CA1286303C - Azole derivatives - Google Patents
Azole derivativesInfo
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- CA1286303C CA1286303C CA000518011A CA518011A CA1286303C CA 1286303 C CA1286303 C CA 1286303C CA 000518011 A CA000518011 A CA 000518011A CA 518011 A CA518011 A CA 518011A CA 1286303 C CA1286303 C CA 1286303C
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Abstract
TITLE OF THE INVENTION;
NOVEL AZOLE DERIVATIVE
ABSTRACT OF THE DISCLOSURE:
The present invention discloses an azole derivative of the formula (I):
(I) wherein A is a nitrogen atom or a CH group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
wherein X is an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom, X can be the same or different atom or group and n is an integer of 1 to 5, provided that when X is a halogen atom n is an integer 3 to 5.
The azole derivative is useful as an active ingredient of an agricultural and horticultural fungicide, a plant growth regulant and a herbicide.
NOVEL AZOLE DERIVATIVE
ABSTRACT OF THE DISCLOSURE:
The present invention discloses an azole derivative of the formula (I):
(I) wherein A is a nitrogen atom or a CH group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
wherein X is an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom, X can be the same or different atom or group and n is an integer of 1 to 5, provided that when X is a halogen atom n is an integer 3 to 5.
The azole derivative is useful as an active ingredient of an agricultural and horticultural fungicide, a plant growth regulant and a herbicide.
Description
BACKGROUND OF THE INVENTION:
The present invention relates to a derivative of azole represented by the formula (I):
HO 2 \ _ I
~ CH2 - R (I) wherein A represents a nitrogen atom or a methine group and R
represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
Xn (II) wherein X represents an alkyl group, a haloalkyl group, a phenylgroup, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom,n represents an integer from 3 to 5, a process for producing the derivative of azole and a method for controlling pests in agriculture and horticulture with its fungicidal activity, plant glowth regulating activity and herbicidal activity.
Field crops are badly damaged by plant diseases every year, and agricultural chemicals to control them cause the serious environmental pollution, which has become people's great concern. Therefore, there has been a great demand for a new fungicide for agriculture and horticulture which has a low level of toxicity to human, animals, birds and fish and also has a low level of phytotoxicity to useful plants. Such a fungicide should be highly safe in handling, have very little adverse effect on the environment, and produce outstanding control effect for a wide variety of plant diseases.
In an effort to develop such an epoch-making fungicide for agriculture and horticulture, the present inventors studied for new compounds instead of mere modifications of existing compounds. To this end, they synthesized a large number of derivatives of azole and tested their usefulness in practical use. As a result, it was found that derivatives of azole represented by the formula (I):
/ A =
H ~ 2 \ = N~
wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
Xn (II) ~28~;3~'3 wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom,n represents an integer from 3 to 5, have the above-mentioned characteristics.
In addition and surprisingly enough, the present inventors have found that the derivative of azole exert not only a fungicidal effect but also a plant growth control effect and herbicidal effect. These findings led to the present invention.
SUMMARY OF THE INVENTION:
It is an object of the present invention to provide a novel derivative of azole represented by the formula (I).
It is another object of the present invention to provide a fungicide for agriculture and horticulture which is effective agains~ a large variety of plant diseases with a low toxicity to human, animals, birds and fish and a low phytotoxicity to useful plant, the fungicide further exerting the plant growth control effect and herbicidal effect.
It is further object of the present invention to provide a method for controlling pests in agriculture and horticulture applying as an active ingredient a derivative of azole represented by the formula (I), said derivative azole being superior in handling safely and environmental protection.
BRIEF EXPLANATION OF THE DRAWINGS:
Figures from 1 to 28 attached hereto are the infrared absorption spéctra of the derivative of azole pertaining to the present invention. The figure numbers correspond to the respective compound numbers shown in Table 1.
DETAILED DESCRIPTION OF THE INVENTION:
The feature of the present invention lies in, (1) a derivative of azole represented by the formula (I):
/A =
~O ~ 2 \ = N (Il wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophen~l group, a 2,4-~ifluorophenyl grGUp, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
Xn (II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom,n represents an integer from 3 to 5, (2) a process for producing the derivative of azole by reacting a derivative of oxirane represented by the formula (III):
~ CH2 R (III) wherein R has the same meaning as in the formula (I), with 1,2,4-triazole or imidazole and (3) a method for controlling pests in agriculture and horticulture with a fungicidal activity, a plant glowth regulating activity and a herbicidal activity applying a derivative of azole represented by the formula (I) as an active ingredient.
A derivative of azole represented by the formula (I) is a novel compound and some of the derivatives are shown in Table 1 below with respective melting points.
A detailed description is given below of the process for producing a derivative of azole represented by the formula (I) and utilization of the derivative of azole for controlling pests in agriculture and horticulture.
A derivative of azole represented by the formula (I) is produced by reacting a derivative of oxirane represented by the formula (III) with 1,2,4-triazole or imidazole represented by the formula (IV) = N (IV) wherein M represents a hydrogen atom or an alkali metal and A represents a nitrogen atom or a methine group, in the presence of a diluent.
6~03 ~ :
Table 1 Number Indication in Formula (1) ¦ Melting point¦
compound ¦ R ~ (C) ¦
1 4-t-Butylphenyl N129 - 130 2 4-t-Butylphenyl CH123 - 124 3 4-Biphenylyl N146 - 147 4 4-Biphenylyl CH182 - 183 3-Trifluoromethylphenyl N152 - 153 6 3-Trifluoromethylphenyl CH87 - 88 7 3-Chlorophenyl N152 - 153 8 3-Chlorophenyl CH105 - 106 9 4-Nitrophenyl N131 - 132 2,6-Difluorophenyl N104 - 105 11 2,6-Difluorophenyl CH150 - 151 12 4-Bromophenyl N106 - 107 13 4-Bromophenyl CH119 - 120 14 2-Chlorophenyl N154 - 155 2-Chlorophenyl . CH103 - 104 16 4-Methylphenyl N128 - 129 17 4-Methylphenyl CH122 - 123 18 2,4-Difluorophenyl N118 - 119 19 2,4-Difluorophenyl CH144 - 145 3,4-Difluorophenyl N119 - 121 21 3,4-Difluorophenyl CH103 - 105 22 4-Cyanophenyl N115 - 116 23 4-Cyanophenyl CH103 - 104 24 2-Fluoro-4-chlorophenyl N125 - 127 2-Fluoro-4-chlorophenyl CH141 - 143 26 2,3,4,5,6-Pentafluorophenyl N 118 - 120 27 4-Trifluoromethylphenyl N102 - 103 28 4-Trifluoromethylphenyl CH91 - 92 The infrared spectrum of each compound in the above Table 1 is shown in attached Figures 1 to 28, respectively.
A derivative of oxirane represented by the formula (III), which is the starting material of the reaction, is prepared by reacting a ketone represented by the formula (V):
~ CH2 - R (V) wherein R has the same meaning as in the formula (I), with, for example, dimethyloxosulfonium methylide or dimethylsulfonium methylide in the presence of a diluent. (See Org. Syn. 49, 78 (1969) and J. Amer. Chem. Soc. (1965), 1353).
An example of the compound represented by the formula (V) is 2-substituted benzylcyclopentanone. It can be prepared from 2-alkoxycarbonylcyclopentanone and a corresponding substi-tuted benzyl halide according to the process described in Org.
Syn., 45, 7 (1965) and J. Chem. Soc., (1950), 325. It can also be prepared from a corresponding substituted benzylhalide and an enamine of cyclopentanone. (See J. Pharm. Sci., 68, 1501 (1979)).
The diluent used in the process of preparing the compound represented by the formula (I) includes hydrocarbons such as benzene, toluene, xylene and hexane; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; alcohols such as methanol and ethanol; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran;
'''~
~Z863~3 and other compounds such as acetonitrile, acetone, dimethyl-formamide and dimethylsulfoxide.
