carried out with an iodinating agent in the presence of a diazotizing agent. Examples of the diazotizing agent include any alkyl ester of nitrous acid, and isopentyl nitrite is particularly preferable. The diazotizing agent can be used usually in a ratio of 1 equivalent to 5 equivalents per 1 mol of the compound of the formula (XII) (wherein hal is a chlorine or bromine atom). Examples of the iodinating agent include iodine and diiodomethane.
The iodinating agent can be used in an amount of 1 to 5 equivalents, preferably 1.5 to 3 equivalents, per mole of the compound of formula (XII) (wherein hal is a chlorine atom or a bromine atom).
This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, ligroin, petroleum benzine; diethyl ether, dipropyl ether, diethylene Examples thereof include ethers such as butyl ether, tetrahydrofuran and dioxane; esters such as methyl acetate and ethyl acetate; nitriles such as acetonitrile and propionitrile; and mixed solvents thereof.
　（ｃ）の反応は、ワンポット反応（One-pot synthesis）として実施することができ、ジアゾ化剤として亜硝酸のアルキルエステルを用いた場合、ヨウ素化剤としてジヨードメタンを共溶媒として使用することができる。反応温度は、通常６０℃～１２０℃、望ましくは７０℃～１１０℃である。反応時間は、通常１～４８時間である。 The reaction of (c) can be carried out as a one-pot synthesis, and when an alkyl ester of nitrous acid is used as a diazotizing agent, diiodomethane can be used as a cosolvent as an iodinating agent. . The reaction temperature is usually 60 ° C. to 120 ° C., desirably 70 ° C. to 110 ° C. The reaction time is usually 1 to 48 hours.
　〔４〕－３；本反応工程では、式（ＸII）の化合物と式（ＸIII）のホウ素化合物とを遷移金属触媒の存在下で鈴木カップリング（Suzuki coupling）させることにより、式（I－３）の化合物を製造できる。 [4] -3; In this reaction step, a compound of formula (XII) and a boron compound of formula (XIII) are subjected to Suzuki coupling in the presence of a transition metal catalyst to give a compound of formula (I-3 ) Can be produced.
　鈴木カップリングは、多くの刊行物中で研究がなされており、公知の方法（例えば、Synth. Commun.、1981、11 (7)、 513-519又はSynlett.、1992、207-210などに記載されている方法）に準じて、本反応工程は実施することができる。 Suzuki coupling has been studied in many publications and is described in known methods (for example, Synth. Commun., 1981, 11 (7), 513-519 or Synlett., 1992, 207-210). This reaction step can be carried out according to the method described above.
　式（ＸIII）中、Ｂ(Ｒ11)ｐで表される置換ホウ素部分において、Ｒ11がフッ素原子であり、ｐが３である -ＢＦ3基は負電荷を帯びるため、通常、カリウム等のアルカリ金属とトリフルオロボレート塩を形成する。式（ＸIII）中のＢ(Ｒ11)ｐで表される置換ホウ素としては、例えばヒドロキシホウ素、アルキルホウ素、アルコキシホウ素、トリフルオロボレートカリウム塩などを挙げることができる。式（ＸIII）のホウ素化合物は、式（ＸII）の化合物１モルに対して０．５～１当量の割合で使用できる。 In formula (XIII), in the substituted boron moiety represented by B (R 11 ) p , R 11 is a fluorine atom, and p is 3. Since the —BF 3 group is negatively charged, Forms trifluoroborate salts with alkali metals. Examples of the substituted boron represented by B (R 11 ) p in formula (XIII) include hydroxyboron, alkylboron, alkoxyboron, and trifluoroborate potassium salt. The boron compound of the formula (XIII) can be used at a ratio of 0.5 to 1 equivalent per 1 mol of the compound of the formula (XII).
　本反応で使用する遷移金属触媒とは、遷移金属化合物または遷移金属化合物と任意の配位子との錯体を意味する。例えばパラジウム-炭素（Pd/C）、テトラキス（トリフェニルホスフィン）パラジウム(0)、ビス(ジベンジリデンアセトン)パラジウム(0)、テトラキス(ジベンジリデンアセトン)ジパラジウム(0)、酢酸パラジウム(II)－トリフェニルホスフィン、酢酸パラジウム(II)－トリシクロヘキシルホスフィンなどを挙げることができる。。錯体の場合、予め単離したものを使用しても良いし、また任意の反応溶媒中で遷移金属化合物と配位子を混合して単離せずに使用しても良い。遷移金属触媒は、式（ＸII）の化合物１モルに対して０．００１～０．２当量、望ましくは０．０１～０．１当量の割合で使用できる。 The transition metal catalyst used in this reaction means a transition metal compound or a complex of a transition metal compound and an arbitrary ligand. For example, palladium-carbon (Pd / C), tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), tetrakis (dibenzylideneacetone) dipalladium (0), palladium (II)- Examples thereof include triphenylphosphine and palladium (II) acetate-tricyclohexylphosphine. . In the case of a complex, one previously isolated may be used, or a transition metal compound and a ligand may be mixed in an arbitrary reaction solvent and used without isolation. The transition metal catalyst can be used in a proportion of 0.001 to 0.2 equivalent, preferably 0.01 to 0.1 equivalent, relative to 1 mol of the compound of formula (XII).
　本反応は通常、塩基の存在下に行うことができる。塩基としては、例えば炭酸ナトリウム、炭酸カリウム、炭酸セシウムのようなアルカリ金属炭酸塩；炭酸水素ナトリウムのようなアルカリ金属の炭酸水素塩；炭酸カルシウムのようなアルカリ土類金属の炭酸塩；水酸化ナトリウム、水酸化カリウムのようなアルカリ金属水酸化物；水酸化カルシウムのようなアルカリ土類金属水酸化物；フッ化セシウム、フッ化カリウムのような無機塩類、トリエチルアミン、ピリジン、4-（N,N-ジメチルアミノ）ピリジンのようなアミン類；などを挙げることができる。塩基類は、式（ＸII）の化合物１モルに対して、通常０．９～２０当量の割合で使用できる。 This reaction can usually be performed in the presence of a base. Examples of the base include alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate; sodium hydroxide , Alkali metal hydroxides such as potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; inorganic salts such as cesium fluoride and potassium fluoride, triethylamine, pyridine, 4- (N, N -Amines such as (dimethylamino) pyridine; The base can be used usually in a proportion of 0.9 to 20 equivalents per 1 mol of the compound of the formula (XII).
　また、本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば水；メタノール、エタノール、プロパノール、ブタノールのようなアルコール類；ベンゼン、トルエン、キシレンのような芳香族炭化水素類；ペンタン、ヘキサン、ヘプタン、石油エーテル、リグロイン、石油ベンジンのような脂肪族炭化水素類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテルのようなエーテル類；アセトニトリル、プロピオニトリルのようなニトリル類；クロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンのようなハロゲン化炭化水素類；及びこれらの混合溶媒などを挙げることができる。反応温度は、通常１５℃～反応混合物の還流温度、望ましくは４０℃～反応混合物の還流温度である。反応時間は反応温度、反応量、反応圧力等により一定しないが通常１～９６時間である。 In addition, this reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, water; alcohols such as methanol, ethanol, propanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; pentane Aliphatic hydrocarbons such as hexane, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether; acetonitrile, propionitrile Nitriles such as: halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane; and mixed solvents thereof. The reaction temperature is usually 15 ° C. to the reflux temperature of the reaction mixture, preferably 40 ° C. to the reflux temperature of the reaction mixture. The reaction time is not constant depending on the reaction temperature, reaction amount, reaction pressure and the like, but is usually 1 to 96 hours.
　式（ＸIII）のホウ素化合物は市場で入手できるか又は常法により合成することもできる。例えば、対応するハロゲン、望ましくは臭素誘導体からtert-ブチルリチウムのような塩基の存在下に、ホウ酸トリメチルを作用させることにより合成できる。 The boron compound of formula (XIII) is commercially available or can be synthesized by a conventional method. For example, it can be synthesized from the corresponding halogen, preferably a bromine derivative, by the action of trimethyl borate in the presence of a base such as tert-butyllithium.
　〔４〕－４；本反応工程では、式（I－３）の化合物と求核剤とを反応させることにより式（I―４）の化合物を製造できる。 [4] -4; In this reaction step, the compound of formula (I-4) can be produced by reacting the compound of formula (I-3) with a nucleophile.
　求核剤としては、例えば、一般式ＨＮＲ4 Ｒ5（式中、Ｒ4及びＲ5は前述の通りである）で表されるアミン類；一般式ＨＯＲ2（式中、Ｒ2は前述の通りである）で表されるアルコール類のアルカリ金属塩（金属アルコキシド）；一般式ＨＳＲ3（式中、Ｒ3は前述の通りである）で表されるチオール類のアルカリ金属塩（金属メルカプチド）；シアン化ナトリウム、アジ化ナトリウムなどの各種アルカリ金属塩；モルホリンのような複素環アミン又はそのアルカリ金属塩；メチルマグネシウムブロミド、エチルマグネシウムブロミド、フェニルマグネシウムブロミドのような有機金属試薬；などを挙げることができる。さらに具体的な例としては、メチルアミン、ジメチルアミン、ピペリジン；ナトリウムメトキシド、ナトリウムエトキシド；ナトリウムメルカプタンなどを挙げることができる。 Examples of the nucleophile include amines represented by the general formula HNR 4 R 5 (wherein R 4 and R 5 are as described above); the general formula HOR 2 (wherein R 2 is the same as that described above). Alkali metal salts (metal alkoxides) of alcohols represented by the general formula HSR 3 (wherein R 3 is as defined above), and alkali metal salts (metal mercaptides) of thiols represented by the general formula HSR 3 Various alkali metal salts such as sodium cyanide and sodium azide; heterocyclic amines such as morpholine or alkali metal salts thereof; organometallic reagents such as methylmagnesium bromide, ethylmagnesium bromide and phenylmagnesium bromide; Can do. More specific examples include methylamine, dimethylamine, piperidine; sodium methoxide, sodium ethoxide; sodium mercaptan and the like.
　求核剤は、式（I－３）の化合物1モルに対して１～３０当量の割合で使用できる。 The nucleophile can be used at a ratio of 1 to 30 equivalents per 1 mol of the compound of the formula (I-3).
　本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばメタノール、エタノール、プロパノールのようなアルコール類；ジエチルエーテル、ブチルエチルエーテル、テトラヒドロフラン、ジオキサン、ジメトキシエタンのようなエーテル類；クロロベンゼン、ジクロロベンゼン、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、トリクロロエタン、ジクロロエチレンのようなハロゲン化炭化水素類；ベンゼン、トルエン、キシレンのような芳香族炭化水素類；ペンタン、へキサンのような脂肪族炭化水素類；酢酸メチル、酢酸エチルのようなエステル類；アセトニトリル、プロピオンニトリルのようなニトリル類；Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリジノンのようなアミド類；ジメチルスルホキシドのようなスルホキシド類；及びこれらの混合溶媒などを挙げることができる。反応温度は、－１００℃～反応混合物の還流温度、望ましくは－３０℃～反応混合物の還流温度である。反応時間は、通常１分～９６時間程度である。
　製法〔５〕 This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, alcohols such as methanol, ethanol and propanol; ethers such as diethyl ether, butyl ethyl ether, tetrahydrofuran, dioxane and dimethoxyethane; Halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatics such as pentane and hexane Hydrocarbons; Esters such as methyl acetate and ethyl acetate; Nitriles such as acetonitrile and propiononitrile; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone Amides such as; sulfoxides such as dimethyl sulfoxide; and the like can be mentioned a mixture of these solvents. The reaction temperature is from −100 ° C. to the reflux temperature of the reaction mixture, preferably from −30 ° C. to the reflux temperature of the reaction mixture. The reaction time is usually about 1 minute to 96 hours.
Manufacturing method [5]
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　製法〔５〕中、Ｒ1dはＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲンで置換されてもよいアリール又はアルキルで置換されてもよい複素環基であり；Ｒ1２はアルキルであり；Ｒ1１、Ａ、Ｘ、Ｙ、Ｚ、ｈａｌ、ｍ及びｐは前述の通りである。 In the production process [5], R 1d is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, and halogen substituted. R 12 is alkyl; R 11 , A, X, Y, Z, hal, m and p are as described above.
　製法〔５〕は、上記〔５〕－１、〔５〕－２及び〔５〕－３の反応工程から成り、式（ＸIＶ）の化合物から式（I－５）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。 Production method [5] comprises the reaction steps of [5] -1, [5] -2 and [5] -3 above, and the compound of formula (XIV) is converted to [1,2,4 of formula (I-5). ] A triazolo [1,5-a] pyrimidine derivative can be produced.
　〔５〕－１；本反応工程では、式（ＸIＶ）の化合物と式（Ｖ）の化合物とを縮合させることによって式（ＸＶ）の化合物を製造できる。 [5] -1; In this reaction step, the compound of formula (XV) can be produced by condensing the compound of formula (XIV) with the compound of formula (V).
　式（Ｖ）の化合物は、式（ＸIＶ）の化合物１モルに対して通常０．８～１０当量、望ましくは０．８～３当量の割合で使用することができる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば酢酸、プロピオン酸のようなカルボン酸類、メタノール、エタノール、プロパノール、ブタノールのようなアルコール類；酢酸メチル、酢酸エチルのようなエステル類；アセトニトリル、プロピオニトリルのようなニトリル類；Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリジノンのような酸アミド類；ジメチルスルホキシドのようなスルホキシド類；スルホランのようなスルホン類；ヘキサメチルホスホルアミドのようなリン酸アミド類；及びこれらの混合溶媒などを挙げることができるが、中でもカルボン酸類が望ましい。反応温度は通常５０～１５０℃、望ましくは８０～１２０℃である。反応時間は、通常０．５～１００時間である。 The compound of the formula (V) can be used in a proportion of usually 0.8 to 10 equivalents, desirably 0.8 to 3 equivalents, relative to 1 mol of the compound of the formula (XIV). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, carboxylic acids such as acetic acid and propionic acid, alcohols such as methanol, ethanol, propanol, and butanol; methyl acetate, ethyl acetate and the like. Nitriles such as acetonitrile and propionitrile; acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfolane Examples thereof include sulfones such as: phosphoric acid amides such as hexamethylphosphoramide; and mixed solvents thereof, among which carboxylic acids are preferable. The reaction temperature is usually 50 to 150 ° C., desirably 80 to 120 ° C. The reaction time is usually 0.5 to 100 hours.
　〔５〕－２；本反応工程では、式（ＸＶ）の化合物をハロゲン化することにより式（XVI）の化合物を製造できる。本反応工程は、前記製法〔４〕の反応工程〔４〕－２に準じて実施することができる。 [5] -2: In this reaction step, the compound of formula (XVI) can be produced by halogenating the compound of formula (XV). This reaction step can be carried out according to the reaction step [4] -2 of the production method [4].
　〔５〕－３；本反応工程では、式（XVI）の化合物と式（XIII）のホウ素化合物とを遷移金属触媒の存在下で鈴木カップリングさせることによって式（I－５）の化合物を製造できる。本反応工程は、前記製法〔４〕の反応工程〔４〕－３に準じて実施することができる。 [5] -3; In this reaction step, a compound of formula (I-5) is produced by Suzuki coupling of a compound of formula (XVI) and a boron compound of formula (XIII) in the presence of a transition metal catalyst. it can. This reaction step can be carried out according to the reaction step [4] -3 of the above production method [4].
　製法〔６〕 Manufacturing method [6]
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　製法〔６〕中、Ｒ3、Ｘ、Ｚ、ｈａｌ及びｍは前述の通りである。 In the production method [6], R 3 , X, Z, hal and m are as described above.
　製法〔６〕は、上記〔６〕－１及び〔６〕－２の反応工程から成り、式（II）の化合物から式（I－６）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造することができる。各反応工程については、以下に詳述する。 The production method [6] comprises the reaction steps of the above [6] -1 and [6] -2. From the compound of formula (II), [1,2,4] triazolo [1,5 of formula (I-6) -A] Pyrimidine derivatives can be produced. Each reaction step will be described in detail below.
　〔６〕－１；本反応工程では、式（II）の化合物と二硫化炭素及び式（ＸＶII）の化合物とを反応させて式（ＸＶIII）のα、β－不飽和ケトン誘導体を製造できる。 [6] -1; In this reaction step, an α, β-unsaturated ketone derivative of formula (XVIII) can be produced by reacting a compound of formula (II) with carbon disulfide and a compound of formula (XVII).
　二硫化炭素及び式（ＸＶII）の化合物は、各々式（II）の化合物１モルに対して１～５当量、望ましくは１～３当量の割合で使用できる。本反応は、通常、塩基及び溶媒の存在下で行うことができる。塩基としては、例えば水素化ナトリウム、水素化カリウムのような金属水素化物；水酸化ナトリウム、水酸化カリウムのような金属水酸化物；ナトリウム、カリウムのようなアルカリ金属；ナトリウムメトキシド、ナトリウムエトキシド、カリウム第３級ブトキシドのようなアルカリ金属アルコキシド；などを挙げることができる。塩基は、式（II）の化合物１モルに対して１～１０当量、望ましくは１～３当量の割合で使用できる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば前記製法〔１〕の反応工程〔１〕－１と同様のものを挙げることができるが、中でもエーテル類が望ましい。反応温度は通常０～１００℃、望ましくは１０～５０℃である。反応時間は通常６～４８時間である。 Carbon disulfide and the compound of formula (XVII) can be used in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents, per 1 mol of the compound of formula (II). This reaction can usually be performed in the presence of a base and a solvent. Examples of the base include metal hydrides such as sodium hydride and potassium hydride; metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as sodium and potassium; sodium methoxide and sodium ethoxide. And alkali metal alkoxides such as potassium tertiary butoxide; and the like. The base can be used in an amount of 1 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of formula (II). The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, the same solvents as those in the reaction step [1] -1 of the above production method [1] can be exemplified, and among these, ethers are desirable. The reaction temperature is usually 0 to 100 ° C., preferably 10 to 50 ° C. The reaction time is usually 6 to 48 hours.
　〔６〕－２；本反応工程では、式（ＸＶIII）の化合物と式（Ｖ）の化合物を縮合させて式（I－６）の化合物を製造できる。 [6] -2: In this reaction step, the compound of the formula (I-6) can be produced by condensing the compound of the formula (XVIII) and the compound of the formula (V).
　式（Ｖ）の化合物は、式（ＸＶIII）の化合物１モルに対して１～５当量、望ましくは１～３当量の割合で使用できる。本反応は、通常、塩基及び溶媒の存在下で行うことができる。塩基としては、例えば水素化ナトリウム、水素化カリウムのような金属水素化物；水酸化ナトリウム、水酸化カリウムのような金属水酸化物；ナトリウム、カリウムのようなアルカリ金属；ナトリウムメトキシド、ナトリウムエトキシド、カリウム第３級ブトキシドのようなアルカリ金属アルコキシド；炭酸ナトリウム、炭酸カリウムのような炭酸塩；重炭酸ナトリウム、重炭酸カリウムのような重炭酸塩；トリエチルアミン、ピリジンなどの有機塩基；などを挙げることができる。塩基は、式（Ｖ）の化合物１モルに対して１～５当量、望ましくは１～３当量の割合で使用できる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば、前記製法〔１〕の反応工程〔１〕－１と同様のものを挙げることができるが、中でも酸アミド類が望ましい。反応温度は通常１００～２００℃である。反応時間は通常０．１～１０時間である。
　製法〔７〕 The compound of the formula (V) can be used in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of the formula (XVIII). This reaction can usually be performed in the presence of a base and a solvent. Examples of the base include metal hydrides such as sodium hydride and potassium hydride; metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as sodium and potassium; sodium methoxide and sodium ethoxide Alkali metal alkoxides such as potassium tertiary butoxide; carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate; organic bases such as triethylamine and pyridine; Can do. The base can be used in a proportion of 1 to 5 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of formula (V). The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include the same as those in the reaction step [1] -1 of the above production method [1]. desirable. The reaction temperature is usually 100 to 200 ° C. The reaction time is usually 0.1 to 10 hours.
Manufacturing method [7]
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　製法〔７〕中、Ｒ3、Ｘ、Ｚ、ｍ及びｎは前述の通りである。 In the production method [7], R 3 , X, Z, m and n are as described above.
　製法〔７〕では、式（I－６）の化合物と酸化剤とを反応させることにより、式（I－７）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。 In the production method [7], a [1,2,4] triazolo [1,5-a] pyrimidine derivative of the formula (I-7) is produced by reacting the compound of the formula (I-6) with an oxidizing agent. it can.
　本反応で使用する酸化剤としては、例えば、過酸化水素、過酢酸、ｍ－クロロ過安息香酸などを挙げることができる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばクロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンのようなハロゲン化炭化水素類、アセトン、メチルエチルケトンのようなケトン類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサンのようなエーテル類；酢酸、プロピオン酸のようなカルボン酸類；及びこれらの混合溶媒などを挙げることができる。反応温度は通常１５℃～還流温度である。反応時間は通常１～２４時間である。
　製法〔８〕 Examples of the oxidizing agent used in this reaction include hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid, and the like. This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction. For example, halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and 1,2-dichloroethane, and ketones such as acetone and methyl ethyl ketone. And ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and dioxane; carboxylic acids such as acetic acid and propionic acid; and mixed solvents thereof. The reaction temperature is usually 15 ° C. to reflux temperature. The reaction time is usually 1 to 24 hours.
Manufacturing method [8]
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　製法〔８〕中、Ｒ1eはＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、ＯＲ2、ＮＲ4Ｒ5又はＮ３であり；Ｒ2、Ｒ4、Ｒ5、Ａ、Ｘ、Ｚ及びｍは前述の通りである。 In production method [8], R 1e is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano, Aryl optionally substituted with halogen, heterocyclic group optionally substituted with alkyl, OR 2 , NR 4 R 5 or N 3 ; R 2 , R 4 , R 5 , A, X, Z and m are As described above.
