JPS6143179A - 1,2,4-thiadiazolin-3-one derivative, preparation thereof and insecticide and agricultural and horticultural germicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is halogen or CH3; Y is H or halogen; R1 is Y, lower alkyl, halogeno lower alkoxy, substituted pyridyloxy, etc. R2 is Y, lower alkyl, lower alkynyl, phenylazo, etc.; R3 is Y, lower alkyl or halogeno lower alkyl except when R3 is H, R1 is H or halogen and R2 is halogen or haloalkoxyl). EXAMPLE:2-( 4-tert-Butoxycarbonylphenyl )-5-( 2,6-difluorophenyl )-DELTA<4>-1,2,4-thiadialine-3-one. USE:An insecticide and agricultural and horticultural germidice, having improved insecticidal and germicidal efficacy against various blights and injurious insects with low toxicity to warm-blooded animals and not only larvicidal but also ovicidal action. PREPARATION:A novel compound expressed by formula I is cyclized with an oxidizing agent in an organic solvent in the presence of an acid binder to afford the aimed compound expressed by formula I.

Description

Detailed Description of the Invention (・Industrial Application Field) The present invention provides a novel 1.21 which has excellent insecticidal and bactericidal effects.
4-thiadiazolin-8-one derivative, method for producing the same,
It is an insecticide and a fungicide for agriculture and horticulture.

(Conventional technology
) 1g76 5 (2-phenyl-5-phenyl-1,2, similar to the compounds of the present invention in lJF 189 to lυ4)
4-47 Ji7:/! A method for producing J-8-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.

(Problems to be solved by the invention) Many insecticides have been used in the past, but it is difficult to control the typical insecticides, such as organic phosphorus agents and carbamate agents, as a wide range of insect pests are resistant to them ( In addition, 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. There is.

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

(Means for solving the problem) The inventors synthesized a large number of 1.2.4-thiadiazoline compounds and made extensive studies, and found that the general formula (wherein X is a halogen atom or a methyl group, Y is a hydrogen atom or a halogen atom; R1 is a hydrogen atom; A substituted pyridyloxy group or quinoxalinyloxy group, R2 is a hydrogen atom, a hydrogen atom, a lower alkyl group, a lower alkynyl group, a lower alkoxy group, a halogeno lower alkenyloxy group, a halogeno lower alkylthio group , a lower alkoxycarbonyl group, a phenylazo group, or a phenoxy group mono- or di-substituted with the same or different hydrogen atoms, cyano groups, or halogeno lower alkyl groups,
pyridyloxy group, quinoxa, or linyloxy group; R3 represents a hydrogen atom, a halogen atom, a lower alkyl group, or a halogeno-lower alkyl group; Except when it is an atom or a haloalkoxy group. The present invention was completed based on the discovery that the compound represented by J 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 Lepidoptera pests such as Spodoptera spp., Fall armyworm, and diamondback moth, as well as various pests such as Coleoptera and Diptera, and have not only larvicidal activity but also ovicidal activity. .

It also shows great effects on kerosene disease, apple scab disease, etc.

The compound of the present invention has the general formula (wherein X, Y, R1, R2, and R3 have the same meanings as above. General inert solvents such as dichloromethane, chloroform, DMF, and ethyl acetate can be used as organic solvents, and organic and inorganic bases such as triethylamine and sodium hydroxide can be used as acid binders. can.

Bromine, chlorine, sodium hypochlorite, etc. are used as the oxidizing agent. The reaction is carried out at θ°C to room temperature for 80 minutes to 1 hour with stirring. After the reaction is completed, the compound of the present invention can be obtained by performing usual post-treatment operations.

The compound of the present invention can also be produced, for example, by the method shown in the reaction formula below, depending on the types of substituents of X, Y, R1, R2, and R3.

The thiobenzoyl urea derivative represented by the general formula 1) is a new compound, and can be easily produced, for example, by the method shown in the reaction formula below.

