JPS6016978A - Triazolone derivative and fungicide - Google Patents

Abstract

NEW MATERIAL:A triazolone derivative shown by the formula (R1 is H, or CH3; R2 is H, alkyl, or benzyl; Z is 1-4C alkylcarbomoyl, phenylcarbamoyl which is replaced with Cl or CH3, or benzoyl which is replaced with Clor CH3). EXAMPLE:4-Methylcarbamoyloxy-1,2,4-triazol-5-one. USE:A fungicide. Effective for controlling wide blights of agricultural and horticultural crops such as black spot of Japanese pears, melanose of citrus, Fusarium yellows of Japanese radish, damping-off of cucumbers, blights of pulses caused by Sclerotiria sclerotiorum, etc. PREPARATION:4-Hydroxy-1,2,4-triazolon-5-one is reacted with a carbamic acid halide or a benzoic acid halide in a solvent such as dioxane, etc. in the presence of dehydrochlorinating agent such as isocyanate or triethylamine, etc., to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bactericidal agent containing a derivative of the present invention and the compound as all active ingredients.

-Z [In the formula, R is a hydrogen atom or a methyl group, R2 is a hydrogen atom, an alkyl group, or a benzyl group, and Z is an alkylcarbamoyl group having 1 to 4 carbon atoms, chlorine or a methyl group. A substituted phenylcarbamoyl group or a benzoyl group substituted with chlorine or methyl group] Typical examples of the compounds of the present invention include those shown in Table 1.

The compounds are indicated by the symbols in the general formula above.

Table 1 (3) This compound was prepared using a known method (Arch Pharm 196
830] (II) 4-hydroxy-L2+4- synthesized based on 827-9)! JAzolon-5-one is melted or suspended in a solvent such as nooxane or dimethylformamide, and isocyanate is applied thereto, or in the presence of a dehydrochlorination agent such as triethylamine or pyridine, carbamic acid halide, Obtained by reacting with benzoic acid halide.

All typical synthesis examples are shown below and will be explained in more detail.

4-Hydroxy-1,2,4-)lyazole-5-oy
0.05mole (5,0!i')'edioxa'/
Suspended in 30ml, 4g of methyl isocyanate
'i and heated under reflux for 3 hours. After cooling to room temperature, the product was collected by filtration. The obtained crystals were recrystallized from ethyl alcohol to obtain 1.91 white crystals with a melting point of 170° (decomposition).

(5) IR-Nu overlap torque data 3320 cnr' (-NT-I-), 1.790
cm-1,17,10m-m-1(-C=O)N (CDCt3+DMSO-c16)2,70～
2.80 ppm (d, 3H), 8.07 ppm (s
, H(), same(b, 1.H), ], 1.90 ppm
(b, 1.H) Synthesis Example 23-Methyl-4-methylcarbamoyloxy-1,2,4-)riazol-5-one 4-hydroxy-3-methyl-1,2,4-triazol-5-off The mixture was heated under reflux for 2 hours with 1 ml of methyl isocyanate. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl alcohol to obtain 1.41 white crystals with a melting point of 141° (decomposed).

NMR overlap (DMso-a6); δ value, 2.0
7 ppm (s, 3H), 2.65-2.75 ppm
(d, 3H), 8.2 ppm (b, 1.H), ]-1
,,67ppm(b,H() Synthesis Example 34-(o-methylbenzoyloxy)-1,,2,4-)riazole-5
-one (6) 4-hydroxy-1,2,4-)lyazol-5-oy
5.0ml methylformamide 3Q ml
(C dissolved, stiff, triethylamine 5.0!?'(
Add z and further add orthotoluylic acid chloride 7.7 at room temperature.
When Pffi is added, it generates intense heat. -After standing overnight, the reaction solution was poured into 300 ml of water, and the resulting crystals were recrystallized from all methanol to give pale brown crystals with a melting point of 78°C (decomposition).O NMR spectrum data ( DMSO-d6) 2, 59
ppm(s, 3I(), 7.3-8.2 ppm(m,
4H), 8, 43 pprn(s, IH), ], 2.
25 ppm (b, 11.T() IR spectrum data] 770 tyn-', 1.728 cm-' (-
C=O) Synthesis Example 41-benzyl-4-methylkat/
/<Moyloxy-1,2,4-triazol-5-one Potassium hydroxide 3.3P' water 30ml methanol 30
Dissolved in rnl, stiff, 4-hydroxy-1,2,
4-triazol-5-one5. OL! − is added.

