JPS6011460A - Carbothioamide derivative and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula [R1 and R2 are methyl or ethyl, or together with adjacent N atom, form 6-membered heterocyclic group having 4-5C alicyclic hydrocarbon group and optionally having O atom; R3 is 1-8C alkyl, cycloalkyl, alkenyl or (halogen-substituted) benzyl, naphthyl, etc.]. EXAMPLE:p-Fluorobenzenesulfonyl N,N-dimethylcarbothioamide. USE:An agricultural and horticultural fungicide. Effective to blast, helminthosporium leaf spot, etc. of paddy rice plant, leaf spot and powdery mildew of wheat, late blight of potato, etc. PREPARATION:The compound of formula can be produced by dissolving N,N- dialkylthiocarbamoyl chloride in an aromatic hydrocarbon such as benzene, toluene, etc., and adding the solution dropwise to an aqueous solution of sodium sulfinate of formula R3-SO2Na at room temperature to effect the reaction of the components.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to Cal? The present invention relates to a thioamide derivative and an agricultural and horticultural fungicide containing the compound as an active ingredient.

-2 (R1 and R2 are methyl, ethyl, or R1 and R2 together with the adjacent N atom form an alicyclic hydrocarbon group having 4 to 5 carbon atoms, or a 6-membered alicyclic hydrocarbon that may contain an oxygen atom) represents a heterocycle of the formula -gCX (where X is chlorine, fluorine, bromine, etc.); halogen atom,
(representing alkyl, cycloalkyl, alkoxy, haloalkoxy, phenoxy, alkylthio, trifluoromethyl and haloalkyl having 1 to 6 carbon atoms)).

The compound of the present invention can be synthesized, for example, by the following method.

Sodium sulfinate represented by the formula R3-8o2Na is dissolved in water, and a solution of N,N-noalkylthiocarpamoyl chloride dissolved in an aromatic hydrocarbon such as benzene or toluene is added dropwise at room temperature. After dropping, the reaction is carried out at a temperature from the chamber to the boiling point of the solvent.

After the reaction, the organic layer is separated, washed with saturated brine, and dried over anhydrous calcium chloride. The solvent is eluted under reduced pressure, and the residue is eluted with silica gel column chromatography or Kehenzen, or is obtained by recrystallization from an alcoholic solvent such as methanol or ethanol.

Typical synthesis examples will be shown below and explained in more detail.

Synthesis Example 1 p-Fluorobenzenesulfonyl N,N-tmethylcar? Thioamide sodium p-fluorobenzenesulfinate dihydrate 34.3.9 (0.157M) was dissolved in 150 cc of water and stirred at room temperature to prepare N,N-tumethylthiocarbamoyl chloride 18.6Ii (0.15M). 150 cc of benzene solution is added dropwise over 10 to 15 minutes.

After dropping, the solution was vigorously stirred while refluxing the solvent for 3 hours. After cooling to room temperature, the benzene layer was separated, washed twice with saturated brine, dried over anhydrous calcium chloride, and the solvent was eluted under reduced pressure. When the residue is recrystallized from methanol, the target product (compound 2
0) is obtained. Yield: 9.9 g Synthesis Example 2 p-Nofluoromethoxybenzenesulfonyl N,N-dimethylcarbothioamide 9.2 g (0.04 M) of dihydrate of sodium p-difluoromethoxybenzenesulfinate was dissolved in 70 cc of water and stirred at room temperature. Benzene solution of 5g (0.04M) of N,N-dimethylthiocarbamoyl chloride and tetra-n-butylammonium bromide o,iy 7
Add 0CC dropwise over 10-15 minutes. 5 hours after dropping5
Stir vigorously at 0°C.

After cooling to room temperature, the benzene layer is separated, washed twice with saturated brine, and dried over anhydrous calcium chloride. When the solvent was eluted under reduced pressure and the residue was recrystallized from methanol, the target product (compound 1) was obtained.
5) is obtained. Yield: 3.6g Synthesis Example 3 8.85' (0.03M) of p-7 enoxybenzenesulfonyl-N,N-tetramethylenecarbothioamide sodium p-phenoxybenzenesulfinate dihydrate was dissolved in 50 cc of water at room temperature. Stir and add 4.5 g (0.03 M) of N,N-tetramethylenethiocarbamoyl chloride and tetra-n-
50 ml of a benzene solution of 0.11 butylammonium bromide is added dropwise over 10 minutes.

