JPS58225077A - 1,2,4-thiadiazole derivative and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is 1-6C lower alkyl; R2 is furyl, thienyl, phenyl, etc.; X and Y are halogen, 1-4C lower alkyl, phenyl, nitro, etc.; m and n are 0-2; excluding the case that R1 is 1-3C lower alkyl, R2 is phenyl, and m=n=0). EXAMPLE:5-(4-Chlorophenylimino)-2-methyl-3-phenyl-DELTA<3>-1,2,4-thiad iazoline. USE:An agricultural and horticultural fungicide having especially excellent controlling effects against downy mildew of cucumber, Pythium damping-off, brown rot of eggplant, downy mildew of grape, scab of apple, Cercospora leaf spot of beet, etc. PROCESS:The compound of formula I can be prepared in the free form by reacting the compound of formula II with bromine in an organic solvent (e.g. CH2Cl2) to effect the cyclization, and reacting the resultant hydrobromide of the compound of formula I with a base.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds and their uses, in particular:
General formula (wherein R1 is a C, ~6 lower alkyl group, R2 is a furyl group, a naenyl group, a phenyl group, or a halodane atom,
A phenyl group mono- or di-substituted with a methyl group or a nitro group, X and Y are a halodane atom, a lower alkyl group of 01 to 4, a halo lower alkyl group, a lower alkoxy group, a lower alkylthio group, a so low M flukylamino basis,
m and n represent a phenyl group, a phenylamino group, a halo-replaced phenoxy group, a hydroxyl group, or a nitro group, and m and n represent 0.1 or 2. ), its inorganic acid or organic acid salt, and a fungicide for common use in farms containing the compound as an active ingredient.

In the cultivation of agricultural and horticultural crops, a large number of pesticides are used to control crop diseases, but their control efficacy may be insufficient, or their use may be restricted due to the emergence of drug-resistant bacteria. In addition, it may cause phytotoxicity or contamination to plants, or be highly toxic to animals and fish.
There are many disinfectants that are not necessarily satisfactory. Therefore, there is a strong demand for a drug that has fewer such drawbacks and can be used safely. The present inventors conducted research on a large number of compounds with the above-mentioned drawbacks in mind, and as a result, they discovered that the group of compounds represented by the above general formula (1) exhibits excellent control effects against various plant diseases. Further, they conducted pharmaceutical research and completed the present invention, thereby providing a new agricultural and horticultural fungicide.

The fungicide of the present invention exhibits control effects against a wide range of plant diseases (7), but is particularly effective against fungal diseases such as downy mildew of cucumbers, pysium seedling blight, eggplant brown rot, and downy mildew of apples. It has excellent efficacy against scab, sugar beet brown spot and bacterial plant diseases.

Among the compounds according to the present invention, in the general formula (1), R1 is an alkyl group of O1 to 3, R2 is a phenyl group, and m and n = Q, Berich
Although its synthesis method is described in te1979, vol12, and PbI2, nothing is known about its bactericidal activity.

The compound of the present invention can be obtained by subjecting a compound represented by the general formula (wherein R1, R2, , its hydrobromide salt can be prepared. As the organic solvent, common inert solvents such as methylene chloride, chloroform, ethyl acetate, and DMF are used. The reaction is carried out at 0°C to 50'C1, preferably 0°C to room temperature, for 0.5 to 3 hours. Furthermore, an equivalent amount of an acid binder such as pyrinone, triethylamine, or sodium hydroxide may be added as required. If this reaction is carried out by adding twice the equivalent amount of acid binding agent, the compound of the present invention can be obtained in one step, but since it becomes difficult to isolate and purify the target product, the HBr salt is isolated. The preferred method is to The free compound of the present invention can be obtained by reacting the hydrobromide salt thus obtained with a base in a suitable organic solvent. As the organic solvent used, common inert solvents such as chloroform and methylene chloride are used, and as the base, inorganic and organic bases such as sodium hydroxide, birinone, and triethylamine are used.

Further, the compound represented by the general formula (II) can be produced, for example, by the method shown in the reaction formula below.