While stirring under cooling, add benzyl bromide 9.4. !
i''(r) was added dropwise, and the apparatus was heated overnight after the addition. The resulting crystals were collected by filtration to give 751 white crystals of 1-benzyl-4-hydroxy-1,2,4-triazol-5-one with a melting point of 125°.
I got it.

IR1710crn-1 NMR (DMso-d6) 5, 18 ppm (8-2H), 7.42 ppm (s
, 5H) 8.0 ppm (s, 1.H), 11.75
ppm (b, ], IH■-benzyl~4-hydroxy-1.2./1-triazol-5-one 481 was dissolved in 1.5 m7! of dioxane, and l.ethylamine 4
When a drop of 1-2.0 P of methyl isocyanate is added, crystals immediately precipitate. This was collected by filtration to crystallize 1-benzyl-4-methylcal/6moyloxy-1.2.4-triazol-5-one with a melting point of 147°5.
2g' was obtained.

The compounds of the present invention are effective in controlling diseases of agricultural and horticultural crops, and the main ones include the following.

Paddy rice Sesame leaf blight; Beans brown spot, sclerotia; Tomato blight, gray mold, leaf mold, ring spot blight; cucumber gray mold, downy mildew, gray blight, black star, seedling die-off, sclerotinia; lettuce sclerotium blight ; Citrus black, scab; Apple monilia, black star, leaf spot; Pear black star, black spot; Peach gray layer, black star, fomopress rot, fungal disease; grapes
Bae, black plague, and late rot.

As mentioned above, the compound of the present invention can be used as a fungicide for agricultural and horticultural purposes, but it can be used as it is or mixed with a carrier (diluent) to form powders, granules, irrigation agents, emulsions, oils, and other suitable agrochemical preparations. used as an agent. In this case, spreading agents, emulsifiers, wetting agents, fixing agents, etc. are used as appropriate, and they can also be used in combination or mixed with other types of fungicides, insecticides, herbicides, fertilizers, etc.

Example 1 Powder Compounds listed in the table 3 parts Clay 40 parts Talc 57 parts (9) Example 2 Compounds listed in the wettable powder table 75 parts Polyoxyethylene alkyl allyl ether 9 parts White carbon 16 parts Regarding the amount of spraying Although there is no particular restriction, when spraying on fields where crops are usually grown, active ingredient compounds (A,
, L) from 100 to 1500.1i'/IQa.

Also, when applying into soil, 1 to 8 kf? A,
1. /10a is appropriate. Of course, this is just a guideline, and it depends on the type of crop, the type of disease, the degree of damage,
The dosage may be adjusted as necessary, taking into consideration factors such as the season, weather, and drug dosage form.

Hereinafter, typical test examples will be shown to specifically explain the effects of the compounds of the present invention. However, these are merely examples, and it goes without saying that the application examples of the present invention are not limited to these.

Test Example-1 Spore germination inhibition test against pear black spot fungus <Test method> Alternari cultured on apricot medium for 7 to 10 days
a(lO) Kikuchiana conidia and a drug solution are mixed and adjusted to about 20 conidia per field of view under a microscope at 100x magnification.

This mixed suspension was dropped onto a slide glass at a temperature of 27°C and a humidity of 1.2ml. After keeping it at OO% for 20 hours, examine it under a microscope to check for spore germination.

Both were repeated twice, and the presence or absence of germination of approximately 200 spores was determined.
Check the degree.

Test Example-2 Spore germination inhibition test against citrus black spot fungus <Test method> Diaporthe citr cultured on dead citrus branches
Mix the conidia of conidia i and the drug solution, and adjust to about 20 conidia per field of view under a microscope at 100x magnification.

0.02 drop of this mixed suspension was placed on a slide glass, kept at a temperature of 27° C. and a humidity of 100° C. for 20 hours, and the presence or absence of spore germination was examined using a microscopic microscope.

