CA1283922C - Azole derivative - Google Patents

Abstract

TITLE OF THE INVENTION;
NOVEL AZOLE DERIVATIVE

ABSTRACT OF THE DISCLOSURE:
The present invention closes an azole derivative represented by the formula:

(I) wherein R is a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group or a2,4-dichlorophewnyl group and A is a nitrogen atom or a CH group.
The derivative is useful as agricultural and horticultural fungicides.

Description

~L~83922 . . _ ~
The present invention relates to a derivative of azole represented by the formula (I):

~10 ~ A- =~

wherein R represents a phenyl group, a 4-chlorophenyl group, a 4-fIuorophenyl group or a 2,4-dichlorophenyl group and A
represents a nitrogen atom or a methine group, a process for producing the derivative of azole, and a method for controlling fungi comprising applying to agricultural or horticultural .
plants a fungicidally effective amount of a derivative of azole.~
Nowadays, the damage of the crops due to the various plant diseases is enormous, and the problem of environmental pollution due to a~ricultural chemicals has been taken up frequently as a topic and has attracted the peoples' concern.
Accordingly, the cry for the fungicide for use in agriculture and horticulture, which is low in toxicity to human, animals, birds and fish, is low in phytotoxicity to useful plants, is high in safety in handling, gives little ~33~

effects to the environment and shows an excellent control effect on the plant diseases of wide range, is very large.
The present inventors considered that in order to develop such an epoch-making fungicide for use in agriculture and horticulture, a simple modification of the conventional chemicalcompounds had little possibility to succeed and it was necessary to study novel chemical compounds, and as a result of synthesizing a number of derivatives of azole and examining the usefulness in practical use thereof, it has been found by the present inventors that thederivatives of azole represented by the formula (I):

HO CH2-N ~ ~

I ~ H2-R (I) wherein R represents a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group or a 2,4-dichlorophenyl group and A represents a nitrogen atom or a methine group, has the above-mentioned specificities, and on the basis of their finding, the present invention has been attained.

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SUI ~ ~RY OF TEE INVENTION
The object of the present invention is to provide novel derivatives of azole represented by the formula (I), which is useful as an active ingredient of a fungicide for use in agriculture and horticulture, and the process for producing the derivatives of azole. Furthermore, the object of the present invention is to provide a fungicide for use in agri-culture and horticulture, which is low in toxicity to human, animals, birds and fish and is low in phytotoxicity to useful plants~
Still further, the object of the present invèntion is to provide a fungicide for use in agriculture and horticul-ture, which has an excellent fungicidal activity on the plant diseases of vide range, at the same time, is excellent in the safety of handling and in keeping an envir~nment clean and contains the derivative of azole represented by the formula (I) as an active ingredient.

BRIEF EXPLANATION. OF DRAWINGS:
The~attached drawings show the infrared absorption spectra of the present compounds (the derivative of azole accordlng to the present invention) and of the drawings as follows:
Fig. 1: IR spectrum of Compound No. 1 in Table 1, ; Fig. 2: IR spectrum of Compound No. 2 in Table 1, Flg. 3: IR spectrum of Compound No. 3 in Table 1, Fig. 4: IR spectrum of Compound No. 4 in Table 1, .

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Fig. 5 I~ sp,a r~ <,~ ~ S T~LI I, Eig. 6: IR spectrum of Compound No. 6 in Table 1, Fig. 7: IR spectrum of Compound No. 7 in Table 1 and Fig. 8: IR spectrum of Compound No. 8 in Table 1.
DETAILED DESCRIPTION OF THE INVENT_ON:
The feature of the present invention lies in (1) the derivative of azole represented by the formula (I):

wherein R represents a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group or a 2,4-dichlorophenyl group and A
represents a nitrogen atom or a methine group, (2) a process for producing the above-mentioned derivative of azole, which comprises the step of bringing a derivative of oxirane ~cpr_sente by the fo ~

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wherein R shows the same meanings as in the formula (I), into re-action with 1,2,4-triazole or imidazole, and (3) a fungicide for use in agriculture and horticulture containing the derivative of azole represented by the formula (I) as an active ingredient.
The derivatives of azole represented by the formula ; (I) are novel chemical compounds not has been mentioned in literatures, and the respective melting-points of some of the derivatives of azole according to the present invention are shown in Table 1.

