JPH08217610A - Insecticidal composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition having synergistically improved insecticidal activity compared with the separate use of the individual components by mixing pyridaphenthion known as an insecticide with a 3-tetrahydrofurylethyl derivative which is a new compound having insecticidal activity. CONSTITUTION: This insecticide composition is produced by mixing pyridaphenthion O,O-diethyl-O-(3-oxo-2-phenyl-2H-pyridazinon-6-yl) phosphorothioate with one or more kinds of 3-tetrahydrofurylmethyl derivatives of formula I (R1 to R4 are each H or a lower alkyl). The new compound of formula I can be produced e.g. by reacting a compound of formula II with a compound of formula III (X1 is amino, a 1-5C alkoxy, a 1-5C alkylthio or benzylthio). The agrochemical preparation produced from the composition preferably contains 0.1-90wt.% (especially 0.5-50wt.%) of pyridaphenthion and 0.01-90wt.% of the compound of formula I. The total of the active components is preferably 10-1,000g per 1ha in the case of applying the composition to farm crops.

Description

Detailed Description of the Invention

[0001]

The present invention relates to known insecticides such as O,
O-diethyl-O- (3-oxo-2-phenyl-2H
TECHNICAL FIELD The present invention relates to an insecticidal composition comprising a mixture of -pyridazinone-6-yl) phosphorothioate (generic name pyridafenthion) and a 3-tetrahydrofurylmethyl derivative which is a novel insecticidal active compound.

[0002]

2. Description of the Related Art O, O-diethyl-O- (3-oxo-
2-Phenyl-2H-pyridazinone-6-yl) phosphorothioate (generic name pyridafenthion) is an organophosphorus insecticide that is actually widely used for controlling agricultural pests and sanitary pests (Agricultural Handbook 1992,
Japan Plant Protection Association, etc.). On the other hand, a certain type of 3-tetrahydrofurylmethyl derivative according to the present invention is a novel compound and has high insecticidal activity by itself, but by mixing pyridafenthion with a compound represented by the formula (1) It is also not known to develop unexpected efficacy beyond that used in.

[0003]

In the past, pesticides have been widely used to harm agricultural crops and their harvests or to reduce the damage from pests that have a harmful effect on humans and livestock. ing. However, these insecticides often result in reduced efficacy due to the development of pest resistance as a result of repeated use. In addition, they are generally toxic to higher animals and aquatic animals, and in addition, they are often used outdoors and may cause adverse side effects in drinking water or in natural ecosystems containing useful organisms. . Therefore, it is possible to exert sufficient efficacy on pests with developed resistance, reduce toxicity without impairing the original usefulness for pest control as much as possible, and reduce the effect on other organisms and the environment. Is desired.

[0004]

[Means for Solving the Problems] As a result of diligent examination of measures for reducing adverse effects on other organisms and the environment without impairing their usefulness as insecticides, pyridafenthion and certain species relating to the present invention The present invention was completed by finding that the insecticidal efficacy is synergistically increased when the 3-tetrahydrofurylmethyl derivative of 1 is mixed and applied as compared with the case where each is used alone.

That is, the present invention relates to O, O-diethyl-O.
-(3-oxo-2-phenyl-2H-pyridazinone-
6-yl) phosphorothioate (generic name pyridafenthion) and formula (1)

[0006]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a lower alkyl group) or a mixture of one or more of the compounds represented by the formula (1). Is. In the formula (1) according to the present invention, R ₂ , R ₃ ,
R ₄ and R ₅ are preferably a hydrogen atom, a methyl group or an ethyl group, and typical examples are shown in Examples.

The derivative represented by the formula (1) according to the present invention has a strong insecticidal action and can be used as an insecticide in various scenes such as agriculture, horticulture, livestock, forestry, epidemics and houses. Further, the derivative represented by the formula (1) of the present invention exerts a proper controlling effect against harmful insects without causing any damage to plants, higher animals, environment and the like.

The insecticidal active compound represented by the formula (1) according to the present invention is a compound which has not been known so far, but it is produced by the following method (A) or (B) depending on the substituents. You can Method (A): The compound represented by the formula (1) has a reaction formula (1)
In accordance with (Chemical Formula 3), the compound represented by Formula (2) and Formula (3)
The compound represented by can be easily produced in a high yield by reacting it in various solvents in the presence of a base or a catalyst, if necessary.

