Pyridine derivative or its salt, pesticide containing it and process for its production

专利摘要:

公开号:AU2009314948A1
申请号:U2009314948
申请日:2009-11-06
公开日:2010-05-20
发明作者:Kumiko Azuma；Takahiro Haga；Kazuhisa Kiriyama；Masayuki Morita
申请人:Ishihara Sangyo Kaisha Ltd；
IPC主号:A01N43-50

专利说明:
WO 2010/055896 1 PCT/JP2009/069305 DESCRIPTION PYRIDINE DERIVATIVE OR ITS SALT, PESTICIDE CONTAINING IT AND PROCESS FOR ITS PRODUCTION 5 TECHNICAL FIELD The present invention relates to a pesticide containing a novel pyridine derivative or its salt as an active ingredient. 10 BACKGROUND ART Patent Document 1 discloses that oxime derivatives having a specific chemical structure are useful as insecticides. However, it discloses nothing specific about the compounds of the present invention represented by the formula (I) given hereinafter. Patent Document 1: JP-A-03-68559 15 DISCLOSURE OF THE INVENTION OBJECT TO BE ACCOMPLISHED BY THE INVENTION For many years, many pesticides have been used, but many of them have various problems such that the effects are inadequate, their use is restricted as pests have acquired 20 resistance, etc. Accordingly, it is desired to develop a novel pesticide substantially free from such problems, for example, a pesticide capable of controlling various pests which create problems in agricultural and horticultural fields or a pesticide capable of controlling pests parasitic on animals. 25 MEANS TO ACCOMPLISH THE OBJECT The present inventors have conducted various studies on pyridine derivatives in an effort to find a superior pesticide. As a result, they have found that a novel pyridine derivative represented by the formula (1) given hereinafter has a high pesticidal effect against pests at a low dose, and have accomplished the present invention. 30 Namely, the present invention relates to a pyridine derivative represented by the formula (1) or its salt: (X)m Na^^wR 1 (I) N )y R2 wherein R' is alkyl, cycloalkyl, alkoxyalkyl or OR 3 ; R 2 is 1 H-1,2,4-triazol-1 -yl which may be substituted by alkyl, 1 H-imidazol-1 -yl which may be substituted by alkyl, 1 H-1,2,3-triazol-1 -yl which may be substituted by alkyl, or 4H-1,2,4-triazol-4-yl which may be substituted by alkyl; X is 35 alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, arylalkoxy which may be substituted by B, silylalkyl which is substituted by B, silylalkoxy which is substituted by B, alkylthio which may be substituted by A, alkenyl which may be substituted by A, alkynyl which may be substituted by A, alkenyloxy which may be substituted by A, alkynyloxy 40 which may be substituted by A, phenoxy which may be substituted by B, hydroxyl, NR 4 R , OCOR , OCOOR 6 , OS(O),R 6 , aryl which may be substituted by B, heteroaryl which may be WO 2010/055896 2 PCT/JP2009/069305 substituted by B, COR 6 , COOR', S(O)nR 6 or CONR 4
R
5 ; R 3 is alkyl which may be substituted by D, cycloalkyl which may be substituted by E, alkenyl which may be substituted by D, alkynyl which may be substituted by D, phenylalkyl which may be substituted by E, pyridylalkyl which may be substituted by E, phenyl which may be substituted by E, silyl which is substituted by E, N 5 alkylcarbamoyl, N-alkoxycarbamoyl or N,N-dialkylcarbamoyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl which may be substituted by A, cycloalkyl which may be substituted by B, arylalkyl which may be substituted by B, heteroarylalkyl which may be substituted by B, COR,
COOR
6 , S(O)nR" or CH 2 CN; R 6 is alkyl, haloalkyl, or aryl which may be substituted by B; A is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy and 10 haloalkoxy; B is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy and haloalkoxy; D is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl and alkylsilyl; E is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, 15 alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkylsilyl, tetrahydropyranyl, 1,3-dioxolan-2-yl and N,N-dialkylamino; m is an integer of from 1 to 4; and n is 1 or 2. The present invention further relates to a pesticide containing the pyridine derivative of the formula (1) or its salt as an active ingredient, a method for controlling a pest by applying it, and a process for its production. 20 EFFECTS OF THE INVENTION A pesticide containing the pyridine derivative of the above formula (1) or its salt as an active ingredient has a high pesticidal effect against pests at a low dose. 25 BEST MODE FOR CARRYING OUT THE INVENTION When m in the formula (1) is an integer of from 2 to 4, the respective X's may be the same or different. As the halogen in the formula (1), an atom of fluorine, chlorine, bromine or iodine may be mentioned. The number of halogens as the substituents may be 1 or more, and if more, the 30 respective halogens may be the same or different. Further, the positions for substitution of such halogens may be any positions. The alkyl in the formula (1) may be linear or branched. As its specific example, C1. alkyl such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl or hexyl may be mentioned. As the cycloalkyl in the formula (I), C3-6 cycloalkyl such as cyclopropyl, cyclobutyl, 35 cyclopentyl or cyclohexyl may, for example, be mentioned. The alkenyl in the formula (I) may be linear or branched. As its specific example, C2-6 alkenyl such as vinyl, 1 -propenyl, allyl, isopropenyl, 1 -butenyl, 1,3-butadienyl or 1 -hexenyl may be mentioned. The alkynyl in the formula (I) may be linear or branched. As its specific example, C2-6 40 alkynyl such as ethynyl, 2-butynyl, 2-pentynyl, 3-methyl-1 -butynyl, 2-penten-4-ynyl or 3-hexynyl may be mentioned. As the aryl in the formula (I), Co.1o aryl such as phenyl or naphthyl may, for example, be mentioned. The heteroaryl in the formula (1) may be monocyclic heteroaryl or fused heteroaryl, and it 45 may contain from 1 to 4 atoms of at least one type selected from the group consisting of 0, S and N. Its specific example may, for example, be 5-membered heteroaryl such as furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, triazolyl, oxadiazolyl, WO 2010/055896 3 PCT/JP2009/069305 thiadiazolyl or tetrazolyl; 6-membered heteroaryl such as pyridyl, thiazinyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl; or 8- to 1 0-membered fused heteroaryl such as benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, indolyl, isoindolyl, benzoxazolyl, benzothiazolyl, indazolyl, benzimidazolyl, quinolyl, isoquinolyl, phthalazinyl, quinazolinyl, quinoxalinyl, 5 imidazopyridyl, naphthyridinyl or pteridinyl. The salt of the pyridine derivative of the above formula (I) includes all kinds so long as they are acceptable in this technical field. For example, an inorganic acid salt such as a hydrochloride, a perchlorate, a sulfate or a nitrate, or an organic acid salt such as an acetate or a methanesulfonate, may be mentioned. 10 The pyridine derivative of the above formula (1) may have isomers such as optical isomers or geometrical isomers, and such isomers and mixtures thereof are both included in the present invention. Further, in the present invention, various isomers other than those mentioned above, may be included within the scope of the common knowledge in this technical field. The pyridine derivative of the above formula (I) or its salt can be produced by the following 15 production processes [1], [2], [3] and [4] and in accordance with a usual method for producing a salt. Now, the respective production processes will be described in detail with reference to the reaction flowcharts. PRODUCTION PROCESS [1] X)m Halogenating (X)m R2-H (X)m H agent (IV) N-
NWAR
1 SeNnR1 N R 1 First step N Second Nl NR 0 Z step R2 ( ii) ( III ) (I ) 20 In production process [1], Z is halogen, and R1, R 2 , X and m are as defined above. As the halogen for Z, an atom of fluorine, chlorine, bromine or iodine may be mentioned. In the first step of the production process [1], a compound of the formula (11) is reacted with a halogenating agent to produce a compound of the formula (ll). The halogenating agent may, for example, be phosphorus pentachloride; phosphorus oxychloride; thionyl chloride; 25 triphenylphosphine and carbon tetrachloride; or triphenylphosphine and carbon tetrabromide. The halogenating agent may be used in a proportion of from 1 to 5 equivalents, preferably from 1 to 2 equivalents, per mol of the compound of the formula (11). This reaction may be carried out in the presence of a solvent, as the case requires. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, be a halogenated 30 hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride, carbon tetrabromide or 1,2-dichloroethane; an aromatic hydrocarbon such as benzene, toluene or xylene; or a nitrile such as acetonitrile or propiononitrile. The reaction temperature is usually from 0 to 150 0 C, preferably from 50 to 120 0 C. The reaction time is usually from 1 to 24 hours. The compound of the formula (111) produced by this reaction step can be used in the second step of the production 35 process [1] without being isolated. In the second step of the production process [1], the compound of the formula (ll) is reacted with a compound of the formula (IV) to produce a compound of the formula (1). The compound of the formula (IV) can be used in a proportion of from 1 to 5 equivalents, preferably from 1 to 2 equivalents, per mol of the compound of the formula (111). This reaction may be 40 carried out in the presence of a base as the case requires. The base may, for example, be an alkali metal hydride such as sodium hydride or potassium hydride; an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkali metal alkoxide such as sodium methoxide, WO 2010/055896 4 PCT/JP2009/069305 sodium ethoxide or potassium tertiary butoxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; or an organic base such as triethylamine or pyridine. The base may be used in a proportion of from 0.01 to 3 equivalents, preferably from 1 5 to 2 equivalents, per mol of the compound of the formula (lll). This reaction can be carried out usually in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, be an ether such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran or dioxane; an ester such as methyl acetate or ethyl acetate; a nitrile such as acetonitrile or propiononitrile; an acid amide such as N,N 10 dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidinone; or a solvent mixture thereof. The reaction temperature is usually from 0 to 120 0 C, preferably from 20 to 100*C. The reaction time is usually from 1 to 24 hours. PRODUCTION PROCESS [2] (X)m R 2 -H (X)m R 3 -L l-(IV) rl/1(VI0I) N N'xOH -NOH NAOR3 Z First step R2 Second N step R (V) M V) ( 1 -1) In production process [2], L is a leaving group, and R 2 , R 3 , X, Z and m are as defined 15 above. The leaving group for L may, for example, be halogen, alkylsulfonyloxy, trifluoromethanesulfonyloxy, or benzenesulfonyloxy which may be substituted by alkyl. In the first step of the production process [2], a compound of the formula (V) is reacted with a compound of the formula (IV) to produce a compound of the formula (VI). The compound of the formula (IV) may be used in a proportion of from 1 to 5 equivalents, preferably from 1.1 to 3 20 equivalents, per mol of the compound of the formula (V). This reaction may usually be carried out in the presence of a base and a solvent. As the base, the same one as mentioned for the second step of the above production process [1] may be mentioned. The base may be used in a proportion of from 1 to 5 equivalents, preferably from 1 to 3 equivalents, per mol of the compound of the formula (V). The solvent is not particularly limited so long as it presents no adverse effect 25 to the reaction, and for example, it may be the same one as mentioned in the second step of the above production process [1]. The reaction temperature is usually from -20 to 1000C, preferably from -10 to 50 0 C. The reaction time is usually from 0.5 to 5 hours. In the second step of the production process [2], the compound of the formula (VI) is reacted with a compound of the formula (VII) to produce a compound of the formula (I-1). The 30 compound of the formula (VII) may be used in a proportion of from 1 to 5 equivalents, preferably from 1.2 to 3 equivalents, per mol of the compound of the formula (VI). This reaction may be carried out in the presence of a base, as the case requires. The base may, for example, be an alkali metal hydride such as sodium hydride or potassium hydride; an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium tertiary butoxide; an alkali metal carbonate 35 such as sodium carbonate or potassium carbonate; or an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate. The base may be used in a proportion of from 0.8 to 3 equivalents, preferably from 1 to 2 equivalents, per mol of the compound of the formula (VI). This reaction may usually be carried out in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the 40 reaction, and it may, for example, be the same one as mentioned in the second step of the above production process [1]. The reaction temperature is usually from 0 to 100 0 C, preferably from 10 WO 2010/055896 5 PCT/JP2009/069305 to 500C. The reaction time is usually from 1 to 5 hours. PRODUCTION PROCESS [3] Nucleophilic X rna a ge nt N(X m a N -N R' N N R1 R 2 R 2 (1-2) (1-3) In the production process [3], Xa is a leaving group; Xb is halogen, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, arylalkoxy which may be 5 substituted by B, silylalkoxy which is substituted by B, alkylthio which may be substituted by A, alkenyloxy which may be substituted by A, alkynyloxy which may be substituted by A, phenoxy which may be substituted by B, NR 4 R5, OCOR 6 , OCOOR 6 or OS(O)nR 6 ; ma is an integer of from 0 to 3; and R 1 , R 2 , X, R 4 , R 5 , R 6 , A, B and n are as defined above. The leaving for Xa may, for example, be halogen, alkylsulfonyloxy, trifluoromethanesulfonyloxy, or benzenesulfonyloxy which 10 may be substituted by alkyl. In the production process [3], a compound of the formula (1-2) is reacted with a nucleophilic agent to produce a compound of the formula (1-3). The nucleophilic agent may, for example, be a metal halide such as cesium fluoride, potassium fluoride or potassium iodide; an alkali metal cyanide such as sodium cyanide or potassium cyanide; an alkali metal alkoxide such as sodium 15 methoxide or sodium ethoxide; an alkali metal thiolate such as sodium thiomethoxide; or an amine represented by the formula HNR 4
R