: Table 1 ~: _ __ _ _. .. _ ~ Number of Indication in Formula (I) Melting point : compound ._ ~-- (C) . .. ~ . .~ .___ .
. 1 Phenyl N 140 - 141-:: 2 Phenyl CH130 - 131 - 3 4-Chlorophenyl N 115 - 116 ~; 4 4-Chlorophenyl CH115 - 116 - 5 4-Fluorophenyl N 135 - 136 6 4-Fluorophenyl CH139 - 140 7 2,4-Dichlorophenyl N 120 - 121 . 2~4-Dichlorophenyl CH 150 - 151 ~ ' ':

~ - 6 -'..... .... :~ : ' ' . ' . ' ~ . '' ~:~83~

The respective infrared absorption spectra of the compound in Table 1 are shown in the attached drawings.
The process for producing the derivatives of azole represented by the formula (I) and the utilization of the derivatives of azole according to the present invention as a fungicide for use in agriculture and horticulture will be explained hereinafter.
A derivative of azole according to the present invention is produced by the following process.
Namely, by bringing a derivative of oxirane repre-sented by the aforementioned formula (II) into reaction with a triazole or an imidazole represented by the formula (III):

: :

U

wherein M is a hydrogen atom or an alkali metal and A
represents a nitrogen atom or a methine group, in the presence of a diluting agent, the object derivative of azole represented by the formula (I) is obtained.
The derivative of oxirane represented by the formula (II) which is used as the starting substance is obtained by bringing the ketone represented by the formula ~IV):

_ CH2-R (IV) lX8:1~'3Z;~
wherein R shows the same meaning as in the formula tI), lnto reaction with, for example, dimethyloxosulonium methylide or dimethylsulfonium methylide in the presence of a diluting agent (See Org. Syn. 49, 78 (1969), J. Amer. Chem. Soc. (1965), 1353).
In this connection, the compound represented by the formula (IV~, for example, 2-substituted benzylcylopen~anone, can be obtained from 2-alkoxycarbonylcyclopentanone and a corresponding substituted benzyl halide by the method described in Organic Synthesis, 45, 7 (1965) and Journal of Chemical Society, (1950), 325.
, Further, the compound represented by the formula (IV) can be obtained also from an enamine of cyclopentanone and a corresponding substituted benzyl halide (refer ~o Journal of Pharmaceutical Science, 68, 1501 (1979)).
As a diluting agent used in the production of the chemisal compound represented by the formula (I) according to the present invention, hydrocarbons such as benzene, toluene, xylene, hexane, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, carbon-tetrachloride, etc.;
alcohols such as methanol, ethanol, etc.; ethers such as diethyl ether, diisopropyl ether, tetrahydrofurane, etc.; acetonitrile, acetone, dimethylformamide, dimethylsulfoxide, etc. may be mentioned.
In addition, in the process according to the present invention, the reaction may be carried out in the presence of a base in addition to the above-mentioned diluting agent.

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~.