　製法〔８〕では、式（I－７）の化合物と求核剤とを反応させることにより、式（I－８）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造することができる。求核剤としては、例えば、一般式ＨＮＲ4 Ｒ5（式中、Ｒ4及びＲ5は前述の通りである）で表されるアミン類；一般式ＨＯＲ2（式中、Ｒ2は前述の通りである）で表されるアルコール類のアルカリ金属塩（金属アルコキシド）；シアン化ナトリウム、アジ化ナトリウムなどの各種アルカリ金属塩；モルホリンのような複素環アミン又はそのアルカリ金属塩；メチルマグネシウムブロミド、エチルマグネシウムブロミド、フェニルマグネシウムブロミドのような有機金属試薬；フッ化カリウム、フッ化セシウム、テトラアンモニウムフルオリドのようなフッ素化剤；などを挙げることができる。さらに具体的な例としては、メチルアミン、ジメチルアミン、ピペリジン；ナトリウムメトキシド、ナトリウムエトキシド；などを挙げることができる。求核剤は、式（I－７）の化合物1モルに対して１～１０当量、望ましくは１．５～３当量の割合で使用できる。 In the production method [8], a [1,2,4] triazolo [1,5-a] pyrimidine derivative of the formula (I-8) is reacted by reacting a compound of the formula (I-7) with a nucleophile. Can be manufactured. Examples of the nucleophile include amines represented by the general formula HNR 4 R 5 (wherein R 4 and R 5 are as described above); the general formula HOR 2 (wherein R 2 is the same as that described above). Alkali metal salts (metal alkoxides) of alcohols represented by the following formulas; various alkali metal salts such as sodium cyanide and sodium azide; heterocyclic amines such as morpholine or alkali metal salts thereof; And organic metal reagents such as ethylmagnesium bromide and phenylmagnesium bromide; fluorinating agents such as potassium fluoride, cesium fluoride and tetraammonium fluoride; More specific examples include methylamine, dimethylamine, piperidine; sodium methoxide, sodium ethoxide; and the like. The nucleophilic agent can be used in an amount of 1 to 10 equivalents, preferably 1.5 to 3 equivalents, relative to 1 mol of the compound of formula (I-7).
　本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばメタノール、エタノール、プロパノール、ブタノールのようなアルコール類；ベンゼン、トルエン、キシレンのような芳香族炭化水素類；ペンタン、ヘキサン、ヘプタン、石油エーテル、リグロイン、石油ベンジンのような脂肪族炭化水素類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサンのようなエーテル類；クロロベンゼン、ジクロロベンゼン、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、トリクロロエタン、ジクロロエチレンのようなハロゲン化炭化水素類；酢酸メチル、酢酸エチルのようなエステル類；アセトニトリル、プロピオニトリルのようなニトリル類；Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリジノンのような酸アミド類；ジメチルスルホキシドのようなスルホキシド類；及びこれらの混合溶媒などを挙げることができる。反応温度は通常－１００～５０℃、望ましくは－７０～２０℃である。反応時間は通常１分～４８時間である。
　製法〔９〕 This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, alcohols such as methanol, ethanol, propanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; pentane and hexane Aliphatic hydrocarbons such as benzene, heptane, petroleum ether, ligroin, petroleum benzine; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride Halogenated hydrocarbons such as chloroethane, dichloroethane, trichloroethane, dichloroethylene; esters such as methyl acetate and ethyl acetate; nitriles such as acetonitrile and propionitrile; N, N-dimethylformua And amides, acid amides such as N, N-dimethylacetamide and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; and mixed solvents thereof. The reaction temperature is usually −100 to 50 ° C., desirably −70 to 20 ° C. The reaction time is usually 1 minute to 48 hours.
Manufacturing method [9]
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　製法〔９〕中、Ｒ13はアルキルであり；Ｒ９、Ｘ、Ｚ、ｈａｌ及びｍは前述の通りである。 In the production process [9], R 13 is alkyl; R 9 , X, Z, hal and m are as described above.
　製法〔９〕は、上記〔９〕-１～〔９〕-５の反応工程から成り、式（ＶIII）の化合物から式（Ｉ－９）又は式（Ｉ－３）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。各反応工程については、以下に詳述する。 The production method [9] comprises the reaction steps of the above [9] -1 to [9] -5, and from the compound of the formula (VIII), the compound of the formula (I-9) or the formula (I-3) [1, 2, 4] A triazolo [1,5-a] pyrimidine derivative can be produced. Each reaction step will be described in detail below.
　〔９〕-１；本反応工程では、式（ＶIII）の化合物と式（ＸIＸ）の化合物とを塩基の存在下で反応させることにより式（ＸＸ）の化合物を製造できる。式（ＸIＸ）の化合物は、式（ＶIII）の化合物１モルに対して０．８当量～大過剰量、望ましくは１～３０当量の割合で使用できる。塩基としては、例えば前記製法〔６〕の反応工程〔６〕－１の反応と同様のものなどを挙げることができる。塩基は、式（ＶIII）の化合物１モルに対して１～５当量、望ましくは１～２当量の割合で使用できる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば前記製法〔２〕の反応工程〔２〕－１の反応と同様のものを挙げることができるが、中でもエーテル類が望ましい。反応温度は通常０～７０℃、望ましくは１０～５０℃である。反応時間は通常０．１～２４時間である。 [9] -1; In this reaction step, the compound of formula (XX) can be produced by reacting the compound of formula (VIII) with the compound of formula (XIX) in the presence of a base. The compound of the formula (XIX) can be used in a proportion of 0.8 equivalent to large excess, desirably 1 to 30 equivalents, relative to 1 mol of the compound of the formula (VIII). Examples of the base include those similar to the reaction in the reaction step [6] -1 of the production method [6]. The base can be used at a ratio of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of the formula (VIII). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include the same reaction as in the reaction step [2] -1 in the above production method [2]. desirable. The reaction temperature is usually 0 to 70 ° C., preferably 10 to 50 ° C. The reaction time is usually 0.1 to 24 hours.
　〔９〕-２；本反応工程では、式（ＸＸ）の化合物を塩基及び水の存在下で加水分解させることにより式（ＸＸI）の化合物を製造できる。塩基としては、例えば水酸化ナトリウム、水酸化カリウムのようなアルカリ金属水酸化物を挙げることができる。塩基は、式（ＸＸ）の化合物１モルに対して１当量～大過剰量、望ましくは２～１０当量の割合で使用できる。反応温度は通常０～７０℃、望ましくは１０～５０℃である。反応時間は通常０．１～２４時間である。 [9] -2; In this reaction step, the compound of the formula (XXI) can be produced by hydrolyzing the compound of the formula (XX) in the presence of a base and water. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The base can be used in an amount of 1 equivalent to large excess, desirably 2 to 10 equivalents, relative to 1 mol of the compound of formula (XX). The reaction temperature is usually 0 to 70 ° C., preferably 10 to 50 ° C. The reaction time is usually 0.1 to 24 hours.
　〔９〕-３；本反応工程では、式（ＸＸI）の化合物とハロゲン化剤とを反応させることにより式（ＸＸII）の化合物を製造できる。ハロゲン化剤としては、塩化チオニル、二塩化オキサリルなどを挙げることができる。ハロゲン化剤は、式（ＸＸI）の化合物１モルに対して１～５当量、望ましくは１～２当量の割合で使用できる。本反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばクロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンのようなハロゲン化炭化水素類を挙げることができる。反応温度は通常０～１００℃、望ましくは１０～５０℃である。反応時間は通常０．１～２４時間である。 [9] -3; In this reaction step, the compound of the formula (XXII) can be produced by reacting the compound of the formula (XXI) with a halogenating agent. Examples of the halogenating agent include thionyl chloride and oxalyl dichloride. The halogenating agent can be used in a proportion of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of formula (XXI). This reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane. The reaction temperature is usually 0 to 100 ° C., preferably 10 to 50 ° C. The reaction time is usually 0.1 to 24 hours.
　〔９〕-４；本反応工程では、式（ＸＸII）の化合物と式（Ｖ）の化合物とを縮合させることにより式（I－９）の４，５－ジヒドロ－５－オキソ［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。式（Ｖ）の化合物は、式（ＸＸII）の化合物１モルに対して０．８～１０当量、望ましくは１～２．５当量の割合で使用できる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては反応に悪影響を与えないものであれば特に限定はなく、例えば前記製法〔２〕の反応工程〔２〕－１と同様のものを挙げることができるが、中でも酸アミド類が望ましい。反応温度は通常０～１５０℃、望ましくは２０～１００℃である。反応時間は通常０．５～１００時間である。 [9] -4; In this reaction step, the compound of formula (XXII) and the compound of formula (V) are condensed to give 4,5-dihydro-5-oxo [1,2 of formula (I-9) , 4] triazolo [1,5-a] pyrimidine derivatives. The compound of the formula (V) can be used in a proportion of 0.8 to 10 equivalents, preferably 1 to 2.5 equivalents, relative to 1 mol of the compound of the formula (XXII). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, the same solvent as in the reaction step [2] -1 in the above production method [2] can be mentioned, and among them, acid amides are preferable. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 100 ° C. The reaction time is usually 0.5 to 100 hours.
　〔９〕-５；本反応工程では、化合物（I－９）の化合物とハロゲン化剤とを反応させることにより式（I－３）の５－ハロ［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。ハロゲン化剤としては、塩化チオニル、オキシ塩化リン、オキシ臭化リンなどを挙げることができる。ハロゲン化剤は、式（I－９）の化合物１モルに対して１～２０当量、望ましくは１～８当量の割合で使用できる。本反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばクロロホルム、ジクロロメタン、四塩化炭素、１，２－ジクロロエタンなどのハロゲン化炭化水素類を挙げることができる。反応温度は通常０～１５０℃、望ましくは２０～１００℃である。反応時間は通常０．１～２４時間である。
　製法〔１０〕 [9] -5; In this reaction step, the compound of compound (I-9) is reacted with a halogenating agent to react with 5-halo [1,2,4] triazolo [1, 5-a] pyrimidine derivatives can be produced. Examples of the halogenating agent include thionyl chloride, phosphorus oxychloride, phosphorus oxybromide and the like. The halogenating agent can be used in a proportion of 1 to 20 equivalents, preferably 1 to 8 equivalents, relative to 1 mol of the compound of formula (I-9). This reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 100 ° C. The reaction time is usually 0.1 to 24 hours.
Manufacturing method [10]
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　製法〔１０〕中、Ｘ、Ｚ、ｈａｌ及びｍは前述の通りである。 In the production method [10], X, Z, hal and m are as described above.
　製法〔１０〕は、式（I－１２）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体の製法例であり、例えば上記〔１０〕－１～〔１０〕－３の何れかの反応よって式（I－１２）の化合物を製造できる。個々の反応については、以下に詳述する。 Production method [10] is a production example of a [1,2,4] triazolo [1,5-a] pyrimidine derivative of the formula (I-12), for example, the above [10] -1 to [10] -3 The compound of the formula (I-12) can be produced by any reaction. Each reaction is described in detail below.
　〔１０〕－１；式（I－１２）の化合物は、式（I－１０）の化合物と酸化剤とを反応させることにより製造できる。酸化剤としては、例えば過ヨウ素酸ナトリウム、二酸化セレン、過マンガン酸カリウムなどを挙げることができる。酸化剤は、式（I－１０）の化合物１モルに対して０．８当量～大過剰量、望ましくは１～３０当量の割合で使用できる。本反応は、通常、溶媒存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば水；Ｎ、Ｎ－ジメチルホルムアミドのようなアミド類；などを挙げることができる。反応温度は、０～２００℃、望ましくは０～１５０℃である。反応時間は１～３０時間である。 [10] -1; The compound of the formula (I-12) can be produced by reacting the compound of the formula (I-10) with an oxidizing agent. Examples of the oxidizing agent include sodium periodate, selenium dioxide, potassium permanganate and the like. The oxidizing agent can be used in a proportion of 0.8 equivalent to large excess, preferably 1 to 30 equivalents, relative to 1 mol of the compound of formula (I-10). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. Examples thereof include water; amides such as N, N-dimethylformamide; and the like. The reaction temperature is 0 to 200 ° C., desirably 0 to 150 ° C. The reaction time is 1 to 30 hours.
　〔１０〕－２；本反応は、上記（１）のメタル化及び（２）のホルミル化の二つの反応を含む。即ち、式（I－１２）の化合物は、式（I－３）の化合物をメタル化し、ホルミル化剤と反応させた後加水分解することにより製造できる。（１）及び（２）の反応は、通常、連続して行うことができる。
　（１）でのメタル化とは、ｎ－ブチルリチウム又はtert-ブチルリチウムなどのリチウム試薬とのハロゲン-リチウム交換反応によるリチウム試薬の調製又はグリニャール試薬とのハロゲン-マグネシウム交換反応によるグリニャール試薬の調製若しくは金属マグネシウムとの反応よるグリニャール試薬の調製を意味しており、その際に用いるリチウム試薬、グリニャール試薬及びマグネシウムがメタル化剤である。メタル化剤は、式（I－３）の化合物に対して１当量～１．５当量の割合で使用できる。反応温度は通常－１００～７０℃、望ましくは－３０～５０℃である。反応時間は通常０．１～２４時間である。 [10] -2: This reaction includes the above two reactions of (1) metalation and (2) formylation. That is, the compound of the formula (I-12) can be produced by metallizing the compound of the formula (I-3), reacting it with a formylating agent and then hydrolyzing it. The reactions (1) and (2) can usually be carried out continuously.
The metalation in (1) means preparation of a lithium reagent by a halogen-lithium exchange reaction with a lithium reagent such as n-butyllithium or tert-butyllithium, or a Grignard reagent by a halogen-magnesium exchange reaction with a Grignard reagent. Alternatively, it means the preparation of a Grignard reagent by reaction with metallic magnesium, and the lithium reagent, Grignard reagent and magnesium used in this case are metallizing agents. The metallizing agent can be used in a proportion of 1 equivalent to 1.5 equivalents relative to the compound of formula (I-3). The reaction temperature is usually −100 to 70 ° C., desirably −30 to 50 ° C. The reaction time is usually 0.1 to 24 hours.
　（２）でのホルミル化剤としては、例えばギ酸メチル、Ｎ、Ｎ－ジメチルホルムアミド、４－ホルミルモルホリンなどを挙げることができる。ホルミル化剤は、式（I－３）の化合物１モルに対して１～５当量、望ましくは１～２当量の割合で使用できる。反応温度は通常－２０～５０℃、望ましくは－１０～３０℃である。反応時間は通常０．１～２４時間である。ホルミル化剤との反応終了後、反応物を酸及び水の存在下で加水分解させることにより式（I－１２）の化合物を製造できる。酸としては、例えば塩酸、硫酸のような無機酸を挙げることができる。酸は、メタル化剤に対して１当量～大過剰量、望ましくは２～１０当量の割合で使用できる。反応温度は通常－１０～３０℃、望ましくは０～２０℃である。反応時間は通常０．１～２４時間である。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば前記製法〔２〕の反応工程〔２〕－１と同様のものを挙げることができるが、中でもエーテル類が望ましい。 Examples of the formylating agent in (2) include methyl formate, N, N-dimethylformamide, 4-formylmorpholine and the like. The formylating agent can be used at a ratio of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of formula (I-3). The reaction temperature is usually −20 to 50 ° C., desirably −10 to 30 ° C. The reaction time is usually 0.1 to 24 hours. After completion of the reaction with the formylating agent, the compound of formula (I-12) can be produced by hydrolyzing the reaction product in the presence of an acid and water. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid. The acid can be used in an amount of 1 equivalent to a large excess, desirably 2 to 10 equivalents, relative to the metallizing agent. The reaction temperature is usually −10 to 30 ° C., preferably 0 to 20 ° C. The reaction time is usually 0.1 to 24 hours. This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction. For example, the same solvent as in reaction step [2] -1 of the above production method [2] can be mentioned, and among these, ethers are desirable.
　〔１０〕－３；式（I－１２）の化合物は、式（I－１１）の化合物と還元剤とを反応させることにより製造できる。還元剤としては、水素化ジイソブチルアルミニウム（ＤＩＢＡＬ）、水素化ビス(２－メトキシエトキシ)アルミニウムナトリウム（ＳＢＭＥＡ）などを挙げることができる。還元剤は、式（I－１１）の化合物１モルに対して１～２当量、望ましくは１～１．５当量の割合で使用できる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばテトラヒドロフランのようなエーテル類、ベンゼン、トルエンのような芳香族炭化水素類；などを挙げることができる。反応温度は通常－８０℃～１００℃、望ましくは－３０～５０℃である。反応時間は通常０．１～２４時間である。
　製法〔１１〕 [10] -3; The compound of the formula (I-12) can be produced by reacting the compound of the formula (I-11) with a reducing agent. Examples of the reducing agent include diisobutylaluminum hydride (DIBAL), sodium bis (2-methoxyethoxy) aluminum hydride (SBMEA), and the like. The reducing agent can be used in a proportion of 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to 1 mol of the compound of formula (I-11). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene. The reaction temperature is usually −80 ° C. to 100 ° C., desirably −30 to 50 ° C. The reaction time is usually 0.1 to 24 hours.
Manufacturing method [11]
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　製法〔１１〕中、Ｒ14はアルキル、シクロアルキルを表し、Ｘ、Ｚ及びｍは前述の通りである。 In the production process [11], R 14 represents alkyl or cycloalkyl, and X, Z and m are as described above.
　製法〔１１〕では、式（I－１１）の化合物と求核剤とを反応させた後、加水分解することにより式（I－１３）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。求核剤としては、例えばメチルマグネシウムブロミド、シクロプロピルマグネシウムクロリドなどのグリニャール試薬などを挙げることができる。求核剤は、式（I－１１）の化合物１モルに対して１～２当量、望ましくは１～１．３当量の割合で使用できる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばテトラヒドロフランのようなエーテル類；ペンタンへキサンのような脂肪族炭化水素類；などを挙げることができる。反応温度は通常－８０℃～１００℃、望ましくは－３０～５０℃である。反応時間は通常０．１～２４時間である。求核付加反応終了後、反応物を酸及び水の存在下で加水分解させることにより式（I－１３）の化合物を得ることができる。酸としては、例えば塩酸、硫酸のような無機酸を挙げることができる。酸は、求核剤に対して１当量～大過剰量、望ましくは２～１０当量の割合で使用できる。反応温度は通常－２０～３０℃、望ましくは０～２０℃である。反応時間は通常０．１～２４時間である。
　製法〔１２〕 In the production method [11], the compound of the formula (I-11) is reacted with a nucleophile and then hydrolyzed to thereby react the [1,2,4] triazolo [1,5- (5) of the formula (I-13). a] Pyrimidine derivatives can be produced. Examples of the nucleophilic agent include Grignard reagents such as methylmagnesium bromide and cyclopropylmagnesium chloride. The nucleophilic agent can be used in an amount of 1 to 2 equivalents, preferably 1 to 1.3 equivalents, relative to 1 mol of the compound of the formula (I-11). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include ethers such as tetrahydrofuran; aliphatic hydrocarbons such as pentane hexane; and the like. The reaction temperature is usually −80 ° C. to 100 ° C., desirably −30 to 50 ° C. The reaction time is usually 0.1 to 24 hours. After completion of the nucleophilic addition reaction, the compound of formula (I-13) can be obtained by hydrolyzing the reaction product in the presence of an acid and water. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid. The acid can be used in an amount of 1 equivalent to a large excess relative to the nucleophile, preferably 2 to 10 equivalents. The reaction temperature is usually −20 to 30 ° C., preferably 0 to 20 ° C. The reaction time is usually 0.1 to 24 hours.
Manufacturing method [12]
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　製法〔１２〕中、Ｒ1fはＡで置換されてもよいアルキル又はアルキルで置換されてもよい複素環基であり；Ｒ14、Ｘ、Ｚ及びｍは前述の通りである。Ｒ1fとしては、例えばジメトキシメチル、ジエトキシメチル、１、３－ジオキソラン－２－イルなどを挙げることができる。 In the production method [12], R 1f is an alkyl which may be substituted with A or a heterocyclic group which may be substituted with alkyl; R 14 , X, Z and m are as described above. Examples of R 1f include dimethoxymethyl, diethoxymethyl, 1,3-dioxolan-2-yl and the like.
　製法〔１２〕では、式（I－１２）又は式（I－１３）の化合物とアルコールとを反応させることにより式（I－１４）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。 In the production method [12], a compound of formula (I-12) or formula (I-13) is reacted with an alcohol to react [1,2,4] triazolo [1,5-a of formula (I-14). Pyrimidine derivatives can be produced.
　アルコールとしては、例えば、メタノール、エタノール、エチレングリコールなどを挙げることができる。アルコールは、式（I－１２）又は式（I－１３）の化合物１モルに対して１当量～大過剰量の割合で使用できる。本反応は、必要に応じ酸触媒の存在で行うことができる。酸触媒としては、濃塩酸、濃硫酸などの無機酸；酢酸、ｐ－トルエンスルホン酸などの有機酸等を挙げることができる。酸触媒は、式（I－１２）又は式（I－１３）の化合物１モルに対して０．００１～０．３当量、望ましくは０．０１～０．２当量の割合で使用できる。本反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばベンゼン、トルエンのような芳香族炭化水素類などを挙げることができる。反応温度は通常０℃～２００℃、望ましくは１０～１００℃である。反応時間は通常０．１～２４時間である。
　製法〔１３〕 Examples of the alcohol include methanol, ethanol, and ethylene glycol. The alcohol can be used in a proportion of 1 equivalent to a large excess with respect to 1 mol of the compound of the formula (I-12) or the formula (I-13). This reaction can be performed in the presence of an acid catalyst, if necessary. Examples of the acid catalyst include inorganic acids such as concentrated hydrochloric acid and concentrated sulfuric acid; organic acids such as acetic acid and p-toluenesulfonic acid. The acid catalyst can be used in a proportion of 0.001 to 0.3 equivalent, desirably 0.01 to 0.2 equivalent, relative to 1 mol of the compound of formula (I-12) or formula (I-13). This reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include aromatic hydrocarbons such as benzene and toluene. The reaction temperature is usually 0 ° C. to 200 ° C., preferably 10 to 100 ° C. The reaction time is usually 0.1 to 24 hours.
