JPS62289576A - Triazole derivative, production thereof and fungicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The triazole derivative of formula I (R is H, lower alkyl, lower alkoxy, halogen or nitro; m is 1-5; Y is -OSO2- or -NH-). EXAMPLE:2-( 2, 4-Dichlorophenyl )-2-( 1H-1,2,4-triazol-1-ylmethyl )-1-,3-dioxolan-4- ylmethyl 4-fluorobenzenesulfonate. USE:Useful as a fungicide exhibiting preventive, remedying and systemic controlling activity against a variety of plant blights such as rice blast, helminthosporium leaf spot of rice, black spot of rose, etc. PREPARATION:The compound of formula I can be produced by reacting 2-(2,4- dichlorophenyl)-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxolan-4-ylmethyl alcohol with a sulfonyl chloride derivative of formula II.

Description

Detailed Description of the Invention [In the formula, RCL- represents an elementary atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a nitro group, m represents an integer of 1 to 5, and Y41-osoz- or a group
Representing -NH-, the triazole derivative represented by ] is referred to as the compound of the present invention. ), as a result of intensive studies aimed at developing high-performance VW1 killer, the present inventors discovered that the compound of the present invention represented by general formula (I) has proven effective as a preventive and therapeutic agent against many plant diseases. The present inventors have discovered that it has a systemic and systemic control effect.

Plant diseases against which the compound of the present invention is effective include rice blast (Pyricu-1aria oryzae);
, Sesame leaf blight (Cochliobolus m1ya)
beanus), sheath blight (Rh-izoctoni)
a 5olani) % Powdery mildew of wheat (Erys
iphe graainis f,sp+hor-de
iJ, sp, tritici), Fusarium head blight (Gi
bberella zeae), Rust (Pucc
in-ia stritformis+ P, gram
inis+ P, recondita, P, horde
i) , snow rot (Typhul-a sp, , Micr
onectriella n1valis), naked smut (Ustilago triticLU, nu-
da), Eye Spot (Pseudocercosp)
orella herpotrichoides)
, Rhynchosporiw 5ecali
s) Septoria tritici
, Le-ptosphaeria nodo
r+ns) % Citrus black spot (Diaporth)
e eitri), Souriki44 (Elsinoe
fawcetti), NX1XlfE? j
(Penicillin+digitatu+m,
PA 1ta- 1icu+i), apple monilia disease C3cler
otinia & l1i), Q leprosy (Valsa
mali), powdery mildew (Podosphaera
1e+x:otricha), leaf spot disease (Al
tern-aria 5ali), scabosis (Ven
turia 1naequalis), pear scab (Ven tur-ia nashicola),
black spot (Alternaria kikuchiana)
), Akaboshi disease (Gywr+ospo-rangiw)
haraeanus), peach mars disease<5cler
otinia cinerea), scuriosis (Cla
dosporiuwcarpophilu+a) % Phowpsis rot (Phowpsis sp, ), Grape black rot (Elsinoe ampelina)
, late rot (GIOIIIerella cingul)
ate), powdery mildew (Uncinula necat)
or), Rust (Phakopsora ampel)
opsidis), oyster anthracnose (G1oeospo
riu* kaki) % leaf fall disease (Cercospo
ra kaki, Mycos-phaerella
nawae), anthracnose disease (Colletot
rich+miagenariu+s), powdery mildew (Sphaerotheca fuliginea)
% Vine blight (Mycosphaerella mel)
-onis) s) Mado ring disease (Alternar)
ia 5olani), leaf mold (C1adosp
ori-uw fulvus+)-Eggplant brown spot disease (P
hosopsis vwans), powdery mildew (Er
ysip-he cichoracear+zm),
Black spot of cruciferous vegetables (Alternaria ja
ponica), vitiligo disease (Cercosporell
a brassicae), allium rust (Puc
cinia allii), soybean purpura (Cerc
ospora kikuchii), black cabbage (E
lsinoe glycines), black spot (Diap
orthe phaseolorus war, 5
ajae), kidney bean anthracnose (Co-11eto)
trichw Iindemuthianus ) %
Mycosphaerellap
ersonatus), Cercosp.
ora arachidicola) % Powdery mildew of pea (Erysiphepisi), summer wasting disease of potato (Alternaria 5olani)
, strawberry powdery mildew (Sphaerotheca h
uwli), tea net blast disease (Exobas-id
iw reticulatull), white star disease (Els
inoe 1eucospila) %Tobacco Erysiphe cichoracear (Alternaria longipes) %Powdery mildew (Erysiphe cichoracear
u+m), anthrax (Colletotrichw t)
ahacum), sugar beet brown spot (Cercosp)
ora beticola), rose blight (Dtpl
ocarpon rosae), powdery mildew (Sp
septoria the-ca pannosa), septoria chrysanthemum
i-4ndici), white rust (Puccinia
horiana), Botrytis blight (Bot
rytis cinerea) Ichinobumi (Among the triacytwill conductors represented by [I], the triacyl-1JvHL body represented by the general formula where Y is a group -osot is 2- (2,4
-dichlorophenyl)-2-(IH-1,2,4-triazol-1-ylmethyl)-1,3 [wherein R and m have the same meanings as above]; It can be produced by reaction.

