JPH01308260A - Benzohydroxymoylazole derivative and insecticide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X is halogen, alkyl, NO2, CN, benzyloxy, alkoxy, CF3, group expressed by formula II (A is H, halogen or CF3) or Xn may form five-membered ring containing O together with carbons at 3 and 4 positions of benzene ring); Y is alkyl, halogen substituted alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, cycloalkylmethyl, etc.; Z is methyn or N; n is 0-4]. EXAMPLE:1-(O-Propyl-2,4-dichlorobenzohydroxymoyl)imidazole. USE:An insecticide. PREPARATION:A compound (new material) expressed by formula III is reacted with a compound expressed by the formula YB (B is halogen) in the presence of a base such as NaOH at 40-80 deg.C for 1-6hr to provide the compound expressed by formula I.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a benzohydroxymoylazole derivative and an insecticide containing the same as an active ingredient.

(Prior Art) Agricultural crops are seriously damaged by pests, especially planthoppers. A large amount of money is spent every year to control these pests, and as a control agent,
For example, organochlorine insecticides, organophosphorus insecticides, carbamay 1-type insecticides, etc. have been put into practical use.

(Problem to be solved by the invention) In recent years, the use of these insecticides has been regulated due to problems such as residue, accumulation, and environmental pollution, and long-term use has led to the development of resistant insects and the use of less effective insecticides. There is.

The present inventors aim to develop new and useful insecticides,
Various benzo-1-roximoylazole derivatives were synthesized and their physiological activities were investigated. As a result, it was discovered that the compound of the present invention has extremely excellent insecticidal activity against various harmful insects, especially susceptible and resistant planthoppers, and the present invention was completed.

(Means for Solving the Problems) The benzohydroxymoylazole derivative of the present invention has the general formula - [wherein X is a halogen atom, an alkyl group,
3-ro group, cyano group, benzyloxy group, alkoxy group, halogen-substituted alkoxy group, I.lifluorome (Formula 11.
Δ represents a hydrogen atom, a halogen atom, or a l-lifluoromethyl group. ), and furthermore, X and n are 3 of the benzene ring.
A 5-membered ring containing an oxygen atom can also be formed together with the carbon atoms at the 4- and 4-position positions.

Y represents an alkyl group, a halogen-substituted alkyl group, an alkenyl group, a halogen-substituted alkenyl group, an alkynyl group, an alkoxyalkyl group, an alkylthioalkyl group, or a cycloalkylmethyl group, Z represents a methine group or a nitrogen atom, and n represents O or Indicates an integer from 1 to 4. ].

The compounds of the present invention represented by the above general formula are illustrated in Table 1. In addition, the compound number will be referred to in the following description.

Table 1 Table 1 continued Table 1 continued = 7 - Table 1 continued Table 1 continued Table 1 continued Table 1 continued The compound of the present invention can be produced by the following method.

[11) [1lT] [1)(
In the formula, B represents a halogen atom. x, y, z and n have the same meanings as above. ) That is, the compound of the present invention represented by general formula C1) can be produced by reacting a benzohydroxymoylazole represented by formula (l) with a halogen compound represented by formula (ITI) in the presence of a base. In this case, the halogen compound can be used in an equivalent amount or more.As bases that can be used, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate,
Inorganic bases such as alkali metal carbonates such as potassium carbonate, thorium hydrogen carbonate, alkali metal bicarbonates such as potassium hydrogen carbonate, or 1-ethylamine, N, N
Examples include organic bases such as -dimethylaniline, pyridine, ]-78-diazabicyclo[5,4,O]]unde-7=cene, and 1-helium hydride.

