JPS59157071A - Azole derivative, its preparation, and fungicide for agriculture and horticulture containing it as active ingredient - Google Patents

Abstract

NEW MATERIAL:An azole derivative shown by the formula I (X is halogen, lower alkyl, lower alkoxy, or nitro; n is 0-3; Y is O or S; Az is imidozol-1-yl, or 1,2,4-triazol-1-yl). EXAMPLE:N-[alpha-(4-Chlorophenylthio)-t-butylacetyl]imidazole. USE:A fungicide for agriculture and horticulture. Useful against blast of rice plant and powdery mildew of barley, etc. It can be used for preventing and remedying several blights of plants, usable for paddy-rice plant, various kinds of grain, vegetables, orchards, lawns, tea plantations, parks, etc. PREPARATION:A substituted acetic acid shown by the formula II or its reactive derivative is reacted with imidazole, triazole, or its reactive derivative in a solvent optionally in the presence of a reaction auxiliary at 10 deg.C- 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 compound of the general formula [I] [wherein X represents a halo poppy atom, a lower alkyl group, a lower alkoxyl group or a nitro group]. n represents an integer from 0 to 3.

Y represents an oxygen atom or a sulfur atom; 1゜Az represents an imidazol-1-yl group or a 1,2゜4-triazole-1
- Represents an yl group. The present invention relates to a method for producing the azole derivative (hereinafter referred to as the compound of the present invention) represented by the following formula, and an agricultural and horticultural fungicide containing the same as an active ingredient.

As a result of intensive research into azole derivatives, the present inventors discovered that the compound of the present invention has excellent efficacy as a fungicide for agricultural and horticultural use, and completed the present invention.

The compounds of the present invention can be used to treat various plant diseases that are problematic in agriculture and horticulture, such as rice blast (Pyricularia rice blast).
oryzae), sesame leaf blight (Cochlio-1
) UIIJS mlyabeanus), apple molinia (Sclerotinia mali), powdery mildew (PodospbaeraIeucotricl)
la), Venturia 1naequal
is ), leaf fall disease (Alternaria mali
), pear black spot (Alternaria kikuc
biana), powdery mildew (Pbyll-acLini
a pyri), Gymnosporang disease
rum har-aeanum), Vent
uria rlashicola), citrus edge or O'fM (Penicillium digita)
turn), 1; Pgnicillium
italicum), powdery mildew of oysters (Phyll.
actinia kakicola), anthracnose (Gl
oeosporium i<aki), leaf fall disease (Ce
rcospora kaki.

Mycosphaerella nawae), grape late rot disease (Glomerella cingulat)
a), powdery mildew (Uncin-ula necaj)
or ), Phakopsora ampel
opsidis), powdery mildew of barley (Erysi
pHe graminis f.

sp, hordei), Rhynchos
porium 5ec-alis), spotted leaf disease (Pyr
enophora graminea), Net Vig4
(Pyrenophora teres), Black Sahih
(Puccinia graminis), yellow rust (Puccinia triiformis), wheat rust (Puccinina recondit)
a), leaf blight (Septoria tritici)
, Leptosphaerianodorum
, ), yellow rust (Puccinia triifor
mis), powdery mildew (Erysiphe gram
inis f, sp, tritici beauty eye spot (Pseudocercosporel la h
erpotrich.

1des), powdery mildew of cucurbits (Sphaerot
heca ful-1g1nea), vine blight (M
ycosphaerella melonis), anthracnose (Colletotrichum lagenar)
ium), tomato powdery mildew (Erysiphec
jcboracearum), Alter
naria 5olani), eggplant powdery mildew (E
, cichoracearum), powdery mildew of green pepper (Leveillula taurica),
Strawberry powdery mildew (Sephaerotheca h)
umuli), tobacco powdery mildew (E, cicho
racearum), Akaboshi disease (Alternaria
Io-ngipes), anthracnose (Colletot
richum tabacum), brown spot of sugar beet (
Cercospora betjcola), summer blight of potatoes (Alternaria 5olani)
, groundnut black astringent disease (Cercosporidium
personatum), brown spot disease (Cercospo
ra arachidicola), brown thrush (Septoria glycines), anthracnose (
Col let -otrichum sp, Cercospora kikuchii, Sclerotinia cinere of stone fruit trees.
a), Botrytis blight, which affects various crops;
S cinerea), Sclerotini
It is useful as a fungicide against bacteria such as Asclerotiorum. It can be used preventively as well as therapeutically as a fungicide against some of these plant diseases.