The process of the present invention may be carried out in the presence of the above-mentioned diluent together with a base. As examples of the base, alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium t-butylate; alkali metal hydrides such as sodium hydride and potassium hydride; and triethylamine and pyridine may be mentioned.
The process of the present invention is carried out in the following manner. An azole represented by the formula (IV) is dissolved in a diluent exemplified above, and to the ~esulting solution is added an oxirane represented by the formula (III) in an amount of 0.5 to 1.0 equivalent. The solution may contain a base exemplified above, if necessary. Alternatively, the oxirane can be dissolved in the diluent first and to the resulting solution can be added an alkali metal salt of the azole.
The reaction temperature ranges from the freezing point to the boiling point of the above-mentioned diluent, but the preferred reaction temperature is from 0C to 100C. The reaction time is from 1 hour to 3 hours. The reaction is preferably carried out with stirring.
After the reaction is completed, the reaction mixture 1~8~
is cooled a extracted wi h an organic solvent such as ethyl acetate, chloroform or benzene in iced water. The organic layer is separated, washed with water and dried. The solvent is distilled off under reduced pressure. The residues are purified to give the desired compound. Purification may be carried out by recrystallization or sillica gel chromatography.
A derivative of azole (a derivative of azolylcyclo-pentanol) represented by the formula (I) exerts the following activities as an active ingredient of agricultural and horticultural composition.
(1) Fungicidal action on plant diseases A derivative of azole of the present in~ention exerts the control effect on a wide variety of plant diseases listed below.
Rice plant: Pyricularia oryzae, Cochliobolus miyabeanus, Xanthomonas oryzae, Rhizoctonia solani, Helminthosporium sigmoideum and Gibberella fujikuroi.
Apple tree: Podosphaera leucotricha, Venturia inaequalis, Sclerotinia mali, Alternaria mali and Valsa mali.
Pear tree : Alternaria kikuchiana, Phyllactinia ~y~, Gymnosporangium haraeonum and Venturia nashicola.
Grape-vine: Unccinula necator and Phakospora ampelopsidis.
Barley: Erysiphe graminis f. sp. hordei, Rhynchosporium secalis, Puccinia graminis and Puccinia triformis.
1;~8630.~
Wheat: Puccinia recondita, ~E~ _ia trlti~i, Puccl~ia triformis and Erysiphe graminis f. sp. tritici.
Oriental melon plant: Sphaerotheca fuliginea.
Watermelon plant: Fusarium oxYsporum.
Tomato plant: Erysiphe cichoracearum, Alternarla solani.
Egg plant: Erysiphe cichoracearum.
Strawberry plant: Sephaerotheca humuli.
Tobacco plant: Erysiphe cichoracearum and Alternaria longipes.
Sugar beat: Cercospora beticola.
Potato plant: Alternaria solani.
Soybean plant: Cercospora kikuchii and Septoria glycines.
Drupe fruit plant: Sclerotinia cinerea.
Other crop plants: Botrytis cinerea and Sclerotinia sclerotiorum.
A derivative of azole of the present invention produces not only the preventive effect but also the therapeutic effect on the some of the above-mentioned plant diseases.
(2) Plant growth regulating effect Recently, plant growth regulators have come into general use in agriculture and horticulture, as the mechanism governing the plant growth regulation by plant hormones has been elucidated. The usage of plant hormones includes, for e~ample, the production of seedless grapes by means of gibberellin, the acceleration of rooting of cuttings by means of ~-naphthalene-acetic acid and the growth retardation of wheat by means of 2-chloroethyltrimethylammonium chloride (trade name "CCC").
~ZB6303 The utilization of techniques in controlling environment of plants applying plant growth regulators is now subjected not only to crops, vegetables and fruit trees but also to ornamental plant such as with flowers and further to wider range of plants such as trees. And there is an increasing possibility that the function of plant growth regulators is going to spread into rooting acceleration, flowering regulation, fruit bearing and thickening, growth acceleration, growth retarding and metabolism regulation. Plant growth regulators are increasing in their kinds and amount of consumption in recent years, but they are not so increasing as can be expected from the above possibilities.
The derivative of azole (derivative of azolylcyclo-pentanol) of the present invention produces the plant growth regulating effect (including herbicidal effect) on a wide variety of plants as shown below.
1) Suppression of vegetative growth of plants, especially suppression of height growth.
2) Increase of available nutrients in plants.
3) Regulation of maturing stage or flowering time of plants.
The first activity mentioned above is useful for the suppression of weed growth (weed-killing function), the suppres-sion of lawn, the prevention of lodging of rice plant and wheat, the suppression of height of soybean and cotton plants which make harvesting machine available, the suppression of axillary buds which promotes the growth of tobacco leaves, the suppression of hedge plant growth which reduces the frequency of pruning and the growth retardation of ornamental plants which leads to an increased commercial value.
The second activity mentioned above contributes to the improvement of beat sugar, sugar cane, and citrus through the increase of sugar content and also to the improvement of crops and soybean through the increase of protein.
The third activity mentioned above makes it possible to ship fresh fruits and flowers at any time according to demands.
A derivative of azole represented by the formula (I) can be used as a fungicide, a plant growth regulator or a herbicide in the form of dust, wettable powder, granule, emulsifiable concentrate or solution with or without mixing a carrier (or diluent). It may also be used as such if necessary, namely, the formulation may contain, in addition to a carrier, adjuvants such as spreader, emulsifier, wetting agent, and sticking agent to ensure the effect.
Incidentally, the derivative of azole of the present invention can be used in the form of inorganic salt, organic salt or metal complex,because it contains the 1,2,4-triazole ring or imidazole ring.
The derivative of azole of the present invention has an azolylmethyl group and a substituted benzyl group at the l-position and 2-position, respectively, of the cyclopentane ring.
.
1;~8~
Therefore, it should exist in the form of stereoisomers, e.g., geometrical isomer (cis form and trans form) and optical isomers. In this invention, the derivative of azole may be a single isomer or a mixture thereof at an arbitrary ratio.
Thus, the agricultural and horticultural chemical pertaining to the present invention may contain one of the isomers or a mixture of the isomers as an active ingredient.
The present invention is now illustrated with the following examples which demonstrate the production of derivatives of azole and the effect of the agricultural and horticultural chemical containing a derivative of azole as an active ingredient.
EXAMPLE 1:
Preparation of 2-(2,4-difluorobenzyl)-1-(lH-imidazol-l-yl-methyl)cyclopentan-l-ol (Compound No. 19 in Table 1):
Into 10 ml of anhydrous dimethylformamide, 324 mg of sodium hydride (prepared by washing 60% oily sodium hydride with dried benzene) were added while stirring under helium atmosphere, and after adding 910 mg of lH-imidazol into the thus prepared mixture, the whole mixture was stirred at room temperature until bubbling was over. A solution of 1.5 g of 4-(2,4-difluorobenzyl)-l-oxaspiro[2.4]heptane in 10 ml of anhydrous dimethylformamide was dropped into the thus obtained solution and the whole mixture was stirred for 2 hours at a room temperature.
After leaving the thus obtained reaction mixture to 1~8~ 03 cool, it was poured into lc-d 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, 830 mg 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 determlned by using TMS as the internal standard and the results are shown by the following marks (the same marks are used in other Examples):
s: singlet d: doublet m: multiplet b: a broad line Physical Properties ~1) Melting point: 144 - 145C
(2) Infrared absorption spectrum (KBr method) is shown in Figure 19 in attached Drawings.
Infrared absorption spectrum (KBr method): vmax 3170, 2940, 1610, 1590, 1490 cm 1.
