JPS62108868A - Azole derivative, production thereof and germicide containing said derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (A is formula IV or V; Az is 1,2,4-triazole or imidazole; X1 and X2 are halogen; n is 1 or 2). EXAMPLE:1-(1,2,4-Triazol-1')-1-[4'-(beta,beta-dichlorovinyl)-2'-chlo-r ophenoxy]-3,3-dime thylbutan-2-one. USE:A germicide having a wide activity spectrum, capable of exhibiting improved germicidal activity against powdery mildew, black spot, loose smut, gray mold, anthracnose, blast, helminthosporium leaf spot, sheath blight, etc., and useful for controlling blights of crops, e.g. vegetable, rice plant, fruit tree, etc. PREPARATION:For example, a halide expressed by formula II (X3 is X1 or X2) is reacted with an azole derivative expressed by formula III in a solvent in the presence of an acid acceptor, e.g. NaH, at room temperature - 100 deg.C for 5-10hr to afford the aimed compound expressed by formula I (A is formula IV), which is then reduced in a solvent in the presence of NaBH4, etc., to give the compound expressed by formula I (A is formula V).

Description

DETAILED DESCRIPTION OF THE INVENTION In the formula 0 0H E, A represents a -C- group or -CHM. Az is 1,
2.4- Represents a triazole group or an imidazole group. xl and x2 represent halogen atoms, n is l or 2
represents. ] An azole derivative represented by

L formula +il XI, X2 and X8 represent a halogen atom, and n represents 1 or 2. ] A halogen compound represented by the general formula % Formula % [wherein Az represents a 1,2.4-triazole group or an imidazole group. ] by reacting with an azole derivative represented by Az [wherein Az Sxl, X2 and n are the same as above. ] A method for producing an azole derivative, characterized by obtaining an azole derivative represented by the following.

(2) General formula [wherein Az represents a 1,2,4-triazole group or an imidazole group. xl and X2 represent /% rogen atoms; n represents 1 or 2; 1. ] by reducing the azole derivative represented by the general formula [wherein Az, Xl, X2 and n are the same as above. ] Process for producing an azole conductor 1 characterized by obtaining an azole derivative represented by the formula (1) General formula % Formula % E where A represents a -C- group or a -CH- group, -.

Az represents a 1,2,4-) lyazole group or an imidazole group. Xl and X2 represent halogen atoms, n
represents l or 2. ] A disinfectant characterized by containing an azole derivative represented by the following as an active ingredient.

Detailed description of the invention.

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel azole derivative, a method for producing the same, and a fungicide containing the derivative as an active ingredient.

Prior Art Compounds that are considered to be most similar to the compounds of the present invention include, for example, compounds with the general formula [wherein R is a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkylthio group, a haloalkylsulfonyl group] Or represents a phenyl group. ] [JP-A-48-80561].

All of the 4 azoles tJrL' expressed by the above general formula have good bactericidal activity against pathogenic bacteria such as powdery mildew, scab, and smut, but they are also effective against diseases other than these, such as botrytis blight. It is said that it has weak bactericidal activity against pathogens such as moxibustion, rice blast, and sesame seeds, and has a narrow spectrum of activity (it has tsukudani).

DETAILED DESCRIPTION OF THE INVENTION The azole derivative of the present invention is a novel compound that has not been described in any literature, and is represented by the following general formula [fl].

Az OOH 1 In the formula, A represents -C-2 or -CH- group. Az represents 1,2.4-) IJ azole Jk or imidazole group. xl and X2 represent a norogen atom, 1° represents 1 or 2, 1 The azole derivative represented by the general formula [11] is effective against pathogenic bacteria such as powdery mildew, scab, and smut. The bactericidal activity is equivalent to or higher than that of conventionally known compounds,
Moreover, it has excellent bactericidal activity against pathogenic bacteria such as gray mold, charcoal stain, rice blast, and sesame leaf blight, which were thought to have weak bactericidal activity with conventionally known compounds, and has the advantage of having a wide spectrum of activity. have.

