JP2000086628A - 3-aryl-3-substituted-2,4-dione-five-membered ring compound, its production and insecticidal and acaricidal agent containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having not only an extremely high insecticidal and acaricidal activity but also high safety for target crops and useful as an insecticidal and acaricidal agent. SOLUTION: A compound of formula I [R1, R2 are each H or a 1-4C alkyl, or R1 and R2 are bound to each other to form a 2-6C alkylene; X is a 1-4C alkyl, a 1-4C halogenoalkyl or the like; Y is a halogen or nitro; Z is O or a group of formula II (R3 is H, a 1-4C alkyl or the like); (n) is 1-3], for example, 3-chloro-3-(2,4-dichlorophenyl)-5,5-pentamethylenepyrrolidine-2,4-dione. The compound of formula I is obtained by halogenating a compound of formula III with a halogenating agent such as chlorine in an inert solvent such as methylene dichloride or in the absence of a solvent usually at -30 deg.C to the boiling point of the used solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel 3-aryl-3-substituted-2,4-dione-5-membered ring compound, a process for producing the same, and an insecticide and acaricide containing the compound.

[0002]

2. Description of the Related Art Conventionally, a general formula:

[0003]

Embedded image Various 3-aryl-2,4-dione-5-membered ring compounds having a basic skeleton represented by the following formulas are known, and these are pest control agents, more specifically, insecticides and pesticides. It is also known that it is effective as an acaricide, fungicide, fungicide, herbicide, etc.
No. 056, JP-A-4-226957, JP-A-5-78314, JP-A-5-221971, JP-A-6-263731, International Publication WO
95/01350).

However, the conventional 3-aryl-2,
Among the 4-dione-5-membered ring compounds, there is no compound in which a halogen atom or a nitro group is substituted at the 3-position on the 5-membered ring (pyrrolidine ring or tetrahydrofuran ring).

[0005]

As a result of the use of insecticides and acaricides for many years, pests have recently gained resistance and have become difficult to control with conventional insecticides.
Therefore, development of a novel insecticide with high efficacy is expected. On the other hand, certain compounds have high insecticidal and acaricidal activity and cause severe phytotoxicity to target crops, which may make practical use difficult.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a novel compound having not only an extremely high insecticidal and acaricidal activity, but also a high safety for a target crop. And completed the present invention.

That is, the present invention provides a compound represented by the following general formula (1):

[0008]

Embedded image Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom or a C _1-4 alkyl group, or R ¹ and R ² are bonded to each other to form a linear C _2-6 alkylene; (The alkylene group may be substituted with a C _1-4 alkyl group or may contain an oxygen atom in a linear alkylene group). X represents a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group or a halogen atom. Y
Represents a halogen atom or a nitro group. Z is an oxygen atom or group:

[0009]

Embedded image Is shown. R ³ represents a hydrogen atom or a C _1-4 alkyl group, or R ³ is bonded to R ² to represent a linear C _2-5 alkylene group (the alkylene group is a C _1-4 alkyl group). May be substituted with an alkyl group). n shows the integer of 1-3. 3-aryl-3-substituted-2,4-dione-5-membered ring compound represented by the formula:

[0010] The present invention also relates to a method for producing a 3-aryl-3-substituted-2,4-dione-5-membered ring compound represented by the above general formula (1).

Further, the present invention relates to an acaricide and an insecticide containing the 3-aryl-3-substituted-2,4-dione-5-membered ring compound represented by the general formula (1).

The compound of the present invention represented by the general formula (1) has isomers based on asymmetric carbon atoms, for example, diastereomers, and the present invention relates to any of these isomers and mixtures thereof. Are also included.

The compound of the present invention represented by the general formula (1)
It shows excellent insecticidal and acaricidal activity to many agricultural pests, equivalent to or better than conventional insecticides and acaricides, without affecting the target crop. Therefore, the compound of the present invention can provide a useful pest control agent.