Therefore, the compound of the present invention can be used not only for paddy rice but also for various grains, vegetables, orchards, lawns, pastures, tea gardens, mulberry gardens, etc.
It is useful as a disinfectant for rubber plantations, etc.

In addition, in the present invention, the i10gen atom refers to a fluorine atom,
Represents a chlorine atom, bromine atom or iodine atom.

In addition, the compound of the present invention has an asymmetric carbon at the acid site and has optical isomers, but the present invention includes both racemates and optical isomers1. Salts of azole bladder conductors represented by J are also included, and salts include acids that are physiologically acceptable to plants, such as inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, and phosphoric acid. Examples include salts with carboxylic acids such as acetic acid, trichloroacetic acid, maleic acid, and succinic acids, and sulfonic acids such as p-1-luenesulfonic acid.

The compound of the present invention has the general formula [kawa [In the formula, X, n and Y have the same meanings as above.

] It can be produced by reacting the substituted acetic acid shown in the following formula or its reactive derivative with imidazole, triazole or their reactive derivative. In this case, the solvent may be hydrocarbons (benzene, toluene, hexane, etc.), halogenated hydrocarbons (chlorobenzene,
(methylene chloride, chloroporm, etc.), ethers (ethyl ether, tetrahydrofuran, dioxane, etc.), ketones (acetone, methyl isobutyl ketone, etc.), esters (ethyl acetate, etc.), nitriles (acetonitrile, etc.), as well as dimethyl sulfoxide, dimethyl Polamide, pyridine, etc. may be used alone or in combination, or may not be used, preferably acetonitrile. In the reaction, 04 to 2.2 equivalents, preferably 0.5 to 1.1 equivalents of a substituted acetic acid represented by the general formula Ell or a reactive derivative thereof is added to imidazole, triazole, or a reactive derivative thereof. Conversely, imidazole, triazole, or a reactive derivative thereof can be added to substituted acetic acid or a reactive derivative thereof. Further, the reaction temperature can be any temperature from the freezing point to the boiling point of the solvent, preferably from 0° C. to the boiling point of the solvent.

The substituted acid or its reactive derivative represented by the general formula [i] is the corresponding carbibone acid anhydride, acid chloride, acid bromide, etc., and includes imidazoyl, triazole, or their reactive derivatives. Examples include imitazonopetriazole, carponyldiimikuzole, thionyldiimidazole, thionyldi, triazole, imidazole, and sodium or potassium salts of triazole.

In addition, suitable reaction aids, such as substituted acetic acid and imidazole, or in the case of triazole, dicyclohexylcarbodiimide, phosphorus pentachloride, thionyl chloride, etc., are added to the substituted acetic acid and the corresponding acid chloride or acid bromide and imidazole or In the case of triazoles, sodium carbonate, sodium bicarbonate, potassium carbonate, triethylamine,
The reaction can be carried out using pyridine, N,N-dimethycyleaniline, N-methylmorpholine, etc., preferably with or without triethylamine in an amount of 0.95 to 1.1 equivalents. After the reaction is completed, the reaction agent 5 or its reaction product is removed by filtration or water sushi, etc., and the solvent is removed to obtain the azole derivative 4 represented by the general formula Fil. This product can be further processed by recrystallizing it with ether, isopropyl ether, hexane, benzene, ethyl alcohol, etc., or by performing column chromatography. .

The substituted vinegar C, which is represented by the general formula [river], which is the starting material, is
Substituted phenol and substituted thiophenol corresponding to α-furomo~t,-butyl acetate grade from J, Am, #em', Sa
The following is a production example which can be obtained by the method described in J. C., 42, 2385 (1920).

Production Example 1 Acetonitrile 3 (l
w, Imiguso” −/I/ 0.7 B y and 0・
Charge 1.1y of triethylamine and stir at room temperature]l-1
4, 2.5y of U-(4-chlorophenylthiono-t-butylacetyl chloride) was added dropwise. After the addition, the reaction solution was stirred for 4 hours, and the reaction mixture was poured into ice water aoom
Pour into 100% ethyl ether. Extracted three times with d.

After drying the organic oil over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from diisopropyl ether to obtain the desired N-(α-(4-chlorophenylthi, t)-t~ Bunalacetyl]imidazole [compound of the present invention +7)" 1.66 y was obtained.

m, p, 98-94°C Production Example 2 1.25y of acetonitrile 30- and 1,2.4-)riazole were charged into a 50-volume 4-volume flask, and while stirring at room temperature, α-(2,4-dichlorophenoxy )-t-butylacetyl chloride, 2.5y, was added dropwise. After the dropwise addition was completed, the reaction solution was stirred for 5 hours, and the reaction mixture was soaked in ice water at 300 °C.
The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography. 1-[α-(2,'4-dichlorophenoxy)-butylacetyl)-1,2,4
-Triazole [Compound (4) of the present invention] m, p, 87-88°C Production Example 3 Into a 59 me volume 4 flask were charged dehydrated tetrahydrofuran Some and Ql, and 2.80 y of 1-carbonyldiimidazole, and stirred at room temperature. Then, α-phenylthio-[-butylacetic acid was added dropwise. After completion of the dropwise addition, the reaction solution was heated and circulated for 6 hours, and a good reaction mixture was concentrated under reduced pressure.

