JP3087344B2 - Pyridine compounds, their production, intermediates thereof and pest control agents containing the same as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pyridine compound, a method for producing the same, an intermediate thereof, and a pesticidal composition containing the same as an active ingredient.

[0002]

2. Description of the Related Art It has been reported that certain pyridine compounds have a pesticidal effect, for example, as described in West German Patent No.
No. 516,331.

[0003]

However, these compounds are not always sufficient as an active ingredient of a pesticide.

[0004]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies to find a compound having a better pest control effect.
It has been found that a pyridine compound represented by Chemical formula 8 (hereinafter, referred to as the compound of the present invention) has extremely high juvenile hormone-like activity, and thus the present invention has been completed. That is, the present invention provides a compound represented by the general formula 8

[0005]

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Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
4 haloalkyl groups, 1 to 3 alkoxy group having a carbon atom, 1 to 3 haloalkoxy group having a carbon atom, a cyano group or a nitro group, l represents an integer of 1 to 5, R ² is independently Represents a hydrogen atom, a halogen atom or a methyl group, m represents an integer of 1 to ³ , R ³ represents a halogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a carbon atom Represents three alkyl groups, and R ⁵ is independently a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms.
Represents 3 alkoxy groups, a haloalkoxy group having 1 to 3 carbon atoms, n represents an integer of 1 to 4, X represents an oxygen atom,
A sulfur atom, a group represented by the formula -C (O)-, a formula -S (O)
A group represented by-, a group represented by formula -S (O) _2- ,
Represents a group represented by NH— or a group represented by the formula —CH ₂ —, and Y represents an oxygen atom or a sulfur atom. A process for producing the same, an intermediate thereof, and a pesticidal composition containing the same as an active ingredient.

The compounds of the present invention are markedly different from most conventional insecticides and have excellent juvenile hormone-like activity against insects. In other words, they exhibit effects such as inhibition of metamorphosis into adults, inhibition of hatching of eggs, and sterilization of adults. As a result, the compounds of the present invention include various pests, including pests that have developed resistance to existing pesticides, that is, agricultural and forestry pests,
It mainly acts as a growth regulator, a sterilizing agent, an ovicidal agent or a growth inhibitor against stored grain pests and sanitary pests, and has a high control effect.

In the compound of the present invention represented by the general formula 8, the halogen atoms represented by R ¹ , R ² , R ³ and R ⁵ are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom,

In the compound of the present invention represented by the general formula 8, an alkyl group having 1 to 4 carbon atoms represented by R ¹ means a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group. , Sec-butyl group, isobutyl group, te
an rt-butyl group,

The haloalkyl group having 1 to 4 carbon atoms represented by R ¹ includes, for example, trifluoromethyl group, difluoromethyl group, 2-fluoroethyl group, 1-fluoroethyl group, 1,2-difluoroethyl Group, 2,2,2-
Trifluoroethyl, 2-chloroethyl, 3-fluoropropyl, 2-fluoropropyl, 1-fluoropropyl, 3-chloropropyl, 3-bromopropyl, 4-fluorobutyl, 4-chlorobutyl Etc.,

Carbon atoms 1 to 3 represented by R ¹ and R ⁵
Alkoxy groups are methoxy, ethoxy, n-
A propoxy group and an isopropoxy group,

Carbon atoms 1 to 3 represented by R ¹ and R ⁵
Haloalkoxy groups include, for example, trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy, 1-fluoroethoxy,
-Difluoroethoxy group, 3-fluoro-n-propoxy group, 2-fluoro-n-propoxy group, 1-fluoro-n-propoxy group, 2-chloroethoxy group, 3-chloro-n-propoxy group, 3-bromo -N-propoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,
1-difluoromethoxy group and the like,

The alkyl group having 1 to 3 carbon atoms represented by R ³ , R ⁴ and R ⁵ means a methyl group, an ethyl group, an n-
A propyl group or an isopropyl group,

The haloalkyl group having 1 to 3 carbon atoms represented by R ³ includes, for example, trifluoromethyl, difluoromethyl, 2-fluoroethyl, 1-fluoroethyl, 1,2-difluoroethyl Group, 2,2,2-
Trifluoroethyl group, 2-chloroethyl group, 3-fluoro-n-propyl group, 2-fluoro-n-propyl group, 1-fluoro-n-propyl group, 3-chloro-n-
Propyl group, 3-bromo-n-propyl group and the like,

