CA1340546C - Azolylalkenes and fungicides containing these compounds - Google Patents
Azolylalkenes and fungicides containing these compoundsInfo
- Publication number
- CA1340546C CA1340546C CA000593771A CA593771A CA1340546C CA 1340546 C CA1340546 C CA 1340546C CA 000593771 A CA000593771 A CA 000593771A CA 593771 A CA593771 A CA 593771A CA 1340546 C CA1340546 C CA 1340546C
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- Prior art keywords
- fluorophenyl
- formula
- chlorophenyl
- set forth
- furanyl
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Abstract
I
where R1 is 4-fluorophenyl, R2 is alkyl, naphthyl, cycloalkyl, cyclo-alkenyl, a heterocycle, biphenyl or phenyl, these radicals being substituted or unsubstituted, and X is CH or N, and their plant-tolerated acid addition salts and metal complexes, and fungicides containing these compounds.
where R1 is 4-fluorophenyl, R2 is alkyl, naphthyl, cycloalkyl, cyclo-alkenyl, a heterocycle, biphenyl or phenyl, these radicals being substituted or unsubstituted, and X is CH or N, and their plant-tolerated acid addition salts and metal complexes, and fungicides containing these compounds.
Description
e..
134Q~~
The present invention relates to novel azolyl-alkenes, processes for their preparation and fungicides containing these compounds.
It is known that 1-(1,2,4-triazol-1-yl)-2-(2,4 dichlorophenyl)-pentane can be used as a fungicide (C.A. No.
66 246-88-6). However, its fungicidal action is unsatisfactory.
We have found that azolylalkenes of the general formula I
~X~N-CH 2 R1~-CH_R2 I
where R1 is fluorophenyl, R2 is C1-C5-alkyl, phenyl, biphenyl, naphthyl, C3-C8 cycloalkyl, C3-C8-cycloalkenyl or a 5-membered or 6 membered heterocycle which contains one or two oxygen, nitrogen or sulfur atoms, these radicals being unsubsti-tuted or monosubstituted to trisubstituted by halogen, nitro, amino or phenoxy or by alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, and X is CH or N, and their plant-tolerated acid addition salts or metal complexes, excluding however the compounds of the general for-mula (I) where:
R1 is 4-fluorophenyl or 2,4-difluorophenyl; and R2 simultaneously denotes 4-fluorophenyl, 4-chloro-phenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl or pyrid-4-yl, have a better fungicidal action, in particular against B
4340~4~
- la -cereal diseases, than the known azolylalkanes.
R1 is, for example, phenyl which is monosubstituted to pentasubstituted, in particular monosubstituted or disubstituted, by fluorine, such as 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl or pentafluorophenyl, and R2 is, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, 1-naphthyl, 2-naphthyl, p-biphenyl, phenyl, halophenyl, 2-chlorophenyl, 2-fluorophenyl, 2-bromo-phenyl, 3-chlorophenyl, 3-bromophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dichloro-phenyl. 2,3-dichlorophenyl, ;'~..~ ~' 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-6-fluorophenyl, alkoxyphenyl, 2-methoxyphenyl, 3-methoxy-phenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, alkyl-phenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butyl-phenyl, 4-tert-butoxyphenyl, 2-chloro-4-fiuorophenyl, 2-chloro-6-methylphenyl, 3,4-dimethoxyphenyl, 3-phenoxy-phenyl, 4-phenoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 3-aminophenyl, 4-aminophenyl, 2-aminophenyl, 2-trifluoro-methylphenyl,3-trifluoromethylphenyl,4-trifluoromethyl-phenyl, cyclohexyl, cyclopentyl, cyclopropyl, cyclo-heptyl, cyclohexenyl, the radical of a 5-membered or 6-membered heterocyclic structure which contains one or two oxygen, nitrogen or sulfur atoms and is saturated or unsaturated, eg. dioxane, thiophene, furan, pyran, tetrahydropyran, pyridine, isoxazole or methylisoxazole, such as 1,3-dioxan-2-yl, 1,4-dioxan-2-yl, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, tetrahydropyranyl, 3-pyridyl or 3-methylisoxazol-5-yl.