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As a base used in the above-mentioned reaction, carbonates of an alkali metal such as sodium carbonate, potassium carbonate, etc.; hydroxide of an alkali metal such as sodium hydroxide, potassium hydroxide, etc.; alcoholates of an alkali metal such as sodium methylate, sodium ethylate, potassium t-butylate, etc.; alkali metal hydrides such as sodium hydride, potassium hydride, etc.; triethylamine, pyridine, etc. may be mentioned.
In the case where the process according to the present invention is actually carried out, for example, into a solution of an azole represented by the formula (III) dissolved in an above-mentioned diluting agent, an oxirane represented by the formula (II) is added in an amount of from 0.5 to 1.0 equivalent, if necessary, in the presence of an above mentioned base, or in the reverse way with the above-mentioned method, an alkali metal salt of the above-mentioned azole is put into a solution of an above-mentioned oxirane in a diluting agent.
~ As the reaction temperature of the above-mentioned process, an optional temperature may be applied from the soLidifying point to the boiling point of the diluting agent used above, however, it is actually preferable to carry out the reaction at a temperature in the range of from 0 to 100C
for from one to three hours. It is preferable to carry out the reaction under stirring.
After the reaction is over, the obtained reaction mixture is cooled and the organic layer is separated by extracting with an organic solvent such as ethyl acetate, chloroform, benzene, etc. in ice-cooled water, and after washing the organic layer with water and drying thereof, the solvent is distilled off under a reduced pressure. By subjecting the thus obtained residue to purification treatment the object compound can be obtained. In addition, the purification treat-ment the object compound can be obtained. In addition, the purification treatment can be carried out by subjecting the reaction product to recrystallization, silica gel column chromatography, etc.
The utilizability of the derivatives of azole represented by the formula (I) as the active ingredient of the fungicide for use in agriculture and horticulture will be explained as follows:
The derivatives of azole according to the present invention show a control effect on the following wide range plant diseases:
Pyricularia oryzae, Cochliobolus miyabeanus, Xanthomonas oryzae, Rhizoctonia solani, Helminthosporium sigmoide-m and Gibberella fujikuroi on rice plant; Podosphaera Ieucotricha, Venturia inaequalis, Sclerotinia mali, Alternaria mali and Valsa mali on apple -tree; Alternaria kikuchiana, Phyllactinia pyri, Gymnosporangium haraeonum and Venturia . . _ . . _ __ nashicola on pear tree; Unccinula necator and Phakospora ampelopsidis on grape-vine; Erysiphe graminis r. sp. hordei, Rhynchosporium secalis, Puccinia graminis and Puccinia triformis lZ839~Z
on barley; Puccinia recondita, ~ tritici, Puccinia triformis and Erysi~e ~raminis f. sp. tritic~ on wheat;
Sphaerotheca uliginea on melon plant; Fusarlum oxys~_rum on water-melon plant; Erysiphe cichoracearum and Alternaria solan on tomato plant; Erysiphe cichoracearum on egg plant;
Sephaerotheca humuli on strawberry plant; Erysiphe cichoracearum and Alternaria longipes on tobacco plant; Cercospora beticola on sugar beet; Alternaria solani on potato plant; Septoria glycines and Cercospora kikuchii on soy bean plant; Sclerotinia cinerea on drupe fruit plant; and Botrytis cinerea and Sclerotlnla sclerotiorum which violate various crop plants.
In addition, the derivatives of azole according to the present invention exhibit not only the preventive effect but also the curative effect on some of the above-mentioned plant diseases.
In order to apply a derivative of azole represented by the formula (I) as the fungicide for use in agriculture and horticulture, the derivative itself or a composition containlng the derivative admixed with a carrier (a diluent) in the-form of powders, wettable powders,-granules, emulsions, solutions, etc. is usable advantageously. Moreover, if necessary, it is also possible to make the effect of the derivative more reliable by adding an auxiliary agent other than th~ above-mentioned carrier, such as a spreader, an emulsifier, a wetting agent, a sticker, etc. to the compound of the derivative of azole according to the present invention.

., ~ .~

.
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In this connection, since the derivatives of azole according to the present invention (hereinafter referred to as the present compound) contains a 1,2,4-triazole ring or an imid-azole ring in the molecule thereof, the present compound may be used in the form of a salt o an organic or an inorganic acid or a metal complex salt. In addition, since in the present compound, an azolylmeth~l group and a substituted benzyl group are contained respectively at l-position and 2-position of the cyclopentane ring, stereochemical isomers such as geometrical isomers of cis and trans and optical isomers, etc. may exist. Ho~ever, the present invention includes all of the single isomers and the mixtures thereof in any optional ratio between them. Accordingly, it should be understood that the fungicide for use in agriculture and horticulture according to the present invention includes the fungicide con-taining the above-mentioned sinyle isomer(s) or the mixture(s) thereof as the active ingredient.
The following Examples 1 and 2 are those respectively showing the preparation of the present compounds (the deriva-tives of azole according to the present invention) and the following Examples 3 and 4 are those showing the preparation of the fungicide (the fungicidal composition) for use in agriculture and horticulture.

