JPS63198676A - Pyridyltriazine derivative, its production and plant blight controlling agent containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The pyridyltriazine derivative of formula I [R<1> is 1-7C alkyl; R<2> and R<3> are H or lower alkyl; R<1> and R<2> may be bonded through (CH2)n to form a cyclic structure; n is 3 or 4; R<4> is lower alkyl; when R<4> is methyl, R<1> is 3-7C alkyl). EXAMPLE:2-(6-Butyl-5-methyl-2-pyridyl)-4,6-dimethyl-S-triazine. USE:A plant blight controlling agent exhibiting excellent effect against plant blights (e.g. rice blast, powdery mildew of wheats, early blight of tomato, etc.) caused by various phytopathogens. PREPARATION:The compound of formula I can be produced by reacting a salt of a picolineamidine derivative of formula II with an imidate derivative of formula III (R<5> is lower alkyl) at 10-100 deg.C. The amount of the compound of formula III is preferably 3 equivalent per 1 equivalent of the salt of the compound of formula II.

Description

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

<Prior Art> Until now, it has not been known at all that pyridyl S-triazine derivatives have bactericidal activity.

In addition, examples of pyridyl S-triazine derivatives include:
An example of the synthesis of 2,4-dimethyl-6-(2-pyridyl)-s-triazine is given in J, Org, Chem.

Nagi, 8608-861B (1962), but there is no mention of biological activity.

<Problems to be Solved by the Invention> The purpose of the present invention is to develop compounds that have preventive or therapeutic effects on many plant diseases.

Means for Solving the Problems In order to achieve the above object, the present inventors have made extensive studies and found that the general formula [wherein R represents an alkyl group having 1 to 7 carbon atoms, R and R represent a hydrogen atom or a lower alkyl group. Furthermore, R1 and R'' can be combined with +CH!i to form a cyclic structure, where n is 8 or 4. R4 represents a lower alkyl group. However, when R4 represents a methyl group,
R represents an alkyl group having 8 to 7 carbon atoms. The pyridyltriazine derivative represented by (hereinafter referred to as the compound of the present invention).

) was found to have excellent bactericidal activity, leading to the present invention.

Plant diseases that can be controlled by the compounds of the present invention include rice blast disease (Pyricularia oryzae).
), sesame leaf blight (Cochliobolus mly
abeanus), sheath blight (Rh1zoctonia
5olani), powdery mildew of wheat, (Erys
iphe graminis f, sp, hord
ei, f, sp, tritici), spotted leaf disease (P
yrenophora graminea), rust (Pucciniastriiiformis, P.
graminis, P. recondita, P.
, hordei), Pseudocerco
sporel la herpotrichoides
), Rhynchosporium 5ec
alis), leaf blight (5eptoria trit
ici), blight (Leptosphaeriano)
dorum), citrus black spot (Diaporth
ectri), EISinoe fa
wcetti), apple powdery mildew (Podosp
haera 1eucotricha), leaf spot disease (Alternaria mali), scab disease (
Venturiainaequalis), pear scab (Venturia nashicola), black spot (Alternaria kikuchiana)
, 5clerotinia ciner
ea ), grape blackhead (Elsinoe amp
elina), late rot (Glomerellacin)
gulata), powdery mildew (Uncinula n.
ecator ), cucurbit anthracnose (CCo11eto
trichu lagenarium), powdery mildew (5phaerotheca fuliginea)
, Alternaria 5olan
i), Phytophthora1nfest
ans), Phomopsis ve
xans), black spot of cruciferous vegetables (Alterna
ria japonica), vitiligo disease (Cercos
Porella Brassicae), green onion rust disease (PU ((INIA ALLII), CERCOSPORAKIKUCHII), CERSINOE GIYCINES, Ingenno Charcoal (CCO11 ETOTRICHUL) IND
emutianum), groundnut black astringency (My
cosphaerel la personatum
), Cercospora arachidi
cola), powdery mildew of pea (Erysiph
e pisi), potato summer blight (Altern
aria 5olani), beetroot brown spot (Ce
rcospora beticola), rose scab (Diploc-arpon rosae), powdery mildew (5phaerothecapannosa),
Botrytisciner of extreme crops
ea ), Sclerotinia scle
rotiorum), etc.