The compound of the present invention represented by the general formula (1)
It is also effective against various pests at low doses. Examples of such pests include the following agricultural pests. Note that, naturally, the following pests are merely examples, and the present invention is not limited to these. Acari: For example, spider mites, red spider mite, apple spider mite, Kanzawa spider mite, Dermatophagoid mite, etc .; Peach aphid, cotton aphid,
Aphids such as apple aphid, stink bugs, stink bugs, white bugs, whiteflies and the like; Leaf fly, etc.

The compounds of the present invention are active not only on agricultural pests but also on various sanitary pests such as Culex pipiens and house flies, and other pests.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The groups defined in the above general formula (1) and other groups described in the present specification are more specifically as follows.

The C _1-4 alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. A linear or branched alkyl group can be mentioned.

C _1-4 haloalkyl groups include fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl,
2-fluoroethyl group, 2-chloroethyl group, 1-fluoroethyl group, pentafluoroethyl group, 1-fluoropropyl group, 2-chloropropyl group, 3-fluoropropyl group, 3-chloropropyl group, 1-fluorobutyl Group, 1-chlorobutyl group, 4-fluorobutyl group, etc.
Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms and substituted with up to 9 halogens.

The C _1-4 alkoxy group includes a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group having 1 to 4 carbon atoms. And a straight-chain or branched alkoxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the linear C _2-6 alkylene group include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
Even C _2-5 alkylene group, like, for example, can be exemplified ethylene group, trimethylene group, tetramethylene group, a pentamethylene group.

C_1-4Number of carbon atoms substituted with alkyl group
Examples of the linear alkylene group of 2 to 6 include -CH (CH_Three) CH
_Two−, −CH (CH_Three) (CH_Two)_Two-, -CH_TwoCH (CH_Three) CH_Two−, −CH (CH
_Three) (CH_Two) _Three-, -CH_TwoCH (CH_Three) (CH_Two)_Two−, −CH (CH_Three) (CH_Two)_Four
-, -CH_TwoCH (CH_Three) (CH_Two)_Three−, − (CH_Two)_TwoCH (CH_Three) (CH_Two)
_Two−, − (CH_Two)_TwoCH (C_TwoH_Five) (CH_Two)_Two−, − (CH_Two)_TwoCH (i-C_ThreeH₇)
(CH_Two)_Two−, − (CH_Two)_TwoCH (t-C_FourH₉) (CH_Two)_Two−, − (CH_Two)_TwoCH (C
H_Three) (CH_Two)_Three-, -CH_TwoCH (CH_Three) CH (CH_Three) CH_TwoCH_Two-, -CH_TwoCH
(CH_Three) CH_TwoCH (CH_Three) CH_Two−, − (CH_Two)_TwoC (CH_Three)_Two(CH_Two)_Two-Etc.
Charcoal substituted with 1 to 2 alkyl groups having 1 to 4 carbon atoms
A linear alkylene group having a prime number of 2 to 6;
You. C_1-4C2-C5 substituted with an alkyl group
The same may be mentioned as the linear alkylene group.
it can.

Examples of the linear alkylene group having 2 to 6 carbon atoms containing an oxygen atom include -CH ₂ OCH _2- and-(CH
₂ ) ₂ O (CH ₂ ) _2- , -CH ₂ OCH ₂ OCH ₂ -,-(CH ₂ ) ₂ O (CH ₂ ) _3- ,
Examples thereof include a linear alkylene group having 2 to 6 carbon atoms and having 1 to 2 oxygen atoms such as-(CH ₂ ) ₃ O (CH ₂ ) _3- .

Examples of the straight-chain alkylene group having 2 to 6 carbon atoms which is substituted with a C _1-4 alkyl group and which contains an oxygen atom include, for example, --CH ₂ CH (CH ₃ ) OCH (CH ₃ ) CH ₂ −, −C
H ₂ OC (CH ₃ ) ₂ OCH ₂ — and the like.

The compound of the present invention represented by the general formula (1) includes a compound represented by the general formula (2):

[0026]

Embedded image Wherein R ¹ , R ² , R ³ , X, Y and n are the same as above. 3-aryl-3-substituted pyrrolidine-
2,4-dione compound and general formula (3):

[0027]

Embedded image Wherein R ¹ , R ² , X, Y and n are the same as above. 3-aryl-3-substituted tetrahydrofuran-
2,4-dione compounds are included.