Manufacturing method [13]
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　製法〔１３〕中、Ｘ、Ｚ、ｈａｌ及びｍは前述の通りである。 In the production method [13], X, Z, hal and m are as described above.
　製法〔１３〕は、式（I－１５）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体の製法例であり、例えば上記〔１３〕－１～〔１３〕－３の何れかの反応よって式（I－１５）の化合物を製造できる。個々の反応については、以下に詳述する。 Production method [13] is an example of production of a [1,2,4] triazolo [1,5-a] pyrimidine derivative of formula (I-15). For example, the production methods [13] -1 to [13] -3 The compound of the formula (I-15) can be produced by any reaction. Each reaction is described in detail below.
　〔１３〕-１；本反応は、（１）のメタル化及び（２）のカルボキシル化の２つの反応を含む。（２）のカルボキシル化では、反応終了後に加水分解を行う。即ち、〔１３〕－１では、式（I－３）の化合物をメタル化し、二酸化炭素と反応後加水分解することによって式（I－１５）の化合物を製造できる。（１）と（２）の反応は、通常、連続的に行う。
　（１）のメタル化は、前記製法〔１０〕の反応工程〔１０〕－２の方法に準じて行うことができる。
　（２）の反応は（１）の反応系に、過剰の二酸化炭素を導入して行う。二酸化炭素との反応後に行う加水分解は、前記製法〔１０〕の反応工程〔１０〕－２の方法に準じて行うことができる。 [13] -1; This reaction includes two reactions of (1) metalation and (2) carboxylation. In the carboxylation (2), hydrolysis is performed after the reaction is completed. That is, in [13] -1, the compound of formula (I-15) can be produced by metallation of the compound of formula (I-3), reaction with carbon dioxide and hydrolysis. The reactions (1) and (2) are usually performed continuously.
The metallization of (1) can be performed according to the method of the reaction step [10] -2 of the above production method [10].
The reaction (2) is carried out by introducing excess carbon dioxide into the reaction system (1). The hydrolysis performed after the reaction with carbon dioxide can be performed according to the method of the reaction step [10] -2 of the production method [10].
　〔１３〕－２；本反応では、式（I－１１）の化合物を加水分解することにより式（I-１５）の化合物を製造できる。本反応は常法に準じて実施できる。例えばOrg.Synth.、III、557（1955）に記載された方法に準じて実施できる。加水分解の種類としては、酸加水分解、アルカリ加水分解、及び酸化的加水分解のいづれの方法であってもよい。 [13] -2: In this reaction, the compound of formula (I-15) can be produced by hydrolyzing the compound of formula (I-11). This reaction can be carried out according to a conventional method. For example, it can be carried out according to the method described in Org. Synth., III, 557 (1955). As a kind of hydrolysis, any of acid hydrolysis, alkali hydrolysis, and oxidative hydrolysis may be used.
　〔１３〕－３；本反応では、式（I－１２）の化合物を酸化剤で酸化することにより式（I－１５）の化合物を製造できる。酸化剤としては、例えば二酸化マンガン、過マンガン酸カリウム、過ヨウ素酸ナトリウム、ジョーンズ試薬、ニクロム酸ピリジウムなどを挙げることができる。酸化剤は、式（I－１２）の化合物１モルに対して、１～３当量、望ましくは１～２当量使用することができる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば水、アセトン、アセトニトリル、メタノールなどを挙げることができる。反応温度は通常０～５０℃である。反応時間は通常０～２４時間である。
　製法〔１４〕 [13] -3: In this reaction, the compound of formula (I-15) can be produced by oxidizing the compound of formula (I-12) with an oxidizing agent. Examples of the oxidizing agent include manganese dioxide, potassium permanganate, sodium periodate, Jones reagent, pyridium dichromate, and the like. The oxidizing agent can be used in an amount of 1 to 3 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the compound of the formula (I-12). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include water, acetone, acetonitrile, methanol and the like. The reaction temperature is usually 0 to 50 ° C. The reaction time is usually 0 to 24 hours.
Manufacturing method [14]
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　製法〔１４〕中、Ｒ15はＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、ＯＲ2、ＳＲ3、ＮＲ4Ｒ5又はＮ３であり；Ｒ２、Ｒ3、Ｒ４、Ｒ５、Ａ、Ｘ、Ｚ、ｈａｌ及びｍは前述の通りである。 In the production method [14], R 15 is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, cyano or halogen. Aryl which may be substituted, heterocyclic group which may be substituted with alkyl, OR 2 , SR 3 , NR 4 R 5 or N 3 ; R 2 , R 3 , R 4 , R 5 , A, X, Z, hal and m are as described above.
　製法〔１４〕は、上記〔１４〕－１及び〔１４〕－２の反応工程から成り、式（I－１５）の化合物から式（I－１７）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造することができる。各反応工程については、以下に詳述する。 The production method [14] comprises the reaction steps of the above [14] -1 and [14] -2. From the compound of the formula (I-15), the [1,2,4] triazolo [1] of the formula (I-17) , 5-a] pyrimidine derivatives can be prepared. Each reaction step will be described in detail below.
　〔１４〕－１；本反応工程では、式（I－１５）とハロゲン化剤とを反応させることにより式（I－１６）の化合物を製造できる。ハロゲン化剤としては、例えば塩化チオニル、塩化オキサリルなどを挙げることができる。ハロゲン化剤は、式（I－１５）の化合物１モルに対して、通常１当量～大過剰量、望ましくは１～５当量の割合で使用できる。本反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては反応に悪影響を与えないものであれば特に限定はなく、例えば前記製法〔９〕の反応工程〔９〕－３と同様のものを挙げることができる。反応温度は通常０～１００℃、望ましくは０～５０℃である。反応時間は通常１～２４時間である。
　〔１４〕－２；本反応工程では、式（I－１６）の化合物と求核剤とを反応させることにより、式（I－１７）の化合物を製造できる。本反応は前記製法〔４〕の反応工程〔４〕－４に準じて実施することができる。
　製法〔１５〕 [14] -1; In this reaction step, the compound of the formula (I-16) can be produced by reacting the formula (I-15) with a halogenating agent. Examples of the halogenating agent include thionyl chloride and oxalyl chloride. The halogenating agent can be used in an amount of usually 1 equivalent to a large excess, desirably 1 to 5 equivalents, relative to 1 mol of the compound of the formula (I-15). This reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, the same solvent as in reaction step [9] -3 of the above production method [9] can be mentioned. The reaction temperature is usually 0 to 100 ° C., preferably 0 to 50 ° C. The reaction time is usually 1 to 24 hours.
[14] -2; In this reaction step, the compound of formula (I-17) can be produced by reacting the compound of formula (I-16) with a nucleophile. This reaction can be carried out according to the reaction step [4] -4 in the above production method [4].
Manufacturing method [15]
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　製法〔１５〕中、Ｘ、Ｚ及びｍは前述の通りである。 In the production method [15], X, Z and m are as described above.
　製法〔１５〕は、式（Ｉ－１９）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体の製法例であり、例えば上記〔１５〕－１又は〔１５〕－２の何れかの方法によって、式（Ｉ－１９）の化合物を製造できる。個々の反応については、以下に詳述する。 Production method [15] is a production example of a [1,2,4] triazolo [1,5-a] pyrimidine derivative of formula (I-19), for example, in the above [15] -1 or [15] -2 The compound of formula (I-19) can be produced by any method. Each reaction is described in detail below.
　〔１５〕－１；本反応では、式（I－１５）の化合物の転位反応によって式（I－１９）の化合物を製造できる。例えば、式（I－１５）の化合物とジフェニルリン酸アジドとをtert－ブタノールとトルエンとの混合溶液中トリエチルアミンの存在下で加熱還流して反応させてtert－ブチルカーバメート誘導体を得た後、該カーバメート誘導体とトリフルオロ酢酸と加熱することによって、式（I－１９）の化合物を製造することができる。 [15] -1; In this reaction, the compound of formula (I-19) can be produced by the rearrangement reaction of the compound of formula (I-15). For example, the compound of formula (I-15) and diphenyl phosphate azide are reacted by heating under reflux in the presence of triethylamine in a mixed solution of tert-butanol and toluene to obtain a tert-butyl carbamate derivative. The compound of formula (I-19) can be produced by heating with a carbamate derivative and trifluoroacetic acid.
　本製法として使用できる転位反応には、公知の方法が多数あり、例えば、クルチウス転位、シュミット転位、ロッセン転位、ホフマン転位などの方法を利用することができる。例えば、Quan Zhangらの J. Org. Chem., 65, 7977（2000）に記載されている方法に準じて実施することができる。 There are many known rearrangement reactions that can be used in the present production method, and for example, methods such as Curtius rearrangement, Schmidt rearrangement, Rossen rearrangement, and Hoffmann rearrangement can be used. For example, it can be carried out according to the method described in Quan Zhang et al. J. Org. Chem., 65, 7977 (2000).
　〔１５〕－２；本反応では、式（I－１８）の化合物と還元剤とを反応させることにより式（I－１９）の化合物を製造できる。還元剤としては、例えば水素化ホウ素ナトリウムなどを挙げることができる。還元剤は、式（I－１８）1モルに対して、１～２当量の割合で使用することができる。本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばアルコール類；エーテル類；などを挙げることができる。反応温度は通常０～５０℃である。反応時間は通常１～２４時間である。
　製法〔１６〕 [15] -2; In this reaction, the compound of formula (I-19) can be produced by reacting the compound of formula (I-18) with a reducing agent. Examples of the reducing agent include sodium borohydride. The reducing agent can be used at a ratio of 1 to 2 equivalents relative to 1 mole of the formula (I-18). This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include alcohols; ethers. The reaction temperature is usually 0 to 50 ° C. The reaction time is usually 1 to 24 hours.
Manufacturing method [16]
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　製法〔１６〕中、Ｑはハロゲン、アルキルカルボニルオキシ、ハロアルキルカルボニルオキシ、トリフラート又はメシラートなどの脱離基であり；Ｒ４、Ｒ５、Ｘ、Ｚ及びｍは前述の通りである。 In the production process [16], Q is a leaving group such as halogen, alkylcarbonyloxy, haloalkylcarbonyloxy, triflate or mesylate; R 4 , R 5 , X, Z and m are as described above.
　製法〔１６〕では、式（Ｉ－２０）の化合物と式（ＸＸIII）の化合物とを反応させることにより、式（Ｉ－２１）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。 In the production process [16], a compound of formula (I-20) and a compound of formula (XXIII) are reacted to produce [1,2,4] triazolo [1,5-a] of formula (I-21). Pyrimidine derivatives can be produced.
　式（ＸＸIII）の化合物は、式（I－２０）の化合物1モルに対して、通常１当量～大過剰量、望ましくは１～２０当量の割合で使用できる。本反応は、必要に応じ塩基の存在下で行うことができる。塩基としては、例えばトリエチルアミン、ピリジンのようなアミン類；炭酸カリウム、炭酸ナトリウムのような無機塩基類；などを挙げることができる。塩基は式（I－２０）の化合物1モルに対して、通常１～１０当量、望ましくは１～５当量の割合で使用できる。本反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばアセトン類；エーテル類；ニトリル類；などを挙げることができる。反応温度は０～５０℃、望ましくは０～３０℃である。反応時間は通常１～２４時間である。本反応においては、触媒量のジメチルアミノピリジンを使用することによって反応速度を促進することができる場合がある。
　製法〔１７〕 The compound of the formula (XXIII) can be used usually in a proportion of 1 equivalent to a large excess, desirably 1 to 20 equivalents, relative to 1 mol of the compound of the formula (I-20). This reaction can be performed in the presence of a base, if necessary. Examples of the base include amines such as triethylamine and pyridine; inorganic bases such as potassium carbonate and sodium carbonate; The base can be generally used in a proportion of 1 to 10 equivalents, preferably 1 to 5 equivalents, relative to 1 mol of the compound of formula (I-20). This reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include acetones; ethers; nitriles; The reaction temperature is 0 to 50 ° C., desirably 0 to 30 ° C. The reaction time is usually 1 to 24 hours. In this reaction, the reaction rate may be accelerated by using a catalytic amount of dimethylaminopyridine.
Manufacturing method [17]
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　製法〔１７〕中、Ｒ16はＯＲ2又はＮＲ4Ｒ5であり；Ｒ2、Ｒ4、Ｒ5、Ｘ、Ｚ及びｍは前述の通りである。 In the production process [17], R 16 is OR 2 or NR 4 R 5 ; R 2 , R 4 , R 5 , X, Z and m are as described above.
　製法〔１７〕では、式（I－１２）の化合物と式（ＸＸIＶ）の化合物とを反応させることにより式（I－２２）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。 In the production method [17], a compound of formula (I-12) is reacted with a compound of formula (XXIV) to react [1,2,4] triazolo [1,5-a] pyrimidine of formula (I-22) Derivatives can be produced.
　本反応において、式（ＸＸIＶ）の化合物は、式（I－１２）の化合物１モルに対して１当量～大過剰量、望ましくは１～２０当量の割合で使用できる。本反応は、必要に応じ酸触媒の存在で行うことができる。酸触媒としては、例えば前記製法〔１２〕と同様のものなどを挙げることができる。酸触媒は、式（I－１２）の化合物１モルに対して０．００１～０．３当量、望ましくは０．０１～０．２当量の割合で使用できる。本反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えば前記製法〔１２〕と同様のものを挙げることができる。反応温度は通常０～１５０℃、望ましくは１０～１００℃である。反応時間は、通常０．１～２４時間である。
　製法〔１８〕 In this reaction, the compound of the formula (XXIV) can be used in an amount of 1 equivalent to a large excess, desirably 1 to 20 equivalents, relative to 1 mole of the compound of the formula (I-12). This reaction can be performed in the presence of an acid catalyst, if necessary. Examples of the acid catalyst include those similar to the above production method [12]. The acid catalyst can be used in a proportion of 0.001 to 0.3 equivalent, preferably 0.01 to 0.2 equivalent, relative to 1 mol of the compound of formula (I-12). This reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include the same as in the above production method [12]. The reaction temperature is usually 0 to 150 ° C., preferably 10 to 100 ° C. The reaction time is usually 0.1 to 24 hours.
Manufacturing method [18]
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　製法〔１８〕中、Ｒ16、Ｘ、Ｚ及びｍは前述の通りである。 In the production process [18], R 16 , X, Z and m are as described above.
　製法〔１８〕では、式（I－１５）と式（ＸＸＶ）の化合物とを触媒又は縮合剤の存在下で反応させることにより式（I－２３）の化合物を製造できる。 In the production method [18], the compound of the formula (I-23) can be produced by reacting the compound of the formula (I-15) with the compound of the formula (XXV) in the presence of a catalyst or a condensing agent.
　式（ＸＸＶ）の化合物としては、例えばメタノール、エタノールのようなアルコール類；メチルアミン、ジメチルアミンのようなアミン類；などを挙げることができる。式（ＸＸＶ）の化合物は、式（I－１５）の化合物１モルに対して、通常１～３０当量の割合で使用できる。触媒の存在下で反応させる場合、触媒としては、例えば無機酸、有機酸などを挙げることができる。この反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、例えばアルコール類；芳香族炭化水素類；ハロゲン化炭化水素類；などを挙げることができる。反応温度は通常１０～１５０℃、望ましくは２０～１００℃である。反応時間は通常１～２４時間である。縮合剤の存在下で反応させる場合、縮合剤としては、例えばジシクロヘキシルカルボジイミド、１，１－カルボニルジイミダゾール、１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミドなどを挙げることができる。縮合剤は、式（I－１５）１モルに対して、通常１～５当量、望ましくは１～２当量の割合で使用できる。この反応は、必要に応じ溶媒の存在下で行うことができる。溶媒としては、例えばアルコール類；芳香族炭化水素類；ハロゲン化炭化水素類；などを挙げることができる。反応温度は通常０～１００℃、望ましくは０～５０℃である。反応時間は通常１～２４時間である。
　製法〔１９〕 Examples of the compound of the formula (XXV) include alcohols such as methanol and ethanol; amines such as methylamine and dimethylamine; The compound of the formula (XXV) can be used usually in a proportion of 1 to 30 equivalents relative to 1 mol of the compound of the formula (I-15). When the reaction is performed in the presence of a catalyst, examples of the catalyst include inorganic acids and organic acids. This reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include alcohols; aromatic hydrocarbons; halogenated hydrocarbons; The reaction temperature is usually 10 to 150 ° C., preferably 20 to 100 ° C. The reaction time is usually 1 to 24 hours. When the reaction is carried out in the presence of a condensing agent, examples of the condensing agent include dicyclohexylcarbodiimide, 1,1-carbonyldiimidazole, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide. The condensing agent can be used in a proportion of usually 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 mol of the formula (I-15). This reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include alcohols; aromatic hydrocarbons; halogenated hydrocarbons; The reaction temperature is usually 0 to 100 ° C., preferably 0 to 50 ° C. The reaction time is usually 1 to 24 hours.
Manufacturing method [19]
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　製法〔１９〕中、Ｒ17は水素原子、ＯＲ2又はＮＲ4Ｒ5であり；Ｒ2、Ｒ4、Ｒ5、Ｘ、Ｚ、ｈａｌ及びｍは前述の通りである。 In the production process [19], R 17 is a hydrogen atom, OR 2 or NR 4 R 5 ; R 2 , R 4 , R 5 , X, Z, hal and m are as described above.
　製法〔１９〕では、式（I－３）の化合物と式（ＸＸＶI）の化合物及び一酸化炭素とを、遷移金属触媒、ホスフィン配位子及び塩基の存在下で反応させることによって、式（I－２４）の［１，２，４］トリアゾロ［１，５－a］ピリミジン誘導体を製造できる。
　式（ＸＸＶI）の化合物としては、例えば水；水素；メタノール、エタノールのようなアルコール類；メチルアミン、ジメチルアミンのようなアミン類；などが挙げられる。式（ＸＸＶI）の化合物は、式（I－３）の化合物１モルに対して、通常１～５当量の割合で使用できる。一酸化炭素は、式（I－３）の化合物１モルに対して、通常１～１０当量、望ましくは１～５当量の割合で使用できる。遷移金属触媒としては、例えばパラジウム又はコバルト触媒などを挙げることができる。ホスフィン配位子は、遷移金属触媒の種類など反応系に応じて選択できる。遷移触媒と配位子の組合せとしては、例えば酢酸パラジウムとジフェニルホスフィノプロパンを挙げることができる。塩基としては、例えば、炭酸ナトリウム、炭酸セシウムのような無機塩；トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、ジイソプロピルエチルアミン、ピリジン、４－ジメチルアミノピリジン、２,６－ジメチルピリジン、４－ピロリジノピリジン、Ｎ－メチルモルホリン、Ｎ,Ｎ－ジメチルアニリン、Ｎ,Ｎ－ジエチルアニリン、Ｎ－エチル－Ｎ－メチルアニリン、１,８－ジアザビシクロ〔５.４.０〕－７－ウンデセン、１,４－ジアザビシクロ〔２.２.２〕オクタンのようなアミン類；などを挙げることができる。 In the production method [19], a compound of the formula (I-3) is reacted with a compound of the formula (XXVI) and carbon monoxide in the presence of a transition metal catalyst, a phosphine ligand and a base, thereby producing a compound of the formula (I -24) [1,2,4] triazolo [1,5-a] pyrimidine derivatives can be produced.
Examples of the compound of the formula (XXVI) include water; hydrogen; alcohols such as methanol and ethanol; amines such as methylamine and dimethylamine; The compound of the formula (XXVI) can be generally used at a ratio of 1 to 5 equivalents per 1 mol of the compound of the formula (I-3). Carbon monoxide can be used in an amount of usually 1 to 10 equivalents, preferably 1 to 5 equivalents, relative to 1 mol of the compound of formula (I-3). Examples of the transition metal catalyst include a palladium or cobalt catalyst. The phosphine ligand can be selected according to the reaction system such as the type of transition metal catalyst. Examples of the combination of the transition catalyst and the ligand include palladium acetate and diphenylphosphinopropane. Examples of the base include inorganic salts such as sodium carbonate and cesium carbonate; trimethylamine, triethylamine, triisopropylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine, 4-pyrrolidinopyridine, N -Methylmorpholine, N, N-dimethylaniline, N, N-diethylaniline, N-ethyl-N-methylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [ 2.2.2] amines such as octane;
　本反応は、通常、溶媒の存在下で行うことができる。溶媒としては、反応に悪影響を与えないものであれば特に限定はなく、例えばＮ,Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチルピロリドンのような極性非プロトン性溶媒などを挙げることができる。反応温度は、通常２５～１２０℃、望ましくは５０～７０℃である。反応時間は、通常１～２４時間程度、望ましくは３～７時間である。必要応じて加圧下で反応を行うこともできる。 This reaction can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include polar aprotic solvents such as N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone. The reaction temperature is usually 25 to 120 ° C., preferably 50 to 70 ° C. The reaction time is usually about 1 to 24 hours, preferably 3 to 7 hours. If necessary, the reaction can be carried out under pressure.
