JPS606680A - Benzoxathiol-2-one derivative and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:A 1,3-benzoxathiol-2-one derivative shown by the formula I [R1 is 1-3C alkyl, or aryl, N,N-dimethylcarbonyl, alkylsulfonyl (1-3C), alkylcarbamoyloxy (1-4C), alkylthiocarbonyl (1-2C); R2 is H, OCH2, group shown by the formula II; R3 is H, or Cl; R4 is H, or OCH3]. EXAMPLE:5-N,N-Dimethylcarbamoyl-1,3-benzoxathiol-2-one. USE:Useful as an agricultural and horticultural fungicide. For example, effective against blast of paddy rice plant, alternaria blotch, blight of potato, etc. PREPARATION:A 1,3-benzoxathiole derivative shown by the formula III, for example, is reacted with a compound shown by the formula R5X (R5 is 1-3C alkylalkene, etc.; X is Cl, etc.) as a binder in an inert organic solvent at a reaction temperature from room temperature - the boiling point of the solvent, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 13-benzoxathiol-2-one derivative represented by the following general formula and a fungicide containing the compound as an active ingredient.

R or 4 (However, R,: CL-C3 alkyl, aryl, N
, N-dimethylcarbonyl, alkylsulfonyl (C+~C3), alkylcarbamoyloxy (c, ~ca), or alkylthiocarbonyl (C+~Cs), R2: H, 0CHs or S<S, R3: H or cl.

R4: represents H or OCHs. ) Representative examples of the compounds represented by the above general formula of the present invention are listed in Table 1.

For example, the compound of the present invention can be prepared using a 1,3-benzoxathiol derivative represented by the general formula 2 (indicating taste) according to the following reaction formula, and Rb"l is 01 to 1 in the formula (1). C3 alkylalkene, NXN-dimethylcarbamoyl, alkylsulfonyl and alkylthiocarbonyl; × is C
1, Bte and °I) in the presence of a binder (e.g., sodium alkoxide, sodium hydride, potassium carbonate, triethylamine, etc.) in an inert organic solvent that does not react with the binding agent. The reaction is carried out at a reaction temperature up to the boiling point.

In addition, in formula (ii), R, yco (where R6
(C1-C4 alkyl) is reacted in an aromatic hydrocarbon in the presence of triethylamine at a reaction temperature from room temperature to the boiling point of the solvent. After the reaction, the inorganic salt in the solvent is filtered off, the solvent is distilled off under reduced pressure, and the residue is recrystallized, or extracted with a solvent such as dichloromethane, washed with water and saturated sodium carbonate, and dried with anhydrous sulfuric acid. The solvent is distilled off, and if the residue is oily, it is purified by column chromatography, and if it is solid, it is recrystallized.

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

Synthesis Example 15-#, N-Dimethylcarbamoyl-13-benzoxathiol-2-one Anhydrous potassium carbonate IOy was suspended in 50me of acetonitrile to give 5-hydroxy-1,3-benzoxathiol-2-one 5y (0 , 03M) and reflux for 30 minutes while stirring. Cool to room temperature and add 3.2y (o, oaM) of NXN-dimethylcarbamoyl chloride to 10
The mixture was added dropwise over several minutes and refluxed for 2 hours while stirring again. The mixture was cooled to room temperature, the inorganic salts were filtered off, and the acetonitrile solution was distilled off under reduced pressure. The residual liquid is recrystallized from benzene. Yield 4
．． 3 no.

Synthesis Example 25-(tert-butylcarbamoyloxy)nia-phenylmercapto 1.3-benzoxathiol-2-one 5-hydroxy-7-phenylmercapto 1.3-
Benzoxathiol-2-one 2.81? (0.01M
) and tert-butyl isocyanate 1y (o, otn
) in benzene and add a few drops of triethylamine. After refluxing for 3 hours, the benzene solution was distilled off under reduced pressure and 5 rM of exo-hexane was added to crystallize. The crystals are filtered and recrystallized from methanol to obtain the desired product. Yield 1.9
The compounds of the present invention are effective in controlling a wide range of diseases in agricultural and horticultural crops, and the main ones include the following.

Water rice blast, leaf blight; Wheat spot disease.

Potato blight, summer blight.

Soybean downy mildew, spot disease, brown spot disease.

Tobacco epidemic.