Among the preferred compounds of the present invention represented by the general formula (8), R ¹ is independently hydrogen, fluorine, chlorine, bromine, methyl or trifluoromethyl, and l is 1 Or 2, R ² is hydrogen atom or chlorine atom, m is 1, R ³ is fluorine atom, chlorine atom, bromine atom or methyl group, R ⁴ is hydrogen atom or methyl group, R ⁵ is independently chlorine atom or methyl A group, n is 1 or 2, X is an oxygen atom or a methylene group, and Y is an oxygen atom. More preferred compounds include R ¹
Is a hydrogen atom, a fluorine atom or a chlorine atom, l is 1 or 2, R ² is a hydrogen atom, m is 1, R ³ is a chlorine atom, R ⁴ is a hydrogen atom, R ⁵ is a chlorine atom or a methyl group, n is 1 , X
Is an oxygen atom or a methylene group, and Y is an oxygen atom. Still more preferably, (R ¹ ) l is a fluorine atom (2,4-
F ₂ ) A fluorine atom (3,5-F ₂ ) at both the 3- and 5-positions is a chlorine atom (3,4-Cl ₂ ) at both the 3- and 4-positions. A fluorine atom (3-F) or a chlorine atom (3-C
l), R ² is a hydrogen atom, m is 1, R ³ is a chlorine atom, R ⁴
Is a hydrogen atom, R ⁵ is a chlorine atom or a methyl group, n is 1,
X is an oxygen atom or the formula -CH ₂ - group represented by, Y is cited an oxygen atom. Incidentally, X has the formula -CH ₂ - when the group represented by, R ¹ is also hydrogen Konomashiii. Most preferably, (R ¹ ) l is a fluorine atom (2,4-F ₂ ) at both the 2- and 4-positions, and a fluorine atom (3,5-F ₂ ) at both the 3- and 5-positions, or The substitution position at the 3-position is a chlorine atom (3-Cl), R ² is a hydrogen atom, m is 1, R ³ is a chlorine atom, R ⁴ is a hydrogen atom, R ⁵ is a chlorine atom or a methyl group, n is 1, X Is an oxygen atom or a formula -CH
_The group Y represented by _2- may be an oxygen atom. When X is a group represented by the formula —CH ₂ —, (R
¹ ) It is preferable that 1 is substituted with a fluorine atom (3-F) at the 3-position. In the compound of the present invention represented by the general formula (8), a preferable substitution position of the phenyl group including X which may be substituted with (R ¹ ) l is 4- or 5-position. Preferred positions of the pyridine ring which may be substituted by (R ⁵ ) n include the 4-position and 5-position. More preferably, the fifth position can be given. The preferred substitution position of (R ⁵ ) n is
The second place is given.

The compound of the present invention represented by the general formula:
For example, it can be manufactured by the following method.

(Production method A)

[0018]

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[Wherein, R ¹ , R ² , R ³ , X, Y, l and m have the same meanings as described above, and M represents an alkali metal atom or a hydrogen atom. And a phenol derivative represented by the following general formula:

[0020]

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[Wherein R ⁴ , R ⁵ and n have the same meanings as described above, and A represents a halogen atom. And a compound represented by the following formula:

The above reaction is preferably carried out in the presence of a suitable base in an inert solvent. However, when M is an alkali metal atom, the presence of a base is not necessarily required.

Examples of the solvent used include methanol, ethanol, propanol, isopropanol, and the like.
Lower alcohols such as tertiary butyl alcohol; ketones such as acetone and methyl ethyl ketone; hydrocarbons such as benzene, hexane and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; Amides such as dimethylformamide, hexamethylphosphoric triamide, dichloromethane, chloroform, 1,2-dichloroethane,
Examples thereof include halogenated hydrocarbons such as chlorobenzene, acetonitrile, nitromethane, dimethyl sulfoxide, and water. If necessary, a mixed solvent of these solvents can also be used.

Examples of the base to be used include caustic alkalis such as caustic potash and caustic soda, alkali carbonates such as potassium carbonate, alkali metals such as sodium metal, hydrides of alkali metals such as sodium hydride or sodium methoxide, sodium ethoxide. Organic bases such as side, triethylamine and pyridine are exemplified. If necessary, a catalyst such as an ammonium salt (eg, triethylbenzylammonium chloride) may be added to the reaction system.

The reaction temperature can usually range from -20 ° C to the boiling point of the solvent used in the reaction.
A temperature from to the boiling point of the solvent used in the reaction is more desirable.

The molar ratio of the starting material and the base to be used for the reaction can be arbitrarily set, but it is advantageous to carry out the reaction in an equimolar or close ratio.

After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by a usual operation such as chromatography, distillation, recrystallization and the like.

(Production method B)

[0029]

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Wherein R ¹ , R ² , R ³ , X, l and m have the same meaning as described above. And a phenol derivative represented by the general formula:

[0031]

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Wherein R ⁴ , R ⁵ and n have the same meaning as described above. And an alcohol derivative represented by the following formula:

The above reaction is particularly advantageous when R ⁴ is not a hydrogen atom, and the reaction is preferably carried out in the presence of a suitable dehydration catalyst or dehydrating agent, if necessary, in an inert solvent.

Examples of the dehydration catalyst used include inorganic salts such as hydrochloric acid and sulfuric acid, and aromatic sulfonic acids and sulfonic acid chlorides. Examples of the dehydrating agents include dicyclohexylcarbodiimide and diisopropylazodicarboxylate. And diethyl azodicarboxylate.

Examples of the solvent used include hydrocarbons such as benzene, xylene and toluene, diethyl ether, diisopropyl ether, tetrahydrofuran,
Examples thereof include ethers such as dioxane, and halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chlorobenzene, and dichlorobenzene.

The reaction temperature can range from -20 ° C to 200 ° C or the boiling point of the solvent used in the reaction.

