JPS608211A - Agricultural and horticultural fungicide - Google Patents

Abstract

PURPOSE:An agricultural and horticultural fungicide comprising a specific 5- methyl-2-pyrazoline derivative as an active ingredient. CONSTITUTION:The titled fungicide containing a compound shown by the formula I [Z is R<1>CO, R<2>R<3>NCO, R<4>NHCS, R<5>OCO, R<6>SCO, R<7>SO2, R<8>R<9>N-SO2, or group shown by the formula II; R<1> is (substituted)alkyl, or (substituted) aryl; R<2> is alkyl, cycloalkyl, etc.; R<3> is H, or alkyl, R<4> is (substituted)alkyl, or alkenyl; R<5> and R<6> are alkyl; R<7> is alkyl, or (lower) aryl; R<8> and R<9> are alkyl or linked to form alkhlene; X is halogen or R<10>NH(R<10> is alkyl)] such as 1-dichloroacetyl-5- methyl-2-pyrazoline, as an active ingredient. The compound shown by the formula I is obtained by reacting 5-methyl-2-pyrazoline with an acid halide, an acid anhydride, a halocarbonic acid (thio)ester, etc. in the presence of a proper base optionally in an inert solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agricultural and horticultural fungicide containing a pyrazoline derivative represented by the following general formula as an active ingredient.

General formula (wherein 2 is a group R'CO-, R2R3NC0-, R'N
HC8-.

R1 represents a lower alkyl group having 1 to 4 carbon atoms which may be substituted with one or more halogen or phenyl groups, or an aryl group which may be substituted with a halogen or lower alkyl group; , R2 represents a lower alkyl or 7-chloroalkyl group having 1 to 6 carbon atoms, or an aryl group optionally substituted with halogen or lower alkyl; R5 represents a hydrogen atom or a lower alkyl group; R4 represents an alkenyl group; represents a lower alkyl or aryl group having 1 to 4 carbon atoms which may be substituted with a group or a phenyl group, R5 and R6 represent a lower alkyl group, and R7 is substituted with lower alkyl or R8 and R9 represent lower alkyl groups, or R8
, X to which R9 may be bonded to form a lower alkylene bridge represents a halogen or a group R''ONH-, and Rio is a lower alkyl having 1 to 4 carbon atoms. It can be synthesized by the general method shown in the formula.

Due to the condensation of crotonaldehyde and hydrazine/hittlede. Known compounds 5-methyl-2-pyrazoline (II) obtained by e. , N-sialkylsulfamoylnolide and optionally in the presence of a suitable base, optionally using an inert solvent such as benzene, toluene, methylene chloride, carbon tetrachloride, etc. ~1
Either react at 50°C for 30 minutes to several hours, or react with isocyanates and optionally an inert solvent such as benzene, toluene, methylene chloride, carbon tetrachloride, etc.
℃ for 30 minutes to several hours, or at 0℃ to 150℃ for 30 minutes to several hours using an appropriate solvent such as ethanol with inthiocyanates as necessary.
4,6-zochloro-2-(5-methyl-2-pyrazolino)-1.3 obtained as necessary by reacting with cyanuric chloride at 0°C in the presence of a suitable base such as alkali hydroxide.
．． Typical synthesis examples are shown below and will be explained in more detail.

[Synthesis Example 1] Synthesis of 1-fuchloroacetyl-5-methyl-2-pyrazoline 3.09% of 5-methyl-2-pyrazoline and 3.09% of dichloroacetyl chloride were dissolved in 30ml of benzene.
After heating under reflux for an hour, the reaction solution was washed with a 5% hydrochloric acid solution, a saturated hydrogen carbonate solution, and a saturated saline solution.
It was dried with anhydrous sodium sulfate. When the solvent was distilled off under reduced pressure, 299 1-dichloroacetyl-5-methyl-2-pyrazoline was obtained as an oil.

[Synthesis Example 2] Synthesis of 1-(o-chlorophenylcarbamoyl)-5-methyl-2-pyrazoline 2.0 g of 5-methyl-2-pyrazoline. - Chlorphenyl in cyanide) 2.0g was dissolved in 30ml of benzene and heated under reflux for 1 hour.
After washing with saturated sodium bicarbonate solution and saturated brine, it was dried over anhydrous sodium sulfate. When the solvent was removed by vacuum distillation, 2.91/O1-(o-chlorophenylcarbamoyl)-5-methyl-2-pyrazoline was obtained as crystals with a melting point of 870-88.0°C.