The solvent is vigorously stirred under reflux for 3 hours after the addition. After cooling to room temperature, the benzene layer was separated, washed twice with saturated brine, dried over anhydrous calcium chloride, and the solvent was eluted under reduced pressure. The desired product (compound 7) is obtained by recrystallizing the residue from methanol. Yield 3.0g Synthesis Example 4 m-IJ fluoromethylbenzenesulfonyl N,N
Dissolve N,N-trimethylthiocarbamoyl chloride 8# (0.06M) in 1'00 ml of water and stir at room temperature. ) of toluene 10
Add the 0M solution dropwise. After dropping, the solution was stirred vigorously while refluxing the solvent for 3 hours. After cooling to room temperature, the toluene layer was separated, washed twice with saturated brine, and dried over anhydrous calcium chloride. The solvent was eluted under reduced pressure, and the residue was subjected to 7 column column chromatography and eluted with benzene (Compound 28).
Yield 4.8g Synthesis Example 5 n-Butanesulfonyl N,N,-tumethylcarbothioamide n-butanesulfinate sodium dihydrate 10.8
g (0.06M) in 100 cc of water, and while stirring at room temperature, a benzene solution of 7.4 g (0.06M) of N,N-dimethylthiocarbamoyl chloride (xoom
/+). After dropping, the mixture was stirred at 30-40°C for 2 hours, and then vigorously stirred for 2 hours while refluxing the solvent. After cooling to room temperature, the benzene layer was separated and diluted with saturated saline.
Wash twice and dry over anhydrous calcium chloride. The solvent was eluted under reduced pressure, and the residue was subjected to 7-licaglu column chromatography and eluted with benzene di-hexane (1:2) to obtain the desired product (compound 36). Yield: 4.8 g Various compounds represented by the above general formula of the present invention are synthesized by a similar method, and representative compounds are shown in Table 1.

However, in compounds (1) to (47), R4 and R2 are CH3,
CH3; In (48) to (54), R1 and R2 are -(C2
H4)0(C2H4)-; R4 in (55) to (68)
, R2 is -(C2H2)4-; (69) to (81)
Here, C2H5 and C2H5 are represented.

The compounds of the present invention shown in Table 1 are effective in controlling diseases of agricultural and horticultural crops, and the main ones include the following.

Paddy rice blast, sheath blight, sesame leaf blight: wheat spot, powdery mildew, yellow rust, sclerotium; potato late blight, summer wasting disease, scab, black bruise; soybean downy mildew 1 Spot disease, brown spot disease,
Sclerotinia rot, rust; Tobacco red star blight, late blight; brown net blast, rice blast, anthracnose two-ring spot; beet downy mildew, brown spot,
Seedling damping off: vegetable tomato late blight, gray mold, single leaf mold,
Wilt, Sclerotinia blight, Seedling damping-off 2-ring disease: Cucumber downy mildew, Gray Phytophthora, Botrytis mold, Sclerotinia blight, Sclerotinia blight, Seedling damping-off,
Anthracnose, vine blight, vine splitting, powdery mildew; radish downy mildew, yellow wilt, black spot; onion downy mildew, gray rot, rust; lettuce downy mildew, sclerotium; Fruit trees Citrus gray mold, black spot, scab; apples Monilia disease, scab 1 spot defoliation.

Powdery mildew; Persimmon Botrytis, 1-yen star leaf drop disease, anthracnose,
Horn blotch defoliation: pear, scab, scab; peach, scab, phomozosis, downy mildew,
black pox, botrytis, and rust.

Powdery mildew, late rot; As mentioned above, the compound of the present invention can be used as a fungicide for agriculture and horticulture, but it can also be used as it is or mixed with a carrier (diluent) to make powders, granules, irrigation agents, emulsions, oils, etc. It is used as a suitable agent commonly used in agricultural chemical formulations. In this case, a spreading agent, an emulsifier, a wetting agent, a fixing agent, etc. are used as necessary, and it can also be mixed with other types of fungicides, insecticides, herbicides, fertilizers, etc.

Example 1 Powder Compound listed in table 3 parts v -40 parts Melt 57 parts Example 2 Wettable powder Compound listed in table 75 parts I lyoxyethylene alkyl allyl ether 9 parts White car? There are no restrictions on the amount of spraying, but usually when spraying on fields where crops are grown, the active ingredient compounds (A,
1. ), 50 to 1000.9/10a, and when applied to soil, approximately 2 to 81 QA/1 oa 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 Antibacterial activity test against plant pathogenic bacteria <Test method> 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 create a uniform grate. . After solidifying, place a piece of paper with a diameter of 8 gourds on it that has absorbed a certain amount of the drug at a predetermined concentration and air-dried.
The diameter of the inhibition circle produced after 8 hours of incubation is measured.

However, the number of stations shall be two.

Test Example-2 Spore germination inhibition test against pear black spot fungus Test method> Alternari cultured on apricot medium for 7 to 10 days
akikuchiana conidia and the drug solution are mixed and adjusted so that the number of conidia is about 20 per field of view under a microscope with a magnification of 100. Spread this mixed suspension 0.02 m on a slide glass.
After adding 1 drop and keeping the temperature at 27°C and humidity at 100°C 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 results> Test example-3 Pear black spot disease efficacy test <Test method> A chemical solution diluted to a specified concentration was sprayed at 20 ml per 5 leaves on the unfolded leaves of pears (variety: Nijusseiki), and air-dried indoors. did. Air dry reading, Alternaria cultured in apricot medium
The conidia of Kikuchjana were inoculated by spraying, and immediately left to stand for 3 days at 25° C. and 100% humidity, and after 3 days, the affected area was examined.

However, the number of runs shall be 5.