Tea: anthracnose; beet: downy mildew, brown spot; vegetable: tomato: late blight, gray mold, leaf mold, wilt.

Kiucumber downy mildew, gray late blight, gray mold, scab, anthracnose, vine blight, vine split; onion downy mildew, gray rot; lettuce downy mildew; fruit trees citrus gray mold, black spot , I see, it's a disease.

Shingo monilia disease, scabrous blight; Persimmon botrytis, botrytis blight, anthracnose, and scab; Sushi scab.

Momo gray layer disease, scab disease, phomopsis rot; Pudoube disease, gray purpura disease, late mourning disease, etc.

As mentioned above, the compound of the present invention can be used as a fungicide for agriculture and horticulture, and it can be used as it is or mixed with a carrier (diluent) to form powders, granules, water preparations, emulsions, oils, and other suitable low-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 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 Example 2 Wettable powder Compounds listed in the table 75 parts Polykicech v7 Ayaki 7,2 Su, Ethe, 9 parts White carbon 16 parts Spread amount Although there are no necessarily restrictions on the amount of active ingredient compound (AX
As I), 50 to 1000y/1Oa1, and when applied to soil, about 2 to 8 Kg A-I/loa is appropriate. Of course, this is only a guideline and may be adjusted as necessary, taking into consideration 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 Rice Blast Efficacy Test (Test Method) An amount equivalent to zootlxoa of a predetermined concentration of a chemical solution is sprayed at the 3-leaf stage of potted rice (cultivar Futagokata). Rice blast fungus (Pyri-curaria or
yzae) conidia per 100x field of view under a microscope.
A suspension adjusted to zero was inoculated by spraying. Immediately after inoculation, incubate in the dark at a temperature of 23 parts and a humidity of 10 l.
After keeping it for 8 hours, it was left in a greenhouse, and after 10 days, the degree of disease onset was determined according to the following criteria.

However, the number of runs shall be three.

N: Number of leaves investigated <Test results> Test example 2 Rice sesame leaf blight efficacy test <Test method> Spray an amount equivalent to 200z/10a of a chemical solution with a prescribed concentration on the 6th leaf stage of potted rice (variety: Kogata). Spread.

Rice blast fungus (Cochl 1obo) cultured after air drying
A suspension of conidia of Conidia lus -miyabeanus) prepared at 40 conidia per 1 field of view at 100x with a microscope was inoculated by spraying. Immediately after inoculation, the temperature is 23℃ and the humidity is 1.
The seedlings were kept in the dark for 48 hours at a temperature of 0.00 cm, then left in a greenhouse, and 10 days after inoculation, the degree of disease onset was determined using the following criteria.

However, the number of runs shall be three.

N: Number of leaves investigated <Test results> Test example 3 Radish chlorosis efficacy test <Test method> Radish chlorosis fungus (Fusarinm oxysporum)
Soil artificially contaminated with chlamydospores of A. 5 raphani) is packed into an unglazed needle with a diameter of up to 15 mm. Sow 910 needles of radish seeds (variety: Aokubi Miyashige) that have been germinated in advance on the surface and cover with contaminated soil. Immediately, a chemical solution diluted to a predetermined concentration is uniformly applied to the surface, and then lightly watered. The pots are then left in the greenhouse and watered accordingly.

60 days after treatment, the presence or absence of disease onset is investigated according to the following criteria.

However, the number of runs shall be 5.

<Test results>

Claims (1)

[Claims] R 4 (where RI: C1 to C3 alkyl, aryl; N, N-dimethylcarbonyl, alkylsulfonyl (C1 to CS), alkylcarbamoyloxy (c+ to c4), or Alkylthiocarbonyl (c, ~C2) Rs: HX0CH* or S, Rs: H or a
t. R4: represents H or OCHs. ) represented by 1,
3-benzoxathiol-2-one derivative. 2) General formula (However, R1: Cx-C3 alkyl, aryl, N
, N-dimethylcarbonyl, alkylsulfonyl (C+~CS), alkylcarbamoyloxy (Ct~c,), or alkylthiocarbonyl (cr~C2), R: H,0CHs or Sbep>, Rs:H or cl. Ra: represents H or OCHs. ) represented by 13
- An agricultural and horticultural fungicide containing a benzoxathiol-2-one derivative as an active ingredient.