[Synthesis Example 3] 1-(t-butylthiocarbamoyl)-5-methyl-2
- Synthesis of pyrazoline 3.0 g of 5-methyl-2-pyrazoline and 3.0.9 g of t-butyl inthiocyanate were dissolved in 30 mA of ethanol and heated under reflux for 2 hours. After distilling off the ethanol under reduced pressure, the obtained The resulting residue was dissolved in 50ml of benzene, washed with 5% hydrochloric acid solution, saturated sodium bicarbonate solution, and saturated brine, and then dried over anhydrous sodium sulfate.

When the solvent was distilled off under reduced pressure, 4.4 g of 1-(t
-butylthiocarbamoyl)-5-methyl-2-pyrazoline was obtained as crystals with a melting point of 108.0-109.0°C.

[Synthesis Example 4] 4. Synthesis of 6-dichloro-2-(5-methyl-2-pyrapurine)-1,3,5-)rianone Cyanuric chloride6.
5.0.9 in 60% acetone aqueous solution at 0℃
5-methyl-2-pyrazoline 3.0
&, Sodium hydroxide aqueous solution (1,40f//10
ml'H20) was sequentially added dropwise while maintaining the temperature inside the reaction system at 0°C, and the mixture was further stirred for 2 hours. The precipitated crystals were washed with water and dried every day to obtain 6.61 g of 4,6-zochloro-2-(5-methyl-2-pyrazolino)-1,3,5-triazine as a white powder.

[Synthesis Example 5] 6-chloro-4-ethylamino-2-(5-methyl-2
Synthesis of 6-cyclo2-(5-methyl-2-pyrazolino)-1,3,5-triazine4. Og was suspended in 40 ml of 50% acetone aqueous solution at room temperature, and 2.2 g of ethylamine 70% aqueous solution was added to this, and the temperature in the reaction system was adjusted to 40°C.
Add the mixture dropwise while maintaining the temperature below, and stir for an additional 2 hours.

When the precipitated crystals were washed with water and dried daily, 2.7 g of 6-
Chloro-4-ethylamino-2-(5-methyl-2-pyrazolino)-1,3,5-triazine has a melting point of 1415
Obtained as crystals at ~1425°C.

Typical examples of the compounds of the present invention include those shown in Table 1.

The NMR numbers in the table are 60 MHz, and compounds 1-45
Compounds 46 to 51 were measured in deuterated chloroform and in deuterated dimethyl sulfoxide using tetramethylsilane as a reference substance, and the symbols s, d, and t
+q+m has peak patterns of 1.2, 3, 4, respectively.
Multiple lines and broad indicate a wide beak i9 turn. In addition, the infrared absorption spectrum indicates the main absorption wavenumber measured with a film or KBr.

The compounds of the present invention are effective in controlling diseases of a wide range of agricultural and horticultural crops, including reeds and the following.

Paddy rice: rice blast, sesame leaf blight, sheath blight, leaf blight; wheat powder, spots, rust, snow rot, sclerotium; potato blight, summer thinning, black bruise; legumes: brown spots, rust, spots, greasy , Sclerotinia; Tobacco Wildfire, Akaboshi, Phytophthora; Brown red burn, mochi, net mochi, anthracnose, ring blight; Beet blight, brown spot, seedling blight; Tomato blight, blight, gray mold, leaf mold , wilt, sclerotia, seedling damping-off, ring spot; cucumber gray mold, downy mildew, gray blight, sclerotia, black star,
Seedling blight, anthracnose, vine blight, vine splitting, powdery mildew; Radish black rot, soft rot, yellowing, black spot, downy mildew; Onion soft rot, downy mildew, gray rot, rust; Lettuce soft rot, sclerotia Diseases; Citrus gray mold, canker, black spot, scab; apple monilia, black star, leaf spot leaf spot, powdery mildew; persimmon gray mold, round star leaf drop, horn spot leaf fall, anthracnose 1 pear, red star, black star, black spot Diseases; peach gray star, black star, phomopsis rot, borehole bacterial disease;
Grape blight, black pox, gray mold, rust, powdery mildew, etc.

