JPH08134040A - Ether compound and its use - Google Patents

Abstract

PURPOSE: To obtain the subject compound of a specific formula showing excellent controlling effect on harmful organisms. CONSTITUTION: This compound is shown by formula I [R<1> , R<3> and R<4> are each H or methyl; R<2> is H, a halogen or methyl; A<1> and A<2> are each H, OH or bonded at its end to form O or OCH2 ; B is a group of formula II (R<5> is H, a halogen or methyl), etc.; X is O, S or methylene; (1) is 1-4; (m) and (n) are each 1 or 2] such as 4-[2,2-(ethylenedioxy)cyclohexa-1-ylmethyl] phenyl-2-(2- pyridyloxy) ethyl ether. The compound, for example, is preferably obtained by reacting (A) a compound of formula III (L<1> is a halogen, mesyloxy or tosyloxy) with (B) a compound of the formula T<1> -X<1> -B<1> (B<1> is a group of formula IV, etc.; X<1> is O or S; T<1> is H or an alkali metal) in the molar ratio used of 1:1.1 to 1:1.5 at -30 to 200 deg.C for 0.5-24 hours.

Description

Detailed Description of the Invention

[0001]

OBJECT OF THE INVENTION The present invention relates to ether compounds and their uses.

The present inventors have conducted extensive studies to find compounds having an excellent pest control effect, and as a result, the ether compound represented by the following general formula 3 has an excellent pest control effect. The inventors have found out that, and have reached the present invention.

That is, the present invention has the general formula

Embedded image [In the formula, R ¹ , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a halogen atom or a methyl group, and A ¹ and A ² represent a hydrogen atom and a hydroxyl group. Represents a combination, or is bonded at the terminal to an oxygen atom, OCH ₂ CH ₂ O or OCH ₂ CH ₂
Represents CH ₂ O, and -B is represented by the general formula:

[Chemical 4]B-1, B-2, B-3, B-4, B-5 or
Or B-6, R ^FiveAre independent hydrogen
Represents a child, a halogen atom or a methyl group, and X is an oxygen source.
Represents a child, a sulfur atom or a methylene group, and l (el) is
Represents an integer of 1 to 4, m and n are each independently
Represents an integer of 1 or 2. ] An ether compound
Compound (hereinafter referred to as the compound of the present invention) and its effective synthesis
The present invention provides a pest control agent.

The compound of the present invention can be produced, for example, by the following method. (Production Method a) General Formula 5

Embedded image [In the formula, R ¹ , R ² , R ³ , R ⁴ , A ¹ , A ² , l (el) and n have the same meanings as described above, and L ¹ is a halogen atom (chlorine atom, bromine atom, iodine atom). Etc.), a mesyloxy group or a tosyloxy group. ] And the compound represented by the general formula:

Embedded image T ¹ -X ¹ -B ¹ wherein, B ¹ represents B-3, B-4, B-5 or B-6, X ¹ represents an oxygen atom or a sulfur atom, T ¹
Represents a hydrogen atom or an alkali metal atom. ] The method of manufacturing by making it react with the compound shown by these.

(Production Method b) General Formula 7

[Chemical 7] ^{Wherein, R 1, R 2, R} 3, R 4, A 1, A 2, l ( el), n and L ¹ have the same meanings as defined above, X ² represents a methylene group. L ² represents a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a mesyloxy group or a tosyloxy group. ] And the general formula
Conversion 8

Embedded image T ¹ -B ² wherein, B ² represents B-1 or B-2, T ¹ are as defined above. ] The method of manufacturing by making it react with the compound shown by these.

(Production Method c) The compound represented by the general formula 5 and the general formula 9

[Image Omitted] T ¹ -X ³ -B ² [wherein B ² and T ¹ have the same meanings as described above, X 1
³ represents an oxygen atom. ] The method of manufacturing by making it react with the compound shown by these.

(Production Method d) General Formula 10

Embedded image[In the formula, R¹, R², R³, R^Four, A¹, A², L (d
Le), n, X¹And T ¹Means the same as above
You. ] And the compound represented by the general formula:

Embedded image L ¹ -B ¹ wherein, L ¹ and B ¹ are as defined above. ]
A method for producing by reacting with a compound represented by:

(Production Method e) General Formula 12

[Chemical 12] ^{Wherein, R 1, R 2, A} 1, A 2, l ( el), T ¹ and n are as defined above. ] And a phenol compound represented by the general formula:

[Chemical 13] [In the formula, R ³ , R ⁴ , B, X and L ¹ have the same meanings as described above. ] The method of manufacturing by making it react with the compound shown by these.

(Production Method f) Of the compounds of the present invention, A ¹ and A ² are bound to each other at their terminals to reduce a ketone compound which is an oxygen atom, whereby A ¹ and A ^{2 of the} compounds of the present invention are hydrogen. A method for producing an alcohol compound which is a combination of an atom and a hydroxyl group.