Acid addition salts of the active ingredients I
are, for example, the hydrochlorides, bromides, sulfates, nitrates, phosphates, oxalates and dodecylbenzenesulfon ates. The activity of the salts is due to the cation, so that in general any anion may be chosen. The active in gredient salts are prepared by reacting an azolylalkene (I) with an acid.
Metal complexes of the active ingredients I or their salts can be formed with, for example, copper, zinc, tin, manganese, iron, cobalt or nickel by reacting the azolylalkene with a corresponding metal salt, for example with copper sulfate, zinc sulfate or zinc chlor-ide.
The compounds of the formula I can be prepared, for example, by reacting a compound of the formula II
R~~CH-R2 II
1340'~4~
134Q~~
The present invention relates to novel azolyl-alkenes, processes for their preparation and fungicides containing these compounds.
It is known that 1-(1,2,4-triazol-1-yl)-2-(2,4 dichlorophenyl)-pentane can be used as a fungicide (C.A. No.
66 246-88-6). However, its fungicidal action is unsatisfactory.
We have found that azolylalkenes of the general formula I
~X~N-CH 2 R1~-CH_R2 I
where R1 is fluorophenyl, R2 is C1-C5-alkyl, phenyl, biphenyl, naphthyl, C3-C8 cycloalkyl, C3-C8-cycloalkenyl or a 5-membered or 6 membered heterocycle which contains one or two oxygen, nitrogen or sulfur atoms, these radicals being unsubsti-tuted or monosubstituted to trisubstituted by halogen, nitro, amino or phenoxy or by alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, and X is CH or N, and their plant-tolerated acid addition salts or metal complexes, excluding however the compounds of the general for-mula (I) where:
R1 is 4-fluorophenyl or 2,4-difluorophenyl; and R2 simultaneously denotes 4-fluorophenyl, 4-chloro-phenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl or pyrid-4-yl, have a better fungicidal action, in particular against B
4340~4~
- la -cereal diseases, than the known azolylalkanes.
R1 is, for example, phenyl which is monosubstituted to pentasubstituted, in particular monosubstituted or disubstituted, by fluorine, such as 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl or pentafluorophenyl, and R2 is, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, 1-naphthyl, 2-naphthyl, p-biphenyl, phenyl, halophenyl, 2-chlorophenyl, 2-fluorophenyl, 2-bromo-phenyl, 3-chlorophenyl, 3-bromophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dichloro-phenyl. 2,3-dichlorophenyl, ;'~..~ ~' 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-6-fluorophenyl, alkoxyphenyl, 2-methoxyphenyl, 3-methoxy-phenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, alkyl-phenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butyl-phenyl, 4-tert-butoxyphenyl, 2-chloro-4-fiuorophenyl, 2-chloro-6-methylphenyl, 3,4-dimethoxyphenyl, 3-phenoxy-phenyl, 4-phenoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 3-aminophenyl, 4-aminophenyl, 2-aminophenyl, 2-trifluoro-methylphenyl,3-trifluoromethylphenyl,4-trifluoromethyl-phenyl, cyclohexyl, cyclopentyl, cyclopropyl, cyclo-heptyl, cyclohexenyl, the radical of a 5-membered or 6-membered heterocyclic structure which contains one or two oxygen, nitrogen or sulfur atoms and is saturated or unsaturated, eg. dioxane, thiophene, furan, pyran, tetrahydropyran, pyridine, isoxazole or methylisoxazole, such as 1,3-dioxan-2-yl, 1,4-dioxan-2-yl, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, tetrahydropyranyl, 3-pyridyl or 3-methylisoxazol-5-yl.
Acid addition salts of the active ingredients I
are, for example, the hydrochlorides, bromides, sulfates, nitrates, phosphates, oxalates and dodecylbenzenesulfon ates. The activity of the salts is due to the cation, so that in general any anion may be chosen. The active in gredient salts are prepared by reacting an azolylalkene (I) with an acid.
Metal complexes of the active ingredients I or their salts can be formed with, for example, copper, zinc, tin, manganese, iron, cobalt or nickel by reacting the azolylalkene with a corresponding metal salt, for example with copper sulfate, zinc sulfate or zinc chlor-ide.