~283~
EXAMPLE 1:
Preparation of 2-(2,4-dichloroben~yl)~ imidazole-l-ylmethyl)cyclopentan-l-Ol (Compound No. 8 in Table 1):
Into 20 ml of anhydrous dimethylformamide, 336 mg of sodium hydride (prepared by washing 60 ~ oily sodium hydride with dried benzene) were added while stirring under helium atmosphere, and after adding 950 mg of lH-imidazol into the thus prepared mixture, the whole mixture was stirred at room temperature until bubbling was over. A solution of 1.8 g of 4-(2,4-dichlorobenzyl)-1-oxaspiro[2.4]heptane in 10 ml of anhy-drous dimethylformamide was dropped into the thus obtained solution, and th~ whole mixture was stirred for 2 hours at 80C.
After leaving the thus obtained reaction mixture to cool, it was poured into iced water, and the mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer with water and drying the layer on anhydrous sodium sulfate, the solvent was distilled off from the layer under a reduced pressure to obtain a residue. By recrystallizing the residue with a mixture of hexane and ethyl acetate, 1.20 g of the compound shown in the above title was obtained.
The results of determination of the physical properties of the thus obtained compound are as follows and in addition, NMR spectrum of the compound was determined by using TMS as the internal standard and the results are shown by the following marks (the same marks are used in other Examples):

~83~ l s: singlet d- doublet m: multiplet b: a broad line Physical Properties (1) Melting point: 150 - 151C.
(2) Infrared absorption spectrum (KBr method): vmax 3130, 2940, 1580, 1430 and 1100 cm 1, ~3) NMR spectrum (CDC13, ppm): ~
1.38 - 1.97 tbs, 7H), 2.50 - 3.18 (m, 2H), 3.53 (bs, lH), 3.83 (dl lH, J=14Hz), 4.22 (d, lH, J=14Hz), 7.03 (s, 2H), 7.27 - 7.55 (m, 3H) and 7.62 (s, lH).
EXAMPLE 2:
Preparation of 2-(4-chlorobenzyl)-1-(lH-1,2,4-triaæole-_ l~ylmethyl)cyclQpentan-l-ol (Compound No. 3 in l`able 1):
Into 15 ml of anhydrous dimethylformamide, 1.0 g of 4-(4-chlorobenzyl)-1-oxaspiro~2.4~heptane was added to be dissolved while stirring under a helium atmosphere, and into the thus prepared solution, 0.6 g of sodium salt o~ lH~1,2 f 4-triazole of 90% in purity (commercial product, made by ALDRICH
Co.) was slowly added. The mixture was stirred for 2 hours at 60~C.
After leaving the thus obtained reaction mixture to be cooled, the cooled reaction mixture was poured into water and the mixture was extracted with ethyl acetate to obtain an ~339~

organic layer. After washing the layer with water and drying thereof on anhydrous sodium sulfate, the solvent was distilled off from the layer under a reduced pressure to obtain a residue.
By purifying the residue through silica gel column chromatography, 0.6 g of the compound of the above title was obtained, the physical properties thereof being shown as follows:
Physical Properties (1) Melting point: 115 - 116C.
(2) Infrared absorption spectrum (KBr method): v max 3260, 2940, 1280, 1140 and 670 cm 1 (3) NMR spectrum (CDC13, ppm): ~
1.35 - 2.13 (m, 7H), 2.48 - 2.77 (m, 2H), 3.02 (bs, lH), - 4.18 (s, 2H), 7.18 (d, 2H, J=~Hz), 7.40 (d, 2H, J=9Hz), ; ~ 8.Q8 (s, lH) and 8.25 (s, lH).
The following two examples (Example 3 and 4) are the examples of the preparation of a fungicide for use in agriculture and horticulture containing a derivative of azole according to the present invention as an active ingredient.
EXAMPLE 3:
_ ~ .. . . .
By pulverizing and mixing 3 parts by weight of one of the present compounds (Compound No. 5 in Table 1), 40 parts by weight of clay and 57 parts by weight of talk, a fungicide dust was prepared.
The thus prepared fungicide dust is used by scattering on the object.