When X is an electron-withdrawing group such as a nitro group, it is preferable to produce by method (2).

The method for producing the compound of the present invention will be explained in more detail below with reference to synthesis examples.

Reference Example I N-methylbenzimidoyl chloride 6114f (
0.4 mol) of sodium thiocyanate was dissolved in 360 mol of acetone, and a solution of 32.4 mol of sodium thiocyanate in 680 mol of sodium thiocyanate in acetone was added dropwise with stirring. -15℃～-20
Stir for 10 minutes at °C & 4-90°C
, 4 mol) in acetone was added dropwise at ℃. The temperature was gradually raised to room temperature, and the mixture was further stirred for 2 hours. The precipitated crystals were filtered, washed with acetate/and water, and 1-(
102.5 t of 4-chlorophenyl)-3-(N-methylbenzimidoyl)thiourea was obtained.

Melting point 167-168.5℃ (yield 84.4q6)
Example 1 Compound 6 1-(4-chlorophenyl)-3- obtained in Reference Example 1
75 t of (N-methylbenzimidoyl)thiourea was suspended in a mixture of 640' ml of methylene chloride and 19.5 F of pyridine, and while stirring at 0 to 5°C, 39.52 t of bromine was suspended.
90 ml of methylene chloride solution was added dropwise. ■ After stirring for a minute, filter the precipitated crystals, add methylene chloride, ethanol,
Wash with water in order and dry, 5-(4-rioo7xnylimi/)-2-methyl-3-phenyl-△3-112.4-
75 tons of thiadiazoline hydrobromide were obtained. Yield 79
% d, p, 224-225°C Example 2 Compound 5 5-(4-chlorophenylimino)-2-methyl-3-
Phenyl-Δ-1,2,4-thianoasorine hydrobromide 75? was suspended in 500 g of chloroform, and 30 t of triethylamine was gradually added dropwise under water cooling. The reaction solution is washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure until crystals begin to precipitate.

- 52 r of the desired product was obtained by adding n-hexane to the ring liquid and crystallizing it.

Yield 88% d, p, 14s to 152c Example 3 Compound 43 Summer 0H3 1-(N-mef-4-chlorobenzimidoyl)-3
5.32 ml of -(4-n-f ropylphenyl)thiourea was suspended in 30 ntl of methylene chloride and 50 ml of ethyl acetate, and 5 ml of a solution of 2.45 r of bromine in ethyl acetate was added dropwise at 0 to 5°C with stirring. After stirring at room temperature for 2 hours, the crystals were filtered and washed with acetone to give 3-(4-chlorophenyl)-2-methyl-5-(4-i-nolopylphenylimino)-Δ”-11214-thi. 5.52% of adiazoline hydrobromide was obtained.

d, p, 205-206°C Yield 84 Compound 14-2-Methyl-5-(4-n-propylphenylimino)-Δ3-1.2.4-Thianoazoline hydrobromide 4
．． 2f was suspended in chloroform 20-, and triethylamine was added dropwise until all the crystals were dissolved.

The reaction solution was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the desired product 3.01.

d, p, 139-145'C Yield 88th Example 5 Compound 4 l-(4-bromphenyl)-3-(N-methyl-2-
thiophenecal (ximidoyl) thiourea 4.31
was suspended in 30 ml of methylene chloride and 604 ml of vinegar, and a solution of 1.95 ml of bromine in ethyl acetate was added dropwise while stirring at -5 to 0°C. After stirring for an additional minute, the precipitated crystals were filtered through the mouth and washed with ethyl acetate.

The obtained crystals were suspended in 50% of chloroform, and 150% of IN-caustic soda aqueous solution was added under water cooling, followed by stirring for 10 minutes. The chloroform layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated until crystals began to precipitate. By adding n-hexane to the concentrated solution and crystallizing it, the desired product 2.
I got 5f.

Yield: 58 cm, d, p, 142-145°C Representative examples of the compounds of the present invention are shown in Table 1.

The fungicide of the present invention can be used as a pure active ingredient compound, and for the purpose of being used as an agricultural chemical, it can be used in the forms that general agricultural chemicals can take, such as wettable powders, granules, powders, emulsions,
It can also be used in the form of an aqueous solvent, aerosol, or the like.