5 (wherein R 4 and R 5 are as defined above). The nucleophilic agent may be used in a proportion of from 1 to 10 equivalents, preferably from 1 to 3 equivalents, per mol of the compound of the formula (1-2). This reaction may be carried out in the presence of a base, as the case requires. The base may, for example, be the same one as 20 mentioned in the second step of the above production process [1]. The base may be used in a proportion of from 1 to 5 equivalents, preferably from 1 to 3 equivalents, per mol of the compound of the formula (1-2). This reaction may usually be carried out in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, 25 be an alcohol such as methanol, ethanol, propanol or butanol; an aromatic hydrocarbon such as benzene, toluene or xylene; an aliphatic hydrocarbon such as pentane, hexane, heptane, petroleum ether, ligroin or petroleum benzine; an ether such as diethyl ether, butyl ethyl ether, tetrahydrofuran, dioxane or dimethoxyethane; an ester such as methyl acetate or ethyl acetate; a halogenated hydrocarbon such as chlorobenzene, chloroform, dichloromethane, carbon 30 tetrachloride or 1,2-dichloroethane; a nitrile such as acetonitrile or propiononitrile; an acid amide such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidinone; a sulfoxide such as dimethylsulfoxide; or a solvent mixture thereof. The reaction temperature is usually from -1 00CC to the reflux temperature of the reaction mixture, preferably from -300C to 1500C. The reaction time is usually from about 1 minute to 96 hours. 35 PRODUCTION PROCESS [4] (X)ma Organometallic (X)ma compound XC-R N , N R2 R2 (I-2) (1-4) WO 2010/055896 6 PCT/JP2009/069305 In the production process [4], Xc is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, alkenyl which may be substituted by A, alkynyl which may be substituted by A, aryl which may be substituted by B, or heteroaryl which may be substituted by B; and R', R 2 , X, Xa, A, B and ma are as defined above. 5 In the production process [4], a compound of the formula (1-2) is reacted with an organometallic compound to produce a compound of the formula (1-4). The organometallic compound may, for example, be an organocopper compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, an organotin compound or an organosilicon compound. The organometallic compound may be 10 used in a proportion of from 1 to 5 equivalents, preferably from 1 to 3 equivalents, per mol of the compound of the formula (1-2). This reaction may usually be carried out in the presence of a catalyst and a base. The catalyst may, for example, be a palladium compound or a nickel compound. The catalyst may be used in a proportion of from 0.0001 to 0.2 equivalent, preferably from 0.001 to 0.1 equivalent, per mol of the compound of the formula (1-2). 15 The base may be the same one as mentioned in the second step of the above-mentioned production process [1]. The base may be used in a proportion of from I to 10 equivalents, preferably from 1 to 5 equivalents, per mol of the compound of the formula (1-2). This reaction may usually be carried out in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, 20 be water; an aromatic hydrocarbon such as benzene, toluene or xylene; an aliphatic hydrocarbon such as pentane, hexane, heptane, petroleum ether, ligroin or petroleum benzine; an ether such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran or dioxane; a ketone such as acetone, methyl ethyl ketone, dimethyl ketone, diethyl ketone or methyl isobutyl ketone; an ester such as methyl acetate or ethyl acetate; a halogenated hydrocarbon such as chloroform, 25 dichloromethane, carbon tetrachloride or 1,2-dichloroethane; a nitrile such as acetonitrile or propiononitrile; an amide such as N,N-dimethylformamide, N,N-dimethylacetamide or N methylpyrrolidinone; a sulfoxide such as dimethylsulfoxide; a sulfone such as sulfolane; a phosphoric acid amide such as hexamethylphosphoramide; or a solvent mixture thereof. The reaction temperature is usually from -100OC to the reflux temperature of the reaction mixture, 30 preferably from -30 0 C to 150 0 C. The reaction time is usually from about 1 minute to 96 hours. The compound of the formula (11) to be used in the first step of the production process [1] may be produced, for example, by the following production process [A] or [B]. Now, the respective production processes will be described in detail with reference to the reaction flowcharts. 35 PRODUCTION PROCESS [A] (X)m Halogenating
RI-NH
2 (X)m agent (X) H C> N COOH First step Second step R1 0 (yMl[) () In production process [A], R 1 , X and m are as defined above. The production process [A] comprises the above first step and second step, and a compound of the formula (II) can be produced from the compound of the formula (Vill). The product of the first step may be used in the second step without being isolated. 40 In the first step of production process [A], a compound of the formula (Vill) is reacted with a halogenating agent. The halogenating agent may, for example, be thionyl chloride or oxalyl dichloride. The halogenating agent may be used in a proportion of from 1 to 10 equivalents, WO 2010/055896 7 PCT/JP2009/069305 preferably from 1 to 5 equivalents, per mol of the compound of the formula (Vill). This reaction may be carried out in the presence of a reaction accelerator, as the case requires. The reaction accelerator may, for example, be N,N-dimethylformamide or a base. The base may, for example, be an organic base such as triethylamine, pyridine or 4-dimethylaminopyridine. The reaction 5 accelerator may be used in a proportion of from 0.001 to 3.0 equivalents, preferably from 0.01 to 0.5 equivalent, per mol of the compound of the formula (Vill). This reaction may be carried out in the presence of a solvent, as the case requires. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, be an aromatic hydrocarbon such as benzene, toluene or xylene; an aliphatic hydrocarbon such as pentane, 10 hexane, heptane, petroleum ether, ligroin or petroleum benzine; an ether such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran or dioxane; an ester such as methyl acetate or ethyl acetate; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or 1,2-dichloroethane; or a solvent mixture thereof. Further, a halogenating agent such as thionyl chloride or oxalyl dichloride may be used as a solvent. The reaction temperature is 15 usually from 0 to 1500C, preferably from 50 to 1000C. The reaction time is usually from 0.5 to 6 hours. In the second step of the production process [A], the product in the first step of the production process [A] is reacted with a compound of the formula (IX) or its salt to obtain the compound of the formula (11). The compound of the formula (IX) may be used in a proportion of 20 from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per mol of the compound of the formula (Vill). This reaction may be carried out in the presence of a base, as the case requires. The base may, for example, be an organic base such as triethylamine, pyridine or 4 dimethylaminopyridine. The base may be used in a proportion of from 0.05 to 10 equivalents, preferably from 0.1 to 2.5 equivalents, per mol of the compound of the formula (Vil). This 25 reaction may usually be carried out in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, be an aromatic hydrocarbon such as benzene, toluene or xylene; an aliphatic hydrocarbon such as pentane, hexane, heptane, petroleum ether, ligroin or petroleum benzine; an ether such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran or dioxane; an ester such as methyl acetate or 30 ethyl acetate; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or 1,2-dichloroethane; an acid amide such as N,N-dimethylformamide, N,N dimethylacetamide or N-methylpyrrolidinone; or a solvent mixture thereof. The reaction temperature is usually from -10 to 1000C, preferably from 0 to 30*C. The reaction time is usually from 0.5 to 6 hours. 35 PRODUCTION PROCESS [B] (X)m R 1
-NH
2 (X)m (IX) i 0 , CN-' N-R1 N COOH 0 (V]l) ( H ) In production process [B], R 1 , X and m are as defined above. In the production process [B], the compound of the formula (Vill) is reacted with a compound of the formula (IX) in the presence of a condensation agent to produce the compound of the formula (11). The compound of the formula (IX) may be used in a proportion of from 1 to 40 10 equivalents, preferably from 2 to 5 equivalents, per mol of the compound of the formula (Vill). The condensation agent may, for example, be a carbodiimide such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide or its salt. The WO 2010/055896 8 PCT/JP2009/069305 condensation agent may be used in a proportion of from 1 to 5 equivalents, preferably from 1 to 2 equivalents, per mol of the compound of the formula (Vill). This reaction may be carried out in the presence of a reaction accelerator, as the case requires. The reaction accelerator may, for example, be 1 -hydroxybenzotriazole, N-hydroxysuccinimide, 1 -hydroxy-7-azabenzotriazole or a 5 base. The base may, for example, be an organic base such as triethylamine, pyridine or 4 dimethylaminopyridine. The reaction accelerator may be used in a proportion of from 1 to 5 equivalents, preferably from 1 to 2 equivalents, per mol of the compound of the formula (VIII). This reaction may usually be carried out in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, 10 be an ether such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran or dioxane; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or 1,2 dichloroethane; an acid amide such as N,N-dimethylformamide, N,N-dimethylacetamide or N methylpyrrolidinone; or a solvent mixture thereof. The reaction temperature is usually from -10 to 100 0 C, preferably from 0 to 300C. The reaction time is usually from 1 to 24 hours. 15 The compound of the formula (V) to be used in the first step of the production process [2] may, for example, be produced by the following production process [C] or [D]. Now, the respective production processes will be described in detail with reference to the reaction flowcharts. PRODUCTION PROCESS[C] Halogenating (X)m X)m NH 2 OH (X)m agent N NO NN NOH N CHO First step N ' Second step (X) (X I) (V) 20 In production process [C], X, Z and m are as defined above. In the first step of the production process [C], a compound of the formula (X) is reacted with hydroxylamine or its salt to produce a compound of the formula (XI). The hydroxylamine or its salt may be used in a proportion of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per mol of the compound of the formula (X). This reaction may be carried out in the 25 presence of a base, as the case requires. The base may, for example, be an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; or an organic base such as triethylamine or pyridine. The base may be used in a proportion of from 1 to 5 equivalents, preferably from 1 to 2 30 equivalents, per mol of the compound of the formula (X). This reaction may usually be carried out in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, be water; an alcohol such as methanol, ethanol, propanol or butanol; an ether such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran or dioxane; a nitrile such as acetonitrile or propiononitrile; or a solvent mixture 35 thereof. The reaction temperature is usually from 0 to 1000C, preferably from 10 to 50'C. The reaction time is usually from 0.5 to 5 hours. In the second step of production process [C], the compound of the formula (XI) is reacted with a halogenating agent to produce a compound of the formula (V). The halogenating agent may, for example, be N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide or chlorine. 40 The halogenating agent may be used in a proportion of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per mol of the compound of the formula (XI). In a case where N chlorosuccinimide is used as the halogenating agent, the reaction may be carried out in the WO 2010/055896 9 PCT/JP2009/069305 presence of a small amount of hydrochloric acid, as the case requires. Such hydrochloric acid may be used in a proportion of e.g. from 0.01 to 0.5 equivalent, per mol of the compound of the formula (XI). This reaction may usually be carried out in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for 5 example, be a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or 1,2-dichloroethane; a nitrile such as acetonitrile or propiononitrile; or an acid amide such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidinone. The reaction temperature is usually from 0 to 800C, preferably from 20 to 500C. The reaction time is usually from 0.25 to 5 hours. 10 PRODUCTION PROCESS [D] Diazotizing agent (X)m (X)m Halogenating (X)m cl- I ~agent nO N CN N OH NetNaOH First step NH 2 Second step z (X II) (X II) (V) In production process [D], X, Z and m are as defined above. In the first step of the production process [D], a compound of the formula (XII) is reacted with hydroxylamine or its salt to produce a compound of the formula (XIII). The hydroxylamine or its salt may be used in a proportion of from 1 to 3 equivalents, preferably from 1 to 1.5 15 equivalents, per mol of the compound of the formula (XII). This reaction may be carried out in the presence of a base, as the case requires. The base may, for example, be the same one as mentioned in the first step of the above production process [C]. The base may be used in a proportion of from 1 to 5 equivalents, preferably from 1 to 2 equivalent, per mol of the compound of the formula (XII). This reaction may usually be carried out in the presence of a solvent. The 20 solvent may, for example, be the same one as mentioned in the first step of the above-mentioned production process [C]. The reaction temperature is usually from 0 to 1000C, preferably from 50 to 800C. The reaction time is usually from 0.5 to 5 hours. In the second step of the production process [D], the compound of the formula (XIII) is reacted with a diazotizing agent and a halogenating agent to produce a compound of the formula 25 (V). The diazotizing agent may, for example, be a nitrite such as sodium nitrite; or a nitrite ester such as isoamyl nitrite. The diazotizing agent may be used in a proportion of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per mol of the compound of the formula (XIII). The halogenating agent may, for example, be hydrochloric acid, hydrobromic acid or copper(I) halide. The halogenating agent may be used in a proportion of from 1 equivalent to a large 30 excess amount, per mol of the compound of the formula (XIII). This reaction may usually be carried out in the presence of a solvent. The solvent is not particularly limited so long as it presents no adverse effect to the reaction, and it may, for example, be water; an acid such as acetic acid or sulfuric acid; a nitrile such as acetonitrile or propiononitrile; or a solvent mixture thereof. Further, a halogenating agent such as hydrochloric acid or hydrobromic acid may be 35 used as a solvent. The reaction temperature is usually from -10 to 800C, preferably from 0 to 500C. The reaction time is usually from 0.5 to 5 hours. Preferred embodiments of pesticides containing the compounds of the present invention will be described below. The pesticides containing the compounds of the present invention are particularly useful, for example, as agents for controlling various pests which become problematic 40 in the agricultural and horticultural fields, i.e. agricultural and horticultural pesticides, or as agents for controlling pests which are parasitic on animals i.e. pesticides against parasites on animals.