　本反応は公知文献に記載の方法に準じて実施することができる。例えば、Tetrahedron Letters、33、1959-1962（1992）に記載されている方法を挙げることができる。 This reaction can be carried out according to the methods described in known literature. For example, the method described in Tetrahedron Letters, 33, 1959-1962 (1992) can be mentioned.
　前記した各製法の中では、製法〔１〕、製法〔３〕、製法〔４〕、製法〔５〕、製法〔９〕、製法〔１０〕、製法〔１２〕、製法〔１５〕又は製法〔１６〕が、特に望ましい態様である。 Among the above-mentioned production methods, production method [1], production method [3], production method [4], production method [5], production method [9], production method [10], production method [12], production method [15] or production method [ 16] is a particularly desirable embodiment.
　本発明の有害生物防除剤の望ましい態様について以下に記述する。本発明の有害生物防除剤は、例えば農園芸分野で問題となる各種有害生物の防除剤、即ち農園芸用有害生物防除剤や、動物に寄生する有害生物の防除剤、即ち動物寄生生物防除剤として特に有用である。本発明の有害生物防除剤は、各種有害生物の中でも、有害動物の防除に特に有用であり、有害動物防除剤は望ましい態様の１つである。 Favorable embodiments of the pest control agent of the present invention are described below. The pest control agent of the present invention includes, for example, various pest control agents that are problematic in the field of agriculture and horticulture, that is, agricultural and horticultural pest control agents, and pest control agents that parasitize animals, that is, animal parasite control agents. As particularly useful. The pest control agent of the present invention is particularly useful for controlling pests among various pests, and the pest control agent is one of desirable embodiments.
　農園芸用有害生物防除剤としては、例えば、殺虫、殺ダニ、殺線虫又は殺土壌害虫剤として有用であるが、具体的には、ナミハダニ、ニセナミハダニ、カンザワハダニ、ミカンハダニ、リンゴハダニ、チャノホコリダニ、ミカンサビダニ、ネダニなどのような植物寄生性ダニ類；モモアカアブラムシ、ワタアブラムシのようなアブラムシ類；コナガ、ヨトウムシ、ハスモンヨトウ、コドリンガ、ボールワーム、タバコバッドワーム、マイマイガ、コブノメイガ、チャノコカクモンハマキ、コロラドハムシ、ウリハムシ、ボールウィービル、ウンカ類、ヨコバイ類、カイガラムシ類、カメムシ類、コナジラミ類、アザミウマ類、バッタ類、ハナバエ類、コガネムシ類、タマナヤガ、カブラヤガ、アリ類などのような農業害虫類；ネコブセンチュウ類、シストセンチュウ類、ネグサレセンチュウ類、イネシンガレセンチュウ、イチゴメセンチュウ、マツノザイセンチュウなどのような植物寄生性線虫類；ナメクジ、マイマイなどのような腹足類；ダンゴムシ、ワラジムシのような等脚類などのような土壌害虫類；イエダニ、ゴキブリ類、イエバエ、アカイエカなどのような衛生害虫類；バクガ、アズキゾウムシ、コクヌストモドキ、ゴミムシダマシ類などのような貯穀害虫類；イガ、ヒメカツオブシムシ、シロアリ類などのような衣類、家屋害虫類；ケナガコナダニ、コナヒョウダニ、ミナミツメダニなどのような屋内塵性ダニ類；などの防除に有効である。
　本発明の農園芸用有害生物防除剤は、植物寄生性ダニ類、農業害虫類、植物寄生性線虫類などの防除に特に有効である。その中でも、植物寄生性ダニ類、農業害虫類の防除にさらに優れた効果を示すため、殺虫又は殺ダニ剤として最も有用である。
　また、本発明の農園芸用有害生物防除剤は、有機リン剤、カーバメート剤、合成ピレスロイド剤などの薬剤に対する各種抵抗性害虫の防除にも有効である。
　さらに、式（I）の化合物は、優れた浸透移行性を有していることから、本発明の農園芸用有害生物防除剤を土壌に処理することによって土壌有害昆虫類、ダニ類、線虫類、腹脚類、等脚類の防除と同時に茎葉部の害虫類をも防除することができる。 Pesticides for agricultural and horticultural use are useful, for example, as insecticides, acaricides, nematicides or soil insecticides. Plant parasitic mites such as rustic mites, mites, aphids such as peach aphids and cotton aphids; diamondback moths, weevil, scallops, codling moths, ball worms, tobacco worms, mai moths, yellow moths, prickly winged clams, Colorado Agricultural pests such as leaf beetle, cucumber beetle, ball weevil, planthoppers, leafhoppers, scale insects, stink bugs, whitefly, thrips, grasshoppers, fly flies, scarab beetles, Tamanayaga, Kaburayaga, ants, etc .; Parasitic nematodes such as mosquitoes, cyst nematodes, nesting nematodes, rice scented nematodes, strawberry nematodes, pine wood nematodes, etc .; gastropods such as slugs, maimai, etc .; Soil pests such as legumes; hygiene pests such as house dust mites, cockroaches, house flies, and mosquitoes; storage pests such as bark moths, azuki beetles, mosquito moths, bark beetles, etc .; It is effective for controlling clothes such as mosquitoes, house pests, and indoor dust mites such as white mites, white mites, and white ticks.
The agricultural and horticultural pest control agent of the present invention is particularly effective for controlling plant parasitic mites, agricultural pests, plant parasitic nematodes and the like. Among them, it is most useful as an insecticidal or acaricidal agent because it exhibits a further excellent effect in controlling plant parasitic mites and agricultural pests.
In addition, the agricultural and horticultural pest control agent of the present invention is also effective in controlling various resistant pests against drugs such as organic phosphorus agents, carbamate agents, and synthetic pyrethroid agents.
Furthermore, since the compound of the formula (I) has an excellent osmotic transfer property, by treating the soil with the agricultural and horticultural pest control agent of the present invention, soil harmful insects, mites, nematodes It is possible to control pests in the foliage at the same time as the control of mosses, gastropods, and isopods.
　本発明の有害生物防除剤の別の望ましい態様としては、前記した植物寄生性ダニ類、農業害虫類、植物寄生性線虫類、腹足類、土壌害虫類などを総合的に防除する農園芸用有害生物防除剤が挙げられる。 As another desirable aspect of the pest control agent of the present invention, there are agricultural and horticultural harmful substances that comprehensively control the above-mentioned plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods, soil pests, etc. Biological control agents are mentioned.
　本発明の農園芸用有害生物防除剤は、通常、該化合物と各種農業上の補助剤とを混合して粉剤、粒剤、顆粒水和剤、水和剤、水性懸濁剤、油性懸濁剤、水溶剤、乳剤、液剤、ペースト剤、エアゾール剤、微量散布剤などの種々の形態に製剤して使用されるが、本発明の目的に適合するかぎり、通常の当該分野で用いられているあらゆる製剤形態にすることができる。
　製剤に使用する補助剤としては、珪藻土、消石灰、炭酸カルシウム、タルク、ホワイトカーボン、カオリン、ベントナイト、カオリナイト、セリサイト、クレー、炭酸ナトリウム、重曹、芒硝、ゼオライト、澱粉などの固型担体；水、トルエン、キシレン、ソルベントナフサ、ジオキサン、アセトン、イソホロン、メチルイソブチルケトン、クロロベンゼン、シクロヘキサン、ジメチルスルホキシド、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、アルコールなどの溶剤；脂肪酸塩、安息香酸塩、アルキルスルホコハク酸塩、ジアルキルスルホコハク酸塩、ポリカルボン酸塩、アルキル硫酸エステル塩、アルキル硫酸塩、アルキルアリール硫酸塩、アルキルジグリコールエーテル硫酸塩、アルコール硫酸エステル塩、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、アリールスルホン酸塩、リグニンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、ポリスチレンスルホン酸塩、アルキルリン酸エステル塩、アルキルアリールリン酸塩、スチリルアリールリン酸塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルアリールエーテル硫酸塩、ポリオキシエチレンアルキルアリールエーテル硫酸エステル塩、ポリオキシエチレンアルキルエーテルリン酸塩、ポリオキシエチレンアルキルアリールリン酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物の塩のような陰イオン系の界面活性剤；ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、脂肪酸ポリグリセライド、脂肪酸アルコールポリグリコールエーテル、アセチレングリコール、アセチレンアルコール、オキシアルキレンブロックポリマー、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンスチリルアリールエーテル、ポリオキシエチレングリコールアルキルエーテル、ポリエチレングリコール、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、ポリオキシプロピレン脂肪酸エステルのような非イオン系の界面活性剤；オリーブ油、カポック油、ひまし油、シュロ油、椿油、ヤシ油、ごま油、トウモロコシ油、米ぬか油、落花生油、綿実油、大豆油、菜種油、亜麻仁油、きり油、液状パラフィンなどの植物油や鉱物油；などが挙げられる。これら補助剤の各成分は、本発明の目的から逸脱しないかぎり、１種又は２種以上を適宜選択して使用することができる。また、前記した補助剤以外にも当該分野で知られたものの中から適宜選んで使用することもでき、例えば、増量剤、増粘剤、沈降防止剤、凍結防止剤、分散安定剤、薬害軽減剤、防黴剤、など通常使用される各種補助剤も使用することができる。
　式（I）の化合物と各種補助剤との配合割合（重量比）は、0.001：99.999～95：5、望ましくは0.005：99.995～90：10である。
　これら製剤の実際の使用に際しては、そのまま使用するか、又は水等の希釈剤で所定濃度に希釈し、必要に応じて各種展着剤（界面活性剤、植物油、鉱物油など）を添加して使用することができる。 The agricultural and horticultural pest control agent of the present invention is usually a powder, granule, granule wettable powder, wettable powder, aqueous suspension, oily suspension by mixing the compound and various agricultural adjuvants. Used in various forms, such as an agent, an aqueous solvent, an emulsion, a liquid, a paste, an aerosol, and a microdispersion, but is generally used in the art as long as it meets the purpose of the present invention. Any formulation can be used.
Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch; water , Toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, alcohol, etc. Solvent; fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, al Sulfuric acid ester salt, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester salt, alkyl aryl phosphate, Styryl aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate Anionic surfactants such as ester salts and salts of naphthalenesulfonic acid formalin condensates; sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides, fats Fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxy Nonionic surfactants such as ethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm oil , Coconut oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, Riabura, vegetable oil or mineral oil such as liquid paraffin; and the like. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the art. For example, a bulking agent, a thickening agent, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a phytotoxicity reduction. Various commonly used adjuvants such as agents, antifungal agents and the like can also be used.
The compounding ratio (weight ratio) of the compound of the formula (I) and various adjuvants is 0.001: 99.999 to 95: 5, preferably 0.005: 99.995 to 90:10.
In actual use of these preparations, use them as they are, or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.
　本発明の農園芸用有害生物防除剤の施用は、気象条件、製剤形態、施用時期、施用場所、病害虫の種類や発生状況などの相違により一概に規定できないが、一般に0.05～800000ppm、望ましくは0.5～500000ppmの有効成分濃度で行ない、その単位面積あたりの施用量は、１ヘクタール当り式（I）の化合物が0.05～50000g、望ましくは1～30000gである。
　また、本発明の有害生物防除剤の別の望ましい態様である農園芸用の有害生物防除剤の施用は、前記有害生物防除剤の施用に準じて行われる。本発明には、このような施用方法による有害生物の防除方法、特に植物寄生性ダニ類、農業害虫類、植物寄生性線虫類の防除方法も含まれる。 The application of the agricultural and horticultural pest control agent of the present invention cannot be defined unconditionally due to differences in weather conditions, formulation form, application time, application location, type of pests and occurrence status, but generally 0.05 to 800,000 ppm, preferably 0.5 The active ingredient concentration is ˜500,000 ppm, and the application amount per unit area is 0.05 to 50,000 g, preferably 1 to 30,000 g, of the compound of formula (I) per hectare.
In addition, application of the agricultural and horticultural pest control agent, which is another desirable embodiment of the pest control agent of the present invention, is performed according to the application of the pest control agent. The present invention includes a method for controlling pests by such an application method, particularly a method for controlling plant parasitic mites, agricultural pests, and plant parasitic nematodes.
　本発明の農園芸用有害生物防除剤の種々の製剤、又はその希釈物の施用は、通常、一般に行なわれている施用方法すなわち、散布（例えば散布、噴霧、ミスティング、アトマイジング、散粒、水面施用等）、土壌施用（混入、灌注等）、表面施用（塗布、粉衣、被覆等）、浸漬毒餌等により行うことができる。また、家畜に対して前記有効成分を飼料に混合して与え、その***物での有害虫、特に有害昆虫の発生及び生育を阻害することも可能である。また、いわゆる超高濃度少量散布法(ultra low volume)により施用することもできる。この方法においては、活性成分を100％含有することが可能である。 The various formulations of the pesticide for agricultural and horticultural use according to the present invention, or the dilutions thereof are usually applied by a commonly used application method, that is, spraying (for example, spraying, spraying, misting, atomizing, dusting, Water surface application, etc.), soil application (mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.), immersion poison bait, etc. It is also possible to feed livestock with the above-mentioned active ingredient mixed with feed to inhibit the occurrence and growth of harmful insects, particularly harmful insects, in the excreta. It can also be applied by the so-called ultra-low concentration low volume method. In this method, it is possible to contain 100% of the active ingredient.
　また、本発明の農園芸用有害生物防除剤は、他の農薬、肥料、薬害軽減剤などと混用或は併用することができ、この場合に一層優れた効果、作用性を示すことがある。他の農薬としては、除草剤、殺虫剤、殺ダニ剤、殺線虫剤、殺土壌害虫剤、殺菌剤、抗ウィルス剤、誘引剤、抗生物質、植物ホルモン、植物成長調整剤、などが挙げられる。特に、式（I）の化合物と他の農薬の有効成分化合物の１種又は２種以上とを混用或は併用した混合有害生物防除用組成物は、適用範囲、薬剤処理の時期、防除活性等を好ましい方向へ改良することが可能である。尚、式（I）の化合物と他の農薬の有効成分化合物は各々別々に製剤したものを散布時に混合して使用しても、両者を一緒に製剤して使用してもよい。本発明には、このような混合有害生物防除用組成物も含まれる。 Further, the agricultural and horticultural pest control agent of the present invention can be used in combination or in combination with other agricultural chemicals, fertilizers, safeners, etc., and in this case, more excellent effects and activities may be exhibited. Other agrochemicals include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. It is done. In particular, a composition for controlling mixed pests in which a compound of formula (I) and one or more active ingredient compounds of other agricultural chemicals are mixed or used in combination is applicable range, timing of chemical treatment, control activity, etc. Can be improved in a preferred direction. In addition, the compound of formula (I) and the active ingredient compound of other agricultural chemicals may be used by mixing separately formulated ones at the time of spraying, or by formulating both together. The present invention includes such a composition for controlling mixed pests.
　式（I）の化合物と他の農薬の有効成分化合物との混合比（重量比）は、気象条件、製剤形態、施用時期、施用場所、病害虫の種類や発生状況などの相違により一概に規定できないが、一般に1：300～300：1、望ましくは1：100～100：1である。また、施用適量は１ヘクタール当りの総有効成分化合物量として0.1～50000g、望ましくは1～30000gである。本発明には、このような混合有害生物防除用組成物の施用方法による有害生物の防除方法も含まれる。 The mixing ratio (weight ratio) between the compound of formula (I) and the active ingredient compound of other pesticides cannot be specified unconditionally due to differences in weather conditions, formulation form, application time, application location, pest type or occurrence status. However, it is generally 1: 300 to 300: 1, preferably 1: 100 to 100: 1. The appropriate amount to be applied is 0.1 to 50000 g, preferably 1 to 30000 g as the total amount of active ingredient compounds per hectare. The present invention also includes a method for controlling pests by a method for applying such a composition for controlling mixed pests.