The reaction is usually carried out without a solvent or in a solvent in the presence of a dehydrohalogenating agent, with a reaction temperature range of 0 to 50°C and a reaction time range of 0.1 to 10 hours. The amount of reagent used is 2-(2,4-dichlorophenyl)-
Sulfonyl chloride derivative (II
I) is 1 to 1.2 equivalents, and the dehydrohalogenating agent is 1 to 10 equivalents.
It is equivalent.

Examples of solvents include hydrocarbons such as hexane, heptane, and Ligloy 7, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and diethylene glycol dimethyl ether, and M ethyl,
Esteno I such as ethyl acetate, butyl acetate, diethyl carbonate, etc.
Nitrogen t such as acetonitrile, isobutyronitrile, etc.
4. Tertiary amines such as pyridine, triethylamine, N, N-diethylaniline, tributylamine, and N-methylformorif; acid amides such as formamide, N, N-dimethylformamide, and acetamide; sulfur such as dimethyl sulfoxide and sulfolane; Examples include compounds and mixtures thereof.

Examples of dehydrohalogenation agents include organic bases such as pyridine, triethylamine, N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride, sodium methoxide, and sodium hydroxide. Examples include alkali metal alkoxides such as ethoxides.

After completion of the reaction, the reaction solution can be subjected to conventional treatments such as organic solvent extraction and concentration, and if necessary, purified by operations such as chromatography, distillation, and recrystallization to obtain the desired compound of the present invention. can.

Among the triazole derivatives represented by the general formula (1), the triazole derivatives in which Y is a group -NH- are:
2-<2.4-dichlorophenyl)-2-(IH-1
,2,4-)riazol-1-ylmethyl)-1,3-
Produced by reacting dioxolan-4-ylmethyl methylsulfonate with an aniline derivative represented by the general formula CV)2 and ΣNl(! (v) (wherein R and m have the same meanings as above). Can be done.

The reaction is usually carried out without a solvent or in a solvent, the reaction temperature ranges from 50 to 180°C, the reaction time ranges from 1 to 50 hours, and the amount of reagents used for the reaction is 2-(2,4 -dichlorophenyl)-2-(IH-1,2,4-triazol-1-ylmethyl)-1,3-dioxolan-4-ylmethyl The aniline derivative (V) is used in an amount of 1 to 5 equivalents per equivalent of methylsulfonate. be.

As a solvent, aromatic hydrocarbons such as benzene, toluene, xylene, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether (14) L4M
, pyridine, triethylamine, N,N-diethylaniline, tributylamine, tertiary amines such as N-methylformorif; acid amides such as formamide, N,N-dimethylformamide, acetamide; sulfur compounds such as dimethylsulfoxide, sulfolane; Or a mixture of them can also be used.

After completion of the reaction, the reaction solution is subjected to conventional treatments such as organic solvent extraction and concentration, and if necessary, purified by operations such as chromatography and recrystallization to obtain the desired compound of the present invention.

Next, production examples of the compounds of the present invention will be shown.