(3) NMR spectrum (CDC13, ppm): ~
1.37-2.13~bs, 7H), 2.33 -2.83(m, 2H), 3.33(s, lH), 3.77(d, lH, J=14Hz), 4.10(d, lH, J=14Hz), 6.57 - 7.60(m, 6H).
~86303 EX~MPLE 2:
Preparation of 2-(4-bromobenzy1)-1-(lH-1,2,4-triazol-1-yl-methyl)cyclopentan-l-ol (Compound No. 12 in Table 1):
Into 30 ml of anhydrous dimethylformamide, 3.0 g of 4-(4-bromobenzyl)-1-oxaspiro I2.4] heptane was added to be dissolved while stirring under a helium atmosphere, and into the thus prepared solution, 1.12 g of sodium salt of lH-1,2,4-triazole of 90% in purity (commercial product, made by ALDRICH
Co.) was slowly added. The mixture was stirred for 1 hour at 80C
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 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, 2.7 g of the compound of the above title was obtained. The physical properties thereof being shown as follows:
Physical Properties (1) Melting point: 106 - 107C
(2) Infrared absorption spectrum (XBr method) is shown in Figure 12 in attached Drawings.
Infrared absorption spectrum (KBr method): vmax 3260, 3100, 2930, 1620, 1270, 1130, 660 cm 1.
lZ86~03 (3) NMR spectrum (CDC13, ppm): ~
1.45 - 3.15(m, lOH), 4.27(s, 2H), 7.20(d, 2H, J=9Hz), 7.60(d, 2H, J=9Hz), 8.13(s, lH), 8.28(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 talc, a fungicide dust was prepared.
The thus prepared ungicide dust is used by scattering on the ob ject.
EXAMPLE 4:
By pulverizing and mixing 50 parts by weight of one of the present compounds (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 power was prepared.
The thus prepared fungicide wettable powder is used after diluting with water.
The following five examples (Examples 5 to 9) are the examples showing the fungicidal effect of the fungicide for use in agriculture and horticulture according to the present invention ~86~(33 EXAMPLE 5:
Pest controI test against Erysiphe graminis f. sp. tritici on wheat:
Onto the leave of seedling of wheat (variety: NORIN
No. 64, 16 seedlings per pot) at the second leaf stage cultured in an unglazed pot, the 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 leave, 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 temperature of from 20 to 25C in a highly humid atmosphere. Thereafter, the thus treated seedlings were left in a glass green house. After 10 days of the inoculation, the morbidity of the seedlings was examined on the basis of the following standard and the control value was calculated by the following formula from the avexage morbidity per leaf:
Standard of the examination 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%, Morbidity index Extent of disease infect 3 A is from 40 to less than 60%r 4 A is from 60 to less than 80% and A is larger than 80%.
ote *11: A is the area rate of disease infect on the surface of the inoculated leaf.
Control value = (1 ~ morbiditY Onn tcontrteod PoOt ) x 100 (%) he results are shown in Table 2.
63():~
Table 2 Compound Concentration number of the sprayedControl value (as in Table 1) liquid (ppm) (~) 6 1225 77o5 18 125 l6o8o 22 1255 l6o2 Triadimefon 1 125 100 Control ¦ --1~863~3 Note: *1: Triadimefon is a commercial fungicide containing the following compound as the active ingredient:
Cl~ ~
EXAMPLE 6:
Pest control test against Sphaerotheca fuliginea on cucumber-plant:
Onto the leave of seedling of cucumber (variety:
SAGAMI-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 wi.th 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 leave from the contracted leaf of cucumber plant by using a brush to inoculate on the leave, and the thus treated pots were left in a glass green house. After 7 days of the inoculation,.the morbidity of the leaf of seedlings (one leaf/
pot, three pots/compound) was examined according to the following standard, and the control value was calculated from the average morbidity per leaf while utilizing the same formula as in Example ~86~'~
Standard of the examination:
Morbidity index Extent of disease infect 0 Not infected 0.5 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%.
ote *1): A is the area rate of disease infect on the surface of the inoculated leaf.
The results are shown in Table 3.
6:~0~3 Table 3 Compound ConcentrationControl value number of the sprayed Table 1 ) liqu d (ppm1 ~ ~
62.5 100 6 62.5 60 7 62.5 100 8 62.5 100 _ , A commercial 12 5 10 0 funglclde Control __ O . .
ote *1): A fungicide of quinoxaline series represented by the following formula:
C~3 ~ ~/X 5 > =
~ Z~3~i3~
EXAMPLE 7:
Pest control test against Puccinia recondita ~. sp.
tritici on wheat:
Onto the leave 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 concentration was sprayed at a rate of 5 ml/pot (control pot was sprayed with water only). After natural drying of the thus sprayed leave, 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 seedlings were left in a glass green house, and after 7 days, the morbidity was examined on the basis of the following standard. The control value of each of the fungicide was calculated by the formula shown in Example 5 from the average morbidity per leaf of the 10 seedlings per pot:
Standards of the examination:
The same as in Example 6.
The results are shown in Table 4.
l 12~30.3 Table 4 Compound ¦ Concentration number of the sprayed Control value -s ]n able 1) ¦ 1iquid (ppm) . 12 200 100 Triadimefon 200 100 Control __ ` - 25 -~8~3()3 EXAMPLE 8:
Pest control test against Cochliobolus miyabeanus on rice plant:
In the unglazed 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 predetermined concentration, and the thus prepared aqueous 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 15 spores in the visual field of a microscope of 150 magnification) preliminarily cultured was sprayed onto the leave of seedlings 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 fifth 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 calculated according to the following formula:
Control value (%) = (1 ~ B ) x 100 wherein A is the number of disease spots in the treated pots and B is that in the control pots (not being sprayed with the fungicide).
The results are shown in Table 5.
~8~303 Compound Concentration number of the sprayed Control value (as in Table 1) liquid (ppm)( ) : 6 300 98 . 24 300 100 .
*l) Control __ _ _ ~6303 Note *1): A commercial fungicide containing the following compound as an active ingredient:
~ 1 ~3 EXAMPLE 9:
In vitro test against several fungal species Antifungal properties of the present compounds against several fungal species 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 suitable 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 medium not containing any fungicide), and on the basis of the following formula, the rate of control of the mycelial growth was obtained:
R = (dc ~ dt) ~
~8630~3 wherein R represents the rate of control of the mycelial growth of a fungus, dt represents the diameter of the fungal colony on the culture medium plate containing each of the present compound and dc represents the diameter of the fungal 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 Table 6.
Standard for evaluation:
Index of growth control Rate of 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~
r I . I . L L ~ L L ~ L L L ~ L L L L ~ L L L L L
. nnnnn nnnnn nnn n nnnnn Lnnnnn n ~ ~ ~ tnnLn~ LnLn~Ln ~ ~
Z LnLnLnLnLn LnLnLnLnLn LnLnLnLnLn LnLnLnLnLn LnLnLnLnLn n ~ e ~Ln~LnLn ~Ln~ ~ L~ L~ ~ ~ Ln ~ ~ Ln Ln ~ ~ ~ Ln L
Ln~ LnLn~ Ln~Ln~Ln ~Ln~ Ln OJ :C ~ LnLn~ ~LnLn~ LnLn~Ln Ln~Ln~ Ln 7 t~ = nLnLnLn~ n ~n Ln Ln ~n ~ ~ Ln ~ Ln Ln Ln Ln Ln Ln Ln Ln ~ Ln Ln Ln ~3 - ~ ~ 7 ~ Ln ~
O L~ L~ ~n Ln Ln ~nLn~n Ln Ln ~n Ln LnLn~n LnLnLnLnLn Ln~LnLn~n Ln S~ ooooo ooooo ooooo ooooo ooooo o ooooo ooooo ooooo ooooo ooooo o O L ~ ~
~ ¢ ¢ ~ Ln ~ 7 ~ o ~ Ln ~ 7 ~ o ~ Ln ~7 3()3 Note: The abbreviation in ABLE 6 indicate the fungal species as follows:
P.o. : Pyricularia oryzae on rice plant C.m. : Cochliobolus m yabeanus on rice plant R.s. : Rhizoctonia solani on rice plant G.f. : Gibberella fuiikuroi on rice plant He.s.: Helminthosporium sigmoideum on rice plant Bo.c.: Botrytis cinerea F.n. : Fusarium oxysporum f. niveum on watermelon S.c. : Sclerotinia cinerea on peach tree A.k. : Alternaria kikuchiana on pear tree V.m. : Valsa mali on apple tree 1~86~30~3 EXAMPLE 10:
Preparation of plant growth regulator composition and herbicide composition containing a derivative of azole as an active ingredient.
