JPH03148267A - 1,2,4-oxadiazin-5-one derivative and agricultural and horticultural germicide - Google Patents

Abstract

NEW MATERIAL:A 1,2,4-oxadiazin-5-one derivative expressed by formula I (R<1> is lower alkyl, phenyl-lower alkyl, lower alkoxy-lower alkyl, pyridyl or phenoxy-lower alkyl which may be substituted with halogen or phenyl, etc., which may be substituted with halogen, etc.; R<2> is lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, phenulthio-lower alkyl, benzoyl, etc.; R<3> is H, lower alkyl or phenyl which may be substituted with halogen group). EXAMPLE:3-(4-Chlorophenyl)-4-(2,6-dimethylphenyl)-1,2,4-oxadiazin-5-one. USE:Useful as an agricultural and horticultural germicide and having great safety without any phytotoxicity. PREPARATION:An amidoxime ether derivative expressed by formula II is reacted with thionyl chloride to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel 1,2,4-oxadiazin-5-one derivatives. More specifically, it is represented by general formula (I) below. 1, 2. having a substituent at the 4th position;
The present invention relates to an agricultural and horticultural fungicide containing a 4-oxadiazin-5-one derivative and a # derivative as active ingredients.

Therefore, the present invention is useful in the chemical industry and agriculture, particularly in the agricultural chemical manufacturing field.

Nijisaraizumi Riushi (Up to now, there have been some literature descriptions of 1,2,4-oxadiazin-5-one derivatives. For example, JP-A-5
Publication No. 2-36679 describes 3 expressed by the following general formula.
-Aryl-substituted 1,2.4-oxadiazin-5-one derivatives and compounds thereof have been described as having phytohormonal and herbicidal activity.

General formula (wherein R represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, or a phenyl group, and Ar represents 1 to 3 atoms selected from a halogen atom, an alkyl group containing 1 to 4 carbon atoms, etc.) Indicates a phenyl group substituted with the same or different substituents.

or Ar contains atoms such as nitrogen as a heteroatom 5
Indicates a membered aromatic heterocyclic group. ) also chemical
Abstract Vol. 108, 5977g (1988) describes the 3-aryl substituted 1,
It is stated that 2,4-oxadiazin-5-one derivatives are obtained by the reaction of amidoximes and α-chlorocarboxylic acid chlorides.

General formula [wherein, R is a hydrogen atom, a nitro group, a bromine atom, a methyl group, a methoxy group, Rt, R-2 is a hydrogen atom or a phenyl group, provided that when R1 is a hydrogen atom, R2 is a methyl group ) However, there is no description of l,2<4-oxadiazin-5-one derivatives having a substituent at the 4-position, nor is it known that they have bactericidal activity.

As shown in the test examples below, conventional 1,2,4-oxadiazin-5-one derivatives have little or low fungicidal activity as agricultural and horticultural fungicides, and they also cause chemical damage to crops. It is impractical as it involves

The present invention has a high control effect on rice blast, which is an important disease of agricultural crops, as well as powdery mildew and rust of wheat, and clubroot diseases of cruciferous vegetables.

Moreover, the present invention provides a novel 1,2,4-oxadiazin-5-one derivative having a substituent at the 4-position and a fungicide for agriculture and horticulture, which is free from phytotoxicity and highly safe.

In order to couple the above objects, the present inventors have developed a number of 1.
2.4-Oxadiazin-5-one derivatives were synthesized and their usefulness was intensively investigated. As a result, 1,2 having a substitution at the 4-position, represented by the following general formula (I),
．． We succeeded in synthesizing a 4-oxadiazin-5-one derivative.

We have discovered that these derivatives are new compounds that have not been described in any literature, and that they have higher bactericidal activity and safety than conventional IR fungicides.