WO 2010/055896 10 PCT/JP2009/069305 The agricultural and horticultural pesticides containing the compounds of the present invention are useful as an insecticide, a miticide, a nematicide or a soil pesticide, and they are effective for controlling plant parasitic mites such as two-spotted spider mite (Tetranychus urticae), carmine spider mite (Tetranychus cinnabarinus), kanzawa spider mite (Tetranychus kanzawai), 5 citrus red mite (Panonychus gitli), European red mite (Panonychus umi), broad mite (Polyphaqotarsonemus latus, pink citrus rust mite (Aculops pelekassi) and bulb mite (Rhizoclyphus echinopus); aphids such as green peach aphid (Myzus persicae) and cotton aphid (Aphis oossypii); agricultural insect pests such as diamondback moth (Plutella xylostella), cabbage armyworm (Mamestra brassicae), common cutworm (Spodoptera litura), codling moth 10 (cydia pomonella), bollworm (Heliothis 2ea), tobacco budworm (Heliothis virescens), gypsy moth (Lymantria dispar), rice leafroller (Cnaphalocrocis medinalis), smaller tea tortrix (Adoxophyes §p.), colorado potato beetle (Leptinotarsa decemlineata), cucurbit leaf beetle (Aulacophora femoralis), boll weevil (Anthonomus qrandis), planthoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworm (Aqrotis ipsilon), cutworm (Aqrotis 15 segetum) and ants; plant parasitic nematodes such as root-knot nematodes, cyst nematodes, root-lesion nematodes, white-tip nematode (Aphelenchoides bessevi), strawberry bud nematode (Nothotylenchus acris), and pine wood nematode (Bursaphelenchus xylophilus); gastropods such as slugs and snails; soil pests such as isopods such as pillbugs (Armadillidium vulgare) and pillbugs (Porcellio scaber); hygienic insect pests such as tropical rat mite (Ornithonyssus bacoti), 20 cockroaches, housefly (Musca domestic) and house mosquito (Culex pipiens); stored grain insect such as angoumois grain moth (Sitotroqa cerealella), adzuki bean weevil (Callosobruchus chinensis), red flour beetle (Tribolium castaneum) and mealworms; household goods insect pests such as casemaking clothes moth (Tinea pellionella), black carpet beetle (Attaqenus iaponicus) and subterranean termites; domestic mites such as mold mite (Tyrophagus putrescentiae), 25 Dermatophaqoides farinae, Chelacaropsis moorei, and so on. Among them, the agricultural and horticultural pesticides containing the compounds of the present invention are particularly effective for controlling plant parasitic mites, agricultural insect pests, plant parasitic nematodes or the like. Particularly, they are more effective for controlling plant parasitic mites and agricultural insect pests, and accordingly they are useful as an insecticide or miticide. Further, 30 they are effective against insect pests having acquired resistance to organophosphorus, carbamate and/or synthetic pyrethroid insecticides. Moreover, the compounds of the present invention have excellent systemic properties, and by the application of the agricultural and horticultural pesticides containing the compounds of the present invention to soil treatment, not only noxious insects, noxious mites, noxious nematodes, noxious gastropods and noxious 35 isopods in soil but also foliage pests can be controlled. Another preferred embodiments of the pesticides containing compounds of the present invention may be agricultural and horticultural pesticides which collectively control the above mentioned plant parasitic mites, agricultural insect pests, plant parasitic nematodes, gastropods and soil pests. 40 The agricultural and horticultural pesticide containing the compound of the present invention, is usually formulated by mixing the compound with various agricultural adjuvants and used in the form of a formulation such as a dust, granules, water-dispersible granules, a wettable powder, a water-based suspension concentrate, an oil-based suspension concentrate, water soluble granules, a water soluble powder, an emulsifiable concentrate, a soluble concentrate, a 45 paste, an aerosol or an ultra low-volume formulation. However, so long as it is suitable for the purpose of the present invention, it may be formulated into any type of formulation which is commonly used in this field. Such agricultural adjuvants include solid carriers such as WO 2010/055896 11 PCT/JP2009/069305 diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaoline, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, mirabilite, zeolite and starch; solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethylsulfoxide, N,N-dimethylformamide, N,N 5 dimethylacetamide, N-methyl-2-pyrrolidone, and alcohol; anionic surfactants such as a salt of fatty acid, a benzoate, an alkylsulfosuccinate, a dialkylsulfosuccinate, a polycarboxylate, a salt of alkylsulfuric acid ester, an alkyl sulfate, an alkylaryl sulfate, an alkyl diglycol ether sulfate, a salt of alcohol sulfuric acid ester, an alkyl sulfonate, an alkylaryl sulfonate, an aryl sulfonate, a lignin sulfonate, an alkyldiphenyl ether disulfonate, a polystyrene sulfonate, a salt of alkylphosphoric 10 acid ester, an alkylaryl phosphate, a styrylaryl phosphate, a salt of polyoxyethylene alkyl ether sulfuric acid ester, a polyoxyethylene alkylaryl ether sulfate, a salt of polyoxyethylene alkylaryl ether sulfuric acid ester, a polyoxyethylene alkyl ether phosphate, a salt of polyoxyethylene alkylaryl phosphoric acid ester, and a salt of a condensate of naphthalene sulfonate with formalin; nonionic surfactants such as a sorbitan fatty acid ester, a glycerin fatty acid ester, a fatty acid 15 polyglyceride, a fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, an oxyalkylene block polymer, a polyoxyethylene alkyl ether, a polyoxyethylene alkylaryl ether, a polyoxyethylene styrylaryl ether, a polyoxyethylene glycol alkyl ether, a polyethylene glycol, a polyoxyethylene fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyoxyethylene hydrogenated castor oil, and a polyoxypropylene fatty 20 acid ester; vegetable and mineral oils such as olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, and liquid paraffins; and so on. Each of the components as such adjuvants may be one or more suitably selected for use, so long as the purpose of the present invention can thereby be accomplished. Further, various additives which are commonly used, such as a filler, 25 a thickener, an anti-settling agent, an anti-freezing agent, a dispersion stabilizer, a phytotoxicity reducing agent, an anti-mold agent, and so on, may also be employed. The weight ratio of the compound of the present invention to the various agricultural adjuvants is usually from 0.001:99.999 to 95:5, preferably from 0.005:99.995 to 90:10. In the actual application of such a formulation, it may be used as it is, or may be diluted to 30 a predetermined concentration with a diluent such as water, and various spreaders e.g. surfactants, vegetable oils or mineral oils may be added thereto, as the case requires. The application of the agricultural and horticultural pesticide containing the compound of the present invention cannot generally be defined, as it varies depending upon the weather conditions, the type of the formulation, the application season, the application site or the types or 35 degree of outbreak of the pest insects. However, it is usually applied in a concentration of the active ingredient being from 0.05 to 800,000 ppm, preferably from 0.5 to 500,000 ppm, and the dose per unit area is such that the compound of the present invention is from 0.05 to 50,000 g, preferably from 1 to 30,000 g, per hectare. Further, the present invention includes such a method for controlling pests, particularly for controlling plant parasitic mites, agricultural insect 40 pests or plant parasitic nematodes by such applications. Various formulations of agricultural and horticultural pesticides containing the compounds of the present invention or their diluted compositions may be applied by conventional methods for application which are commonly employed, such as spraying (e.g. spraying, jetting, misting, atomizing, powder or grain scattering or dispersing in water), soil application (e.g. mixing or 45 drenching), surface application (e.g. coating, powdering or covering) or impregnation to obtain poisonous feed. Further, it is possible to feed domestic animals with a food containing the above active ingredient and to control the outbreak or growth of pests, particularly insect pests, WO 2010/055896 12 PCT/JP2009/069305 with their excrements. Furthermore, the active ingredient may also be applied by a so-called ultra low-volume application method. In this method, the composition may be composed of 100% of the active ingredient. Further, the agricultural and horticultural pesticides containing compounds of the present 5 invention may be mixed with or may be used in combination with other agricultural chemicals, fertilizers or phytotoxicity-reducing agents, whereby synergistic effects or activities may sometimes be obtained. Such other agricultural chemicals include, for example, a herbicide, an insecticide, a miticide, a nematicide, a soil pesticide, a fungicide, an antivirus agent, an attractant, an antibiotic, a plant hormone, a plant growth regulating agent, and so on. Especially, with a 10 mixed pesticide having a compound of the present invention mixed with or used in combination with one or more active compounds of other agricultural chemicals, the application range, the application time, the pesticidal activities; etc. may be improved to preferred directions. The compound of the present invention and the active compounds of other agricultural chemicals may separately be formulated so that they may be mixed for use at the time of application, or they may 15 be formulated together. The present invention includes such a mixed pesticidal composition. The mixing ratio of the compound of the present invention to the active compounds of other agricultural chemicals can not generally be defined, since it varies depending upon the weather conditions, the types of formulations, the application time, the application site, the types or degree of outbreak of insect pests, etc., but it is usually within a range of from 1:300 to 300:1, preferably 20 from 1:100 to 100:1, by weight. Further, the dose for the application is such that the total amount of the active compounds is from 0.1 to 50,000 g, preferably from 1 to 30,000 g, per hectare. The present invention includes a method for controlling pests by an application of such a mixed pesticide composition. The active compounds of insect pest control agents such as insecticides, miticides, 25 nematicides or soil pesticides in the above-mentioned other agricultural chemicals, include, for example, (by common names, some of them are still in an application stage, or test codes) organic phosphate compounds such as profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiofos, fosthiazate, cadusafos, dislufoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate, 30 sulprofos, thiometon, vamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorvinphos, chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, azinphos-methyl, fenthion, heptenophos, methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, methamidophos, imicyafos, parathion-methyl, terbufos, phosphamidon, phosmet and phorate; carbamate compounds such as 35 carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC and fenothiocarb; nereistoxin derivatives such as cartap, thiocyclam, bensultap and thiosultap-sodium; organic chlorine compounds such as dicofol, tetradifon, endosulfan, dienochlor and dieldrin; organic metal compounds such as fenbutatin oxide and cyhexatin; pyrethroid 40 compounds such as fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, ethofenprox, flufenprox, cyfluthrin, fenpropathrin, flucythrinate, fluvalinate, cycloprothrin, lambda cyhalothrin, pyrethrins, esfenvalerate, tetramethrin, resmethrin, protrifenbute, bifenthrin, zeta cypermethrin, acrinathrin, alpha-cypermethrin, allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta-cypermethrin, beta-cyfluthrin, metofluthrin, 45 phenothrin and flumethrin; benzoylurea compounds such as diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, triflumuron, hexaflumuron, lufenuron, novaluron, noviflumuron, bistrifluron and fluazuron; juvenile hormone-like compounds such as methoprene, pyriproxyfen, WO 2010/055896 13 PCT/JP2009/069305 fenoxycarb and diofenolan; pyrazole compounds such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole and pyriprole; neonicotinoids such as imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran and nithiazine; hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide and 5 halofenozide; pyridine compounds such as pyridalyl and flonicamid; tetronic acid compounds such as spirodiclofen; strobilurin compounds such as fluacrypyrim; pyrimidinamine 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, chlorenapyr, 10 indoxacarb, acequinocyl, etoxazole, cyromazine, 1,3-dichloropropene, diafenthiuron, benclothiaz, bifenazate, spiromesifen, spirotetramat, propargite, clofentezine, metaflumizone, flubendiamide, cyflumetofen, chlorantraniliprole, cyenopyrafen, pyrifluquinazon, fenazaquin, pyridaben, amidoflumet, chlorobenzoate, sulfluramid, hydramethylnon, metaldehyde, HGW 86, ryanodine and verbutin. Further, microbial pesticides such as insecticidal crystal protein produced by 15 Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis or Bacillus thuringiensis, insect viruses, etomopathogenic fungi, and nematophagous fungi; antibiotics or semisynthetic antibiotics such as avermectin, emamectin-benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin, emamectin and spinetoram; natural products such as 20 azadirachtin and rotenone; and repellents such as deet may, for example, be mentioned. The fungicidal active compounds in the above-mentioned other agricultural chemicals include, for example, (by common names, some of them are still in an application stage, or test codes of Japan Plant Protection Association) anilinopyrimidine compounds such as mepanipyrim, pyrimethanil, cyprodinil and ferimzone; triazolopyrimidine compounds such as 5-chloro-7-(4 25 methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine; pyridinamine compounds such as fluazinam; azole compounds such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, myclobutanil, cyproconazole, tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, 30 difenoconazole, fluquinconazole, fenbuconazole, bromuconazole, diniconazole, tricyclazole, probenazole, simeconazole, pefurazoate, ipconazole and imibenconazole; quinoxaline compounds such as quinomethionate; dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb and thiram; organic chlorine compounds such as fthalide, chlorothalonil and quintozene; imidazole compounds such as benomyl, thiophanate 35 methyl, carbendazim, thiabendazole, fuberiazole and cyazofamid; cyanoacetamide compounds such as cymoxanil; phenylamide compounds such as metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, ofurace, benalaxyl, benalaxyl-M (another name: kiralaxyl, chiralaxyl), furalaxyl and cyprofuram; sulfenic acid compounds such as dichlofluanid; copper compounds such as cupric hydroxide and oxine copper; isoxazole compounds such as hymexazol; organophosphorus 40 compounds such as fosetyl-AI, tolclofos-methyl, edifenphos, iprobenfos, S-benzyl 0,0 diisopropylphosphorothioate, O-ethyl S,S-diphenylphosphorodithioate and aluminum ethylhydrogen phosphonate; N-halogenothioalkyl compounds such as captan, captafol and folpet; dicarboximide compounds such as procymidone, iprodione and vinclozolin; benzanilide compounds such as flutolanil, mepronil, zoxamid and tiadinil; anilide compounds such as 45 carboxin, oxycarboxin, thifluzamide, penthiopyrad, boscalid, isothianil, bixafen and mixture of 2 syn-isomers 3-(difluoromethyl)-1 -methyl-N-[(1 RS,4SR,9RS)-1,2,3,4-tetrahydro-9-isopropyl-1,4 methanonaphthalen-5-yl]pyrazole-4-carboxamide and 2 anti-isomers 3-(difluoromethyl)-1 -methyl- WO 2010/055896 14 PCT/JP2009/069305 N-[(1 RS,4SR,9SR)-1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl]pyrazole-4 carboxamide (isopyrazam); piperazine compounds such as triforine; pyridine compounds such as pyrifenox; carbinol compounds such as fenarimol and flutriafol; piperidine compounds such as fenpropidine; morpholine compounds such as fenpropimorph, spiroxamine and tridemorph; 5 organotin compounds such as fentin hydroxide and fentin acetate; urea compounds such as pencycuron; cinnamic acid compounds such as dimethomorph and flumorph; phenylcarbamate compounds such as diethofencarb; cyanopyrrole compounds such as fludioxonil and fenpiclonil; strobilurin compounds such as azoxystrobin, kresoxim-methyl, metominofen, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin, pyraclostrobin and fluoxastrobin; oxazolidinone 10 compounds such as famoxadone; thiazolecarboxamide compounds such as ethaboxam; silylamide compounds such as silthiopham; aminoacid amidecarbamate compounds such as iprovalicarb, benthiavalicarb-isopropyl and methyl N-(isopropoxycarbonyl)-L-valyl-(3RS)-3-(4 chlorophenyl)-p-alaninate (valifenalate); imidazolidine compounds such as fenamidone; hydroxanilide compounds such as fenhexamid; benzenesulfonamide compounds such as 15 flusulfamide; oxime ether compounds such as cyflufenamid; phenoxyamide compounds such as fenoxanil; antibiotics such as validamycin, kasugamycin and polyoxins; guanidine compounds such as iminoctadine and dodine; quinoline compounds such as 6-tert-butyl-8-fluoro-2,3 dimethylquinolin-4-yl acetate (tebufloquin); thiazolidine compounds such as 2-[2-fluoro-5 (trifluoromethyl)phenythio]-2-[3-(2-methoxyphenyl)thiazolidin-2-ylidenelacetonitrile (flutianil); and 20 other compounds such as isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, metam-sodium, nicobifen, metrafenone, MTF-753, UBF 307, diclocymet, proquinazid, amisulbrom (another name: amibromdole), pyribencarb, mandipropamid, fluopicolide, carpropamid, meptylidinocap, fluopyram, BCF-051, BCM-061 and BCM-062. 