JPH02279662A - Oxime ether and controller against harmful organism containing same ether - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [A is OH, OH, methoxy, ethoxy or halogen; X is H, methyl, ethyl, phenyl or p-chlorophenyl; when Y is 2-fluoroethyl, Z is 1 to 4C (halo)alkyl, 2 to 4C (halo)alkenyl, (halo-substituted) phenyl, N,N-dimethylsulfamoyl or N,N-dimethylcarbamoyl and when Z is 2- fluoroethyl, Y is H, 1 to 4C (halo)alkyl (except 2-fluoroethyl), 2 to 4C (halo) alkenyl or alkoxycarbonylmethyl; (n) is 1 or 2]. USE:An organic phosphorous agent and a controller against harmful organism and having high effects on harmful organisms with resistance to synthetic pyrethroid agents. PREPARATION:For example, a compound shown by formula II is reacted with 1-bromo-2-fluoroethane in the presence of a base to give a compound shown by formula I wherein Y and Z are simultaneously 2-fluoroethyl.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to novel oxime ethers and pest control agents containing the same. A is hydrogen, hydroxy, methoxy, ethoxy,
Halogen, X is hydrogen, methyl, ethyl, phenyl, p-
represents fluorophenyl, and when Y is 2-fluoroethyl,
Z is CI-C4 alkyl, 01-C4 haloalkyl, C! ~C4 alkenyl, cl~C4 haloalkenyl, phenyl, halo-substituted phenyl, N,N-dimethylsulfamoyl, N,N-dimethylcarbamoyl, when Z is 2-fluoroethyl, Y is hydrogen, Ci ”
” Ca alkyl, C7-C1 haloalkyl (2-
Fluoroethyl is excluded <), Cg to C1 alkenyl, C3
-C1 represents a group selected from haloalkenyl and alkoxycarbonylmethyl, and n represents 1 or 2], and a pest control agent containing the compound.

(Conventional technology) When cultivating agricultural and horticultural crops, many chemicals are used to control crop pests and diseases. Many of them are not necessarily satisfactory pest control agents because their use is restricted or they are highly toxic to animals, animals, and fish.

Conventionally, regarding oxime ether pest control agents,
There are various proposals, for example, Japanese Patent Publication No. 47-17994, Japanese Patent Publication No. 51-26483, and Japanese Patent Publication No. 14174-1974.
No. 0, JP-A-59-193862, U.S. Patent No. 407
No. 9149 and JP-A-61-72733 (US Pat. No. 4,647,698). Among these, JP-A-61-72733 has a wide range of proposals as shown by the following formula, but no specific pest control effect is shown. Regarding the representative compound (compound N (12)) specifically exemplified as preferable, a comparative activity test was conducted against various pests (citrus spider mite, red-bottomed planthopper, Japanese armyworm, and diamondback moth) (see Test Example 5 in the present specification). It has not yet reached a level that is fully satisfactory from the viewpoint of activity.

(Problems to be Solved by the Invention) Under these circumstances, the present inventors have developed a drug that overcomes the drawbacks of conventional drugs and can be used safely for humans and animals, and exhibits stable effects even under outdoor conditions. It's about finding out.

(Means for Solving the Problems) The present inventors have synthesized and conducted research on a large number of compounds with the above-mentioned drawbacks in mind. The present invention has been completed and a novel pest control agent has been provided.

The compound group according to the present invention is represented by the formula (1), where A represents hydrogen, hydroxy, methoxy, ethoxy, halogen, preferably hydrogen, chlorine, and X represents hydrogen, methyl, ethyl,
phenyl, p-fluorophenyl, preferably hydrogen, methyl, ethyl; when Y is 2-fluoroethyl, Z is C, -C4 alkyl, C1-C4 haloalkyl, c
i-C4 alkenyl, C8-C4 haloalkenyl,
Phenyl, halo-substituted phenyl, N,N-dimethylsulfamoyl, N,N-dimethylcarbamoyl, preferably isopropyl, 2-fluoroethyl, allyl, 2-butenyl, 3-chloro-2--17"lovenyl, N,N −'；
selected from methylsulfamoyl, when Z is 2-fluoroethyl, Y is hydrogen, C1-C4 alkyl, 01-C
Haloalkyl of 4 [excluding 2-fluoroethyl<), C1 ~
C4 alkenyl, C1I-C, haloalkenyl, alkoxycarbonylmethyl, preferably isopropyl,
Represents a group selected from allyl, 2-butenyl, and 3-chloro-2-propenyl, where n is 1 or 2, preferably l
However, as a particularly preferable group of compounds, A is hydrogen,
X is hydrogen, methyl, ethyl, and Y and Z are 2 at the same time
-fluoroethyl, when n is 1. ], which are either YSZ or simultaneously 2-fluoroethyl, and -0
Although it is a new substance that has not been described in any literature, it is characterized by being directly linked to the formula (II) ring, but its effects extend to a wide range of harmful organisms. In particular, it has an excellent control effect on Lepidoptera pests such as Spodoptera spp. and the diamondback moth, Hemiptera pests such as the brown leafhopper and green peach aphid, and spider mites such as the two-spotted spider mite, orange spider mite, and Kanzawa spider mite. In particular, in recent years, we have discovered that the same agent is highly effective and practically useful against harmful organisms resistant to so-called organic phosphorus agents and synthetic pyrethroids, whose control effect has decreased due to repeated use of the same agent, and we have completed the present invention. Ta.