[0009]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent the above meanings, X ₁ represents an amino group, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms or a benzylthio group. Examples of the base include carbonates such as potassium carbonate and sodium carbonate, phosphates such as tripotassium phosphate, trisodium phosphate, dipotassium monohydrogen phosphate and disodium monohydrogen phosphate, and acetates such as sodium acetate and potassium acetate. Can be used. As the catalyst, organic bases such as 4- (dimethylamino) pyridine, DABCO, triethylamine, diazabicycloundecene, sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid, and mineral acids such as sulfuric acid, hydrogen chloride and phosphoric acid. , Ion exchange resins, silica gels, zeolites and the like can be used.

Examples of the solvent include water, alcohols such as methanol, ethanol, propanol and butanol, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and petroleum benzine, and dimethyl. Formamide, dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, aprotic polar solvent such as 1-methyl-2-pyrrolidinone, ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, Ethers such as dioxane, nitriles such as acetonitrile and propionitrile, and ketones such as acetone and diisopropyl ketone can be used.

The reaction temperature and reaction time can be varied over a wide range, but in general, the reaction temperature is -20 to 20.
200 ° C., preferably 0-150 ° C., reaction time 0.0
It is 1 to 50 hours, preferably 0.1 to 15 hours.

The compound represented by the formula (2) in the reaction formula (1) can be produced by the method of the reaction formula (1A) (formula 4).

[0013]

[Chemical 4] (In the formula, R ₁ and R ₂ represent the above meanings, and X ₂ represents a halogen atom, a toluenesulfonyloxy group, a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group.) That is, (tetrahydro-3-furanyl) Methanol derivatives can be treated with halogenating agents such as thionyl chloride, phosphorus oxychloride, phosphorus tribromide, triphenylphosphine / carbon tetrabromide, triphenylphosphine / carbon tetrachloride, etc., or tosyl chloride, methanesulfonyl chloride, trifluoride. It can be produced by converting it to a sulfonated product with a sulfonating agent such as romethanesulfonic anhydride, and then using a known amine synthesis method such as the Delpin method using hexamethylenetetramine, or a reaction with an alkylamine. The compound represented by the reaction formula (1) and the formula (3) can be prepared according to Chem. Be
r. , Volume 100, page 591.

Method (B): In the formula (1), the formula (1a) in which R ₂ and R ₃ represent a hydrogen atom can also be produced by the production method of the reaction formula (2) (Chemical formula 5). it can.

[0015]

Embedded image (In the formula, R ₁ and R ₄ have the above-mentioned meanings, and R ₅ represents an alkyl group having 1 to ₅ carbon atoms or a benzyl group.) That is, the compound represented by the formula (4) is acid or if necessary. Easily react in various solvents in the presence of catalyst,
And it can be produced in high yield.

Acids or catalysts used include sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid,
Mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, ion exchange resins, silica gels and zeolites can be used. As a solvent, water, alcohols such as methanol, ethanol, propanol, butanol, benzene, toluene, aromatic hydrocarbons such as xylene, hexane, heptane, aliphatic hydrocarbons such as petroleum benzine,
Aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, 1-methyl-2-pyrrolidinone, ethyl ether, diisopropyl ether,
Ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, nitriles such as acetonitrile and propionitrile, and ketones such as acetone and diisopropyl ketone can be used. Although the reaction temperature and the reaction time can be varied over a wide range, the reaction temperature is generally -20 to 150 ° C, preferably room temperature to
The reaction time is 100 ° C and the reaction time is 0.01 to 50 hours, preferably 0.1 to 10 hours.

The compound represented by the formula (4) in the reaction formula (2) is represented by the compound represented by the formula (5) and the formula (6) according to the method of the reaction formula (2A) (formula 6). If necessary, the compound can be reacted in various solvents in the presence of a base or a catalyst to easily produce it at a high yield.

[0018]

[Chemical 6] (In the formula, R ₁ and R ₄ have the above-mentioned meanings, X ₃ represents a chlorine atom, a bromine atom, a toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and R ₅ has 1 to 1 carbon atoms. 5 represents an alkyl group or a benzyl group.) As the base, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, sodium hydride potassium hydride Alkali metal hydrides such as, sodium methylate, sodium ethylate and other alkali metal alcoholates, sodium oxide and other alkali metal oxides, potassium carbonate, sodium carbonate and other carbonates, tripotassium phosphate, trisodium phosphate, etc. Phosphates such as dipotassium monohydrogen phosphate, disodium monohydrogen phosphate, sodium acetate Acetic acid salts such as potassium acetate and organic bases such as 4- (dimethylamino) pyridine, DABCO, triethylamine and diazabicycloundecene can be used.