25 Further, agricultural chemicals which may be used in admixture with or in combination with the compounds of the present invention, may, for example, be the active ingredient compounds in the herbicides as disclosed in The Pesticide Manual (14th edition), particularly those of soil treatment type. The pesticides against parasites on animals are effective for controlling e.g. external 30 parasites which are parasitic on the body surface of host animals (such as the back, the axilla, the lower abdomen or inside of the thigh) or internal parasites which are parasitic in the body of host animals (such as the stomach, the intestinal tract, the lung, the heart, the liver, the blood vessels, the subcutis or lymphatic tissues), but they are particularly effective for controlling the external parasites. 35 The external parasites may, for example, be animal parasitic acarus or fleas. Their species are so many that it is difficult to list all of them, and therefore, their typical examples will be given. The animal parasitic acarus may, for example, be ticks such as Boophilus microplus, Rhipicephalus sanauineus, Haemaphysalis longicornis, Haemaphysalis flava, Haemaphysalis 40 campanulata, Haemaphysalis concinna, Haemaphysalis aponica, Haemaphysalis kitaokai, Haemaphysalis ias, Lxodes ovatus, Ixodes nipponensis, Ixodes persulcatus, Amblyomma testudinarium, Haemaphysalis meqaspinosa, Dermacentor reticulatus, and Dermacentor taiwanesis; red mite (Dermanyssus qallinae); northern fowl mites such as Ornithonyssus sylviarum, and Ornithonyssus bursa; trombiculidae such as Eutrombicula wichmanni, 45 Leptotrombidium akamushi, Leptotrombidium palidum, Leptotrombidium fui, Leptotrombidium tosa, Neotrombicula autumnalis, Eutrombicula afredduqesi, and Helenicula miyaqawai; cheyletidae such as Cheyletiella yasquri, Cheyletiella parasitivorax, and Cheyletiella blakei; WO 2010/055896 15 PCT/JP2009/069305 sarcoptic.mange mites such as Psoroptes cuniculi, Chorioptes bovis, Otodectes cynotis, Sarcoptes scabiei, and Notoedres cati; and Demodicidae such as Demodex canis. The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of ticks among them. 5 The fleas may, for example, be externally parasitic wingless insects belonging to Siphonaptera, more specifically, fleas belonging to Pulicidae, Ceratephyllus, etc. Fleas belonging to Pulicidae may for example, be Ctenocephalides canis, Ctenocephalides fells, Pulex irritans, Echidnophaqa qallinacea, Xenopsylla cheopis, Leptopsylla seqnis, Nosopsyllus fasciatus, and Monopsyllus anisus. The pesticides against parasites on animals, containing the 10 compounds of the present invention, are particularly effective for the control of fleas belonging to Pulicidae, particularly Ctenocephalides canis and Ctenocephalides felis, among them. Other external parasites may, for example, be sucking lice (Anoplura) such as shortnosed cattle louse (Haematopinus eurysternus), horse sucking louse (Haematopinus asini), sheep louse, longnosed cattle louse (Linognathus vituli), and head louse (Pediculus capitis); biting lice such as 15 dog biting louse (Trichodectes canis); and blood-sucking dipterous insects such as horsefly (Tabanus triqonus), biting midges (Culicoides schultzei), and blackfly (Simulium ornatum). Further, the internal parasites may, for example, be nematodes such as lung worms, whipworms (Trichuris), tuberous worms, gastric parasites, ascaris, and filarioidea; cestoda such as Spirometra erinacei, Diphyllobothrium latum, Dipylidium caninum, Taenia multiceps, 20 Echinococcus granulosus, and Echinococcus multilocularis; trematoda such as Schistosoma aponicum and Fasciola hepatica; and protozoa such as coccidia, malaria parasites (Plasmodium malariae), intestinal sarcocyst, toxoplasma, and cryptosporidium. The host animals may, for example, be pet animals, domestic animals, and poultry, such as dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (such as pigeons, 25 parrots, hill mynas, Java sparrows, honey parrots, lovebirds and canaries), cows, horses, pigs, sheep, ducks and chickens. The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of pests parasitic on pet animals or domestic animals, especially for the control of external parasites, among them. Among pet animals or domestic animals, they are effective particularly for dogs and cats, cows 30 and horses. When the compound of the present invention is used as a pesticide against parasites on animals, it may be used as it is or may be used together with suitable adjuvants, as formulated into various formulations such as a dust, granules, tablets, a powder, capsules, a soluble concentrate, an emulsifiable concentrate, a water-based suspension concentrate and an oil 35 based suspension concentrate. In addition to such formulations, it may be formulated into any type of formulation which is commonly used in this field, so long as it is suitable for the purpose of the present invention. The adjuvants to be used for formulations may, for example, be anionic surfactants or nonionic surfactants exemplified above as adjuvants for formulation of agricultural and horticultural pesticides; a cationic surfactant such as cetyl trimethylammonium bromide; a 40 solvent such as 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 ether, diethylene glycol n-butyl ether, dipropylene 45 glycol monomethyl ether, or dipropylene glycol n-butyl ether; an antioxidant such as butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium hydrogenmetasulfite, propyl gallate or sodium thiosulfate; a coating film-forming agent such as polyvinylpyrrolidone, polyvinyl WO 2010/055896 16 PCT/JP2009/069305 alcohol, or a copolymer of vinyl acetate and vinyl pyrrolidone; the vegetable oils and mineral oils as exemplified above as adjuvants for formulation of agricultural and horticultural pesticides; a carrier such as lactose, sucrose, glucose, starch, wheat flour, corn powder, soybean cake and meal, defatted rice bran, calcium carbonate or other commercially available feed materials; and 5 so on. One or more of the respective components of these adjuvants may be suitably selected for use, so long as such will not depart from the purpose of the present invention. Further, other than the above-mentioned adjuvants, some among those known in this field may suitably be selected for use, and still further, some among the above-mentioned various adjuvants to be used in the agricultural and horticultural field may suitably be selected for use. 10 The blend ratio of the compound of the present invention to various adjuvants is usually from 0.1:99.9 to 90:10, by weight. In the actual use of such a formulation, it may be used as it is, or may be diluted to a predetermined concentration with a diluent such as water, and various spreaders (e.g. surfactants, vegetable oils or mineral oils) may be added thereto, as the case requires. 15 Administration of the compound of the present invention to a host animal is carried out orally or parenterally. As an oral administration method, a method of administering a tablet, a liquid agent, a capsule, a wafer, a biscuit, a minced meat or other feed, containing the compound of the present invention, may be mentioned. As a parenteral administration method, there may, for example, be mentioned a method wherein the compound of the present invention is 20 formulated into a suitable formulation and then taken into the body by e.g. intravenous administration, intramuscular administration, intradermal administration, hypodermic administration, etc.; a method wherein it is administered on the body surface by spot-on treatment, pour-on treatment or spray treatment; or a method of embedding a resin fragment or the like containing the compound of the present invention under the skin of the host animal. 25 The dose of the compound of the present invention to a host animal varies depending upon the administration method, the purpose of administration, the deceased symptom, etc., but it is usually administered in a proportion of from 0.01 mg to 100 g, preferably from 0.1 mg to 10 g, per 1 kg of the body weight of the host animal. The present invention also includes a method for controlling a pest by the above 30 mentioned administration method or by the above-mentioned dose, particularly a method for controlling external parasites or internal parasites. Further, in the present invention, by controlling pests parasitic on animals as described above, it is possible to prevent or cure various diseases of the host animal thereby caused in some cases. Thus, the present invention also includes a preventive or therapeutic agent for an 35 animal disease caused by parasites, containing the compound of the present invention as an active ingredient, and a method for preventing or curing an animal disease caused by parasites. When the compound of the present invention is used as a pesticide against parasites on animals, various vitamins, minerals, amino acids, nutrients, enzymes, antipyretics, sedatives, antiphlogistics, fungicides, colorants, aromatic substances, preservatives, etc., may be used in 40 admixture with or in combination with the adjuvants. Further, as the case requires, other animal drugs or agricultural chemicals, such as vermicides, anti-coccidium agents, insecticides, miticides, pulicides, nematicides, bactericides or antibacterial agents, may be mixed or combined for use, whereby improved effects may sometimes be obtained. The present invention includes such a mixed pesticidal composition having the above-mentioned various components mixed or 45 combined for use, and further a method for controlling a pest by using it, particularly a method for controlling external parasites or internal parasites. Now, preferred embodiments of the present invention will be described, but it should be WO 2010/055896 17 PCT/JP2009/069305 understood that the present invention is by no means thereby restricted. (1) A pyridine derivative represented by the formula (1) or its salt, wherein R 1 is alkyl, cycloalkyl, alkoxyalkyl or OR 3 ; R 2 is 1 H-1,2,4-triazol-1 -yl which may be substituted by alkyl, 1 H imidazol-1 -yl which may be substituted by alkyl, 1 H-1,2,3-triazol-1 -yl which may be substituted by 5 alkyl, or 4H-1,2,4-triazol-4-yl which may be substituted by alkyl; X is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, arylalkoxy which may be substituted by B, silylalkyl which is substituted by B, silylalkoxy which is substituted by B, alkylthio which may be substituted by A, alkenyl which may be substituted by A, alkynyl which may be 10 substituted by A, alkenyloxy which may be substituted by A, alkynyloxy which may be substituted by A, or phenoxy which may be substituted by B; R 3 is alkyl which may be substituted by D, cycloalkyl which may be substituted by E, alkenyl which may be substituted by D, alkynyl which may be substituted by D, phenylalkyl which may be substituted by E, pyridylalkyl which may be substituted by E, phenyl which may be substituted by E, silyl which is substituted by E, N 15 alkylcarbamoyl, N-alkoxycarbamoyl or N,N-dialkylcarbamoyl; A is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy and haloalkoxy; B is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy and haloalkoxy; D is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl and 20 alkylsilyl; E is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkylsilyl, tetrahydropyranyl, 1,3-dioxolan-2-yl and N,N-dialkylamino; and m is an integer of from 1 to 4. (2) The pyridine derivative or its salt according to the above (1), wherein X is alkyl which may 25 be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, or alkoxy which may be substituted by A; R 3 is alkyl which may be substituted by D, cycloalkyl which may be substituted by E, or alkenyl which may be substituted by D; and E is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl and alkylsilyl. 30 (3) The pyridine derivative or its salt according to the above (2), wherein R 1 is OR 3 ; and R 2 is 1 H-1,2,4-triazol-1 -yl, 1 H-imidazol-1 -yl, 1 H-1,2,3-triazol-1 -yl or 4H-1,2,4-triazol-4-yl. (4) A process for producing a pyridine derivative represented by the formula (1) or its salt, wherein R 1 is alkyl, cycloalkyl, alkoxyalkyl or OR 3 ; R 2 is 1 H-1,2,4-triazol-1 -yl which may be substituted by alkyl, 1 H-imidazol-1 -yl which may be substituted by alkyl, 1 H-1,2,3-triazol-1 -yl 35 which may be substituted by alkyl, or 4H-1,2,4-triazol-4-yl which may be substituted by alkyl; X is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, arylalkoxy which may be substituted by B, silylalkyl which is substituted by B, silylalkoxy which is substituted by B, alkylthio which may be substituted by A, alkenyl which may be substituted by A, 40 alkynyl which may be substituted by A, alkenyloxy which may be substituted by A, alkynyloxy which may be substituted by A, or phenoxy which may be substituted by B; R 3 is alkyl which may be substituted by D, cycloalkyl which may be substituted by E, alkenyl which may be substituted by D, alkynyl which may be substituted by D, phenylalkyl which may be substituted by E, pyridylalkyl which may be substituted by E, phenyl which may be substituted by E, silyl which is 45 substituted by E, N-alkylcarbamoyl, N-alkoxycarbamoyl or N,N-dialkylcarbamoyl; A is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy and haloalkoxy; B is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, WO 2010/055896 18 PCT/JP2009/069305 alkoxy and haloalkoxy; D is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl and alkylsilyl; E is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, 5 haloalkylcarbonyl, alkoxycarbonyl, alkylsilyl, tetrahydropyranyl, 1,3-dioxolan-2-yl and N,N dialkylamino; and m is an integer of from 1 to 4; which comprises (a) reacting a compound represented by the formula (lli), wherein Z is halogen; and R 1 , X and m are as defined above, with a compound represented by the formula (IV), wherein R 2 is as defined above; or 10 (b) reacting a compound represented by the formula (VI), wherein R 2 , X and m are as defined above, with a compound represented by the formula (VII), wherein L is halogen, alkylsulfonyloxy, trifluoromethanesulfonyloxy, or benzenesulfonyloxy which may be substituted by alkyl; and R 3 is as defined above. (5) A compound represented by the formula (VI) or its salt, wherein R 2 is 1 H-1,2,4-triazol-1 -yl 15 which may be substituted by alkyl, 1 H-imidazol-1 -yl which may be substituted by alkyl, 1 H-1,2,3 triazol-1 -yl which may be substituted by alkyl, or 4H-1,2,4-triazol-4-y which may be substituted by alkyl; X is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, arylalkoxy which may be substituted by B, silylalkyl which is substituted by B, silylalkoxy which is 20 substituted by B, alkylthio which may be substituted by A, alkenyl which may be substituted by A, alkynyl which may be substituted by A, alkenyloxy which may be substituted by A, alkynyloxy which may be substituted by A, or phenoxy which may be substituted by B, A is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy and haloalkoxy; B is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, 25 alkoxy and haloalkoxy; and m is an integer of from 1 to 4. EXAMPLES Now, the present invention will be described in further detail with reference to Examples, but it should be understood that the present invention is by no means restricted thereto. Firstly, Preparation Examples of the compounds of the present invention will be described. 