Next, the manufacturing method will be explained in detail.

-a The compound of the present invention represented by formula (1) can be produced by the following method, but is not limited thereto.

■The compound of the present invention represented by the general formula (1) can be prepared by converting the compound Y'(Y'
represents C1-C4 haloalkyl, C1-C4 dihaloalkyl, C-rich-C4 haloalkenyl, C:-C4 dihaloalkenyl, alkoxycarbonylhalomethyl).

Specifically, the compound Y° includes methyl iodide, ethyl bromide, 2-bromopropane, 5ec-butyl chloride, 1-bromo-2-fluoroethane, 1-bromo-3-chloro-2-methylpropane, allyl Examples include bromide, 1-chloro-2-butene, 4-bromo-1-7'thene, 1,3-dichloropropene, methoxycarbonylchloromethyl, and the like.

The amounts of reagents used in the reaction are 1 to 1.5 equivalents of base and 1 to 1.5 equivalents of Yo per 1 equivalent of the compound of formula (n), and these are mixed in a solvent at a reaction temperature of 10 to 80°C. 1~2
It is enough to react for 4 hours.

Examples of the base include sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and the like.

Examples of the solvent include methanol, ethanol, dioxane, N,N-dimethylformamide, and tetrahydrofuran.

After the reaction is completed, normal post-operations are performed to remove water-soluble unnecessary substances, and if necessary, the product can be purified by chromatographic distillation or the like.

■Among the compounds represented by general formula (1), if Y and Z are 2-fluoroethyl at the same time, -formula (]II) (in the formula,
A, X are the same as above) In the presence of a compound represented by and a base, l-bromo-2-
It can be obtained by reacting with fluoroethane.

The amounts of reagents used in the reaction are 2 to 4.5 equivalents of base and 2 to 4.5 equivalents of 1-bromo-2-fluoroethane per equivalent of the compound of formula (If), and these are mixed in a solvent with 20 to 4.5 equivalents of base and 2 to 4.5 equivalents of 1-bromo-2-fluoroethane.
What is necessary is just to make it react at the reaction temperature of 100 degreeC for 1 to 24 hours.

Examples of the base include sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and the like.

As a solvent, methanol, ethanol, dioxane,
Examples include N,N-dimethylformamide and tetrahydrofuran.

After the reaction is completed, a normal post-treatment is performed to remove water-soluble unnecessary substances, and if necessary, the product can be purified by chromatographic distillation or the like.

■The oxime compound represented by the formula (■) which is the intermediate raw material compound of the present invention is represented by the formula (fV) (wherein A,
(X and Z are the same as above) It can be obtained by reacting a benzoyl compound represented by the following with a hydroxylamine salt in the presence of a base.

The amount of reagent used in the reaction is - hydroxylamine hydrochloride (or sulfate) per equivalent of the compound of formula (IV).
The desired product can be obtained by reacting these in a solvent at a reaction temperature of 10 to 70°C for 1 to 48 hours.

Examples of the base include pyridine, triethylamine, and tributylamine.

As a solvent, methanol, ethanol, dioxane,
Examples include N,N-dimethylformamide and tetrahydrofuran.

After the reaction is completed, the desired product can be obtained by carrying out usual post-treatments and, if necessary, purifying by chromatography or the like.

■The benzoyl compound represented by the above-mentioned formula (■), which is an intermediate raw material compound of the present invention, is represented by the formula (V) (wherein A,
hydroxybenzoyl or dihydroxybenzoyl compound or its metal salt represented by (X is the same as above) and compound Z'
(Z' is CI-C1 haloalkyl, 01-C4 dihaloalkyl, C2-C4 haloalkenyl, C□-C
4 dihaloalkenyl, halophenyl, polyhalophenyl, N,N-dimethylsulfamoyl chloride, N,N
-representing dimethylcarbamoyl chloride).

