JPS606673A - 1,3,5-dithiazin-5-one derivative, and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:A 2-benzenesulfonylimino-1,3,5-dithiazin-6-one derivative shown by the formula(R1 is H, 1-4C alkyl, or halogen; R2 is 1-6C alkyl, cyclohexylalkenyl, or phenyl). EXAMPLE:5-Aryl-2-benzenesulfonylimino-1,3,5-dithiazine-6-one. USE:An agriculatural and horticultural fungicide effective against controlling blights of a wide range of agricultural and horticultural crops. PREPARATION:Sodium benzenesulfonyliminocarbodithioate is reacted with an N-chloromethyl-N-alkyl(or aryl) carbamoyl chloride, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 2-benzenesulfonylimino-1,a,s-dithiazin-6-one derivative represented by the following general formula and a fungicide containing the compound as an active ingredient.

(However, R1: H, Ct to C4 alkyl or halogen atom, R2: C1 to C6 alkyl, cyclohexylalkenyl or haphenyl.) Representative examples of the compounds represented by the above general formula of the present invention are shown below. A typical example is as shown in Table 1.

The dithiazine derivative (1) of the present invention includes, for example, the sodium salt of benzenesulfonyliminocarbodithioate and N-chloromethyl-alkyl (or aryl).
It can be produced by reacting with carbamoyl chloride. In this reaction, both may be mixed in approximately equal moles, or in some cases, a slightly larger amount of one of the two may be added.

In order for this reaction to proceed smoothly, it is preferable to carry out the reaction in an organic solvent. In this case, the solvent may be acetone, ketones such as methane, aromatic hydrocarbons such as benzene toluene, etc. It is preferable to use a mixed solvent of two types with water.

This reaction is usually preferably carried out at a temperature of 30 to 100°C, and in some cases may be carried out near the reflux temperature of the solvent.

Reaction times range from several hours to several tens of hours.

Although the presence of a catalyst is not essential for this reaction, when the reaction is carried out in a mixed solvent of aromatic hydrocarbon and water, tetra-butylammonium bromide, 18-crown-6, etc. may be used as a phase transfer catalyst.

After completion of the reaction, if the reaction solvent is miscible with water, water is added and the resulting crude product is purified using recrystallization or column chromatography. For water and aromatic hydrocarbons,
The organic solvent was separated, washed with saturated saline, and then dehydrated.
Obtained by distilling off the solvent.

The crude product is purified by crystallization or column chromatography.

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

Synthesis Example 1 7.6 g (0, 045M) was added dropwise.

Stir at room temperature for 1 hour, then continue stirring for 6 hours while refluxing the solvent. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the residue was extracted with dichloromethane. Wash the dichloromethane twice with saturated brine and dry over anhydrous sodium sulfate. When the solvent was distilled off and diethyl ether was added to the residue, crystallization occurred. The crystals were separated and washed with a small amount of diethyl ether to obtain the desired product. Yield: 4.6 g Synthesis Example 2 15.6 g of disodium salt of 2-(p-chlorobenzenesulfonylimino)-5-phenyl-1,a, 5-dithiadi/-6-one p-chlorobenzenesulfonyliminocarbodithiolate (0 , 05M) in 50 ml of water and stirred at room temperature to give 6.2 g of N-10 romethyl-N-phenylcarbamoyl chloride.
(0.03M) and tetra-ni-butylammonium promi)” 0.5 g tr F# x 7100
Add ml of solution dropwise. After dropping, while refluxing the solvent,
Stir for a while. After cooling to room temperature, the toluene layer is separated, washed twice with saturated brine, and dried over anhydrous sodium sulfate.

The solvent was distilled off under reduced pressure and the remaining 5 moles were recrystallized from ethanol.

Yield: 5.1 g The compounds of the present invention are effective in controlling diseases of sensitive agricultural and horticultural crops, and the following are the main examples.

Muzy rice Blast, Sesame leaf root disease Wheat Spot disease Potato Phytophthora, Summer Phytophthora Dog bean Downy mildew, Spot disease, Brown spot Tobacco Red star blight, Phytophthora tea Anthracnose beet Downy mildew, Brown spot vegetable Tomato Phytophthora, Gray mold, leaf mold, ring spot Cucumber Downy mildew, Botrytis blight, Botrytis blight, Scotch blight, Anthracnose, Vine blight Lettuce Downy mildew Citrus Botrytis, black spot, scab Apple
monilia, scab, leaf spot, gray mold,
No defoliation, anthracnose, and horn spot defoliation. Scotch blight, black spot peach. Peach blight, scabrous blight, fuomopress rot.
Downy mildew, gray mold, gray mold, 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 or mixed with other types of fungicides, insecticides, herbicides, fertilizers, etc. .

Example 1 Compounds listed in the powder table 3 'μ Clay 40 parts Talc 5 υ parts Example 2 Wettable powders Compounds listed in the table 75 1 Polyoxyethylene alkyl oryl ether 9 ■White carbon 1 [parts amount However, when spraying on fields where crops are grown, the active ingredient compound (
A.1. ) as 50~t, ooo g/10a,
In addition, when applying throughout the soil, 2 to 8' kg A,
1. /loa 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 in order to clarify the effects of the compounds of the present invention in detail. However, these are merely examples, and it goes without saying that the application f1 of the present invention is not limited to these.

Test Example 1 Spore germination inhibition test against citrus black spot fungus <Test method> Diaporthe cit' leaves cultured on dead citrus branches
Conidia of ri and a drug solution are mixed and adjusted so that the number of conidia is about 20 per field of view under a microscope at 100x magnification.

Place this mixed suspension on a slide glass at 0.02 mA'.
After dropping the mixture and keeping it at a temperature of 27° C. and a humidity of 100° C. for 20 hours, the chains are tested to determine whether or not spores have germinated.

Each test was repeated twice, and the presence or absence of germination of about 200 spores was examined.

<Test results> Test example 2 Pear black spot efficacy test <Test method> For the development of pears (variety: Nijusseiki), a chemical solution diluted to a specified concentration was sprayed at 20 ml per 5 leaves and air-dried indoors. .

Alternaria K cultured in apricot medium after air drying
Conidia of 1 kuchiana were spray-inoculated and immediately left to stand for 3 days at 25° C. and humidity of 100° C. After 3 days, the affected area was examined.

However, the number of runs shall be 5.

(Test results) Test example 3 Spore germination inhibition test against pear spot fungus <Test method> Alte-rna cultured in apricot medium for 7 to 10 days
The conidia of Ria Kikuchiana and the drug solution are mixed and adjusted to about 20 conidia per 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° C. for 20 hours, and examined under a microscope to check for spore germination.

Each test was repeated twice, and the presence or absence of germination of about 200 spores was examined.

<Test results> 62

Claims (1)

[Scope of Claims] 1) 2-benzenesulfonyl represented by the general formula (R1: H, C1-C4 alkyl or halogen atom, R2: C1-Ce alkyl, cyclohexylalkenyl or haphenyl); imino-1,3,5-dithiazine-6
-one derivative. 2) 2-benzenesulfonylimino-1,3 represented by the general formula (RI: H, C1 to C4 alkyl or halokene atom, R2: C1 to C6 alkyl, cyclohexylalkenyl or haphenyl t) ,5-dithiazine-6
An agricultural and horticultural fungicide containing a -one derivative as an active ingredient.