JP2010065024A - Pest control agent containing triazolopyrimidine derivative or salt thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new pest control agent containing a triazolopyrimidine derivative or a salt thereof as an active ingredient. <P>SOLUTION: The pest control agent contains as an active ingredient the triazolopyrimidine derivative or a salt thereof represented by formula (I) [wherein, R<SP>1</SP>indicates a hydrogen atom, substitutable alkyl, substitutable cycloalkyl, substitutable alkenyl, substitutable alkynyl or the like; X indicates alkyl, hydroxyalkyl, alkenyl, alkynyl, aryl or the like; Y indicates a hydrogen atom or fluorine atom; Z indicates CH, CX or N; and m indicates an integer of 1 to 4]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel pesticide 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. There is no specific description about the triazolopyrimidine derivative represented by the following formula (I-α).

U.S. Pat.No. 2,439,210 U.S. Pat.No. 2,443,136

ACS Symposium Series (1992), 504 (Synth. Chem. Agrochem. III), 91-102 Tetrahedron, 50, 12113-12124 (1994)

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 being restricted. Therefore, development of a new pest control agent with few such disadvantages, 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 are problematic in the field of agriculture and horticulture without the disadvantages of 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.

  That is, the present invention relates to the formula (I)

[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 No, 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):

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 of 1 to 4; n is an integer of 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.

  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.

  When m in the formula (I) is 2 or more, each X may be the same or different.

  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.

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.

Examples of the cycloalkyl in the formula (I) 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. C _{2-6 and} the like can be mentioned.

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 - and the like as a C _2-6, such as hexynyl.

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, 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 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 of at least one atom selected from the group consisting of O, S and N are desirable.

  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 triazolopyrimidine derivative of formula (I) may have isomers such as optical isomers and geometric isomers, but the present invention includes both isomers and isomer mixtures. In the present specification, unless otherwise specified, isomers are described as a mixture. 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.

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]

In the production 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.

[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).

  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 80 to 200 ° C, preferably 100 to 150 ° C. The reaction time is usually 6 to 48 hours.

[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).

The compound of the formula (V) can be used in a ratio of 1 to 10 equivalents, desirably 1 to 2.5 equivalents, relative to 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 influence 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; such as 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, preferably 80 to 120 ° C. The reaction time is usually 0.5 to 100 hours.
Manufacturing method [2]

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. An optionally substituted aryl or alkyl heterocyclic group; 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.

[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, per 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; and the like. A base can be used in the ratio of 1-5 equivalent with respect to 1 mol of compounds of a formula (II), desirably 1-2 equivalent. 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, etc. 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: 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 formula (V) can be used in a proportion of 1 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 mol of the compound of 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 affect 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 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]

In the production process [3], 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.

[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).

The compound of the formula (IX) can be used in a proportion of 0.8 equivalent to a large excess, desirably 1 to 10 equivalents, 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 of the production method [2]. A base is 1-5 equivalent normally with respect to 1 mol of compounds of Formula (VIII), It can be desirably used in the ratio of 1-2 equivalent. 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 [2] -1 in 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).

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]

In the production process [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; an 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.

  The production method [4] comprises the reaction steps of the above [4] -1, [4] -2, [4] -3 and [4] -4, from the compound of the formula (X) to the compound of the 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: 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, 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: This reaction step is a reaction step of halogenating the compound of 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) As a chlorinating agent, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride etc. can be mentioned, for example. 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) 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 a proportion of 1 to 5 equivalents, preferably 1.5 to 3 equivalents, per 1 mol 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) 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 20 ° 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.

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 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 a proportion 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, diene 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.

  The reaction (c) can be carried out as a one-pot reaction. 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, preferably 70 ° C to 110 ° C. The reaction time is usually 1 to 48 hours.

[4] -3 In this reaction step, a compound of formula (I-3) is produced by Suzuki coupling of a compound of formula (XII) and a boron compound of formula (XIII) in the presence of a transition metal catalyst. it can.

  Suzuki coupling has been studied in many publications and described in known methods (for example, Synth. Commun., 1981, 11 (7), 513-519 or Synlett., 1992, 207-210, etc.). This reaction step can be carried out according to the method described above.

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, trifluoroborate potassium salt and the like. The boron compound of the formula (XIII) can be used at a ratio of 0.5 to 1 equivalent with respect to 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. 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 the formula (XII).

  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).