~ --EXAMPL~ 4 By pulverizing and mixing 50 parts by weight of one of the present cornpounds (Compound No. 3 in Table 1), 5 parts by weight of a salt of ligninsulfonic acid, 3 parts by weight of a salt of an alkylsulfonic acid and 42 parts by weight of diatomaceous earth, a fungicide wettable powder was prepared.
The thus prepared fungicide wettable powder is used after diluting with water.
The following five examples (Examples S to 9) are the examples showing the fungicidal effect of the fungicide for use in agriculture and horticulture according to the present invention.
EXAMPLE 5:
Pest control test against Erysiphe graminis f. sp.
trlticl on wheat:
Onto the leaves of seedling of wheat (variety: NORIN
No. 64, 16 seedlings per pot) at the second leaf stage cultured in an unglazed pot, a fungicide wettable powder prepared ~according to the method in Example 4 diluted with water to a predetermined concentration was sprayed at a rate of 5 ml/pot (control pot was sprayed with water only). After natural drying of the thus sprayed leaves, an aqueous suspension of the spores of Erysiphe graminis f. sp. tritici collected from the attacked leaves of wheat was sprayed onto the thus dried leaves of the potted wheat and the thus treated seedlings were kept for 24 hours at a temperature of 20 to 25C in a highly humid atmosphere. Thereafter, the thus treated seedlings were left in a green house made of glass. After 10 days of the inoculation, the morbidity of the seedlings was examined on the basis of the following standard and the ~ 16 -1~ 9~:~

control value was calculated by the following formula from the average morbidity per leaf:
Standard of the examination Morbidity index Extent of disease infect 0 Not infected 0O5 A 1) is less than 10 ~, 1 A is from 10 to less than 20%, 2 A is from 20 to less than 40%, 3 A is from 40 to less than 60%, 4 A is from 60 to less than 80% and A is larger than 80 %.
Note *l) : A is the area rate of disease infect on the surface of the inoculated leaf.
: . .
; ; : Control value = (1 ~ morrbiditY Onn tcorn~rod pot) x 100 (%) ' The results are shown in Table 2.

: :
:
:: ~

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Table 2 . .~
Compound Concentration number of the sprayed Control value : (as in Table 1) liquid (ppm) (~) . ... _ .. . _ . ...... ___ : 1 125 100 4~ 125 100 12,5 100 6~ 125 100 ; : ~ ~ 7: ` ; 125 100 : _ . .. ~ ~. ~ .. __ . ...... .. _ __ ~
~Trladimefon 125 ____ Control~

; ~Note~ *l:~ Triadimefon is a commercial funyicide containing the fol-10wlng compound as the active ingredient:

:: ~ : : O CH
C~ );CH-C ~--CH

: ~ :
~: :

: ~

: : - 18 -~:~

~: . .

Example 6:
__ .__ Pest control test against Sphaerotheca fuliginea on cucumber plant-..._ Onto the leaves of seedling of cucumber (variety:
SAG~MI-HAMPAKU, one seedling per pot, 3 pots in a test of one compound) at the second leaf stage cultured in an : unglazed pot of 10 cm in diameter, a fungicide wettable :~: powder prepared according to the method in Example 4 diluted : : with water to a predetermined concentration was sprayed at a: rate of 5 ml/~pot (control pot was sprayed with water only), and then the spores of Sphaerotheca fuliginea of cucumber were~scattered onto the thus sprayed leaves from the contracted ;leaf~of cucumber plant by using a brush to inoculate on the ~leaves, and the~thus treated pots were left in a glass green : ~house.~ After 7~:days of the inoculation, the morbldity of the : ~ l:eaf of seedlings (one leaf/pot, three pots/compound) was examined~accordi~ng to the following standard, and the control value was~calculated from the average morbidity per leaf while ~ut~llizing the~same formula~:as~ in Exsmple 5:
Standard of thè examination~
I ~ Morbidity index Extent:of disease infect 0 : : : Not infected 0.5 ~ A l) is less than 10 ~, 1 ~ A:is from 10 to less than 20 ~, 2 A is from 20 to less than 40 ~, 3 A is from 40 to less than 60 ~, : : : 4 A is from 60 to less than 80 ~ and A is larger than 80 %.
: ~

::
:~
i ,. ~ . , ~: ~ . - .

.
l . . . _ . ' . _ : ' . _ ' ., ' . . . ~, _ _ . . _ ., . _, . ! . . _ ., _ .
~;~a39~2 Note *1): A is the area rate of disease infect on the surface of the inoculated leaf.

