JPH0686437B2 - Oxime ether derivative and insecticide / miticide and fungicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to an oxime ether derivative, or a salt thereof, and an insecticidal / miticide and an agricultural / horticultural fungicide containing the derivative as an active ingredient. It is a thing.

(Prior Art) The oxime ether derivative of the present invention is a novel compound, and a relatively close compound is not known.

[Structure of the Invention] (Means for Solving the Problems) The compound of the present invention has the following formula (I): [Wherein, R ¹ and R ² represent a lower alkyl group or a halogen atom, and R ³ represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, a biphenylyl group, a naphthyl group, a benzyl group or a styryl group. the stands, R ⁴ is a hydrogen atom, a lower alkyl group, a cyclopropyl group, a trifluoromethyl group, a cyano group, a lower alkyl benzyl thio group, a lower alkylthio group, a lower alkylthioalkyl group, a lower alkylsulfinyl group or a lower alkylsulfonyl alkyl Represents a group] or an acid addition salt thereof.

In the above formula (I), the lower alkyl group refers to a linear or branched alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-
Butyl, amyl, isoamyl and sec-amyl.

Halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, sec-
Butyl, t-butyl, amyl, isoamyl, hexyl,
Examples thereof include 3-methylhexyl, 2-ethylhexyl, heptyl and octyl.

Examples of the substituent of the substituted phenyl group include 1 to 3 lower alkyl groups, a halogen atom, a trifluoromethyl group or a methoxy group, or a phenoxy group substituted with a lower alkyl, halogen, trifluoromethyl or methoxy. .

Examples of the lower alkyl substituent in the lower alkylthio group, lower alkylthioalkyl group, lower alkylsulfinylalkyl group, and lower alkylsulfonylalkyl group include the alkyl groups having 1 to 5 carbon atoms exemplified above.

In formula (I), compounds having the following substituents are preferably used for the purpose of the present invention.

R ₁ is preferably methyl, ethyl and chloro.

R ₂ is preferably methyl and chloro.

R ₃ is preferably butyl, amyl and substituted or unsubstituted phenyl.

R ₄ is preferably methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl and methylthio.

As can be understood from the above formula (I), the compound of the present invention has an amino group and thus can easily form an acid addition salt, and such a salt is also included in the present invention.

Examples of the salt-forming acid include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid and phosphoric acid; formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid and aconitic acid. Carboxylic acid; methanesulfonic acid, benzenesulfonic acid, organic sulfonic acids such as p-toluenesulfonic acid, and the like.

Further, the compounds of the present invention include cis-trans isomers based on R ³ and R ⁴ , both of which are included in the present invention.

The compound (I) of the present invention can be easily produced, for example, by a method known per se shown below.

In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, and X represents a leaving group.) The above method is known per se, and there is no limitation on the leaving group X. For example, a halogen atom such as chlorine, bromine or iodine; an alkylthio group such as methylthio, ethylthio, propylthio and butylthio; an alkanesulfonyloxy group such as methanesulfonyloxy, ethanesulfonyloxy and trifluoromethanesulfonyloxy group; benzenesulfonyloxy, arenesulfonyloxy groups such as p-toluenesulfonioxy; mercapto groups and hydroxyl groups.

As is clear from the above reaction formula, in this reaction, the compound H-
Since X is eliminated, it is preferable to carry out in the presence of a base in order to capture it and allow it to react smoothly.

The reaction is usually carried out in the presence of a solvent, but with a screw solvent of formula (II)
Alternatively, the compound of formula (III) can be melted by heating.

The solvent is not particularly limited as long as it does not participate in this reaction, for example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane,
Chlorinated, non-chlorinated aromatic, aliphatic or alicyclic hydrocarbons such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane; diethyl ether, ethylyl glycol dimethyl ether, Tetrahydrofuran, ethers such as dioxane; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide; pyridine, a mixture of an organic base such as N, N-dimethylaniline and the above solvent. Can be mentioned.

Examples of the base include organic bases such as triethylamine, pyridine and N, N-dimethylaniline; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; hydrogenated sodium, sodium amide, sodium hydroxide, potassium hydroxide and carbonic acid. Inorganic bases such as sodium and potassium carbon may be mentioned.

The reaction temperature is usually room temperature or higher to the reflux temperature of the solvent,
It is desirable to heat to shorten the reaction time.

The compound of formula (III), which is the starting amine for this reaction, can be easily synthesized by the following method.