  Moreover, this reaction can be normally performed in 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 , Hexane, heptane, petroleum ether, ligroin, aliphatic hydrocarbons such as 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. 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: In this reaction step, the compound of formula (I-4) can be produced by reacting the compound of formula (I-3) with a nucleophile.

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.

  The nucleophilic agent 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. 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, dichloroethylene; aromatic hydrocarbons such as benzene, toluene, 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, desirably 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]

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.

  The production method [5] comprises the reaction steps of the above [5] -1, [5] -2 and [5] -3, from the compound of the formula (XIV) to [1,2,4 of the formula (I-5). ] A triazolo [1,5-a] pyrimidine derivative can be produced.

[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).

  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 with respect 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, preferably 80 to 120 ° C. The reaction time is usually 0.5 to 100 hours.

[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: 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 process can be implemented according to reaction process [4] -3 of the said manufacturing method [4].

Manufacturing method [6]

In the production method [6], 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.

[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).

  Carbon disulfide and the compound of formula (XVII) can be used in a ratio 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 at a ratio of 1 to 10 equivalents, preferably 1 to 3 equivalents, per 1 mol of the compound of formula (II). 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 [1] -1 in 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 formula (I-6) can be produced by condensing the compound of formula (XVIII) and the compound of formula (V).

The compound of Formula (V) can be used in the ratio of 1-5 equivalent with respect to 1 mol of compounds of Formula (XVIII), desirably 1-3 equivalent. 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. A base can be used in the ratio of 1-5 equivalent with respect to 1 mol of compounds of Formula (V), desirably 1-3 equivalent. 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 in 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]

In the production method [7], R ³ , X, Z, m and n are as described above.

  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.

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 influence 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]

In the production process [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.

In the production method [8], the [1,2,4] triazolo [1,5-a] pyrimidine derivative of the formula (I-8) is reacted by reacting the 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; methylmagnesium bromide; 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 a proportion 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. 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; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride Halogenated hydrocarbons such as 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., preferably −70 to 20 ° C. The reaction time is usually 1 minute to 48 hours.
Manufacturing method [9]

In the production process [9], 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 compounds [1, 2, 3 of the formula (I-9) or the formula (I-3) 4] A triazolo [1,5-a] pyrimidine derivative can be produced. Each reaction step will be described in detail below.

[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 a large excess, desirably 1 to 30 equivalents, relative to 1 mol of the compound of the formula (VIII). As a base, the thing similar to reaction of reaction process [6] -1 of the said manufacturing method [6] etc. can be mentioned, for example. A base can be used in the ratio of 1-5 equivalent with respect to 1 mol of compounds of Formula (VIII), desirably 1-2 equivalent. 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: In this reaction step, the compound of formula (XXI) can be produced by hydrolyzing the compound of 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 a large excess, desirably 2 to 10 equivalents, per 1 mol of the compound of the 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: In this reaction step, the compound of formula (XXII) can be produced by reacting the compound of formula (XXI) with a halogenating agent. Examples of the halogenating agent include thionyl chloride and oxalyl dichloride. The halogenating agent can be used at a ratio of 1 to 5 equivalents, preferably 1 to 2 equivalents, per 1 mol of the compound of the 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: 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 reaction step [2] -1 in the above production method [2] can be exemplified, but acid amides are particularly 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: In this reaction step, 5-halo [1,2,4] triazolo [1,3 of formula (I-3) is reacted with the compound of compound (I-9) and a halogenating agent. 5-a] pyrimidine derivatives can be produced. Examples of the halogenating agent include thionyl chloride, phosphorus oxychloride, phosphorus oxybromide and the like. A halogenating agent can be used in the ratio of 1-20 equivalent with respect to 1 mol of compounds of Formula (I-9), desirably 1-8 equivalent. 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]

  In the production process [10], X, Z, hal and m are as described above.

  Production method [10] is a production example of the [1,2,4] triazolo [1,5-a] pyrimidine derivative of 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: 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, desirably 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 affect the reaction. Examples thereof include water; amides such as N, N-dimethylformamide; and the like. The reaction temperature is 0 to 200 ° C, preferably 0 to 150 ° C. The reaction time is 1 to 30 hours.

[10] -2: This reaction includes the 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) is a 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. A metallizing agent can be used in the ratio of 1 equivalent-1.5 equivalent with respect to the compound of Formula (I-3). The reaction temperature is usually −100 to 70 ° C., preferably −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 in a proportion of 1 to 5 equivalents, preferably 1 to 2 equivalents, per 1 mol of the compound of formula (I-3). The reaction temperature is usually -20 to 50 ° C, preferably -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 influence the reaction. For example, the same solvent as in reaction step [2] -1 in the above production method [2] can be exemplified, and among these, ethers are desirable.