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

Example 1 Compounds listed in the powder table 3 parts Clay 40 parts Talc 57 parts Example 2 Wettable powder Compounds listed in the table 75 parts Polyoxyethylene alkyl ether 9 parts White carbon 16 parts There are no restrictions on the amount of spraying. However, when spraying on fields where crops are grown, the active ingredient compound (, A
-1,) as 50-1ooog/loa, or 2-8 kg A, I,/1 when applied in soil.
Approximately 0a is appropriate. Of course, this is only a guideline and may be adjusted as necessary, taking into account factors such as the type of crop, type of disease, degree of damage, season, weather, and dosage form of the drug.

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 Test method for antibacterial activity against plant pathogenic bacteria> Conidia of plant pathogenic bacteria cultured in a specified medium are uniformly mixed in a PSA medium, and a certain amount is poured into a specified container to form a uniform plate. . After solidification, a filter paper with a diameter of 8 mm that has absorbed a certain amount of the drug at a predetermined concentration and air-dried is placed thereon, and the diameter of the inhibition circle produced after 48 hours of culture is measured.

However, the number of stations shall be two.

Test results> p, o, : Rice blast fungus C, t, : Bovine anthracnose fungus, C, : Citrus black spot fungus A, Ni, : Pear black spot fungus B, C, : Vegetable gray mold fungus test Example-2 Pear black spot efficacy test <Test method>.

To develop pears (variety 220th century), a chemical solution diluted to a predetermined concentration was sprayed at 20 ml per 5 leaves and air-dried indoors.

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

However, the number of runs shall be 5.

Test Results> Test Example-3 Rice Blast Efficacy Test Test Method> 40 potted rice plants (cultivar Nijukoku) at the 3-leaf stage were sprayed with an amount equivalent to 200t/10a of a chemical solution of a prescribed concentration. Spray inoculate with a spore suspension adjusted to
, and placed under dark conditions with a humidity of 10%. After 48 hours, the seeds were taken out and left in a greenhouse. One day after inoculation, the degree of disease onset was investigated, and the control value was calculated as follows.

However, the number of runs shall be three.

Test Example-4 Test method for trial sales of radish chlorosis efficacy
After filling soil contaminated with chlamydospores of P. porumf, rapbani) into pots with a diameter of 15 cm, 15 seeds of sprouted radish (variety: Aokubi Miyaju) were sown per pot.
The soil was covered with contaminated soil. 3 of the drug solution immediately diluted to the prescribed concentration.
An amount equivalent to t/m2 was irrigated uniformly over the surface. After irrigation, the surface was lightly sprinkled with water and then left in the greenhouse. After the treatment, the plants were watered appropriately and investigated 60 days after the treatment, and the disease severity was calculated using the following method.

However, the number of runs shall be 4.

Claims (1)

[Claims] General formula (wherein 2 is a group RCO-, R2R3NC0-, R'NI
(C8-. R50CO-, R65CO-, R'5O2-, R8R9
N-8O2-, or L R1 is substituted with lower alkyl having 1 to 4 carbon atoms, which may be substituted with one or more ]-locations or phenyl groups; R2 represents an aryl group which may be substituted with lower alkylcycloalkyl having 1 to 6 carbon atoms, or an aryl group which may be substituted with lower alkyl having 1 to 6 carbon atoms. R4 represents a hydrogen atom or a lower alkyl group, R4 represents a lower alkyl or aryl group having 1 to 4 carbon atoms which may be substituted with an alkenyl group or a phenyl group, R7 represents a lower alkyl group, and R5 and R6 represent a lower alkyl group; R represents a lower alkyl group or an aryl group which may be substituted with halogen or lower alkyl; R and R represent a lower alkyl group, or R represents a lower alkyl group;
X to which R may be bonded to form a lower alkylene bridge represents a location or a group R1ONH-, and RI
An agricultural and horticultural fungicide whose active ingredient is a pyrazoline derivative represented by (Q represents lower alkyl having 1 to 4 carbon atoms).