The molar ratio of the starting material and the dehydrating agent to be used for the reaction can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar or close ratio.

After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by a usual operation such as chromatography, distillation, recrystallization and the like.

When the compound of the present invention has an asymmetric carbon atom, the compound of the present invention is an optically active isomer having a biological activity ((+)-isomer,
(-)-Isomer) and mixtures thereof in all proportions.

Among the phenol derivatives represented by the general formulas 9 as starting materials of the compound of the present invention, the phenol derivatives in which M represents a hydrogen atom are obtained by converting the phenol derivatives represented by the general formula 11 into the usual phenol derivatives. It can be synthesized by a method. For example, it can be produced by the following method (reaction formula 13).

[0041]

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In the above reaction, when R ³ represents a chlorine atom, particularly in the reaction represented by the reaction formula (13),

[0043]

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[Wherein R ¹ , R ² , l and m have the same meaning as described above. The phenol derivative represented by the general formula 15 is reacted with a chlorinating agent in the presence of a solvent.

[0045]

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[Wherein, R ¹ , R ² , l and m have the same meaning as described above. ] Can be obtained according to the usual method of synthesizing the phenol derivative represented by the formula

In the above reaction formula, chlorine, t-butyl hypochlorite, sulfuryl chloride or the like can be used as the chlorinating agent. In addition, a solvent can be used if necessary, and examples of the solvent that can be used include dichloromethane, dichloroethane, carbon tetrachloride, benzene, and acetic acid. It goes without saying that the solvent used here is properly used depending on the type of the chlorinating agent. The reaction temperature can range from -78 ° C to the boiling point of the solvent or chlorinating agent (sulfuryl chloride, etc.) used in the reaction. ) Is desirable.
The molar ratio of the raw material and the chlorinating agent to be used for the reaction can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar or close ratio. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, it can be purified by a usual operation such as chromatography, distillation, recrystallization and the like.

As the phenol derivative represented by the general formula (14), a commercially available compound is used, or a phenol derivative is produced from a commercially available compound by, for example, a method shown below (reaction formulas (16) to (18)). can do.

[0049]

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[0050]

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[0051]

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Next, the compounds of the present invention which can be produced according to these production methods are shown in Tables 1 to 33. However, these compounds are for illustration only, and the present invention is not limited to these.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

[Table 6]

[0059]

[Table 7]

[0060]

[Table 8]

[0061]

[Table 9]

[0062]

[Table 10]

[0063]

[Table 11]

[0064]

[Table 12]

[0065]

[Table 13]

[0066]

[Table 14]

[0067]

[Table 15]

[0068]

[Table 16]

[0069]

[Table 17]

[0070]

[Table 18]

[0071]

[Table 19]

[0072]

[Table 20]

[0073]

[Table 21]

[0074]

[Table 22]

[0075]

[Table 23]

[0076]

[Table 24]

[0077]

[Table 25]

[0078]

[Table 26]

[0079]

[Table 27]

[0080]

[Table 28]

[0081]

[Table 29]

[0082]

[Table 30]

[0083]

[Table 31]

[0084]

[Table 32]

[0085]

[Table 33]

Examples of pests against which the compound of the present invention exerts effects include the following.

Hemiptera pests Planthoppers such as brown planthoppers, brown planthoppers and brown planthoppers, leafhoppers such as red leafhopper, leafhopper leafhopper, leafhopper leafhopper, leafhopper leafhopper, leafhopper leafhopper, leafhopper leafhopper such as leafhopper leafhopper, cotton aphid, etc. Aphids, stink bugs, whiteflies such as tobacco whiteflies, whiteflies, etc., scale insects, firebugs, psyllids, etc.

Pests such as Lepidopteran pests, P. persica, P. persicae, P. persicae, P. persicae, P. persicae, P. persicae, P.
Agrotis spp., Heliothis spp., Such as Leaf moths, Hosoga, Kibaga, Dokuga, Uwaba, Kaburayaga, Tamanayaga, etc.
p.), Conaga, Iga, Koiga, etc.

Diptera pests Culex pipiens such as Culex pipiens and Culex pipiens, Aedes aegypti and Aedes albopictus, Anopheles such as Aedes aegypti, houseflyes such as midge larvae, house flies, house flies such as housefly, blowflies, and a house fly, Musca domestica Flies, such as onions and flies, flies, fruit flies, olive flies, drosophila,
Drosophila, flies, blackflies, sand flies, etc.

Coleoptera pests Corn rootworms such as western corn rootworm and southern corn rootworm, scarab beetles such as Douganebuui and Himekonega, weevil such as weevil, rice weevil, adzuki weevil, and corn beetle such as black beetle mealworm such, Kisujinomihamushi, Chrysomelidae such as corn rootworm, beetles such, Epilachna genera such as the beetle, Epilachna vigintioctopunctata (Epilachna spp.), Hiratakiimushi such, Naga Shinkuimushi class, beetles, etc.

Reticulate pests German cockroaches, black cockroaches, cockroaches, brown cockroaches, cockroaches, etc.

Thrips pests Thrips palmi, Thrips palmi, Thrips palmi, etc.