Preferred compounds among the compounds of the present invention represented by the general formula (1) include the following compounds.

When R ¹ and R ² are the same or different, and
Represents an _1-4 alkyl group or R ¹ and R ² are bonded to each other to form a 6-membered saturated alicyclic ring (however, the 6-membered saturated alicyclic ring may contain an oxygen atom) 3-aryl-
3-substituted-2,4-dione-5-membered ring compounds.

A 3-aryl-3-substituted-2,4-dione-5-membered ring compound wherein Y represents a chlorine atom, a bromine atom or a nitro group;

Wherein Z is an oxygen atom or a group:

[0032]

Embedded image (R ³ represents a hydrogen atom or a C _1-4 alkyl group, or R ³ is bonded to R ² to represent a tetramethylene group.) 3-Aryl-3-substituted-2,4-dione A 5-membered ring compound.

Among the compounds of the present invention represented by the general formula (1), it is particularly preferred that R ¹ and R ² are the same or different and each represent a C _1-4 alkyl group, or R ¹ and R 2 ² bond to each other to form a 6-membered saturated alicyclic ring (provided that
The 6-membered saturated alicyclic ring may contain an oxygen atom. ), X represents a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group or a halogen atom;
Represents a chlorine atom, a bromine atom or a nitro group, and Z represents an oxygen atom or a group:

[0034]

Embedded image (R ³ represents a hydrogen atom or a C _1-4 alkyl group, or R ³ is mutually bonded to R ² to represent a tetramethylene group), and n represents an integer of 1 to 3, Aryl-3-
Substituted-2,4-dione-5-membered ring compounds are exemplified.

Of the compounds of the present invention represented by general formula (1), general formula (5):

[0036]

Embedded image Wherein R ¹ , R ² , X, Z and n are the same as above. Y ¹
Represents a halogen atom. The compound of the present invention represented by
For example, general formula (4):

[0037]

Embedded image Wherein R ¹ , R ² , X, Z and n are the same as above. The 3-aryl-2,4-dione-5-membered ring compound represented by the formula [1] can be produced by halogenation.

The present halogenation reaction is carried out in an inert solvent or without solvent in the presence of a 3-aryl-2,
The reaction is carried out by reacting a 4-dione-5-membered ring compound with a halogenating agent. Specifically, it is as follows.

The 3-aryl-2,4-dione-5-membered ring compound represented by the general formula (4) as a raw material is a known compound, and is, for example, disclosed in JP-A-4-226957 and JP-A-5-226957. -294953, JP-A-4-211
No. 056, JP-A-5-78314, JP-A-5-221971, JP-A-6-263731, and International Publication WO95 / 01350.

Examples of the halogenating agent include chlorine, thionyl chloride, sulfuryl chloride, phosgene, phosphorus trichloride,
Inorganic halides such as phosphorus pentachloride, bromine, thionyl bromide, sulfuryl bromide, phosphorus pentabromide, phosphorus oxybromide, hypochlorous acids such as sodium hypochlorite, tert-butyl hypochlorite, N -Chlorosuccinimide (NCS), N-
Organic halides such as bromosuccinimide (NBS) and the like can be mentioned. The amount of the halogenating agent used is the 3-aryl-2,4-dione- represented by the general formula (4).
The amount is 1 to 10 mol, preferably 1 to 4 mol, per 1 mol of the 5-membered ring compound.

As the inert solvent, methylene chloride, 1,1,
Examples thereof include halogenated hydrocarbons such as 2-dichloroethane and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, xylene and o-chlorobenzene, and ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane. it can.

The reaction can be obtained, for example, by mixing the compound represented by the general formula (4) with a halogenating agent (and, if necessary, a solvent) and causing the mixture to react. Alternatively, the compound represented by the general formula (4) is mixed (dissolved) in a solvent in advance, and a halogenating agent (which may be previously dissolved in the solvent if necessary) is mixed or dropped therein. Reaction.