30 PREPARATION EXAMPLE 1 Preparation of N-{[3-chloro-5-(trifluoromethyl)pyridin-2-y] (1 H-imidazol-1 -yl)methylene}propane-2 amine (Compound No. 1) (1) To 1.0 g of 3-chloro-5-(trifluoromethyl)picolinic acid, 1.0 ml of thionyl chloride and 0.1 ml of N,N-dimethylformamide were added, followed by heating and refluxing for 3 hours. After 35 completion of the reaction, the reaction mixture was concentrated under reduced pressure. A mixture of the obtained residue and 1 ml of tetrahydrofuran was dropwise added to a mixture of 0.52 g of isopropylamine and 10 ml of tetrahydrofuran under cooling with ice, followed by stirring for 1 hour under cooling with ice. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and washed with a saturated aqueous sodium chloride solution. 40 The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was subjected to washing with hexane to obtain 1.05 g of 3-chloro-N isopropyl-5-(trifluoromethyl)picolinamide as colorless needle crystals. Its NMR spectrum data are as follows. 'H NMR (400MHz, CDCI 3 ): 6 ppm = 1.27(6H, d, J=6.4Hz), 4.19-4.28(1H, m), 7.49(1H, broad 45 singlet), 8.03(1 H, d, J=1.2Hz), 8.67(1 H, d, J=1.2Hz) (2) To a mixture of 0.50 g of 3-chloro-N-isopropyl-5-(trifluoromethyl)picolinamide and 5 ml of toluene, 0.39 g of phosphorus pentachloride was added, followed by heating and refluxing for 3 WO 2010/055896 19 PCT/JP2009/069305 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain 1.1 ml of an oil containing 3-chloro-N-isopropyl-5-(trifluoromethyl)picolinimidoyl chloride. (3) To a mixture of 0.10 g of imidazole and 2 ml of acetonitrile, 0.4 ml of the oil obtained in (2) 5 was dropwise added at room temperature , followed by stirring for 1.5 hours at room temperature. After completion of the reaction, water was added to the reaction mixture, followed by extraction with ethyl acetate and washing with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (eluent: n-hexane/ethyl acetate) to 10 obtain 0.11 g of the desired product as yellow crystals. PREPARATION EXAMPLE 2 Preparation of [3-chloro-5-(trifluoromethyl)pyridin-2-y] (1 H-1,2,4-triazol-1 -yl)methanone O-ethyl oxime (Compound No. 10) (1) To 2.0 g of 3-chloro-5-(trifluoromethyl)picolinic acid, 2.0 ml of thionyl chloride and 0.2 ml of 15 N,N-dimethylformamide were added, followed by heating and refluxing for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. A mixture of the obtained residue and 1 ml of tetrahydrofuran was dropwise added to a mixture of 0.95 g of O-ethylhydroxylamine hydrochloride, 1.99 g of triethylamine, 10 ml of tetrahydrofuran and 10 ml of N,N-dimethylformamide, under cooling with ice, followed by stirring for 1 hour at 20 room temperature. After completion of the reaction, the reaction mixture was put into water, extracted with ethyl acetate and washed with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was subjected to washing with hexane to obtain 2.20 g of 3-chloro-N ethoxy-5-(trifluoromethyl)picolinamide as colorless needle crystals. Its NMR spectrum data are 25 as follows. 'H NMR (400MHz, CDCIs): 6 ppm = 1.33(3H, t, J=7.OHz), 4.10(2H, q, J=6.9Hz), 8.05(1 H, s), 8.66(1H, s), 9.82(1H, s) (2) To a mixture of 0.50 g of 3-chloro-N-ethoxy-5-(trifluoromethyl)picolinamide and 10 ml of acetonitrile, 0.98 g of triphenylphosphine and 0.3 ml of carbon tetrachloride were added, followed 30 by heating and refluxing for 15 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=7/1) to obtain 0.13 g of 3-chloro-N-ethoxy-5 (trifluoromethyl)picolinimidoyl chloride. Its NMR spectrum data are as follows. 1 H NMR (400MHz, CDCI 3 ): 6 ppm = 1.37(3H, t, J=7.6Hz), 4.37(2H, q, J=7.1 Hz), 8.03(1 H, s), 35 8.81(1H, s) (3) To a mixture of 32 mg of 1,2,4-triazole and 5 ml of N,N-dimethylformamide, 19 mg of sodium hydride (60 wt% dispersion in mineral oil) was added under cooling with ice, followed by stirring at room temperature for 15 minutes. Then, 90 mg of 3-chloro-N-ethoxy-5 (trifluoromethyl)picolinimidoyl chloride was dropwise added at room temperature, followed by 40 stirring at 1 00*C for 20 hours. After completion of the reaction, the reaction mixture was returned to room temperature, and water was added, followed by extraction with ethyl acetate and washing with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (eluent: n-hexane/ethyl acetate) to obtain 5 mg of 45 the desired product as a colorless oil. PREPARATION EXAMPLE 3 Preparation of [3-chloro-5-(trifluoromethyl)pyridin-2-y](1 H-1,2,4-triazol-1 -yl)methanone 0- WO 2010/055896 20 PCT/JP2009/069305 isopropyl oxime (Compound No. 13) (1) To a mixture of 3.0 g of 3-chloro-5-(trifluoromethyl)picolinaidehyde, 30 ml of methanol and 30 ml of water, a mixture of 1.2 g of hydroxylamine hydrochloride, 0.91 g of sodium carbonate and 10 ml of water, was dropwise added at room temperature, followed by stirring at room 5 temperature for 30 minutes. After completion of the reaction, 30 ml of water was added to the reaction mixture, followed by stirring at room temperature for 30 minutes. Precipitated crystals were collected by filtration, washed with water and dried to obtain 2.19 g of 3-chloro-5 (trifluoromethyl)picolinaldehyde oxime as colorless crystals. Its NMR spectrum data are as follows. 10 1 H NMR (400MHz, CDCI 3 ): 6 ppm = 7.68(1H, s), 8.36(1 H, s), 8.52(1 H, s) , 9.15(1H, s) (2) To a mixture of 1.0 g of 3-chloro-5-(trifluoromethyl)picolinaldehyde oxime and 5 ml of N,N dimethylformamide, 0.67 g of N-chlorosuccinimide was added, and hydrochloric acid gas was blown thereinto for 2 seconds, followed by stirring at room temperature for 1 hour. After completion of the reaction, water was added to the reaction mixture, followed by extraction with 15 diethyl ether and washing with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 1.20 g of 3-chloro-N-hydroxy-5-(trifluoromethyl)picolinimidoyl chloride as an oil. Its NMR spectrum data are as follows. 1 H NMR (400MHz, CDCI 3 ): 6 ppm = 8.05(1 H, s), 8.79(1 H, s), 9.58(1 H, s) 20 (3) To a mixture of 0.40 g of 1,2,4-triazole and 10 ml of N,N-dimethylformamide, 0.23 g of sodium hydride (60 wt% dispersion in mineral oil) was added under cooling with ice, followed by stirring at room temperature for 30 minutes. Then, a mixture of 1.0 g of 3-chloro-N-hydroxy-5 (trifluoromethyl)picolinimidoyl chloride and 5 ml of N,N-dimethylformamide, was dropwise added under cooling with ice, followed by stirring at room temperature for 2 hours. After completion of 25 the reaction, water was added to the reaction mixture, followed by extraction with ethyl acetate and washing with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (eluent: n-hexane/ethyl acetate) to obtain 0.29 g of [3-chloro-5-(trifluoromethyl)pyridin-2-yl](1 H-1,2,4-triazol-1 -yl)methanone oxime (Compound No. 30 VI-2) as a colorless amorphous solid. (4) To a mixture of 0.20 g of [3-chloro-5-(trifluoromethyl)pyridin-2-yl(1 H-1,2,4-triazol-1 yl)methanone oxime and 4 ml of N,N-dimethylformamide, 30 mg of sodium hydride (60 wt% dispersion in mineral oil) was added under cooling with ice, followed by stirring at room temperature for 15 minutes. Then, a mixture of 0.17 g of isopropyl iodide and 1 ml of N,N 35 dimethylformamide, was dropwise added under cooling with ice, followed by further stirring at room temperature for 1.5 hours. After completion of the reaction, water was added to the reaction mixture, followed by extraction with ethyl acetate and washing with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel flash 40 chromatography (eluent: n-hexane/ethyl acetate) to obtain 0.19 g of the desired product as a colorless oil. PREPARATION EXAMPLE 4 Preparation of [3-methyl-5-(trifluoromethyl)pyridin-2-yl](1 H-1,2,4-triazol-1 -yl)methanone O-ethyl oxime (Compound No.33) 45 (1) To a mixture of 0.53 g of 3-methyl-5-(trifluoromethyl)picolinonitrile and 10 ml of ethanol, a mixture of 0.22 g of hydroxylamine hydrochloride, 0.17 g of sodium carbonate and 10 ml of water, was added, followed by heating and refluxing for 1 hour. After completion of the reaction, the WO 2010/055896 21 PCT/JP2009/069305 reaction mixture was concentrated under reduced pressure, and 50 ml of water was added, followed by stirring at room temperature. Precipitated crystals were collected by filtration, washed with water and dried to obtain 0.58 g of N'-hydroxy-3-methyl-5 (trifluoromethyl)picolinimidamide as colorless crystals. Its NMR spectrum data are as follows. 5 'H NMR (400MHz, CDC13): 6 ppm = 2.62(3H, s), 5.63(2H, broad singlet), 7.75(1H, s), 8.69(1H, s) (2) To a mixture of 0.58 g of N'-hydroxy-3-methyl-5-(trifluoromethyl)picolinimidamide and 10 ml of a 10 wt% hydrochloric acid aqueous solution, a mixture of 0.22 g of sodium nitrite and 2 ml of water, was dropwise added under cooling with ice, followed by stirring for 1 hour under cooling 10 with ice. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and washed with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 0.57 g of N-hydroxy-3-methyl-5-(trifluoromethyl)picolinimidoy chloride as a solid. Its NMR spectrum data are as follows. 15 1 H NMR (400MHz, CDC13): 6 ppm = 2.47(3H, s), 7.79(lH, s), 8.72(1H, s) (3) To a mixture of 0.20 g of 1,2,4-triazole and 20 ml of N,N-dimethylformamide, 116 mg of sodium hydride (60 wt% dispersion in mineral oil) was added under cooling with ice, followed by stirring at room temperature for 30 minutes. Then, a mixture of 0.57 g of N-hydroxy-3-methyl-5 (trifluoromethyl)picolinimidoyl chloride and 10 ml of N,N-dimethylformamide was dropwise added 20 under cooling with ice, followed by stirring for 30 minutes under cooling with ice and further stirring at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was put into water, followed by extraction with ethyl acetate and washing with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel flash 25 chromatography (eluent: n-hexane/ethyl acetate) to obtain 0.13 g of [3-methyl-5 (trifluoromethyl)pyridin-2-yl](1 H-1,2,4-triazol-1 -yl)methanone oxime (Compound No. VI-5) as a colorless amorphous solid. (4) To a mixture of 0.13 g of [3-methyl-5-(trifluoromethyl)pyridin-2-y](1H-1,2,4-triazol-1 yl)methanone oxime and 4 ml of N,N-dimethylformamide, 21 mg of sodium hydride (60 wt% 30 dispersion in mineral oil) was added under cooling with ice, followed by stirring at room temperature for 30 minutes. Then, a mixture of 0.11 g of ethyl iodide and 1 ml of N,N dimethylformamide was dropwise added under cooling with ice, followed by stirring at room temperature for 1.5 hours. After completion of the reaction, water was added to the reaction mixture, followed by extraction with ethyl acetate and washing with a saturated aqueous sodium 35 chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (eluent: n-hexane/ethyl acetate) to obtain 72 mg of the desired product as a colorless oil. PREPARATION EXAMPLE 5 40 Preparation of [3-methylthio-5-(trifluoromethyl)pyridin-2-yl](1 H-1,2,4-triazol-1 -yl)methanone 0 ethyl oxime (Compound No. 67) To a mixture of 0.10 g of [3-chloro-5-(trifluoromethyl)pyridin-2-y]((1 H-1,2,4-triazol-1 yl)methanone O-ethyl oxime (Compound No. 10) and 2 ml of dimethylsulfoxide, 25 mg of sodium thiomethoxide was added at room temperature, followed by stirring at 800C for 15 hours. After 45 completion of the reaction, water was added to the reaction mixture, followed by extraction with ethyl acetate and washing with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The WO 2010/055896 22 PCT/JP2009/069305 residue was purified by silica gel flash chromatography (eluent: n-hexane/ethyl acetate) to obtain 74 mg of the desired product as a colorless oil. Typical examples of the compound of the above formula (I) will be given in Table 1. These compounds can be prepared by the above-described Preparation Examples or by the 5 above-described various processes for the production of the compound of the present invention. In Table 1, No. represents the Compound No., Me methyl, Et ethyl, n-Pr normal propyl, i-Pr isopropyl, n-Bu normal butyl, t-Bu tertiary butyl, sec-Bu secondary butyl and Ph phenyl, and the temperature shown as the physical properties is the melting point. Further, with respect to some compounds of the above formula (I), 1 H-NMR is shown in Table 2. 10 The compound of the above formula (VI) includes novel compounds, and typical examples thereof will be given in Table 3. These compounds can be prepared by the above described Preparation Examples or by the above-described production processes. Further, the compound of the formula (VI) can form a salt, and such a salt includes all kinds so long as they are acceptable in this technical field, and it may, for example, be an alkali metal salt such as a 15 sodium salt or a potassium salt; an alkaline earth metal salt such as a magnesium salt or a calcium salt; an inorganic acid salt such as a hydrochloride, a perchlorate, a sulfate or a nitrate; or an organic acid salt such as an acetate or a methanesulfonate. In Table 3, No. represents the Compound No., Me methyl and t-Bu tertiary butyl, and the temperature shown as the physical properties is the melting point. Further, with respect to some compounds of the above formula 20 (VI), 'H-NMR is shown in Table 4.
WO 2010/055896 23 PCT/JP2009/069305 x2 I C NuJxrR' 4 NN v' TABLE 1 No X1 x2 X' 3 X4 Physical No. R' R_ properties T 1 i-Pr N Cl H CF 3 H 52-540C 2 i-Pr (N N Cl H CF 3 H oil N-J_ T 3 Et (NN Cl H CF 3 H 4 Me (NN Cl H CF 3 H N-JI 5 n-Pr (NN C1 H CF 3 H
N-J
1 6 (NN Cl H CFS H
N
1 N 7 CH 2 OMe (NN Cl H CF 3 H 8 CH 2
CH
2 OMe (N N Cl H CF 3 H amorphous 9 CH 2 OEt NN Cl H CF 3 H N-JI T 10 OEt N N Cl H CF 3 H oil N- _ T 11 OEt N CI H CF 3 H oil 12 OEt N Cl H CF 3 H 75-761C N-N 13 O(i-Pr) NN Cl H CF 3 H oil N-J'_ _ __ _ _ _ WO 2010/055896 24 PCT/JP2009/069305 TABLE 1 (continued) No.R2 X2 R3 4 Physical properties 14 OMe( N C1 H CF 3 H 83-840C N-J_ 15 O(sec-Bu) (NN Cl H CF 3 H oil N I 16 O(n-Pr) (N N CI H CF 3 H 17 O(n-Bu) ~ N N CI H CF 3 H
N
2 T 18 O(t-Bu) IN N Cl H CF 3 H 19 N N Cl H CF 3 H (N '/ T 20 OEt N N Cl H CF 3 H oil 21 OCH 2 Ph (N N Cl H CF 3 H 89-90*C N/ 22 OCH 2
CH
2 N Cl H CF 3 H oil Me (%N _ _ _ __ _ _ 23 OEt (NN H H H Me 69-700C
N