Therefore, the gist of the first invention is as follows: or a phenoxy lower alkyl group which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom, a halo-lower alkyl group, or a lower alkyl group, and R2 is a lower alkyl group, a lower alkenyl group. , lower alkynyl group, lower cycloalkyl group,
phenylthio lower alkyl group, benzoyl group,
or represents a phenyl lower alkyl group optionally substituted with a halogen atom, or up to 2 halogen atoms,
Represents a phenyl group that may be substituted with a halo-lower alkyl group, a lower alkyl group, or a lower alkoxy group, and R:' represents a hydrogen atom, a lower alkyl group, or a phenyl group that may be substituted with a halogen atom. 1,2,4-oxadiazin-5-one derivatives represented by ).

In the definition of general formula (I), the group appended with "lower" is 1-
Each group containing 6 carbon atoms is meant.

Furthermore, the second gist of the present invention is an agricultural and horticultural fungicide characterized by containing the above-mentioned 1,2,4-oxadiazin-5-one derivative of general formula (I) as an active ingredient. It is in.

Next, typical examples of the compounds of the present invention represented by the formula (I) are shown in Table 1.

In addition, the compounds listed in Table 1 are also referred to in the following Examples and Test Examples.

1st Figure 10 Toner Cart (Tori@H”7 Figure 1) Remaining amount of toner in the diagram
GNDT: Toner [rod member]
2) Action The compound of the present invention represented by the general formula (I) is a new compound. This compound of general formula (I) acts as an active ingredient of a fungicide for agricultural and horticultural use.

3) Stream side (Part 1) Method for producing the compound The first compound of formula (I) according to the present invention can be produced by the method described below. That is, a compound of the general formula (2) can be produced by a method of reacting an amidoxime ether derivative of the following general formula (II) with thionyl chloride.

(n) (I) (wherein 12R has the same meaning as above) This reaction can be carried out by mixing the formula (II) and thionyl chloride in a usual solvent, and further This can also be accomplished by mixing an acid binder.

As the solvent, hydrocarbons such as benzene, toluene, and xylene, and chlorine solvents such as methylene chloride, dichloroethane, chloroform, and carbon tetrachloride can be used. As the acid binder, inorganic bases such as sodium hydroxide, sodium hydride, potassium carbonate, etc., and organic bases such as sodium methoxide, triethylamine, pyridine, etc. can be used.

Although the reaction proceeds at room temperature, the reaction time can be shortened by heating up to the boiling point of the solvent.
If salts of the acid binder are present, the desired compound can be obtained by filtering them out and distilling off the solvent. In addition, the desired product can also be obtained by adding water and an organic solvent such as benzene, toluene, tetrahydrofuran, chloroform, etc. to extract the desired product, and then distilling off the solvent. Examples 1-2 below
It was shown to.

In addition, the compound of formula (n) which is a raw material is a known compound or a known manufacturing method, for example, JP-A-64-34.
A manufacturing example of a compound of formula 0 (■) that can be manufactured by the method described in Publication No. 954 is shown in the reference manufacturing example below.

4-chloro-N-carboxymethoxy-N'(2,6-
dimethylphenyl)-benzenecarboximidamide 3
3.21 was dissolved in 600 mu of toluene, 11.9 g of thionyl chloride was added, and the mixture was stirred and refluxed for 1 hour. After cooling, 10.1 g of triethylamine was added, and the mixture was further stirred at room temperature for 1 hour. The precipitated inorganic salt was filtered off and the solvent was distilled off under reduced pressure to obtain 20.4 g of the title compound as pale brown crystals. Recrystallization from a hexane/toluene mixed solvent gave white crystals with a melting point of 123-125°C.

2-Methyl-N-carboxymethoxy-N'(α-methylbenzyl)-benzenecarboximidamide 31.2
Dissolve 11.g of thionyl chloride in 600ml of benzene.
After adding 9 g, the mixture was stirred and refluxed for 1 hour. The precipitated inorganic salt was separated by filtration, and 200 mJL of water was added to the benzene layer to separate the benzene layer. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to give the title compound as pale brown crystals.
2.0g was obtained. Recrystallization from a hexane/ethyl acetate mixed solvent gives white crystals with a melting point of 86.5-89°C.
showed that.