Production Example 1 2-(2,4-dichlorophenyl)-2-(IH-1) of the invention compound (4)
,2,4-)lyazol-1-ylmethyl)-1,3
-Dioxolan-4-yl methyl alcohol 3.30g
, 2.34 g of 4-fluorobenzenesulfonyl chloride
and pyridine 20M1 were mixed and stirred in a greenhouse for 3 hours. After distilling off the pyridine under reduced pressure, dichloromethane 5
0- was added and washed sequentially with water and 20 d of saturated saline solution. After drying over anhydrous sodium sulfate, dichloromethane was distilled off under reduced pressure. The concentrated residue was subjected to silica gel chromatography using chloroform to obtain crystals. Recrystallized from benzene to give 2-(2,4-dichlorophenyl)-2
-(IJ(-1,2,4-)riazol-1-ylmethyl)-1,3-dioxolan-4-ylmethyl 4-fluorobenzenesulfone) 3.94 g was obtained. (Yield 80.7%, temperature 121-122°C) Production Example 2 Preparation of Invention Compound (12) 2-(2,4-dichlorophenyl)-2-(IH-1,2,4-triazole-1
3.92 g of -1,3-dioxolan-4-ylmethylmethylsulfonate and 3.24 g of 2,4-dichloroaniline were added to 30 d of xylene, and the solution was heated under reflux for 15 hours. After cooling to room temperature, xylene was distilled off under reduced pressure. 50 ml of dichloromethane was added to the concentrated residue, and the mixture was washed successively with a saturated aqueous sodium bicarbonate solution and saturated saline solution 30Pt. After drying over anhydrous sodium sulfate, dichloromethane was distilled off under reduced pressure. The target product was subjected to chloroform rechromatography using a sieve, and 2.90 g of 2- (2,4-
Dichlorophenyl)-2-(IH-1,2,4-triazol-1-ylmethyl)-4-(2,4-dichloroanilinomethyl)-1,3-dioxolane was obtained. (
(Yield: 61.2%) Some of the compounds of the present invention that can be produced by such a production method are summarized (optical isomers of these are also included in the present invention).

・2- which is a raw material compound when producing the compound of the present invention
(2,4-dichlorophenyl')-2-(IH-1,2
,4-triazol-1-ylmethyl)-1,3-dioxolan-4-ylmethyl alcohol and 2-(2
,4-dichlorophenyl)-2-(1)! -1, 2, 4
-) Riazol-1-ylmethyl)-1,3-dioxolan-4-ylmethyl Methyl sulfonate is Jour
nal of Medicinal Che
It is a known compound described in Mistry Vol. 22, p. 1003 (1979).

When using an uninvented compound as an active ingredient of a fungicide,
It can be used as is without adding any other ingredients (usually the active ingredient content in solid carriers, liquid carriers, and formulations of compounds is 0.1 to 99.9%, preferably 1 to 90%). %
It is.

Examples of the above-mentioned solid materials include kaolin clay, aphthapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrous silicon oxide, etc. 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, and soybeans. For example, organic solvents, organic solvents such as cottonseed oil, dimethyl sulfoxide, acetonitrile, water, etc. Surfactants used for emulsification, dispersion, wetlands, etc. include alkyl)L4m ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid. Also included are anionic surfactants such as formalin metal condensates, polyoxyethylene alkyl ether block copolymers, sorbitan fatty acid esters, and nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters.

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

Next, formulation examples are shown. Note that ``bu'' represents 1 mon rikai.

Formulation Example 1 50 parts of the compounds (1) to (16) of the present invention, 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrated silicon oxide are ground and mixed to obtain a wettable powder.

Formulation Example 2 25 parts of the compounds (1) to (16) of the present invention, 3 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 S micron or less. to obtain a suspension.

Formulation Example 3 2 parts of the compounds (1) to (16) of the present invention, 8 parts of kaolin clay
7 parts and 10 parts of talc (pulverized and mixed to obtain a powder).

Formulation Example 4 20 parts of the compounds (1) to (16) of the present invention, polyoxine ethylene styrylphenyl ether and 60 parts of xylene are thoroughly mixed to obtain an emulsion.

Compounds of the present invention (1) to (16) of the Preparation Foundation! 30 parts of bentonite and 87 parts of kaolin clay were thoroughly ground and mixed,
After adding water and kneading well, the mixture is granulated and dried to obtain granules.

These formulations J are sprayed or treated on seeds as they are or after being diluted with water. Also, by mixing it with other fungicides, the killing effect can be enhanced. In addition, insecticides, insecticides, green insecticides, weed killers, etc. It can also be used in combination with plant growth 22 Qi 1 and fertilizer.

When the compound of the present invention is used as an active ingredient of Bactericidal Seri 1,
The application amount of the active ingredient is usually 0. 1
~100g, preferably 0.2-20g, emulsion,
When applying wettable powders, suspension agents, etc. diluted with water, the application concentration is 0.001 to 0.5%, preferably o, oos.
~0.2%, and powdered or granulated seeds can be applied as is without any dilution.