　上記他の農薬中の、殺虫剤、殺ダニ剤、殺線虫剤或いは殺土壌害虫剤の有効成分化合物（一般名；一部申請中を含む、又は試験コード）としては、例えばプロフェノホス（profenofos）、ジクロルボス（dichlorvos）、フェナミホス（fenamiphos）、フェニトロチオン（fenitrothion）、ＥＰＮ、ダイアジノン（diazinon）、クロルピリホス(chlorpyrifos)、クロルピリホスメチル(chlorpyrifos-methyl)、アセフェート(acephate)、プロチオホス(prothiofos)、ホスチアゼート（fosthiazate）、カズサホス（cadusafos）、ジスルホトン(dislufoton)、イソキサチオン（isoxathion）、イソフェンホス(isofenphos)、エチオン(ethion)、エトリムホス(etrimfos)、キナルホス(quinalphos)、ジメチルビンホス(dimethylvinphos)、ジメトエート(dimethoate)、スルプロホス(sulprofos)、チオメトン(thiometon)、バミドチオン(vamidothion)、ピラクロホス(pyraclofos)、ピリダフェンチオン(pyridaphenthion)、ピリミホスメチル(pirimiphos-methyl)、プロパホス(propaphos)、ホサロン(phosalone)、ホルモチオン(formothion)、マラチオン(malathion)、テトラクロルビンホス(tetrachlovinphos)、クロルフェンビンホス(chlorfenvinphos)、シアノホス(cyanophos)、トリクロルホン(trichlorfon)、メチダチオン(methidathion)、フェントエート(phenthoate)、ＥＳＰ、アジンホスメチル(azinphos-methyl)、フェンチオン(fenthion)、ヘプテノホス(heptenophos)、メトキシクロル（methoxychlor）、パラチオン（parathion）、ホスホカルブ(phosphocarb)、デメトン-Ｓ-メチル（demeton-S-methyl）、モノクロトホス（monocrotophos）、メタミドホス（methamidophos）、イミシアホス（imicyafos）、パラチオン-メチル（parathion-methyl）、テルブホス（terbufos）、ホスファミドン（phosphamidon）、ホスメット（phosmet）、ホレート（phorate）のような有機リン酸エステル系化合物；
　カルバリル(carbaryl)、プロポキスル(propoxur)、アルジカルブ(aldicarb)、カルボフラン(carbofuran)、チオジカルブ(thiodicarb)、メソミル(methomyl)、オキサミル（oxamyl）、エチオフェンカルブ(ethiofencarb)、ピリミカルブ(pirimicarb)、フェノブカルブ(fenobucarb)、カルボスルファン（carbosulfan）、ベンフラカルブ（benfuracarb）、ベンダイオカルブ（bendiocarb）、フラチオカルブ(furathiocab)、イソプロカルブ(isoprocarb)、メトルカルブ(metolcarb)、キシリルカルブ(xylylcarb)、ＸＭＣ、フェノチオカルブ（fenothiocarb）のようなカーバメート系化合物；
　カルタップ（cartap）、チオシクラム（thiocyclam）、ベンスルタップ（bensultap）、チオスルタップナトリウム（thiosultap-sodium）のようなネライストキシン誘導体；　ジコホル(dicofol)、テトラジホン(tetradifon)、エンドスルファン(endosulfan)、ジエノクロル（dienochlor）、ディルドリン（dieldrin）のような有機塩素系化合物； Examples of active ingredient compounds (generic name; including some pending applications or test codes) of insecticides, acaricides, nematicides or soil pesticides in the above other pesticides include, for example, profenofos , Dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiofos, fothiaz , Cadusafos, dislufoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate, sulfophos ( sulprofos), thiometon, bamidithione (vamidot) hion), pyraclofos, pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlovinphos, chlorfen Chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, azinphos-methyl, fenthion, heptenophos, methoxychlor, Parathion, phosphocarb, demeton-S-methyl, monocrotophos, methamidophos, imicyafos, parathion-methyl, terbufos ( terbufos), phospamidon (phosp) organophosphate compounds such as hamidon, phosmet, phorate;
Carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, fenobucarb Carbamates such as carbosulfan, benfuracarb, bendiocarb, furathiocab, isoprocarb, metolcarb, xylylcarb, XMC, fenothiocarb Compound;
Nereistoxin derivatives such as cartap, thiocyclam, bensultap, thiosultap-sodium; dicophor, tetradifon, endosulfan, dienochlor ), Organochlorine compounds such as dieldrin;
　酸化フェンブタスズ（fenbutatin Oxide）、シヘキサチン（cyhexatin）のような有機金属系化合物；
　フェンバレレート(fenvalerate)、ペルメトリン（permethrin）、シペルメトリン（cypermethrin）、デルタメトリン（deltamethrin）、シハロトリン（cyhalothrin）、テフルトリン（tefluthrin）、エトフェンプロックス（ethofenprox）、フルフェンプロックス（flufenprox）、シフルトリン（cyfluthrin）、フェンプロパトリン（fenpropathrin）、フルシトリネート（flucythrinate）、フルバリネート(fluvalinate)、シクロプロトリン（cycloprothrin）、ラムダシハロトリン(lambda-cyhalothrin)、ピレスリン（pyrethrins）、エスフェンバレレート（esfenvalerate）、テトラメスリン（tetramethrin）、レスメスリン（resmethrin）、プロトリフェンブト(protrifenbute)、ビフェンスリン（bifenthrin）、ゼータシペルメトリン（zeta-cypermethrin）、アクリナトリン（acrinathrin）、アルファシペルメトリン（alpha-cypermethrin）、アレスリン（allethrin）、ガンマシハロトリン（gamma-cyhalothrin）、シータシペルメトリン（theta-cypermethrin）、タウフルバリネート（tau-fluvalinate）、トラロメスリン（tralomethrin）、プロフルスリン（profluthrin）、ベータシペルメトリン（beta-cypermethrin）、ベータシフルトリン（beta-cyfluthrin）、メトフルトリン（metofluthrin）、フェノトリン（phenothrin)のようなピレスロイド系化合物；
　ジフルベンズロン(diflubenzuron)、クロルフルアズロン(chlorfluazuron)、テフルベンズロン(teflubenzuron)、フルフェノクスロン(flufenoxuron)、トリフルムロン(triflumuron)、ヘキサフルムロン(hexaflumuron)、ルフェヌロン(lufenuron)、ノバルロン(novaluron)、ノビフルムロン（noviflumuron）、ビストリフルロン（bistrifluron）、フルアズロン（fluazuron）のようなベンゾイルウレア系化合物；
　メトプレン(methoprene)、ピリプロキシフェン(pyriproxyfen)、フェノキシカルブ(fenoxycarb)、ジオフェノラン（diofenolan）のような幼若ホルモン様化合物；
　フェンピロキシメート(fenpyroximate)、フィプロニル(fipronil)、テブフェンピラド（tebufenpyrad）、エチプロール(ethiprole)、トルフェンピラド（tolfenpyrad）、アセトプロール(acetoprole)、ピラフルプロール（pyrafluprole）、ピリプロール（pyriprole）のようなピラゾール系化合物；
　イミダクロプリド（imidacloprid）、ニテンピラム（nitenpyram）、アセタミプリド（acetamiprid）、チアクロプリド（thiacloprid）、チアメトキサム（thiamethoxam）、クロチアニジン（clothianidin）、ジノテフラン（dinotefuran）、ニチアジン（nithiazine）などのネオニコチノイド；
　テブフェノジド（tebufenozide）、メトキシフェノジド（methoxyfenozide）、クロマフェノジド（chromafenozide）、ハロフェノジド（halofenozide）などのヒドラジン系化合物； Organometallic compounds such as fenbutatin oxide and cyhexatin;
Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprox, flufenprox, cyfluthrin , Fenpropathrin, flucytrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrin, esfenvalerate, Tetramethrin, resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypermethri n), allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta cypermethrin ( pyrethroid compounds such as beta-cypermethrin, beta-cyfluthrin, metofurthrin, phenothrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, triflumuron, hexaflumuron, lufenuron, novaluron, novaluron, ), Bistrifluron, benzoylurea compounds such as fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, phenoxycarb, diofenolan;
Pyrazole compounds such as fenpyroximate, fipronil, tebufenpyrad, etiprole, tolfenpyrad, acetoprole, pyrafluprole, pyriprole;
Neonicochioids such as imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, nithiazine;
Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide;
　ピリダリル（pyridalyl）、フロニカミド（flonicamid）などのようなピリジン系化合物；
　スピロジクロフェン（spirodiclofen）などのようなテトロニック酸系化合物；
　フルアクリピリム（fluacrypyrim）などのようなストロビルリン系化合物；
　フルフェネリム（flufenerim）などのようなピリジナミン系化合物；
　ジニトロ系化合物；有機硫黄化合物；尿素系化合物；トリアジン系化合物；ヒドラゾン系化合物；また、その他の化合物として、ブプロフェジン（buprofezin）、ヘキシチアゾクス（hexythiazox）、アミトラズ（amitraz）、クロルジメホルム（chlordimeform）、シラフルオフェン（silafluofen）、トリアザメート（triazamate）、ピメトロジン（pymetrozine）、ピリミジフェン（pyrimidifen）、クロルフェナピル（chlorfenapyr）、インドキサカルブ（indoxacarb）、アセキノシル（acequinocyl）、エトキサゾール（etoxazole）、シロマジン（cyromazine）、１,３－ジクロロプロペン（1,3-dichloropropene）、ジアフェンチウロン（diafenthiuron）、ベンクロチアズ（benclothiaz）、ビフェナゼート（bifenazate）、スピロメシフェン（spiromesifen）、スピロテトラマット（spirotetramat）、プロパルギット（propargite）、クロフェンテジン（clofentezine）、メタフルミゾン（metaflumizone）、フルベンジアミド（flubendiamide）、シフルメトフェン（cyflumetofen）、クロラントラニリプロール（chlorantraniliprole）、シエノピラフェン(cyenopyrafen)、ピリフルキナゾン(pyrifluquinazon)、フェナザキン(fenazaquin)、ピリダベン（pyridaben）、アミドフルメト（amidoflumet）、クロロベンゾエート（chlorobenzoate）、スルフルアミド（sulfluramid）、ヒドラメチルノン（hydramethylnon）、メタアルデヒド（metaldehyde）、HGW 86、リアノジン（ryanodine）のような化合物；などが挙げられる。更に、Bacillus thuringienses aizawai、Bacillus thuringienses kurstaki、Bacillus thuringienses israelensis、Bacillus thuringienses japonensis、Bacillus thuringienses tenebrionis、Bacillus thuringiensesが生成する結晶タンパク毒素、昆虫病原ウイルス剤、昆虫病原糸状菌剤、線虫病原糸状菌剤などのような微生物農薬；アベルメクチン（avermectin）、エマメクチンベンゾエート（emamectin-benzoate）、ミルベメクチン（milbemectin）、ミルベマイシン（milbemycin）、スピノサド（spinosad）、イベルメクチン（ivermectin）、レピメクチン（lepimectin）、ＤＥ-１７５、アバメクチン（abamectin）、エマメクチン（emamectin）のような抗生物質及び半合成抗生物質；アザディラクチン（azadirachtin）、ロテノン（rotenone）のような天然物；ディート（deet）のような忌避剤；などが挙げられる。 Pyridine compounds such as pyridalyl, flonicamid and the like;
Tetronic acid compounds such as spirodiclofen;
Strobilurin-based compounds such as fluacrypyrim;
Pyridinamine compounds such as flufenerim;
Dinitro compounds; organic sulfur compounds; urea compounds; triazine compounds; hydrazone compounds; and other compounds such as buprofezin, hexythiazox, amitraz, chlordimeform, silafluofen ), Triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, cyromazine, 1,3-dichloropropene (1,3-dichloropropene), diafenthiuron, benclothiaz, bifenazate, spiromesifen, spirotetramat, propargi Propargite, clofentezine, metaflumizone, flubendiamide, cyflumetofen, chlorantraniliprole, cyenopyrafen, pyrifluquinazon, pirafluquinazon ), Pyridaben, amidoflumet, chlorobenzoate, sulfluramid, hydramethylnon, metaldehyde, HGW 86, ryanodine, and the like; Can be mentioned. Furthermore, Bacillus thuringienses aizawai, Bacillus thuringienses kurstaki, Bacillus thuringienses israelensis, Bacillus thuringienses japonensis, Bacillus thuringienses tenebrionis, crystalline protein toxins produced by Bacillus thuringienses, entomopathogenic fungi, nematode pathogenic fungi, etc. Microbial pesticides such as: avermectin, emamectin-benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin and antibiotics such as abamectin and emamectin; semi-synthetic antibiotics; natural products such as azadirachtin and rotenone; repellents such as deet;
　上記他の農薬中の、殺菌性有効成分化合物（一般名；一部申請中を含む、又は日本植物防疫協会供試試験コード）としては、例えば、メパニピリム（mepanipyrim）、ピリメサニル（pyrimethanil）、シプロジニル（cyprodinil）、フェリムゾン（ferimzone）のようなアニリノピリミジン系化合物；
　5-クロロ-6-(2,4,6-トリフルオロフェニル)-7-(4-メチルピペリジン-1-イル)[1,2,4]トリアゾロ[1,5-a]ピリミジンのようなトリアゾロピリミジン系化合物；
　フルアジナム（fluazinam）のようなピリジナミン系化合物；
　トリアジメホン（triadimefon）、ビテルタノール（bitertanol）、トリフルミゾール（triflumizole）、エタコナゾール（etaconazole）、プロピコナゾール（propiconazole）、ペンコナゾール（penconazole）、フルシラゾール（flusilazole）、マイクロブタニル（myclobutanil）、シプロコナゾール（cyproconazole）、テブコナゾール（tebuconazole）、ヘキサコナゾール（hexaconazole）、ファーコナゾールシス（furconazole‐cis）、プロクロラズ（prochloraz）、メトコナゾール（metconazole）、エポキシコナゾール（epoxiconazole）、テトラコナゾール（tetraconazole）、オキスポコナゾールフマル酸塩（oxpoconazole fumarate）、シプコナゾール（sipconazole）、プロチオコナゾール（prothioconazole）、トリアジメノール（triadimenol）、フルトリアホール（flutriafol）、ジフェノコナゾール（difenoconazole）、フルキンコナゾール（fluquinconazole）、フェンブコナゾール（fenbuconazole）、ブロムコナゾール（bromuconazole）、ジニコナゾール（diniconazole）、トリシクラゾール（tricyclazole）、プロベナゾール（probenazole）、シメコナゾール（simeconazole）、ペフラゾエート（pefurazoate）、イプコナゾール（ipconazole）、イミベンコナゾール（imibenconazole）のようなアゾール系化合物； In the above-mentioned other agricultural chemicals, the bactericidal active ingredient compound (generic name; including partial application, or Japan Plant Protection Association test code) includes, for example, mepanipyrim, pyrimethanil, cyprodinil ( cyprodinil) and anilinopyrimidine compounds such as ferimzone;
Tria such as 5-chloro-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidin-1-yl) [1,2,4] triazolo [1,5-a] pyrimidine Zolopyrimidine compounds;
Pyridinamine compounds such as fluazinam;
Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, o Oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, difenoconazole , Fluquinconazole, fenbuconazole, bromuconazole, diniconazole, tricyclazole, probenazole, cimeconazole, pefurazoate, ipconazole, ipconazole ), Azole compounds such as imibenconazole;
　キノメチオネート（quinomethionate）のようなキノキサリン系化合物；
　マンネブ（maneb）、ジネブ（zineb）、マンゼブ（mancozeb）、ポリカーバメート（polycarbamate）、メチラム（metiram）、プロピネブ（propineb）、チラム(thiram)のようなジチオカーバメート系化合物；
　フサライド（fthalide）、クロロタロニル（chlorothalonil）、キントゼン（quintozene）のような有機塩素系化合物；
　ベノミル（benomyl）、チオファネートメチル（thiophanate‐methyl）、カーベンダジム（carbendazim）、チアベンダゾール(thiabendazole)、フベリアゾール(fuberiazole)、シアゾファミド（cyazofamid）のようなイミダゾール系化合物；
　シモキサニル（cymoxanil）のようなシアノアセトアミド系化合物；
　メタラキシル（metalaxyl）、メタラキシル－Ｍ（metalaxyl-M）、メフェノキサム(mefenoxam）、オキサジキシル（oxadixyl）、オフレース（ofurace）、ベナラキシル（benalaxyl）、ベナラキシル－Ｍ(benalaxyl-M、別名キララキシル(kiralaxyl、chiralaxyl)）、フララキシル（furalaxyl）、シプロフラム（cyprofuram）のようなフェニルアミド系化合物； Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram;
Organochlorine compounds such as fthalide, chlorothalonil, quintozene;
Imidazole compounds such as benomyl, thiophanate-methyl, carbendazim, thiabendazole, fuberiazole, cyazofamid;
Cyanoacetamide compounds such as cymoxanil;
Metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, offurace, benalaxyl, benalaxyl-M, also known as kiralaxyl, chiax ), Phenylamide compounds such as furalaxyl, cyprofuram;
　ジクロフルアニド（dichlofluanid）のようなスルフェン酸系化合物；
　水酸化第二銅（cupric hydroxide）、有機銅（oxine　copper）のような銅系化合物；　ヒメキサゾール（hymexazol）のようなイソキサゾール系化合物；
　ホセチルアルミニウム（fosetyl‐Al）、トルクロホスメチル（tolclofos‐methyl）、エジフェンホス（edifenphos）、イプロベンホス（iprobenfos）、Ｓ－ベンジル　Ｏ，Ｏ－ジイソプロピルホスホロチオエート、Ｏ－エチル　Ｓ，Ｓ－ジフェニルホスホロジチオエート、アルミニウムエチルハイドロゲンホスホネートのような有機リン系化合物；
　キャプタン（captan）、キャプタホル（captafol）、フォルペット（folpet）のようなＮ－ハロゲノチオアルキル系化合物；
　プロシミドン（procymidone）、イプロジオン（iprodione）、ビンクロゾリン（vinclozolin）のようなジカルボキシイミド系化合物； Sulfenic acid compounds such as dichlofluanid;
Copper-based compounds such as cupric hydroxide and oxine copper; isoxazole-based compounds such as hymexazol;
Fosetyl aluminum (fosetyl-Al), tolclofos-methyl, edifenphos, iprobenfos, S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum Organophosphorus compounds such as ethyl hydrogen phosphonate;
N-halogenothioalkyl compounds such as captan, captafol, folpet;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
　フルトラニル（flutolanil）、メプロニル（mepronil）、ゾキサミド（zoxamid）、チアジニル（tiadinil）のようなベンズアニリド系化合物；
　カルボキシン(carboxin)、オキシカルボキシン(oxycarboxin)、チフルザミド(thifluzamide)、ペンチオピラド（penthiopyrad)、ボスカリド(boscalid) 、イソチアニル（isothianil）、ビキサフェン（bixafen）、3-(ジフロロメチル)-1-メチル-N-[(1RS,4SR,9RS)-1,2,3,4-テトラヒドロ-9-イソプロピル-1,4-メタノナフタレン-5-イル]ピラゾール-4-カルボキサミドと3-(ジフロロメチル)-1-メチル-N-[(1RS,4SR,9SR)-1,2,3,4-テトラヒドロ-9-イソプロピル-1,4-メタノナフタレン-5-イル]ピラゾール-4-カルボキサミドの混合物（イソピラザム（isopyrazam））のようなアニリド系化合物；
　トリホリン（triforine）のようなピペラジン系化合物；
　ピリフェノックス（pyrifenox）のようなピリジン系化合物；
　フェナリモル（fenarimol）、フルトリアフォル（flutriafol）のようなカルビノール系化合物；
　フェンプロピディン（fenpropidine）のようなピペリジン系化合物；
　フェンプロピモルフ（fenpropimorph）、スピロキサミン（spiroxamine）、トリデモルフ(tridemorph)のようなモルフォリン系化合物； Benzanilide compounds such as flutolanil, mepronil, zoxamid, tiadinil;
Carboxin (carboxin), oxycarboxin, thifluzamide, penthiopyrad, boscalid, isothianil, bixafen, 3- (difluoromethyl) -1-methyl-N- [(1RS, 4SR, 9RS) -1,2,3,4-Tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl] pyrazole-4-carboxamide and 3- (difluoromethyl) -1-methyl- Of a mixture of N-[(1RS, 4SR, 9SR) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl] pyrazole-4-carboxamide (isopyrazam) Such anilide compounds;
Piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox;
Carbinol compounds such as fenarimol, flutriafol;
Piperidine-based compounds such as fenpropidine;
Morpholine compounds such as fenpropimorph, spiroxamine, tridemorph;
　フェンチンヒドロキシド（fentin　hydroxide）、フェンチンアセテート（fentin　acetate）のような有機スズ系化合物；
　ペンシキュロン（pencycuron）のような尿素系化合物；
　ジメトモルフ（dimethomorph）、フルモルフ（flumorph）のようなシンナミック酸系化合物；
　ジエトフェンカルブ（diethofencarb）のようなフェニルカーバメート系化合物；
　フルジオキソニル（fludioxonil）、フェンピクロニル（fenpiclonil）のようなシアノピロール系化合物；
　アゾキシストロビン（azoxystrobin）、クレソキシムメチル（kresoxim‐methyl）、メトミノフェン（metominofen）、トリフロキシストロビン（trifloxystrobin）、ピコキシストロビン（picoxystrobin）、オリザストロビン（oryzastrobin）、ジモキシストロビン（dimoxystrobin）、ピラクロストロビン（pyraclostrobin）、フルオキサストロビン（fluoxastrobin）、フルアクリピリム（fluacrypyrim）のようなストロビルリン系化合物； Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Synamic acid compounds such as dimethomorph and flumorph;
Phenyl carbamate compounds such as dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, kresoxim-methyl, metominofen, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin Strobilurin compounds such as pyraclostrobin, fluoxastrobin, fluacrypyrim;
　ファモキサドン（famoxadone）のようなオキサゾリジノン系化合物；
　エタボキサム（ethaboxam）のようなチアゾールカルボキサミド系化合物；
　シルチオファム（silthiopham）のようなシリルアミド系化合物；
　イプロバリカルブ（iprovalicarb）、ベンチアバリカルブ－イソプロピル（benthiavalicarb-isopropyl）、メチル[S-(R,S)]-[3-(N-イソプロポキシカルボニルバリニル)-アミノ]-3-(4-クロロ-フェニル)プロパオネート（バリフェナール (valiphenal)）のようなアミノアシッドアミドカーバメート系化合物；
　フェナミドン（fenamidone）のようなイミダゾリジン系化合物；
　フェンヘキサミド（fenhexamid）のようなハイドロキシアニリド系化合物；
　フルスルファミド（flusulfamide）のようなベンゼンスルホンアミド系化合物；
　シフルフェナミド（cyflufenamid）のようなオキシムエーテル系化合物；
　フェノキサニル（fenoxanil）のようなフェノキシアミド系化合物；
　バリダマイシン（validamycin）、カスガマイシン（kasugamycin）、ポリオキシン(polyoxins)のような抗生物質；
　イミノクタジン（iminoctadine）、ドディン(dodine)のようなグアニジン系化合物；
　6-ターシャリーブチル-8-フルオロ-2,3-ジメチルキノリン-4-イル アセテートのような４－キノリノール誘導体化合物；
　2-(2-フルオロ-5-(トリフルオロメチル)フェニルチオ)-2-(3-(2-メトキシフェニル)チアゾリジン-2-イリデン)アセトニトリルのようなシアノメチレン系化合物； Oxazolidinone compounds such as famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Silylamide compounds such as silthiopham;
Iprovalicarb, Benthiavalicarb-isopropyl, methyl [S- (R, S)]-[3- (N-isopropoxycarbonylvalinyl) -amino] -3- (4-chloro Aminoacid amide carbamate compounds such as -phenyl) propionate (valiphenal);
Imidazolidine compounds such as fenamidone;
Hydroxyanilide compounds such as fenhexamid;
Benzenesulfonamide compounds such as flusulfamide;
Oxime ether compounds such as cyflufenamid;
Phenoxyamide compounds such as fenoxanil;
Antibiotics such as validamycin, kasugamycin, polyoxins;
Guanidine compounds such as iminoctadine and dodine;
4-quinolinol derivative compounds such as 6-tertiarybutyl-8-fluoro-2,3-dimethylquinolin-4-yl acetate;
Cyanomethylene compounds such as 2- (2-fluoro-5- (trifluoromethyl) phenylthio) -2- (3- (2-methoxyphenyl) thiazolidine-2-ylidene) acetonitrile;
　また、その他の化合物として、イソプロチオラン（isoprothiolane）、ピロキロン（Pyroquilon）、ジクロメジン（diclomezine）、キノキシフェン（quinoxyfen）、プロパモカルブ塩酸塩（propamocarb　hydrochloride）、クロルピクリン（chloropicrin）、ダゾメット（dazomet）、メタムナトリウム塩（metam‐sodium）、ニコビフェン（nicobifen）、メトラフェノン（metrafenone）、MTF-753、UBF-307、ジクロシメット（diclocymet）、プロキンアジド（proquinazid）、アミスルブロム（amisulbrom）、ピリベンカルブ（pyribencarb）、マンジプロパミド（mandipropamid）、フルオピコリド(fluopicolide)、カルプロパミド（carpropamid）、メプチルジノカップ（meptyldinocap）、フルオピラム(fluopyram)、BCF051、BCM061、BCM062；などが挙げられる。 As other compounds, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, metam sodium salt ( metam-sodium, nicobifen, metrafenone, MTF-753, UBF-307, diclocymet, proquinazid, amisulbrom, pyribencarb, mandipropamid, flupropamide fluopicolide), carpropamid, meptyldinocap, fluopyram, BCF051, BCM061, BCM062; and the like.
　その他、本発明化合物と混用或いは併用することが可能な農薬としては、例えば、The Pesticide Manual（第14版）に記載されているような除草剤の有効成分化合物、特に土壌処理型のものなどがある。 Other pesticides that can be used in combination with or combined with the compounds of the present invention include, for example, active ingredient compounds of herbicides such as those described in The な ど Pesticide Manual (14th edition), especially those of soil treatment type. is there.
　動物寄生生物防除剤としては、例えば、宿主動物の体表（背、腋下、下腹部、内股部など）に寄生する外部寄生生物や、宿主動物の体内（胃、腸管、肺、心臓、肝臓、血管、皮下、リンパ組織など）に寄生する内部寄生生物の防除に有効であるが、中でも、外部寄生生物の防除に有効である。 Examples of animal parasite control agents include ectoparasites that parasitize on the body surface of the host animal (back, armpit, lower abdomen, inner thigh, etc.) and the host animal body (stomach, intestinal tract, lung, heart, liver). , Vascular, subcutaneous, lymphoid tissue, etc.) are effective in controlling endoparasites, and in particular, are effective in controlling ectoparasites.
　外部寄生生物としては、例えば、動物寄生性のダニやノミなどが挙げられる。これらの種類は非常に多く、全てを列記することが困難であるので、その一例を挙げる。 Examples of ectoparasites include animal parasitic mites and fleas. There are so many of these types that it is difficult to list them all.