The compounds of the formula I can be prepared, for example, by reacting a compound of the formula II
R~~CH-R2 II
1340'~4~
where R1 and R2 have the abovementioned meanings and L is a leaving group which can be nucleophilically substituted (halogen, OH, tosylate, mesylate or triflate), with a compound of the formula III
He III
where Me is hydrogen or a metal atom (Na or K) and X has the abovementioned meanings.
Where Me is hydrogen, the reaction is carried out in the presence or absence of a solvent or diluent and with or without the addition of an inorganic or organic base and of a reaction accelerator, at from 10 to 120~C.
The preferred solvents and diluents include ketones, such as acetone, methyl ethyl ketone or cyclohexanone, ni-triles such as acetonitrile or propionitrile, alcohols, such as methanol, ethanol, isopropanol, n-butanol or glycol, esters, such as ethyl acetate, methyl acetate or butyl acetate, ethers, such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or diispropyl ether, amides, such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, and dimethyl sulfoxide, sulfolane and mixtures of these.
Examples of suitable bases, which may also be used as acid acceptors in the reaction, are alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate or cesium car-bonate, or sodium bicarbonate, potassium bicarbonate or cesium bicarbonate, pyridine or 4-dimethylaminopyridine.
However, other conventional bases may also be used.
Preferred reaction accelerators are metal hal-ides, such as sodium iodide or potassium iodide, quater-nary ammonium salts, such as tetrabutylammonium chloride, bromide, iodide or bisulfate, benzyltriethylammonium chloride or bromide, or crown ethers, such as 12-crown-4, 134Q~~d 15-crown-5, 18-crown-6, dibenzo-18-crown-6 or dicyclo-hexano-18-crown-6.
The reaction is generally carried out at from 20 to 150~C, under atmospheric or superatmospheric pressure, continuously or batchwise.
Where Me is a metal atom, the reaction is carried out in the presence or absence of a solvent or diluent.
The preferred solvents and diluents include ketones, such as acetone, methyl ethyl ketone or cyclohexanone, ni-triles, such as acetonitrile or propionitrile, alcohols, such as methanol, ethanol, isopropanol, n-butanol or glycol, esters, such as ethyl acetate, methyl acetate or butyl acetate, ethers, such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or diisopropyl ether, amides, such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, and dimethyl sulfoxide, sulfolane and mixtures of these.
The reaction is carried out in general at from 0 to 100~C, preferably from 20 to 80~C. In the presence of a solvent having a low boiling point, the reaction is advantageously carried out at the boiling point.
The compound III is prepared by, for example, halogenating or oxidizing an olefin of the formula IV
R ~ ~-C H-tt Z I V
in the allyl position by a known method.
Suitable halogenating reagents are N-chloro- and N-bromosuccinimide in a halohydrocarbon such as carbon tetrachloride, trichloroethane, methylene chloride or chlorobenzene, at from 20 to 100~C. The allyl oxidation is carried out using peresters, such as tert-butyl perbenzoate or tert-butyl peracetate, in the presence of a heavy metal salt, eg. copper(I) chloride or copper(I) bromide, in an inert solvent at from 10 to 100~C.
13~0~4 The alcohols obtained from an oxidation are reacted with methanesulfonyl chloride, toluenesulfonyl chloride, benzenesulfonyl chloride or trifluoromethyl-sulfonyl chloride with the use of an auxiliary base in an inert solvent to give the esters of the compounds of the formula III, or are converted into the allyl halides by the action of a hydrohalic acid.
The compounds IV can be prepared by generally known processes for olefin synthesis (Houben-Weyl-Miiller, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1972, Vol. V, lb).
It is also possible to use substituted diphenyl-propenals of the formula CHO
\C=CH-R2 R~/
as starting materials and to reduce them to the allyl alcohols of the formula C\ZOH
/C=CH-R2 R~
The ally alcohols can be converted into the azolylalkenes by the reactions described above.
The active ingredients can occur as Z or E
isomers. The present invention relates to both forms as well as to the isomer mixtures having different isomer ratios, and to fungicides which contain one of these forms or mixtures.
The Examples which follow illustrate the prepara-tion of the active ingredients.