The reaction temperature is not particularly limited, but when the reaction is carried out in an inert solvent, it is usually in the range of -30 ° C to the boiling point of the solvent used. Alternatively, the reaction can be carried out at 0 ° C. to the reflux temperature of the halogenating agent in the absence of a solvent. The reaction time varies depending on the above-mentioned concentration, temperature, etc., but the reaction may usually be carried out for 0.1 to 6 hours.

If necessary, the reaction may be carried out in the presence of a catalyst. Examples of the catalyst used include radical initiators such as benzoyl peroxide (BPO), 2,2′-azobisisobutyronitrile (AIBN), and 4,4′-azobis-4-cyanovaleric acid (ACVA). Can be The amount used is not particularly limited as long as it is a commonly used amount, but the amount of 3-aryl-2,
0.000 to 1 mol of the 4-dione-5-membered ring compound
The amount is from 01 to 1 mol, preferably from 0.0001 to 0.1 mol.

Further, among the compounds of the present invention represented by general formula (1), general formula (6):

[0046]

Embedded image Wherein R ¹ , R ² , X, Z and n are the same as above. The present compound represented by the general formula (4) can be produced by nitrating a 3-aryl-2,4-dione-5-membered ring compound represented by the general formula (4).

This nitration reaction is carried out by reacting a 3-aryl-2,4-dione-5-membered ring compound represented by the general formula (4) with a nitrating agent in a solvent. Specifically, it is as follows.

Examples of the nitrating agent include mixed acid, nitric acid, fuming nitric acid, and alkali metal nitrates such as potassium nitrate. The amount of the nitrating agent to be used is 1 to 10 mol, preferably 1 to 10 mol, per 1 mol of the 3-aryl-2,4-dione-5-membered ring compound represented by the general formula (4).
2 moles.

When a mixed acid is used as the nitrating agent, the concentrated sulfuric acid, which is a component thereof, can be used as a solvent.
Examples of the solvent include halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, and chloroform, and acid anhydrides such as acetic anhydride.

The reaction can be obtained, for example, by mixing the compound represented by the general formula (4) with a nitrating agent (and, if necessary, a solvent) and causing the mixture to react. Alternatively, the compound represented by the general formula (4) is previously mixed (dissolved) in a solvent, and a nitrating agent (which may be previously dissolved in the solvent if necessary) is mixed or dropped therein. Reaction.

The reaction temperature is not particularly limited, but is 0 ° C.
It is within the range of the boiling point of the solvent used. The reaction time varies depending on the concentration, the temperature and the like, but is usually 0.1 to 6 hours.

The compound of the present invention obtained in each of the above reactions can be easily isolated and purified from the reaction mixture according to ordinary isolation and purification means such as solvent extraction, recrystallization and chromatography.

When the compound of the present invention represented by the general formula (1) is used as an active ingredient of an insecticide or acaricide, it may be used as it is without adding other components. , A liquid carrier, a gaseous carrier, and, if necessary, a surfactant and other formulation auxiliaries, and an oil, emulsion, wettable powder, flowable, granule, powder, aerosol,
It is formulated into an aerosol and used.

In these preparations, the compound of the present invention represented by the general formula (1) as an active ingredient is usually added in a weight ratio of 0.1.
The content is preferably from 01 to 95% by weight, more preferably from 0.1 to 50% 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 (celite). , Quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, salt ammonium, etc.)
And the like, fine powder or granular material.

Examples of the liquid carrier include water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methyl ethyl ketone), aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), and fats. Group hydrocarbons (hexane, cyclohexane, kerosene, gas oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amide (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil and the like. .

As the gaseous carrier, that is, the propellant, for example, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like can be mentioned.

Depending on the dosage form and various purposes, emulsification, dispersion,
Surfactants are used for stabilization and the like, and examples thereof include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof,
Examples include polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohol compounds.