Examples of the solvent include water, alcohols such as methanol, ethanol, propanol and butanol, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and petroleum benzine, and dimethyl. Formamide, dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, aprotic polar solvent such as 1-methyl-2-pyrrolidinone, ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, Ethers such as dioxane, nitriles such as acetonitrile and propionitrile, and ketones such as acetone and diisopropyl ketone can be used.

The reaction temperature and reaction time can be varied over a wide range, but in general, the reaction temperature is -30 to -30.
The temperature is 200 ° C., preferably −20 to 150 ° C., and the reaction time is 0.01 to 50 hours, preferably 0.1 to 15 hours.

The compound represented by the formula (5) in the reaction formula (2A) is obtained by converting a (tetrahydro-3-furanyl) methanol derivative into thionyl chloride, phosphorus oxychloride, phosphorus tribromide, triphenylphosphine / tetraodor. It can be produced by halogenation with a halogenating agent such as carbon dioxide, triphenylphosphine / carbon tetrachloride or the like, or sulfonate with a sulfonation agent such as tosyl chloride, methanesulfonyl chloride or trifluoromethanesulfonic anhydride.

The compound represented by the formula (6) in the reaction formula (2A) can be produced from a monoalkyl-substituted nitroguanidine or a monobenzyl-substituted nitroguanidine, a primary amine and formaldehyde.

The insecticidal composition of the present invention has a synergistically increased insecticidal effect and an improved repellent effect as compared with the case where each insecticide is used alone, and the agricultural, horticultural, livestock, forestry, epidemic prevention, It can be used against pests in various situations such as houses. Examples of such pests include armyworm, Tamana moth, White-spotted armyworm, Spodoptera litura, Kaburagaga, Spodoptera frugiperda, Tamanaginouwaba, Nikameiga, Kobunomaiga, Hyugadaragaiga, Beetle, Cottonweed, Potato moth, White butterfly,
Lepidoptera insect pests such as Nosima Madaraiga, Chanocha sukuensis, Kinmon Hosoga, Mikanhamogiga, Nashihime Shinkoi, Mameshino Shinga, Peach mosquito, Grape scabbard, Koga, Tobacco whitefly, Onitsutsuko whitefly, Mikantoge whitefly, Whitefly
Yukiyanagi aphid, apple aphid, green peach aphid, radish aphid, harbor aphid, bean aphid, orange aphid, wheat aphid, potato aphid, green aphid, green tea leafhopper, leafhopper leafhopper, blackhopper planthopper, blackhopper planthopper, blackhopper planthopper, leafhopper planthopper Taiwantsuno Tuna leafhopper, Yanoe scale scale, stag beetle scale, citrus scale scale,
Hemiptera pests such as the moss bug, the southern green stink bug, the leaf beetle, the beetle bug, the rice leaf weevil, the rice droopyworm, the dwarf worm, Diabrotica spp. Coleoptera pests such as, Pleurotus ostreatus, Pleurotus cornucopiae, Astragalus vulgaris, etc .; Culex pipiens, Culex pipiens, Aedes albopictus, Pleurotus spp. Thrips, oysters, Thrips palmi, Thrips palmi L., Thrips palmi, Rice Thrips, Thrips palmi Thysanoptera insects such as horses;
Orthoptera such as black cockroaches, Yamato cockroaches, American cockroaches, German cockroaches, German cockroaches, scutellaria, and grasshoppers; pteropteran pests such as turnip wasps; house dust mites, chiggers, mosquito mites, spider mites, other mites and mites , Head lice, Yamato termites, millipedes, and gudge.