The results are shown in Table 3.
, Table 3 .. ,~
Compound ConcentrationControl value n~m~er of the sprayed (as in Table 1) liquid (ppm) (%) : .. ., . ~
; ~ 1 62~5 100 ` ~ 2 62~5 100 3 6~2~5 ~ 100 ; 4 62~5 100 62~5 100 6 62~5 100 7 62~5 ; 100 ~; ~ 8 ; ~2oS ~ ~ 95 : ~ ~ -: commercia~ : I25;~ 100 ::: :~: ~ fungicide 1) :

`~:: Control : -- 0 ::
, ~ ~ , , .: ~
: Note~*l): A ungiclde of quinoxaline series represented : ~ by the following formula:

X s, ~ ~'~ , . . . .
~ ' : , ~ '., , ' ,: . ` - `

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EXAMPLE 7:
Pest control test against Puccinia recondita f. sp.
tritici on wheat:
Onto the leaves of seedling of wheat (variety:
NORIN No. 64, 16 seedlings per pot) at the second leaf stage cultured in an unglazed pot of 10 cm in diameter, a fungicide wettable powder prepared according to the method in Example 4 diluted with water at a predetermined concen-tration was sprayed at a rate of 5 ml/pot (control pot was sprayed with water only). After natural drying of the ; thus sprayed leaves,an aqueous suspension of the uredospores of Puccinia recondita f. sp. tritici collected from the : ~ : :
attacked leaves of wheat was sprayed onto the thus dried leaves~of the potted wheat, and the thus treated seedlings were ;kept for 24 hours at a temperature of from 20 to 25C in a highly humid atmosphere. Thereafter, the thus treated seed1ings were left in a glass green house, and after 7 days, ~the morbidity~was examined on the basis of the following ~standard. The control va1ue~of each of the fungicide was calculated by the formula shown~in Example 5 from the average morbidity p~er leaf of the 10 seedlings per pot:
Standards of the examination:~
The same as in Example 6.
The~results are shown in Table 4.

::: ~ :
: :

; ~ ~ - 21 -:

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. Table 4 : :Compound Concentration Control value number of the sprayed (as in Table l) liquid (ppm) (%) : ~ ._ _. . . .. . ... _ _ . _ ; ~ l 200 lO0 ; ~ 2 200: lO0 3 200 : lO0 ~4 :2:00 lO0 200 lO0 :: ~ ~ 6~: ~ 200~ lO0 ~,~ : '~; 7~ ~200 lO0 . ::
~ ~ 8 : ~200:~ lO0 ~: ~ ~
~Triadimefon : : ~ 200 lO0 Control~ o : :~ ~ :

~ = ~ '. ~
EXAMPLE~8~ :
Pest~control_test against:~Cochl1obolus miyabeanus ::on':rice~plant~
In the~ungla:zed~pots~of 10~cm in diameter, the~seeds;~of~rice plant (variety:~SASANISHIKI) were sown ~;at a rate;~of 16 seeds/pot, and at~the~stage of 4 to 5 ; ~leaves, the fungicide wettable powder prepared according ~to~the~method~in,Example 4;was diluted:with water to a , ~:predeterm1ned~concentration, and~the thus prepared aqueous ; ; - 22 -39'i~ 1 suspension of the fungicide was sprayed onto the seedlings of rice plant at a rate of 5 ml/pot. After natural drying the thus treated leaves of the rice seedlings, an aqueous suspension of the spores of Cochliobolus miyabeanus (at a concentration of lS spores in the visual field of a microscope of 150 magnification) preliminarily cultured was sprayed onto the leaves of seedl~ings at a rate of 5 ml/pot for inoculation. After inoculation, the pots were immediately taken into an inoculation : ~ ~
room of 25C and of saturated humidity, and after keeping thereof for 2 days, the pots were moved into a glass green house to be~attacked. At the fi~fth day after the inoculation, : the number of~the disease spots on 10 leaves per pot was ~enumerated, and the control value~of each of the fungicides was càlculated according to the following formula:

Control value (%) = (1:- B ) x 100 ~

. ~ whereln A is~the number of di;sease spots in the treated pots ; l ~ and;~B:is~that in~the control pots (not being sprayed with the funglcide)~
:~ The results;are shown~in Table 5.

: :: : ~

:: :
~ :
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, . . .