[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. A reducing agent can be used in the ratio of 1-2 equivalent with respect to 1 mol of compounds of Formula (I-11), Desirably 1-1.5 equivalent. 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, aromatic hydrocarbons such as benzene and toluene. The reaction temperature is usually −80 ° C. to 100 ° C., preferably −30 to 50 ° C. The reaction time is usually 0.1 to 24 hours.
Manufacturing method [11]

In the production process [11], R ¹⁴ represents alkyl or cycloalkyl, and X, Z and m are as described above.

In the production method [11], the compound of the formula (I-11) and a nucleophile are reacted 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 a proportion of 1 to 2 equivalents, preferably 1 to 1.3 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 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., preferably −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, desirably 2 to 10 equivalents, relative to the nucleophile. 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]

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.

  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.

Examples of the alcohol include methanol, ethanol, and ethylene glycol. Alcohol can be used in the ratio of 1 equivalent-large excess with respect to 1 mol of compounds of a formula (I-12) or a 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]

  In the production process [13], X, Z, hal and m are as described above.

  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 above [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: 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 the formula (I-15) can be produced by metallation of the compound of the formula (I-3) and hydrolysis after reaction with carbon dioxide. 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 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: 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 method of acid hydrolysis, alkali hydrolysis, and oxidative hydrolysis may be used.

[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. An oxidizing agent can be used in the ratio of 1-3 equivalent with respect to 1 mol of compounds of a formula (I-12), desirably 1-2 equivalent. 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 water, acetone, acetonitrile, methanol and the like. The reaction temperature is usually 0-50 ° C. The reaction time is usually 0 to 24 hours.
Manufacturing method [14]

In the production process [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.

  The production method [14] comprises the reaction steps of the above [14] -1 and [14] -2, from the compound of the formula (I-15) to the [1,2,4] triazolo [1] of the formula (I-17). , 5-a] pyrimidine derivatives can be produced. Each reaction step will be described in detail below.

[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 usually in a proportion of 1 equivalent to a large excess, desirably 1 to 5 equivalents, per 1 mol of the compound of 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, and examples thereof include the same as those in the reaction step [9] -3 of the production method [9]. 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 reaction step [4] -4 in the above production method [4].
Manufacturing method [15]

  In the production process [15], X, Z and m are as described above.

  Production method [15] is an example of production 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 the formula (I-19) can be produced by any method. Each reaction is described in detail below.

[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 diphenylphosphoric acid 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.

  There are many known rearrangement reactions that can be used in this production method. For example, methods such as Curtius rearrangement, Schmidt rearrangement, Rossen rearrangement, and Hoffman 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: 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. A reducing agent can be used in the ratio of 1-2 equivalent with respect to 1 mol of 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 influence the reaction, and examples thereof include alcohols; ethers. The reaction temperature is usually 0-50 ° C. The reaction time is usually 1 to 24 hours.
Manufacturing method [16]

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.

  In the production method [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.

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; A base is 1-10 equivalent normally with respect to 1 mol of compounds of a formula (I-20), It can be desirably used in the ratio of 1-5 equivalent. 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 acetones; ethers; nitriles; The reaction temperature is 0 to 50 ° C, preferably 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]

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.

In the production method [17], a [1,2,4] triazolo [1,5-a] pyrimidine of the formula (I-22) is prepared by reacting the compound of the formula (I-12) with the compound of the formula (XXIV). Derivatives can be produced.

In this reaction, the compound of the formula (XXIV) can be used in a proportion of 1 equivalent to a large excess, desirably 1 to 20 equivalents, per 1 mol 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, desirably 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 affect the reaction. For example, the same solvent as in the above production method [12] can be mentioned. 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]

In the production process [18], R ¹⁶ , X, Z and m are as described above.

  In the production process [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.

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 ratio 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 performed in the presence of a condensing agent, examples of the condensing agent include dicyclohexylcarbodiimide, 1,1-carbonyldiimidazole, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, and the like. A condensing agent is 1-5 equivalent normally with respect to 1 mol of Formula (I-15), It can be desirably used in the ratio of 1-2 equivalent. 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]

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.

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 used usually in a ratio of 1 to 5 equivalents with respect to 1 mol of the compound of the formula (I-3). Carbon monoxide can be used in the ratio of 1-10 equivalent normally with respect to 1 mol of compounds of a formula (I-3), desirably 1-5 equivalent. 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;

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 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.