(Production Method g) Among the compounds of the present invention, a ketone compound in which A ¹ and A ² are bonded at the terminal to form an oxygen atom and a compound of the general formula 14

Embedded image H—O— (CH₂)_p-OH [In the formula, p represents an integer of 2 or 3. ]
The compound of the present invention can be obtained by reacting with a diol compound.
A of the things ¹And A²Is OCH₂CH₂O or OCH
₂CH₂CH₂A method for producing a compound representing O.

(Production Method h) Of the compounds of the present invention, A ¹ and A ² of the compounds of the present invention are oxidized by oxidizing an alcohol compound having a combination of a hydrogen atom and a hydroxyl group.
A method for producing a compound in which ¹ and A ² are bonded at the terminal to form an oxygen atom.

(Production Method i) General Formula 15

[Chemical 15][In the formula, R¹, R², R³, R^Four, B, X, l (L)
And n have the same meanings as described above, and R⁶And R⁷Is
An alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group
Group, etc.) or R⁶And R⁷Join at the end
To represent an ethylene group or a trimethylene group.
You. ] To hydrolyze the enamine compound
Therefore, among the compounds of the present invention, A ¹And A²Are joined at the ends
A method for producing a compound which is an oxygen atom. (Production Method j) Of the compounds of the present invention, A¹And A²Is OCH
₂CH₂O or OCH₂CH₂CH₂A compound that represents O
Of the compounds of the present invention, A
¹And A²A ketone compound in which is bonded at the end to form an oxygen atom
A method of manufacturing.

In the production methods a, b, c, d and e,
The reaction is preferably carried out in the absence of a solvent or in an inert organic solvent in the presence of a base (however, the production methods a, b, c, d
In and e, when the compounds represented by Chemical formula 6, Chemical formula 8, Chemical formula 9 and Chemical formula 10 are alkali metal salts, no base is necessary. ) Examples of inert organic solvents that can be used include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, nitriles such as acetonitrile, propionitrile and isobutyronitrile, acetone, methyl isobutyl ketone and methyl ethyl ketone. Such as ketones, methanol, ethanol, alcohols such as n-propyl alcohol, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran,
Examples include ethers such as dioxane, polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane and hexamethylphosphoric triamide, water and the like, or a mixture thereof. In order to proceed smoothly, a phase transfer catalyst such as benzyltriethylammonium chloride or tetra-n-butylammonium bromide may be added, and usable bases are, for example, alkali metals such as sodium and potassium, sodium hydroxide. , Alkali metal hydroxides such as potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride, metal alkoxides such as sodium ethoxide and sodium methoxide, pyridine and triethylamine , N, N-di Chiruanirin a 4-N, organic bases such as N- dimethylaminopyridine. Manufacturing method a,
In b, c, d and e, the reaction temperature is not particularly limited, but is usually in the range of -30 ° C to 200 ° C or the boiling point of the solvent, and the reaction is usually completed in 0.5 to 24 hours. In the production method a, the molar ratio of the compound represented by the general formula 5 to the compound represented by the general formula 6 is usually 1: 1 to 10, preferably 1: 1.1.
~ 1.5. In the production method b, the molar ratio of the compound represented by the general formula (7) to the compound represented by the general formula (8) is usually 1: 1 to 10, preferably 1: 1.1.
~ 1.5. In the production method c, the molar ratio of the compound represented by the general formula 5 to the compound represented by the general formula 9 is usually 1: 1 to 10, preferably 1: 1.1.
~ 1.5. In the production method d, the molar ratio of the compound represented by the general formula 10 to the compound represented by the general formula 11 is usually 1: 0.5 to 10, preferably 1: 0.8 to 2.0. In the production method e, the molar ratio of the phenol compound represented by the general formula 12 to the compound represented by the general formula 13 is usually 1: 0.5 to 2.0, preferably 1: 0.7 to 1.5.

Examples of the reducing agent which can be used in the production method f include metal hydrides such as sodium borohydride and lithium aluminum hydride, boron compounds such as borane, and the like. ¹ and A ² are usually used in a ratio of 1 to 2 mol per 1 mol of a ketone compound having an oxygen atom bonded at the terminal, and the solvent used in this reaction should be selected according to the kind of the reducing agent. Although not limited, examples thereof include water, alcohols such as methanol and ethanol, ethers such as diethyl ether and tetrahydrofuran, and mixtures thereof. The reaction temperature is usually -10 to 50 ° C, and the reaction time is Usually, it is 0.5 to 50 hours. In the production method g, the reaction can be carried out without a solvent, but when a solvent is used, the solvent used is N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide or the like. Polar solvent,
Examples include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, etc., and the reaction temperature is usually 50 to 2
The temperature is in the range of 50 ° C., the reaction time is usually 0.5 to 50 hours, and as the reaction catalyst, for example, an acidic substance such as sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, or activated silica gel is used. Of these, 0.0001 to 1 weight can be used with respect to 1 weight of the ketone compound in which A is an oxygen atom, and the molar ratio of the raw materials to be subjected to the reaction can be arbitrarily set, but the reaction is performed at an equimolar ratio or a ratio close thereto. It is advantageous.