Specific examples of compound Z' include methyl iodide, ethyl bromide, 2-bromopropane, 5ee-butyl chloride, 1-bromo-2-fluoroethane, l-bromo-3
-chloro-2-methylpropane, allyl bromide, 1
-chloro-2-butene, 4-bromo-1-butene, 1,
Examples include 3-dichloropropene, iodobenzene, 2,6-dichloropropenzene, N+N-dimethylsulfamoyl chloride, N,N-dimethylcarbamoyl chloride, and the like.

The amount of the reagent used in the reaction is -1 equivalent of the hydroxybenzoyl or dihydroxybenzoyl compound represented by the formula (V) and its metal salt, and the amount of the compound Z°
are 1 to 1.5 equivalents and 2 to 3 equivalents, respectively, and the base is also 1 to 1.5 equivalents and 2 to 3 equivalents, respectively,
These may be reacted in a solvent at a reaction temperature of 50 to 130°C for 1 to 8 hours.

Examples of the base include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and the like.

Examples of the solvent include methanol, ethanol, dioxane, N,N-dimethylformamide, and tetrahydrofuran.

After the reaction is completed, normal post-operations are performed to remove water-soluble unnecessary substances, and if necessary, the product can be purified by chromatography, distillation, recrystallization, etc.

The pest control agent of the present invention can be used as a pure active ingredient compound, and for the purpose of using it as an agricultural chemical,
Possible forms of general agricultural chemicals: hydrating powders, granules,
It can also be used in the form of powder, emulsion, aqueous solution, aerosol, etc. As additives and carriers, when a solid agent is intended, vegetable powders such as soybean flour and wheat flour, and fine mineral powders such as diatomaceous earth, apatite, gypsum, talc, pyrophyllite, and clay are used. When a liquid dosage form is intended, kerosene, mineral oil, petroleum, turbate naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, water, etc. are used as the solvent. In these preparations, a surfactant may be added if necessary to obtain a uniform and stable form. The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the powders and granules are used as they are by spraying them on plants.

The obtained preparation can also be used in combination with other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

When the compound of the present invention is used as an active ingredient of a pest control agent, the application amount is usually 10 g per 10 are.
to 1000g, and the application concentration is 10 to 11000p.
It is p. Preferably from 50g to 50 per 10ares
0 g, and the application concentration is 50-500 ppm.

These application amounts and application concentrations vary depending on the type of preparation, application time, application location, application method, type of pest, degree of damage, etc., and are not limited to the above ranges.

(Example) The present invention will be explained in more detail below with reference to production examples, formulation examples, and test examples, but of course the present invention is not limited to these examples.

First, a production example of the compound of the present invention will be shown.

Production Example 1 (Production of 0 compounds of the present invention) 2 g of p-allyloxyacetophenone oxime (0,0
105 mol) was dissolved in ethanol 10-, and 0.72 g (0,0105 mol) of sodium ethoxide was dissolved in this.
, l-bromo-2 with fluoroethane 1°33g (0,0
105 mol) was added thereto, and the mixture was stirred at room temperature (10 to 15°C) overnight. Add 50 d of ethyl acetate to the reaction solution, and add 2 d of water.
The organic layer was washed twice with 5+f and dried over anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure, and the residue was applied to thin layer chromatography (hereinafter referred to as T, L, C; manufactured by Merck & Co., Ltd., No. 5717), developed with toluene solvent, and Reactants and impurities were removed to obtain 0.53 g of a mixture of stereoisomers of Compound 021. Yield 21.7%,
Note that a stereoisomer mixture may give one spot for T, L, and C, or may be separated into two spots.

The physical properties, Rf values at T, L, C, and 'H-NMR (PMX-60Si type 1 manufactured by JEOL Ltd.) analysis values of these compounds are shown in Tables 1-1 to 2-2). Ta. In the table, the viscous liquid shown in the physical property tank is the property at room temperature immediately after synthesis. Further, the Rf values based on T, L, and C were determined using a 5729 silica gel plate manufactured by Merck and Co., Ltd. using toluene as a developing solvent. For Rf values at T, L, and C, if there are two spots, the two are written in parentheses, and the average value (marked with *)
It was shown in Note that Rf values determined using the developing solvent toluene/acetone = 9/1 (V/V") are indicated with a *.