(1) Wettable powder The following components were pulverized and mixed to prepare a wettable powder, which would be applied after dilution with water.
Compound of the invention 50 parts by weight (compound No. 3 in Table 1) Lignin sulfonate5 parts by weight Alkyl sulfonate3 parts by weight Diatomaceous earth42 parts by weight (2) Emulsifiable concentrate The following components were uniformly mixed to prepare an emulsifiable concentrate, which would be applied after dilution with water.
Compound of this invention 25 parts by weight (compound No. 20 in Table 1) Xylene 65 parts by weight Polyoxyethylene alkylaryl ether 10 parts by weight (3) Granule The following components were uniformly mixed together with water and the mixture was granulated by an extrusion granulator, followed by drying.
Compound of this invention 8 parts by weight (compound No. 12 in Table 1) ~286303 sentonite40 parts by weight Clay 45 parts by weight Lignin sulfonate7 parts by weight EXAMPLE 11:
Plant lenqth inhibition for wheat Ten wheat grains were sown in a glass petri dish 8.5 cm in diameter, containing 5 ml of 50 ppm solution of the compound under test. (The variety of wheat is AOBA No. 3). After growing indoors at 27C for 7 days, the plant length was measured.
The results are shown in Table 7.
It i5 noted from Table 7 that all the compounds tested produced a pronounced effect of inhibiting the growth of plant length, particularly in the case of triazole-type compounds.
No phytotoxicity was observed.
~ 1286~30;~
Table 7 Compound ¦Inhibition ¦ i number of plant Phytotoxicity (as in Table 1) length (~6) 1 3.8 None 2 3.1 None 3 3 5 NNone 20.4 None 7 7 2 NNone 9 45 6 NOnne 81.8 None 11 16.5 None 12 3 7 NNone 14 54.1 None 15.2 None 16 85.4 None 17 38.1 None 18 15.8 None 19 11.8 None 62.6 None . 21 19.6 None 22 11 2 NNone 24 79.0 None 14.7 None 26 72.5 None 27 35.5 None 28 14.3 None Average length of wheat in the control group was 80.5 mm.
1 12~ 03 EXAMPLE 12:
Weeds killing test (soil treatment before g~rmination) Several kinds of weed seeds were sown in sandy loam filled in a planter (650 x 210 x 220 mm). On the day subsequent to sowing, the soil surface was sprayed with a properly diluted liquid of the emulsifiable concentrate prepared according to the method in Example 10 (2).
The weeds were grown in a greenhouse made of glass, and the weeding effect was observed on 21st day after treatment.
The weeding effect was rated according to the following standard.
The results are shown in Table 8.
Index Rate of killing O No weeding effect 1 Weeding effect of 30%
2 Weeding effect of 31 to 50%
3 Weeding effect of 51 to 70%
4 Weeding effect of 71 to 90%
Weeding effect of 91 to 100%
86~30~-~ l Table 8 Compound ¦ Weeds tested (Refer to Note) (as in Table 1) ¦ A.r. ¦ B.p. ¦ S.n ¦ E. L . ¦ S .V.
Note: The abbreviations in TABLE 8 indicate the weeds as follows:
A.r. : Amaranthus retyofiexus B.p. : Bidens pilosa S.n. : Solanum nigrum E.f. : Echinochloa frumentaceum S.v. : Setaria viridis
The present invention relates to a derivative of azole represented by the formula (I):
HO 2 \ _ I
~ CH2 - R (I) wherein A represents a nitrogen atom or a methine group and R
represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
Xn (II) wherein X represents an alkyl group, a haloalkyl group, a phenylgroup, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom,n represents an integer from 3 to 5, a process for producing the derivative of azole and a method for controlling pests in agriculture and horticulture with its fungicidal activity, plant glowth regulating activity and herbicidal activity.
Field crops are badly damaged by plant diseases every year, and agricultural chemicals to control them cause the serious environmental pollution, which has become people's great concern. Therefore, there has been a great demand for a new fungicide for agriculture and horticulture which has a low level of toxicity to human, animals, birds and fish and also has a low level of phytotoxicity to useful plants. Such a fungicide should be highly safe in handling, have very little adverse effect on the environment, and produce outstanding control effect for a wide variety of plant diseases.
In an effort to develop such an epoch-making fungicide for agriculture and horticulture, the present inventors studied for new compounds instead of mere modifications of existing compounds. To this end, they synthesized a large number of derivatives of azole and tested their usefulness in practical use. As a result, it was found that derivatives of azole represented by the formula (I):
/ A =
H ~ 2 \ = N~
wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
Xn (II) ~28~;3~'3 wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom,n represents an integer from 3 to 5, have the above-mentioned characteristics.
In addition and surprisingly enough, the present inventors have found that the derivative of azole exert not only a fungicidal effect but also a plant growth control effect and herbicidal effect. These findings led to the present invention.
SUMMARY OF THE INVENTION:
It is an object of the present invention to provide a novel derivative of azole represented by the formula (I).
It is another object of the present invention to provide a fungicide for agriculture and horticulture which is effective agains~ a large variety of plant diseases with a low toxicity to human, animals, birds and fish and a low phytotoxicity to useful plant, the fungicide further exerting the plant growth control effect and herbicidal effect.
It is further object of the present invention to provide a method for controlling pests in agriculture and horticulture applying as an active ingredient a derivative of azole represented by the formula (I), said derivative azole being superior in handling safely and environmental protection.
BRIEF EXPLANATION OF THE DRAWINGS:
Figures from 1 to 28 attached hereto are the infrared absorption spéctra of the derivative of azole pertaining to the present invention. The figure numbers correspond to the respective compound numbers shown in Table 1.
DETAILED DESCRIPTION OF THE INVENTION:
The feature of the present invention lies in, (1) a derivative of azole represented by the formula (I):
/A =
~O ~ 2 \ = N (Il wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophen~l group, a 2,4-~ifluorophenyl grGUp, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
Xn (II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom,n represents an integer from 3 to 5, (2) a process for producing the derivative of azole by reacting a derivative of oxirane represented by the formula (III):
~ CH2 R (III) wherein R has the same meaning as in the formula (I), with 1,2,4-triazole or imidazole and (3) a method for controlling pests in agriculture and horticulture with a fungicidal activity, a plant glowth regulating activity and a herbicidal activity applying a derivative of azole represented by the formula (I) as an active ingredient.
A derivative of azole represented by the formula (I) is a novel compound and some of the derivatives are shown in Table 1 below with respective melting points.
A detailed description is given below of the process for producing a derivative of azole represented by the formula (I) and utilization of the derivative of azole for controlling pests in agriculture and horticulture.
A derivative of azole represented by the formula (I) is produced by reacting a derivative of oxirane represented by the formula (III) with 1,2,4-triazole or imidazole represented by the formula (IV) = N (IV) wherein M represents a hydrogen atom or an alkali metal and A represents a nitrogen atom or a methine group, in the presence of a diluent.