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

Example 1 2-(4-tert-butoxycarbonylphenyl J
-5-(2,,6-difluorophenyl l-Δ-1,8
,4-thiadiazolin-3-one (compound 8):1-
(4-tert-butoxycarbonylphenyl J-8
-(2,6-difluorothiobenzoylun-urea 1.
8. ! 9 (0,00895 mol), triethylamine 0
．． 84.9 (0,00813 mol) dichloromethane 2
bromine 0.889 (0) while stirring under water cooling.
, 00895 mol J of dichloromethane solution 101 nl!
was dripped. After stirring at room temperature for 80 minutes, the mixture was added to water 5017' and separated by shaking in a separatory funnel. The dichloromethane layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure. N-hexane IOM was added to the concentrated solution to crystallize the target product.

Yield 1, ON, m, I) 195-196°0 Production Example 1 l-(4-tertiaIJ-7'toxycarbonylphenyl-8-(Z, 6-difluorothiobenylnourea) 1 5-12 .6-Difluor to 7xs-le)-i, 2.4-
dithiazol-8-one 1.210.00b18 mol)
was dissolved in dichloromethane (80°C), and while stirring under water cooling, t-butyl 4-ami7benzoate was added. ir (0,
00518 Soru J,) Liptylphosphine 1.05i0
．． A solution prepared by dissolving 0.00518 mol) in 2011 liters of dichloromethane was added dropwise. After stirring at room temperature for 1 hour, the reaction solution was concentrated under reduced pressure, and the resulting residue was washed with ligroin to obtain the desired product. Yield 1.8I Example 2 5-(2-chlorophenyl)-2-(8,5-diq4-4-(1,1,2-1lifluoro-2-chloroethoxy]phenyl)-Δ-1, 2,4-f Asiazolin-8
-one (compound 2g): 1-(2-chlorothiobenzoyl)-3-[8,5-dichloro-(1,1,2-)lifluoro-2-chloroethoxyJphenyl]urea 0.95 g ( 0,00
19 mol of 0.81 (0,0089 mol) of triethylamine was dissolved in 80 molar dichloromethane, and bromine o, ag (0,001 SJ mol of dichloromethane solution) was added dropwise in 5 dichloromethane solution while stirring under water cooling.

809 After stirring, 40a of water! 'Add and shake to separate the liquids.

The dichloromethane layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was washed with tn-hexane to obtain the desired product. Yield 0.8g (yield 86% 3m, I) 14
5-148℃ Example 8! -(8,5-dichloro-4-(8-chloro-5-trifluoromethyl-2-pyridyloxyJ7enyl) -
5-(g,6--/fluorophenyl]-Δ4-1.2
．． 4-Thiadiazolin-8-one (compound 86): 1-(8,5-dichloro-ru(8-chloro-5-trifluoromethyl-2-pyridyloxy)pheny, u)-
8-(Z,6-difluorothiobenzoyl)urea 1.
7. ? , ) ethylamine 0.7. Add i9 to 80 m/m of methylene chloride and add 0.55 ml of bromine while stirring under water cooling.
A solution of F in dichloromethane (5d"Ik) was added dropwise. After stirring for 80 minutes, 50#+Jy of water was added and the layers were separated by shaking. The dichloromethane layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was diluted with CH!cl, -n-hexane-l
:1 mixture to obtain the desired product. Yield 0.85.9
(Yield 50%) m, p14-10'.

Production Example 2 1-12-chlorothiobenzoyl)-8-(8,5-dichloro-4-(1,1,2-trifluoro-2-chloroethoxynophenyl)urea: 5-(2-chlorophenyl 2- 1. 0.78 g (0,0084 mol) of dithiazol-8-one! In 80 m of dichloromethane, add 8.5-dichloro-4-(1,1,21-)realol-2- while stirring under water cooling. Chlorethoxyl aniline 1, li' (0,0084 mol J morphylphosphine 0.6, li' (0,0
084 mol J 'k 80 ml (D si) A solution dissolved in lormethane was added dropwise. After stirring at room temperature for 80 minutes, the reaction solution was concentrated under reduced pressure, and the resulting residue was washed with Ikn-hexane to obtain the desired product. Ta.

Yield: 1.1 #m, p17B-174°0 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. Although the compound can be used as a pure product, it is usually used in the form of a common agricultural chemical, such as an irrigation agent, powder, emulsion, or flowable.

As additives and carriers, if the purpose is to use solid agents,
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.

For liquid formulations, use kerosene, mineral oil, petroleum,
Solvent 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 in order to obtain a uniform and stable form. The water preparations, emulsions, flowables, etc. obtained in this way are diluted with water to a predetermined concentration to form suspensions or emulsions, and powders and granules are made into '1! Well, it is used by spraying it on plants. .