The obtained residue was purified by silica gel column chromatography to obtain N-(α-phenylthio-''tt-butylacetylmixol [compound of the present invention (5j) 1.
Obtained 81y.

Table 1 shows some of the compounds of the present invention that can be prepared by a method such as nD221J63.

Table 1 (Note) 1m is imidazol-1-yl group, Tr is 1,
2. Indicates a 4-triazol-1-yl group.

When the compound of the present invention is actually applied, it is usually mixed with a solid or liquid carrier in order to improve the dispersion of the active ingredient at the point of use, and if necessary, various formulation auxiliaries, such as surface active It is formulated into oils, emulsions, wettable powders, granules, powders, sol, etc. by adding agents, wetting agents, fixing agents, thickeners, and stabilizers. These preparations contain the compound of the present invention in a weight ratio of 0.1 to 99.9%, preferably 0.2 to 8%.
Prepare according to the usual formulation method so that it contains 0%.

Solid carriers include vegetable carriers (e.g., tobacco, corn, wheat flour, rice flour, walnut flour, wood flour, cellulose powder), synthetic resin carriers (e.g., vinyl chloride, polystyrene, polyethylene, petroleum resin), and mineral materials. Supports (e.g. clays such as attaparkus clay, kaolin clay, bentonite, acid clay, sericite, vermiculite, and phyllite, talcum, anhydrite, diatomaceous earth, zeolite, light oil, borax, activated carbon, white carbon, gypsum) , fertilizer carriers (for example, ammonium sulfate, ammonium phosphorus, ammonium nitrate, ammonium chloride, urea, or their chemical fertilizers).

Liquid carriers include aliphatic and cycloaliphatic hydrocarbon carriers (
The analogy is kerosene1. Machine oil, mineral spirits, solvent naphtha), aromatic hydrocarbon carriers (e.g. xylene, methylnaphthalene), alcohol carriers (e.g. xylene, methylnaphthalene), alcohol carriers (e.g. methyl alcohol, ethyl alcohol, ethylene glycol) , polyethylene polyseal, polypropylene glycol), ether carriers (e.g., cyoxane, selonulf), ketone carriers (e.g., methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, impolon), halokenized hydrocarbon carriers (e.g., dichloroethane, trichloro), minitan, carbon tetrachloride), esters, nidocyl, amides and other carriers (such as dioctyl phthalate, tricresyl phosphate-1-, acetonitrile, dimethylformamide, dimethyl sulfoxide, nonylphenol, fats and oils) and water. The carrier is opened.

Next, various formulation auxiliaries, such as surfactants, wetting agents, fixing agents, thickeners, and stabilizers, include sulfonic acids such as alkylsulfodiFla salts, sulfosuccinates, and alkylarylsulfonates. salts, ester sulfates, alkyl sulfates, ether sulfates, sulfate ester salts such as alkylaryl ether sulfur phosphate, phosphate ester salts such as alkylaryl ether phosphate, formalin condensed sulfonates, other carboxylic acids, etc. anionic surfactants, ethers such as alkyl and alkylaryl polyoxyethylene ether block polymers, ether esters such as polyoxyethylene ethers of sorbitan esters, esters of sorbitol polyoxyethylene ethers, polyoxyethylene fatty acid esters, chrycerin esters, Nonionic surfactants such as esters such as sorbitan ester and sucrose ester, casein, ceratin, starch, CMC (carboxymethyl cellulose), PVA (polyvinyl alcohol), gum abyss, water bath polymeric calcium such as alginic acid, molasses, agar, etc. Sodium lignosulfonate, stearic acid, oleic acid, palmity, wisteria, pine oil,
Various fatty acids or their esters such as tall oil, pine oil, soybean oil, liquid paraffin, epoxidized parts, 'I'C
Examples include P (+ licresyl phosphate), PAP (isopropyl acid phosphate), and bentonite.

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 Compound of the present invention (7) sO parts, 3 parts of lignin sulfone rice calcium, sodium lauryl sulfate. 8 oyo. , 8
58, I, silicon ↓ 5 parts.