The compound of the present invention can be produced by various methods, and one preferred example thereof is produced by the following method.

Reaction formula-1 1111[[OzC[;l] [In the formula, x8 represents a halogen atom. Az, XI, x2
and n are the same as above. ] Among the compounds of the present invention, compounds in which Ab<~C- group (
That is, the compound of general formula [Ia)] is produced by gJ by reacting a halogen compound represented by general formula [111] with an azole compound represented by general formula υ+IJ.

The above reaction is carried out in a suitable solvent. Examples of the solvent used include ethers such as ethyl ether, butyl ether, tetrahydrofuran, and dioxane, aromatic solvents such as benzene, toluene, and xylene, dimethylformamide, and diethylformamide. J:, the reaction is a dehydrohalogenation reaction,
This is usually carried out in the presence of an acid acceptor in the reaction system. Examples of acid acceptors used include sodium metal, sodium alcoholade, and sodium hydride. The usage ratio of the compound of general formula 10 and the compound of general formulae is 1
Although not limited to this, the latter is usually 05 for +〕J person.
1 to 80 times the molar amount, preferably 1.0 to 15 times the molar amount, and the use of the acid acceptor 11 is based on the general formula [usually 05 to 3.0 times the molar amount, preferably 1 to 1 molar amount of the compound is 1.0~
It is 1.5 times the molar weight. The reaction temperature is room temperature to 100°C, and the reaction time is about 5 to 10 hours.

Reaction formula-2 Az [Ia] Az [Ib] [In the formula, Az, Xl, X2 and n are 41! Same as above.

] Among the compounds of the present invention, the compound in which A is a -C1l- group (ie, the compound of general formula [Ib]) is produced by reducing the compound of general formula [1a] obtained above. The reduction of the compound of the general formula C1al is carried out in a conventional manner, for example using sodium borohydride. The reduction with sodium borohydride is carried out in water, methanol, ethanol, alcohols such as propane, or a mixed solvent of water and alcohols. The amount of sodium borohydride used is usually 1.0 to 5.0 times the molar amount of the compound of general formula [Ia]. The reaction temperature is 0
~50°C, and the reaction time is about 1 to 5 hours.

. The halogen compound of the general formula (1) used as a starting material is a new compound, and is prepared, for example, according to the method shown in Reaction Formula 3 below.

Reaction formula-3 [IV] [V]
f[[1 In formula 1, x4 represents a halogen atom. xl, x2, x8
and n are the same as above. 1 In the above reaction formula-8, the phenol derivative 2g compound represented by the general formula shown above, which is used as a starting material, can be obtained, for example, by a known method shown in JP-A-57-146786 @, and can also be obtained by the general formula [ Halobina Colon represented by Vl is also a known compound 3. The reaction between the compound of the general formula [1v1 and the compound of the general formula [1v1] is carried out without a solvent or in a solvent 4. Examples of the solvent used include ethyl ether, butyl ether, etc. , ethers such as tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, and cyclohexanone, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, aromas such as benzene, toluene, and xylene. Examples include family solvents, ethyl acetate, acetonitrile, dimethylformamide, and the like.

Since this reaction is a dehydrogenation reaction, an acid acceptor is usually present in the reaction system. Examples of the acid acceptor used include sulfur hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, 8th class amines such as triethylamine and tributylamine, and pyridine.

The ratio of the compound of general formula [IV] and the compound of general formula [ma] to be used is not particularly limited, but usually 0.5 to 8.0 times the molar amount of the latter to the former, preferably 1.0 to 8.0 times the molar amount of the latter. 2.0
The use of double the molar amount of 1J acid-acid acceptor is based on the general formula lvI
It is usually 1.0 to 5.0 times the molar amount, preferably 1.0 to 2.0 times the molar amount of the compound. The reaction temperature is room temperature to 150°C, and the reaction time is about 5 to 10 hours.