(In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, and X-ray represents a leaving group.) The target compound (I) obtained by the above method is recrystallized,
It can be appropriately purified by a known means such as various chromatography.

The acid addition salt can be easily obtained, for example, by dissolving the compound of the formula (I) in a solvent such as ether or acetone and introducing an acid.

The insecticidal and acaricidal agents and fungicides of the present invention contain the compound of formula (I) or a salt thereof as an active ingredient. The compound of formula (I) may be used as such but is usually a conventional carrier,
A surfactant, a dispersant, an auxiliary agent or the like is blended and prepared into a composition such as a powder, a wettable powder, an emulsion, a fine granule, a granule, water or an oil suspension, an aerosol, etc. by a conventional method. use.

Suitable carriers are, for example, talc, bentonite, clay,
Solid carriers such as carion, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate and urea;
Hydrocarbons such as kerosene and mineral oil; aromatic hydrocarbons such as benzene, toluene and xylene; chlorinated hydrocarbons such as chloroform and carbon tetrachloride; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, cyclohexanone and isophorone, Examples thereof include esters such as acetic acid, ethyl, ethylene glycol acetate and dibutyl maleate; alcohols such as methanol, n-hexanol and ethylene glycol; polar solvents such as dimethylformamide and dimethyl sulfoxide; and liquid carriers such as water. Further, air, nitrogen, carbon dioxide gas, Freon or the like may be used as the gas carrier, and mixed injection may be performed.

In addition, as a surfactant for improving the performance such as adhesion of this agent to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading, etc., for example, alcohol sulfates, alkyl sulfonates, lignin sulfate Formic acid salts, polyoxyethylene glycol ethers, etc. are used.

Further, in order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic, etc. are used as an auxiliary agent.

The above-mentioned carrier, surfactant, dispersant and auxiliary agent are used alone or in combination according to the purpose.

When the compound of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions and 0.3 to 25 for powders.
% By weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oil solutions, and usually 0.1 to 5% by weight for aerosols.

These preparations may be diluted to an appropriate concentration and sprayed on the plant foliage, soil, water surface of paddy fields, or applied directly to them for various purposes according to their respective purposes.

[Effects of the Invention] The compound of the present invention is a hemiptera, for example, planthoppers, leafhoppers, aphids, whiteflies, etc .; For example, in addition to weevils, beetles, etc., it exhibits an excellent effect against acarids, for example, agricultural and horticultural harmful insects such as citrus spider mites and spider mites.

It is also effective for controlling hygienic pests such as flies, mosquitoes, and cockroaches, and is also effective for other stored-grain pests.

Furthermore, the compounds of the present invention are also effective against root-knot nematodes, pine wood nematodes, and ticks in soil.

Further, the compound of the present invention is also effective in the prevention and treatment of agricultural and horticultural diseases, for example, rice blast disease, barley powdery mildew,
It is extremely effective against cucumber downy mildew, cucumber gray mold, and tomato epidemic.

As described above, the compound of the present invention has an extremely wide range of applications and application situations, has high efficacy, and can be put to practical use in various dosage forms.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples do not limit the scope of the present invention in any way.

Example 1 Synthesis of 5-chloro-6-ethyl-4- [2- (α-methylbenzylideneiminooxy) ethylamino] pyrimidine (Compound No. 3) 4,5-dichloro-6-ethylpyrimidine 1.2 g, 2- (Α
-Methylbenzylideneiminooxy) ethylamine 1.1 g
And 1 ml of triethylamine are dissolved in 30 ml of toluene,
Heated to reflux for hours. The reaction solution was washed with water, dried over anhydrous sodium sulfate, and toluene was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wakogel C-20
(0, toluene; ethyl acetate = 3: 1 elution) to obtain 0.3 g of the desired product as a colorless oil.

n ^22.0 _D 1.5862 Example 2 Synthesis of 5-chloro-6-ethyl-4- [2- (α-ethylbenzylideneiminooxy) ethylamino] pyrimidine (Compound No. 10) 4,5-dichloro-6-ethylpyrimidine 1.2 g, 2- (α
-Ethylbenzylideneiminooxy) ethylamine 1.0
g, 1 ml of triethylamine and a catalytic amount of 4-dimethylaminopyridine were dissolved in 30 ml of toluene and heated under reflux for 6 hours. The reaction solution was washed with water, dried over anhydrous sodium sulfate, and toluene was distilled off under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 6: 1 elution) to obtain 1.2 g of the desired product as a colorless oily substance.

n ^24.0 _D 1.5758 By treating in the same manner as in Examples 1 and 2, compounds shown in Table 1 were obtained.