Examples of the oxidizing agent that can be used in the production method h include Jones reagent, Collins reagent, pyridinium chlorochromate, manganese dioxide and dimethyl sulfoxide. Among the compounds of the present invention, A ¹ and A ² Is used in a ratio of 1 to 2 mol per 1 mol of the alcohol compound which is a combination of a hydrogen atom and a hydroxyl group, and the solvent used in this reaction must be selected depending on the oxidizing agent and the kind, but acetone, Ketones such as methyl ethyl ketone, chloroform, dichloromethane,
Halogenated hydrocarbons such as 1,2-dichloroethane, n
There may be mentioned hydrocarbons such as -pentane, n-hexane and n-heptane, dimethyl sulfoxide and the like, or a mixture thereof, and the reaction temperature is usually -10 to 10
The reaction time is 0.5 to 50 hours. In the production method i, the solvent usually used is water, but it is also possible to use a mixture of water with an organic solvent such as alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, and if necessary. Accordingly, as a reaction catalyst, for example, sulfuric acid, hydrochloric acid, ammonium chloride,
An acidic substance such as benzenesulfonic acid or p-toluenesulfonic acid can be used in an amount of 0.0001 to 1 weight per 1 weight of the enamine compound represented by the general formula 15, and the reaction temperature in this reaction is usually 50 to The temperature is in the range of 200 ° C., and the reaction time is 0.5 to 50 hours. In the production method j, usable solvents include, for example, ketones such as acetone, ethers such as tetrahydrofuran and dioxane, carboxylic acids such as acetic acid, halogenated hydrocarbons such as dichloromethane, aromatic hydrocarbons such as benzene. And a mixture of water with an organic solvent such as nitriles such as acetonitrile, and, if necessary, as a reaction catalyst, for example, sulfuric acid, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, pyridinium p- Toluene sulfonic acid,
Among the compounds of the present invention, acidic substances such as activated silica gel are
A ¹ and A ² are OCH ₂ CH ₂ O or OCH ₂ CH ₂ C
0.0001 to 1 weight can be used with respect to 1 weight of the compound representing H ₂ O. In this reaction, the reaction temperature is usually in the range of 0 to 250 ° C., and the reaction time is 0.5 to 50 hours. In the production methods a, b, c, d, e, f, g, h, i and j, the reaction solution after completion of the reaction is subjected to usual post-treatments such as extraction with an organic solvent and concentration, and re-used as necessary. The compound of the present invention can be isolated by further purification by means such as crystallization or column chromatography.

Next, examples of the compounds of the present invention are shown in Tables 1 to 6. Each table has the general formula

Embedded image The respective substituents of the compound of the present invention represented by are shown below.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

[0019]

[Table 4]

[0020]

[Table 5]

[0021]

[Table 6]

General formula which is an intermediate for the production of the compound of the present invention
The compounds represented by Chemical formulas 5 and 7 are, for example, Org. Syn.
th. Coll. Vol. 1, 435 (1941) and US Pat. No. 4,943,586, the compound can be produced from the compound represented by the general formula (12). As the compounds represented by the general formulas 6, 8, 11 and 14, commercially available compounds can be used. The compound represented by the general formula 9 can be produced according to the method described in US Pat. No. 4,492,689. The compound represented by the general formula 12 is Collect. Czech. Chem. Commun. 46 ,
It can be produced according to the method described in 2573 (1981). The compound represented by the general formula 13 is, for example, Synt
It can be produced according to the method described in hesis, 573 (1980). The compound represented by the general formula:

[Chemical 17] [Wherein R ¹ , R ² , R ⁶ , R ⁷ , T ¹ , n and l
(El) has the same meaning as above. ] The compound shown by these can be manufactured by the method according to the said manufacturing method a, b, c, d, or e. The compound represented by the general formula 17 is Collect. Czech. Chem. Commun. 46 ,
It can be produced according to the method described in 2573 (1981).

The compound represented by the general formula 10 can be prepared, for example, from the compound represented by the general formula 12 by the following reaction route.

Embedded image [In the formula, R ¹ , R ² , R ³ , R ⁴ , A ¹ , A ² , l (el) and n have the same meanings as described above, and L'is a halogen atom (chlorine atom, bromine atom, iodine atom). Etc., and R ⁸ is a C ₁ -C ₄ alkyl group (for example, a methyl group,
Ethyl group). ]