Further, the composition of the present invention can be used with higher efficacy, safer, more labor-saving and economically by blending and using other insecticidal components. Such other insecticidal and acaricidal components include, for example, allethrin, tetramethrin, resmethrin, phenothrin, flamethrin, permethrin, cypermethrin, deltamethrin, cyhalothrin, cyfluthrin, fenpropatrine, tralomethrin, cycloprothrin, flucitrinate, fluvalitin. Nate, acrinathrin, tefluthrin, bifenthrin, enpentrin,
Synthetic pyrethroid insecticides such as beta-cyfluthrin and zetacypermethrin, and their various isomers or pyrethrum extract, DDVP, cyanophos, phenthion, fenitrothion, tetrachlorvinphos, dimethylvinphos, propaphos, methylparathion, temefos, phoxim, acephate, isofenphos, salithion, DEP, EPN, ethion, mecarbam, diazinon, pirimiphos-methyl, etrimfos, isoxathion, quinalphos, chlorpyrifos-methyl, chlorpyrifos, phosalone, phosmet, methidathion, Okishideburohosu, vamidothion, malathion, phenthoate, dimethoate, formothion, thiometon , Ethyl thiomethone, folate, terbufos, profenofos,
Organophosphorus insecticides such as prothiophos, sulprophos, pyraclophos, monocrotophos, naredo, fosthiazate, NAC, MTMC, MIPC, BPMC, XMC,
Carbamate insecticides such as PHC, MPMC, ethiophene carb, bendiocarb, pirimicarb, carbosulfan, benfulacarb, fratiocarb, mesomil, oxamyl, aldicarb, nicotine sulfate, polynactin complex, avermectin, milbemectin, BT
Insecticidal natural products such as agents, cartap, thiocyclam, bensultap, diflubenzuron, chlorfluazuron,
Teflubenzuron, triflumuron, flufenoxuron, flucycloxuron, hexaflumuron, fluazuron, imidacloprid, nitenpyram, acetamiprid, pymetrozine, fipronil, buprofezin,
Phenoxycarb, pyriproxyfen, methoprene,
Insecticides such as hydroprene, quinoprene, endosulfan, diafenthiuron, triazuron, tebufenozide, benzoepine, silafluophene, dicofol, chlorbenzilate, phenisobromolate, tetradiphone, CPCBS, BPPS, quinomethionate, amitraz, benzomate, hexithia Acaricides such as Zox, fenbutatin oxide, cyhexatin, dienochlor, clofentezine, pyridaben, fenpyroximate, fenazaquin, tebufenpyrad, and pyrimidinamine can be mentioned. Not only insecticidal and acaricidal components, but also compounding with plant protectants such as fungicides, herbicides, fertilizers, soil improvers, plant growth regulators and agricultural materials to enhance the effect and obtain labor-saving effect. It goes without saying that things are possible.

When actually applying the composition of the present invention,
Although it can be used in a plain form without adding other components, it is generally used by formulating it with a carrier in order to make it easy to use as a controlling agent.

The formulation of the composition of the present invention does not require any special conditions, and the emulsion, wettable powder, powder, granule, fine granule, Flowables, microcapsules, oils, aerosols, foams, fumes, poison baits, tablets, packs, seed coatings or compounds used in combustors, eg fumigation cartridges, fumigation cans, fumigation The coil can be adjusted to an arbitrary dosage form such as a ULV cold mist composition and a warm mist composition, and these can be used for various applications according to their respective purposes. The carrier as referred to herein, helps the active ingredient to reach the site to be treated, and also stores the active ingredient compound,
It means a liquid, solid or gaseous synthetic or natural inorganic or organic substance that is formulated to facilitate transportation and handling.

Suitable solid carriers include, for example, montmorillonite, kaolinite, diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel,
Inorganic substances such as ammonium sulfate, soybean flour, sawdust, wheat flour, pectin,
Examples include organic substances such as methyl cellulose, urea, sodium alginate, petrolatum, lanolin, lactose, liquid paraffin, lard, and vegetable oils and fats. Suitable gas carriers include, for example, butane, propane, carbon dioxide, nitrogen gas, halogenated hydrocarbons.

Suitable liquid carriers include, for example, toluene,
Aromatic hydrocarbons such as xylene, cumene and solvent naphtha, paraffin hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, ketones such as acetone, methyl ethyl ketone and cyclohexanone, Ethers such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl acetate, acetic acid butyl ester, dioctyl phthalate ester, fatty acid glycerin ester, etc., acetonitrile, pro Nitriles such as pionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol and ethylene glycol. Le ethers, dimethylformamide, dimethyl sulfoxide, water and the like. Further, in order to accurately exert the efficacy of the composition of the present invention, the following auxiliary agents may be used alone or in combination depending on the purpose in consideration of the dosage form of the preparation, the application scene, etc. it can.

As an auxiliary agent used for the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as lignin sulfonates, alkylbenzene sulfonates,
Alkyl sulfates, polyoxyethylene alkylaryl ethers, nonionic surfactants such as polyhydric alcohol esters, lubricants such as calcium stearate and wax, stabilizers such as isopropylhydrodiene phosphate, other methyl cellulose, carboxymethyl cellulose, Examples include casein and gum arabic.
However, these components are not limited to those described above.