The reaction of halogenating the compound of general formula (11) to obtain the compound of general formula (11) is carried out in a solvent. The solvent used can be the solvent used in the reaction of the compound of general formula [iv] and the compound of general formula [ma] above. Although general reagents such as chlorine, bromine, thionyl chloride, thionyl bromide, phosphorus trichloride, and phosphorus tribromide can be used as the dihalogenating agent, it is preferable to avoid escaping dihalide by-products. uses N-710 Genoconoquimid. General formula layer]
and N/10 Genocohakuimide in the ratio C (although not limited to, the latter is usually 0 to the former).
．． It is used in an amount of 5 to 8 times the mole, preferably 1.0 to 1.5 times the mole. The reaction may or may not use a catalyst.1) As the catalyst used, peroxides such as benzoyl peroxide can be exemplified, and the catalyst used has the general formula [Vl
-(0,001 to 0.01 times molar fP
! The reaction temperature is from room temperature to 150"C, and the reaction time is from 5 to IO hours.

Compounds that can be extracted under such conditions can be easily purified without using any separation methods such as solvent extraction, bath medium dilution, recrystallization, column chromatography, etc. The compound of the present invention is characterized in that it has a wide spectrum of activity, and can be used to obtain an azole derivative represented by the general formula Lll with high purity. It exhibits excellent killing activity against anthrax mania, rice blast, sesame leaf blight, sheath blight, etc., so it can be used to control agricultural diseases such as vegetables, fruits, mulberries, etc. My number is 11.

When applying the compound of the present invention as a fungicide, the compound of the present invention may be used as it is, but generally it is mixed with an adjuvant commonly used in agricultural formulations to form one of the following dosage forms: can also be used.

Among these, powders, emulsions, and wettable powders are preferably used. In this case, examples of auxiliary agents to improve the stability and effectiveness of the effect include propagating agents such as diatomaceous earth, kaolin, clay, bentonite, white carbon, and talc, polyoxyethylene alkyl ether, and polyoxyethylene alkylphenyl. Ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, sodium alkylbenzene sulfonate,
Surfactants such as sodium lignin sulfonate, sodium alkyl sulfate, sodium polyoxyezalene alkyl sulfate, benzene, toluene, xylene, acetone,
Cyclohequinanone, methanol, ethanol, isopropyl alcohol, dioxane, dimethylformamide,
Organic solvents such as dimethyl sulfoxide and carbon tetrachloride are used.

The formulation of the fungicide composition of the present invention is formulated by adding an adjuvant so that the active ingredient is about 0.1 to 90% by weight, preferably 1 to 70% by weight, in an appropriate amount for application. varies depending on the formulation form of the drug, the method of application, the time of application, the t4m of the target disease, etc., and is selected as appropriate;
oooi% by weight, preferably 0. It is sprayed at about 1 to 0.0001% by weight.

EXAMPLES The present invention will be explained in more detail by referring to reference examples, production examples, and test examples below.

Reference example 1 1-[4-(β,β-dichlorovinyl)-2-chloro-
Production of phenoxy 1-'1,3-dimethylbutan-2-one 22.49 y of 4-(β,β-dichlorovinyl)-2-chlorophenol and 13.8 y of anhydrous potassium carbonate were added to 200
ml of methyl ethyl ketone and stirred at 60"C for 1 hour. After cooling, 18.5 F of chlorvina cologne was added and heated under reflux with stirring for 6 hours. After filtering the potassium chloride precipitated after the reaction, methyl ethyl ketone was removed under reduced pressure. Distillation gave 28.5 cm of pale yellow oil (yield: 92%).
MR(CDCj?s); Jl, 132(s, 9H), 4
．． 68 (s, 211).

6.72 (s, IH), 6.94-7.4 (1 (m
, 8H) ppm.

