JPS61275271A - 1,2,4-oxa(thia)diazoline derivative, production thereof and insecticide and agricultural and horticultural germicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X and Y are O or S; R1 is halogen, alkyl, haloalkyl or alkoxy; R2 is halogen, hydrocarbon, alkoxycarbonyl, alkylamino, phenylazo, tetramethylene, etc.; R is hydrocarbon or aromatic group; n is 0 or an integer 1-3; m is an integer 1-5). EXAMPLE:2-(4-Chlorophenyl)-5-(2,6-difluorophenyl)-DELTA<4>-1,2,-4-thia diazolin-3-one. USE:An insecticide and agricultural and horticultural germicide. PREPARATION:For example, a compound expressed by formula II is reacted with an oxidizing agent to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides novel 1, 2.
A 4-oxa(thia)cyasily/-3-one derivative, its production method, an insecticide, and a fungicide for agriculture and horticulture.

(Prior art) Chemische Berichte (Chem, Ber,) 196
699(3) p7B2-792. 1973106 (5
) 91496-1500 and Heterocycles (He
terocycles) 19765 (1) p 18
9-194, 2-7enyl-5- similar to the compounds of the present invention
A method for producing phenyl-1,2,4-thiadiazolin-3-ones has been reported. However, a compound in which the 2-position is a substituted phenyl group has not been described, and its biological activity has not been studied at all.

(Problem to be solved by the invention) Many insecticides have been used in the past, but a wide range of insect pests have become resistant to the typical insecticides, such as organic phosphorus agents and carbamate agents, making them difficult to control. It has become. Furthermore, the development of resistance to synthetic pyrethroid insecticides, which have attracted attention in recent years, has been reported, and the emergence of insecticides with novel structures not found in conventional insecticides is expected.

Furthermore, new and highly effective fungicides for agricultural and horticultural use are expected to emerge.

(Means for Solving the Problems) The present inventors synthesized a large number of 1,2,4-oxa(thia)diazoline compounds and conducted various studies, and found that the general formula [where x and y are respectively independently represents an oxygen atom or a sulfur atom, R□ represents a different or similar substituent selected from a halogen atom, a lower alkyl group, a lower haloalkyl group, and a lower alkoxy group; R2 represents a halogen atom or a substituent substituted with a halogen atom; optionally substituted saturated or unsaturated lower hydrocarbon group, lower alkoxycarbonyl group, lower alkylamino group, phenylazo group optionally substituted with lower alkyl group, tetramethylene group, formula -CH=CH-CH
A different or similar substituent selected from the group represented by =α- and the group represented by the formula -A-R, (wherein A is an oxygen atom or a sulfur atom, and R is]), a rogen atom, a phenyl or a saturated or unsaturated lower hydrocarbon group which may be substituted with a phenoxy group, or a halogen atom, a cyano group, a lower alkyl group, or a nitro group, the number of which is 10. In the following, K represents an aromatic group in which two or less of its constituent atoms may be nitrogen atoms.) n represents O or an integer from 1 to 3, and m represents an integer from 1 to 5. The present invention was completed based on the discovery that the compound represented by the following formula has excellent insecticidal and bactericidal efficacy against various pests and has low toxicity to warm-blooded animals. The compounds of the present invention are highly effective against various pests of the Lepidoptera order, such as armyworm, fall armyworm, and Naga, as well as various pests of the order Coleoptera and Diptera, and have not only larvicidal action but also ovicidal action. There is. In addition, K is also highly effective against apple rot and apple scab.

The compound of the present invention can be produced by the following method.

(1) When X is a sulfur atom and Y is an oxygen atom in the general formula (1,), a compound represented by the general formula (2) is added in an organic solvent in the presence of an acid binder,
It is manufactured by ring closure with an oxidizing agent. As the organic solvent, common inert solvents such as dichloromethane, chloroform, ethyl acetate, etc. can be used, and as the acid binder, organic and inorganic bases such as triethylamine and sodium hydroxide can be used.