　動物寄生性のダニとしては、例えばオウシマダニ（Boophilus microplus）、クリイロコイタマダニ（Rhipicephalus sanguineus）、フタトゲチマダニ（Haemaphysalis longicornis）、キチマダニ（Haemaphysalis flava）、ツリガネチマダニ（Haemaphysalis campanulata）、イスカチマダニ（Haemaphysalis concinna）、ヤマトチマダニ（Haemaphysalis japonica）、ヒゲナガチマダニ（Haemaphysalis kitaokai）、イヤスチマダニ（Haemaphysalis ias）、ヤマトマダニ（Ixodes ovatus）、タネガタマダニ（Ixodes nipponensis）、シュルツェマダニ（Ixodes persulcatus）、タカサゴキララマダニ（Amblyomma testudinarium）、オオトゲチマダニ（Haemaphysalis megaspinosa）、アミノカクマダニ（Dermacentor reticulatus）、タイワンカクマダニ（Dermacentor taiwanesis）のようなマダニ類；ワクモ（Dermanyssus gallinae）；トリサシダニ（Ornithonyssus sylviarum）、ミナミトリサシダニ（Ornithonyssus bursa）のようなトリサシダニ類；ナンヨウツツガムシ（Eutrombicula wichmanni）、アカツツガムシ（Leptotrombidium akamushi）、フトゲツツガムシ（Leptotrombidium pallidum）、フジツツガムシ（Leptotrombidium fuji）、トサツツガムシ（Leptotrombidium tosa）、ヨーロッパアキダニ（Neotrombicula autumnalis）、アメリカツツガムシ（Eutrombicula alfreddugesi）、ミヤガワタマツツガムシ（Helenicula miyagawai）のようなツツガムシ類；イヌツメダニ（Cheyletiella yasguri）、ウサギツメダニ（Cheyletiella parasitivorax）、ネコツメダニ（Cheyletiella blakei）のようなツメダニ類；ウサギキュウセンダニ（Psoroptes cuniculi）、ウシショクヒダニ（Chorioptes bovis）、イヌミミヒゼンダニ（Otodectes cynotis）、ヒゼンダニ（Sarcoptes scabiei）、ネコショウセンコウヒゼンダニ（Notoedres cati）のようなヒゼンダニ類；イヌニキビダニ（Demodex canis）のようなニキビダニ類などが挙げられる。中でも、式（I）の化合物を含有する動物寄生生物防除剤は、マダニ類などの防除に特に有効である。 The animal parasitic mites, for example Boophilus microplus (Boophilus microplus), Rhipicephalus sanguineus (Rhipicephalus sanguineus), Haemaphysalis longicornis (Haemaphysalis longicornis), Haemaphysalis flava (Haemaphysalis flava), Adenophora chima tick (Haemaphysalis campanulata), Isukachimadani (Haemaphysalis concinna), Yamatochimadani (Haemaphysalis japonica), H. kitaokai (Haemaphysalis kitaokai), Iyasuchimadani (Haemaphysalis ias), Ixodes ovatus (Ixodes ovatus), I. nipponensis (Ixodes nipponensis), Schulze ticks (Ixodes persulcatus), Takasago testudinarium (Amblyomma testudinarium), Ootogechimadani (Haemaphysalis megaspinosa ), tick such as Dermacentor reticulatus , Dermacentor taiwanesis ; duck ( Dermanyssus gallinae ); Shidani (Ornithonyssus sylviarum), Torisashidani, such as Southern tri sand mite (Ornithonyssus bursa); Nan iodine tsutsugamushi (Eutrombicula wichmanni), red mites (Leptotrombidium akamushi), L. pallidum (Leptotrombidium pallidum), Fuji chiggers (Leptotrombidium fuji), Tosa mites ( Leptotrombidium tosa), Europe Aki mites (Neotrombicula autumnalis), the United States chiggers (Eutrombicula alfreddugesi), chiggers, such as Miyagawa Tama chiggers (Helenicula miyagawai); Inutsumedani (Cheyletiella yasguri), rabbit Tsumedani (Cheyletiella parasitivorax), Nekotsumedani (Cheyletiella blakei) Tsumedani, such as; rabbits 9,000 mite (Psoroptes cuniculi), Ushishokuhidani (Chorioptes bovis), dog ear mites (Otodectes cynotis), mange mites (Sar coptes scabiei ), mite mites like Notoedres cati ; mite mites like Demodex canis , and the like. Among them, the animal parasite control agent containing the compound of the formula (I) is particularly effective for controlling ticks and the like.
　ノミとしては、例えば、ノミ目（Siphonaptera）に属する外部寄生性無翅昆虫、より具体的には、ヒトノミ科（Pulicidae）、ナガノミ科（Ceratephyllus）などに属するノミ類が挙げられる。ヒトノミ科に属するノミ類としては、例えば、イヌノミ（Ctenocephalides canis）、ネコノミ（Ctenocephalides felis）、ヒトノミ（Pulex irritans）、ニワトリフトノミ（Echidnophaga gallinacea）、ケオプスネズミノミ（Xenopsylla cheopis）、メクラネズミノミ（Leptopsylla segnis）、ヨーロッパネズミノミ（Nosopsyllus fasciatus）、ヤマトネズミノミ（Monopsyllus anisus）などが挙げられる。中でも、式（I）の化合物を含有する動物寄生生物防除剤は、ヒトノミ科に属するノミ類、特にイヌノミ、ネコノミなどの防除に有効である。 Examples of fleas include ectoparasite worms belonging to the order Flea ( Siphonaptera ), and more specifically fleas belonging to the family Flea family ( Pulicidae ), Nagano family ( Ceratephyllus ) and the like. Examples of fleas belonging to the family flea family include, for example, dog fleas ( Ctenocephalides canis ), cat fleas ( Ctenocephalides felis ), human fleas ( Purex irritans ), elephant fleas ( Echidnophaga gallinacea ), keops mouse fleas ( Xenopsylla cheopis ) Leptopsylla segnis ), European mud minnow ( Nosopsyllus fasciatus ), and Yamato mud mink ( Monopsyllus anisus ). Among them, the animal parasite control agent containing the compound of the formula (I) is effective for controlling fleas belonging to the family flea family, especially dog fleas, cat fleas and the like.
　その他の外部寄生生物としては、例えば、ウシジラミ、ウマジラミ、ヒツジジラミ、ウシホソジラミ、アタマジラミのようなシラミ類；イヌハジラミのようなハジラミ類；ウシアブ、ウアイヌカカ、ツメトゲブユのような吸血性双翅目害虫などが挙げられる。また、内部寄生生物としては、例えば、肺虫、ベンチュウ、結節状ウオーム、胃内寄生虫、回虫、糸状虫類のような線虫類；マンソン裂頭条虫、広節裂頭条虫、瓜実条虫、多頭条虫、単包条虫、多包条虫のような条虫類；日本住血吸虫、肝蛭のような吸虫類；コクシジウム、マラリア原虫、腸内肉胞子虫、トキソプラズマ、クリプトスポリジウムのような原生動物など；が挙げられる。 Other ectoparasites include, for example, lice such as bovine lice, foal lice, sheep lice, bovine white lice, head lice; lice such as dog lice; blood-sucking dipterous pests such as bovine abs, quail sharks, . In addition, examples of endoparasites include nematodes such as lungworms, benthic worms, tuberous worms, gastric parasites, roundworms, and filamentous worms; Tapeworms such as real tapeworms, multi-headed tapeworms, single-banded tapeworms, multi-banded tapeworms; Japanese schistosomiasis, fluke like liver fluke; coccidium, malaria parasite, intestinal granulocyst, toxoplasma, chestnut Protozoa such as Ptosporidium, and the like.
　宿主動物としては、種々の愛玩動物、家畜、家禽などが挙げられ、より具体的には、イヌ、ネコ、マウス、ラット、ハムスター、モルモット、リス、ウサギ、フェレット、鳥（例えば、ハト、オウム、九官鳥、文鳥、インコ、ジュウシマツ、カナリアなど）、ウシ、ウマ、ブタ、ヒツジ、アヒル、ニワトリ、などが挙げられる。中でも、式（I）の化合物を含有する動物寄生生物防除剤は、愛玩動物又は家畜に寄生する有害生物、特に外部寄生生物の防除に有効である。愛玩動物又は家畜の中ではイヌ、ネコ、ウシ又はウマに特に有効である。 Examples of host animals include various pet animals, livestock, poultry, etc., and more specifically dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (eg, pigeons, parrots, (E.g., nine-bird, bird, parakeet, juvenile pine, canary, etc.), cattle, horses, pigs, sheep, ducks, chickens, etc. Among them, the animal parasite control agent containing the compound of the formula (I) is effective for controlling pests parasitic on pet animals or livestock, particularly ectoparasites. Among pet animals or domestic animals, it is particularly effective for dogs, cats, cows or horses.
　式（I）の化合物を動物寄生生物防除剤として使用する際、そのまま使用してもよく、また、適当な補助剤と共に粉剤、粒剤、錠剤、散剤、カプセル剤、液状剤、乳剤、水性懸濁剤、油性懸濁剤などの種々の形態に製剤して使用することもできる。尚、前記製剤形態以外にも、本発明の目的に適合するかぎり、通常の当該分野で用いられているあらゆる製剤形態にすることができる。製剤に使用する補助剤としては、前記した農園芸用有害生物防除剤の製剤用補助剤として例示した陰イオン系の界面活性剤や非イオン系の界面活性剤；セチルトリメチルアンモニウムブロミドのような陽イオン系の界面活性剤；水、アセトン、アセトニトリル、Ｎ－メチルアセトアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ,Ｎ－ジメチルホルムアミド、２-ピロリドン、Ｎ-メチル-２-ピロリドン、ケロシン、トリアセチン、メタノール、エタノール、イソプロパノール、ベンジルアルコール、エチレングリコール、プロピレングリコール、ポリエチレングリコール、液体ポリオキシエチレングリコール、ブチルジグリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールノルマルブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールノルマルブチルエーテルのような溶剤；ブチルヒドロキシアニソール、ブチルヒドロキシトルエン、アスコルビン酸、メタ亜硫酸水素ナトリウム、プロピル没食子酸塩、チオ硫酸ナトリウムのような酸化防止剤；ポリビニルピロリドン、ポリビニルアルコール、酢酸ビニルとビニルピロリドンのコポリマーのような被膜形成剤；前記した農園芸用有害生物防除剤の製剤用補助剤として例示した植物油や鉱物油；乳糖、蔗糖、ブドウ糖、澱粉、麦粉、コーン粉、大豆油粕、脱脂米糠、炭酸カルシウム、その他市販の飼料原料のような担体；などが挙げられる。これら補助剤の各成分は、本発明の目的から逸脱しないかぎり、１種又は２種以上を適宜選択して使用することができる。また、前記した補助剤以外にも当該分野で知られたものの中から適宜選択して使用することもでき、更には、前記した農園芸分野で使用される各種補助剤などから適宜選択して使用することもできる。 When the compound of the formula (I) is used as an animal parasite control agent, it may be used as it is, and together with suitable adjuvants, powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions. It can also be formulated and used in various forms such as a suspending agent and an oily suspension. In addition to the above-mentioned preparation forms, any preparation forms used in the normal field can be used as long as the object of the present invention is met. Examples of the adjuvant used in the preparation include anionic surfactants and nonionic surfactants exemplified as the above-mentioned preparation adjuvants for agricultural and horticultural pest control agents; positive agents such as cetyltrimethylammonium bromide. Ionic surfactants: water, acetone, acetonitrile, N-methylacetamide, N, N-dimethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, kerosene, triacetin, methanol, Ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl Solvents such as ether, diethylene glycol normal butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol normal butyl ether; oxidations such as butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium metabisulfite, propyl gallate, sodium thiosulfate Inhibitors; Film forming agents such as polyvinylpyrrolidone, polyvinyl alcohol, vinyl acetate and vinylpyrrolidone copolymers; vegetable oils and mineral oils exemplified as preparations for the aforementioned agricultural and horticultural pest control agents; lactose, sucrose, glucose , Starch, wheat flour, corn flour, soybean oil cake, defatted rice bran, calcium carbonate, and other carriers such as commercially available feed materials. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the field, and further, selected from various adjuvants used in the above-mentioned agricultural and horticultural fields. You can also
　式（I）の化合物と各種補助剤との配合割合（重量比）は、通常、0.1：99.9～90：10程度である。これら製剤の実際の使用に際しては、そのまま使用するか、又は水等の希釈剤で所定濃度に希釈し、必要に応じて各種展着剤（界面活性剤、植物油、鉱物油など）を添加して使用することができる。 The compounding ratio (weight ratio) of the compound of formula (I) and various adjuvants is usually about 0.1: 99.9 to 90:10. In actual use of these preparations, use them as they are, or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.
　宿主動物への式（I）の化合物の投与は、経口又は非経口によって行われる。経口投与法としては、例えば式（I）の化合物を含有する錠剤、液状剤、カプセル剤、ウエハース、ビスケット、ミンチ肉、その他の飼料等を投与する方法などが挙げられる。非経口投与方法としては、例えば式（I）の化合物を適当な製剤に調製した上で、静注投与、筋肉内投与、皮内投与、皮下投与等により体内に取り込ませる方法；スポットオン（spot-on）処理、ポワオン（pour-on）処理、スプレー処理等により体表面に投与する方法；宿主動物の皮下に式（I）の化合物を含有する樹脂片等を埋め込む方法などが挙げられる。 Administration of the compound of formula (I) to the host animal is performed orally or parenterally. Examples of the oral administration method include a method of administering tablets, liquid agents, capsules, wafers, biscuits, minced meat, and other feeds containing the compound of formula (I). As a parenteral administration method, for example, a compound of formula (I) is prepared into an appropriate formulation and then taken into the body by intravenous administration, intramuscular administration, intradermal administration, subcutaneous administration, etc .; spot-on (spot -on) treatment, pour-on treatment, spray treatment, and the like; and a method of embedding a resin piece containing the compound of formula (I) under the skin of a host animal.
　宿主動物への式（I）の化合物の投与量は、投与方法、投与目的、疾病症状等によって異なるが、通常、宿主動物の体重１Kgに対して０.０１ｍｇ～１００ｇ、望ましくは０.１mg～１０ｇの割合で投与するのが適当である。 The dose of the compound of formula (I) to the host animal varies depending on the administration method, administration purpose, disease symptoms, etc., but is usually 0.01 mg to 100 g, preferably 0.1 mg to 1 kg body weight of the host animal. It is appropriate to administer at a rate of 10 g.
　本発明には、前記したような投与方法又は投与量による有害生物の防除方法、特に外部寄生生物又は内部寄生生物の防除方法も含まれる。 The present invention includes a method for controlling pests according to the administration method or dosage as described above, particularly a method for controlling ectoparasites or endoparasites.
　また、本発明においては、前述のようにして動物寄生性の有害生物を防除することにより、それらに起因する宿主動物の各種疾患を予防又は治療できる場合がある。このように、本発明には、式（I）の化合物を有効成分として含有する寄生生物起因動物疾患の予防又は治療剤並びに、寄生生物起因動物疾患を予防又は治療する方法も含まれる。 Further, in the present invention, there are cases where various diseases of host animals caused by them can be prevented or treated by controlling animal parasitic pests as described above. Thus, the present invention includes a prophylactic or therapeutic agent for parasite-derived animal diseases containing the compound of formula (I) as an active ingredient, and a method for preventing or treating parasite-derived animal diseases.
　式（I）の化合物を動物寄生生物防除剤として使用する際、補助剤と共に各種ビタミン類、ミネラル類、アミノ酸類、栄養剤、酵素製剤、解熱剤、鎮静剤、消炎剤、殺菌剤、着色剤、芳香剤、保存剤等と混用又は併用することができる。また、必要に応じて他の各種動物薬や農薬、例えば駆虫剤、抗コクシジウム剤、殺虫剤、殺ダニ剤、殺ノミ剤、殺線虫剤、殺菌剤、抗菌剤などと混用又は併用することができ、この場合に一層優れた効果を示すこともある。本発明には、前記したような各種成分を混用又は併用した混合有害生物防除用組成物が含まれ、また、それを使用した有害生物の防除方法、特に外部寄生生物又は内部寄生生物の防除方法も含まれる。 When using the compound of formula (I) as an animal parasite control agent, various vitamins, minerals, amino acids, nutrients, enzyme preparations, antipyretics, sedatives, anti-inflammatory agents, fungicides, coloring agents, It can be mixed with or used in combination with a fragrance, a preservative and the like. Also, if necessary, mix or use with other animal drugs and pesticides such as anthelmintics, anticoccidials, insecticides, acaricides, fleas, nematicides, fungicides, antibacterials, etc. In this case, a more excellent effect may be exhibited. The present invention includes a composition for controlling mixed pests in which various components as described above are mixed or used together, and a method for controlling pests using the composition, particularly a method for controlling ectoparasites or endoparasites. Is also included.
　次に本発明の望ましい態様の一例を記載するが、本発明はこれらに限定して解釈されるものではない。
　（１）式（I）中、Ｒ1が水素原子、Ａで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、Ｃ＝ＮＯＲ２、Ｃ＝ＮＮＲ4Ｒ5、ＣＯＲ２、ＣＯＯＲ２、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、Ｎ３又はＣＯＮＲ4Ｒ5であり；Ｘがアルキル、ヒドロキシアルキル、アルケニル、アルキニル、アリール、ハロゲン、ハロアルキル、シアノ、ニトロ、ＮＲ4Ｒ5、Ｓ(Ｏ)nＲ3、ＯＲ2、ＣＯＲ２又はＣＯＯＲ２であり；Ｙが水素原子又はフッ素原子であり；ＺがＣＨ、ＣＸ又はＮであり；Ａがハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、アルキル、シクロアルキル、アリール、複素環基、ＳＣＨ２ＣＯＯＲ２ 、ＮＨＮＲ4Ｒ5 、ＣＯＯＲ２、ニトロ又は－ＣＨ（ＣＮ）2であり；Ｒ2が水素原子、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシアルキル、アセチル又はアリールであり；Ｒ3がアルキル又はアセチルであり；Ｒ4が水素原子又はアルキルであり；Ｒ5が水素原子、アルキル、ハロアルキル、ＣＯＲ２、ＣＯＯＲ２、ＣＨ２ＣＨ２ＯＲ2又はシアノアルキルであり；ｍが１～４の整数であり；ｎが０～２の整数であるトリアゾロピリミジン誘導体又はその塩を有効成分として含有する有害生物防除剤。 Next, although an example of the desirable mode of the present invention is described, the present invention is not limited to these.
(1) In formula (I), R 1 is a hydrogen atom, alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, optionally substituted with A Alkynyl, halogen, cyano, aryl optionally substituted with halogen, heterocyclic group optionally substituted with alkyl, C═NOR 2 , C═NNR 4 R 5 , COR 2 , COOR 2 , OR 2 , S (O ) n R 3 , NR 4 R 5 , N 3 or CONR 4 R 5 ; X is alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, NR 4 R 5 , S (O) n R 3 , OR 2 , COR 2 or COOR 2 ; Y is a hydrogen atom or a fluorine atom; Z is CH, CX or N; A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5, cyano, A Kill, cycloalkyl, aryl, heterocyclic group, SCH 2 COOR 2, NHNR 4 R 5, COOR 2, a nitro or -CH (CN) 2; R 2 is a hydrogen atom, an alkyl, alkenyl, alkynyl, haloalkyl, alkoxy R 3 is alkyl or acetyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl, haloalkyl, COR 2 , COOR 2 , CH 2 CH 2 OR 2 or A pest control agent comprising, as an active ingredient, a triazolopyrimidine derivative or a salt thereof, which is cyanoalkyl; m is an integer of 1 to 4; and n is an integer of 0 to 2.
　（２）式（I）中、Ｒ1がＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ＯＲ2、Ｓ(Ｏ)nＲ3又はＮＲ4Ｒ5であり；Ｘがアルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、シアノ又はニトロであり；Ａがハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、シクロアルキル、アリール又は複素環基であり；Ｒ2が水素原子、アルキル、アルケニル、アルキニル、ハロアルキル又はアリールであるトリアゾロピリミジン誘導体又はその塩を有効成分として含有する有害生物防除剤。なお、Ｒ3、Ｒ４、Ｒ５、Ｙ、Ｚ、ｍ及びｎは上記（１）と同義である。 (2) In formula (I), R 1 is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen , Cyano, OR 2 , S (O) n R 3 or NR 4 R 5 ; X is alkyl, alkenyl, alkynyl, halogen, haloalkyl, cyano or nitro; A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5 , cyano, cycloalkyl, aryl or a heterocyclic group; R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl or aryl, a triazolopyrimidine derivative or a salt thereof as an active ingredient Contains pest control agents. R 3 , R 4 , R 5 , Y, Z, m, and n have the same meanings as (1) above.
　（３）式（I－α）中、Ｒ1αがＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ＯＲ2又はＳ(Ｏ)nＲ3であり；Ｘがアルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、シアノ又はニトロであり；Ａがハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、シクロアルキル、アリール又は複素環基であり；Ｒ2が水素原子、アルキル、アルケニル、アルキニル、ハロアルキル又はアリールであり；ｍが２～４の整数であるトリアゾロピリミジン誘導体又はその塩。なお、Ｒ3、Ｒ４、Ｒ５、Ｙ、Ｚ、及びｎは上記（１）と同義である。 (3) In formula (I-α), R 1α is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A , Halogen, cyano, OR 2 or S (O) n R 3 ; X is alkyl, alkenyl, alkynyl, halogen, haloalkyl, cyano or nitro; A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5 , cyano, cycloalkyl, aryl or heterocyclic group; R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl or aryl; and m is an integer of 2 to 4, a triazolopyrimidine derivative Or its salt. R 3 , R 4 , R 5 , Y, Z, and n are as defined in (1) above.