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, stoneback, talc, flat fluorite, and clay are used. When a liquid dosage form is intended, kerosene, mineral oil, petroleum, turbait naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, nometer sulfoside, 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 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.

Next, some examples of compositions of the present invention will be shown, but the additives and their addition ratios should not be limited to these examples and can be varied over a wide range.

Example 6 Hydrating agent compound 40 parts Diatomaceous earth 53 parts Higher alcohol sulfuric acid ester 4 parts Alkylnaphthalene sulfonic acid If 3 parts or more are mixed uniformly and finely ground, the active ingredient will be 40%.
Obtain irrigant.

Example 7 Emulsion compound 30 parts xylene 33 parts methylformamide 30 parts polyoxyethylene alkyl allyl ether By mixing and dissolving 7 or more parts, an emulsion containing 30% of the active ingredient is obtained.

“Example 8 Powder Compound 10 parts Melt
By uniformly mixing 89 parts or more of polyoxyethylene alkyl allyl ether and pulverizing it finely, a powder containing 10 parts of the active ingredient is obtained.

Although it goes without saying that the compound of the present invention is sufficiently effective alone, it is insufficiently or weakly effective against pests and diseases other than those shown in the examples below, so various fungicides may be used to compensate for this. It can also be used in combination with one or more insecticides and acaricides.

Typical examples of fungicides, insecticides, and acaricides that can be used in combination with the compounds of the present invention are shown below.
Fenfram, Frapax, Arietch, Norothiocalf, Triatumephon, Triatummenol, Polyoxin, Tridemolk, Metaxanine, Cycloxyl, Triforine, Isonorothiolane, Norobenazole,
'Plasticidin-81 gasgamycin, validamycif, PONB, inolodione, vinclozolin, glocymidone, benomyl, thio7anatomethyl, basic copper chloride, basic copper sulfate, triphenyltin hydroxide, quinomethionate, gulono4mocarb, binano9cryl [Insecticide/acaricide): EOPF! , Chlorpenturate, Chlorfuropyrate, Proclonol, Fenisozolomorate, Kelsen, Zipton, Chlorphenaminone, Amitraz, BPPS, PPPS, Benzomate, Cyhexatin, Distanoxane 1, T5 Rinactin, Thiogynotux, OPC! BS, Tetranophone,
Tetrasul, cycloplate, kayaside, kayahono, polysulfide lime, 3-n-dodecyl-1,4-nafquinone-2-yl acetate, phenothion, fenitrothion, dianonon, chlorpyrifos, gsp, pamidothion, fuentate, nomethoate, formothion, marathon, Tunoterex, Thiometone, Phosmet, Menazone, Dichlormeth, Acephate, Fli, P
BF, noariphor, methyl parathion, oxytumeton methyl, ethio/, aldicaf, solopoxur, 79-methrin, cyno-methrin, decamerin, fueno-9relate, fe/frono-sulin, pyrethrin, ryorethrin, tetramethrin, resmethrin,
Parsulin, tumesulin, solono! Surin, N0 Roslin, 3-Phenoxypentrue 2,2-Cycloro 1-
(4-Ethoxyphenyl)-1-cyclozolo/4'carxylate, α-cyan-3-phenoxybenzyl-2,2-dichloro-1-(4-ethoxyphenyl)-
1-Cycloglono(carxylate, (R8)-α)
-cyano-3 phenoxybenzyl (R8)-2-(4-
trichloromethoxyphenyl)-3-methylbutyrate, (RB)-α-cyano-3-phenoxypennol (R
8)-2-(2-chloro-4-trichloromethylanilino)-3-methylbutyrate, machine oil.

Next, the bactericidal activity of the compounds of the present invention will be explained in detail by giving test examples.