Production Example 2 (Synthesis of intermediate raw material P-allyloxyacetophenone oxime for compound 02 of the present invention) 3.52 g (0.02 mol) of p-allyloxyacetophenone was dissolved in 25 N1 ethanol, and 1.4 ml of hydroxylamine hydrochloride was dissolved in 25 N1 ethanol.
3g (0,021 mol), triethylamine 2.02
(0.02 mol) was added and stirred overnight at room temperature. 100 ml of ethyl acetate was added to the reaction solution, which was washed twice with 50 ml of water. The organic layer was dried over anhydrous sodium sulfate, and then vacuumed under reduced pressure. The solvent was distilled off to obtain a slag-like residue. The slag-like residue was then crystallized and weighed 3.81 g.
, yield 99.7%. This compound was used in Production Example 1.

Production Example 3 (Synthesis of raw material p-allyloxyacetophenone containing 0 compounds of the present invention) 5 g (0,0368 mol) of p-hydroxyacetophenone was added with 73% N/2 potassium hydroxide (ethanol solution).
6jd was added, and the solvent was distilled off under reduced pressure at a temperature below 40°C. 20 d of dimethylformamide, 5.08 g (0,0368 mol) of potassium carbonate, and 4.45 g (0,0368 mol) of allyl bromide were added to the residue, and the mixture was reacted by heating at 60 to 70°C in an oil bath.

After 2 hours, 1 oad of ethyl acetate was added to the reaction solution, and 50 oz of water was added.
The organic layer was washed twice with R1, dehydrated and dried by adding anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. After distilling off the solvent,
After a while it crystallized. Weight: 15.9g, yield: 91.
0%0 This compound was used in Production Example 2.

Production Example 4 (Production of Compound (22) of the Present Invention) 12°4 g of p-hydroxypropiophenone oxime (0,07
5 mol) to N/2 potassium hydroxide (ethanol solution) 3
001d was added, and the solvent was distilled off under reduced pressure at 40°C or lower. After adding dimethylformamide 2511 to the residue and dissolving it, 10.4 g (0,075 mol) of potassium carbonate and 19.1 g (0,15 mol) of 1-bromo-2-fluoroethane were added.
The mixture was immediately heated to 60 to 70°C in an oil bath for reaction. After reacting for 2 hours, 300 ml of ethyl acetate was added to the reaction solution.
- was added thereto, washed three times with 150 - of water, and anhydrous sodium sulfate was added to the organic layer for dehydration and drying. After drying, the solvent was distilled off under reduced pressure to obtain a crude reaction product. This was purified by color chromatography packed with silica gel, and 9.4g
Compound (22) of the present invention was obtained. Yield 48.7%.

Production Example 5 (Synthesis of raw material p-hydroxypropiophenone oxime for the compound of the present invention <22)) 22.53 g of p-human a-xypropiophenone (0,1
Add 75 m of ethanol to 5 mol) and dissolve L, 10.43 g of hydroxylamine hydrochloride (0.15 mol),) 1
．． After adding 715.18 g (0.15 mol) of lz-chill 7, it was reacted for 2 hours at 60 to 70°C in an oil bath. After the reaction was completed, 200 d of ethyl acetate was added, and the mixture was washed twice with 100 ml of water. After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 24.06 g of the desired product. Yield 97.1%.

This compound was used in Preparation Example 4.

Examples of formulations are shown below. In addition, the compound numbers are from Table 1-1)
It is shown by the compound number of the present invention in Table n-2).

Formulation Example 1 Emulsion 20 parts by weight of the compounds (1) to 29) of the present invention, 20 parts by weight of Tween 20 (manufactured by Wako Pure Chemical Industries, Ltd.) and 60 parts by weight of xylene were thoroughly mixed to obtain a 20% emulsion.

Formulation Example 2 Wettable powder 25 parts by weight of the compound of the present invention (1) to 29), 65 parts by weight of diatomaceous earth, 5 parts by weight of higher alcohol sulfuric ester, and 5 parts by weight of alkylnaphthalene sulfonic acid are uniformly mixed and finely ground. A 25% hydrating agent was obtained.

Formulation Example 3 Fine Granules 3 parts by weight of the present compound (1) to 29), 45 parts by weight of talc, 45 parts by weight of bentonite, 5 parts by weight of sodium ligninsulfonate, and 2 parts by weight of sodium dodecylbenzenesulfonate were thoroughly ground and mixed. After adding water and kneading well, the mixture was granulated and dried to a particle size of 30 to 300 microns to obtain 3% fine granules.