Hymenoptera pests Ants, wasps such as wasps, etc.

[0094] Orthoptera pests Kera, grasshoppers, etc.

Pests of the order Coleoptera, human fleas, etc.

Louse pests Human lice, lice, etc.

It is effective against the insects of the order Isoptera, such as the termite Yamato and the house termite. Further, among them, it is more suitable for controlling Hemiptera pests, and exhibits particularly excellent effects on planthoppers and leafhoppers that injure rice crops, and exhibits excellent control effects.

The addition of other insecticides and / or acaricides enables the pest control of the compounds according to the invention to be applied practically to a wider variety of insect pests and more diverse application situations. Suitable additives include, for example, BPMC [2
-Sec-butylphenylmethyl carbamate], benfracarb [ethyl N- [2,3-dihydro-2,2-
Dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl
N-methyl carbamate], carbosulfan [2,3
-Dihydro-2,2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate], mesomil [S-methyl-N-[( Methylcarbamoyl) oxy] thioacetimidate], ethiophencarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxime], oxamil [N, N -Dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide] and the like.

Etofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS) -α-
Cyano-3-phenoxybenzyl (RS) -2- (4-
Chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl) -3-methylbutyrate], fenpropatrin [( RS) -α-
Cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-phenoxybenzyl (1RS, 3RS)-(1RS, 3RS) -3 −
(2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS, 3RS)-(1RS, 3R
S) -3- (2,2-Dichlorovinyl) -2,2-methylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS) -3 -(2-chloro-3,
3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-cyano-m-phenoxybenzyl (1
R, 3R) -3 (2,2-dibromovinyl) -2-dimethylcyclopropanecarboxylate], cycloprothrin [(RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro- Pyrethroid compounds such as 1- (4-ethoxyphenyl) cyclopropanecarboxylate],

Thiadiazine derivatives such as buprofezin (2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-triadiazin-4-one) and imidacloprid [1- (6-chloro-3-pyridyl) Nitroimidazolidine derivatives such as methyl) -N-nitroimidazolidine-2-ylideneamine, cartap [S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N-dimethyl-1,2,2 Nereistoxin derivatives such as 3-trithian-5-ylamine], bensultap [S, S'-2-dimethylaminotrimethylenedi (benzenethiosulfonate)], and endosulfan [6,7,8,9,
10,10-hexachloro-1,5,5a, 6,9,9
a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide], γ-BHC
Chlorinated hydrocarbon compounds such as [1,2,3,4,5,6-hexachlorocyclohexane] and chloroflubron [1- (3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridine) -2-yloxy) phenyl] -3- (2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-
2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], flufenoxuron [1-
Benzoylphenylurea-based compounds such as [4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea], amitraz [N, N '[( Methylimino)
Dimethylidin] di-2,4-xylysine], chlordimeform [N '-(4-chloro-2-methylphenyl)-
N, N-dimethylmethanimidamide] and the like.

When the compound of the present invention is used as an active ingredient of a pesticidal agent, it may be used as it is without adding any component of the present invention, but it is usually used as a solid carrier, a liquid carrier, a gaseous carrier, or a bait. Add surfactants and other formulation auxiliaries as needed, and add oils, emulsions, wettable powders, suspensions in water, emulsions in water, etc., flowables, granules, powders,
Aerosol, self-burning type smoke agent, chemical reaction type smoke agent, heating smoke agent such as perforated ceramic plate smoke agent, ULV agent, poison bait and the like are used.

These preparations usually contain the compound of the present invention as an active ingredient in an amount of 0.001% to 95% by weight.
Examples of the solid carrier used in the formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite, quartz, Sulfur, activated carbon, calcium carbonate, hydrated silica, etc.),
Examples include fine powders or granular materials such as chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, salt ammonium, etc.). Examples of liquid carriers include water, alcohols (methanol, ethanol, etc.) and ketones (acetone, acetone, etc.). Methyl ethyl ketone),
Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile) , Isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, tetrachloride) Carbon), dimethyl sulfoxide, soybean oil, vegetable oils such as cottonseed oil, and the like.
Examples of the gaseous carrier, that is, the propellant include Freon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohols Derivatives and the like.

Examples of auxiliary agents for preparations such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers. (Polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.) and the like. Examples of the stabilizer include PAP (acidic isopropyl phosphate), BH
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , A surfactant, a fatty acid or an ester thereof, and the like.

As the base material of the self-combustion type smoke agent, for example, nitrate, nitrite, guanidine salt, potassium chlorate,
Combustion heating agents such as nitrocellulose, ethylcellulose, and wood flour; thermal decomposition stimulants such as alkali metal salts, alkaline earth metal salts, dichromates, and chromates; oxygen supply agents such as potassium nitrate; melamine; wheat starch; And a bulking agent such as diatomaceous earth, and a binder such as synthetic paste. As the base material of the chemical reaction type smoke agent, for example, alkali metal sulfide, polysulfide, hydrosulfide, hydrated salt,
Exothermic agents such as calcium oxide, catalytic agents such as carbonaceous materials, iron carbide, and activated clay; organic blowing agents such as azodicarbonamide, benzenesulfonylhydrazine, dinitrosopentamethylenetetramine, polystyrene, and polyurethane; natural fiber fragments and synthetic fibers And fillers such as pieces.