Example 3 5 parts by weight of the compound of Compound No. 3, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Atlas) and 2 parts by weight of sodium lignin sulfonate were uniformly mixed. Then, after adding a small amount of water and kneading, the mixture was granulated and dried to obtain granules.

Example 4 10 parts by weight of the compound of Compound No. 6, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of neoperex powder (trade name; manufactured by Kao Atlas) and 0.5 parts by weight of demol (trade name; manufactured by Kao Atlas) And were uniformly mixed and then pulverized to obtain a wettable powder.

Example 5 To 20 parts by weight of the compound of Compound No. 18 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Kasei Co., Ltd.) were added and uniformly mixed and dissolved to obtain an emulsion.

Example 6 5 parts by weight of the compound of Compound No. 47, 50 parts by weight of talc and 45 parts by weight of kaolin were uniformly mixed to obtain a dust.

Example 7 Efficacy test against diamondback moth The compounds shown in Table 1 were prepared according to Example 4 to prepare a wettable powder containing surfactant (0.01%) in water of 300 ppm, and cabbage leaf pieces (5 cm x 5 cm) was soaked for 30 seconds and placed in a plastic cup. After air-drying, 10 third-instar larvae of diamondback moth
The head was released, the lid was placed, and the sample was left in a constant temperature room at 25 ° C. Two days later, the number of dead insects was counted, and the dead insect rate was calculated and shown in Table 2.

A with a mortality of 100% is A, 99-80% is B, 79
-60% is shown as C, and 60% or less is shown as D.

Example 8 Efficacy test against leafhopper leafhoppers Compounds shown in Table 1 were prepared according to Example 4, and a wettable powder was added to a solution containing a surfactant (0.01%) at a concentration of 300 ppm in water. It was dipped for 2 seconds, air-dried, and then placed in a glass cylinder. Ten 4th instar larvae of the leafhopper leafhopper were released, capped with a porous plug, and allowed to stand in a constant temperature room at 25 ° C. The number of dead insects was counted 4 days later, and the dead insect rate was calculated and shown in Table 3.

The mortality rate is shown based on the same criteria as in Table 2.

Example 9 Efficacy test against adult female mites of the genus Nymphodendron A compound shown in Table 1 was prepared according to Example 4, and the solution was diluted to 300 ppm with water containing a surfactant (0.01%).
Leaf beans of kidney bean (diameter 20
mm) was soaked for 10 seconds. The sample was allowed to stand in a constant temperature room at 25 ° C., and the number of live and dead insects was counted 3 days later, and the miticidal rate was calculated and shown in Table 4.

The acaricidal rate is shown based on the same criteria as in Table 2.

Example 10 Efficacy test against Nymphalid mite eggs Five adult females of Nymphalid mite were inoculated into kidney leaf pieces (20 mm in diameter) and allowed to lay eggs for 1 day. After that, adults were removed and the number of eggs was counted. On the other hand, the compounds shown in Table 1 were prepared according to Example 4, and 300 ppm with water containing a surfactant (0.01%).
The leaf pieces were immersed in the chemical solution diluted to 10 seconds. It was left to stand in a constant temperature room at 25 ° C, and after 6 days, the number of unhatched eggs was counted to determine the ovicidal rate, which is shown in Table 5. The ovicidal rate was shown based on the same criteria as in Table 2.

Example 11 Control efficacy test against gray mold of cucumber One cucumber (cultivar: Sagamihanjiro) was cultivated in a plastic flower pot having a diameter of 6 cm, and the seedlings with cotyledons were expanded according to Example 4. The prepared wettable powder is diluted with water containing a surfactant (0.01%) to 500 ppm, and 20
After spraying, the mixture was cultivated at room temperature for 2 days after spraying, and then a cucumber gray mold fungal spore suspension (5 × 10 ⁵ spores / ml) was uniformly spray-inoculated.

After inoculation, the plants were grown in an inoculation room for 2 days, and the degree of cucumber gray mold disease lesions appearing on the cotyledons was investigated. The drug effect was judged by comparing with the degree of lesions in the untreated section. The results are shown in Table 6.

The evaluation is shown in 6 grades of 5 to 0, and those without lesions are 5,
Compared to the untreated plot, the lesion area product of 10% or less was 4, 20% was 3, 40% was 2, 60% was 1, and the diseased area was 0.