  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.

  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.

  Preferred 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.

  Pesticides for agricultural and horticultural use are useful, for example, as insecticides, acaricides, nematicides, or soil insecticides. Specifically, urticae, spider mites, kanzawa spider mites, citrus spider mites, apple spider mites, citrus dust mites, mandarin oranges 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 the control of clothing such as mosquitoes, house pests; indoor dust mites such as mite, mite, mite. 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 on the foliage at the same time as the control of gastropods and isopods.

  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.

  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 formula (I) and the various adjuvants is 0.001: 99.999 to 95: 5, desirably 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 ˜500000 ppm, and the application amount per unit area is 0.05 to 50000 g, preferably 1 to 30000 g, of the compound of formula (I) per hectare. Moreover, application of the agricultural and horticultural pest control agent, which is another preferred embodiment of the pest control agent of the present invention, is performed in accordance with the application of the pest control agent. The present invention also 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. 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 volume application method (ultra low volume). In this method, it is possible to contain 100% of the active ingredient.

  In addition, the agricultural and horticultural pest control agent of the present invention can be used in combination with or used in combination with other agricultural chemicals, fertilizers, phytotoxicity reducing agents, and the like. 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.

  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. In addition, the appropriate amount to be applied is 0.1 to 50000 g, preferably 1 to 30000 g as the total active ingredient compound amount per hectare. The present invention also includes a method for controlling pests by a method for applying such a composition for controlling mixed pests.

Examples of active ingredient compounds (generic name; including some pending applications or test codes) of pesticides, 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, bamidthione (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, sodium thiosultap-sodium;
Organochlorine compounds such as dicofol, tetradifon, endosulfan, dienochlor, dieldrin;

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, metofluthrin, phenothrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, triflumuron, hexaflumuron, lufenuron, novaluron, novaluron, ), Bistrifluron, benzoylurea compounds such as fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, fenoxycarb, 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;

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 antibiotics such as abamectin) and emamectin and semi-synthetic antibiotics; natural products such as azadirachtin and rotenone; repellents such as deet;

Examples of the bactericidal active ingredient compounds (generic name; including some pending applications, or the Japan Plant Protection Association test code) in the above-mentioned other pesticides include mepanipyrim, pyrimethanil, cyprodinil ( cyprodinil), anilinopyrimidine compounds such as ferimzone;
Tria like 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;

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 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 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;

Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Synamic acid compounds such as dimethomorph, flumorph;
Phenyl carbamate compounds such as dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, kresoxim-methyl, metominofen, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin Strobilurin-based 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;
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;

  Other compounds include 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.

  Other pesticides that can be used in combination with or combined with the compounds of the present invention include, for example, active compound compounds of herbicides, particularly those treated with soil, as described in The Pesticide Manual (14th edition). is there.

  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.

  Examples of ectoparasites 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 (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 formula (I) is particularly effective for controlling ticks and the like.

Examples of fleas include ectoparasite insects 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 mouse minnow ( Nosopsyllus fasciatus ), and Yamato mouse minnow ( 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.

  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 such as liver cirrhosis; coccidium, malaria parasite, intestinal granulocyst, toxoplasma, chestnut Protozoa such as Ptosporidium, and the like.

  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.

  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

  The blending 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 carried out 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.

  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 also includes a method for controlling pests by the administration method or dosage as described above, particularly a method for controlling ectoparasites or endoparasites.

  Moreover, in the present invention, by controlling animal parasitic pests as described above, there are cases where various diseases of host animals caused by them can be prevented or treated. 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.

  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 used in combination with or in combination with fragrances, preservatives and the like. Also, if necessary, 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 mixed pest control composition in which various components as described above are mixed or used together, and a pest control method using the composition, in particular, an ectoparasite or endoparasite control method. Is also included.

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 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 as an active ingredient.

(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 are the same as in (1) above.

(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; m is an integer of 2 to 4 triazolopyrimidine derivative Or a salt thereof. R ³ , R ⁴ , R ⁵ , Y, Z and n are the same as in (1) above.

(4) In 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 A 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.

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 the 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) A mixed solution of 1.19 g of methyl 2-chloro-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 shall apply 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 light brown oil.
(2) To a mixed solution of 1.33 g of the compound (intermediate No. VII-1) obtained in the previous step (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 0 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.

Synthesis example 2
Preparation of 5-chloro-7- [2-chloro-4- (trifluoromethyl) phenyl] [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 21)
(1) A suspension obtained by mixing 919 mg of 5,7-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.