Examples of the base material of the poison bait include bait ingredients such as cereal flour, vegetable essential oil, sugar and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid; preservatives such as dehydroacetic acid; Powder and the like, and inducing flavors such as cheese flavor, onion flavor and the like.

Formulations of flowables (suspension in water or emulsions in water) generally contain 0.5% to 15% of the compound.
% Of a dispersant, 0.1 to 10% of a suspending aid (for example, a protective colloid or a compound imparting thixotropic properties),
Fine water in water containing 1.0% of appropriate adjuvants (eg antifoaming agents, rust inhibitors, stabilizers, spreading agents, penetration aids, antifreezing agents, antibacterial agents, antismoking agents, etc.) To be obtained. It is also possible to use an oil in which the compound hardly dissolves in place of water and use it as a suspension in oil. As the protective colloid, for example, gelatin, casein, gums, cellulose ether, polyvinyl alcohol and the like are used. Examples of the compound imparting thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid and the like.

The preparation thus obtained is used as it is or after dilution with water or the like. Also other pesticides,
They can be used together with or without mixing with nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feeds and the like.

When the compound of the present invention is used as an agricultural pesticide, the application rate is usually 0.001 g to 500 g, preferably 0.1, per 10 ares.
g to 500 g. When the emulsion, wettable powder, flowable and the like are diluted with water and used, the application concentration is usually 0.1.
0001 ppm to 1000 ppm, and granules, dusts, etc. are applied as they are without any dilution. When used as a pest control agent for epidemic control, emulsions, wettable powders, flowables, etc. are usually diluted with water to 0.0001 ppm to 10,000 ppm and applied, and oils, aerosols, smokers, ULVs, For poison bait, etc., apply as it is.

These application rates and application concentrations vary depending on the type of preparation, application time, application place, application method, type of pest, degree of damage, etc., and may be increased without being related to the above range. Or can be reduced.

[0111]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples, but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention will be shown.

Production Example 1 (Production method of compound (1) of the present invention) In a solution of 0.09 g (60% oil) of sodium hydride and 10 ml of dimethylformamide, 0.45 g of 2-chloro-4-phenoxyphenol and dimethylformamide were added. 3ml
Was added dropwise with stirring under ice cooling. After 30 minutes, this was added at room temperature with 2-chloro-5-chloromethylpyridine.
A solution of 34 g of dimethylformamide (5 ml) was added and stirred at room temperature. After 10 hours, the reaction solution was poured into ice water and extracted twice with 100 ml of ethyl acetate. The ethyl acetate layers were combined, washed with water, dried and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography to give 2-chloro-5.
0.50 g of-(2-chloro-4-phenoxyphenoxy) methylpyridine was obtained. Yield: 71% n ²² _D: 1.6173

Production Example 2 (Production method of compound (33) of the present invention) To a solution of 0.07 g (60% oil) of sodium hydride and 10 ml of dimethylformamide were added 2-chloro-4- (3-
A solution of 0.50 g of trifluoromethylphenoxy) phenol and 3 ml of dimethylformamide is added dropwise with stirring under ice cooling. After 30 minutes, this was added to 2-chloro-
A solution of 0.28 g of 5-chloromethylpyridine in 5 ml of dimethylformamide is added and stirred at room temperature. After 10 hours, the reaction solution is poured into ice water and extracted twice with 100 ml of ethyl acetate. The ethyl acetate layers are combined, washed with water, dried and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography to give 2-chloro-5- [2-chloro-4- (3
-Trifluoromethylphenoxy) phenoxy] methylpyridine is obtained.

Production Example 3 (Production method of compound (34) of the present invention) To a solution of 0.07 g of sodium hydride (60% oil) and 10 ml of dimethylformamide were added 2-chloro-4- (3-
A solution of 0.50 g of (bromophenoxy) phenol and 3 ml of dimethylformamide is added dropwise with stirring under ice cooling. After 30 minutes, a solution of 0.27 g of 2-chloro-5-chloromethylpyridine in 5 ml of dimethylformamide is added thereto at room temperature, and the mixture is stirred at room temperature. After 10 hours, the reaction solution is poured into ice water and extracted twice with 100 ml of ethyl acetate. The ethyl acetate layers are combined, washed with water, dried and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography to give 2-chloro-5- [4- (3-bromophenoxy)
-2-chlorophenoxy] methylpyridine is obtained.