Test Example 1 Cucumber and disease control test A cucumber (cultivar variety "Sumo Hanka") fungus grown for about 3 weeks was sprayed with a chemical solution of a predetermined concentration of an irrigation agent containing the compound of the present invention, and after air-drying, samples were collected from cucumber and diseased leaves. The leaves were inoculated with a suspension of Tamotozono Yusei and kept in an inoculation box at 5°C and 100% humidity for 2 days, then transferred to a greenhouse, and the onset of disease on each leaf was examined 7 times after inoculation. The control value was calculated based on the disease severity in the untreated area. The results are shown in the second layer.

Table 2 *Commercial product: Tetrachloroinphthalonitrile 75% hydrating powder Test example 2 Cucumber damping-off (by Visium bacterium) Pot test 7 Five cucumber seeds (product #lli "Four Leaves") are sown in a pot. Then, cucumber seedling blight disease fungus (Takkan-ku Usudan-za-ko dermatu) cultured in soil, bran, and rice husk medium in advance.
m), and after covering the soil, the soil was irrigated with a chemical solution of an irrigation agent containing the compound of the present invention at a predetermined concentration, and after 5 days, the degree of disease onset was investigated, and the control value was determined based on the degree of disease onset in the untreated control plot. was calculated. The results are shown in Table 3.

Table 3 *Ichi [*IM'Tachigaren'': 3-Hydroxy-5-methylisoxazole 40% solution test example 3 Su/ga scabosis control test Apple seedlings grown in 2.5-inch pots (variety ``Kogyoku'') , 3~
After spraying a chemical solution of a predetermined concentration of an aquarium containing the compound of the present invention and air-drying it, the apple scab fungus (ventur
Ia imaequali 3) inoculated with conidia, 1
After the plants were kept in a greenhouse at 6°C, they were kept in a greenhouse at 15-20°C for two weeks, the degree of disease onset was investigated, and the control value was calculated based on the disease onset in the untreated control plot. The results are shown in Table 4.

Table 4 *Commercial agent "Canotan": N-(trichloromethylthio)-4-cyclohexene-1,2-nocarpoximide (
(Source) Chi hydrating powder test example 4 Sugar beet brown spot disease control test Video of sugar beet grown in 90 pots (variety "Monohill", 5
At the 6th leaf stage), a predetermined chemical solution of an irrigation agent containing the compound of the present invention was sprayed, and the leaves were air-dried.
Conidia of Ercospora beticda) were spray-inoculated, kept at 24-26°C and high humidity for 1 day, and then kept in a greenhouse at ~4°C for 2 weeks. The number of lesions formed was calculated, and the control value was determined for each drug-treated plot based on the onset of disease in the untreated control plot. The results are shown in Table 5.

Table 5 *Commercial agent 1 tin H”: fentin hydrox
ide 17% irrigation agent Page 1 continued 0 Inventor Susumu Shimoda 2-18-18 Ogimachi, Odawara City

Claims (2)

[Claims] (1) A phenyl group substituted by the general formula (in the formula, R1 is a lower alkyl group of 01-6, R2 is a furyl group, chenyl group, phenyl group, or a halogen atom, a methyl group, or a nitro group, mono- or mono-substituted) , X and Y are a halogen atom, a lower alkyl group of CI to 4, a halo-lower alkyl group, a lower alkoxy group, a lower alkylthio group, a di-lower alkylamino group, a phenyl group, a phenylamino group, a oro-substituted phenoxy group , a human loxyl group, or a nitro group, m and n are 0.
Indicates l or 2. However, in the lower alkyl group of FL 艷to, ~S, R1 is 7
Except for the case where it is an ale group and m = n :IO. ) and its inorganic acid or organic acid salt. (2) General formula (wherein R1 is a lower alkyl group of 01 to 6, R2 is a phenyl group mono- or di-substituted with a furyl group, chenyl group, phenyl group, or a halogen atom, methyl group, or nitro group) and Y is a halogen atom, a lower alkyl group of 01 to 4, a halo lower alkyl group, a lower alkoxy group, a lower alkylthio group, a di-lower alkylamino group, a phenyl group, a phenylamino group, a hao-substituted phenoxy group, a hydroxyl group, or An agricultural and horticultural fungicide characterized by containing a compound represented by the following formula (where m and n are 0.1 or 2) and its inorganic acid or organic acid salt as active ingredients.