　（４）式（I－α）中、Ｒ1αがＡで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、Ｃ＝ＮＯＲ２、Ｃ＝ＮＮＲ4Ｒ5、ＣＯＲ２、ＣＯＯＲ２、ＯＲ2、Ｓ(Ｏ)nＲ3又はＣＯＮＲ4Ｒ5であり；Ｘがアルキル、ヒドロキシアルキル、アルケニル、アルキニル、アリール、ハロゲン、ハロアルキル、シアノ、ニトロ、ＮＲ4Ｒ5、Ｓ(Ｏ)nＲ3、ＯＲ2、ＣＯＲ２、ＣＯＯＲ２又はＣＯＮＲ4Ｒ5であり；Ｙが水素原子又はフッ素原子であり；ＺがＣＨ、ＣＸ又はＮであり；Ａがハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、アルキル、シクロアルキル、アリール、複素環基、ＳＣＨ２ＣＯＯＲ２ 、ＮＨＮＲ4Ｒ5 、ＣＯＯＲ２、ニトロ又は－ＣＨ（ＣＮ）2であり；Ｒ2が水素原子、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシアルキル、アセチル又はアリールであり；Ｒ3がアルキル又はアセチルであり；Ｒ4が水素原子又はアルキルであり；Ｒ5が水素原子、アルキル、ハロアルキル、ＣＯＲ２、ＣＯＯＲ２、ＣＨ２ＣＨ２ＯＲ2又はシアノアルキルであり；ｍが１～４の整数であり；ｎが０～２の整数であるトリアゾロピリミジン誘導体又はその塩。 (4) In the formula (I-α), R 1α is substituted with cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano, halogen It may be aryl, alkyl which may be substituted heterocyclic group, at C = NOR 2, C = NNR 4 R 5, COR 2, COOR 2, oR 2, S (O) n R 3 or CONR 4 R 5 There; X is alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, in NR 4 R 5, S (O ) n R 3, oR 2, COR 2, COOR 2 or CONR 4 R 5 Y; hydrogen atom or fluorine atom; Z is CH, CX or N; A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5 , cyano, alkyl, cycloalkyl, aryl , Heterocycle The group SCH 2 COOR 2 , NHNR 4 R 5 , COOR 2 , nitro or —CH (CN) 2 ; R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, acetyl or aryl; R 3 is alkyl or acetyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl, haloalkyl, COR 2 , COOR 2 , CH 2 CH 2 OR 2 or cyanoalkyl; A triazolopyrimidine derivative or a salt thereof, wherein n is an integer of 4, and n is an integer of 0 to 2.
　次に本発明の実施例を記載するが、本発明はこれらに限定して解釈されるものではない。まず、式（I）の化合物の合成例を記載する。
合成例１
　７－[２－クロロ－５－(トリフルオロメチル)フェニル]－５－メチル[１,２,４]トリアゾロ[１,５－ａ]ピリミジン（化合物No．１８）の合成
　(1) ２－クロロ－５－トリフルオロメチル安息香酸メチル１．１９ｇ、アセトン２ｍｌ及びテトラヒドロフラン１０ｍｌの混合溶液を氷冷し、固体のナトリウムエトキシド４３２ｍｇを少しずつ加えた。反応混合物を室温まで昇温し、３０分間攪拌した。反応終了後、反応液に希塩酸を加えて酸性とした後、酢酸エチルで２回抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加えて乾燥した。溶媒を減圧下に留去し、得られた残渣をシリカゲルクロマトグラフィー（溶離液：ｎ－ヘキサン／酢酸エチル＝８／１（体積比、以下同様である。））で精製し、１－[２－クロロ－５－(トリフルオロメチル)フェニル]ブタン－１，３-ジオン（中間体No.ＶII－1）１．３３ｇを淡褐色の油状物として得た。
　(2)前工程(1)で得た化合物（中間体No.ＶII－1）１．３３ｇと酢酸１０ｍｌの混合溶液に３－アミノ－１Ｈ－１,２,４－トリアゾール５００ｍｇを加え、約１００℃の温度で、７時間加熱した。反応終了後、溶媒を減圧下に留去し、得られた残渣をシリカゲルクロマトグラフィー（溶離液：ｎ－ヘキサン／酢酸エチル＝３／２）で精製し、目的物１．３６ｇを淡黄色結晶として得た。 Next, examples of the present invention will be described, but the present invention should not be construed as being limited thereto. First, synthesis examples of the compound of formula (I) will be described.
Synthesis example 1
Synthesis of 7- [2-chloro-5- (trifluoromethyl) phenyl] -5-methyl [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 18) (1) 2-Chloro A mixed solution of 1.19 g of methyl -5-trifluoromethylbenzoate, 2 ml of acetone and 10 ml of tetrahydrofuran was ice-cooled, and 432 mg of solid sodium ethoxide was added little by little. The reaction mixture was warmed to room temperature and stirred for 30 minutes. After completion of the reaction, the reaction solution was acidified with dilute hydrochloric acid and extracted twice with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (eluent: n-hexane / ethyl acetate = 8/1 (volume ratio, the same applies hereinafter)) to give 1- [2 1.33 g of -chloro-5- (trifluoromethyl) phenyl] butane-1,3-dione (intermediate No. VII-1) was obtained as a pale brown oil.
(2) To a mixed solution of 1.33 g of the compound obtained in the previous step (1) (Intermediate No. VII-1) and 10 ml of acetic acid, 500 mg of 3-amino-1H-1,2,4-triazole was added, and about 100 Heated at a temperature of 7 ° C. for 7 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (eluent: n-hexane / ethyl acetate = 3/2) to give 1.36 g of the desired product as pale yellow crystals. Obtained.
合成例２
　５－クロロ－７－[２－クロロ－４－(トリフルオロメチル)フェニル][１,２,４]トリアゾロ［１，５－ａ］ピリミジン（化合物No．２１）の合成
　(1)５，７－ジヒドロキシ[１,２,４]トリアゾロ[１，５－ａ]ピリミジン９１９ｍｇとオキシ塩化リン３ｍｌとを混合した懸濁液を３時間還流した。反応終了後、得られた透明な反応液から過剰のオキシ塩化リンを留去した後、１０ｍｌの氷水を注意深く添加し、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加えて乾燥した後、溶媒を留去した。得られた残渣をシリカゲルクロマトグラフィー（溶離液：ｎ－ヘキサン／酢酸エチル＝１／１）で精製し、５，７－ジクロロ[１,２,４]トリアゾロ[１,５－ａ]ピリミジン４５６ｍｇを黄色結晶として得た。
　(2)１，４－ジオキサン５ｍｌ及び２規定炭酸ナトリウム水溶液１．５ｍｌの混合溶液に、前工程(1)で得た５，７－ジクロロ[１,２,４]トリアゾロ[１，５－ａ]ピリミジン３００ｍｇ、２－クロロ－４－トリフルオロメチルフェニルボロン酸１７８ｍｇ及びテトラキス(トリフェニルホスフィン)パラジウム３０ｍｇを加え、約８０℃の温度で、１時間加熱した。反応終了後、反応混合物を室温まで冷却し、水を５ｍｌ加えた後、酢酸エチルで２回抽出した。有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加えて乾燥した後、溶媒を減圧下に留去した。得られた残渣をシリカゲルクロマトグラフィー（溶離液：ｎ－ヘキサン／酢酸エチル＝２／１）で精製し、目的物８１ｍｇを油状物質として得た。 Synthesis example 2
Synthesis of 5-chloro-7- [2-chloro-4- (trifluoromethyl) phenyl] [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 21) (1) 5,7 A suspension of 919 mg of dihydroxy [1,2,4] triazolo [1,5-a] pyrimidine and 3 ml of phosphorus oxychloride was refluxed for 3 hours. After completion of the reaction, excess phosphorus oxychloride was distilled off from the obtained transparent reaction solution, 10 ml of ice water was carefully added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The obtained residue was purified by silica gel chromatography (eluent: n-hexane / ethyl acetate = 1/1) to obtain 456 mg of 5,7-dichloro [1,2,4] triazolo [1,5-a] pyrimidine. Obtained as yellow crystals.
(2) To a mixed solution of 5 ml of 1,4-dioxane and 1.5 ml of 2N aqueous sodium carbonate solution, the 5,7-dichloro [1,2,4] triazolo [1,5-a obtained in the previous step (1) was added. ] 300 mg of pyrimidine, 178 mg of 2-chloro-4-trifluoromethylphenylboronic acid and 30 mg of tetrakis (triphenylphosphine) palladium were added and heated at a temperature of about 80 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, 5 ml of water was added, and the mixture was extracted twice with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel chromatography (eluent: n-hexane / ethyl acetate = 2/1) to obtain 81 mg of the desired product as an oily substance.
合成例３
　５－メチルアミノ－７－[２－クロロ－４－(トリフルオロメチル)フェニル][１,２,４]トリアゾロ[１,５－ａ]ピリミジン（化合物No．２３）の合成
　５－クロロ－７－[２－クロロ－４－(トリフルオロメチル)フェニル][１,２,４]トリアゾロ[１,５－ａ]ピリミジン（化合物Ｎｏ．２１）８３ｍｇとテトラヒドロフラン２ｍｌの混合溶液にメチルアミンの４０質量％水溶液０．５ｍｌを加えた後、室温で１時間攪拌した。反応終了後、溶媒を減圧下に留去し、得られた残渣をシリカゲルクロマトグラフィー（溶離液：ｎ－ヘキサン／酢酸エチル＝１／１）で精製し、目的物３１ｍｇを薄い褐色結晶として得た。 Synthesis example 3
Synthesis of 5-methylamino-7- [2-chloro-4- (trifluoromethyl) phenyl] [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 23) 5-Chloro-7 40 masses of methylamine in a mixed solution of 83 mg of [2-chloro-4- (trifluoromethyl) phenyl] [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 21) and 2 ml of tetrahydrofuran A 0.5% aqueous solution was added, followed by stirring at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (eluent: n-hexane / ethyl acetate = 1/1) to obtain 31 mg of the desired product as light brown crystals. .
合成例４
　７－[２－クロロ－６－(トリフルオロメチル)ピリジン－３－イル]－５－メチル[１,２,４]トロアゾロ[１,５－ａ]ピリミジン（化合物No．２９）の合成
　(1)３－アセチル－２－クロロ－６－(トリフルオロメチル)ピリジン１．１８ｇとＮ，Ｎ－ジメチルアセトアミドジメチルアセタール８４３ｍｇをトルエン１１ｍｌ中１００℃にて一晩反応させた。反応終了後、反応液を減圧下濃縮した後、得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘキサン/酢酸エチル＝３/７）で精製し、１－[２－クロロ－６－(トリフルオロメチル)ピリジン－３－イル]－３－(ジメチルアミノ)－２－ブテン－１－オン（中間体No.IＶ－１）５９２ｍｇを油状物として得た。
　(2)前工程(1)で得た化合物（中間体No.IＶ－１）５９２ｍｇを酢酸２ｍｌに溶解し、３－アミノ－１Ｈ－１,２,４－トリアゾール１７０ｍｇを加え一晩加熱還流した。反応終了後、反応液に水を加え、さらに酢酸エチルで抽出した。有機層を水洗後、無水硫酸マグネシウムで乾燥し、減圧下溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：酢酸エチル）で精製し、目的物４９０ｍｇを淡褐色の油状物として得た。 Synthesis example 4
Synthesis of 7- [2-chloro-6- (trifluoromethyl) pyridin-3-yl] -5-methyl [1,2,4] troazolo [1,5-a] pyrimidine (Compound No. 29) ) 1.18 g of 3-acetyl-2-chloro-6- (trifluoromethyl) pyridine and 843 mg of N, N-dimethylacetamide dimethylacetal were reacted overnight at 100 ° C. in 11 ml of toluene. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 3/7) to give 1- [2-chloro-6- 592 mg of (trifluoromethyl) pyridin-3-yl] -3- (dimethylamino) -2-buten-1-one (intermediate No. IV-1) was obtained as an oil.
(2) 592 mg of the compound (intermediate No. IV-1) obtained in the previous step (1) was dissolved in 2 ml of acetic acid, 170 mg of 3-amino-1H-1,2,4-triazole was added and the mixture was heated to reflux overnight. . After completion of the reaction, water was added to the reaction mixture, and the mixture was further extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain the desired product (490 mg) as a pale brown oil.
合成例５
　７－[２－クロロ－４－(トリフルオロメチル)フェニル]－６－フルオロ－５－メチル[１,２,４]トロアゾロ[１，５－ａ]ピリミジン（化合物No．３４）の合成
　(1)２－フルオロ－３－オキソブタン酸エチル４．２ｇを酢酸８ｍＬ中に溶解し、３－アミノ－１Ｈ－１,２,４－トリアゾール２ｇを加え１００℃にて２時間反応させた。反応液を室温に戻し析出個体をろ過し、メタノール洗浄して６－フルオロ－７－ヒドロキシ－５－メチル[１,２,４]トロアゾロ[１，５－ａ]ピリミジン（中間体No.ＸＶ－４）４０７ｍｇを白色結晶として得た。
　(2)前工程(1)で得た化合物（中間体No.ＸＶ－４）４０７ｍｇとオキシ塩化リン９ｍｌとを混合した懸濁液を３時間還流した。反応終了後、得られた透明な反応液から過剰のオキシ塩化リンを留去した後、水中に投入し、酢酸エチルで抽出した。抽出した有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加えて乾燥した後、溶媒を減圧下に留去し、得られた残渣をシリカゲルクロマトグラフィー（溶離液：ｎ－ヘキサン／酢酸エチル＝７／３）で精製し、７－クロロ－６－フルオロ－５－メチル[１,２,４]トロアゾロ[１，５－ａ]ピリミジン（中間体No.ＸＶI－4）４０７ｍｇを白色結晶として得た。
　(３)エチレングリコールジメチルエーテル６ｍｌと２規定炭酸ナトリウム水溶液１．７ｍｌの混合液に、前工程(2)で得た化合物（中間体No.ＸＶI－４）２０８ｍｇ、２-クロロ-４-(トリフルオロメチル)フェニルボロン酸２５０ｍｇ及びテトラキス(トリフェニルホスフィン)パラジウム６４ｍｇを加え、７０℃で１時間攪拌した。反応終了後、反応混合物を室温まで冷却し、水を加え酢酸エチルで抽出した。その後、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加えて乾燥した。溶媒を減圧下に留去し、得られた残渣をシリカゲルクロマトグラフィー（溶離液：ｎ－ヘキサン／酢酸エチル＝４／１）で精製し目的物５０ｍｇを白色結晶として得た。 Synthesis example 5
Synthesis of 7- [2-chloro-4- (trifluoromethyl) phenyl] -6-fluoro-5-methyl [1,2,4] troazolo [1,5-a] pyrimidine (Compound No. 34) ) 4.2 g of ethyl 2-fluoro-3-oxobutanoate was dissolved in 8 mL of acetic acid, and 2 g of 3-amino-1H-1,2,4-triazole was added and reacted at 100 ° C. for 2 hours. The reaction solution is returned to room temperature, the precipitated solid is filtered, washed with methanol, and washed with 6-fluoro-7-hydroxy-5-methyl [1,2,4] troazolo [1,5-a] pyrimidine (intermediate No. XV- 4) 407 mg was obtained as white crystals.
(2) A suspension obtained by mixing 407 mg of the compound (intermediate No. XV-4) obtained in the previous step (1) and 9 ml of phosphorus oxychloride was refluxed for 3 hours. After completion of the reaction, excess phosphorus oxychloride was distilled off from the obtained transparent reaction solution, and then poured into water and extracted with ethyl acetate. The extracted organic layer was washed with saturated brine, dried by adding anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the obtained residue was chromatographed on silica gel (eluent: n-hexane / ethyl acetate = 7/3) to obtain 407 mg of 7-chloro-6-fluoro-5-methyl [1,2,4] troazolo [1,5-a] pyrimidine (intermediate No. XVI-4) as white crystals. It was.
(3) To a mixture of 6 ml of ethylene glycol dimethyl ether and 1.7 ml of 2N aqueous sodium carbonate solution, 208 mg of the compound obtained in the previous step (2) (Intermediate No. XVI-4), 2-chloro-4- (trifluoro 250 mg of methyl) phenylboronic acid and 64 mg of tetrakis (triphenylphosphine) palladium were added and stirred at 70 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added and extracted with ethyl acetate. Thereafter, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (eluent: n-hexane / ethyl acetate = 4/1) to obtain 50 mg of the desired product as white crystals.
合成例６
　７－[２－クロロ－４－(トリフルオロメチル)フェニル]－５－シクロプロピル[１,２,４]トリアゾロ[１,５－ａ]ピリミジン（化合物No．４８）の合成
　１－[２－クロロ－４－(トリフルオロメチル)フェニル]－３－シクロプロパン－１，３-ジオン（中間体No.ＶII-3）１４５ｍｇと酢酸３ｍｌの混合溶液に３－アミノ－１Ｈ－１,２,４－トリアゾール５６ｍｇを加え、約１００℃の温度で、１２時間加熱した。反応終了後、溶媒を減圧下に留去し、得られた残渣をシリカゲルクロマトグラフィー（溶離液：ｎ－ヘキサン／酢酸エチル＝２／１）で精製し、目的物３３ｍｇを淡黄色結晶として得た。 Synthesis Example 6
Synthesis of 7- [2-chloro-4- (trifluoromethyl) phenyl] -5-cyclopropyl [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 48) 1- [2- 3-amino-1H-1,2,4 in a mixed solution of 145 mg of chloro-4- (trifluoromethyl) phenyl] -3-cyclopropane-1,3-dione (intermediate No. VII-3) and 3 ml of acetic acid -Add 56 mg of triazole and heat at a temperature of about 100 ° C. for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (eluent: n-hexane / ethyl acetate = 2/1) to obtain 33 mg of the desired product as pale yellow crystals. .
　式（I）の化合物の代表例を第１表に挙げる。これら化合物には、前記式（I－α）で表される新規化合物が含まれ、前記合成例或は前記した種々の製造方法に基づいて合成することができる。第１表中、No.は化合物No.を示し、Meはメチル、Etはエチルを、i-Prはイソプロピルを、i‐Buはイソブチルを、t-Buはターシャリーブチルを各々示し、物性として示した温度は融点である。また、第１表の物性欄がoil又はamorphousとなっている化合物につき、1H-NMR（1H-核磁気共鳴）を第２表に示す。 Representative examples of compounds of formula (I) are listed in Table 1. These compounds include novel compounds represented by the above formula (I-α), and can be synthesized based on the above synthesis examples or the various production methods described above. In Table 1, No. indicates compound No., Me indicates methyl, Et indicates ethyl, i-Pr indicates isopropyl, i-Bu indicates isobutyl, and t-Bu indicates tertiary butyl. The indicated temperature is the melting point. In addition, 1 H-NMR ( 1 H-nuclear magnetic resonance) is shown in Table 2 for compounds in which the physical property column of Table 1 is oil or amorphous.
　前記した製法[１]中の式（IＶ）の化合物の代表例を第３表に挙げる。これら化合物は、前記合成例或は前記した種々の製造方法に基づいて合成することができる。第３表中、No.は中間体No.を示し、Meはメチル、i‐Buはイソブチルを各々示す。また、第３表に記載の化合物につき、1H-NMRを第４表に示す。 Table 3 lists representative examples of the compound of the formula (IV) in the above production method [1]. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 3, No. represents intermediate No., Me represents methyl, and i-Bu represents isobutyl. Further, 1 H-NMR is shown in Table 4 for the compounds described in Table 3.
　前記した製法[５]中の式（ＸＶ）の化合物の代表例を第５表に挙げる。これら化合物は、前記合成例或は前記した種々の製造方法に基づいて合成することができる。第５表中、No.は中間体No.を示し、Meはメチル、Etはエチルを、i-Prはイソプロピルを各々示し、物性として示した温度は融点である。また、第５表の物性欄がamorphousとなっている化合物につき、1H-NMRを第６表に示す。 Table 5 shows representative examples of the compound of formula (XV) in the production method [5]. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 5, No. represents intermediate No., Me represents methyl, Et represents ethyl, i-Pr represents isopropyl, and the temperatures shown as physical properties are melting points. Table 1 shows the 1 H-NMR for the compounds whose physical properties in Table 5 are amorphous.
　前記した製法[５]中の式（ＸＶI）の化合物の代表例を第７表に挙げる。これら化合物は、前記合成例或は前記した種々の製造方法に基づいて合成することができる。第７表中、No.は中間体No.を示し、Meはメチル、Etはエチルを、i-Prはイソプロピルを各々示し、物性として示した温度は融点である。また、第７表の物性欄がsolid又はoilとなっている化合物につき、1H-NMRを第８表に示す。 Table 7 lists representative examples of the compound of formula (XVI) in the above production method [5]. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 7, No. represents intermediate No., Me represents methyl, Et represents ethyl, i-Pr represents isopropyl, and the temperatures shown as physical properties are melting points. Table 8 shows the 1 H-NMR for the compounds whose physical properties in Table 7 are solid or oil.
　前記した製法[２]中の式（ＶII）の化合物の代表例を第９表に挙げる。これら化合物は、前記合成例或は前記した種々の製造方法に基づいて合成することができる。第９表中、No.は中間体No.を示す。また、第９表に記載の化合物につき、1H-NMRを第１０表に示す。 Table 9 shows representative examples of the compound of formula (VII) in the above production method [2]. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 9, No. indicates intermediate No. Further, 1 H-NMR is shown in Table 10 for the compounds described in Table 9.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　次に試験例を記載する。
　試験例１　モモアカアブラムシに対する効果試験
　ダイコン葉を水の入った試験管に挿し、その葉上にモモアカアブラムシ１齢幼虫を約２０頭放飼した。翌日、ダイコン葉上に寄生している幼虫数を数えた後、寄生したダイコン葉を式（I）の化合物の濃度が２００ｐｐｍとなるように調整した薬液に約１０秒間浸漬処理した。薬液が風乾した後に、２５℃の照明付恒温室内に放置した。処理５日後にモモアカアブラムシの生死を判定し、下記の計算式により死虫率を求めた。尚、離脱虫及び異常虫は死亡虫とみなした。前記化合物No.13、20、32、33、48、49及び53を供試したところ、全ての化合物が９０％以上の死虫率を示した。 Next, test examples are described.