6~03 ~ :
Table 1 Number Indication in Formula (1) ¦ Melting point¦
compound ¦ R ~ (C) ¦
1 4-t-Butylphenyl N129 - 130 2 4-t-Butylphenyl CH123 - 124 3 4-Biphenylyl N146 - 147 4 4-Biphenylyl CH182 - 183 3-Trifluoromethylphenyl N152 - 153 6 3-Trifluoromethylphenyl CH87 - 88 7 3-Chlorophenyl N152 - 153 8 3-Chlorophenyl CH105 - 106 9 4-Nitrophenyl N131 - 132 2,6-Difluorophenyl N104 - 105 11 2,6-Difluorophenyl CH150 - 151 12 4-Bromophenyl N106 - 107 13 4-Bromophenyl CH119 - 120 14 2-Chlorophenyl N154 - 155 2-Chlorophenyl . CH103 - 104 16 4-Methylphenyl N128 - 129 17 4-Methylphenyl CH122 - 123 18 2,4-Difluorophenyl N118 - 119 19 2,4-Difluorophenyl CH144 - 145 3,4-Difluorophenyl N119 - 121 21 3,4-Difluorophenyl CH103 - 105 22 4-Cyanophenyl N115 - 116 23 4-Cyanophenyl CH103 - 104 24 2-Fluoro-4-chlorophenyl N125 - 127 2-Fluoro-4-chlorophenyl CH141 - 143 26 2,3,4,5,6-Pentafluorophenyl N 118 - 120 27 4-Trifluoromethylphenyl N102 - 103 28 4-Trifluoromethylphenyl CH91 - 92 The infrared spectrum of each compound in the above Table 1 is shown in attached Figures 1 to 28, respectively.
A derivative of oxirane represented by the formula (III), which is the starting material of the reaction, is prepared by reacting a ketone represented by the formula (V):
~ CH2 - R (V) wherein R has the same meaning as in the formula (I), with, for example, dimethyloxosulfonium methylide or dimethylsulfonium methylide in the presence of a diluent. (See Org. Syn. 49, 78 (1969) and J. Amer. Chem. Soc. (1965), 1353).
An example of the compound represented by the formula (V) is 2-substituted benzylcyclopentanone. It can be prepared from 2-alkoxycarbonylcyclopentanone and a corresponding substi-tuted benzyl halide according to the process described in Org.
Syn., 45, 7 (1965) and J. Chem. Soc., (1950), 325. It can also be prepared from a corresponding substituted benzylhalide and an enamine of cyclopentanone. (See J. Pharm. Sci., 68, 1501 (1979)).
The diluent used in the process of preparing the compound represented by the formula (I) includes hydrocarbons such as benzene, toluene, xylene and hexane; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; alcohols such as methanol and ethanol; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran;
'''~
~Z863~3 and other compounds such as acetonitrile, acetone, dimethyl-formamide and dimethylsulfoxide.
The process of the present invention may be carried out in the presence of the above-mentioned diluent together with a base. As examples of the base, alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium t-butylate; alkali metal hydrides such as sodium hydride and potassium hydride; and triethylamine and pyridine may be mentioned.
The process of the present invention is carried out in the following manner. An azole represented by the formula (IV) is dissolved in a diluent exemplified above, and to the ~esulting solution is added an oxirane represented by the formula (III) in an amount of 0.5 to 1.0 equivalent. The solution may contain a base exemplified above, if necessary. Alternatively, the oxirane can be dissolved in the diluent first and to the resulting solution can be added an alkali metal salt of the azole.
The reaction temperature ranges from the freezing point to the boiling point of the above-mentioned diluent, but the preferred reaction temperature is from 0C to 100C. The reaction time is from 1 hour to 3 hours. The reaction is preferably carried out with stirring.
After the reaction is completed, the reaction mixture 1~8~
is cooled a extracted wi h an organic solvent such as ethyl acetate, chloroform or benzene in iced water. The organic layer is separated, washed with water and dried. The solvent is distilled off under reduced pressure. The residues are purified to give the desired compound. Purification may be carried out by recrystallization or sillica gel chromatography.
A derivative of azole (a derivative of azolylcyclo-pentanol) represented by the formula (I) exerts the following activities as an active ingredient of agricultural and horticultural composition.
(1) Fungicidal action on plant diseases A derivative of azole of the present in~ention exerts the control effect on a wide variety of plant diseases listed below.
Rice plant: Pyricularia oryzae, Cochliobolus miyabeanus, Xanthomonas oryzae, Rhizoctonia solani, Helminthosporium sigmoideum and Gibberella fujikuroi.
Apple tree: Podosphaera leucotricha, Venturia inaequalis, Sclerotinia mali, Alternaria mali and Valsa mali.
Pear tree : Alternaria kikuchiana, Phyllactinia ~y~, Gymnosporangium haraeonum and Venturia nashicola.
Grape-vine: Unccinula necator and Phakospora ampelopsidis.
Barley: Erysiphe graminis f. sp. hordei, Rhynchosporium secalis, Puccinia graminis and Puccinia triformis.
1;~8630.~
Wheat: Puccinia recondita, ~E~ _ia trlti~i, Puccl~ia triformis and Erysiphe graminis f. sp. tritici.
Oriental melon plant: Sphaerotheca fuliginea.
Watermelon plant: Fusarium oxYsporum.
Tomato plant: Erysiphe cichoracearum, Alternarla solani.
Egg plant: Erysiphe cichoracearum.
Strawberry plant: Sephaerotheca humuli.
Tobacco plant: Erysiphe cichoracearum and Alternaria longipes.
Sugar beat: Cercospora beticola.
Potato plant: Alternaria solani.
Soybean plant: Cercospora kikuchii and Septoria glycines.
Drupe fruit plant: Sclerotinia cinerea.
Other crop plants: Botrytis cinerea and Sclerotinia sclerotiorum.
A derivative of azole of the present invention produces not only the preventive effect but also the therapeutic effect on the some of the above-mentioned plant diseases.
(2) Plant growth regulating effect Recently, plant growth regulators have come into general use in agriculture and horticulture, as the mechanism governing the plant growth regulation by plant hormones has been elucidated. The usage of plant hormones includes, for e~ample, the production of seedless grapes by means of gibberellin, the acceleration of rooting of cuttings by means of ~-naphthalene-acetic acid and the growth retardation of wheat by means of 2-chloroethyltrimethylammonium chloride (trade name "CCC").
~ZB6303 The utilization of techniques in controlling environment of plants applying plant growth regulators is now subjected not only to crops, vegetables and fruit trees but also to ornamental plant such as with flowers and further to wider range of plants such as trees. And there is an increasing possibility that the function of plant growth regulators is going to spread into rooting acceleration, flowering regulation, fruit bearing and thickening, growth acceleration, growth retarding and metabolism regulation. Plant growth regulators are increasing in their kinds and amount of consumption in recent years, but they are not so increasing as can be expected from the above possibilities.
The derivative of azole (derivative of azolylcyclo-pentanol) of the present invention produces the plant growth regulating effect (including herbicidal effect) on a wide variety of plants as shown below.
1) Suppression of vegetative growth of plants, especially suppression of height growth.
2) Increase of available nutrients in plants.
3) Regulation of maturing stage or flowering time of plants.
The first activity mentioned above is useful for the suppression of weed growth (weed-killing function), the suppres-sion of lawn, the prevention of lodging of rice plant and wheat, the suppression of height of soybean and cotton plants which make harvesting machine available, the suppression of axillary buds which promotes the growth of tobacco leaves, the suppression of hedge plant growth which reduces the frequency of pruning and the growth retardation of ornamental plants which leads to an increased commercial value.
The second activity mentioned above contributes to the improvement of beat sugar, sugar cane, and citrus through the increase of sugar content and also to the improvement of crops and soybean through the increase of protein.
The third activity mentioned above makes it possible to ship fresh fruits and flowers at any time according to demands.