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 [wherein R1, R2 and R1 have the same meanings as above. ] A salt of a picolinamidine derivative represented by the general formula [wherein R4 represents the same meaning as above, and R5 represents a lower alkyl group. ] It can be obtained by reacting with the imidate derivative shown below.

Examples of salts of picolamidine derivatives include hydrochloride, hydrobromide, acetate, and formate.

In the above reaction, the reaction temperature is typically 10'C~
100''C and reaction time is 10 minutes to 48 hours.

Further, 1 of the reagents used in the above reaction is usually of the above general formula [
The amount of the imidate derivative represented by the general formula [1113] is 8 equivalents per equivalent of the salt of the picolinamidine derivative represented by [11].

In the above reaction, a reaction solvent may be present, but
It is usually carried out in the absence of a solvent.

After completion of the reaction, the reaction solution is subjected to usual post-treatments such as organic solvent extraction, and if necessary, the desired compound can be obtained by operations such as chromatography and recrystallization.

The salt of the picolinamidine derivative represented by the general formula LII, which is a raw material compound for producing the compound of the present invention, can be produced, for example, by the following route.

[W] [] one [U [wherein R, R and R represent the same meanings as above]
R8 represents a lower alkyl group, and M represents an alkali metal atom. ] i.e., J, Org, Chem,, 48.18
75-1377 (198 g) etc., by reacting a cyanopyridine derivative represented by the general formula [fl] with an alkoxide represented by the general formula [V]. An imidate derivative is obtained, and by reacting the imidate derivative with an ammonium salt, a salt of a picolinamidine derivative represented by the general formula (button) is obtained.

The above manufacturing method will be explained in detail below.

In the reaction between the cyanopyridine derivative represented by the general formula [II] and the alkoxide represented by the general formula [v], examples of the alkali metal atom of the alkoxide used include a sodium atom and a potassium atom.

In addition, in this reaction, the reaction temperature is typically 10 to 50°C.
℃, the reaction time was 1 to 48 hours, and the reagent fish used for the reaction was 1 cyanopyridine derivative represented by the general formula [11/] and 0 alkoxide represented by the general formula [V]. .1 to 1 equivalent.

In the above reaction, although a reaction solvent is not necessarily required, it is generally carried out in the presence of a solvent.

Examples of solvents that can be used include lower alcohols corresponding to R6 in the alkoxide represented by the general formula [v], such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol, preferably methanol, Ethanol can be given.

After the reaction, the reaction solution is neutralized with an acid, concentrated under reduced pressure, dissolved in an organic solvent, the insoluble alkali metal salt is removed, and the F solution is concentrated under reduced pressure. Through this operation, the desired imidate derivative represented by the general formula [M] can be obtained.

Next, in the reaction of the imidate derivative represented by the general formula [v] obtained above with an ammonium salt, examples of the ammonium salt used include hydrochloric acid, hydrobromic acid,
Examples include ammonium salts such as acetic acid and formic acid.

In addition, in this reaction, the reaction temperature is typically 80 to 10
The reaction time is 80 minutes to 6 hours at 0°C. It is.

Although a solvent is not necessarily required in the above reaction, it is generally carried out in the presence of a solvent.

Examples of solvents that can be used include lower alcohols, preferably a mixed solvent of ethanol and water.

After completion of the reaction, the reaction solution is subjected to normal post-treatments such as concentration under reduced pressure, and if necessary, recrystallization and other operations are performed to obtain the general formula [I[]
It is possible to obtain the hydrochloric acid, hydrobromic acid, acetic acid, formic acid, etc. salts of the picolinamidine derivative represented by

Imidate derivatives represented by the general formula [m] include, for example, Organic Functional Gr.
oupPreparations Vol, m, C
hapter 8. Academic Pness.

New York, 1971.

When the compound of the present invention is used as an active ingredient in a plant disease control agent, it may be used as is without adding any other ingredients, but it is usually used in combination with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries. It is used by mixing it with emulsions, wettable powders, suspensions, granules, powders, etc.

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%.

Examples of solid carriers include fine powders such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. 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, 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, Examples include nonionic surfactants such as sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester.

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 regulators, 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 200 F per are, preferably 1 to 100 F, and emulsions, wettable powders, suspensions, etc. are diluted with water. When applied, the application concentration is 0.005 to 0.
．． 5%, preferably 0.01 to 0.2%, and granules, powders, etc. are applied as they are without any dilution.