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.

Typical 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
8P, vamidothion, phenthoate, dimethoate,
Formothion, Marathon, Dibuterex, Thiometone, Dichlorvos, A7phate, Cyanophos, Virimiphos Methyl, Inxathion, Pyridafenthione, Chlorpyrifos, DMTP, Prothiofos, Sulprofos, Profenofos, CvMP1 Salithion, BPNl
CYP, aldicarb, propoxyl, virimicarp, methomyl, cartap, carbaryl, thiodicarp, carbosul7an, carbosulfen, nicotine pyrethroid insecticide permethrin, cypermethrin, decamerin, fenvalerate, 7enpropathrin, cyhalothrin,
fluparinate, phencyflate, tralomethrin,
Cyfluthrin, fluparinate, pyrethrin, allethrin, tetramethrin, resmethrin, parethrin, cymethrin, cyfluthrin, prosulin (Examples - Insecticides and agricultural and horticultural fungicides) Examples of formulations are shown below, including carriers to be added and surfactants. The agents and the like are not limited to these examples.

Example 4. Emulsion Compound of the present invention 10 parts Alkylphenylpolyoxyethylene 5 Dimethylformamide 35 Xylene
Mix and dissolve 50 or more ingredients, dilute with water before use, and spray as an emulsion.

Example 5. Irrigation agent Compound of the present invention 20 parts High and grade alcohol sulfate ester 5 parts
stomach
74 part white carbon
1. Mix the above ingredients, grind into fine powder, dilute with water and spray as a suspension before use.

Example 6. Powder Compound of the present invention 5 parts Tal
ri 91
〃Silica
3 Alkylphenylpolyoxyethylene 1 Mix and crush the above ingredients and spray as is before use.

(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. Example 4 shows the efficacy of the compounds of the present invention against fall armyworm. The emulsion was diluted with water to a compound concentration of 500, 1251) pm according to the emulsion formulation shown in . Corn leaves were immersed in the chemical solution for a few seconds, and after air drying, the leaves were placed in a petri dish containing five 3rd instar armyworm larvae. Close the glass lid and heat to 25℃.
The samples were placed in a constant temperature room with a humidity of 65%, and the insect killing rate was determined after 5 days. The results are shown in Table 2.

Table 2 Fall armyworm larva Fall armyworm larva Fall armyworm larva Fall armyworm larva Test Example 2 Efficacy against fall armyworm The compounds of the present invention were tested in Example 5. According to the formulation of the hydrating powder shown in , the compound was diluted with water so that the compound concentration was 125.31.31)I)m. Sweet potato leaves were soaked in the chemical solution for several seconds, and after air drying,
The leaves were placed in a 9-sided petri dish containing 5 third instar Spodoptera larvae and covered with a glass lid. The petri dish was placed in a thermostatic chamber at a temperature of 25°C and humidity of 65%, and the insect kill rate was determined after 5 days. The results are shown in Table 3.

Table 3 Spodoptera larvae Spodoptera larva Test Example 3 Efficacy against diamondback moth The compound of the present invention was tested in Example 5. According to the formulation of the aquarium shown in 1., the compound was diluted with water to a compound concentration of 500.125 ppm. Cilantro leaves were dipped in the chemical solution for a few seconds, and after air drying, the leaves were placed in a 9 cm diameter petri dish containing five 3rd instar diamondback moth larvae and covered with a glass lid. Place the petri dish in a constant room with a temperature of 25°C and humidity of 65%,
The insect killing rate was investigated after several days. The results are shown in Table 4.

Table 4 Diamondback moth larva* diflubenzuron Test Example 4 Efficacy against Spodoptera eggs The compounds of the present invention were tested in Example 4. The emulsion was diluted with water to a compound concentration of 50 to 1251)I)m according to the emulsion formulation shown in . Spodoptera japonica eggs were immersed in the chemical solution for 30 seconds, air-dried, and then placed in a petri dish. Close the glass lid and heat to 25°C.
The eggs were placed in a constant temperature room with a humidity of 65%, and the egg killing rate was examined after 7 days. The results are shown in Table 5.