Reference example 2 1-[4-(β,β-dichlorovinyl)-2-chlorophenoxy]-1-from-a,a-dimethylbutane-2
-1 Production of lorphenoxy] -d, 8-dimethylbutan-2-one 3.1f, N-bromosuccinimide 2.0y and benzoyl peroxide 0.81 were added to 100ml of tetrachloride carbon water and stirred for 4 hours. It refluxed. After the reaction was cooled and the precipitate was filtered, carbon tetrachloride was distilled off under reduced pressure to give a yellow oily substance of 8.88 g.
f (yield constant ht) was obtained.

(to IR) 1718Cm-' (C=O absorption)
NMR (CDCea): δ1.32 (s, 9fl)
, 6.64 (,s, IH).

6.70 (s, 111), 6.98-7.42 (
ni, 8H) I) p+n From the above results, r was confirmed.

Example 1 = (β, β-dichlorovinyl)-2-chlorophenoxy) - Production of a, a-dimethylbutan-2-one 0.5 y of 50% oily sodium hydride was added to 10 mn of anhydrous dimethylformamide and further 1. 2.4-Triazole 0,69j' was added. After stirring for 80 minutes, 10″
1-[4-(β,β-dichlorovinyl)-2- under CU
30 ml of an ether solution containing 8.89N of chlorophenoxy]-1-bromo-3,8-dimethylbutan-2-one was added dropwise. After the dropwise addition, the mixture was reacted at room temperature for 5 hours. After reaction 5
0 m# of water was added to separate oil j-, and water Jm was extracted with ether again. The oil and needle layers were combined, washed with water, dried, and the ether was distilled off under reduced pressure to obtain a yellow colored product. = 10:1) to obtain 3.01f (yield: 80%) of a yellow oil.

IR (=-t) 1780cm-' (C=O absorption)
NMR (CDC773) iδ1.25 (s, 9H),
6.58 (s, IH).

6.86 (s, IH), 6.90-7.48 (m, 8H
).

7.84 (s, IH), 8. :(8(s,IH)ppm
From the above results, Example 2 1-(1,2,4-triazolyl-1)-1-[4'
Production of -(β,β-dichlorovinyl)-2-chlorophenoxy]-8,8-dimethylbutan-2-ol 1 -(1,2,4,-triazolyl)
-1) -1-[4-(β,β-dichlorovinyl)-2'
-Chlorphenoxy I -3,8-dimethylbutane-2
2.5 of -one was dissolved in methanol aOm6, and sodium borohydride o and sy were added little by little while stirring at room temperature. After stirring for 7 hours at a temperature of M, methanol was removed under reduced pressure. 9Ad was extracted with chloroform, washed with water, dried on a 7゜ bed, and chloroborm was removed under normal pressure to obtain a pale yellow oil (a, 6oyc yield: 96%). 011 absorption) NMR (C
DC773); δ0.98(s, 91(), 2.64f
broad.

IH), 4.10 (m, LH), 6.18 (m, IH)
.

6.62 (s, IH), 6.72 7J8jm, 8H)
.

7.76 (s, IH), 8.30 (s, IH) ppm confirmed from the above results.

Examples 3 to 25 The compounds of Examples 3 to 25 were synthesized in the same manner as in Examples 1 to 2 and Examples 1 to 2. The physical properties and spectroscopic data are summarized in Table 1. .

Test Example 1 Cucumber powdery mildew (Powdery mildew)
) Control effect on tc A pot (47.5 cm, 200 mJl! volume) and a planted cucumber seedling (variety: Natsuaki Setsei No. 2, 2-8 leaf stage) were sprayed with 5 ml/pot of a chemical solution at a predetermined concentration. After air drying, cucumber powdery mildew fungus (5phaerotheca fuligi)
nea ) spores 11! One or two weeks after spray inoculation with the suspension, the area ratio of laminae was measured and the control value was calculated.