Examples of pests against which the compound of the present invention exerts a controlling effect include the following. Hemoptera pests Planthoppers such as the brown planthopper, sedge brown planthopper, and brown planthopper, leafhopper leafhoppers, leafhopper leafhoppers, leafhopper leafhoppers, leafhopper leafhoppers, leafhopper leafhoppers, leafhoppers, leafhoppers, leafhoppers, leafhoppers, leafhoppers, leafhoppers Amberjack, aphid, apple aphid, aphid such as potato aphid, radish aphid, etc., American beetle stink bug, leaf-bug beetle, beetle beetle, beetle bug, beetle bug, beetle bug, beetle bug Stink bugs such as stink bugs, whitefly on tobacco, whitefly on white, whitefly on mandarin orange, whitefly on white mandarin orange, etc.,
Scale insects, gum beetles, psyllids, etc. Lepidopteran pests Nikameichu, Kobunomeika, Nosume Koga, Watanomaiga, Sankamaiga, Netaimaichu, Rice mizuga, Shiromeichu, Monomonogadagaima, Black-spotted moths
Uthwestern Corn Borer, European corn borer, etc., Lotus japonicus, armyworm, armyworm, rice armyworm, yellow armyworm, yellow-throated armyworm, yellow-tailed moth, Tamanaga moth,
White-spotted armyworm, Cottonweed, Cottonweed,
Tobacco moth, Nesuji mushrooms, Nokometogarikiriga, Akebikonoha, Akaeguriba, Kaburayaga, Tamanayaga, Tamanaginuwaba, Kikukinwaba, Mitsumonkinawaba, Nagashirushitaba, Cotton leafhoppers, etc. Apple crested beetle, Apple beetle crested beetle, Midare beetle crested beetle,
Red-faced cod, Periwinkle, Crimiga, Tenguhamaki, Atoboshihamaki, Apple-mongered, Black-billed beetle, Fruittree Leafroller, etc. Genus, dog moth, minnow moth, false moth mosquito, callehaga moth, killer whale moth, mosquito moth,
Sparrows, rhododendrons, mosquitoes, tribaga,
Iraga species, Heliothis spp., Plutella mosquitoes such as diamondback moth, squid, squid, etc. Culex pipiens such as Culex pipiens, Culex pipiens, etc. Such as house flies such as house flies, blow flies, flesh flies, flesh flies, sand flies, onion flies, etc., gall flies, fruit flies, fruit flies, fruit flies,
Welves, flies, gnats, flies, etc.Coleoptera pests Weevil, Weevil Weevil, Weevil, Weevil, Weevil, Weevil, Weevil, Weed Weevil, Banded Cucumber Beetle, We
stern Corn Rootworm, Sourthen Corn Rootworm, Padd
y Hispid and other leaf beetles, white rice beetle, beetle such as stag beetle, corn beetle, corn beetle such as burdock beetle, grape tiger beetle, chafer beetle, beetle beetle, beetle beetle, black beetle, beetle, beetle, beetle Beetles, bark beetles, flat beetles, long-tailed beetles, bollworms,
Click beetles, ladybirds such as stag beetles, and beetles, etc. Pests Ants, wasps such as bees, etc., Orthoptera pests Kerala, grasshoppers, etc. Coleoptera pests Human flea etc. Lice eye pests Effective against harmful insects such as human larvae, lice etc.

By adding other insecticides and / or acaricides, the pest control of the compound of the present invention can be applied practically to a wider variety of pests and a wider variety of use situations. Suitable additives include, for example, fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate], phenithione [O, O-dimethyl O- (3-methyl-4- (methylthio) phenyl). Phosphorothioate], diazinon [O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate], chlorpyrifos [O, O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate] ], Acephate [O, S-dimethylacetylphosphoramide thioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazole-3-]
Ilmethyl O, O-dimethyl phosphorodithioate], ethyl thiomethone [O, O-diethyl S-2-
Ethylthioethyl phosphorodithioate], DDVP
[2,2-dichlorovinyl dimethyl phosphate], sulprophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O, O-dimethyl phosphorothioate], salicione [2-methoxy-4H-
1,3,2-benzodioxaphosphinin-2-sulfide], dimethoate [O, O-dimethyl-S- (N-
Methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro- 1-hydroxyethylphosphonate], azinphos-methyl [S-3,4-dihydro-4-oxo-1,
2,3-benzotriazin-3-ylmethyl O, O-
Dimethylphosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], and other organic phosphorus compounds,

BPMC (2-sec-butylphenylmethylcarbamate), benfuracarb [ethyl N-
[2,3-Dihydro-2,2-dimethylbenzofuran-
7-yloxycarbonyl (methyl) aminothio] -N
-Isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], 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], etiophencarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxy ], Carbamate compounds such as oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide],

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], phenpropatrine [( 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-3-phenoxybenzyl (1
R, 3R) -3 (2,2-dibromovinyl) -2,2-
Pyrethroid compounds such as dimethylcyclopropanecarboxylate] and cycloprothrin [(RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate] ,

Thiadiazine derivatives such as buprofezin (2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-triadiazin-4-one), imidacloprid (1- (6-chloro-3-pyridyl). Methyl) -N-nitroimidazolidine-2-indeneamine] and the like, nitroimidazolidine derivatives, cartap (S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N-dimethyl-1,2]. , 3-Trithian-5-ylamine], benzultap [S, S′-2-dimethylaminotrimethylene di (benzenethiosulfonate)], and other nereistoxin derivatives, endosulfan [6,7,8,
9,10,10-hexachloro-1,5,5a, 6
9,9a-hexahydro-6,9-methano-2,4,3
-Benzodioxathiepine oxide], γ-BHC
Chlorinated hydrocarbon compounds such as (1,2,3,4,5,6-hexachlorocyclohexane], chlorfluabrone [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 compounds such as (4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea], amitraz [N, N ′ [( Methylimino)
Dimethyridin] di-2,4-xylidine], chlordimeform [N '-(4-chloro-2-methylphenyl)-
N, N-dimethylmethanimidamide] and the like formamidine derivatives and the like.