Mix well to obtain a wettable powder.

Formulation Example 2 8110 parts of the compound of the present invention, 14 g of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulposinate, and 70 parts of xylene are thoroughly mixed to obtain an emulsion.

Formulation Example 3 Compound of the present invention (1)2. @, Synthetic hydrated silicon oxide 1,! J
2 parts of calcium genin sulfonate, 30 parts of bentonite and 65f4 of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, and then granulated and dried to obtain a powder.

Formulation Example 4 25 parts of the compound of the present invention (4), 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water were mixed together and suspended by wet grinding until the particle size of the active ingredient became 5 microns or less. get the agent.

Preparation 2 Example 5 Compound θ7/0.2 parts of the present invention, kaolin clay 89
．． 8@ and 10 parts of Hytalc are thoroughly ground and mixed to obtain a powder. The preparation thus prepared is applied as it is or diluted with water according to a conventional method.

Of course, it can also be applied simultaneously with or without mixing with other five fungicides, fungicides, nematicides, insecticides, seed disinfectants, herbicides, fertilizers, soil conditioners, etc. in,
Wear.

When applying the compound of the present invention as a fungicide for agricultural and horticultural purposes, the amount of application depends on weather conditions, the type of target plant, the growth stage, the growth situation, the type of disease, the state of disease onset, the application/timing of the cross-reagent, or the method of application. Although it varies depending on conditions such as dosage form, the active ingredient is usually 2 to 5. OOy is appropriate. Furthermore, the applied concentration is 0.001 in terms of effective strength.
A range of ~10% is desirable. Application methods include spraying, dusting, and foliage treatment on crops, soil mixed layer treatment,
Examples include soil irrigation, root immersion treatment, and seed treatment.

Next, tests and examples will show that the three unexploded compounds are useful as active ingredients of agricultural and horticultural 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 2.

Table 2 The bactericidal effect was determined by visually observing the disease state of the test plants at the time of the survey, that is, the degree of lesions on leaves, stems, etc.
If the disease is not observed, it is U3-1, if about 10 parts of untreated plants are observed, it is 4, and if about 80 parts are observed, it is 1.
3, if about 50 parts are observed, r2J is observed, if about 70 parts are observed, rB, and if it is above 70 parts, no difference from the disease state of untreated plants should be observed. For example, it is evaluated as "0" and evaluated in six stages from 0 to 5, and is shown as 0, 1.2.3.4.5.

Test Example 1 Oumki udon disease control test (preventive effect) Fill a plastic pot with sandy loam, sow Oumuki (variety: Goune Shiseki), and keep it in a greenhouse for 6 days. , L
,Ta. A test compound prepared as an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration, and sprayed on the foliage of young seedlings whose first true leaves had developed so as to sufficiently adhere to the leaf surface.

After spraying, the plants were grown in a greenhouse for one day and inoculated with spores of powdery mildew fungus. After inoculation, the plants were grown for 10 days under artificial lighting at 23°C, and the bactericidal effect was investigated. The results are shown in Table 3.

Table 3

Claims (1)

[Claims] fil General formula In the formula, X represents a halogen atom, a lower alkyl group, a lower alkoxyl group or a nitro group, Cn represents an integer from O to 8, and Y represents an oxygen atom or a sulfur atom. The former represents an imidazol-1-yl group or a 1.2.4-triazol-1-yl group. ] An azole derivative represented by (2) Claim 1, wherein X is a halogen atom, n is l or 2, Y is an oxygen atom, and is Az or 1,2,4-triazol-1-yl group Azole derivatives described in. (3) In claim 1, wherein X is a halogen atom, a methoxy group, or a nitro group, n is 1 or 2, Y is a sulfur atom, and Az is an imidazol-1-yl group. Azole derivatives as described. (4) General formula [wherein X represents a halogen atom, a lower alkyl group, a lower alkoxyl group or a nitro group]. n represents an integer from 0 to 3. Y represents an oxygen atom or a sulfur atom. [In the formula, X, 1] and Y have the same meanings as above. Az is imidazol-1-yl group or 1.2.44
Represents a lyazol-1-yl group. ] Method for producing an azole derivative represented by the following (5) General formula [wherein, X represents a halogen atom, a lower alkyl group, a lower alkoxyl group, or a nitro group. n represents an integer from 0 to 3. , Y represents an oxygen atom or a sulfur atom. Az is imidazol-1-yl group or 1,2.4-)
Represents a lyazole-nyyl group. ] An agricultural and horticultural fungicide characterized by containing an azole derivative represented by the following as an active ingredient.