41 14-Chloro-N-carboxymethoxy 4-chloro-N-hydroxy-N”-(2,6-dimethylphenyl)-benzenecarboximidamide 27.4
14.0 g of bromoacetic acid, and 200 ml of acetonyl was added with 13.6 g of sodium ethoxide under cooling with water, and the mixture was stirred at room temperature for 3 hours. After acetonitrile was distilled off under reduced pressure, chloroform and IN-hydrochloric acid aqueous solution were added to the residue to make it acidic, and then the chloroform layer was separated. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 29.9 g of the title compound as pale brown crystals. Recrystallization from a hexane/ethyl acetate mixed solvent gave white crystals with a melting point of 178-180°C.

4) Example (Part 2) Horticulture Method for formulating a fungicide Furthermore, the second agricultural and horticultural fungicide of the present invention has the general formula (
The compound of I) can be formulated and used according to a conventional formulation. That is, the compound of general formula (I) is blended with appropriate carriers and auxiliary agents, such as surfactants, binders, stabilizers, etc., to form wettable powders, emulsions, liquids, sols (flowables), and oils. , powder, DL (1'liftless type) powder, fine powder, coarse powder, etc.

The content of the compound of the present invention in these preparations is 1 to 90% (wt%:
(same below) range, powder, DL powder, 1w granule powder, coarse powder, 0.5 to 5% range, powder, 1-10
It can be contained within a range of %.

The method of using the agricultural and horticultural fungicide of the present invention is generally as follows. i.e. hydrating agents, liquid formulations.

In the case of emulsions, sol formulations (flowable formulations) and oil formulations, the active ingredients are generally diluted 500 to 2000 times with water.
The solution is prepared to have a concentration of ~110,000 pp. and 1
50 to 300 sentences of this diluted liquid per 0 are, usually 1
00 to 200 g is sprayed on the leaves and foliage of the plant where the disease occurs.

In addition, liquids, emulsions, and sol (flowables) can be used as concentrated liquids without diluting them with water, or by diluting them up to 10 times with water. UL
50-3000 mj per 10 ares as VL cloth agent)
The amount of L is dispersed using a helicopter or the like.

In addition, powders, DL powders, fine granules, and coarse powders are applied at a dose of 2 to 5 kg (approximately 50 to 500 g of active ingredient) per 10 are to the foliage, soil surface, soil, or water surface of the diseased site of the plant. Ru.

Furthermore, various formulations as described above are used as soil fungicides. In other words, in the case of preparations such as powders and fine granules, ■ Before sowing or planting crop seeds, apply a preparation amount of 910 to 50 kg of lOAR (approximately 0.5 to 10 kg of active ingredient) to almost the entire surface. ■ Method of spraying and mixing well with the soil, ■ Method of spraying in the ridges before sowing or planting and mixing well with the soil, ■ Method of spraying a certain amount of planting holes before planting (
For example, 1 to 7 g of preparation per large pot = 0.1 active ingredient
~ Ig) is applied, mixed, and then planted. In addition, in the case of hydrating powders and emulsions, add 5% with water.
Dilute 00 to 2000 times and apply a certain amount (for example, about 1 to 51 per square meter) to the base of the plant after sowing or planting.
Irrigate.

A method for formulating the compound of the present invention of general formula (1) as an agricultural and horticultural fungicide is shown in Examples 3 to 6 below.

[Toun 3 I compound? &) 2 parts of the compound of 34, 1 part of PAP (physical property modifier) and 97 parts of clay are mixed uniformly and ground to obtain a powder containing 2% of the active ingredient.

Ego Negative 1 Tomotan 1 20 parts of compound No. 40, 3 parts of potassium alkylbenzene sulfonate, 5 parts of polyoxyethylene noniphenyl ether, and 72 parts of white clay were mixed uniformly and pulverized to obtain 20% active ingredient. A hydrating agent containing the powder is obtained.