When the compound of the present invention is used as an active ingredient of a pest control agent, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, liquid carrier, gaseous carrier or bait. Etc., and if necessary, add surfactants and other auxiliaries for formulation, oils, emulsions, wettable powders, flowable agents such as water-suspending agents / emulsifiers, granules, powders,
It is used as a formulation for aerosols, self-combustion type smoke agents / chemical reaction type smoke agents, heated smoke agents such as porous ceramic plate smoke agents, ULV agents, and poison baits. In these formulations, the compound of the present invention is usually added as an active ingredient in an amount of 0.001% to 95% by weight.
contains. As the solid carrier used in the formulation,
For example, clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talc, ceramics, other inorganic minerals (serisite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.) , Fine fertilizers such as chemical fertilizers (ammonium sulphate, ammonium phosphide, ammonium nitrate, urea, ammonium chloride) and the like, and liquid carriers include, for example, water, alcohols (methanol, ethanol, etc.), ketones (acetone). , Methyl ethyl ketone, etc.), 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, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oil such as cottonseed oil, and the like, and examples of the gaseous carrier, that is, propellant include freon gas and butane gas. , LPG (liquefied petroleum gas),
Examples thereof include dimethyl ether and carbon dioxide gas. Examples of the surfactant include alkyl sulfate salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give.
Examples of auxiliary agents for formulations such as sticking agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol). , Polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of the stabilizer include PAP.
(Acid isopropyl phosphate), BHT (2,6-di-te
rt-Butyl-4-methylphenol), BHA (2-te
rt-Butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

Examples of base materials for self-burning smoke agents include nitrates, nitrites, guanidine salts, potassium chlorate,
Combustion exothermic agent such as nitrocellulose, ethyl cellulose, wood flour, thermal decomposition stimulant such as alkali metal salt, alkaline earth metal salt, dichromate, chromate, oxygen supply agent such as potassium nitrate, melamine, wheat starch, etc. Examples include a combustion-supporting agent, a filler such as diatomaceous earth, and a binder such as a synthetic paste. As the base material of the chemical reaction type smoke agent, for example, alkali metal sulfide, polysulfide, hydrosulfide, hydrous salt,
Exothermic agents such as calcium oxide, carbonaceous substances, iron carbide, catalysts such as activated clay, azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, organic foaming agents such as polystyrene and polyurethane, natural fiber pieces, synthetic fibers Examples include fillers such as pieces. As a base material for poison baits, for example, cereal flour, vegetable essential oil, sugar, bait components such as crystalline cellulose, dibutylhydroxytoluene,
Examples thereof include antioxidants such as nordihydroguaseletic acid, preservatives such as dehydroacetic acid, ingestion inhibitors such as pepper powder, cheese flavors, and attractive flavors such as onion flavors.
Formulations of flowable agents (suspension in water or emulsions in water) generally include 1-75% of the compound, 0.5-15% of the dispersant, 0.1-10% of the suspending aid (eg protective colloid or thixotropic properties). A compound which imparts 0 to 0.1% of a suitable auxiliary agent (for example, an antifoaming agent, an antirust agent, a stabilizer,
It can be obtained by finely dispersing it in water containing a spreading agent, a penetration aid, an antifreezing agent, an antibacterial agent, a smokeproofing agent, etc.). It is also possible to use an oil in which the compound is hardly dissolved in place of water to prepare a suspension in oil. As the protective colloid, for example, gelatin, casein, gums, cellulose ether, polyvinyl alcohol, etc. are used. Examples of the compound that imparts thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid, and the like.

The thus obtained preparation is used as it is or after diluted with water or the like. Also other pesticides,
It can be used simultaneously with or without mixing with nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, animal feeds and the like. When the compound of the present invention is used as an agricultural pest control agent, its application amount is usually 0.001 g to 500 g per 10 ares.
And preferably 0.1 g to 500 g. When using emulsions, wettable powders, flowable agents, etc. diluted with water, the application concentration is usually 0.0001ppm to 1000ppm, and granules, powders, etc. are applied as they are without being diluted. . When used as a pest control agent for epidemics, emulsions, wettable powders, flowable agents, etc.
Apply it after diluting it to 001ppm-10000ppm, and apply it as it is for oils, aerosols, fumigants, ULV agents, poison baits, etc. The application amount and application concentration depend on the type of formulation, application time, application site, application method, pest type, degree of damage, etc., and may be increased or decreased without regard to the above range. can do.