Production Example 4 (Production method of compound (17) of the present invention) 0.82 g of 2-chloro-5-phenoxyphenol, 0.54 g of 2-methyl-5-hydroxymethylpyridine, 1.01 g of triphenylphosphine, diethylazaza Dicarboxyle
0.65 g and 90 ml of tetrahydrofuran were placed in a reaction vessel and stirred at room temperature. After 48 hours, the reaction was concentrated,
50 ml of diethyl ether was added and the precipitate was filtered.
After concentrating the filtrate, it was subjected to silica gel chromatography,
0.66 g of 2-methyl-5- [2-chloro-5-phenoxyphenoxy] methylpyridine was obtained. Yield: 51% mp: 64.9 ° C

Production Example 5 (Method for producing compound (35) of the present invention) 0.80 g of 2-chloro-5-phenoxyphenol, 0.57 g of 2-chloro-5- (1-hydroxyethyl) pyridine,
0.95 g of triphenylphosphine, 0.63 g of diethylazadicarboxylate and 100 ml of tetrahydrofuran are put into a reaction vessel and stirred at room temperature. After 48 hours, the reaction was concentrated, 50 ml of diethyl ether was added and the precipitate was filtered. The filtrate was concentrated and then subjected to silica gel chromatography to give 2-chloro-5- [1- (2-chloro-4-
[Phenoxyphenoxy) ethyl] pyridine is obtained. Next, some of the compounds of the present invention obtained according to these production methods are shown in Tables 34 to 41.

[0117]

[Table 34]

[0118]

[Table 35]

[0119]

[Table 36]

[0120]

[Table 37]

[0121]

[Table 38]

[0122]

[Table 39]

[0123]

[Table 40]

[0124]

[Table 41]

Next, an intermediate production example will be described. Production Example 6 (Production of Intermediate Compound (42) of Compound of the Present Invention) p- (3,5-difluorophenoxy) phenol 5.0
g was dissolved in 50 ml of carbon tetrachloride, and 2.45 g of t-butyl hypochlorite was slowly added dropwise with vigorous stirring under ice cooling. After completion of the dropwise addition, the mixture was stirred at room temperature. After 5 hours, the reaction solution was concentrated, 200 ml of ethyl acetate was added to the residue, and the mixture was washed with 5% aqueous sodium bicarbonate. After drying and concentrating the ethyl acetate solution, the residue was subjected to silica gel chromatography to give 2-
5.31 g of chloro-4- (3,5-difluorophenoxy) phenol was obtained. Yield: 92% n ²⁵ _D : 1.5639 Some of the intermediate compounds of the present invention obtained according to these production methods are shown in Tables 42 to 45.

[0126]

[Table 42]

[0127]

[Table 43]

[0128]

[Table 44]

[0129]

[Table 45]

Next, formulation examples will be shown. In addition, a part represents a weight part and this invention compound is represented by the compound number of Table 34-41.

Formulation Example 1 Emulsion 10 parts of each of the compounds (1) to (40) of the present invention are dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and polyoxyethylenestyryl phenyl ether 14
Parts and 6 parts of calcium dodecylbenzenesulfonate were added and mixed well with stirring to obtain 10% emulsions of each.

Formulation Example 2 Wettable powder 20 parts of each of the present compounds (1) to (40) were mixed with 4 parts of sodium lauryl sulfate and 2 parts of calcium ligninsulfonate.
Parts, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of silicon earth were mixed and stirred with a juice mixer to obtain a 20% wettable powder.

Formulation Example 3 Granules Compounds of the present invention (1), (2), (7), (10), (13)
To (15), (19), (30), and (37), 5 parts each of sodium dodecylbenzenesulfonate and Bentonite 30
Parts and 60 parts of clay, and sufficiently stirred and mixed. Then, an appropriate amount of water was added to these mixtures, and further stirred,
Granulate with a granulator and dry with ventilation to obtain 5% granules.

Formulation Example 4 Granules Compounds of the present invention (3) to (6), (8), (9), (1)
1), (12), (16)-(18), (20)-(29), (3
1), (32), 5 parts of (38) to (40), 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay are added and mixed with sufficient stirring. . Then, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain 5% granules.

Formulation Example 5 Powder Compounds of the present invention (1), (2), (7), (10), (13)
~ (15), (19), (30), (37) each 0.3 parts, synthetic hydrous silicon oxide fine powder 1 part, trade name Drilles B as coagulant
After well mixing 1 part (manufactured by Sankyo) and 7.7 parts of clay with a mortar, the mixture is stirred and mixed with a juice mixer. 90 parts of cut clay were added to the obtained mixture, and the mixture was mixed in a bag.
Get 3% dust.

Formulation Example 6 Powder Compounds of the present invention (3) to (6), (8), (9), (1)
1), (12), (16)-(18), (20)-(29), (3
1), (32), (38) to (40), 0.3 part of each, and 0.03 part of synthetic fine powder of hydrous silicon oxide are mixed well with a juice mixer, and then pulverized with a centrifugal pulverizer. 0.97 parts of synthetic hydrous silicon oxide fine powder, 1 part of trade name Doreless B (manufactured by Sankyo Co., Ltd.) and 7.7 parts of clay as coagulants were added to the obtained pulverized mixture. I do. 90 parts of cut clay are added to the resulting mixture and mixed in a bag to obtain a 0.3% powder of each.