Examples of auxiliary agents for preparations such as fixing agents and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose compounds, alginic acid, etc.), lignin compounds, bentonite, saccharides, synthetic water-soluble compounds. Molecules (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.). 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, Examples thereof include a surfactant, a fatty acid or an ester thereof.

The preparation thus obtained is used as it is or diluted with water or the like. Also used with or without mixing with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, soil conditioners, animal feed, etc. it can.

When the compound of the present invention is used as an agricultural pesticide or acaricide, the application rate of the compound of the present invention is usually
0.1-500 g per 100 m ² . When the emulsion, wettable powder, flowable and the like are diluted with water and used, the application concentration of the compound of the present invention is usually 1 to 1000 ppm, preferably 10 to 500 ppm, and granules and powders are diluted at all. It is applied as is without preparation.

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.

[0063]

The present invention will be described more specifically with reference to the following examples, preparation examples and test examples.

Example 1 3-chloro-3- (2,4-dichlorophenyl) -5
5-pentamethylenepyrrolidine-2,4-dione (this invention
Synthesis of 3- (2,4-dichlorophenyl) -5,5-pentamethylenepyrrolidine-2,4-dione 0.31 g (1.0
Mmol), 0.16 g of N-chlorosuccinimide
(1.2 mmol), 10 mg of benzoyl peroxide (0.
04 mmol) and 20 ml of carbon tetrachloride in 30 ml.
Heated to reflux for minutes. Water was added to the reaction solution and extracted with chloroform. The extract was washed with a saturated aqueous solution of sodium hydrogencarbonate and saturated saline, and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography (hexane: ethyl acetate = 4:
Purified in 1) to give 3-chloro-3- (2,4-dichlorophenyl) -5,5-pentamethylenepyrrolidine-2,4
0.15 g of dione (43% yield) was obtained.

Example 2 3-chloro-1,5,5-trimethyl-3- (2,4,
6-trimethylphenyl) pyrrolidine-2,4-dione
Synthesis of (Invention Compound 28) 1,5,5-Trimethyl-3- (2,4,6-trimethylphenyl) pyrrolidine-2,4-dione 0.52 g
(2.0 mmol), 0.71 g of thionyl chloride (6.0
(Mmol) and benzene (10 ml) was heated to reflux for 6 hours. After cooling the reaction solution, 50 ml of ethyl acetate
Was added, washed with water, 1N sodium hydroxide and saturated saline in this order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with hexane to give 3-chloro-
0.35 g of 1,5,5-trimethyl-3- (2,4,6-trimethylphenyl) pyrrolidine-2,4-dione
(50% yield).

Example 3 3-bromo-5,5-dimethyl-1-n-propyl-3
-(2,4,6-trimethylphenyl) pyrrolidine-
Synthesis of 2,4-dione (the present compound 32) 5,5-dimethyl-1-n-propyl-3- (2,4,
A mixture of 0.20 g (0.70 mmol) of 6-trimethylphenyl) pyrrolidine-2,4-dione, 0.15 g (0.84 mmol) of N-bromosuccinimide, 7 mg of benzoyl peroxide and 15 ml of carbon tetrachloride was added to 1 mixture. Heated to reflux for an hour. Water was added to the reaction solution and extracted with chloroform. The extract was washed with a saturated aqueous solution of sodium hydrogencarbonate and saturated saline, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to give 3-bromo-5,5-dimethyl-1-n-propyl-3- (2 There was obtained 0.11 g (43% yield) of (4,6-trimethylphenyl) pyrrolidine-2,4-dione.

Example 4 5,5-Dimethyl-3-nitro-1-n-propyl-3
-(2,4,6-trimethylphenyl) pyrrolidine-
Synthesis of 2,4-dione (Compound 33 of the present invention) 5,5-dimethyl-1-n-propyl-3- (2,4,
0.25 g (0.87 mmol) of 6-trimethylphenyl) pyrrolidine-2,4-dione in 15 m of chloroform
To the solution at room temperature was added 0.11 g (1.74 mmol) of fuming nitric acid. This mixture was stirred at room temperature for 30 minutes. The reaction solution was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (benzene: ethyl acetate = 3: 1) to give 5,5-dimethyl-3-nitro-1-n-propyl-3- (2,4 There was obtained 0.22 g (76% yield) of (6,6-trimethylphenyl) pyrrolidine-2,4-dione.