Bromine, chlorine, sodium hypochlorite, etc. are used as the oxidizing agent. The reaction is carried out at 0° C. to room temperature with stirring for 30 minutes to 1 hour. After the reaction is completed, the compound of the present invention is obtained by performing usual post-treatment operations.

Further, depending on the type of substituents of (R,)n and (R)m, it can also be produced, for example, by the method shown in the following reaction formula.

The thiobenzoyl urea derivative represented by the general formula (I) is a novel compound, and can be easily produced, for example, by the method shown in the reaction formula below.

(II) (■) (V) (In the formula, W represents an alkyl group or a phenyl group that may have a substituent.) (2) When X and Y are oxygen, the general formula (It) The compound represented, the general formula, and the general formula (
V) in an inert solvent at -20°C to 5°C.
It is prepared by reacting at 0°C. As the solvent, common inert solvents such as dichloromethane, chloroform, THF, benzene, toluene, acetoyl, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, methyl acetate, and dioxane can be used. After the reaction is completed, the desired compound is obtained by carrying out usual post-treatments. [Ch
eTn, Ber, 1061496 (1973))
The target compound can be obtained in a better yield than the method described above.

The starting compound represented by the general formula CM) can be obtained by reducing the corresponding nitro compound with zinc.

In addition, when (R4)m represents a substituent at the 2-position of the benzene ring, the compound represented by the general formula (Vl) is unstable, so it is usually carried out as follows without isolation after reduction. used in the process.

(3) When X is an oxygen atom or a sulfur atom and Y is a sulfur atom, the compound represented by the general formula (2) and the Ronon reagent represented by the general formula (wherein R3 represents a lower alkyl group) are mixed in an inert solvent. It is produced by reacting at a temperature of 50°C to 100°C. As the solvent, inert solvents such as dimethoxyethane and toluene can be used.

The reaction ratio between the compound represented by formula (1) and Lawesson's reagent is preferably 2:1 to 1:5.

After the reaction is completed, the target compound is obtained by performing usual post-treatments.

The structure of the obtained compound was determined by NMR, Mass and IR spectral analysis.

(Example) Next, the compounds of the present invention will be explained in more detail with reference to Examples.

Example 1 2-(4-chlorophenyl)-5-(2,6-difluorophenyl)-Δ'-L2t4-thiadiazolin-3-
(Compound No. 26): 1-(4-chlorophenyl)-3-(2,6-cyfluorothiopenzoyl)urea 1.3 f (0,004 mol), triethylamine 0.8 f (0,008 mol) , put dichloromethane 3QWJIL into the flask,
While maintaining the internal temperature at 00 to 5° C., 5 mfi of a dichloromethane solution containing 0.6 g of bromine was added to the bottom of the stirred mixture. After stirring at room temperature for 30 minutes, 20 ml of water was added to the reaction solution and washed with water.

The dichloromethane layer was dehydrated over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. Wash the residue with ethanol to remove the target object.
．． I got 9f.

Yield 70% Melting point 170-172°C Example 2 2-(3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)pheny/Iz
)-5-(2t6-difluorophenyl)-Δ4-1cy2-4-thiadiazolin-3-one (compound number 107
): 1-(3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl)-
3-(2,6-cyfluorothiopenzoyl)urea 1.
7F, triethylamine 0.7f methylene chloride 30
In addition to -, 5 ml of a dichloromethane solution of 0.55 F of bromine was added dropwise while stirring under water cooling.