Formulation Example 7 Powder Compounds of the present invention (1), (2), (7), (10), (13)
To (15), (19), (30), and (37), 2 parts of BPMC (O-sec-butylphenyl N-methylcarbamate) as a carbamate-based compound, and fine powder of synthetic silicon-oxide hydroxide 3 Parts, 1 part of trade name Drilles B (manufactured by Sankyo) as a coagulant, and 3.7 parts of clay are mixed well in a mortar,
Stir and mix with a juice mixer. 90 parts of cut clay is added to the obtained mixture, and the mixture is mixed in a bag to obtain each powder.

Formulation Example 8 Powder Compounds of the present invention (3) to (6), (8), (9), (1)
1), (12), (16)-(18), (20)-(29), (3
1), (32), (38) to (40), 0.3 part of each, and 0.03 part of synthetic fine powder of hydrous silicon oxide are mixed well with a juice mixer, and then pulverized with a centrifugal pulverizer. BPMC (O-sec −) was added to the obtained pulverized mixture as a carbamate compound.
2 parts of butylphenyl N-methylcarbamate), 2.97 parts of synthetic hydrous silicon oxide fine powder, 1 part of Doreless B (manufactured by Sankyo) as a coagulant and 3.7 parts of clay were added.
After mixing well in a mortar, stir and mix with a juice mixer. 90 parts of cut clay is added to the obtained mixture and mixed in a bag to obtain each powder.

Formulation Example 9 Powder One part of each of the present compounds (1) to (40) is dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder,
0.3 parts of AP and 93.7 parts of Cle are added, and the mixture is stirred and mixed with a juice mixer.
Obtain a powder.

Formulation Example 10 Flowable agent Compounds of the present invention (1), (2), (7), (10), (13)
10 parts of each of (15), (19), (30), and (37) are added to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol, and the mixture is stirred with a mixer to obtain a dispersant. In this, 0.05 parts of xanthan gum and aluminum magnesium silicate
Add 40 parts of an aqueous solution containing 0.1 part, and further add 10 parts of propylene glycol and mix gently with stirring to obtain each 10% emulsion in water.

Formulation Example 11 Flowable agent Compounds of the present invention (3) to (6), (8), (9), (1)
1), (12), (16)-(18), (20)-(29), (3
1), (32), 20 parts of each of (38) to (40) and 1.5 parts of sorbitan trioleate were added to polyvinyl alcohol 2
After mixing with 28.5 parts of an aqueous solution containing 3 parts by weight and finely pulverizing with a sand grinder (particle size of 3 μm or less), 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesilicate are added thereto, and propylene glycol is further added. Add 10 parts and stir and mix to obtain a 20% suspension in water.

Formulation Example 12 Oil 0.1 parts of each of the compounds (1) to (40) of the present invention was dissolved in xylene 5
And 5 parts of trichloroethane, and this is mixed with 89.9 parts of deodorized kerosene to obtain a 0.1% oil solution.

Formulation Example 13 Oily aerosol 0.1 parts of each of the present compounds (1) to (40), 0.2 part of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene are mixed and dissolved. Then, after filling in an aerosol container and attaching a valve portion, 30 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve portion to obtain an oily aerosol.

Formulation Example 14 Aqueous aerosol 0.2 parts of each of the compounds (1) to (40) of the present invention, 0.2 parts of d-aresulin, 0.2 parts of d-phenothrin, 5 parts of xylene,
An aerosol container is charged with 3.4 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark of Atlas Chemical Co.)} mixed and dissolved, and 50 parts of pure is filled in an aerosol container. An aqueous aerosol is obtained by pressure-filling 40 parts of an agent (liquefied petroleum gas).

Formulation Example 15 Heat Smoke Agent 100 mg of each of the compounds (1) to (40) of the present invention is dissolved in an appropriate amount of acetone, and impregnated into a 4.0 cm × 4.0 cm, 1.2 cm thick porous ceramic plate. Obtain a heat smoker.

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of a pesticidal agent. In addition, the compound of this invention is shown by the compound number of Table 34-41, and the compound used for the comparison control is shown by the compound number of Table 46.

[0147]

[Table 46]

Test Example 1 Metamorphosis inhibitory action against brown planthopper larvae The emulsion of the test compound obtained according to Formulation Example 1 was diluted to a predetermined concentration with water, and added to a rice seedling planted in a polyethylene cup in a volume of 20 ml / 2 pots. Sprayed at a rate. After air-drying, 10 larvae of the brown planthopper, 3rd instar, were released per pot.
After a day, the eclosion inhibition rate was determined. The results are shown in Tables 47 to 52.
Shown in

[0149]

[Table 47]

[0150]

[Table 48]

[0151]

[Table 49]

[0152]

[Table 50]

[0153]

[Table 51]

[0154]

[Table 52]

Test Example 2 Growth Inhibitory Effect on Blacktip Leafhopper The emulsion of the test compound obtained according to Formulation Example 1 was diluted to a predetermined concentration with water, and rice seedlings (length: about 20 cm) planted in pots (1 / 5000a) ) Was sprayed at a ratio of 40 ml / 2 pots. After air-drying, the pots were covered with a wire mesh gauge, and 10 males and 10 females were released per pot and left in a greenhouse. After about three weeks, the number of surviving nymphs of the next generation was examined, and the growth inhibition rate was determined. Table 53 shows the results.