[0032]

EXAMPLES The present invention will be described in more detail below 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 of Compound (1) of the Present Invention by Production Method d) A mixture of 10 ml of anhydrous N, N-dimethylformamide and 87 mg of sodium hydride (60% oil dispersion) was stirred under stirring with 2- {4- A solution of 578 mg of [2,2- (ethylenedioxy) cyclohex-1-ylmethyl] phenoxy} ethanol (produced in Reference Production Example 1 below) in anhydrous N, N-dimethylformamide (5 ml) was added dropwise over 10 minutes. After stirring at 60 to 70 ° C for 2 hours, 5 to 1
After cooling to 0 ° C, a solution of 211 mg of 2-fluoropyridine in anhydrous N, N-dimethylformamide (5 ml) was added dropwise over 30 minutes. After dropping, stir at room temperature overnight, and
The mixture was stirred at 0 to 70 ° C for 2 hours. The reaction solution was poured into 50 ml of ice water and extracted twice with 30 ml of toluene. The organic layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 310 mg of 4- [2,2- (ethylenedioxy) cyclohex-1-ylmethyl] phenyl 2- (2-pyridyloxy) ethyl ether (compound (1)). Yield 51% mp 67.5 ℃

Production Example 2 (Production of Compound (2) of the Present Invention by Production Method b) 100 mg of pyrazole was added to a mixture of 5 ml of anhydrous N, N-dimethylformamide and 65 mg of sodium hydride (60% oil dispersion). And stirred for 30 minutes. Next, 3- {4- [2,2- (ethylenedioxy)
5 ml of anhydrous N, N-dimethylformamide solution of 542 mg of cyclohex-1-ylmethyl] phenoxy} propyl bromide (produced in Reference Production Example 3 described below) was added dropwise. After the completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction mixture was diluted with 50 ml of ethyl acetate, washed twice with a saturated aqueous solution of ammonium chloride, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography to give 1- {3- {4- as colorless oil.
398 mg of [2,2- (ethylenedioxy) cyclohex-1-ylmethyl] phenoxy} propyl} pyrazole (compound (2)) was obtained. Yield 76% n _D ^26.6 1.5415

Production Example 3 (Production of Compound (2) of the Present Invention by Production Method g) 500 mg of ethylene glycol, 1- {3- [4- (2-
Oxocyclohex-1-ylmethyl) phenoxy] propyl} pyrazole (manufactured according to Manufacturing Example 4 described below) 358
To a mixture of 20 mg of toluene and 20 ml of toluene, a catalytic amount of p-toluenesulfonic acid monohydrate was added, and water produced was Dean-s
While being removed using a tark water separator, the mixture was heated under reflux for 2 hours with stirring. After completion of the reaction, the reaction mixture was poured into 100 ml of 5% sodium hydrogen carbonate and extracted with toluene. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to give 1- {3- {4- [2,
399 mg of 2- (ethylenedioxy) cyclohex-1-ylmethyl] phenoxy} propyl} pyrazole (compound (2)) was obtained. Yield 97%

Production Example 4 (Production of Compound (3) of the Present Invention by Production Method b) 143 mg of pyrazole was added to a mixture of 5 ml of anhydrous N, N-dimethylformamide and 84 mg of sodium hydride (60% oil dispersion). And stirred for 30 minutes. Next, 619 mg of 2- [4- (3-bromopropoxy) benzyl] cyclohexan-1-one (manufactured by Reference Manufacturing Example 2 described below) (5 mg) of anhydrous N, N-dimethylformamide was added dropwise. After the completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction mixture was diluted with 50 ml of ethyl acetate, washed twice with a saturated aqueous solution of ammonium chloride, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography, and 358 mg of colorless oily 1- {3- [4- [2- (oxocyclohex-1-ylmethyl) phenoxy] propyl} pyrazole (compound (3)) was obtained. Obtained. Yield 60% Production Example 5 (Production of Compound (4) of the Present Invention by Production Method j) Acetone 20 ml, water 2 ml and 4- [2,2- (ethylenedioxy) cyclohex-1-ylmethyl] phenyl 2- (2 10 mg of p-toluenesulfonic acid monohydrate was added to a mixture of 601 mg of -pyridyloxy) ethyl ether (compound (1)), and the mixture was heated under reflux with stirring for 4 hours. Most of the acetone in the reaction mixture was removed under reduced pressure, the residue was added to 50 ml of water, and diethyl ether 5 was added.
Extracted twice with 0 ml. The organic layers were combined, washed successively with a 5% aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, 4-
354 mg of [2-oxocyclohex-1-ylmethyl] phenyl 2- (2-pyridyloxy) ethyl ether (compound (4)) was obtained. Yield 67%

Next, examples of the compounds of the present invention are shown in Table 7 together with compound numbers and physical property values.