Example 5 3-chloro-5,5-pentamethylene-3- (2,4,
6-trimethylphenyl) pyrrolidine-2,4-dione
Synthesis of (the present compound 37) 0.15 g of 5,5-pentamethylene-3- (2,4,6-trimethylphenyl) pyrrolidine-2,4-dione
To a solution of (0.5 mmol) in 10 ml of methylene chloride was added dropwise a solution of 0.074 g (0.55 mmol) of sulfuryl chloride in 5 ml of methylene chloride under ice-cooling. This mixture was stirred under ice cooling for 3 hours. The reaction solution was washed with water, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give 3-chloro-5,5-pentamethylene-3- (2,4,6-trimethylphenyl). )
0.08 g of pyrrolidine-2,4-dione (50% yield)
I got

Example 6 3-chloro-5,5-pentamethylene-3- (2,4,
6-trimethylphenyl) tetrahydrofuran-2,4
Synthesis of 5-dione (Compound 53 of the Invention) 5,5-pentamethylene-3- (2,4,6-trimethylphenyl) tetrahydrofuran-2,4-dione
29 g (1.0 mmol) of tetrahydrofuran 10 m
tert-butyl hypochlorite 0.12 g
(1.1 mmol) and stirred at room temperature for 6 hours. After the reaction solution was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography (hexane: ethyl acetate = 6: 1).
To give 3-chloro-5,5-pentamethylene-3-
0.31 g (yield 97%) of (2,4,6-trimethylphenyl) tetrahydrofuran-2,4-dione was obtained.

The compounds prepared according to any of the methods described in the above Examples and their physicochemical properties are shown in Tables 1 to 5. In the table, Me is methyl, n-Pr is n-
Propyl and i-Pr represent isopropyl. Table 1
Table 6 shows the NMR spectrum data of each compound shown in Table 6.
10 to 10. In addition, it measured using tetramethylsilane (TMS) as a reference substance.

Compound 3 and Compound 4 or Compound 34 and Compound 35 are diastereomers separated by silica gel chromatography of the reaction crude product, respectively.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

[0079]

[Table 8]

[0080]

[Table 9]

[0081]

[Table 10] Next, formulation examples are shown. Parts indicate parts by weight.

Formulation Example 1 Emulsion 10 parts of each of the compounds of the present invention were mixed with 45 parts of an organic solvent (trade name: Solvesso 150, manufactured by Exxon Chemical Co., Ltd.) and N
Dissolved in 35 parts of methylpyrrolidone, and emulsifier (trade name: Solpol 3005X, manufactured by Toho Chemical Co., Ltd.) 10
Parts were added and mixed with stirring to obtain each 10 w / w% emulsion.

Formulation Example 2 Wettable powder 20 parts each of the compound of the present invention were added to a mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium ligninsulfonate, 20 parts of fine powder of synthetic silicon hydroxide and 54 parts of clay, The mixture was stirred and mixed with a juice mixer to obtain a 20% w / w wettable powder.

Formulation Example 3 Granules To 5 parts of each of the compounds of the present invention, 2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite and clay 83
Add and mix well with stirring. An appropriate amount of water was added, the mixture was further stirred, granulated by a granulator, and dried by ventilation to obtain a 5 w / w% granule.

Formulation Example 4 Powder One part of each of the compounds of the present invention was dissolved in an appropriate amount of acetone.
5 parts of synthetic hydrous silicon oxide fine powder, 0.3 parts of acid isopropyl phosphate (PAP) and 93.7 parts of clay were added, and the mixture was stirred and mixed with a juice mixer, and acetone was evaporated to remove 1 w / w% powder. Obtained.