<Examples> The present invention will be explained in more detail below using production examples, reference examples, formulation examples, and test examples.

First, a manufacturing example will be shown.

Production example (compound 8) Ethylacetimidate 1,151 was added to 6-buteru-5-methyl-2-picolinamidine hydrochloride 1f at 60°C.
The mixture was stirred for 80 minutes.

Water 80- and chloroform 80- were added to the reaction solution for extraction,
The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (eluent; hexane:ethyl acetate = 1:2) to obtain 2-(6-butyl-5-methyl-2-pyridyl)-4.
, 0.9f of 6-dimethyl-S-triazine was obtained.

m, p, 78.5°C PMR (CDCl m) δppm 2.40 (s, 8H, CHs) 2.74 (s, 6H, CHs) 7.51 (d,
IH, pyridine-H'*J=8.4Hz) 8.20(d
, IH, pyridi', =H, J=8.4H2) Next, some of the pyridyl S-triazine conductors represented by the general formula [I] produced by such a production method are shown in Table 1. .

Table 1 m Next, as a reference example, a production example of a salt of a picolinamidine derivative represented by the general formula [2], which is a raw material compound for the compound of the present invention, is shown.

Reference example [Production of picolinamidine derivative [n] (hydrochloride)] 2-cyano-6-n-propylpyridine 10 is dissolved in a sodium oxide methanol solution prepared from 100 methanol and 0.82 F of metallic sodium. did. −
After the night, 0.82jF of acetic acid was added and concentrated under reduced pressure. Ether 2001R1 was added to the obtained residue to remove insoluble matter, and then concentrated under reduced pressure to methyl 2-picolinimidate 11.
5F (yield 94%) was obtained.

Next, 8.461 lζ ammonium chloride was added to 20 -
A solution of 80-80% of ethanol was added thereto, and the mixture was heated under reflux for 1 hour. After the reaction solution was left to cool, it was sufficiently compressed under reduced pressure, and the obtained crystalline residue was washed with acetone to give 6++
fi++propyl-2-picoria [gin hydrochloride 12.
I got 21.

m, p, 178-0°C Next, the general formula [II
Table 2 shows some salts of the picolinamidine derivatives represented by the following.

Table 2 General formulas Examples of 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 50 parts each of the compounds (1) to (11) of the present invention, 8 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to prepare a wettable powder containing 50% of the active ingredient. get.

Formulation Example 2 25 parts each of the compounds (1) to (11) of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 8 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 containing 26% of the active ingredient is obtained.

Formulation Example 8 2 parts each of the compounds (1) to (11) of the present invention, 88 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain a powder containing 2% of the active ingredient.

Formulation Example 4 20 parts each of the compounds (1) to (11) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 60 parts of xylene
Mix well to obtain an emulsion containing 20% active ingredient.

Formulation Example 5 2 parts each of the compounds (1) to (11) of the present invention, 1 part of synthetic hydrous 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 2% of the active ingredient.

Next, test examples demonstrate that the compounds of the present invention are useful as plant disease control agents. 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 3.

Table 8 Control efficacy is determined by visual observation of 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 ``5''; If around 10 copies are accepted, ``4'', if around 80 copies are accepted, ``8'', if around 50 copies are accepted, r2J, if around 70 copies are accepted, ``1'',
If there is no difference from the disease onset state when no compound is tested, it is evaluated as "0" and evaluated on a 6-level scale, with 5, 4, 8, 2, and 1.0, respectively.

Test Example 1 Rice blast control test (preventive effect) A plastic pot was filled with sandy loam, m varieties of rice (Kinki No. 88) were planted, and grown in a greenhouse for 20 days. A test chemical prepared as a hydrating powder according to Formulation Example 1 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 inoculated by spraying with a spore suspension of the blast fungus. After inoculation, the plants were kept in a 28"C1 dark and humid environment for 4 days, and then the control efficacy was investigated. The results are shown in Table 4.

Table 4 Test Example 2 Rice blast control test (therapeutic effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 20 days. Spores of blast fungus hang onto young rice seedlings! 1 solution was sprayed and inoculated. After inoculation, 28°
C1 After being placed in darkness and high humidity for 16 hours, the test drug prepared as an emulsion according to Formulation Example 4 was diluted with water to a predetermined concentration, and sprayed on the leaves so that it would sufficiently adhere to the leaf surface. After spraying,
The plants were grown for 8 days at 28° C. in darkness and high humidity, and their pesticidal efficacy was investigated.