[0156]

[Table 53]

Test Example 3 Growth Inhibitory Effect on Brown Planthopper An emulsion of the test compound obtained according to Formulation Example 1 was diluted to a predetermined concentration with water, and rice seedlings (length: about 20 cm) planted in pots (1 / 5000a) ) Was sprayed at a ratio of 40 ml / 2 pots. After air-drying, the pot was covered with a wire mesh gauge, and five males and five females of adult brown planthoppers were released per pot and left in a greenhouse. After about three weeks, the number of surviving nymphs of the next generation was examined, and the growth inhibition rate was determined. Table 54 shows the results.

[0158]

[Table 54]

Test Example 4 Test for Cotton Aphid Emulsion of the test compound obtained according to Formulation Example 1 was diluted to a predetermined concentration with water, and 8 to 9 days after seeding with the first infested cotton aphid larvae 3 in potted cotton (early leaf stage)
It was sprayed at a rate of 0 ml / 2 pots. Before spraying and spraying 7
After a day, the total number of cotton aphids on the plants was investigated. The control effect index was calculated according to the following formula as an indicator of the control effect. The criteria for determining the effect are as follows: A: The control effect index is 1 or less, and the growth inhibitory effect is sufficiently recognized. B: When the control effect index is greater than 1 and 3 or less, a growth inhibitory effect is observed. C: The control effect index is larger than 3, and a slight growth inhibitory effect is observed. D: The control effect index is equivalent to that of the untreated group, and no growth inhibitory effect is observed. And Table 55 shows the results.

[0160]

[Table 55]

[0161]

EFFECTS OF THE INVENTION The compound of the present invention can be used as a pest of the order Hemiptera, Lepidoptera, Diptera, Coleoptera, Pests of the order, Psitoptera, Orthoptera, Hymenoptera, Hymenoptera, Insecta It has an excellent controlling effect against eye pests, lice pests, isoptera pests and the like, and can be used for various uses as a pest control agent.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kimitoshi Umeda 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Industries Co., Ltd. (72) Inventor Noritada Matsuo 4-2-1 Takashi Takarazuka-shi Hyogo Sumitomo (56) References JP-A-54-84535 (JP, A) UK Patent Application Publication 916506 (GB, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 213 / 00-213/61 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A compound represented by the general formula: Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, 3 represents a haloalkoxy group, a cyano group or a nitro group, 1 represents an integer of 1 to 5, R ² independently represents a hydrogen atom, a halogen atom or a methyl group, and m represents 1 to 3
R ³ represents a halogen atom or a carbon atom 1 to
R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ independently represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms.
Represents 3 haloalkyl groups, an alkoxy group having 1 to 3 carbon atoms, a haloalkoxy group having 1 to 3 carbon atoms, n represents an integer of 1 to 4, X represents an oxygen atom, a sulfur atom, and a formula -C
A group represented by (O)-, a group represented by the formula -S (O)-,
Represents a group represented by the formula —S (O) ₂ —, a group represented by the formula —NH—, or a group represented by the formula —CH ₂ —, and Y represents an oxygen atom or a sulfur atom. A pyridine compound represented by the formula: 2. A compound represented by the general formula: Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, 3 represents a haloalkoxy group, a cyano group or a nitro group, 1 represents an integer of 1 to 5, R ² independently represents a hydrogen atom, a halogen atom or a methyl group, and m represents 1 to 3
R ³ represents a halogen atom or a carbon atom 1 to
And X represents an oxygen atom, a sulfur atom, a group represented by the formula -C (O)-, a group represented by the formula -S (O)-, or a group represented by the formula -S (O) _2-. Represents a group represented by the formula —NH— or a group represented by the formula —CH ₂ —, Y represents an oxygen atom or a sulfur atom, and M represents an alkali metal atom or a hydrogen atom. And a phenol derivative represented by the following general formula: [Wherein, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ independently represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms. An alkoxy group having 1 to 3 carbon atoms,
Represents three haloalkoxy groups, n represents an integer of 1 to 4, and A represents a halogen atom. The method for producing a pyridine compound according to claim 1, wherein the compound is reacted with the compound represented by the formula (1). 3. A compound of the general formula Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, 3 represents a haloalkoxy group, a cyano group or a nitro group, 1 represents an integer of 1 to 5, R ² independently represents a hydrogen atom, a halogen atom or a methyl group, and m represents 1 to 3
R ³ represents a halogen atom or a carbon atom 1 to
And X represents an oxygen atom, a sulfur atom, a group represented by the formula -C (O)-, a group represented by the formula -S (O)-, or a group represented by the formula -S (O) _2-. A group represented by the formula —NH— or a group represented by the formula —CH ₂ —. And a phenol derivative represented by the general formula: [Wherein, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ independently represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms. An alkoxy group having 1 to 3 carbon atoms,
Represents three haloalkoxy groups, and n represents an integer of 1 to 4. 3. The method for producing a pyridine compound according to claim 1, wherein the reaction is carried out with an alcohol compound represented by the formula: 4. A pesticide characterized by containing the pyridine compound of 請 Motomeko 1 as an active ingredient.