The results and the presence or absence of drug damage are shown in Table II.

Table [1 Table II continued Bone 1-(1,2,4-F riazolyl-1)-1-(4-
chlorophenoxy) -3,3-dimethylbutane-2-
On (Triadimehon) Test Example 2 Control effect against gray mold (Grey mold) on cucumber Pot (47.5 cm, 200 mj' capacity) Planted on young cucumber (variety: Natsuaki Setsei No. 2) seedlings (2-8 leaf stage) Predetermined L
5 me/pot of chemical solution was sprayed. Botrytis cinerea after air drying
The cells were inoculated by spraying with Ala IGr solution. The lesion area ratio after 7 Els was measured and the control value was calculated. The method for calculating the control side is the same as Test Example 1. The results and presence or absence of drug damage are shown in the table.

Table ■ Table ■ Continued Table ■ Continued Table Triadimephon Test Example 8 Therapeutic effect against rice blast (Rlce blast) Pot (-7.5 cm, 200 mj/volume) Planted rice seedlings (product 111: Nipponbare, 4-leaf stage) with rice blast Disease ω(
Three injections of a spore suspension of Pyricularia oryzac were inoculated. After 24 hours, chemical solution 5 with a predetermined concentration
rnll/pot was sprayed. After 7 days, the percentage of lesions is 8.
The control value was calculated. The prevention side calculation method is Test Example 1
Same as.

The results and the presence or absence of drug damage are shown in Table ■.

Table ■ Table ■ Continued Aotriadimephon Test Example 4 Rice sesame leaf blight (Helminthosporium)
1 eafspot) Planted rice seedlings (variety: Nipponbare, 6-leaf stage) in pots (φ7.5 cm, 200 ml volume) were sprayed with a predetermined concentration of the chemical solution 5+J/pot. After air drying, rice sesame leaf blight fungus (Cochl)
iobolus mlyabeanus) was inoculated by spraying.

Seven days later, the lesion area ratio was measured and the control value was calculated. .

The method for calculating the control side is the same as Test Example 1. The results are shown in Table V.

Table V Continued from Table V Test Example 5 Control efficacy against cucumber Anthracnose (Anthracnose) Month 1 Pot (φ7.5 cm, 200 mj? capacity) Planted cucumber seedlings (Shinahiro Risakimae) Adult No. 2, 2 to 3 leaves After spraying 5 ml/pot of a predetermined concentration of the chemical solution on the cucumber anthrax (Colletotrichum lag stage) and air-drying it,
The area ratio of 7-caliber lesions was measured and the control value was calculated. The control side calculation method was the same as Test Example 1, and the results are shown in Table 1.

Table ■ Table ■Continued Yoshitriadimehon that's all

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Group or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a group. Az is 1
, 2,4-triazole group or imidazole group. X_1 and X_2 represent halogen atoms, and n represents 1 or 2. ] An azole derivative represented by (2) General formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, X_1, X_2 and X_3 represent halogen atoms, and n represents 1 or 2. ] A halogen compound represented by the general formula H-Az [wherein Az represents a 1,2,4-triazole group or an imidazole group. ] By reacting with the azole derivative shown in ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Az, X_1, X_2 and n are the same as above. ] A method for producing an azole derivative, characterized by obtaining an azole derivative represented by the following. (3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, Az represents a 1,2,4-triazole group or an imidazole group. X_1 and X_2 represent halogen atoms, and n represents 1 or 2. ] The azole derivative represented by is reduced to give the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [In the formula, Az, X_1, X_2 and n are the same as above. ] A method for producing an azole derivative, characterized by obtaining an azole derivative represented by the following. (4) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Group or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a group. Az represents a 1,2,4-triazole group or an imidazole group. X_1 and X_2 represent halogen atoms,
n represents 1 or 2. ] A disinfectant characterized by containing an azole derivative represented by the following as an active ingredient.