JPH0383972A - Thiadiazinone derivative, production of the same derivative and control agent of plant disease containing the same derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A thiadiazinone derivative expressed by formula I [R<1> and R<2> are lower alkyl, H or alkylene in bonding R<1> with R<2>; R<3> is H or lower alkyl; R<4> is lower alkyl or phenyl containable substituting group (halogen or lower alkyl)]. USE:Used as controlling agent of plant disease. Furthermore, used as insecticide, miticide, herbicide, plant growth-regulating agent or intermediate of agricultural chemical or medicine. PREPARATION:Ketone- or aldehyde-derivative expressed by formula II is reacted with hydrazine derivative expressed by the formula R<4>-NH-NH2 and thioglycol derivative expressed by formula III in the presence of a catalyst such as ammonium carbonate, as necessary, at a temperature of 0-150 deg.C to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thiadiazinone derivative, a method for producing the same, and a plant disease control agent containing the same as an active ingredient.

<Prior Art> Conventionally, various compounds have been used as plant disease control agents, but it cannot be said that they are completely satisfactory.

<Problems to be Solved by the Invention> The object of the present invention is to develop a compound yJAM;x that has an excellent control effect against plant diseases.

Means for Solving the Problems> In order to achieve the above object, the present inventors have made extensive studies and found that thiadiazinone derivatives have excellent bactericidal efficacy, and have conducted further studies. As a result, the present invention was achieved. That is, the present invention relates to the general formula [wherein R1 and R1 are the same or different and represent a lower alkyl group or a hydrogen atom, or R1 and R2 combine to represent an alkylene group, and R11 represents a hydrogen atom or a lower alkyl group] In the formula, R4 represents a lower alkyl group or a phenyl group optionally substituted with 10 G atoms or a lower alkyl group. ] Thiadiazinone derivative (hereinafter referred to as the compound of the present invention),
The present invention provides a method for producing the same and a plant disease control agent containing the same as an active ingredient.

Plant diseases that can be controlled by the compounds of the present invention include Pyricularia oryzae and Pyricularia oryzae.
Sesame leaf blight (Cochl 1obolus m1ya)
beanus), apple scab (Venturia
1naequalis), pear scab (Ventur
ia nashicola), Agi's eye spot disease (Pseu
do-cercosporella herpotri
choides), anthracnose of cucurbits (Colletot
richum lagenarium), groundnut brown spot (Cercospora arachidico)
la), etc. The compounds of the present invention can also be used as insecticides, acaricides, herbicides, plant growth regulators, agricultural chemicals, and pharmaceutical intermediates.

Next, the method for producing the compound of the present invention will be explained in detail.

The compound of the present invention has the general formula % formula % (3) [wherein R1, H! are the same or different and represent a lower alkyl group, a hydrogen atom, or combine with R1R2 to represent an alkylene group. ] and a ketone or aldehyde derivative represented by the general formula % [wherein R4 represents a lower alkyl group or a phenyl group which may be substituted with a halogen atom or a lower alkyl group]. ] A hydrazine derivative represented by the general formula c, where Rs represents a hydrogen atom or a lower alkyl group. ] It can be obtained by reacting the thioglycolic acid derivative shown in the following in the presence of a catalyst if necessary.

Examples of catalysts that can be used in the above reaction include ammonium carbonate and the like.

In the above reaction, the reaction temperature is typically 0 to 150
℃, the reaction time is 1 to 48 hours, and the amount of reagent used for the nuclear reaction is usually 1 mole of the ketone or aldehyde derivative represented by the general formula (2) above.
) The amount of the hydrazine derivative represented by formula 4 and the thioglycolic acid derivative represented by general formula 4 is 1 to 1.2 mol.

Further, the above reaction is usually carried out in the presence of a solvent, and examples of solvents that can be used include aromatic hydrocarbons such as benzene and toluene. Further, the above reaction is usually carried out while separating water.

After completion of the reaction, the desired compound of the present invention can be obtained by carrying out usual post-treatments and, if necessary, purifying by chromatography, recrystallization, etc.