Example 12 Control efficacy test against wheat leaf rust Wheat was prepared according to Example 4 by growing 10 wheats (cultivar: Kobushi-komugi) per pot in a plastic flower pot having a diameter of 60 cm, and preparing 1.5-leaf stage seedlings according to Example 4. 20ml per pot after diluting the agent to 500ppm with water containing surfactant (0.01%)
Sprayed.

After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then spray-inoculated with a wheat rust spore suspension (7 × 10 ⁴ spores / ml) uniformly.

After inoculation, the seedlings were grown in a glass greenhouse for 1 week, and the degree of wheat leaf rust lesions appearing on the first leaf was investigated. The drug effect was judged by comparing with the degree of lesions in the untreated section. The results are shown in Table 7. The evaluation is shown according to the same criteria as in Table 6.

Example 13 Control efficacy test against barley powdery mildew 10 barleys (cultivar: black wheat) were grown in a plastic flower pot with a diameter of 6 cm, and 1.5 leaf stage seedlings were prepared according to Example 4. The wettable powder is diluted to 500ppm with water containing surfactant (0.01%) and 20ml per pot
Sprayed.

After spraying, the plants were cultivated in a glass greenhouse for 2 days, then conidia of barley powdery mildew fungi were collected from the diseased leaves and sprinkled evenly over the plants to inoculate.

After inoculation, it was grown in a glass greenhouse for 1 week, and the degree of barley powdery mildew lesions appearing on the first leaf was investigated. The drug effect was judged by comparing with the degree of lesions in the untreated section. 8th result
Shown in the table. The evaluation is shown according to the same criteria as in Table 6.

Example 14 Control efficacy test against rice blast 10 rice (cultivar: Nihonbare) was grown in a plastic flower pot with a diameter of 6 cm, and seedlings at 1.5 leaf stage were treated with water prepared according to Example 4. Add a detergent to the surfactant (0,01
%) And diluted to 500 ppm, and sprayed with 20 ml per pot.

After spraying, the plant was cultivated in a glass greenhouse for 2 days, and then the plant leaves were spray-inoculated uniformly with the rice blast fungus conidia prepared from the diseased leaves.

After inoculation, the plants were grown in a 28 ° greenhouse for 5 days, and the degree of rice blast lesions appearing on the leaves was examined. The drug effect was judged by comparing with the degree of diseased group in the untreated section. The results are shown in Table 9. The evaluation is shown according to the same criteria as in Table 6.

Example 15 Control efficacy test against cucumber downy mildew One rice plant (cultivar: Sagamihanjiro) was grown in a plastic flower pot with a diameter of 6 cm, and seedlings of 1.5 leaf stage were grown.
A wettable powder prepared according to Example 4 was treated with a surfactant (0,01
%) And diluted to 500 ppm, and sprayed with 20 ml per pot.

After spraying, it was cultivated in a glass greenhouse for 2 days, and then cucumber downy mildew zoospores prepared from diseased leaves were uniformly spray-inoculated on the back surface of the plant leaves.

After inoculation, it was kept in the dark at 20 ° C. for 2 days and then grown in a glass greenhouse for 5 days to examine the degree of cucumber downy mildew lesions appearing on the first leaf. The drug effect was judged by comparing with the degree of lesions in the untreated section. The results are shown in Table 9. The evaluation is shown according to the same criteria as in Table 6.

Front page continued (72) Inventor Yasuhisa Fukuda 5 1978, Oji City, Ube, Yamaguchi Prefecture, Ube Institute of Industrial Research, Ltd. (72) Inventor, Kiyoshi Shitsuchi, 5 1978, Obe, Oguchi City, Yamaguchi Prefecture, Ube Industries Ube Co., Ltd. In the laboratory

Claims (3)

[Claims] 1. The following equation [Wherein, R ¹ and R ² represent a lower alkyl group or a halogen atom, and R ³ represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, a biphenylyl group, a naphthyl group, a benzyl group or a styryl group. the stands, R ⁴ is a hydrogen atom, a lower alkyl group, a cyclopropyl group, a trifluoromethyl group, a cyano group, a lower alkyl benzyl thio group, a lower alkylthio group, a lower alkylthioalkyl group, a lower alkylsulfinyl group or a lower alkylsulfonyl alkyl Represents a group] or an acid addition salt thereof. 2. An insecticide / acaricide containing the compound according to claim 1 or an acid addition salt thereof as an active ingredient. 3. A fungicide for agriculture and horticulture, which comprises the compound according to claim 1 or an acid addition salt thereof as an active ingredient.