1. Preparation of the starting materials Method 1 E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-propenal 4.2 g of sodium hydroxide in 30 ml of water are added to a solution of 35 g of 2-chlorobenzaldehyde in 1340~4~
He III
where Me is hydrogen or a metal atom (Na or K) and X has the abovementioned meanings.
Where Me is hydrogen, the reaction is carried out in the presence or absence of a solvent or diluent and with or without the addition of an inorganic or organic base and of a reaction accelerator, at from 10 to 120~C.
The preferred solvents and diluents include ketones, such as acetone, methyl ethyl ketone or cyclohexanone, ni-triles such as acetonitrile or propionitrile, alcohols, such as methanol, ethanol, isopropanol, n-butanol or glycol, esters, such as ethyl acetate, methyl acetate or butyl acetate, ethers, such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or diispropyl ether, amides, such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, and dimethyl sulfoxide, sulfolane and mixtures of these.
Examples of suitable bases, which may also be used as acid acceptors in the reaction, are alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate or cesium car-bonate, or sodium bicarbonate, potassium bicarbonate or cesium bicarbonate, pyridine or 4-dimethylaminopyridine.
However, other conventional bases may also be used.
Preferred reaction accelerators are metal hal-ides, such as sodium iodide or potassium iodide, quater-nary ammonium salts, such as tetrabutylammonium chloride, bromide, iodide or bisulfate, benzyltriethylammonium chloride or bromide, or crown ethers, such as 12-crown-4, 134Q~~d 15-crown-5, 18-crown-6, dibenzo-18-crown-6 or dicyclo-hexano-18-crown-6.
The reaction is generally carried out at from 20 to 150~C, under atmospheric or superatmospheric pressure, continuously or batchwise.
Where Me is a metal atom, the reaction is carried out in the presence or absence of a solvent or diluent.
The preferred solvents and diluents include ketones, such as acetone, methyl ethyl ketone or cyclohexanone, ni-triles, such as acetonitrile or propionitrile, alcohols, such as methanol, ethanol, isopropanol, n-butanol or glycol, esters, such as ethyl acetate, methyl acetate or butyl acetate, ethers, such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or diisopropyl ether, amides, such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, and dimethyl sulfoxide, sulfolane and mixtures of these.
The reaction is carried out in general at from 0 to 100~C, preferably from 20 to 80~C. In the presence of a solvent having a low boiling point, the reaction is advantageously carried out at the boiling point.
The compound III is prepared by, for example, halogenating or oxidizing an olefin of the formula IV
R ~ ~-C H-tt Z I V
in the allyl position by a known method.
Suitable halogenating reagents are N-chloro- and N-bromosuccinimide in a halohydrocarbon such as carbon tetrachloride, trichloroethane, methylene chloride or chlorobenzene, at from 20 to 100~C. The allyl oxidation is carried out using peresters, such as tert-butyl perbenzoate or tert-butyl peracetate, in the presence of a heavy metal salt, eg. copper(I) chloride or copper(I) bromide, in an inert solvent at from 10 to 100~C.
13~0~4 The alcohols obtained from an oxidation are reacted with methanesulfonyl chloride, toluenesulfonyl chloride, benzenesulfonyl chloride or trifluoromethyl-sulfonyl chloride with the use of an auxiliary base in an inert solvent to give the esters of the compounds of the formula III, or are converted into the allyl halides by the action of a hydrohalic acid.
The compounds IV can be prepared by generally known processes for olefin synthesis (Houben-Weyl-Miiller, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1972, Vol. V, lb).
It is also possible to use substituted diphenyl-propenals of the formula CHO
\C=CH-R2 R~/
as starting materials and to reduce them to the allyl alcohols of the formula C\ZOH
/C=CH-R2 R~
The ally alcohols can be converted into the azolylalkenes by the reactions described above.
The active ingredients can occur as Z or E
isomers. The present invention relates to both forms as well as to the isomer mixtures having different isomer ratios, and to fungicides which contain one of these forms or mixtures.
The Examples which follow illustrate the prepara-tion of the active ingredients.