2 24 OEt (N N H H CF 3 H oil 25 OEt (N N CF 3 H H H 89-90'C NJ T 26 OEt (N H CF 3 H H 70-71 C N-J T
CH
2 CH, . 27 OEt (NN H H H (t-Bu) N CC H 28 OCH 2 CN (NN C1 H CF 3 H oil ____________ N 2 _ __ _ _ __ _ __ _ _ WO 2010/055896 25 PCT/JP2009/069305 TABLE I (continued) No. R' R2 XXX X4 properties 29 OCH 2 COOMe (NN CI H CF 3 H oil
IN-
4 __ 30 OCH 2 CH = ( N Cl H CF 3 H oil C2N- 4 ____ 31 OEt NN Br H CF 3 H oil 32 'NN CI H CF 3 H oil 32__ __ _ NN 1 33 OEt IN N Me H CF 3 H oil
N
T 34 OEt NN H Me CF 3 H N-JI 3 QHCH 2
CH
2 (t 35 OEt NN H Bu) CF3 H _____ _____ N-J 1
CH
2
CH
2 36 OEt N N Cl H H (t-Bu) 3 tCH 2
CH
2 (t 37 OEt NN CI Bu) H H N -' T 38 OEt CNN e H CF 3 H N-J 39 O(i-Pr) (NN H CF 3 H 40 OEt N N CH 2 OMe H CF 3 H N -//_ T 41 OEt (NN H H H CH 2 OMe N-J 42 OEt (NN CH 2 OEt H CF 3 H N j' 43 OEt N N 2 O(n- H CF 3 H CN Pr) 1_ __ _ __1_ _ WO 2010/055896 26 PCT/JP2009/069305 TABLE 1 (continued) No. R' R2 X1 x2X 3
X
4 Physical X71 ro erties 44 OEt N N CH 2 O(i-Pr) H CF 3 H N-J T 45 OEt N CH 2
CH
2 0 H CF 3 H C~t N Et
N-
1 46 OEt N CH 2
CH
2 0 H CF 3 H
N-
1 47 OEt N N H H H N-J T 48 OEt (NN H H H 49 OEt ( N H H H 50 OEt N N NO 2 H CF 3 H
N
2 J 51 OEt (N CN H CF 3 H N-' 52 OEt (N N OMe H CF 3 H N-JI 53 O(i-Pr) (N OMe H CF 3 H N -// 54 OEt (N N OEt H CF 3 H 55 OEt N N O(n-Pr) H CF 3 H
N-
1 __ __ _ T 56 OEt N N O(n-Bu) H CF 3 H Na 57 OEt (N N e H CF 3 H
N-
1 58 OEt (N N O H CF 3 H
N
2 -J_ _ _ _ __ _ _ _ _ __ _ _ _ _ WO 2010/055896 27 PCT/JP2009/069305 TABLE 1 (continued) No. RX R 2 X3 X4 Physical 59 OEt N OCH 2
CH
2 H CF 3 H O~t N OMe N-JI 60 O(i-Pr) ( N OCH 2
CH
2 H CF 3 H (I N OMe T
OCH
2 C 61 OEt (N N H H H H 2 OMe T
OCH
2 C 62 O(i-Pr) (NN H H H H 2 OMe
N
63 OEt N N OCH 2
CH
2 H CF 3 H
(NOCF
3 N-_ _ 64 OEt (NN OCH 2 Ph H CF 3 H N -J 65 OEt (NN CH 2 SiMe 3 H CF 3 H N-J 66 OEt N OCH 2 SiM H CF 3 H
N
67 OEt (NN SMe H CF 3 H oil N -J' I T CH=CH 68 OEt (NN H H H (t-Bu) T 69 OEt (N H H H C=CH
N-
1 _ _ __ _ _ _ _ _ _ 70 OEt (NN OPh H CF 3 H N 71 OEt (NN CI H CF 3 H
N
73 OCH 2
CF
3 (NN Cl H CF 3 H
|N-J
WO 2010/055896 28 PCT/JP2009/069305 TABLE 1 (continued) No. R 1
R
2 Xx2 X3 X properties T 74 OCH 2 SMe N N C1 H CF 3 H N -' T 75 OCH 2 COMe CNN C1 H CF 3 H N-JI 76 OCH 2
COCF
3 (NN CI H CF 3 H N- _ _ T 77 OCH 2 SiMe 3 (NN C1 H CF 3 H N-J 78 0 ( N CI H CF 3 H T 79 O N N CI H CF 3 H 80 OCH 2 CH=CH N N C| H CF 3 H
OH
3 NNJ 81 OCH 2 CH=CCI N CI H CF 3 H 2
~N-
0 ' 82 OCH 2 CH=CH N N C1 H CF 3 H
CN-
WO 2010/055896 29 PCT/JP2009/069305 TABLE 1 (continued)
N.RR
2 X1 X2 X3 X4 Physical No. R1 RX proprtis 83 OEt NN H H H CF 3 67-680C N-//__ _ __ _ 84 OEt (NN CI H H CFq 93-940C N-J T 85 CH 2
CH
2 OMe CN) CI H CF 3 H oil N-N
OCH
2 (t 86 OEt CNN CI H H Bu) N-JI
CH
2
CH
2 87 0(i-Pr) N N Cl H H (t-Bu) N-// CH=CH 88 OEt (NN Cl H H t-Bu) Na C=C(t 89 OEt N N CI H H Bu)
N-
1 90 OEt N N F H CF 3 H NJ 91 OEt CNN NH 2 H CF 3 H N-J 92 OEt (N NHCOCFs H CF 3 H N-N ___IN N 93 OEt N N H / OMe H CF 3 H
N
94 OEt CNN Cl H H CI N-" I T
OCH
2 Si 95 OEt N N CI H H Me 3 N-_ T 96 QEt CNN CI H OCOCF 3 ___________ ~ N- 1 _ _ _ _ _ _ _ _ __ _ _ _ WO 2010/055896 30 PCT/JP2009/069305 TABLE 1 (continued) No. R'
R
2 X2 x 3 x 4 Physical No. 4 R2 X X2X Xproperties 97 OEt NN NMe 2 H CF 3 H N-' 98 OEt ( N NHCH 2 O H CF 3 H _______ (% N Me 99 OEt N N NHCH 2 CF H CF 3 H N 100 OEt (NN NHCH 2 CN H CF 3 H N-J/ T 102 OEt ~ .N NHSOM H CF 3 H 103 OEt (NN NHSO 2 Me H CF 3 H N-J' 104 OEt (.NN CI H H NHCOPh 105 OEt NNCl H H N K 106 OEt (NN NC H H OCOPh Na 107 OEt (N N Cl H H OCOOMe
N-
0 108 OEt (NN Cl H H OSOMe Na 110 OEt ( N Cl H H KCF 3
N-
4 WO 2010/055896 31 PCT/JP2009/069305 TABLE 1 (continued N RI X2 R 2 43 Physical No. R' R___X__ properties 111 OEt (NNC H H Ph N-f 112 OEt (Ig N Cl H H P NJ 112 OEt (NNC1 H H COIe 114 O~t (N N ClHH COs N-J T 113 OEt (N N Cl H H COme N-J_ 114 OEt (N N Cl H H COOF 3 N- _ T 115 OEt N N Cl H H COPh N-_ T 116 OEt (N N Cl H H COOPh N- _ 117 OEt (N N Cl H H SMe ____ N 118 OEt (N N Cl H H some
N
119 OEt N N Cl H H SO 2 Me
N-
1 120 OEt N N Cl H H CONMe 2 N-JI 4 OCONHC 121 OEt (IN N CI H H H 2 CN
N-
1 _____ 122 QEt (I NN Cl H H SCH 2
CF
3 T 123 OEt .N N CI H H OH
N-J
1 124 OEt NN I H CF 3 H ___________ N- 2 ' _ _ _ __ _ _ __ _ _ _ WO 2010/055896 32 PCT/JP2009/069305 TABLE 2 N H-NMR Sppm (Solvent: CDC 3 400MHz) 2 1.20(6H, d, J=9.6Hz), 3.35(1 H, m), 7.90(1 H, s),8.08(1H, d, J=2.OHz), 8.88(1 H, d, J=1.2Hz), 9.05(1 H, s) 8 3.39(3H, s), 3.53(2H, t, J=6.OHz), 3.69(2H, t, J=6.OHz), 7.93(1H, s), 8.11(1H, d, J=1.6Hz), 8.91(1 H, d, J=1.6Hz), 9.09(1 H, s) 10 1.43(3H, t, J=7.0Hz), 4.43(2H, q, J=7.2Hz), 7.92(1H, s), 8.05(1H, d, J=1.6Hz), 8.83(1H, d, J=1.2Hz), 9.30(1H, s) 11 1.34(3H, t, J=7.2Hz), 4.31(2H, q, J=6.8Hz), 7.02(2H, m), 8.03(2H, m), 8.80(1 H, s) 13 1.41(6H, d, J=6.4Hz), 4.63(1 H, m), 7.92(1 H, s), 8.06(1 H, s), 8.83(1 H, s), 9.32(1 H, s) 15 0.98(3H, t, J=7.2Hz), 1.38(3H, d, J=6.4Hz), 4.44(1H, m), 7.92(1 H, s), 8.05(1 H, s), 8.83(1 H, s), 9.31 (1H, s) 20 1.41(3H, t, J=7.2Hz), 4.43(2H, q, J=6.9Hz), 7.80 (1H, s), 8.04(1 H, d, J=2.OHz), 8.71 (1 H, s), 8.83(1 H, d, J=1.6Hz) 22 3.41(3H, s), 3.37(2H, m), 4.50(2H, m), 7.92(1H, s), 8.04(1H, broad singlet), 8.83(1H, broad singlet), 9.35(1 H, s) 24 1.37(3H, t, J=7.2Hz), 4.42(2H, q, J=7.1Hz), 8.09(1H, d, J=8.4Hz), 8.16(1 H, s), 8.25(1 H, dd, J=8.6Hz, J=2.2Hz), 8.85(1 H, broad singlet), 9.01(1 H, s) 27 0.91(9H, s), 1.36(3H, t, J=7.2Hz), 1.53(2H, m), 2.73(2H, m), 4.36(2H, q, J=7.1 Hz), 7.23(1H, d, J=8.OHz), 7.52(1H, d, J=7.2Hz), 7.67(1 H, t, J=7.8Hz), 8.02(1 H, s), 8.90(1 H, s) 28 5.00(2H, s), 7.96(1 H, s), 8.08(1 H, d, J=0.8Hz), 8.84(1 H, d, J=1.6Hz), 9.17(l H, s) 29 3.79(3H, s), 4.90(2H, s), 7.93(1 H, s), 8.04(1 H, s), 8.82(1H, s), 9.41 (1 H, s) 30 4.85(2H, dd, J=6.6Hz, J=1.2Hz), 5.40(2H, dt, J=27.6Hz, J=10.4Hz), 6.07(1 H, m), 7.92(1H, s), 8.05(1 H, d, J=1.6Hz), 8.83(1 H, d, J=0.8Hz), 9.30(1 H, s) 31 1.42(3H, t, J=6.8Hz), 4.43(2H, q, J=6.8Hz), 7.94(1 H, s), 8.24(1H, s), 8.87(1H, s), 9.31 (1H, s) 32 0.38(2H, m), 0.67(2H, m), 1.29(1H, m), 4.20(2H, d, J=7.2Hz), 7.95(1H, s), 8.06(1H, d, J=2.0Hz), 8.85(1 H, d, J=1.2Hz), 9.40(1 H, s) 33 1.40(3H, t, J=7.2Hz), 2.45(3H, s), 4.39(2H, q, J=7.2Hz), 7.86(1H, s), 7.92(1H, s), 8.74(1H, s), 9.27(1H, s) 67 1.45(3H, t, J=7.OHz), 2.50(3H, s), 4.44(2H, q, J=7.OHz), 7.84(1H, s), 7.97(1H, s), 8.66(1H, s), 9.24(1 H, s) 85 3.34(3H, s), 3.49(2H, t, J=5.6Hz), 3.66(2H, t, J=5.6Hz), 8.21 (1 H, s), 8.41(2H, s), 8.99(1 WO 2010/055896 33 PCT/JP2009/069305 X2 X - Nav'OH R 2 TABLE 3 No. R X3 X 2 X Physical properties VI-1 (N) CI H CF 3 H amorphous N-N T VI-2 ( N Cl H CF 3 H amorphous N VI-3 (N N H H H Me powder T VI-4 (NN Br H CF 3 H powder
N
VI-5 NN Me H CF 3 H amorphous VI-6 (N N CF 3 H H H _ _ _ N- 4 __ _ __ _ T VI-7 NN H CF 3 H H Na VI-8 (NN H H CF 3 H
N-J
1 T VI-9 (N N H H H CH 2
CH
2 (t-Bu) VI-10 ( NN C1 H H CF 3 amorphous N-J VI-11 N Cl H H C=C(t-Bu) oil N-J VI-12 (NN H H H CF 3 powder VI-13 CNN Cl H H OH VI-14 N N Cl H H Cl WO 2010/055896 34 PCT/JP2009/069305 TABLE 4 No. 'H-NMR 6ppm (Solvent: CD 3 OD 400MHz) VI-1 8.45(1H, s), 8.89(1 H, s), 8.93(2H, s) VI-2 8.02(1H, s), 8.41 (1 H, s), 8.89(lH, s), 9.54(1 H, s) 2.47(3H, s), 7.34(1H, d, J=8.OHz), 7.55(1 H, d, J=7.2Hz), 7.77(1 H, t, J=7.8Hz), 8.12(1H, s), VI-3 9.05(1 H, s) VI-4 8.02(1H, s), 8.54(1 H, s), 8.93(1H, s), 9.55(1H, s) 2.24(3H, s), 7.83(1H, s), 7.90(1H, s), 8.68(1H, s), 9.40(1H, s), 12.5(1H, broad singlet) VI-5 (Solvent: CDCi 3 ) - 07.77(1H, d, J=8.8Hz), 8.00(1H, d, J=8.OHz), 8.00(1H, s), 9.54(1H, s), 11.83(1H, broad V__-10 singlet) ( Solvent: CDC1 3 ) 1.35(9H, s), 7.45(1H, d, J=8.8Hz), 7.73(1H, d, J=8.4Hz), 7.96(1H, s), 9.38(1H, s), V I_11 10.74(1H, broad singlet) (Solvent: CDCI 3 ) Now, Test Examples will be described. TEST EXAMPLE 1 Test on controlling effects against green peach aphid (Myzus persicae) 5 A Japanese radish leaf was inserted in a test tube in which water was put, and about 20 first instar nymphs of green peach aphid were released on the leaf. On the next day, the number of nymphs parasitic on the leaf was counted, and then the leaf was dipped for about 10 seconds in an insecticidal solution adjusted to bring the concentration of the compound of the present invention to 200 ppm, dried in air and left in a constant temperature chamber at 250C with 10 lightening. Dead nymphs were counted 5 days after the treatment, and the mortality was calculated by the following equation. The insects dropped from the leaf or presented toxic symptom were counted as dead insects. The test was carried out with respect to the above mentioned compound Nos. 10, 11, 14, 27, 31, 32 and 33, whereby all compounds showed a mortality of at least 90%. 15 Mortality (%)=(1 -(number of survived insects/number of treated insects))x1 00 TEST EXAMPLE 2 Test on controlling effects against brown planthopper (Nilaparvata lugens) Rice seedling was dipped for about 10 seconds in an insecticidal solution adjusted to bring the concentration of the compound of the present invention to 200 ppm and then dried in air, its 20 root was wrapped with a wet absorbent cotton, and the seedling was put into a test tube. Then, 10 second-third instar nymphs of Brown Planthopper were released therein, and the test tube was covered with a gauze and left in a constant temperature chamber at 250C with lightening. On the 5th day after the release, dead nymphs were counted, and the mortality was calculated by the following equation. 25 The test was carried out with respect to the above-mentioned Compound Nos. 10, 11, 12, 13,14,15, 22, 23, 24, 25, 26, 27, 28, 30, 31, 32, 33, 83 and 84, whereby all compounds showed a mortality of at least 90%. Mortality (%)=(number of dead insects/number of released insects)xl 00 TEST EXAMPLE 3 30 Test on controlling effects against silverleaf whitefly (Bemisia argentifolii) An insecticidal solution adjusted to bring the concentration of the compound of the present invention to 200 ppm was applied by a hand spray to cucumber seedling planted in a pot on which first-second instar nymphs of silverleaf whitefly were parasitic, and dried in air. Thereafter, WO 2010/055896 35 PCT/JP2009/069305 the cucumber seedling was left in a constant temperature chamber at 250C with lightening. The number of old instar nymphs was counted 7 days after the treatment, and the protective value (%) was obtained by the following equation. The test was carried out with respect to the above mentioned compound Nos. 10, 31, 32 and 84, whereby all the compounds showed a protective 5 value of at least 80%. Protective value (%) = (1 -((TaxCb)/(TbxCa)))xl 00 Ta: The number of old instar nymphs after the treatment at the treated cucumber seedling Tb: The number of first-second instar nymphs before the treatment at the treated cucumber seedling 10 Ca: The number of old instar nymphs after the treatment at the untreated cucumber seedling Cb: The number of first-second instar nymphs before the treatment at the untreated cucumber seedling TEST EXAMPLE 4 15 Pesticidal test against HaemaphVsalis longicornis employing a dog A gelatin capsule containing the compound of the present invention at a dose of 10 mg/kg weight is applied to a dog (Beagle, 8 months old), and immediately after the application, about 50 young mites of Haemaphvsalis lonaicornis are released on the auricle of the dog and artificially parasitized. After the treatment, observation is carried out to inspect the parasitic number, the 20 fallen number and the mortality of the fallen Haemaphysalis lonqicornis. As a result, the compound of the present invention is effective to have the parasitized Haemaphysalis longicornis fallen or dead. TEST EXAMPLE 5 Pesticidal test against cat flea (Ctenocephalides ftes) employing a dog 25 A gelatin capsule containing the compound of the present invention at a dose of 10 mg/kg weight is applied to a dog (Beagle, 8 months old), and immediately after the application, about 100 non-bloodsucked adults of cat flea are released on the dorsal fur of the dog and artificially parasitized. After the treatment, the cat flea is recovered by means of a flea catching comb, and the parasitized number is counted. As a result, the compound of the present invention is 30 effective to control the parasitizing of cat flea. Now, Formulation Examples are described below. FORMULATION EXAMPLE 1 (1) Compound of the present invention 20 parts by weight (2) Clay 70 parts by weight 35 (3) White carbon 5 parts by weight (4) Sodium polycarboxylate 3 parts by weight (5) Sodium alkylnaphthalene sulfonate 2 parts by weight The above components are uniformly mixed to obtain a wettable powder. FORMULATION EXAMPLE 2 40 (1) Compound of the present invention 5 parts by weight (2) Talc 60 parts by weight (3) Calcium carbonate 34.5 parts by weight (4) Liquid paraffin 0.5 part by weight The above components are uniformly mixed to obtain a dust. 45 FORMULATION EXAMPLE 3 (1) Compound of the present invention 20 parts by weight (2) N,N-dimethylacetamide 20 parts by weight WO 2010/055896 36 PCT/JP2009/069305 (3) Polyoxyethylene tristyryl phenyl ether 10 parts by weight (4) Calcium dodecylbenzene sulfonate 2 parts by weight (5) Xylene 48 parts by weight The above components are uniformly mixed and dissolved to obtain an emulsifiable 5 concentrate. FORMULATION EXAMPLE 4 (1) Clay 68 parts by weight (2) Sodium lignin sulfonate 2 parts by weight (3) Polyoxyethylenealkylaryl sulfate 5 parts by weight 10 (4) White carbon 25 parts by weight The mixture of the above components is mixed with compound of the present invention in a weight ratio of 4:1 to obtain a wettable powder. FORMULATION EXAMPLE 5 (1) Compound of the present invention 50 parts by weight 15 (2) Sodium alkylnaphthalene sulfonate condensation product of formaldehyde 2 parts by weight (3) Silicone oil 0.2 part by weight (4) Water 47.8 parts by weight The above components are uniformly mixed and pulverized to obtain a base liquid, and 20 (5) Sodium polycarboxylate 5 parts by weight (6) Anhydrous sodium sulfate 42.8 parts by weight are added, and the mixture is uniformly mixed, granulated and dried to obtain water-dispersible granules. FORMULATION EXAMPLE 6 25 (1) Compound of the present invention 5 parts by weight (2) Polyoxyethyleneoctylphenyl ether 1 part by weight (3) Polyoxyethylene alkyl ether phosphoric acid ester 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight The above components (1) to (3) are preliminarily uniformly mixed and diluted with a 30 proper amount of acetone, and then the mixture is sprayed onto the component (4), and acetone is removed to obtain granules. FORMULATION EXAMPLE 7 (1) Compound of the present invention 2.5 parts by weight (2) N,N-dimethylacetamide 2.5 parts by weight 35 (3) Soybean oil 95.0 parts by weight The above components are uniformly mixed and dissolved to obtain an ultra low volume formulation. FORMULATION EXAMPLE 8 (1) Compound of the present invention 40 parts by weight 40 (2) Potassium polyoxyethylene styryl phenyl ether phosphate 4 parts by weight (3) Silicone oil 0.2 part by weight (4) Xanthan gum 0.1 part by weight (5) Ethylene glycol 5 parts by weight (6) Water 50.7 parts by weight 45 The above components are uniformly mixed and pulverized to obtain a water-based suspension concentrate. FORMULATION EXAMPLE 9 WO 2010/055896 37 PCT/JP2009/069305 (1) Compound of the present invention 10 parts by weight (2) Diethylene glycol monoethyl ether 80 parts by weight (3) Polyoxyethylenealkyl ether 10 parts by weight The above components are uniformly mixed to obtain a soluble concentrate. 5 The entire disclosure of Japanese Patent Application No. 2008-292881 filed on November 17, 2008 including specification, claims and summary is incorporated herein by reference in its entirety.