[Table 7]

Next, production examples of the compound represented by the general formula 10 will be shown. Reference Production Example 1 Production of 2- {4- [2,2- (ethylenedioxy) cyclohex-1-ylmethyl] phenoxy} ethanol 10 ml of anhydrous N, N-dimethylformamide and 139 mg of sodium hydride (60% oil dispersion) 4- [2,2- (ethylenedioxy) cyclohex-1-ylmethyl] phenol (Helv. Chim. Ac
ta 77. , 1241 (manufactured by the method described in 1944)) 820 mg
1 part of anhydrous N, N-dimethylformamide (5 ml) solution of
It was added dropwise over 0 minutes. After stirring at room temperature for 1 hour, acetic acid 2
A solution of 551 mg of -bromoethyl in anhydrous N, N-dimethylformamide (5 ml) was added dropwise over 10 minutes. After the dropping, the mixture was stirred at room temperature overnight and further at 60 to 70 ° C. for 2 hours. The reaction solution was poured into 50 ml of ice water, and ethyl acetate 50 was added.
Extracted twice with ml. The organic layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to give colorless oily 2- {4- [2,2- (ethylenedioxy) cyclohex-1-ylmethyl] phenoxy} ethyl acetate 725.
to obtain mg. Yield 66% Acetic acid obtained by the above reaction 2- {4- [2,2-
(Ethylenedioxy) cyclohex-1-ylmethyl]
A mixture of 725 mg of phenoxy} ethyl, 5.2 ml of 0.5N aqueous sodium hydroxide solution and 10 ml of ethanol was stirred overnight at room temperature. Most of the ethanol in the reaction solution was removed under reduced pressure, the residue was added to 50 ml of water, and the mixture was mixed with 50 ml of ethyl acetate to 2 times.
Extracted. The organic layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to give a colorless oily 2-
{4- [2,2- (ethylenedioxy) cyclohexa-
578 mg of 1-ylmethyl] phenoxy} ethanol was obtained. Yield 91%

Next, production examples of the compound represented by the general formula 7 will be shown. Reference Production Example 2 Production of 2- [4- (3-bromopropoxy) benzyl] cyclohexane-1-one 2- (4-hydroxybenzyl) cyclohexane-1-
On (Collect. Czech. Chem. Commun. 46 2573 (1981)
2 g of an aqueous solution of 187 mg of sodium hydroxide was added dropwise to a mixture of 1 g of 1,3 dibromopropane 1.19 g of water and 7 ml of water with stirring while heating under reflux for 2 hours. After stirring for 30 minutes while heating under reflux, the reaction mixture was poured into 200 ml of ice water and the mixture was mixed with 100 ml of ethyl ether to 2 times.
Extracted times. The organic layers were combined, washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 619 mg of 2- [4- (3-bromopropoxy) benzyl] cyclohexane-1-one as a colorless oil. Yield 39%

Reference Production Example 3 Production of 3- {4- [2,2- (ethylenedioxy) cyclohex-1-ylmethyl] phenoxy} propyl bromide 4- [2,2- (ethylenedioxy) cyclohexa-1
-Ylmethyl] phenol (Helv. Chem. Acta. 77 124
1 (manufactured by the method described in 1994) 1 g, 1,3-dibromopropane 976 mg and a mixture of water 7 ml, while heating under reflux with stirring, an aqueous solution of sodium hydroxide 153 mg 2
ml was added dropwise over 2 hours. After stirring for 30 minutes while heating under reflux, the reaction solution was poured into 200 ml of ice water, and ethyl ether 1 was added.
Extracted twice with 00 ml. The organic layers were combined, washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and colorless oily 3- {4- [2,2-
(Ethylenedioxy) cyclohex-1-ylmethyl]
Phenoxy} propyl bromide (447 mg) was obtained. yield
30%