Synthesis example 3
Synthesis of 5-methylamino-7- [2-chloro-4- (trifluoromethyl) phenyl] [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 23)
In a mixed solution of 83 mg of 5-chloro-7- [2-chloro-4- (trifluoromethyl) phenyl] [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 21) and 2 ml of tetrahydrofuran After adding 0.5 ml of a 40 mass% aqueous solution of methylamine, the mixture was stirred 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. .

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) 1.18 g of 3-acetyl-2-chloro-6- (trifluoromethyl) pyridine and 843 mg of N, N-dimethylacetamidodimethylacetal 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 solution and 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.

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)
(1) 4.2 g of ethyl 2-fluoro-3-oxobutanoate was dissolved in 8 mL of acetic acid, 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 purified by silica gel chromatography (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 mixed solution of 6 ml of ethylene glycol dimethyl ether and 1.7 ml of 2N aqueous sodium carbonate solution, 208 mg of the compound (intermediate No. XVI-4) obtained in the previous step (2), 2-chloro-4- (trifluoro 250 mg of methyl) phenylboronic acid and 64 mg of tetrakis (triphenylphosphine) palladium were added, and the mixture was stirred at 70 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was 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.

Synthesis Example 6
Synthesis of 7- [2-chloro-4- (trifluoromethyl) phenyl] -5-cyclopropyl [1,2,4] triazolo [1,5-a] pyrimidine (Compound No. 48) Chloro-4- (trifluoromethyl) phenyl] -3-cyclopropane-1,3-dione (Intermediate No. VII-3) in a mixed solution of 145 mg and 3 ml of acetic acid was added 3-amino-1H-1,2,4 -Triazole 56mg was added and it heated at the temperature of about 100 degreeC 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. .

Representative examples of compounds of formula (I) are listed in Table 1. These compounds include novel compounds represented by the formula (I-α), and can be synthesized based on the synthesis examples or the various production methods described above. In Table 1, No. represents compound No., Me represents methyl, Et represents ethyl, i-Pr represents isopropyl, i-Bu represents isobutyl, and t-Bu represents tertiary butyl. The indicated temperature is the melting point. Further, ¹ H-NMR ( ¹ H-nuclear magnetic resonance) is shown in Table 2 for the compounds whose physical property column in Table 1 is oil or amorphous.

Representative examples of the compound of the formula (IV) in the production method [1] are listed in Table 3. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 3, No. represents an intermediate No., Me represents methyl, and i-Bu represents isobutyl. In addition, ¹ H-NMR is shown in Table 4 for the compounds listed in Table 3.

Table 5 lists representative examples of the compound of formula (XV) 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 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 6 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 lists 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.

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 of the peach aphid were released on the leaves. The next day, after counting the number of larvae parasitic on the 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 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.

  Death rate (%) = (1− (number of surviving insects / number of treated insects)) × 100

Test Example 2 Effect test on brown 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 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 the compounds showed a death rate of 90% or more.
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 larvae 1 to 2 instar before treatment in untreated cucumber seedlings

Test Example 4 Medicinal Efficacy Test Using Dogs for Phytophthora 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 tick mites were collected. Release them into the pinna of dogs and artificially infest them. 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 Drug efficacy test using a dog against a cat flea 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 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 adult laying eggs.

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.

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 is 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 A mixture of 25 parts by weight or more of each component of 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 parts 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 mixed and pulverized stock solution, and the mixture is uniformly mixed, granulated and dried to obtain a granulated wettable powder.

Formulation Example 6
(1) Compound of formula (I) 5 parts by weight (2) Polyoxyethylene octyl phenyl 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 uniformly mixed in advance and diluted with an appropriate amount of acetone, and then sprayed on (4) to remove the acetone to obtain 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 give 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 pulverized 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.

Claims (8)

Formula (I):

[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 No, 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. 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. An agricultural and horticultural pest control agent comprising the triazolopyrimidine derivative according to claim 1 or a salt thereof as an active ingredient. An insecticide, acaricide, nematicide or soil insecticide containing the triazolopyrimidine derivative or salt thereof according to claim 1 as an active ingredient. An insecticide or acaricide containing the triazolopyrimidine derivative or a salt thereof according to claim 1 as an active ingredient. A method for controlling pests by applying an effective amount of the triazolopyrimidine derivative or a salt thereof according to claim 1. Formula (I-α):

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 of 1 to 4; n is an integer of 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. 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.