Both were repeated twice, and the presence or absence of germination of approximately 200 spores was determined.
Check the degree.

<Test Results> Test Example-3 Pear Black Spot Efficacy Test <Test Method> A chemical solution diluted to a specified concentration was sprayed at 20 times per 5 leaves on the unfolded leaves of pears (variety: Uni Jussei), and air-dried indoors. did.

Alternaria cultured in apricot medium after air drying
Conidia of Kikuchiana were spray inoculated and left to stand for 3 days at 25° C. and humidity of 100%, and the diseased area was examined after 3 days.

However, the number of runs shall be 5.

<Test Results> Test Example-4 Citrus Black Spot Efficacy Test <Test Method> When the new shoots of potted mandarin oranges (variety: Natsukan) were developing, a sufficient amount of a chemical solution diluted to a specified concentration was sprayed and then air-dried in a greenhouse. . Diaporthe cultivated on mandarin orange branches
Immediately after spray inoculation with conidia of C. citri, temperature 2.
It was kept in the dark at 3°C and 100% humidity for 2 days. Two days later, the plants were left in a greenhouse, and the degree of disease onset was investigated 30 days after inoculation.

However, the number of runs shall be three.

(13) Disease severity Number of lesions 7 leaves 0 1 1-3 2 4-6 3 7-10 4 11- <Test results> Test example-5 Canine root wilt efficacy test <Test method> Canine root wilt yellow disease fungus (Fusariuw) oxysporum
Clay pots with a diameter of (14) 15 m+ are filled with soil artificially contaminated with chlamydospores of F. rophani). 910 radish seeds (variety: Aokubi Miyaju) that have been germinated in advance are sown on the surface of the pot, and the soil is covered with contaminated soil. Immediately, a chemical solution diluted to a predetermined concentration is uniformly applied to the surface, and then lightly sprinkled with water. after that,
Leave the pot in the greenhouse and water as needed.

60 days after treatment, the presence or absence of disease onset and its severity are investigated according to the following criteria.

However, the number of runs shall be 5.

Test Example-6 Efficacy Test for Pythium Seedling Blight (Test Method) Pythium apharid
ermatum) in a diameter of 15 mm.
Pour into an M clay pot. After sowing 20 pre-germinated cucumber seeds (variety: Sumo Hanshiro) on the surface, cover the soil with contaminated soil, and immediately sprinkle the equivalent of 317 m2 of a chemical solution diluted to the specified concentration uniformly over the surface. do. After irrigation, the plants were lightly watered and left in the greenhouse. During the test, the plants were watered appropriately, and 14 days after the treatment, the number of germinated plants and the number of lodging plants were examined, and the control value was calculated as follows.

<Test Results> Test Example-7 Bean Sclerotinia Disease Efficacy Test <Test Method> A chemical solution diluted with water to a specified concentration was applied to the first leaves of Japanese bean (variety: Masterpiece) at 10 m/(equivalent amount) per two leaves. After air-drying, the legume sclerotia fungus (Scleroteria sclerotide) cultured on PDA medium was sprayed.
iorum) was punched out with a cork polar and inoculated onto the leaf surface. Immediately after inoculation, the temperature is 23℃ and the humidity is 100℃.
The samples were placed under dark conditions. Three days after inoculation, the lesion area (17
) investigated.

However, the number of runs shall be 5.

<Test results> (18)

Claims (1)

[Scope of Claims] 1) General formula [wherein R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, an argyl group or a benzyl group, and Z is an alkylcarbamoyl group having 1 to 4 carbon atoms] a phenylcarbamoyl group substituted with chlorine or methyl group, or a benzoyl group substituted with chlorine or methyl group]. 2) General formula (1) [In the formula, R11d: hydrogen atom or methyl group, R2
represents a hydrogen atom, an alkyl group or a benzyl group,
2 represents an alkylcar-gumoyl group having 1 to 4 carbon atoms, a phenylcarbamoyl group substituted with chlorine or methyl group, or a benzoyl group substituted with chlorine or methyl group]. A disinfectant contained as an ingredient.