The reaction can be carried out in the presence of a suitable diluent if necessary. Diluents that can be used include water or inert organic solvents, including ketones such as acetone and butanone, aromatic hydrocarbons that may be halogenated such as benzene, toluene, xylene, and glolobenzene, and petroleum. Aliphatic hydrocarbons such as ether and ligroin, ethers such as diethyl ether, te-1-herahy-1-lofuran, and dioxane, 21-helyl compounds such as ace-nitrile, propioni[-lyl, etc.], or dimethylformamide, dimethyl Examples include formamide, amide compounds such as methylpyrrolone, and the like.

The reaction temperature is any temperature from 0°C to the reflux temperature in the reaction system, preferably /10 to 80°C.

The reaction time varies depending on the compound, but may be reacted for 1 to 6 hours.

In producing the compound of the present invention, the raw material formula CIl
The benzohydroxymoylazoles represented by 'l are new compounds and can be produced by the following method (IV)
[V) (n) (In the formula, X, Z, n and B have the same meanings as above.) That is, the benzohydroxymoylazole compound represented by the formula [I[) is represented by the formula (TV) It can be produced by reacting benzohydroxymoylhalites with azoles represented by formula (V) in a solvent such as ace1-21-lyl in the presence of a base such as potassium carbonate, for example. can.

The reaction temperature is any temperature from 0°C to the reflux temperature in the reaction system, preferably 50 to 80°C. The reaction time varies depending on the compound, but may be reacted for 1 to 6 hours. Table 2 shows examples of benzohydroxymoylazoles represented by the above general formula [■].

Table 2-15= (VI) (V) (1
) (In the formula, X, Y, Z, n and B have the same meanings as above.) That is, the benzohydroxymoylazole represented by the general formula [■] is the benzohydroxymoyl azole represented by the formula [VI]. It can be produced by reacting a halide with an azole represented by formula (V) in the presence of a base. In this case, the azole can be used in an amount equivalent to or more than the base or solvent. Usable bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metals such as 1-lium hydrogen carbonate and potassium hydrogen carbonate. or inorganic bases such as triethylamine, N,N-dimethylaniline, pyridine, 1,8-diazabicyclo(5,4,01unde-7-
Examples include organic bases such as sen, sodium hydride, and the like.

The reaction can be carried out in the presence of a suitable diluent if necessary. Diluents that can be used include water or inert organic solvents, such as ketones such as acetone and butanone, aromatic hydrocarbons that may be halogenated such as benzene, 1-toluene, xylene, and chlorobenzene; Aliphatic hydrocarbons that may be halogenated such as petroleum ether, ligroin, methylene chloride, and chloroform, ethers such as diethyl ether, tetrahydrofuran, and dioxane, nitriles such as acetonitrile and propionitrile, or dimethylformamide and dimethylacetamide. , amides such as methylpyrrolidone, and the like.

The reaction temperature is any temperature from room temperature to the reflux temperature of the reaction system, preferably 80 to 130°C. Although the reaction time varies depending on the compound, the desired product can be produced in good yield by reacting for 2 to 10 hours.

Next, the manufacturing method will be specifically explained with reference to Examples.

In addition, a production example of a benzo-1-roximoylazole represented by the formula El is shown as a reference example. Note that the present invention is not limited to the following examples.

Reference Example 2. Production of 4-diglolopenzohydroximoylimidazole 2.4-dichlorobenzohydroxymoyl chloride 33
．． 7g (0,1,5 mol) of acetonitryl 1-lyl 200m
After dissolving in 11, 20.4 g of imidazole was stirred at room temperature.
(0.3 mol) in acetonyl chloride solution 150
mQ was added dropwise. After the dropwise addition was completed, the mixture was stirred at 60 to 70°C for 2 hours. After cooling, the solvent was distilled off under reduced pressure, and the residue was washed with water, dried, and further washed with isopropyl ether to obtain 303 g (yield 79.0%) of the target compound with a decomposition point of 229-
Obtained as a white powder at 231°C.