After stirring for 30 minutes, 50% of water was added and the mixture was shaken to separate the liquids. The dichloromethane layer was dehydrated over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was washed with a 1:1 mixture of CH2Cl2-n)hexane to obtain the desired product. Yield 0.8
5f (yield so1m, p. 204-210°C Example 3 5-(2-chlorophenyl)-2-(4-)lifluoromethoxyphenyl)-Δ'-1$2j4-thiadiazolin-3-thione (compound no. 214): 5-(2-chlorophenyl')-2-(4-trifluoromethoxyphenyl)-Δ'-1*L4 f''Asiazoline-3-
Dry 3.7 tons of onion and 40 9 dimethoxyethane! dK was suspended, and Lawesson's reagent 2.1f was added thereto. When the mixed solution was heated at 80° C. for 10 minutes, the solution became uniform. After dimethoxyethane was distilled off under reduced pressure, the residue was dissolved in 49 ml of chloroform. Add this chloroform solution to 5e
After sequentially washing with an aqueous caustic soda solution and water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain the desired product. Yield L 9f/m, p, 75-77°C Example 4 2-(4-chlorophenyl)-5-(216-difluorophenyl)-Δ'-1e2a4-oxathia, zolin-3-one (compound number 256): N-(4-10lophenyl)hydroxylamine 0.759 and tributylphosphine 1.05 f dichloromethane 60 mff1K
The dissolved liquid is 5-(2,6-difluorophenyl) -
A solution of 1,2,4-dithiazol-3-one 1.2jF dissolved in 60all dichloromethane was heated to a temperature of 0 to 10'.
It was added dropwise while maintaining CGC.

After stirring the mixture at room temperature for 1 hour, the solvent was distilled off. The residue was recrystallized from dioxane to obtain the desired product.

Yield 0.8f m, p, 178-181°C Example 5 2-(2,5-dichloro-3-trifluoromethylphenyl)-5-(2,6-si,yfluorophenyl)-△
' L2y4-Oxadiazolin-3-one (Compound No. 244): Solution t in which 0.3 t of ammonium chloride was dissolved in 2 mg K of water,
2.5-1 Chloro-3-trifluoromethylnitrobenzene 1.45 t and zinc powder 0.75 f were mixed with 5 ml of hot ethanol! It was added little by little to the suspension in the solution to maintain gentle reflux. After the reaction was completed, the sheep mixture was treated with F, and the F solution was extracted with chloroform 5o-. The chloroform layer was washed twice with 50 mt of water and then dried over anhydrous magnesium sulfate. Chloroform solution of 9N-(2,5-dichloro-3-trifluoromethylphenyl)hydroxylamine obtained by furnace separation of magnesium sulfate K 5-
(2,6-difluorophenyl') -1#2F4-
After adding 1.1f of dithiazol-3-one and cooling the mixture to 0 to 10°C, 1f of tributylphosphine was added.
was added thereto and stirred for 1 hour. After distilling off the solvent,
The residue was purified by column chromatography to obtain the desired product. Yield: 0.25 fm, p, 143-145°C Next, representative examples of the compounds of the present invention are shown in Table 1.

(Means for Solving the Problems - Insecticides and Fungicides for Agriculture and Horticulture) The insecticides and fungicides of the present invention contain the compound represented by formula [1] as an active ingredient, and are effective. Although the component compounds can be used as pure products, they are usually used in forms that can be obtained from common agricultural chemicals, such as irrigation agents, powders, emulsions, flowables, etc.

As additives and carriers, if the purpose is to use solid agents,
Vegetable powders such as soybean flour and wheat flour, and mineral fine powders such as diatomaceous earth, apatite, gypsum, Merck, ζ-ilophyllite, and clay are used.

For liquid formulations, use kerosene, mineral oil, petroleum,
Solvent naphtha, xylene, Schiff-tetrahexane, cyclohexanone, dimethane, methylformamide, dimethyl sulfoxide, alcohol, acetone, water, etc. are used as the solvent. In these preparations, a surfactant may be added if necessary in order to obtain a uniform and stable form. Irrigation agents, emulsions, flowables, etc. obtained in this manner can be diluted with water to a predetermined concentration and made into suspensions or emulsions, and powders and granules can be used as they are by spraying them on plants. Ru.