A derivative of azole represented by the formula (I) can be used as a fungicide, a plant growth regulator or a herbicide in the form of dust, wettable powder, granule, emulsifiable concentrate or solution with or without mixing a carrier (or diluent). It may also be used as such if necessary, namely, the formulation may contain, in addition to a carrier, adjuvants such as spreader, emulsifier, wetting agent, and sticking agent to ensure the effect.
Incidentally, the derivative of azole of the present invention can be used in the form of inorganic salt, organic salt or metal complex,because it contains the 1,2,4-triazole ring or imidazole ring.
The derivative of azole of the present invention has an azolylmethyl group and a substituted benzyl group at the l-position and 2-position, respectively, of the cyclopentane ring.
.
1;~8~
Therefore, it should exist in the form of stereoisomers, e.g., geometrical isomer (cis form and trans form) and optical isomers. In this invention, the derivative of azole may be a single isomer or a mixture thereof at an arbitrary ratio.
Thus, the agricultural and horticultural chemical pertaining to the present invention may contain one of the isomers or a mixture of the isomers as an active ingredient.
The present invention is now illustrated with the following examples which demonstrate the production of derivatives of azole and the effect of the agricultural and horticultural chemical containing a derivative of azole as an active ingredient.
EXAMPLE 1:
Preparation of 2-(2,4-difluorobenzyl)-1-(lH-imidazol-l-yl-methyl)cyclopentan-l-ol (Compound No. 19 in Table 1):
Into 10 ml of anhydrous dimethylformamide, 324 mg of sodium hydride (prepared by washing 60% oily sodium hydride with dried benzene) were added while stirring under helium atmosphere, and after adding 910 mg of lH-imidazol into the thus prepared mixture, the whole mixture was stirred at room temperature until bubbling was over. A solution of 1.5 g of 4-(2,4-difluorobenzyl)-l-oxaspiro[2.4]heptane in 10 ml of anhydrous dimethylformamide was dropped into the thus obtained solution and the whole mixture was stirred for 2 hours at a room temperature.
After leaving the thus obtained reaction mixture to 1~8~ 03 cool, it was poured into lc-d 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, 830 mg 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 determlned by using TMS as the internal standard and the results are shown by the following marks (the same marks are used in other Examples):
s: singlet d: doublet m: multiplet b: a broad line Physical Properties ~1) Melting point: 144 - 145C
(2) Infrared absorption spectrum (KBr method) is shown in Figure 19 in attached Drawings.
Infrared absorption spectrum (KBr method): vmax 3170, 2940, 1610, 1590, 1490 cm 1.
(3) NMR spectrum (CDC13, ppm): ~
1.37-2.13~bs, 7H), 2.33 -2.83(m, 2H), 3.33(s, lH), 3.77(d, lH, J=14Hz), 4.10(d, lH, J=14Hz), 6.57 - 7.60(m, 6H).
~86303 EX~MPLE 2:
Preparation of 2-(4-bromobenzy1)-1-(lH-1,2,4-triazol-1-yl-methyl)cyclopentan-l-ol (Compound No. 12 in Table 1):
Into 30 ml of anhydrous dimethylformamide, 3.0 g of 4-(4-bromobenzyl)-1-oxaspiro I2.4] heptane was added to be dissolved while stirring under a helium atmosphere, and into the thus prepared solution, 1.12 g of sodium salt of lH-1,2,4-triazole of 90% in purity (commercial product, made by ALDRICH
Co.) was slowly added. The mixture was stirred for 1 hour at 80C
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 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, 2.7 g of the compound of the above title was obtained. The physical properties thereof being shown as follows:
Physical Properties (1) Melting point: 106 - 107C
(2) Infrared absorption spectrum (XBr method) is shown in Figure 12 in attached Drawings.
Infrared absorption spectrum (KBr method): vmax 3260, 3100, 2930, 1620, 1270, 1130, 660 cm 1.
lZ86~03 (3) NMR spectrum (CDC13, ppm): ~
1.45 - 3.15(m, lOH), 4.27(s, 2H), 7.20(d, 2H, J=9Hz), 7.60(d, 2H, J=9Hz), 8.13(s, lH), 8.28(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 talc, a fungicide dust was prepared.
The thus prepared ungicide dust is used by scattering on the ob ject.
EXAMPLE 4:
By pulverizing and mixing 50 parts by weight of one of the present compounds (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 power was prepared.
The thus prepared fungicide wettable powder is used after diluting with water.
The following five examples (Examples 5 to 9) are the examples showing the fungicidal effect of the fungicide for use in agriculture and horticulture according to the present invention ~86~(33 EXAMPLE 5:
Pest controI test against Erysiphe graminis f. sp. tritici on wheat:
Onto the leave of seedling of wheat (variety: NORIN
No. 64, 16 seedlings per pot) at the second leaf stage cultured in an unglazed pot, the 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 leave, 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 temperature of from 20 to 25C in a highly humid atmosphere. Thereafter, the thus treated seedlings were left in a glass green house. After 10 days of the inoculation, the morbidity of the seedlings was examined on the basis of the following standard and the control value was calculated by the following formula from the avexage morbidity per leaf:
Standard of the examination 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%, Morbidity index Extent of disease infect 3 A is from 40 to less than 60%r 4 A is from 60 to less than 80% and A is larger than 80%.
ote *11: A is the area rate of disease infect on the surface of the inoculated leaf.
Control value = (1 ~ morbiditY Onn tcontrteod PoOt ) x 100 (%) he results are shown in Table 2.
63():~
Table 2 Compound Concentration number of the sprayedControl value (as in Table 1) liquid (ppm) (~) 6 1225 77o5 18 125 l6o8o 22 1255 l6o2 Triadimefon 1 125 100 Control ¦ --1~863~3 Note: *1: Triadimefon is a commercial fungicide containing the following compound as the active ingredient:
Cl~ ~
EXAMPLE 6:
Pest control test against Sphaerotheca fuliginea on cucumber-plant:
Onto the leave of seedling of cucumber (variety:
SAGAMI-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 wi.th 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 leave from the contracted leaf of cucumber plant by using a brush to inoculate on the leave, and the thus treated pots were left in a glass green house. After 7 days of the inoculation,.the morbidity of the leaf of seedlings (one leaf/
pot, three pots/compound) was examined according to the following standard, and the control value was calculated from the average morbidity per leaf while utilizing the same formula as in Example ~86~'~
Standard of the examination:
Morbidity index Extent of disease infect 0 Not infected 0.5 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%.
ote *1): A is the area rate of disease infect on the surface of the inoculated leaf.
The results are shown in Table 3.
6:~0~3 Table 3 Compound ConcentrationControl value number of the sprayed Table 1 ) liqu d (ppm1 ~ ~
62.5 100 6 62.5 60 7 62.5 100 8 62.5 100 _ , A commercial 12 5 10 0 funglclde Control __ O . .
ote *1): A fungicide of quinoxaline series represented by the following formula:
C~3 ~ ~/X 5 > =
~ Z~3~i3~
EXAMPLE 7:
Pest control test against Puccinia recondita ~. sp.
tritici on wheat:
Onto the leave 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 concentration was sprayed at a rate of 5 ml/pot (control pot was sprayed with water only). After natural drying of the thus sprayed leave, 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 seedlings were left in a glass green house, and after 7 days, the morbidity was examined on the basis of the following standard. The control value of each of the fungicide was calculated by the formula shown in Example 5 from the average morbidity per leaf of the 10 seedlings per pot:
Standards of the examination:
The same as in Example 6.
The results are shown in Table 4.
l 12~30.3 Table 4 Compound ¦ Concentration number of the sprayed Control value -s ]n able 1) ¦ 1iquid (ppm) . 12 200 100 Triadimefon 200 100 Control __ ` - 25 -~8~3()3 EXAMPLE 8:
Pest control test against Cochliobolus miyabeanus on rice plant:
In the unglazed 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 predetermined concentration, and the thus prepared aqueous 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 15 spores in the visual field of a microscope of 150 magnification) preliminarily cultured was sprayed onto the leave of seedlings 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 fifth 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 calculated according to the following formula:
Control value (%) = (1 ~ B ) x 100 wherein A is the number of disease spots in the treated pots and B is that in the control pots (not being sprayed with the fungicide).