In addition, the ketone or aldehyde derivative represented by the general formula (9), the hydrazine derivative represented by the general formula (2), and the thioglycolic acid derivative represented by the general formula 4, which are raw material compounds for producing the compound of the present invention. can be commercially available or synthesized by conventional methods.

Table 1 shows some of the compounds of the present invention that can be obtained by such a production method.

No. table Me iPr M e -CH,CH,CH,CH,- -CH, CH, CH, CHICH.

Me Me -CH2CHIICH,CH,CH,--CH,C)I
,CH,CH,CH,--CH,CH2CH,CH,C
H, - 1Pr H Et ) 1 -CH, CH, CH, CH, - M e M e M e M e M e M e Me Me Me Me Et Me Me Me Me Me h 2-methylphenyl Me Me 4-chlorophenyl 4-f luorophenyl 4-bromophenyl 8-methylphenyl Me When the compound of the present invention is used as an active ingredient of a plant disease control agent, it may be used as it is without adding any other ingredients, but it is usually used in the presence of solid carriers, liquid carriers, and interfaces. It can be mixed with active agents and other formulation auxiliaries to form emulsions, wettable powders, suspensions,
It is used in formulations such as granules and powders.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99%, preferably 0.2 to 95%.

As solid carriers, fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn ear powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide are used. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, soybean oil, cottonseed oil, etc. Examples include vegetable oil, dimethyl sulfoxide, acetonitrile, water, etc.

Surfactants used for emulsification 1 dispersion, wet layer, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan Nonionic surfactants such as BWI fatty acid ester and polyoxyethylene sorbitan fatty acid ster are used.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isopropyl acid phosphate), etc.

These preparations can be used as they are, or diluted with water and sprayed on foliage, sprinkled or granulated on the soil, or applied to the soil. Furthermore, by mixing it with other plant disease control agents, it can be expected that the control efficacy will be enhanced. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth inhibitors, fertilizers, soil conditioners, and the like.

When the compound of the present invention is used as an active ingredient of a plant disease control agent, the amount to be treated depends on weather conditions, formulation form, treatment time,
Although it varies depending on the method, location, target disease, target crop, etc., it is usually 0.5 to 20Of per are, preferably 1
~100f, and when applying emulsions, wettable powders, F1 clouding agents, etc. diluted with water, the applied concentration is 0.005~0.
5%, preferably o, oi to 0.2%, and granules, powders, etc. are applied as they are without any dilution.

The compound of the present invention can be used as an insecticide for controlling cockroaches, etc.
It can also be used as an active ingredient in acaricides.

<Examples> The present invention will be explained in more detail below using production examples, formulation examples, and test examples. First, a manufacturing example will be shown.

Example (compound (4))
iO1) was dissolved in toluene, 0.92f (20ml) of methylhydrazine was added, and the mixture was stirred at room temperature for 80 minutes.

To this, 1.84 t of f-oglycolic acid (20 mmoJ
) while removing the water generated in the water separator.
The mixture was heated to reflux for an hour. After cooling, deionized water was added, and the mixture was extracted twice with chloroform. After drying over anhydrous magnesium sulfate, the remaining aroma was recrystallized from ethyl acetate.
．． 4! :l P (12,5 mmols yield 68%)
Compound (4) of the present invention was obtained.

mp 188-136゜' H-NIuiR(CDCJ s/T'Ms1δ(p
pm)) 1.0-2.1 (to 10H), 8.18 (s
, 8H), 8.25 (S, 2H), 4.58 (br
%LH) Mass spectrum (in//e% 70eV)2
00 (M+), 157 Elemental analysis * (as C9H111Nμ) CHN
S Actual value 58.99 8.11 14.01 15.
8 Calculated value 5g, 97 8.05 1B, 98 16.
01 Some of the compounds of the present invention produced by such a production method are shown in Table 2.

2 shown in the table! (-1,8,4-thiadiazine-5(6
Example formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 508 parts of each of the present compounds (1) to (14), 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed to prepare a hydrating agent for each of the present compounds. get.

Formulation Example 2 25 parts each of the compounds (1) to (14) of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water were mixed and wet-pulverized until the particle size of the active ingredient became 5 microns or less. A suspension of the compound of the present invention is obtained.