Formulation Example 5 Flowable agent 20 parts of each of the compound of the present invention, 3 parts of polyoxyethylene tristyryl phenyl ether phosphate triethanolamine as a surfactant, 0.2 parts of a silicone antifoaming agent (trade name) : RHODORSIL
426R, manufactured by Rhodia) and 16.8 parts of water were mixed, and wet-pulverized using a Dynomill, followed by 8 parts of propylene glycol as an antifreezing agent, 0.32 part of xanthan gum as a thickener and 51 parts of water. Was mixed with a liquid containing 0.68 parts to obtain a 20% w / w suspension in water.

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of acaricide and insecticide.

Test Example 1 Acaricide test against spider mite Spider bean leaf (approximately 3.5 × 4.5 cm) was placed on a nonwoven fabric (4.5 × 5.5 cm) that had sufficiently absorbed water, and an adult female spider mite (approx. 30 individuals) and 25 ±
It was left still in a constant temperature room at 2 ° C. and a humidity of 40%.

Next, a 0.1 w / v% aqueous solution of Solpol 355 (manufactured by Toho Kagaku) was added to each of the 4 w / v% methanol solutions of the compound of the present invention to prepare a chemical solution (concentration: 200 ppm) of each of the compound of the present invention. Next, 2.0 ml of this drug solution
Was sprayed, air-dried, and allowed to stand in a constant temperature room (25 ± 2 ° C., humidity 50%). Two days after the treatment, the mortality of the spider mite was examined. As a result, the following compounds showed a mortality of 50% or more. The following numbers correspond to the compound numbers produced in the above examples. Compound number of the present invention: 1, 2, 3, 4, 9, 10, 12,
13, 14, 16, 17, 18, 22, 24, 25, 2,
6, 27, 28, 29, 31, 32, 34, 35, 3,
6, 37, 38, 43, 45, 48, 49, 50, 5
1, 53, 54, 55.

Test Example 2 Killing of peach aphids
Insect test A leaf piece (2 cm in diameter) of the second leaf of cabbage parasitic on peach aphid larvae (approximately 30 individuals) is placed on a nonwoven fabric (4.5 × 5.5 cm) that has sufficiently absorbed water, and placed in a thermostatic chamber (25 ± 2).
(C, 50% humidity). The next day, 2.0 ml of a drug solution of the compound of the present invention prepared according to Test Example 1 (concentration: 200 p
pm) were sprayed, air-dried, and allowed to stand in a constant temperature room for 3 days, and the mortality of peach aphid was investigated. As a result, the following compounds showed a mortality of 50% or more. The following numbers correspond to the compound numbers produced in the above examples. Compound number of the present invention: 14, 37, 39, 43, 45, 4
9, 53, 54, 55, 56.

Test Example 3 Trial of insecticidal activity against brown planthopper
To a rice plant (1.5 leaves stage, 5 plants) planted in a test pot (3 × 4 × 4 cm), 2.5 ml (concentration: 200 ppm) of a drug solution of the compound of the present invention prepared according to Test Example 1 was dropped on the soil surface. did. After the chemical solution penetrated the soil, the third instar larvae of the brown planthopper were released (approximately 30 individuals) and kept in a constant temperature room (25 ± 2).
C., humidity 50%), and 7 days after the treatment, the mortality of the brown planthopper was examined. As a result, the following compound is 50
% Mortality. The following numbers correspond to the compound numbers produced in the above examples. Compound number of the present invention: 1, 2, 6, 9, 10, 11, 1
2, 13, 14, 15, 16, 18, 19, 20, 2
1, 22, 23, 25, 26, 27, 28, 29, 3
0, 31, 32, 33, 34, 35, 36, 37, 3
9, 41, 42, 43, 45, 46, 47, 48, 4
9, 50, 51, 55, 56.

Test Example 4 Test for phytotoxicity The phytotoxicity of the compound 43 of the present invention produced in the above example was tested using the following compounds A and B disclosed in International Patent Application Publication No. WO95 / 01358 as comparative substances. Compound A:

[0093]

Embedded image Compound B:

[0094]

Embedded image That is, each of the liquid chemicals 10 prepared according to Test Example 1 was added to a kidney bean (1 strain) planted in a pot in which primary leaves were developed.
ml (concentration: 200 ppm) was sprayed, air-dried, and allowed to stand in a glass house.