The results are shown in Table 5.

Table 5 Test Example 8 Rice sheath blight control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 28 days. Formulation Example 1 for rice seedlings
A test chemical prepared as a hydrating powder according to the method was diluted with water to a predetermined concentration, and the solution was sprayed on the foliage so that it would sufficiently adhere to the leaf surface.

After spraying, the plants were air-dried and inoculated by spraying with a edible agar suspension of the sheath blight fungus. After inoculation, the plants were kept in the apparatus for 4 days at 28° C. in the dark and humid, and then the pesticidal efficacy was investigated. The results are shown in Table 6.

Table 6 Test Example 4 Cucumber anthracnose control test (preventive effect) A plastic pot was filled with sandy loam, and cucumbers (Sumo Hanshiro) were sown and grown in a greenhouse for 14 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 cucumber seedlings with developed cotyledons so as to sufficiently adhere to the leaf surface. After spraying, a spore suspension of cucumber anthracnose was sprayed and inoculated. After inoculation, the seeds were left at 28°C under high humidity for 18 days, and then grown under lighting for 4 days, and the pesticidal efficacy was investigated. The results are shown in Table 7.

Table 7 Test Example 5 Apple Scotch Disease Control Test (Preventive Effect) Plastic pots were filled with sandy loam, apples were sown, and grown in a greenhouse for 20 days. A test chemical prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on the leaves of apple seedlings so as to sufficiently adhere to the leaf surface.

After spraying, a spore solution of apple scab fungus 11i was sprayed and inoculated. After grafting, the plants were grown in 4 apparatuses at 15"C and high humidity, and then grown under lighting for 15 days, and their pesticidal efficacy was investigated. The results are shown in Table 8.

Table 8 Test Example 6 Wheat leaf blight control test (therapeutic effect) A plastic pot was filled with sandy loam, and wheat (Norin No. 78) was sown and grown in a greenhouse for 8 days. Wheat seedlings were sprayed and inoculated with a spore suspension of the leaf blight fungus. After inoculation, 15℃,
After growing for 8 days in the dark and humid environment, and for 4 days under light, dilute the test drug made into an emulsion according to Formulation Example 4 with water to a specified concentration, and make sure that it adheres sufficiently to the leaf surface. Sprayed on foliage. After spraying, the plants were allowed to grow for 11 days under illumination at 15°C, and the control efficacy was investigated. The results are shown in Table 9.

Table 9 <Effects of the Invention> The compounds of the present invention have excellent effects against plant diseases caused by various plant pathogenic bacteria, and therefore can be used in various applications as active ingredients of plant disease control agents.

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 represents an alkyl group having 1 to 7 carbon atoms,
R^2 and R^3 represent a hydrogen atom or a lower alkyl group. Moreover, R^1 and R^2 can also be combined with -(CH_2)_n- to form a cyclic structure, where n is 8 or 4. R^4 represents a lower alkyl group. however,
When R^4 represents a methyl group, R^1 has 3 to 7 carbon atoms.
represents an alkyl group. ] A pyridyltriazine derivative represented by: (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents an alkyl group having 1 to 7 carbon atoms,
R^2 and R^3 represent a hydrogen atom or a lower alkyl group. Moreover, R^1 and R^2 can also be combined with -(CH_2)_n- to form a cyclic structure, where n is 8 or 4. ] Salts of picolinamidine derivatives shown by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R^4 and R^5 represent lower alkyl groups. ] A general formula characterized by reacting an imidate derivative represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2, R^3 and R^4 have the same meanings as above. represents. However, when R^4 represents a methyl group, R^1 represents an alkyl group having 3 to 7 carbon atoms. ] A method for producing a pyridyltriazine derivative shown in the following. (8) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents an alkyl group having 1 to 7 carbon atoms,
R^2 and R^3 represent a hydrogen atom or a lower alkyl group. Moreover, R^1 and R^2 can also be combined with -(CH_2)-n to form a cyclic structure, where n is 8 or 4. R^4 represents a lower alkyl group. However, R
When ^4 represents a methyl group, R^1 is an alkyl group having 3 to 7 carbon atoms. ] A plant disease control agent characterized by containing a pyridyltriazine derivative represented by the following as an active ingredient.