The composition of the present invention is stable to light, heat, oxidation, etc., but if necessary, it may be an antioxidant or an ultraviolet absorber such as BHT (2,6-di-t-butyl-4-).
Stable with phenol derivatives such as methylphenol) and BHA (butylhydroxyanisole), bisphenol derivatives, arylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, and condensation products of phenetidine and acetone, or benzophenone compounds. By adding an appropriate amount as an agent, a composition having a more stable effect can be obtained.

When the composition of the present invention is formulated, pyridafenthion is contained in an amount of 0.1 to 90% by weight and the compound represented by the formula (1) is contained in an amount of 0.01 to 90% by weight, preferably pyridafenthion is O ． 5-50% by weight, formula (1)
0.1 to 50% by weight of the compound represented by When the composition of the present invention is applied to agricultural products, generally, the total amount of active ingredients is 10 to 1000 g per ha.

[0032]

EXAMPLES In order to clarify the content of the present invention, the production examples, examples and test examples of the compound of the formula (1) will be specifically described below. The compound numbers shown in the following text are those shown in Table 1, and all parts are parts by weight. Production Example 1 Production of 1-{(tetrahydro-3-furanyl) methyl} -2-nitro-3-methylguanidine (Compound No. 1) (Tetrahydro-3-furanyl) methanol 10.0
g, anhydrous trifluoromethanesulfonic acid 29.5 g, pyridine 10.0 g, and dichloromethane 200 ml were stirred at room temperature for 1 hour. Water was poured into the reaction solution, the organic layer was separated, washed with 1N hydrochloric acid, water and saturated brine, dried and concentrated to obtain 20.0 g of 3-tetrahydrofuranylmethyl triflate. 1,5-Dimethyl-2-nitroiminohexahydro-1,3,5-triazine 12.5 g, DMF
3.25 g of 60% sodium hydride at room temperature in 60 ml
Was added and stirred for 1 hour, 20.0 g of 3-tetrahydrofuranylmethyl triflate was added at room temperature, and the mixture was stirred at 50 ° C. for 2 hours. After cooling to room temperature, add 50 ml of 2N hydrochloric acid,
The mixture was stirred at 50 ° C for 2 hours. After neutralization with sodium bicarbonate, extraction with dichloromethane, drying and concentration, the residue was subjected to silica gel column chromatography (developing solvent; ethyl acetate: hexane =
1: 1) and 7.8 g of 1-{(tetrahydro-
3-furanyl) methyl} -2-nitro-3-methylguanidine was obtained.

Production Example 2 Production of N-{(tetrahydro-3-furanyl) methyl} -N- (methyl) nitroguanidine (Compound No. 3) (Tetrahydro-3-furanyl) methyl tosylate 0,
71 g, sodium iodide 0.08 g, potassium carbonate 0.85 g, 40% methylamine methanol solution 9 ml
The mixture was heated to reflux for 5 hours. The insoluble material was filtered off, and the reaction solution was concentrated under reduced pressure to obtain crude N-{(tetrahydro-3-
To furanyl) methyl} -N-methylamine, 0.38 g of S-methyl-N- (nitro) isothiourea and 7 ml of acetonitrile were added, and the mixture was heated under reflux for 5 hours. The reaction solution was concentrated under reduced pressure, purified by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 1: 1),
10 g of N-{(tetrahydro-3-furanyl) methyl} -N- (methyl) nitroguanidine was obtained.

Production Example 3 Production of 1-{(tetrahydro-3-furanyl) methyl} -1-ethyl-2-nitro-3-methylguanidine (Compound No. 4) N-{(tetrahydro-3-furanyl) methyl} -N-
5.5 g of ethylamine and S-methyl-N-nitro-N '
-Methylisothiourea 3.0 g, ethanol 30 m
A mixture of 1 and DMAP 0.5 g was heated under reflux for 4 hours. Then, the reaction solution was concentrated under reduced pressure, and the obtained crude oily substance was purified by column chromatography. 1-{(tetrahydro-3-furanyl) methyl} -1-ethyl-2
1.1 g of -nitro-3-methylguanidine was obtained.