Example 1 Production of -(○-propyl-2,4-dichlorobenzohydroxymoyl)imidazole (compound 49) 1- (2,4-dichlorobenzohydroxymoyl)imidazole 5.1 g (0.02 mol) and carbonic acid 4.1 g (0.03 mol) of potassium was added to 0 ml of N,N-dimethylacetate I amitro, and while stirring at room temperature, 3.4 g (0.03 mol) of propyl iodide was added. 20 mQ of a solution of N,N-dimethylacetate 1 to amine 1 in which g (002 mol) was dissolved was added dropwise over 10 minutes. After completion of dropping, further at room temperature for 60 to 65 hours.
After stirring at °C for 2 hours and cooling, the reaction solution was poured into water and the precipitate was diluted with benzene. After washing the organic layer with water,
It was dried with anhydrous magnesium sulfate. The oily substance obtained by distilling off the solvent under reduced pressure was purified using Kara 11 Chroma I Craffy to obtain 29 g (yield 725%) of the target compound as white prism crystals with a melting point of 645-65°C.

-19 Example 2 1- (0-(3,3-dichloro-2-propenyl)
-Production of 3-1-lifluoromethylbenzohydroxymoylcoimidazole (compound 73) 1- (3-1-lifluoromethylbenzohydroxymoyl)imidazole 3.8 g (0,01,5 mol) and potassium carbonate 2
．． 3 g (0,017 mol) of N.

1. Add to 50 mQ of N-dimethylacetamide and stir at room temperature. , l, 10 mA of a solution of N,N-dimethylacetate 1 to amide 1 in which 24 g (0,015 mol) of 3-trichloro-1-propene was dissolved was added dropwise over 10 minutes. Thereafter, the same treatment as in Example 1 was carried out to obtain 49 g (yield: 891%) of the target compound as a yellow oily substance. Refractive index n 4 '-1,, 5460° Example 3 Production of l-(0-ethyl-2,5-dichlorobenzohydroxymoyl)imidazole (compound 27) 〇-Ethyl-2,5-dichlorobenzohydroxymoyl chloride 5 .0 g (0.02 mol), imidazole 2.0 g (0.03 mol) and potassium carbonate 28 g
(○ 02 mol) to N,N-dimethylacetyl-amyl'
50 mQ, ], ], O-1, and stirred at 20°C for 5 hours. After cooling, the reaction solution was poured into water, and the precipitate was extracted with 1-toluene. The organic layer was washed with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure,
The residue was purified by column chromatography to obtain 4.0 g (yield 70.2%) of the target compound as a white powder with a melting point of 54 to 56°C.

Example 4 ]-[○-(1-methylethyl)-2-chloro-5-1
\Lifluoromethylbenzohyroximoyl]i
Production of H-1,2,4,-triazole (compound 118) 1-2 g (0.03 mol) of 60% oily sodium hydride was washed with hexane to remove oil, and then washed with N,N-dimethylacetamide. In addition to 50mQ], , 2
, 2 cog (0.03 mol) of 4-1-riazole were added. After the addition was complete, the mixture was stirred at room temperature for 1 hour and then O-
(]-Methylethyl)-2-chloro=5-trifluoromethylbenzohydroxymoyl chloride 6.0 g (
0.02 mol) to 10 m of N,N-dimethylacetamide
12 was added dropwise over 10 minutes. Furthermore,
Stirred at room temperature for 1 hour and at 100-120°C for 5 hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was poured into water, the precipitate was extracted with toluene, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography to obtain 2.7 g of the target compound (yield 415%).

(melting point 61-64°C) was obtained.

Example 5 1-(0-(1-methylethyl)-2,4=dichlorobenzohydroxymoyl)-LH-1,.

2. Production of 4-1-lyazole (compound 84) 2.2 g (0,056 mol) of 60% oily sodium hydride was washed with hexane to remove oil, and then added to 50 mQ of N,N-dimethylacetamide. , further 1,2.4-1-
4.2 g (0.06 mol) of lyazole were added.