By mixing and dissolving 30 parts of the compound of Aino Wataru 1 plastic compound Nb22, 40 parts of methylethimeketone, and 30 parts of polyoxyethylene noniphenyl ether, an emulsion containing 30% of the active ingredient is obtained.

A sol containing 40% active ingredient by uniformly mixing 40 parts of Compound No. 26, 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of acetoxypropylcellulose, and 55 parts of water. get the agent.

i supervised amount 1 The novel compound having a unique chemical structure of the present invention can be used to treat important diseases such as rice blast, powdery mildew, and rust of wheat.
It is useful as a fungicide for agriculture and horticulture because it shows a high control effect against clubroot disease of cruciferous vegetables, which is a pest control disease.

Next, the usefulness and specific examples of the compound of the present invention represented by formula (I) are shown in Test Examples 1 to 4.

A chemical solution of a predetermined concentration of a wettable powder prepared according to Example 4 was sprayed on third leaf stage seedlings of cultivated paddy rice (variety Niasahi). Then - at night, under greenhouse conditions (humidity 95-100%, humidity 24-2
5℃), and one day after spraying, the rice blast fungus (Piri
A spore suspension of cularia oryzae was inoculated by spraying. t1 species 3rd after 5 days
The number of rice blast lesions per leaf was investigated, and the control value (%) was calculated using the following formula. In addition, phytotoxicity to rice was expressed using the following criteria.

This test was conducted in triplicate per 1 chemical solution concentration, and the average control value (%) was determined. The results are shown in Table 2.

In addition, the evaluation value of bactericidal effect and the investigation index of chemical damage were similarly used in Test Examples 2 to 4 below.

× 00 Defense exclusion value 100% 80-less than 100% Less than 60-80% Less than 40-60% Less than 20-40% less than 20% Drug damage investigation index 5: Severe 4: Serious 3: Many 2: Somewhat l: slightly 0: None No. table note) Non-sprayed area ( ) The numbers in the box are lesions per -tJ. Show the number.

(Compound described in JP-A-52-36679) (Chemical Abstract Vol. 1O8 77g (1988
9 (Common name: IBP) Test Example 2 Barley powdery mildew control Fruit test First leaf of barley (variety: Azuma Golden) grown in soil in a clay pot with a diameter of 9 cm in a greenhouse. A chemical solution of a predetermined concentration of a hydrating powder prepared according to Example 4 was sprayed onto stage seedlings over a distance of 10 m, and -
After the device at night.

A spore suspension of the powdery mildew fungus (■■ Bean-added graminis graminis) was inoculated by spraying. Seven days after inoculation, the lesion area ratio (%) of barley powdery mildew was investigated, and the control value (%) was calculated using a linear formula.The degree of chemical damage to barley was also investigated using the same criteria as Test Example 1, and displayed as 1. The results are shown in Table 3.

00 Table Note 1) Comparative drugs A and B are the same as the compounds shown in Table 2.

Note 2) In non-sprayed area Shows the current number.

The numbers in parentheses are the disease per leaf (generic name: kinomethionate) Koka Watayu Wheat rot disease control effect Diameter 9 in the test greenhouse
A diluted solution of a predetermined concentration of a hydrating powder prepared according to Example 4 was applied to wheat seedlings in the first leaf stage (variety: Norin No. 61) cultivated in soil in clay pots with a size of 3 cm at 20 m per 3 pots. It was sprayed in an amount of One day later, the wheat rot fungus (Puccinia recondi) that had previously formed on the wheat leaves was infected.
ta: puccinia recondita) 150 times m
Using a microscope, suspend the spores in sterile water containing 50 ppm of Tween 20 (trade name of polyoxyethylene sorbitan monolaurate manufactured by Kao Soap) so that the spore concentration is approximately 50 per field of view. The suspension was spray inoculated onto the leaves to be treated. - After keeping the room temperature at 20°C overnight, the plants were transferred to a greenhouse at 20°C to induce disease onset. After 10 days of inoculation, the number of infected pediceliums per leaf was investigated, and the control value (%) was calculated using the linear formula.The test was conducted using 3 pots per 1 concentration of chemical solution, and the average control value was calculated. I asked for it. In addition, the degree of drug damage to wheat was investigated using the same criteria as in Test Example 1 and displayed. The results are shown in Table 4.