It goes without saying that the compound of the present invention is sufficiently effective alone, but since it is slow-acting against larvae, it is extremely useful when used in combination with one or more fast-acting insecticides. . In addition to fast-acting insecticides, the compound of the present invention can also be used in combination with one or more fungicides and acaricides.

Representative examples of insecticides that can be used in combination with the compounds of the present invention are shown below.

Organophosphorus insecticide, carbamate insecticide fenthion,
Fenitrothion, diazinon, chlorpyrifos, E
SP, vamidothion, phenthoate, dimethoate,
Formothion, Marathon, Dizoterex, Thiometone, Dichlorvos, Acephate, Cyanophos, Virimiphos Methyl, Inxathion, Pyridafenthione, Chlorpyrifos, DMI'P, Prothiofos, Sulzolofos, Profenofos, CVMP, Salithion, EPN,
C.Y.P.

Aldicarb, professional? Kysur, virimicarb, methomyl, cartap, carbaryl, thiodicarb, carbosulfan, carbosulfen, nicotine pyrethroid insecticides 2-methrin, cyno-methrin, decamerin,
Fenvalerate, 7 EnpronoZsurin, Cyhalosthrin, FlucislJ$-), Fensifre)%) 70 Methrin, Cyfluthrin, Fluparinate, Pyrethrin, Allethrin, Tetramethrin, Resmethrin, Nozorethrin, Dimethrin, Pronomythrin, Furosulin (Example - Insecticide and agricultural and horticultural fungicides) Examples of formulations are shown next, but the carriers, surfactants, etc. to be added are not limited to these examples.

Example 6 Emulsion Compound of the present invention 10 parts Alkylphenyl I lyoxyethylene 51 Dimethylformamide 35 I Xylene
Mix and dissolve 50 parts or more, dilute with water before use, and spray as an emulsion.

Example 7 Irrigation agent Compound of the present invention 20 parts Higher alcohol sulfate ester 5I clay
741 White Carbon 11 or more are mixed together, ground into fine powder, diluted with water before use, and sprayed as a suspension.

Example 8 Powder Compound of the present invention 5 parts Talc
911 Silica
31 Alkylphenyl Ilioxyethylene 11 or more are mixed and pulverized,
When using, spray No. 11.

(Effects of the Invention) Next, test examples will be given to demonstrate the insecticidal and bactericidal activities of the compounds of the present invention.

Test Example 1 Effect against fall armyworm The compound of the present invention was prepared according to the emulsion formulation shown in Example 6
It was diluted with water so that the compound concentration was 500,125 ppm. Soak corn leaves in the chemical solution for 30 seconds,
After air-drying, the leaves were placed in a petri dish containing five 3rd instar armyworm larvae. The container was covered with a glass lid and placed in a constant temperature room with a temperature of 25°C and a humidity of 65°C, and the insecticidal rate was determined after 5 days.

The results are shown in Table 2.

Test Example 2 Efficacy against Spodoptera spp. The compound of the present invention was added according to the formulation of the water conservancy shown in Example 7, and the compound concentration was 1.
Diluted with water to 25.31.3 ppmK. Soak sweet potato leaves in the chemical solution for 30 seconds, air dry, and then
The leaves were placed in a 9-diameter petri dish containing five third-instar Spodoptera larvae and covered with a glass lid. The petri dish was placed in a thermostatic chamber at a temperature of 25 degrees Celsius and humidity of 65 degrees Celsius, and the insect killing rate was determined after 5 days. The results are shown in Table 3.

Test Example 3 Efficacy against diamondback moth The compound of the present invention was diluted with water according to the formulation of an aquarium shown in Example 7 so that the compound concentration was 500,125 ppm. I soaked the Cilantro leaves in the chemical solution for 30 seconds, and after air-drying it, I left it with a diameter of 95mm containing 5 3rd instar diamondback moth larvae! The leaves were placed in a petri dish and covered with a glass lid. The petri dish was placed in a thermostatic chamber at a temperature of 25 degrees Celsius and humidity of 65 degrees Celsius, and the insect killing rate was determined after 5 days.