Table 5 Test Example 5 Cucumber and disease control test Cucumber seedlings (cultivar "Sumo Hanpaku") grown for about 3 weeks were sprayed with a liquid solution of an irrigation agent containing the compound of the present invention at a predetermined concentration, and after air-drying, the disease control test was conducted. A suspension of zoospores of this fungus collected from leaves was spray inoculated and kept in an inoculation box at 5°C and 100% humidity. Two days after inoculation, the treated cucumber seedlings were placed in a greenhouse (2
One day after inoculation, the degree of disease onset on each cucumber leaf was investigated according to the following criteria, and the control value (%) of the treated plot was calculated using the following formula. The results are shown in Table 6.

Research Standards No. 5 (Table 5 *1: Tetraphthalonitrile 75% irrigation agent *2
: Manganani〆Ethylene bisdithiocano mate 7
5% irrigation agent

Claims (4)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, an alkoxy group, or a pyridyloxy group or a quinoxalinyloxy group mono- or di-substituted with the same or different halogen atom or halogeno-lower alkyl group; R_2 is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkynyl group; ,
Halogeno lower alkoxy group, halogeno lower alkenyloxy group, halogeno lower alkylthio group, lower alkoxycarbonyl group, phenylazo group, or phenoxy group mono- or di-substituted with the same or different halogen atom, cyano group, or halogeno lower alkyl group, Pyridyloxy group or quinoxalinyloxy group, R_3
represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogeno-lower alkyl group. However, the case where R_3 is a hydrogen atom, R_1 is a hydrogen atom or a halogen atom, and R_2 is a halogen atom or a haloalkoxy group is excluded. ). (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A lower alkoxy group, or a pyridyloxy group or a quinoxalinyloxy group mono- or di-substituted with the same or different halogen atom or halogeno-lower alkyl group, and R_2 is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkynyl group. group, halogeno lower alkoxy group, halogeno lower alkenyloxy group, halogeno lower alkylthio group, lower alkoxycarbonyl group, phenylazo group, or phenoxy group mono- or di-substituted with the same or different halogen atom, cyano group or halogeno lower alkyl group , pyridyloxy group or quinoxalinyloxy group, R_3
represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogeno-lower alkyl group. However, the case where R_3 is a hydrogen atom, R_1 is a hydrogen atom or a halogen atom, and R_2 is a halogen atom or a haloalkoxy group is excluded. ) There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by the action of an oxidizing agent on the compound represented by ▼ (wherein X, Y, R_1, R_2, and R_3 have the same meanings as above. ) A method for producing a compound represented by (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A lower alkoxy group, or a pyridyloxy group or a quinoxalinyloxy group mono- or di-substituted with the same or different halogen atom or halogeno-lower alkyl group, and R_2 is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkynyl group. group, halogeno lower alkoxy group, halogeno lower alkenyloxy group, halogeno lower alkylthio group, lower alkoxycarbonyl group, phenylazo group, or phenoxy group mono- or di-substituted with the same or different halogen atom, cyano group or halogeno lower alkyl group , pyridyloxy group or quinoxalinyloxy group, R_3
represents a hydrogen atom, a halogen atom, a lower alkyl group, or a halogeno-lower alkyl group. However, the case where R_3 is a hydrogen atom, R_1 is a hydrogen atom or a halogen atom, and R_2 is a halogen atom or a haloalkoxy group is excluded. ) An insecticide characterized by containing a compound represented by the following as an active ingredient. (4) General formulas ▲ Numerical formulas, chemical formulas, tables, etc. an alkoxy group or a pyridyloxy group or a quinoxalinyloxy group mono- or di-substituted with the same or different halogen atom or halogeno-lower alkyl group, R_2 is a hydrogen atom,
Halogen atom, lower alkyl group, lower alkynyl group, halogeno lower alkoxy group, halogeno lower alkenyloxy group, halogeno lower alkylthio group, lower alkoxycarbonyl group, phenylazo group, or the same or different halogen atom, cyano group or halogeno lower alkyl group R_3 represents a hydrogen atom, a halogen atom, a lower alkyl group, or a halogeno-lower alkyl group. However, the case where R_3 is a hydrogen atom, R_1 is a hydrogen atom or a halogen atom, and R_2 is a halogen atom or a haloalkoxy group is excluded. ) An agricultural and horticultural fungicide characterized by containing a compound represented by the following as an active ingredient.