No. table Note 1) Comparative drug A, B is a compound shown in Table 2 and are the same.

Note 2) Non-sprayed area ( ) The numbers in the box are diseases per leaf. Shows the current number.

W Chinese cabbage clubroot disease control Test Chinese cabbage clubroot disease fungus (Plasmodiophora
brassic-ae: Contaminated soil from brassimodio (7 years old) was passed through a 5 mm sieve, and this 1k
g into a plastic bag and mix well with the prescribed amount of powder prepared according to Example 3. This chemically treated soil is placed in a square pot (20 cm x l O cm x l O cm), and seeds of Chinese cabbage (variety: Sakumidori) are sown in 5 locations. After that, Chinese cabbage will be cultivated and managed in a glass greenhouse. Then, when the cotyledons of Chinese cabbage are in the stage of expansion, remove the remaining 5 leaves per lbot.

To investigate the onset of disease, all the plants from each pot were pulled out 10 days after sowing, and the roots were examined according to the degree of disease, and the degree of disease was determined. From this, the control value (%) was calculated in comparison with the disease severity in the untreated area, as shown by the following formula.

N: Comprehensive research strain: A large gall has grown on the base of the taproot, and growth has been severely suppressed.b: A gall has grown on the tips of the taproot and lateral roots, but the gall is small. C: There are a few galls attached to the lateral roots, but the growth is almost normal. d: Healthy. On the other hand, regarding chemical damage, we examined the degree of growth, yellowing of leaves, etc. by visual observation, and determined the following criteria: Displayed by.

0: No chemical damage, 1: Little, 2/Medium, 3: Heavy, 4: Severe, 5.2 blight This test was conducted in triplicate for each 1 chemical treatment.

The results are shown in Table 5.

No. 5 table Note 1) Comparative drug A.

B is a compound shown in Table 2 and are the same.

Note 2) Non-sprayed area ( ) The numbers in the box indicate the severity of the disease. vinegar.

Comparative drug F:

Claims (1)

[Claims] 1) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R^1 represents a lower alkyl group, a phenyl lower alkyl group, a lower alkoxy lower alkyl group, a pyridyl group, or a phenoxy lower alkyl group which may be substituted with a halogen atom, or a halogen atom,
It represents a halo lower alkyl group, a phenyl group which may be substituted with a lower alkyl group, and R^2 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower cycloalkyl group, a phenylthio lower alkyl group, a benzoyl group. or a phenyl lower alkyl group which may be substituted with a halogen atom, or a phenyl group which may be substituted with up to two halogen atoms, a halo-lower alkyl group, a lower alkyl group, a lower alkoxy group, R^3 represents a hydrogen atom, a lower alkyl group, or a phenyl group which may be substituted with a halogen atom. ) A 1,2,4-oxadiazin-5-one derivative represented by 2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 represents a lower alkyl group, a phenyl lower alkyl group, a lower alkoxy lower alkyl group, a pyridyl group, or is substituted with a halogen atom. represents an optional phenoxy lower alkyl group, or a halogen atom,
It represents a halo lower alkyl group, a phenyl group which may be substituted with a lower alkyl group, and R^2 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower cycloalkyl group, a phenylthio lower alkyl group, a benzoyl group. or a phenyl lower alkyl group which may be substituted with a halogen atom, or a phenyl group which may be substituted with up to two halogen atoms, a halo-lower alkyl group, a lower alkyl group, a lower alkoxy group, R^3 represents a hydrogen atom, a lower alkyl group, or a phenyl group which may be substituted with a halogen atom. ) An agricultural and horticultural fungicide containing a 1,2,4-oxadiazin-5-one derivative represented by the following as an active ingredient.