The results are shown in Table 4.

Test Example 4 Effect on Spodoptera ring The compound of the present invention was diluted with water according to the emulsion formulation shown in Example 6 so that the compound concentration was 500,125 ppm. Immerse the Spodoptera ring in the chemical solution for 30 seconds, and after air drying, place it in a petri dish and cover with a glass lid.The temperature is 25℃ and the humidity is 6℃.
It was placed in a 5% constant temperature room, and the egg killing rate was examined after 7 days. The results are shown in Table 5.

Test Example 5 Keuuribe and disease control test A chemical solution of a predetermined concentration of an irrigation agent containing the compound of the present invention was sprayed on seedlings of Kieuribe (cultivar "Sumo Hanpaku") that had been grown for about 3 weeks, and after air-drying, the diseased leaves of Keuuribe A suspension of Honzono zoospores collected from the soil was spray inoculated and kept in an inoculation box at 25° C. and humidity of 1 oos. Two days after inoculation, the treated C. cucurbita seedlings were transferred to a greenhouse (23-28°C), and 7 days after inoculation, the degree of disease onset on each C. cucumber leaf was investigated according to the following criteria, and the control value of the treated area (chi. ) was calculated. The results are shown in Table 6.

Investigation criteria

Claims (6)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X and Y each independently represent an oxygen atom or a sulfur atom, and R_1 represents a halogen atom, lower alkyl group, lower haloalkyl group, and lower alkoxy group. R_2 is a halogen atom, a saturated or unsaturated lower hydrocarbon group optionally substituted with a halogen atom, a lower alkoxycarbonyl group, a lower alkylamino group, a lower alkyl Phenylazo group, tetramethylene group, which may be substituted with a group, formula -CH=CH-
Different or similar substituents selected from the group represented by CH=CH- and the group represented by the formula -A-R (in the formula,
A is an oxygen atom or a sulfur atom, R is a halogen atom, a saturated or unsaturated lower hydrocarbon group which may be substituted with a phenyl group or a phenoxy group, or a halogen atom, a cyano group, a lower haloalkyl group or a nitro group represents an aromatic group in which the number of constituent atoms which may be substituted with is 10 or less, and two or less of the constituent atoms may be nitrogen atoms. )n represents 0 or an integer from 1 to 3, and m represents an integer from 1 to 5. ] A compound represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. atoms, halogen atoms, saturated or unsaturated lower hydrocarbon groups, lower alkoxycarbonyl groups, lower alkylamino groups, phenylazo groups optionally substituted with lower alkyl groups, tetramethylene groups , formula -CH=C
Different or similar substituents selected from the group represented by H-CH=CH- and the group represented by the formula -A-R, (wherein A is an oxygen atom or a sulfur atom, R is a halogen atom, The number of saturated or unsaturated lower hydrocarbon groups optionally substituted with a phenyl group or phenoxy group, or constituent atoms optionally substituted with a halogen atom, cyano group, lower haloalkyl group, or nitro group is 10 or less Furthermore, it represents an aromatic group in which two or less of its constituent atoms may be nitrogen atoms.) n represents 0 or an integer from 1 to 3, and m represents an integer from 1 to 5. ] A general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, n and m have the same meanings as above.) Methods for making the represented compounds. (3) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is an oxygen atom or a sulfur atom, and R_1 is a heterogeneous or The same type of substituent, R