权利要求:
Claims (11)
[1] 1. A pyridine derivative represented by the formula (1) or its salt: (X)m Na^ R' (I) N R2 wherein R' is alkyl, cycloalkyl, alkoxyalkyl or OR 3 ; R 2 is 1 H-1,2,4-triazol-1-yl which may be substituted by alkyl, I H-imidazol-1 -yl which may be substituted by alkyl, 1 H-1,2,3-triazol-1 -yl 5 which may be substituted by alkyl, or 4H-1,2,4-triazol-4-yl which may be substituted by alkyl; X is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, arylalkoxy which may be substituted by B, silylalkyl which is substituted by B, silylalkoxy which is substituted by B, alkylthio which may be substituted by A, alkenyl which may be substituted by A, 10 alkynyl which may be substituted by A, alkenyloxy which may be substituted by A, alkynyloxy which may be substituted by A, phenoxy which may be substituted by B, hydroxyl, NR 4 R , OCOR, OCOOR 6 , OS(O),R 6 , aryl which may be substituted by B, heteroaryl which may be substituted by B, COR , COOR , S(O),R or CONR 4 R 5 ; R 3 is alkyl which may be substituted by D, cycloalkyl which may be substituted by E, alkenyl which may be substituted by D, alkynyl which 15 may be substituted by D, phenylalkyl which may be substituted by E, pyridylalkyl which may be substituted by E, phenyl which may be substituted by E, silyl which is substituted by E, N alkylcarbamoyl, N-alkoxycarbamoyl or N,N-dialkylcarbamoyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl which may be substituted by A, cycloalkyl which may be substituted by B, arylalkyl which may be substituted by B, heteroarylalkyl which may be substituted by B, COR , 20 COOR , S(O),R 6 or CH 2 CN; R 6 is alkyl, haloalkyl, or aryl which may be substituted by B; A is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy and haloalkoxy; B is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy and haloalkoxy; D is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, 25 haloalkylcarbonyl, alkoxycarbonyl and alkylsilyl; E is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkylsilyl, tetrahydropyranyl, 1,3-dioxolan-2-yl and N,N-dialkylamino; m is an integer of from 1 to 4; and n is 1 or 2.
[2] 2. A pyridine derivative represented by the formula (1) or its salt: (X)m N R2 30 wherein R 1 is alkyl, cycloalkyl, alkoxyalkyl or OR 3 ; R 2 is 1 H-1,2,4-triazol-1 -yl which may be substituted by alkyl, 1 H-imidazol-1 -yl which may be substituted by alkyl, 1 H-1,2,3-triazol-1 -yl which may be substituted by alkyl, or 4H-1,2,4-triazol-4-yl which may be substituted by alkyl; X is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, 35 arylalkoxy which may be substituted by B, silylalkyl which is substituted by B, silylalkoxy which is WO 2010/055896 39 PCT/JP2009/069305 substituted by B, alkylthio which may be substituted by A, alkenyl which may be substituted by A, alkynyl which may be substituted by A, alkenyloxy which may be substituted by A, alkynyloxy which may be substituted by A, or phenoxy which may be substituted by B; R 3 is alkyl which may be substituted by D, cycloalkyl which may be substituted by E, alkenyl which may be substituted 5 by D, alkynyl which may be substituted by D, phenylalkyl which may be substituted by E, pyridylalkyl which may be substituted by E, phenyl which may be substituted by E, silyl which is substituted by E, N-alkylcarbamoyl, N-alkoxycarbamoyl or N,N-dialkylcarbamoyl; A is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy and haloalkoxy; B is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, 10 alkoxy and haloalkoxy; D is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl and alkylsilyl; E is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkylsilyl, tetrahydropyranyl, 1,3-dioxolan-2-yl and N,N 15 dialkylamino; and m is an integer of from 1 to 4.
[3] 3. The pyridine derivative or its salt according to Claim 2, wherein X is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, or alkoxy which may be substituted by A; R 3 is alkyl which may be substituted by D, cycloalkyl which may be substituted by E, or alkenyl which may be substituted by D; and E is at least one substituent 20 selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl and alkylsilyl.
[4] 4. The pyridine derivative or its salt according to Claim 3, wherein R 1 is OR 3 ; and R 2 is 1H 1,2,4-triazol-1 -yl, 1 H-imidazol-1 -yl, 1 H-1,2,3-triazol-1 -yl or 4H- 1,2,4-triazol-4-yl.
[5] 5. A pesticide containing the pyridine derivative or its salt as defined in Claim 1, as an active 25 ingredient.
[6] 6. An agricultural and horticultural pesticide containing the pyridine derivative or its salt as defined in Claim 1, as an active ingredient.
[7] 7. An insecticide, miticide, nematicide or soil pesticide containing the pyridine derivative or its salt as defined in Claim 1, as an active ingredient. 30
[8] 8. An insecticide or miticide containing the pyridine derivative or its salt as defined in Claim 1, as an active ingredient.
[9] 9. A method for controlling a pest, which comprises applying an effective amount of the pyridine derivative or its salt as defined in Claim 1.
[10] 10. A process for producing a pyridine derivative represented by the formula (1) or its salt: (X)m N. N^^R (I) R 2 35 wherein R' is alkyl, cycloalkyl, alkoxyalkyl or OR 3 ; R 2 is 1 H-1,2,4-triazol-1 -yl which may be substituted by alkyl, 1 H-imidazol-1 -yl which may be substituted by alkyl, 1 H-1,2,3-triazol-1 -yl which may be substituted by alkyl, or 4H-1,2,4-triazol-4-yl which may be substituted by alkyl; X is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, 40 arylalkoxy which may be substituted by B, silylalkyl which is substituted by B, silylalkoxy which is substituted by B, alkylthio which may be substituted by A, alkenyl which may be substituted by A, WO 2010/055896 40 PCT/JP2009/069305 alkynyl which may be substituted by A, alkenyloxy which may be substituted by A, alkynyloxy which may be substituted by A, phenoxy which may be substituted by B, hydroxyl, NR 4 R 5 OCOR 6 , OCOOR , OS(O)nR , aryl which may be substituted by B, heteroaryl which may be substituted by B, COR", COOR , S(O),R 6 or CONR 4 R 5 ; R 3 is alkyl which may be substituted by D, 5 cycloalkyl which may be substituted by E, alkenyl which may be substituted by D, alkynyl which may be substituted by D, phenylalkyl which may be substituted by E, pyridylalkyl which may be substituted by E, phenyl which may be substituted by E, silyl which is substituted by E, N alkylcarbamoyl, N-alkoxycarbamoyl or N,N-dialkylcarbamoyl; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl which may be substituted by A, cycloalkyl which may be substituted by B, 10 arylalkyl which may be substituted by B, heteroarylalkyl which may be substituted by B, COR 6 , COOR 6 , S(O)nR 6 or CH 2 CN; R 6 is alkyl, haloalkyl, or aryl which may be substituted by B; A is at least one substituent selected from the group consisting of cycloalkyl, halogen, alkoxy and haloalkoxy; B is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy and haloalkoxy; D is at least one substituent selected from the group 15 consisting of cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl and alkylsilyl; E is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkylthio, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkylsilyl, tetrahydropyranyl, 1,3-dioxolan-2-yl and N,N-dialkylamino; m is an integer of from 1 to 4; and n is 1 or 2, which comprises 20 (1) reacting a compound represented by the formula (lli): (X)m NSJRI (III) N -- R Z z wherein Z is halogen; and R 1 , X and m are as defined above, with a compound represented by the formula (IV): R 2 -H wherein R 2 is as defined above; or (2) reacting a compound represented by the formula (VI): (X)m N--"OH (VI) N R2 wherein R 2 , X and m are as defined above, with a compound represented by the formula (VII): 25 R 3 -L wherein L is halogen, alkylsulfonyloxy, trifluoromethanesulfonyloxy, or benzenesulfonyloxy which may be substituted by alkyl; and R 3 is as defined above.
[11] 11. A compound represented by the formula (VI) or its salt: (X)m N-OH (V) R 2 wherein R 2 is 1 H-1,2,4-triazol-1 -yl which may be substituted by alkyl, 1 H-imidazol-1 -yl which may be substituted by alkyl, 1 H-1,2,3-triazol-1-yl which may be substituted by alkyl, or 4H-1,2,4-triazol 30 4-yl which may be substituted by alkyl; X is alkyl which may be substituted by A, cycloalkyl which may be substituted by B, halogen, nitro, cyano, alkoxy which may be substituted by A, cycloalkyloxy which may be substituted by B, arylalkoxy which may be substituted by B, silylalkyl WO 2010/055896 41 PCT/JP2009/069305 which is substituted by B, silylalkoxy which is substituted by B, alkylthio which may be substituted by A, alkenyl which may be substituted by A, alkynyl which may be substituted by A, alkenyloxy which may be substituted by A, alkynyloxy which may be substituted by A, phenoxy which may be substituted by B, hydroxyl, NR 4 R 5 , OCOR , OCOOR , OS(O),R , aryl which may be substituted 5 by B, heteroaryl which may be substituted by B, COR 6 , COOR , S(O),R or CONR 4 R ; R 4 is a hydrogen atom or alkyl; R 5 is a hydrogen atom, alkyl which may be substituted by A, cycloalkyl which may be substituted by B, arylalkyl which may be substituted by B, heteroarylalkyl which may be substituted by B, COR , COOR 6 , S(O),R 6 or CH 2 CN; R 6 is alkyl, haloalkyl, or aryl which may be substituted by B; A is at least one substituent selected from the group consisting of 10 cycloalkyl, halogen, alkoxy and haloalkoxy; B is at least one substituent selected from the group consisting of alkyl, haloalkyl, cycloalkyl, halogen, alkoxy and haloalkoxy; m is an integer of from 1 to 4; and n is 1 or 2.