<Test results> Test example-4 Spore germination inhibition test against citrus black spot fungus <Test method> Diaporthe citr cultured on dead citrus branches
Mix the conidia (i) and the drug solution, and adjust the amount to about 20 conidia per 1 field of view under a microscope at 100x magnification.

A drop of 0.02 ml of this mixed suspension is placed on a slide glass, kept at a temperature of 27° C. and a humidity of 100% for 20 hours, and then subjected to microscopic examination to examine the presence or absence of spore germination.

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

<Test Results> Test Example-5 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. . DLaporthe cultured 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.

N2 Survey Total Leaf Number Test Example-6 Rice Blast Efficacy Test <Test Method> At the 3rd leaf stage of potted rice (variety: Kogata), an amount equivalent to 2 O0l/ ], Oa of a chemical solution with a prescribed concentration was sprayed. do.

Rice blast fungus (Pyriculari) cultured after air-drying
A suspension of 40 conidia of A. aoryzae per field of view under a microscope at 100 magnification was inoculated by spraying.

Immediately after inoculation, the plants were kept in the dark at a temperature of 23° C. and a humidity of 100% for 48 hours, and then left in a greenhouse. Ten days after inoculation, the degree of disease onset was determined using the following criteria.

However, the number of runs shall be three.

N: Inspected leaf number test example-7 Rice sheath blight efficacy test <Test method> First leaves of Incane (variety: Masterpiece) were cut and removed, and 20 m of a chemical solution diluted to a specified concentration was applied to 10 first leaves.
1 was sprayed and air-dried indoors. After air-drying, the rice sheath blight fungus (Rhizocto blight) was cultured in PDA medium in advance.
A bacterial pulp of P. ria 5olari IA) was punched out with a cork polar and inoculated. Immediately after inoculation, the plants were kept in a constant temperature room at a temperature of 28° C. and a humidity of 100% for 4 days, and then the diseased area was investigated.

However, the number of rows was 10, and 10 primary leaves were examined.

<Test Results> Test Example-8 Legume Sclerotinia Disease Efficacy Test <Test Method> First leaves of Ink 8 (variety: Masterpiece) were cut and removed, and 20ml of a chemical solution diluted to a specified concentration was applied to 10 first leaves.
1! After spraying and air drying indoors, apply PD in advance.
Bean Sclerotinia bacterium (Sclerotivi) cultured in A medium
A sclerotiorum) fungus was punched out with a cork polar and inoculated. Immediately after inoculation, the temperature was 28°C.
After keeping it in a constant temperature room with 100% humidity for 4 days, the diseased area was investigated.

However, the number of rows was 10 and 10 primary leaves were examined.

<Test Results> Test Example-9 Radish Yellowing Disease Efficacy Test <Test Method> Radish Yellowing Disease Fungus (Fusarium oxysporum)
Clay pots with a diameter of 15 cm are filled with soil artificially contaminated with chlamydospores of A. 5 raphani). 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, the surface is uniformly coated with a chemical solution diluted to a predetermined concentration, and then lightly rubbed. The pots are then left in the greenhouse and watered accordingly.

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 rows was 5, and 50 seedlings were investigated.

Test Example 10 Tomato Late Blight Efficacy Test Test Method> An amount equivalent to 2007710a diluted to a predetermined concentration was sprayed on potted tomatoes (variety Nidai Fukuju) at the two-leaf stage. After air-drying, pre-cultured Tomato Phytophthora blight (Phytophthora blight)
zoospores of Tophthora 1nfestars) were spray inoculated and immediately kept in a constant temperature room at 20° C. and 100% humidity for 7 days, and the degree of disease onset was examined using the following criteria.

However, the number of rows shall be 20, and 40 leaves will be examined, and the numbers will be listed according to the degree of disease.

Claims (1)

[Claims] 1) General formula (wherein R1 and R2 are methyl, ethyl or R1゜R
2 together with the adjacent N atom has an alicyclic hydrocarbon group having 4 to 5 carbon atoms or may contain an oxygen atom 6
represents a membered heterocycle, and R5 is a pencil or naphthyl which may be substituted with an alkyl, cycloalkyl, alkenyl or halogen atom having 1 to 8 carbon atoms, or atom,
Represents alkyl, cycloalkyl, alkoxy, haloalkoxy, phenoxy, alkylthio, trifluoromethyl and hyhaloalkyl having 1 to 6 carbon atoms. )) Carbothioamide derivative. 2) General formula (where R1 and R2 are methyl, ethyl or R1゜R
2 together with the N atom in instant contact may have an alicyclic hydrocarbon group having 4 to 5 carbon atoms or may contain an oxygen atom 6
R3 is a pencil or naphthyl or a formula -()-X (where X is chlorine, fluorine, Halogen atoms such as bromine,
It includes alkyl, cycloalkyl, alkoxy, haloalkoxy, phenoxy, alkylthio, trifluoromethyl and haloalkyl having 1 to 6 carbon atoms. )) An agricultural and horticultural fungicide containing a carbothioamide derivative as an active ingredient.