Test Example 1 Effect test on peach aphid Japanese radish leaves were inserted into a test tube containing water, and about 20 first-instar larvae were released on the leaves. The next day, after counting the number of larvae parasitic on radish leaves, the parasitic radish leaves were immersed in a chemical solution adjusted to a concentration of 200 ppm of the compound of formula (I) for about 10 seconds. After the chemical solution was air-dried, it was left in a constant temperature room at 25 ° C. with illumination. Five days after the treatment, the viability of the peach aphid was determined, and the mortality rate was determined by the following formula. The detached insects and abnormal insects were regarded as dead insects. When the compound Nos. 13, 20, 32, 33, 48, 49 and 53 were tested, all the compounds showed a death rate of 90% or more.
　死虫率(％)＝（１－（生存虫数／処理虫数））×１００ Death rate (%) = (1− (number of surviving insects / number of treated insects)) × 100
　試験例２　トビイロウンカに対する効果試験
　式（I）の化合物の濃度が２００ｐｐｍとなるよう調整した薬液に、イネ幼苗を約10秒間浸漬処理した。薬液が風乾した後に、湿った脱脂綿で根部を包んで試験管に入れた。この中へトビイロウンカ２～３齢幼虫を１０頭放ち、管口をガーゼでふたをして２５℃の照明付恒温室内に放置した。放虫５日後にトビイロウンカの生死を判定し、下記の計算式により死虫率を求めた。前記化合物No.13、14、18、20、22、23、24、26、27、29、32、33、35、37、40、43、48、49、53、55、56及び71を供試したところ、全ての化合物が９０％以上の死虫率を示した。
　死虫率（％）＝（死虫数／放虫数）×１００ Test Example 2 Effect test on green planthopper Rice seedlings were immersed for about 10 seconds in a chemical solution adjusted so that the concentration of the compound of formula (I) was 200 ppm. After the chemical solution was air-dried, the root was wrapped with wet absorbent cotton and placed in a test tube. Ten 10-year-old larvae of the green planthopper were released into this, and the tube mouth was covered with gauze and left in a constant temperature room at 25 ° C. Five days after the insect release, the dead planthopper was judged to be alive or dead, and the mortality rate was determined by the following formula. Compound Nos. 13, 14, 18, 20, 22, 23, 24, 26, 27, 29, 32, 33, 35, 37, 40, 43, 48, 49, 53, 55, 56 and 71 As a result, all compounds showed a death rate of 90% or more.
Death rate (%) = (Number of dead insects / Number of dead insects) × 100
　試験例３　シルバーリーフコナジラミに対する効果試験
　シルバーリーフコナジラミ１～２齢幼虫が寄生したポット植えのキュウリ苗に、式（I）の化合物の濃度が２００ｐｐｍとなるよう調整した薬液を、ハンドスプレーを用い散布処理した。薬液が風乾した後に、２５℃の照明付恒温室内に放置した。処理７日後に老齢幼虫数を調査し、下記計算式により防除効率(％)を求めた。前記化合物No.1、5、7、13、18、29、32、33、48及び49を供試したところ、全ての化合物が８０％以上の防除効率を示した。 Test example 3 Effect test on silver leaf whitefly Silver leaf whitefly 1-2 years old infested cucumber seedlings infested with a chemical solution adjusted so that the concentration of the compound of formula (I) is 200 ppm using a hand spray Processed. After the chemical solution was air-dried, it was left in a constant temperature room at 25 ° C. with illumination. Seven days after the treatment, the number of old larvae was examined, and the control efficiency (%) was determined by the following formula. When the compound Nos. 1, 5, 7, 13, 18, 29, 32, 33, 48 and 49 were tested, all the compounds showed a control efficiency of 80% or more.
　防除効率（％）＝（１－（Ta×Cb）/（Tb×Ca））×１００
Ta: 処理キュウリ苗における処理後の老齢幼虫
Tb：処理キュウリ苗における処理前の１～２齢幼虫数
Ca: 無処理キュウリ苗における処理後の老齢幼虫数
Cb：無処理キュウリ苗における処理前の１～２齢幼虫数 Control efficiency (%) = (1− (Ta × Cb) / (Tb × Ca)) × 100
Ta: old larvae after treatment in treated cucumber seedlings
Tb: Number of 1-2 instar larvae before treatment in treated cucumber seedlings
Ca: number of old larvae after treatment in untreated cucumber seedlings
Cb: Number of 1-2 instar larvae before treatment in untreated cucumber seedlings
　試験例４　フタトゲチマダニに対するイヌを用いた薬効試験
　イヌ（ビーグル、８ヶ月齢）に１０ｍｇ／ｋｇ体重の式（I）の化合物を含むゼラチンカプセルを投与し、その直後にフタトゲチマダニの若ダニ約５０頭をイヌの耳介に放ち、人工寄生させる。処理後、寄生数、落下数及び落下したフタトゲチマダニの生死を観察する。その結果、式（I）の化合物は、寄生させたフタトゲチマダニを落下又は致死させる。 Test Example 4 Medicinal Efficacy Test Using Dogs Against Phytophyllum Tick A dog (beagle, 8 months old) was administered a gelatin capsule containing 10 mg / kg body weight of the compound of formula (I), and immediately after that about 50 young mite mites were collected. Release to the pinna of the dog and let it artificially infest. After the treatment, observe the number of infestations, the number of drops, and the life and death of the fallen spider mites. As a result, the compound of formula (I) drops or kills the parasitic spider mite.
　試験例５　ネコノミに対するイヌを用いた薬効試験
　イヌ（ビーグル、８ヶ月齢）に１０ｍｇ／ｋｇ体重の式（I）の化合物を含むゼラチンカプセルを投与し、その直後にネコノミ未吸血成虫約１００頭を背部被毛上に放ち人工寄生させる。式（I）の化合物は、処理された成虫の産下卵に対し、孵化阻止効果を示す。 Test Example 5 Medicinal Efficacy Test Using Dogs for Cat Fleas A dog (beagle, 8 months old) was administered a gelatin capsule containing 10 mg / kg body weight of the compound of formula (I), and immediately after that about 100 cat flea non-blood-sucking adults were administered. Let go on the back coat and let it artificially infest. The compound of the formula (I) exhibits a hatching-inhibiting effect on the treated laying eggs of adults.
　次に製剤例を記載する。
製剤例１
（１）式（I）の化合物　２０重量部
（２）クレー　７０重量部
（３）ホワイトカーボン　５重量部
（４）ポリカルボン酸ナトリウム　３重量部
（５）アルキルナフタレンスルホン酸ナトリウム　２重量部
以上のものを均一に混合して水和剤とする。 Next, formulation examples are described.
Formulation Example 1
(1) Compound of formula (I) 20 parts by weight (2) Clay 70 parts by weight (3) White carbon 5 parts by weight (4) Sodium polycarboxylate 3 parts by weight (5) Sodium alkylnaphthalenesulfonate 2 parts by weight or more Mix things uniformly to make a wettable powder.
製剤例２
（１）式（I）の化合物　５重量部
（２）タルク　６０重量部
（３）炭酸カルシウム　３４．５重量部
（４）流動パラフィン　０．５重量部
以上のものを均一に混合して粉剤とする。 Formulation Example 2
(1) Compound of formula (I) 5 parts by weight (2) Talc 60 parts by weight (3) Calcium carbonate 34.5 parts by weight (4) Liquid paraffin To do.
製剤例３
（１）式（I）の化合物　２０重量部
（２）Ｎ,Ｎ－ジメチルアセトアミド　２０重量部
（３）ポリオキシエチレントリスチリルフェニルエーテル　１０重量部
（４）ドデシルベンゼンスルホン酸カルシウム　２重量部
（５）キシレン　４８重量部
以上のものを均一に混合、溶解して乳剤とする。 Formulation Example 3
(1) Compound of formula (I) 20 parts by weight (2) N, N-dimethylacetamide 20 parts by weight (3) Polyoxyethylene tristyryl phenyl ether 10 parts by weight (4) Calcium dodecylbenzenesulfonate 2 parts by weight (5 ) Xylene 48 parts by weight or more are uniformly mixed and dissolved to prepare an emulsion.
製剤例４
（１）クレー　６８重量部
（２）リグニンスルホン酸ナトリウム　２重量部
（３）ポリオキシエチレンアルキルアリールサルフェート　５重量部
（４）ホワイトカーボン　２５重量部
以上の各成分の混合物と、式（I）の化合物とを４：１の重量割合で混合し、水和剤とする。 Formulation Example 4
(1) Clay 68 parts by weight (2) Sodium lignin sulfonate 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) White carbon 25 parts by weight A mixture of each component and formula (I) The compound is mixed at a weight ratio of 4: 1 to obtain a wettable powder.
製剤例５
（１）式（I）の化合物　５０重量部
（２）アルキルナフタレンスルホン酸ナトリウムホルムアルデヒド縮合物　２重量部
（３）シリコーンオイル　０．２重量部
（４）水 ４７．８重量部
以上のものを均一に混合、粉砕した原液に更に
（５）ポリカルボン酸ナトリウム　５重量部
（６）無水硫酸ナトリウム　４２．８重量部
を加え均一に混合、造粒、乾燥して顆粒水和剤とする。 Formulation Example 5
(1) Compound of formula (I) 50 parts by weight (2) Sodium alkylnaphthalenesulfonate formaldehyde condensate 2 parts by weight (3) Silicone oil 0.2 part by weight (4) Water 47.8 parts by weight or more uniform (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are added to the stock solution mixed and pulverized, and mixed uniformly, granulated, and dried to obtain a granulated wettable powder.
製剤例６
（１）式（I）の化合物　５重量部
（２）ポリオキシエチレンオクチルフェニルエーテル　１重量部
（３）ポリオキシエチレンアルキルエーテルリン酸エステル　０．１重量部
（４）粒状炭酸カルシウム　９３．９重量部
（１）～（３）を予め均一に混合し、適量のアセトンで希釈した後、（４）に吹付け、アセトンを除去して粒剤とする。 Formulation Example 6
(1) Compound of formula (I) 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene alkyl ether phosphate 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight Parts (1) to (3) are mixed uniformly in advance, diluted with an appropriate amount of acetone, sprayed onto (4), and acetone is removed to form granules.
製剤例７
（１）式（I）の化合物　２．５重量部
（２）Ｎ，Ｎ－ジメチルアセトアミド　２．５重量部
（３）大豆油　９５．０重量部
以上のものを均一に混合、溶解して微量散布剤(ultra low volume formulation)とする。 Formulation Example 7
(1) Compound of formula (I) 2.5 parts by weight (2) N, N-dimethylacetamide 2.5 parts by weight (3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to form a trace amount Use as an ultra low volume formulation.
製剤例８
（１）式（I）の化合物　４０重量部
（２）ポリオキシエチレントリスチリルフェニルエーテルリン酸カリウム　４重量部
（３）シリコーンオイル　０．２重量部
（４）キサンタンガム　０．１重量部
（５）エチレングリコール　５重量部
（６）水　５０．７重量部
以上のものを均一に混合、粉砕して水性懸濁剤とする。 Formulation Example 8
(1) Compound of formula (I) 40 parts by weight (2) Polyoxyethylene tristyryl phenyl ether potassium phosphate 4 parts by weight (3) Silicone oil 0.2 parts by weight (4) Xanthan gum 0.1 parts by weight (5) Ethylene glycol 5 parts by weight (6) Water 50.7 parts by weight or more are uniformly mixed and ground to obtain an aqueous suspension.
製剤例９
（１）式（I）の化合物 １０重量部
（２）ジエチレングリコールモノエチルエーテル　８０重量部
（３）ポリオキシエチレンアルキルエーテル　１０重量部
以上の成分を均一に混合し、水溶性液剤とする。 Formulation Example 9
(1) Compound of formula (I) 10 parts by weight (2) Diethylene glycol monoethyl ether 80 parts by weight (3) Polyoxyethylene alkyl ether 10 parts by weight or more of ingredients are mixed uniformly to obtain an aqueous solution.
　本発明のトリアゾロピリミジン誘導体又はその塩を有効成分として含有する有害生物防除剤は、低薬量で効力が十分にあり、農園芸分野における各種有害生物の防除剤として、また動物に寄生する有害生物の防除剤である動物寄生生物防除剤として有用である。
　なお、２００８年８月１４日に出願された日本特許出願２００８－２０９０５９号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The pest control agent containing the triazolopyrimidine derivative or salt thereof of the present invention as an active ingredient is sufficiently effective at a low dose, and is used as a control agent for various pests in the field of agriculture and horticulture, and is harmful to animals. It is useful as an animal parasite control agent that is a biological control agent.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-209059 filed on Aug. 14, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (8)

  1. 　式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000001
     〔式中、Ｒ1は水素原子、Ａで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、Ｃ＝ＮＯＲ２、Ｃ＝ＮＮＲ4Ｒ5、ＣＯＲ２、ＣＯＯＲ２、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、Ｎ３又はＣＯＮＲ4Ｒ5であり；Ｘはアルキル、ヒドロキシアルキル、アルケニル、アルキニル、アリール、ハロゲン、ハロアルキル、シアノ、ニトロ、ＮＲ4Ｒ5、Ｓ(Ｏ)nＲ3、ＯＲ2、ＣＯＲ２、ＣＯＯＲ２又はＣＯＮＲ4Ｒ5であり；Ｙは水素原子又はフッ素原子であり；ＺはＣＨ、ＣＸ又はＮであり；Ａはハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、アルキル、シクロアルキル、アリール、複素環基、ＳＣＨ２ＣＯＯＲ２ 、ＮＨＮＲ4Ｒ5 、ＣＯＯＲ２、ニトロ又は－ＣＨ（ＣＮ）2であり；Ｒ2は水素原子、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシアルキル、アセチル又はアリールであり；Ｒ3はアルキル又はアセチルであり；Ｒ4は水素原子又はアルキルであり；Ｒ5は水素原子、アルキル、ハロアルキル、ＣＯＲ２、ＣＯＯＲ２、ＣＨ２ＣＨ２ＯＲ2又はシアノアルキルであり；ｍは１～４の整数であり；ｎは０～２の整数である〕で表されるトリアゾロピリミジン誘導体又はその塩を有効成分として含有することを特徴とする有害生物防除剤。     Formula (I):
    Figure JPOXMLDOC01-appb-C000001
     [Wherein, R 1 is a hydrogen atom, alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano , Aryl optionally substituted with halogen, heterocyclic group optionally substituted with alkyl, C═NOR 2 , C═NNR 4 R 5 , COR 2 , COOR 2 , OR 2 , S (O) n R 3 , NR 4 R 5 , N 3 or CONR 4 R 5 ; X is alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, NR 4 R 5 , S (O) n R 3 , OR 2 , COR 2 , COOR 2 or CONR 4 R 5 ; Y is a hydrogen atom or a fluorine atom; Z is CH, CX or N; A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5 , shear , Alkyl, cycloalkyl, aryl, heterocyclic group, SCH 2 COOR 2 , NHNR 4 R 5 , COOR 2 , nitro or —CH (CN) 2 ; R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl R 3 is alkyl or acetyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl, haloalkyl, COR 2 , COOR 2 , CH 2 CH 2 OR 2 or cyanoalkyl; m is an integer of 1 to 4; n is an integer of 0 to 2], and contains a triazolopyrimidine derivative or a salt thereof as an active ingredient Biocontrol agent.
  2. 　Ｒ1がＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ＯＲ2、Ｓ(Ｏ)nＲ3又はＮＲ4Ｒ5であり；Ｘがアルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、シアノ又はニトロであり；Ａがハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、シクロアルキル、アリール又は複素環基であり；Ｒ2が水素原子、アルキル、アルケニル、アルキニル、ハロアルキル又はアリールである請求項１に記載の有害生物防除剤。 R 1 is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano, OR 2 , S (O n is R 3 or NR 4 R 5 ; X is alkyl, alkenyl, alkynyl, halogen, haloalkyl, cyano or nitro; A is halogen, OR 2 , S (O) n R 3 , NR 4 R 5 , The pesticidal agent according to claim 1, which is a cyano, cycloalkyl, aryl or heterocyclic group; and R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl or aryl.
  3. 　請求項１に記載のトリアゾロピリミジン誘導体又はその塩を有効成分として含有する農園芸用有害生物防除剤。 An agricultural and horticultural pest control agent comprising the triazolopyrimidine derivative or a salt thereof according to claim 1 as an active ingredient.
  4. 　請求項１に記載のトリアゾロピリミジン誘導体又はその塩を有効成分として含有する殺虫、殺ダニ、殺線虫又は殺土壌害虫剤。 An insecticide, acaricide, nematicide or soil insecticide containing the triazolopyrimidine derivative according to claim 1 or a salt thereof as an active ingredient.
  5. 　請求項１に記載のトリアゾロピリミジン誘導体又はその塩を有効成分として含有する殺虫又は殺ダニ剤。 An insecticide or acaricide containing the triazolopyrimidine derivative or a salt thereof according to claim 1 as an active ingredient.
  6. 　請求項１に記載のトリアゾロピリミジン誘導体又はその塩の有効量を施用して有害生物を防除する方法。 A method for controlling pests by applying an effective amount of the triazolopyrimidine derivative or a salt thereof according to claim 1.
  7. 　式（I－α）：
    Figure JPOXMLDOC01-appb-C000002
     　〔式中、Ｒ1αはＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ハロゲンで置換されてもよいアリール、アルキルで置換されてもよい複素環基、Ｃ＝ＮＯＲ２、Ｃ＝ＮＮＲ4Ｒ5、ＣＯＲ２、ＣＯＯＲ２、ＯＲ2、Ｓ(Ｏ)nＲ3又はＣＯＮＲ4Ｒ5であり；Ｘはアルキル、ヒドロキシアルキル、アルケニル、アルキニル、アリール、ハロゲン、ハロアルキル、シアノ、ニトロ、ＮＲ4Ｒ5、Ｓ(Ｏ)nＲ3、ＯＲ2、ＣＯＲ２、ＣＯＯＲ２又はＣＯＮＲ4Ｒ5であり；Ｙは水素原子又はフッ素原子であり；ＺはＣＨ、ＣＸ又はＮであり；Ａはハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、アルキル、シクロアルキル、アリール、複素環基、ＳＣＨ２ＣＯＯＲ２ 、ＮＨＮＲ4Ｒ5 、ＣＯＯＲ２、ニトロ又は－ＣＨ（ＣＮ）2であり；Ｒ2は水素原子、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシアルキル、アセチル又はアリールであり；Ｒ3はアルキル又はアセチルであり；Ｒ4は水素原子又はアルキルであり；Ｒ5は水素原子、アルキル、ハロアルキル、ＣＯＲ２、ＣＯＯＲ２、ＣＨ２ＣＨ２ＯＲ2又はシアノアルキルであり；ｍは１～４の整数であり；ｎは０～２の整数である；但し、(1)Ｒ1αがメチルであり、Ｘが4-メトキシであり、ＺがＣＨである場合、(2)Ｒ1αがメチルであり、Ｘが3，4-ジメトキシであり、ＺがＣＨである場合及び(3)Ｒ1αがメチルであり、Ｘが4-メチルであり、ＺがＣＨである場合を除く〕で表されることを特徴とするトリアゾロピリミジン誘導体又はその塩。     Formula (I-α):
    Figure JPOXMLDOC01-appb-C000002
     Wherein R 1α is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano, halogen Aryl which may be substituted, heterocyclic group which may be substituted with alkyl, C═NOR 2 , C═NNR 4 R 5 , COR 2 , COOR 2 , OR 2 , S (O) n R 3 or CONR 4 R It is 5; X is an alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, cyano, nitro, NR 4 R 5, S ( O) n R 3, oR 2, COR 2, COOR 2 or CONR 4 R It is 5; Y is a hydrogen atom or a fluorine atom; Z is CH, CX or n; A is a halogen, oR 2, S (O) n R 3, NR 4 R 5, cyano, alkyl, cycloalkyl , Aryl, heterocyclic group, SCH 2 COOR 2 , NHNR 4 R 5 , COOR 2 , nitro or —CH (CN) 2 ; R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, acetyl or R 3 is alkyl or acetyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl, haloalkyl, COR 2 , COOR 2 , CH 2 CH 2 OR 2 or cyanoalkyl. M is an integer from 1 to 4; n is an integer from 0 to 2; provided that (1) when R 1α is methyl, X is 4-methoxy, and Z is CH, (2 ) R 1α is methyl, X is 3,4-dimethoxy, Z is CH, and (3) R 1α is methyl, X is 4-methyl, and Z is CH. Except] Triazolopyrimidine derivative or a salt thereof, wherein.
  8. 　Ｒ1αがＡで置換されてもよいアルキル、Ａで置換されてもよいシクロアルキル、Ａで置換されてもよいアルケニル、Ａで置換されてもよいアルキニル、ハロゲン、シアノ、ＯＲ2又はＳ(Ｏ)nＲ3であり；Ｘがアルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、シアノ又はニトロであり；Ａがハロゲン、ＯＲ2、Ｓ(Ｏ)nＲ3、ＮＲ4Ｒ5、シアノ、シクロアルキル、アリール又は複素環基であり；Ｒ2が水素原子、アルキル、アルケニル、アルキニル、ハロアルキル又はアリールであり；ｍが２～４の整数である請求項７に記載のトリアゾロピリミジン誘導体又はその塩。 R 1α is alkyl optionally substituted with A, cycloalkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, halogen, cyano, OR 2 or S (O ) be n R 3; X is alkyl, alkenyl, alkynyl, halogen, haloalkyl, cyano or nitro; A is halogen, oR 2, S (O) n R 3, NR 4 R 5, cyano, cycloalkyl, The triazolopyrimidine derivative or a salt thereof according to claim 7, which is an aryl or heterocyclic group; R 2 is a hydrogen atom, alkyl, alkenyl, alkynyl, haloalkyl or aryl; and m is an integer of 2 to 4.
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