On the second and eighth days after spraying, the degree of phytotoxicity of the whole strain was observed. Also, on the 16th day after spraying, the degree of phytotoxicity of the new leaves developed after spraying was observed and evaluated according to the following five grades. -: No phytotoxicity ±: Leaf deformation is slightly observed, but there is no problem. +: Slightly curled leaves are present. ++: Rolled leaves and leaf margin withering. +++: Severe curly leaves and shoot dying. Table 11 shows the results.

[0096]

[Table 11] The compound 43 of the present invention showed 200
At the application concentration of ppm, no phytotoxicity was shown. on the other hand,
Compounds A and B described in International Patent Application Publication No. WO 95/01358 exhibited moderate to severe phytotoxicity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 471/04 102 C07D 471/04 102 (72) Inventor Yasuhiro Endo 615 Satoura, Satoura-cho, Satoura-cho, Naruto City, Tokushima Prefecture. Otsuka Chemical Co., Ltd. Naruto Research Laboratories (72) Inventor Yoshinori Endo 3-2-2, Ote-dori, Chuo-ku, Osaka City, Osaka Prefecture Otsuka Chemical Co., Ltd. Address Otsuka Chemical Co., Ltd. Naruto Research Laboratory (72) Inventor Yasuhiro Sasama 615 Satoura, Satoura-cho, Naruto-shi, Naruto City, Tokushima Prefecture F-term Otsuka Chemical Co., Ltd. KK04 PP03 QQ04 4C069 AC28 BA01 BA08 BB08 BB12 BB16 BC01 BC02 BC12 CC14 CC19 4C204 BB02 CB01 DB07 DB11 DB15 DB 28 EB10 FB01 FB03 GB01 GB03 4H011 AC01 AC04 DE17

Claims (6)

[Claims] 1. General formula (1): Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom or a C _1-4 alkyl group, or R ¹ and R ² are bonded to each other to form a linear C _2-6 alkylene; (The alkylene group may be substituted with a C _1-4 alkyl group or may contain an oxygen atom in a linear alkylene group). X represents a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group or a halogen atom. Y
Represents a halogen atom or a nitro group. Z is an oxygen atom or a group: Is shown. R ³ represents a hydrogen atom or a C _1-4 alkyl group, or R ³ represents a linear C _2-5 alkylene group bonded to R ² (the alkylene group is a C _1- alkyl group). _{4 It} may be substituted by an alkyl group.). n shows the integer of 1-3. A 3-aryl-3-substituted-2,4-dione-5-membered ring compound represented by the formula: 2. General formula (2): Wherein R ¹ , R ² , R ³ , X, Y and n are the same as above. 3-aryl-3- according to claim 1, which is represented by the formula:
Substituted pyrrolidine-2,4-dione compounds. 3. A compound of the general formula (3): Wherein R ¹ , R ² , X, Y and n are the same as above. The 3-aryl-3-substituted tetrahydrofuran-2,4-dione compound according to claim 1, which is represented by the formula: 4. A compound of the general formula (4): Wherein R ¹ , R ² , X, Z and n are the same as above. Wherein the 5-aryl-5-membered 3-aryl-2,4-dione compound represented by the general formula (5) is halogenated. Wherein R ¹ , R ² , X, Z and n are the same as above. Y ¹
Represents a halogen atom. 3-aryl-3 represented by the formula:
A method for producing a 5-halo-2,4-dione-5-membered ring compound. 5. General formula (4): Wherein R ¹ , R ² , X, Z and n are the same as above. Wherein the 3-aryl-2,4-dione-5-membered ring compound represented by the general formula (6) is nitrated. Wherein R ¹ , R ² , X, Z and n are the same as above. 3-aryl-3-nitro-2,4-dione-
A method for producing a 5-membered ring compound. 6. An insecticidal or acaricide comprising at least one of the 3-aryl-3-substituted-2,4-dione-5-membered ring compounds according to claim 1 as an active ingredient.