After the addition was complete, the mixture was stirred at room temperature for 1 hour. Next, 10 mL of an N,N-dimethylacetamide solution in which 0-(1-methylethyl)-2,4-dichloropenzohydroximoylchlori+: 5, ag (0.02 mol) was dissolved was added to 10 ml of N,N-dimethylacetamide solution.
It was added dropwise over a period of minutes. Further at room temperature for 2 hours, 120-13
The mixture was stirred at 0°C for 5 hours. After the reaction was completed, the reaction solution was cooled to room temperature, poured into water, and the precipitate was extracted with benzene. The organic layer was washed with water and then dried over anhydrous sodium sulfate.

The residue obtained by distilling off the solvent under reduced pressure was recrystallized from a mixed solvent of n-hexane and benzene to obtain the target compound 31.
g (yield 51.7%) was obtained as white prismatic crystals with a melting point of 129-130°C.

(Hereinafter, blank spaces) The insecticide of the present invention contains the compound of the present invention as an active ingredient. To use the compound of the present invention as an insecticide,
The compound of the present invention may be used by itself, but it may be mixed with carriers, surfactants, dispersants, or auxiliary agents commonly used in formulation to form powders, aqueous agents, emulsions, fine granules, or granules. Prepare and use it. Carriers used in formulation include solid carriers such as dicrite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, isopropyl alcohol, xylene, cyclohexanone, methylnaphthalene, etc. liquid carriers and the like. As surfactants and dispersants, alkylbenzene sulfonic acid metal salts, dinaphthylmethane disulfonic acid metal salts, alcohol sulfate ester salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether,
Examples include polyoxyethylene sorbitan monoalkylate. Examples of the adjuvant include carboxymethylcellulose, polyethylene glycol, gum arabic, and the like. When using it, either dilute it to an appropriate concentration and spray it, or apply it directly.

The insecticide of the present invention can be used by foliar spraying, soil application, seedling box application, water surface application, etc.

The blending ratio of the active ingredient is selected as appropriate, but it is 0.1 to 20% (by weight) for powders or granules, and 5 to 80% (by weight) for emulsions or wettable powders. is appropriate.

The application rate of the insecticide of the present invention depends on the type of compound used,
It depends on the target pest, outbreak tendency, degree of damage, environmental conditions, dosage form used, etc., but when used as is as a powder or granule, the active ingredient is 0 per 10 ares.
．． It is recommended to appropriately select from the range of 1 g to 5 kg, preferably 1 g to 1 kg. In addition, when used in three-component form as emulsions and irrigation agents, 0.1-1'0
．． 000ppm, preferably 10-3,00”Op
It is preferable to select an appropriate value from the range 'p' and 'm.

Moreover, the insecticide of the present invention can also be used in combination with other insecticides and fungicides.

Next, examples of the insecticide of the present invention will be specifically explained. The types and blending ratios of compounds and additives are not limited to these, and can be varied within a wide range. In addition, % (J) in the following examples indicates weight percentage.

Example 6 Emulsion An emulsion was prepared by uniformly dissolving 30% of emulsion compound (6), 20% of cyclohexanone, 11% of polyoxyethy I nonalkylaryl ether, 4% of calcium alkylbenzenesulfonate, and 35% of methylnaphthalene.

Example 7 Wettable powder compound (51) 4.0%, diatom ±15%, clay 15%
, Why 1 to 25% carbon, 2% I-lium dinaphthylmethane disulfonate, and 3% sodium likuninsulfonate were uniformly mixed and pulverized to prepare a wettable powder.

Example 8 Powder 2% of compound (57), 5% of diatomaceous earth, and 93% of clay were uniformly mixed and pulverized to obtain a powder.

Example 9 Granule compound (72) 5%, sodium 1-lium salt of lauryl alcohol sulfate 2%, 1-helium lignin sulfonate 5%, carboxymethyl cellulose 2% and clay 8
Mix 6% uniformly and grind.