Next, formulation examples are shown. In addition, parts represent parts by weight, and the compounds of the present invention are represented by compound numbers described in Production Examples. Formulation Example 1 Emulsion 10 parts of each of the compounds (1) to (4) of the present invention were mixed with 35 parts of xylene.
Parts and 35 parts of dimethylformamide, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzene sulfonate are added thereto, and well mixed with stirring to obtain 10% emulsions of each. Formulation Example 2 Wettable powder 20 parts of each of the compounds (1) to (4) of the present invention, 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate,
20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of silicon earth are added into a mixture and mixed by stirring with a juice mixer to obtain each 20% wettable powder. Formulation Example 3 Granules To 5 parts of each of the compounds (1) to (4) of the present invention, 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 thoroughly with stirring. To do. Then, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated by a granulator, and air-dried to obtain each 5% granule. Formulation Example 4 Granules 5 parts of polypropylene glycol was added to 2 parts of each of the compounds (1) to (4) of the present invention, and after dissolving by heating to a temperature equal to or higher than the melting point, 93 parts of heated granular calcined diatomaceous earth was impregnated, 2% of
Get granules. Formulation Example 5 Dust agent 1 part of each of the compounds (1) to (4) of the present invention was dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder and PAP were added thereto.
0.3 parts and 93.7 parts of clay are added, and the mixture is stirred and mixed with a juice mixer to remove acetone by evaporation to obtain each 1% powder. Formulation Example 6 Flowable agent 20 parts of each of the compounds (1) to (4) of the present invention and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely ground with a sand grinder (particle size: 3 μm). After this), add xanthan gum to this.
40 parts of an aqueous solution containing 05 parts and 0.1 parts of aluminum magnesium silicate was added, and 10 parts of propylene glycol was further added and mixed by stirring to obtain each 20% suspension in water. Formulation Example 7 Oil formulation 0.1 parts of each of the compounds (1) to (4) of the present invention was dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this was deodorized kerosene 8
Mix with 9.9 parts to obtain each 0.1% oil solution. Formulation Example 8 Oily aerosol 0.1 parts of each of the compounds (1) to (4) of the present invention, tetramethrin
0.2 part, d-phenothrin 0.1 part, trichloroethane 1
After mixing and dissolving 0 part and 59.6 parts of deodorized kerosene, filling the aerosol container and attaching the valve part, 30 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain each oil-based aerosol. . Formulation Example 9 Aqueous aerosol 0.2 parts of each of the compounds (1) to (4) of the present invention, d-allethrin
An aerosol container was filled with a mixture of 0.2 parts, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark of Atlas Chemical Co.)}, and 50 parts of pure water. Then, attach the valve part, and through the valve part, the propellant (liquefied petroleum gas) 4
0 parts are pressure filled to obtain each aqueous aerosol. Formulation Example 10 Mosquito coil Incense 0.3 g of each of the compounds of the present invention (1) to (4) was d-allethrin.
0.3 g was added and dissolved in 20 ml of acetone, and a carrier for mosquito coil (mixing tab powder: lees powder: wood powder at a ratio of 4: 3: 3) 9
After uniformly stirring and mixing with 9.4 g, 120 ml of water was added, and the well kneaded mixture was molded and dried to obtain each mosquito coil. Formulation Example 11 Electric Mosquito Repellent Mat 0.4 g of each of the compounds (1) to (4) of the present invention, d-allethrin
Acetone is added to 0.3 g and 0.4 g of pipenyl butoxide to dissolve, and the total volume is 10 ml. This solution 0.5
ml is uniformly impregnated with a 2.5 cm × 1.5 cm, 0.3 cm thick base for electric mats (a fibril mixture of cotton linter and pulp is hardened into a plate), and each electric mosquito mat is obtain. Formulation Example 12 Heating Smoke Agent Each of 100 mg of each of the compounds (1) to (4) of the present invention is dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate having a size of 4.0 cm × 4.0 cm and a thickness of 1.2 cm. Get smoke. Formulation Example 13 Poison bait The present compounds (1) to (4) (10 mg) are each added to acetone (0.5 ml).
, And this solution was added to the solid feed powder for animals (solid feed powder for breeding and breeding CE-2, trade name of CLEA Japan, Inc.)
Process to 5 g and mix evenly. Then air dry with acetone to obtain 0.5% of each bait.

Next, it will be shown by test examples that the compound of the present invention is useful as an active ingredient of a pest controlling agent. The compound of the present invention is shown by the compound number described in Production Examples. Test Example 1 (Insecticidal test against cotton aphid) An emulsion of a test compound obtained according to Formulation Example 1 was diluted with water to a predetermined concentration, and 15 cc was added to a polyethylene cup planted cucumber in which cotton aphid larvae were released. Sprayed at a ratio of 1 pot. 14 days after the chemical application, the control value was calculated by the formula 1.

[Equation 1] Cb: Number of insects before treatment in untreated plot Cai: Number of insects observed in untreated plot Tb: Number of insects before treatment in experimental plot Tai: Number of insects observed in experimental plot Table 8 shows the results.

[Table 8]

[0042]

The compound of the present invention exhibits an excellent pest control effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A01N 43/647 43/78 CE B C07D 213/64 213/70 239/26 239/30 239 / 34 239/38 249/04 502 504 277/14 277/16 277/34 277/36 405/12 213 231 239 249 417/12 317 319

Claims (2)

[Claims] 1. A general formula: ## STR1 ##[In the formula, R¹, R³And R^FourAre each independently hydrogen
Represents an atom or a methyl group, R²Is hydrogen atom, halogen
Represents a hydrogen atom or a methyl group, A¹And A²Is a hydrogen atom
Represents a combination of and hydroxyl groups, or is bonded at the end
Then oxygen atom, OCH₂CH₂O or OCH₂CH₂
CH₂Represents O, and -B is represented by the general formula:B-1, B-2, B-3, B-4, B-5 or
Or B-6, R ^FiveAre independent hydrogen
Represents a child, a halogen atom or a methyl group, and X is an oxygen source.
Represents a child, a sulfur atom or a methylene group, and l (el) is
Represents an integer of 1 to 4, m and n are each independently
Represents an integer of 1 or 2. ] An ether compound
Stuff. 2. A pest control agent comprising the ether compound according to claim 1 as an active ingredient.