Formulation Example 8 2 parts each of the compounds (1) to (14) of the present invention, 88 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain powders for each of the compounds of the present invention.

Formulation Example 4 20 parts each of the compounds (1) to (14) of the present invention, 14M polyoxyethylene steryl phenyl ether, 6 parts calcium dodecylbenzenesulfonate, and 60 parts xylene
The components are thoroughly mixed to obtain an emulsion containing the compound of the present invention.

Formulation Example 5 2 parts each of the compounds (1) to (14) of the present invention, 1 part of synthetic hydrated silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, and water may be added. After kneading, the mixture is granulated and dried to obtain granules containing the compound of the present invention.

Next, test examples will show that the compounds of the present invention are useful as fungicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 8.

1! Table I8 Control efficacy is determined by visually observing the diseased state of the test plants at the time of investigation, i.e., the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, the rating is ``6'', 1096 If the degree is approved, r4J, if about 80 copies are approved, it is l”'8J, 50
If it is found to be about 96, it is given a "2", if it is about 7,096, it is given a "1", and if it is more than 7,096, it is given a "0", and if there is no difference from the disease state when no compound is tested, it is given a score of 6. 5.4.8.2.1.0.

Test Example 1 Rice blast control test (preventive effect) A glass pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 20 days. A test drug prepared as an emulsion in accordance with Formulation Example 4 was diluted with water to a predetermined concentration, and sprayed on rice seedlings so as to sufficiently adhere to the leaf surface.

After spraying, the plants were air-dried and then sprayed and inoculated with a spore suspension of the blast fungus. After inoculation, the plants were grown for 4 days at 28° C. in the dark and humid, and the control efficacy was investigated. The results are shown in Table 4.

Table 2 Test Example 2 Rice blast control test (osmotic transfer effect) Plastic pots were filled with sandy loam, and rice plants (Goki No. 88) were sown and grown in a greenhouse for 14 days. A test drug prepared as an emulsion according to Formulation Example 4 was diluted with water and a predetermined amount of the drug was sprinkled onto the soil of rice seedlings. After irrigation, the plants were grown in a greenhouse for 7 days, and then sprayed and inoculated with a spore suspension of the blast fungus. After inoculation, the seeds were weighed for 4 days at 1.28°C in the dark and humid, and then the control efficacy was investigated. The results are shown in Table 6.

Table 5 Test Example 8 Apple scab control test (preventive effect) Plastic bottles were filled with sandy loam, apples were sown, and grown in a greenhouse for 20 days. A test drug prepared as a suspension according to Formulation Example 2 was diluted with water to a predetermined concentration, and the solution was sprayed onto apple seedlings so as to sufficiently adhere to the leaf surface. After spraying,
A spore suspension of apple scab fungus was sprayed and inoculated.

After inoculation, the plants were kept at 16° C. under humid conditions for 4 days, and then grown under lighting for 16 days, and their pesticidal efficacy was investigated.

The results are shown in Table 6.

<Effects of the Invention> Since the compound of the present invention has excellent effects against plant diseases caused by various plant pathogens, it can be used for various purposes as an active ingredient of plant disease control agents. It may also serve other uses Cζ, such as insecticides and acaricides.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are the same or different and represent a lower alkyl group, a hydrogen atom, or R^1 and R^2 R^3 represents a hydrogen atom or a lower alkyl group, and R^4 represents a lower alkyl group, or a phenyl group which may be substituted with a halogen atom or a lower alkyl group. represent. ] A thiadiazinone derivative represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are the same or different and represent a lower alkyl group, a hydrogen atom, or R^1 and R^2
is combined with to represent an alkylene group. ] and a ketone or aldehyde derivative represented by the general formula R^4-NH-NH_2 [wherein R^4 represents a lower alkyl group, or a phenyl group optionally substituted with a halogen atom or a lower alkyl group] represents. ] and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^3 represents a hydrogen atom or a lower alkyl group. ] The method for producing a thiadiazinone derivative according to item 1, which comprises reacting with a thioglycolic acid derivative represented by the following. (3) A plant disease control agent containing the thiadiazinone derivative described in item 1 as an active ingredient.