20 parts by weight of water were added to 100 parts by weight of this mixture, kneaded, processed into granules of 14 to 32 mesh using an extrusion type granulator, and then dried to form granules.

(Effect of the invention) The benzo-1-roximoylazole derivative of the present invention has the following properties:
Planthoppers such as brown planthoppers, brown planthoppers, and red planthoppers; Hemipterans such as leafhoppers, aphids, and stink bugs; Lepidoptera such as the diamondback moth and Spodoptera; Diptera such as houseflies and Culex mosquitoes; coleopterans such as rice water weevils and adzuki bean weevils. It is effective in controlling orthoptera pests such as the German cockroach and spider mites such as the two-spotted spider mite and the orange spider mite.

Furthermore, the compound of the present invention also has fungicidal activity, and is effective against rice blast, rice sheath blight, cucumber blight, cucumber gray mold,
It can effectively control cucumber powdery mildew, cucumber bacterial spot and Komatsuna black sooty. In particular, in the cucumber powdery mildew control test, compound 20.23.27
．． 31.44.46.51.66.74.90.95.
96.99.102,]1.1.112.114.11
5.116, Co-17, 123, 124, 126, 13
1,133,]34.143,''44 and 145 are 50
The control effect was 90-100% when sprayed at 0 ppm.

Next, the effects of the compounds of the present invention will be explained using test examples.

Test Example 1 Brown Planthopper Insecticide Test An irrigation agent prepared according to Example 7 was diluted with water to a concentration of 500 ppm. Rice stalks and leaves were immersed in the chemical solution, air-dried, and then left in a test tube. 1 Hebiiroun power larva in it 1
0 was released and the cap was plugged with cotton wool.

Thereafter, they were placed in a constant temperature room at 25° C., and the number of deaths was investigated after 6 days to calculate the mortality rate. The test was conducted in duplicate. The results are shown in Table 3.

Table 3 Table 3 Continued Table 3 Continued Table 3 Continued Table 3 Continued Test Example 2 A wettable powder prepared according to Example 7 of the diamondback moth insecticidal test was diluted with water to a concentration of 500 pPm. Cabbage leaves were immersed in this chemical solution, air-dried, and then placed in a polyethylene cup with a diameter of 55 mm.

Ten 3rd instar diamondback moth larvae were released into the container and the lid was placed. Thereafter, it was placed in a constant temperature room at 25° C., and the number of dead and alive was investigated after 3 days to calculate the mortality rate. The test was conducted in duplicate. The results are shown in Table 4.

Table 4 Patent applicant: 1 person other than Kumiai Chemical Industry Co., Ltd.

Claims (2)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, The group ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, A represents a hydrogen atom, a halogen atom, or a trifluoromethyl group), and Xn represents a carbon atom at the 3rd and 4th positions of the benzene ring , a five-membered ring containing an oxygen atom can also be formed. Y represents an alkyl group, a halogen-substituted alkyl group, an alkenyl group, a halogen-substituted alkenyl group, an alkynyl group, an alkoxyalkyl group, an alkylthioalkyl group, or a cycloalkylmethyl group, Z represents a methine group or a nitrogen atom, and n is 0 or Indicates an integer from 1 to 4. ] A benzohydroxymoylazole derivative represented by (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, The group ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, A represents a hydrogen atom, a halogen atom, or a trifluoromethyl group), and Xn represents a carbon atom at the 3rd and 4th positions of the benzene ring , a five-membered ring containing an oxygen atom can also be formed. Y represents an alkyl group, a halogen-substituted alkyl group, an alkenyl group, a halogen-substituted alkenyl group, an alkynyl group, an alkoxyalkyl group, an alkylthioalkyl group, or a cycloalkylmethyl group, Z represents a methine group or a nitrogen atom, and n is 0 or Indicates an integer from 1 to 4. ] An insecticide containing a benzohydroxymoylazole derivative represented by the following as an active ingredient.