_2 is a halogen atom, a saturated or unsaturated lower hydrocarbon group optionally substituted with a halogen atom, a lower alkoxycarbonyl group, a lower alkylamino group, a phenylazo group optionally substituted with a lower alkyl group, a tetra A different or similar substituent selected from a methylene group, a group represented by the formula -CH=CH-CH=CH-, and a group represented by the formula -A-R (wherein A is an oxygen atom or a sulfur atom) , R is a saturated or unsaturated lower hydrocarbon group which may be substituted with a halogen atom, a phenyl group or a phenoxy group, or a halogen atom, a cyano group, a lower haloalkyl group or a nitro group This represents an aromatic group having 10 or less constituent atoms, and 2 or less of the constituent atoms may be nitrogen atoms.) n represents 0 or an integer from 1 to 3, and m represents an integer from 1 to 5. ] and the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_3 represents a lower alkyl group). There are chemical formulas, tables, etc. ▼ A method for producing a compound represented by (wherein, X, R_1, R_2, n and m have the same meanings as above). (4) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a different or similar substituent selected from a halogen atom, a lower alkyl group, a lower haloalkyl group, and a lower alkoxy group, and n is 0 or an integer from 1 to 3) and the general formula ▲ Numerical formula, chemical formula, table, etc. Lower hydrocarbon group, lower alkoxycarbonyl group, lower alkylamino group, phenylazo group optionally substituted with lower alkyl group, tetramethylene group, formula -CH=CH-CH=CH
A different or similar substituent selected from the group represented by - and the group represented by the formula -A-R, (wherein A is an oxygen atom or a sulfur atom, R is a halogen atom, a phenyl group or a phenoxy group) A saturated or unsaturated lower hydrocarbon group which may be substituted with , or a halogen atom, a cyano group, a lower haloalkyl group, or a nitro group, in which the number of constituent atoms is 10 or less, and the constituent atoms are further substituted with Of these, two or less are aromatic groups which may be nitrogen atoms.)
m represents an integer from 1 to 5. ] A compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R_1, R_2, n and m have the same meanings as above) manufacturing method. (5) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X and Y each independently represent an oxygen atom or a sulfur atom, and R_1 is a halogen atom, lower alkyl group, lower haloalkyl group, and lower alkoxy group. R_2 is a halogen atom, a saturated or unsaturated lower hydrocarbon group optionally substituted with a halogen atom, a lower alkoxycarbonyl group, a lower alkylamino group, a lower alkyl Phenylazo group, tetramethylene group, which may be substituted with a group, formula -CH=CH-
Different or similar substituents selected from the group represented by CH=CH- and the group represented by the formula -A-R, (wherein A
is an oxygen atom or a sulfur atom, and R is a halogen atom, a saturated or unsaturated lower hydrocarbon group which may be substituted with a phenyl group or a phenoxy group, or a halogen atom, a cyano group, a lower haloalkyl group or a nitro group. It represents an aromatic group in which the number of optionally substituted constituent atoms is 10 or less, and two or less of the constituent atoms may be nitrogen atoms. ) n is 0 or an integer from 1 to 3, m is from 1 to 5
indicates an integer. ] An insecticide characterized by containing a compound represented by the following as an active ingredient. (6) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X and Y each independently represent an oxygen atom or a sulfur atom, and R_1 represents a halogen atom, lower alkyl group, lower haloalkyl group, and lower alkoxy group. R_2 is a halogen atom, a saturated or unsaturated lower hydrocarbon group optionally substituted with a halogen atom, a lower alkoxycarbonyl group, a lower alkylamino group, a lower alkyl Phenylazo group, tetramethylene group, which may be substituted with a group, formula -CH=CH-
Different or similar substituents selected from the group represented by CH=CH- and the group represented by the formula -A-R, (wherein A
is an oxygen atom or a sulfur atom, and R is a halogen atom, a saturated or unsaturated lower hydrocarbon group which may be substituted with a phenyl group or a phenoxy group, or a halogen atom, a cyano group, a lower haloalkyl group or a nitro group. It represents an aromatic group in which the number of optionally substituted constituent atoms is 10 or less, and two or less of the constituent atoms may be nitrogen atoms. ) n is 0 or an integer from 1 to 3, m is from 1 to 5
indicates an integer. ] An agricultural and horticultural fungicide characterized by containing a compound represented by the following as an active ingredient.