The results are shown in Table 5.
~8~303 Compound Concentration number of the sprayed Control value (as in Table 1) liquid (ppm)( ) : 6 300 98 . 24 300 100 .
*l) Control __ _ _ ~6303 Note *1): A commercial fungicide containing the following compound as an active ingredient:
~ 1 ~3 EXAMPLE 9:
In vitro test against several fungal species Antifungal properties of the present compounds against several fungal species 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 suitable 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 medium not containing any fungicide), and on the basis of the following formula, the rate of control of the mycelial growth was obtained:
R = (dc ~ dt) ~
~8630~3 wherein R represents the rate of control of the mycelial growth of a fungus, dt represents the diameter of the fungal colony on the culture medium plate containing each of the present compound and dc represents the diameter of the fungal 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 Table 6.
Standard for evaluation:
Index of growth control Rate of 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~
r I . I . L L ~ L L ~ L L L ~ L L L L ~ L L L L L
. nnnnn nnnnn nnn n nnnnn Lnnnnn n ~ ~ ~ tnnLn~ LnLn~Ln ~ ~
Z LnLnLnLnLn LnLnLnLnLn LnLnLnLnLn LnLnLnLnLn LnLnLnLnLn n ~ e ~Ln~LnLn ~Ln~ ~ L~ L~ ~ ~ Ln ~ ~ Ln Ln ~ ~ ~ Ln L
Ln~ LnLn~ Ln~Ln~Ln ~Ln~ Ln OJ :C ~ LnLn~ ~LnLn~ LnLn~Ln Ln~Ln~ Ln 7 t~ = nLnLnLn~ n ~n Ln Ln ~n ~ ~ Ln ~ Ln Ln Ln Ln Ln Ln Ln Ln ~ Ln Ln Ln ~3 - ~ ~ 7 ~ Ln ~
O L~ L~ ~n Ln Ln ~nLn~n Ln Ln ~n Ln LnLn~n LnLnLnLnLn Ln~LnLn~n Ln S~ ooooo ooooo ooooo ooooo ooooo o ooooo ooooo ooooo ooooo ooooo o O L ~ ~
~ ¢ ¢ ~ Ln ~ 7 ~ o ~ Ln ~ 7 ~ o ~ Ln ~7 3()3 Note: The abbreviation in ABLE 6 indicate the fungal species as follows:
P.o. : Pyricularia oryzae on rice plant C.m. : Cochliobolus m yabeanus on rice plant R.s. : Rhizoctonia solani on rice plant G.f. : Gibberella fuiikuroi on rice plant He.s.: Helminthosporium sigmoideum on rice plant Bo.c.: Botrytis cinerea F.n. : Fusarium oxysporum f. niveum on watermelon S.c. : Sclerotinia cinerea on peach tree A.k. : Alternaria kikuchiana on pear tree V.m. : Valsa mali on apple tree 1~86~30~3 EXAMPLE 10:
Preparation of plant growth regulator composition and herbicide composition containing a derivative of azole as an active ingredient.
(1) Wettable powder The following components were pulverized and mixed to prepare a wettable powder, which would be applied after dilution with water.
Compound of the invention 50 parts by weight (compound No. 3 in Table 1) Lignin sulfonate5 parts by weight Alkyl sulfonate3 parts by weight Diatomaceous earth42 parts by weight (2) Emulsifiable concentrate The following components were uniformly mixed to prepare an emulsifiable concentrate, which would be applied after dilution with water.
Compound of this invention 25 parts by weight (compound No. 20 in Table 1) Xylene 65 parts by weight Polyoxyethylene alkylaryl ether 10 parts by weight (3) Granule The following components were uniformly mixed together with water and the mixture was granulated by an extrusion granulator, followed by drying.
Compound of this invention 8 parts by weight (compound No. 12 in Table 1) ~286303 sentonite40 parts by weight Clay 45 parts by weight Lignin sulfonate7 parts by weight EXAMPLE 11:
Plant lenqth inhibition for wheat Ten wheat grains were sown in a glass petri dish 8.5 cm in diameter, containing 5 ml of 50 ppm solution of the compound under test. (The variety of wheat is AOBA No. 3). After growing indoors at 27C for 7 days, the plant length was measured.
The results are shown in Table 7.
It i5 noted from Table 7 that all the compounds tested produced a pronounced effect of inhibiting the growth of plant length, particularly in the case of triazole-type compounds.
No phytotoxicity was observed.
~ 1286~30;~
Table 7 Compound ¦Inhibition ¦ i number of plant Phytotoxicity (as in Table 1) length (~6) 1 3.8 None 2 3.1 None 3 3 5 NNone 20.4 None 7 7 2 NNone 9 45 6 NOnne 81.8 None 11 16.5 None 12 3 7 NNone 14 54.1 None 15.2 None 16 85.4 None 17 38.1 None 18 15.8 None 19 11.8 None 62.6 None . 21 19.6 None 22 11 2 NNone 24 79.0 None 14.7 None 26 72.5 None 27 35.5 None 28 14.3 None Average length of wheat in the control group was 80.5 mm.
1 12~ 03 EXAMPLE 12:
Weeds killing test (soil treatment before g~rmination) Several kinds of weed seeds were sown in sandy loam filled in a planter (650 x 210 x 220 mm). On the day subsequent to sowing, the soil surface was sprayed with a properly diluted liquid of the emulsifiable concentrate prepared according to the method in Example 10 (2).
The weeds were grown in a greenhouse made of glass, and the weeding effect was observed on 21st day after treatment.
The weeding effect was rated according to the following standard.
The results are shown in Table 8.
Index Rate of killing O No weeding effect 1 Weeding effect of 30%
2 Weeding effect of 31 to 50%
3 Weeding effect of 51 to 70%
4 Weeding effect of 71 to 90%
Weeding effect of 91 to 100%
86~30~-~ l Table 8 Compound ¦ Weeds tested (Refer to Note) (as in Table 1) ¦ A.r. ¦ B.p. ¦ S.n ¦ E. L . ¦ S .V.
Note: The abbreviations in TABLE 8 indicate the weeds as follows:
A.r. : Amaranthus retyofiexus B.p. : Bidens pilosa S.n. : Solanum nigrum E.f. : Echinochloa frumentaceum S.v. : Setaria viridis
Claims (28)
1. A derivative of azole represented by the formula (I):
(I) wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom n represents an integer from 3 to 5.
(I) wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom n represents an integer from 3 to 5.
2. A derivative of azole according to claim 1, wherein said X represents a nitro group, a methyl group, a t-butyl group, a phenyl group or a trifluoromethyl group, said n is 1 and said A represents a nitrogen atom or a methine group.
3. A derivative azole according to claim 1, wherein R
represents a 4-bromophenyl group, a 4-methylphenyl group, a 2,4-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-
represents a 4-bromophenyl group, a 4-methylphenyl group, a 2,4-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-
4-chlorophenyl group or a 2,3,4,5,6-pentafluorophenyl group and A represents a nitrogen atom.
4. A process for producing a derivative of azole represented by the formula (I):
(I) wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom n represents an integer from 3 to 5, said process comprising the step of bringing a derivative of oxirane represented by the formula (III):
(III) wherein R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group, or a halogen atom and X
can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom n represents an integer from 3 to 5, into reaction with a 1,2,4-triazole or an imidazole represented by the formula (IV):
(IV) wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a methine group.