The usefulness of the compounds according to the invention as pest control agents is shown in the following test examples. In addition, citrus spider mite,
For the diamondback moth test example, the average value of two replicates was
The test example for Spodoptera trifoliata is shown as the average value of three replicates, and the compounds of the present invention among the test compounds are shown in Tables 1-1) to 1.
[-2) Indicated by the compound number listed in the table.

Test Example 1 Effect against citrus spider mites Citrus leaf pieces with a diameter of 1 cm were placed on the opening paper at the top of a cup that allows moisture to be supplied from the bottom, and 3 adult citrus spider mites (Panonycus citri) were inoculated on each leaf piece. , and kept in a high temperature room at 25°C. After 24 hours, the number of eggs laid was examined under a microscope, and two healthy insects were additionally inoculated on each leaf. A water diluted solution of a hydrating powder of the test compound prepared according to Formulation Example 2 (250pp
m) with a glass spray and kept at 25°C.

Two days after the treatment with the chemical solution, the viability was determined using a microscope, and the insecticidal rate (%) was determined. The number of insects tested was 20 adult male insects. In addition, the ovicidal rate (%) of the eggs that were mowed down before and 2 days after the chemical solution treatment was determined on the 10th day after the treatment. The number of eggs tested was 40 or more during the treatment. The results are shown in Table ①.

Table ■ (Continued) Test Example 2 Effect on the brown planthopper An emulsion of the test compound prepared according to Formulation Example 1 was diluted to 50 ppm.
Rice seedlings around the 5-leaf stage were immersed in this diluted solution to absorb the chemical solution, then air-dried and kept in a test tube containing a small amount of water at the bottom. In the test tube, there was a
hax 5triatellus) 10 adults each
inoculated and kept at 25°C. The insecticidal rate (%) was determined 48 hours after the treatment. The results are shown in Table ①.

(Continued) Test Example 3 Effect on Spodoptera spp. Spread paper on the bottom and top of a Petri dish with a diameter of 9C11, and drop 2 m of a 1100pp diluted solution of the test compound hydrate shown in Formulation Example 2 evenly with a pipette. do. On the top slip,
Attach artificial bait in advance, leave it for about 1 hour, and once the mouthpaper has dried properly, add Spodoptera grub (S) to the bottom.
podoptera 1itura) were inoculated with 10 first instar larvae and kept at 25°C.

The insecticidal rate (%) was investigated 48 hours after the treatment. The results are shown in Table V.

Test Example 4 Effect on diamondback moth Prepare a radish that has sprouted in an ice cream cup in advance, and add it to the diamondback moth (Plutella xylost).
3rd instar larvae of S. ella) were inoculated. A water diluted solution of the emulsion of the test compound prepared according to Formulation Example 1 (2
50 ppm) was sprayed for 2 m using a glass sprayer. A survey was conducted on the third day after the chemical solution treatment, and the insecticidal rate (%) was determined.

The number of test animals was 10 per section. The results are shown in Table ①.

(Continued) Test Example 5 Comparative test of activity against various insect pests A test compound hydrating powder prepared according to Formulation Example 2 was applied to the planthopper (50
ppm), armyworm (100ppm), diamondback moth (
250,125ppm), orange spider mite (250pp+
a), and the insecticidal rate and egg killing rate were investigated. The results are shown in Table 1.

(Effects of the Invention) The compounds of the present invention have excellent effects against Lepidoptera pests, Hemiptera pests, and spider mites that damage vegetables, fruit trees, rice, etc., and have particularly high ovicidal effects.

1 other person

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A is hydrogen, hydroxy, methoxy, ethoxy,
Halogen, X is hydrogen, methyl, ethyl, phenyl, p-
represents fluorophenyl, and when Y is 2-fluoroethyl,
Z is alkyl of C_1 to C_4, haloalkyl of C_1 to C_4, alkenyl of C_2 to C_4, C_2 to C_
4 haloalkenyl, phenyl, halo-substituted phenyl, N
, N-dimethylsulfamoyl, N,N-dimethylcarbamoyl, and when Z is 2-fluoroethyl, Y
is hydrogen, alkyl of C_1 to C_4, haloalkyl of C_1 to C_4 (excluding 2-fluoroethyl), C_2 to C
alkenyl of _4, haloalkenyl of C_2 to C_4,
represents a group selected from alkoxycarbonylmethyl,
n represents 1 or 2. ] An oxime ether represented by (2) A pest control agent comprising the oxime ether represented by the general formula (I) according to claim 1 and an inert diluent or carrier.