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Table 5 ; ~ .... _ . _ . . ... _ Compound Concentration number of the sprayed Control value (as in Table 1) liquid (ppm) (~) ~ ~ 1 300 100 ; ~ 2 300 100 ~:~ ~ ~ 6 ~ ~ 3ao lOO
: ~ 7 ~300 92 :~ ~ 8 300 100 ~ ~ Ep * l J ~ 300 ~ ~ 88 : ~ ~ , :~ ~; ~Control ~ ~ O .

. ~ Note~*~ A~commercial~fungicide containing the following compound as~cn active ingredient:

, ~ ~5:~5~

: - _ ~;:: :

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In vitro test against several fungal species Antifungal properties of the present compounds against several fungal sp~cies were examined as follows:
After thoroughly mixing each of the present compounds with the PSA culture medium at a prescribed concentration, the thus prepared mixture was poured into dishes of 9 cm in diameter in an amount of 10 ml. per dish to prepare plate culture medium. On the other hand, each of the fungal species cultured in a~plate culture medium was punched by a cork borer of 6 mm in diameter and inoculated on the thus prepared plate culture medium~in the dishes. After inoculating, each of the ~thus;inoculated fungi was cultured for from one to three days ~at~a;temperature suita~le;for each fungus, and the growth of ~the~fungus was~determined by the diameter of each fungal colony.
~The~results were compared to the result on the control (the ;
culture medlum not containing any fungicide), and on the basis of the~following formula, the rate of control of the mycelial ~grGwth was obtained: ~

;~ ; R = (dc ~ dt) dc ~whereln R represents the rate of control of the mycelial growth of a fungus, dt represents the diameter of the fungal ~colony on the culture medlum plate containing each of the ~present compound~and dc represent5 the diameter of the fungal ~ :

~ - 25 -~ :::

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colony on the culture medium plate not containing any fungicide (control).
The thus obtained results were evaluated on the basis of the following standard into 5 ranks and are shown in Tahle 6.
Standard for _valuation:
Index of growth control Rate _f control of mycelial_growth from 100 to 90 %
~: ~ 4 from 89 to 70 %
: 3 from 69 to 40 %
::: :: ~
: ~ 2 from 39 to 20 %

~: : 1 less than 20 ~
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Claims (7)

1. A derivative of azole represented by the formula (I):
(I) wherein R represents a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group or a 2,4-dichlorophenyl group and A represents a nitrogen atom or a methine group.

2. A derivative of azole according to claim 1, wherein said R is a 4-chlorophenyl group and said A is a nitrogen atom.

3. A process for producing a derivative of azole represented by the formula (I):

(I) wherein R represents a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group or a 2,4-dichlorophenyl group and A

represents a nitrogen atom or a methine group, said process comprising the step of bringing a derivative of oxirane represented by the formula (II):

(II) wherein R represents a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group or a 2,4-dichlorophenyl group and A represents a nitrogen atom or a methine group, into reaction with a 1,2,4-triazole or an imidazole represented by the formula (III):

(III) wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a methine group.

4. A method for controlling a fungal species comprising applying to plants a fungicidally effective amount of a derivative of azole according to claim 1.

5. A method for controlling a fungal species according to claim 4, wherein said fungal species is one of Erysiphe graminis f. sp. tritici on wheat, Sphaerotheca fuliginea on cucumber plant, Puccinia recondita f. sp. tritici on wheat, Pyricularia oryzae on rice plant, Cochliobolus miyabeanus on rice plant, Rhizoctonia solani on rice plant, Gibberella fujikuroi on rice plant, Helminthosporium sigmoideum on rice plant, Botrytis cinerea on cucumber plant, Alternaria kikuchiana pear plant, Fusarium oxysporum f. niveum on water-melon, Sclerotinia cinerea on peach plant or Valsa mali on apple plant or a combination of said fungal species.

6. A method for controlling fungal species comprising applying to plants a fungicidally effective amount of a derivative of azole according to claim 2.

7. The use of a funicidally effective amount of a derivative of azole represented by the formula (I) (I) wherein R represents a phenyl group, a 4-chlorophenyl group, a 4-flourophenyl group or a 2,4-dichlorophenyl group; and A
represents a nitrogen atom or a CH group, for controlling a fungi infesting plants.