Next, test examples will show that the compounds of the present invention are useful as seedlings.

Observe the degree of plexus and lesions with the naked eye, and if no lesions are observed at all, it will be 752, and if about 10% is observed, it will be ``4'', 3.
If it is observed in about 0%, it is ``3'', if it is observed in 50%, it is ``2'', if it is observed in 70%, it is ``1'', and if it is more than that, it is rated ``1''. 0", and evaluated on a 6-level scale, with 5.4.3 respectively.
．． 2. Indicated by 1,0.

wM41 Groundnut brown spot disease control test (preventive effect) A quasi-suspended solution of Formulation Example 4 was applied to young groundnut seedlings, which were filled with sandy loam in plastic pots, sown with Chiba Hantateya, and grown in a greenhouse for 14 days. The solution was inoculated by spraying. After inoculation, it was kept at 23℃ and high humidity for 7 days, and then grown in a greenhouse for another 7 days to investigate the control efficacy. The results are shown in Table 3. Table 3 Test Example 2 Apple Black Star Disease control test (preparation) V-biting plastic pots were filled with sandy loam, apples were sown, and grown in a greenhouse for 20 days. Apple seedlings with the 4th to 5th true leaves developed were treated with heavy liquid in Formulation Example 1. was sprayed and inoculated.After inoculation,
After being kept at 15℃ for 4 days under high humidity, it was further kept under lighting for 1
The plants were grown for 5 days and their pesticidal efficacy was investigated. The results are shown in Table 4 Table 4 Test Example 3 Wheat powdery mildew control test
Plastic bores) were filled with sandy loam, and Wheat (Wheat No. 73) was sown and grown in a room 11 for 10 days. Wheat seedlings that had developed their second leaves were sprinkled with spores of wheat powdery mildew and inoculated. After inoculation, the test compound was grown in a greenhouse at 23° C. for 3 days and made into a suspension according to Formulation Example 2. The test compound was diluted with water to a predetermined concentration and sprayed on the foliage so that it would sufficiently adhere to the leaf surface. After spraying, the plants were grown in an IW room at 23°C for 6 days and their pesticidal efficacy was investigated. The results are shown in Table 5.

Table 5 Test Example 4 Wheat Rust Control Test (Plastic pots for the treatment were filled with sandy loam, Wheat My Lin No. 73) were sown and grown in a greenhouse for 10 days. Wheat seedlings that had developed their second leaves were inoculated with spores of the wheat rust fungus. After inoculation, the plants were grown for 1 day at 23° C. under humid conditions, and the test compound was made into an emulsion according to Formulation Example 4, 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 6 days under illumination at 23°C and their pesticidal efficacy was investigated. The results are shown in Table 6.

Table 6 Test Example 5 Wheat powdery mildew control test (Plastic pots filled with sandy loam soil
No. 3) was sown and grown in a greenhouse for 10 days. Wheat seedlings that had opened their second leaf were inoculated by pouring Formulation Example 1 on them. After inoculation, the plants were grown in a greenhouse at 23°C for 7 days, and their pesticidal efficacy was investigated.

The results are shown in Table 7.

Table 7

Claims (1)

[Claims] 1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or a nitro group, and m is 1 to
represents an integer of 5, Y is a group -OSO_2- or a group -N
Represents H-. ] A triazole derivative represented by (2) 2-(2,4-dichlorophenyl)-2-(1H
-1,2,4-triazol-1-ylmethyl)-1,
3-dioxolan-4-yl methyl alcohol and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or a nitro group, and m is 1 ~
Represents an integer of 5. ] There are general formulas ▲ numerical formulas, chemical formulas, tables, etc. ▼ [wherein R and m have the same meanings as above. ] A method for producing a triazole derivative. (3) 2-(2,4-dichlorophenyl)-2-(1H
-1,2,4-triazol-1-ylmethyl)-1,
3-Dioxolan-4-ylmethylmethylsulfonate and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a hydrogen atom, lower alkyl group, lower alkoxy group, halogen atom or nitro group, m is 1~
Represents an integer of 5. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [wherein R and m have the same meanings as above. ] A method for producing a triazole derivative. 4) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or a nitro group, and m is 1 to
represents an integer of 5, Y is a group -OSO_2- or a group -N
Represents H-. ] A disinfectant characterized by containing a triazole derivative represented by the following as an active ingredient.