Production Example 4 N- [4-{(2-methyl) tetrahydrofuranyl} methyl] -N'-methyl-N "-
Preparation of nitroguanidine (Compound No. 5) 2-methyl-4-hydroxymethyltetrahydrofuran 1.00 g and triethylamine 1.05 g in a dichloromethane 50 ml solution under ice-cooling trifluoromethanesulfonic anhydride 2.91 g dichloromethane 10 ml
The solution was added dropwise over 5 minutes. The reaction solution was stirred under ice-cooling for 30 minutes and at room temperature for 5 hours, and then the reaction solution was concentrated under reduced pressure to give an oily product, which was sodium hydride (about 60%).
To a suspension of 32 g of dimethylformamide in 5 ml of 1-methyl-2-nitroimino-5-methyl-1,
A solution of 1.24 g of 3,5-triazine in 5 ml of dimethylformamide was added, and the mixture was stirred at 60 ° C. for 30 minutes, and then added as a 5 ml solution of dimethylformamide at room temperature, and stirred at 60 ° C. for 4 hours. Hydrochloric acid (2M) in the reaction solution
7.2 ml was added, and the mixture was further stirred at 60 ° C. for 3 hours.
The reaction solution was allowed to cool to room temperature, ethyl acetate was added, this was washed with water, and the organic layer was dried over anhydrous magnesium sulfate. The oily substance obtained by concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent; ethyl acetate) to give N- [4-{(2-methyl) tetrahydrofuranyl} methyl] -N'-. Methyl-
77 mg of N "-nitroguanidine were obtained as a reddish brown oil.

The physical properties of the compounds of formula (1) of compound Nos. 1 to 5 produced according to the above production examples are shown in Table 1 (Table 1,
2).

[0037]

[Table 1]

[0038]

[Table 2]

Example 1 30 parts of pyridafenthion, compound 5 of compound number 1
Part, dimethylformamide 5 parts, Solpol 355S
(Toho Chemical, surfactant) 20 parts, xylene 40 parts,
The above was uniformly dissolved by stirring to obtain 100 parts of emulsion.

Example 2 20 parts of pyridafenthion, compound 10 of compound number 1
Parts, sodium alkylnaphthalene sulfonate 2 parts, sodium lignin sulfonate 1 part, white carbon 5
Parts, diatomaceous earth 67 parts, and the above were stirred and mixed uniformly to obtain 100 parts of a wettable powder.

Example 3 2 parts of pyridafenthion, compound 0.5 of compound No. 5
Parts and 0.5 parts of white carbon were uniformly mixed, and 96.8 parts of clay and 0.2 parts of Dorilles A (manufactured by Sankyo) were added and uniformly pulverized and mixed to obtain 100 parts of dust.

Example 4 2 parts of pyridafenthion, 1 part of compound No. 5,
3 parts of white carbon, 2 parts of sodium lignin sulfonate, 92 parts of bentonite, after uniformly pulverizing and mixing the above,
Water was added and kneaded, and the mixture was granulated and dried to obtain 100 parts of granules.

Test Example 1 Effect on the brown leafhopper, an acetone solution prepared by mixing pyridafenthion and the compound of formula (1) in a predetermined ratio was uniformly sprayed on rice seedlings at about 3 leaf stage. After the treatment, the seedlings were covered with a wire netting cylinder, and 10 female adults of the flying squirrel planthopper were released inside, and 48 hours later, the mortality was examined. The results are shown in Table 2 (Table 3).

[0044]

[Table 3]

Test Example 2 Effect on housefly A filter paper is laid on the bottom of a petri dish having a diameter of 9 cm, and 1 ml of an acetone solution prepared by mixing pyridafenthion and the compound of the formula (1) in a predetermined ratio is added thereto. After the acetone was distilled off, 10 female housefly female adults were released inside,
Mortality was investigated 24 hours later. The results are shown in Table 3 (Table 4).
Shown in

[0046]

[Table 4]

Test Example 3 Effect on Spodoptera litura Pyridafenthione and the compound of formula (1) are made into an acetone solution and mixed in a predetermined ratio. Then 10m of this solution
1 was added to 40 ml of water to make a suspension, and cabbage leaves were immersed therein for about 30 seconds. The treated leaves were air-dried, transferred to a plastic cup, and then infested with Spodoptera litura second-instar larvae for 72 hours to determine the mortality rate. The results are shown in Table 4 (Table 5).

[0048]

[Table 5]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Odaka 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. O, O-diethyl-O- (3-oxo-
2-Phenyl-2H-pyridazinone-6-yl) phosphorothioate and a compound of formula (1) (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a lower alkyl group) One or more compounds of the formula (1) or a mixture of two or more compounds are used for the insecticidal composition. Stuff.