4. A process for producing a derivative of azole represented by the formula (I):
(I) wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom n represents an integer from 3 to 5, said process comprising the step of bringing a derivative of oxirane represented by the formula (III):
(III) wherein R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group, or a halogen atom and X
can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom n represents an integer from 3 to 5, into reaction with a 1,2,4-triazole or an imidazole represented by the formula (IV):
(IV) wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a methine group.
5. A method for controlling fungal species comprising applying to plants a fungicidally effective amount of a derivative of azole represented by the formula (I):
(I) wherein A represents a nitrogen atom or a methine group and R
represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom a represents an integer from 3 to 5.
(I) wherein A represents a nitrogen atom or a methine group and R
represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom a represents an integer from 3 to 5.
6. A method for controlling fungi according to claim 5, wherein said fungal specy attacking plant(s) 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, Alternaria kikuchiana on pear tree, Fusarium oxysporum f. niveum on watermelon, Sclerotinia cinerea on peach tree or Valsa mali on apple tree or a combination of said fungal specy.
7. A method for controlling fungi according to claim 5, wherein said X represents a nitro group, a methyl group, a t-butyl group, a phenyl group or a trifluoromethyl group, said n is 1 and said A represents a nitrogen atom or a methine group.
8. A method for controlling fungi according to claim 5, wherein said R represents a 4-bromophenyl group, a 4-methyl-phenyl group, a 4-t-butyphenyl group, a 4-biphenylyl group, a 2,4-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a 2,3,4,5,6-pentafluorophenyl group and said A is a nitrogen atom.
9. A method for controlling fungi according to claim 5, wherein said R represents a 4-bromophenyl group, a 4-t-butylphenyl group, a 4-biphenylyl group, a 2,4-difluorophenyl group, a 3,4-difluorophenyl group or a 2-fluoro-4-chlorophenyl group and said A is a methine group.
10. A method for controlling fungi according to claim 8, wherein said R represents a 4-bromophenyl group, a 4-methyl-phenyl group, a 2,4-difluorophenyl group, a 3,4-difluorophenyl group or a 2-fluoro-4-chlorophenyl group.
11. A method for controlling fungi according to claim 10, wherein said R represents a 4-bromophenyl group or a 3,4-difluorophenyl group.
12. A method for regulating the growth of plants comprising applying to plants an effective amount of a derivative of azole represented by the formula (I):
(I) wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom, n represents an integer from 3 to 5, as a plant growth regulator.
(I) wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom, n represents an integer from 3 to 5, as a plant growth regulator.
13. A method for regulating the growth of plants according to claim 12, wherein said plant growth regulator is used for inhibiting the growth of plant length.
14. A method for regulating the growth of plants according to claim 12, wherein said plant is wheat.
15. A method for regulating the growth of plant according to claim 12, wherein said plant growth regulator is used for increasing the content of available nutrients in the plant.
16. A method for regulating the growth of plants according to claim 12, wherein said plant growth regulator is used for the regulation of the maturing stage or flowering stage of the plants.
17. A method for regulating the growth of plants according to claim 12, wherein said X represents a nitro group, a methyl group, a t-butyl group, a phenyl group or a trifluoro-methyl group, said n is 1 and said A represents a nitrogen atom or a methine group.
18. A method for regulating the growth of plants according to claim 12, wherein said R represents a 4-bromophenyl group, a 2-chlorophenyl group, a 4-methylphenyl group, a 4-cyanophenyl group, a 2,6-difluorophenyl aroup, a 3,4-difluoro-phenyl group, a 2-fluoro-4-chlorophenyl group or a 2,3,4,5,6-pentafluorophenyl group, n is 1 and A is a nitrogen atom.
19. A method for regulating the growth of plants according to claim 18, wherein said R represents a 4-methylphenyl group, a 2,6-difluorophenyl group or a 2-fluoro-4-chlorophenyl group.
20. A method for regulating the growth of plants according to claim 18, wherein said R is a 4-methylphenyl group.
21. A method of killing weeds comprising applying to plants a herbicidally effective amount of a derivative of azole represented by the formula (I):
(I) wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom, n represents an integer from 3 to 5.
(I) wherein A represents a nitrogen atom or a methine group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
(II) wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom and X can be the same or different atom or group and n represents an integer of from 1 to 5, provided that when X represents a halogen atom, n represents an integer from 3 to 5.
22. A method of killing weeds according to claim 21, wherein said weeds are any one of or a combination of Amaranthus retyofiexus, Bidens pilosa, Solanum nigrum, Echinochloa frumentaceum or Setaria viridis.
23. A method of killing weeds according to claim 21, wherein said X represents a nitro group, a methyl group, a t-butyl group, a phenyl group or a trifluoromethyl group, said n is 1 and said A represents a nitrogen atom or a methine group.
24. A method of killing weeds according to claim 21, wherein said R represents a 4-bromophenyl group, a 4-methylphenyl group, a 2,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a 2,3,4,5,6-pentafluorophenyl group and A is a nitrogen atom.
25. A method of killing weeds according to claim 21, wherein said R is a trifluoromethylphenyl group and A is a methine group.
26. A use of a fungicidally effective amount of a derivative of azole represented by the formula (I):
(I) wherein A represents a nitrogen atom or a CH group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom, X can be the same or different atom or group and n is an integer of 1 to 5, provided that when X represents a halogen atom n is an integer of 3 to 5, for controlling fungi infecting plants.
(I) wherein A represents a nitrogen atom or a CH group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom, X can be the same or different atom or group and n is an integer of 1 to 5, provided that when X represents a halogen atom n is an integer of 3 to 5, for controlling fungi infecting plants.
27. A use of an effective amount of a derivative of azole represented by the formula (I):
(I) wherein A represents a nitrogen atom or a CH group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom, X can be the same or different atom or group and n is an integer of 1 to 5, provided that when X represents a halogen atom n is an integer of 3 to 5, for regulating growth of plants.
(I) wherein A represents a nitrogen atom or a CH group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom, X can be the same or different atom or group and n is an integer of 1 to 5, provided that when X represents a halogen atom n is an integer of 3 to 5, for regulating growth of plants.
28 A use of a herbicidally effective amount of a derivative of azole represented by the formula (I):
, (I) wherein A represents a nitrogen atom or a CH group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom, X can be the same or different atom or group and n is an integer of 1 to 5, provided that when X represents a halogen atom n is an integer of 3 to 5, for killing weeds.
, (I) wherein A represents a nitrogen atom or a CH group and R represents a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2-fluoro-4-chlorophenyl group or a formula (II):
wherein X represents an alkyl group, a haloalkyl group, a phenyl group, a cyano group, a nitro group or a halogen atom, X can be the same or different atom or group and n is an integer of 1 to 5, provided that when X represents a halogen atom n is an integer of 3 to 5, for killing weeds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP147175/86 | 1986-06-25 | ||
| JP61147175A JPS62149667A (en) | 1985-09-12 | 1986-06-25 | Novel azole derivative, production thereof and use of same as agricultural and horticultural agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1286303C true CA1286303C (en) | 1991-07-16 |
Family
ID=15424279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000518011A Expired - Lifetime CA1286303C (en) | 1986-06-25 | 1986-09-11 | Azole derivatives |
Country Status (3)
| Country | Link |
|---|---|
| CA (1) | CA1286303C (en) |
| DK (1) | DK164548C (en) |
| ES (1) | ES2006179A6 (en) |
-
1986
- 1986-09-11 CA CA000518011A patent/CA1286303C/en not_active Expired - Lifetime
-
1987
- 1987-06-23 ES ES8701829A patent/ES2006179A6/en not_active Expired
- 1987-06-24 DK DK322187A patent/DK164548C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DK322187A (en) | 1987-12-26 |
| ES2006179A6 (en) | 1989-04-16 |
| DK164548B (en) | 1992-07-13 |
| DK322187D0 (en) | 1987-06-24 |
| DK164548C (en) | 1992-11-30 |
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