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US20110195930A1|2011-08-11|Pyridine derivative or its salt, pesticide containing it and process for its production

---

WO2010087294A1|2010-08-05|Triazolopyrimidine derivative or its salt, process for producing the same and pesticide containing the same

---

WO2011049232A1|2011-04-28|Diaryltriazole derivative as insecticide, miticide, nematicide or soil pesticide

---

AU2013364857B2|2017-02-02|Pest control agent

---

WO2010018853A1|2010-02-18|Pyridyl-triazolopyrimidine derivative or salt thereof, and harmful organism control agent comprising the same

---

WO2012029968A1|2012-03-08|Benzamide derivative or its salt, and insecticide, miticide, nematicide or soil pesticide containing it

同族专利:

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公开号 | 公开日

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ZA201102819B|2012-06-27|

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TW201029571A|2010-08-16|

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KR20110082175A|2011-07-18|

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US20110195930A1|2011-08-11|

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WO2010055896A3|2010-07-15|

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CN102216288A|2011-10-12|

---

CA2740340A1|2010-05-20|

---

AR074334A1|2011-01-05|

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IL212662D0|2011-07-31|

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MX2011005158A|2011-06-17|

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WO2010055896A2|2010-05-20|

---

MA32791B1|2011-11-01|

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JP2010138166A|2010-06-24|

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CO6331471A2|2011-10-20|

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EP2346851A2|2011-07-27|

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BRPI0921776A2|2015-08-18|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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JPH0368559A|1989-08-09|1991-03-25|Kumiai Chem Ind Co Ltd|Oxime derivative and insecticide|

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EP1184382A4|1999-06-09|2005-01-05|Dainippon Ink & Chemicals|Oxime derivatives, process for the preparation thereof and pesticides|

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US8129415B2|2006-07-13|2012-03-06|Bayer Cropscience Ag|Fungicide hydroximoyl-tetrazole derivatives|TWI547482B|2011-01-25|2016-09-01|陶氏農業科學公司|Improved process of increasing the amount of recoverable 3-chloro-4,5,6-trifluoropicolinonitrile|

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JP2014159413A|2013-01-28|2014-09-04|Nippon Soda Co Ltd|Azolyloxime compound or salt thereof, pest control agent, insecticide or acaricide, sterilizer, and ectoparasite control agent|

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WO2015199065A1|2014-06-24|2015-12-30|日本曹達株式会社|Pyridine compound and use of same|

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CN108402047B|2018-03-07|2020-12-08|上海应用技术大学|Use of 2-amino-1- [ 3-oxo-3-propyl ] pyridinium nitrate derivatives|

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CN110590656B|2019-09-27|2020-10-09|中国农业大学|Guanidyl derivative containing pyridine amide and preparation method and application thereof|

法律状态:
2014-05-29| MK4| Application lapsed section 142(2)(d) - no continuation fee paid for the application|

优先权:

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申请号 | 申请日 | 专利标题

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JP2008-292881||2008-11-17||

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JP2008292881||2008-11-17||

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PCT/JP2009/069305|WO2010055896A2|2008-11-17|2009-11-06|Pyridine derivative or its salt, pesticide containing it and process for its production|

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