1. Preparation of the starting materials Method 1 E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-propenal 4.2 g of sodium hydroxide in 30 ml of water are added to a solution of 35 g of 2-chlorobenzaldehyde in 1340~4~
300 ml of methanol. The reaction mixture is cooled to 10~C and 36 g of 4-fluorophenylacetaldehyde are rapidly added, the temperature of the solution increasing to 30-40~C. The mixture is stirred for 10 hours at 40~C, after which the precipitated crystals are filtered off under suction from the cooled reaction solution.
Method 2 E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl alcohol Sodium borohydride solution is added dropwise to a solution of 26 g of E/Z-2-(4-fluorophenyl)-3-(2-chloro-phenyl)-propenal in 150 ml of isopropanol until starting material can no longer be detected chromatographically.
The reaction mixture is poured onto ice water and ex-tracted with dichloromethane. Drying and evaporation of the organic phase give 25 g of an oily end product.
Method 3 E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide g of E/Z-2-(4-fluorophenyl)-3-(2-chloro-phenyl)-allyl alcohol are dissolved in 150 ml of methyl-20 ene chloride and a slow stream of HBr gas is passed through in the course of several hours. When allyl alcohol is no longer detectable, the mixture is worked up with dilute aqueous sodium carbonate solution. Drying and distilling off the organic phase give 31 g of oily 25 E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide.
Method 4 Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide is heated at 200~C for a few hours. During this procedure, the isomer ratio used is shifted toward the Z
isomer. The Z isomer is isolated by recrystallization of the resulting reaction mixture from isopropanol. Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide has a melting point of 71-73~C.
II. Preparation of the end products 10 g of Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-_ 7 _ allyl bromide are dissolved in 70 ml of dimethylfor-mamide, and 4 g of triazole and 6 g of potassium car-bonate are added. While the mixture is stirred at room temperature (20~C), the decrease in the content of allyl bromide is monitored by thin layer chromatography. The reaction solution is worked up after the end of the reaction (4 hours) by pouring the reaction solution into ice water and extracting with methylene chloride. Z-1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl)-3-(2-chloro-phenyl)-allyl (compound No. 1) having a melting point of 105-107~C is isolated.
The E isomer is obtained in the same manner by reacting the chromatographically purified E-allyl bromide with triazole and potassium carbonate in dimethylfor mamide.
The compounds listed in the Table below are ob-tained by a similar method:
13~a~~
Table ~~ -C R 2~=C H_R 2 No. R1 R2 Isomer X m.p.
1 4-fluorophenyl 2-chlorophenyl Z N 107C
2 4-fluorophenyl 2-chlorophenyl E N 63-74C
3 4-fluorophenyl 2-chlorophenyl Z CH 104-106C
4 4-fluorophenyl 2-chlorophenyl E CH ?3-81C
5 4-fluorophenyl 4-chlorophenyl Z N
6 4-fluorophenyl 4-chlorophenyl E N
Method 2 E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl alcohol Sodium borohydride solution is added dropwise to a solution of 26 g of E/Z-2-(4-fluorophenyl)-3-(2-chloro-phenyl)-propenal in 150 ml of isopropanol until starting material can no longer be detected chromatographically.
The reaction mixture is poured onto ice water and ex-tracted with dichloromethane. Drying and evaporation of the organic phase give 25 g of an oily end product.
Method 3 E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide g of E/Z-2-(4-fluorophenyl)-3-(2-chloro-phenyl)-allyl alcohol are dissolved in 150 ml of methyl-20 ene chloride and a slow stream of HBr gas is passed through in the course of several hours. When allyl alcohol is no longer detectable, the mixture is worked up with dilute aqueous sodium carbonate solution. Drying and distilling off the organic phase give 31 g of oily 25 E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide.
Method 4 Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide E/Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide is heated at 200~C for a few hours. During this procedure, the isomer ratio used is shifted toward the Z
isomer. The Z isomer is isolated by recrystallization of the resulting reaction mixture from isopropanol. Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-allyl bromide has a melting point of 71-73~C.
II. Preparation of the end products 10 g of Z-2-(4-fluorophenyl)-3-(2-chlorophenyl)-_ 7 _ allyl bromide are dissolved in 70 ml of dimethylfor-mamide, and 4 g of triazole and 6 g of potassium car-bonate are added. While the mixture is stirred at room temperature (20~C), the decrease in the content of allyl bromide is monitored by thin layer chromatography. The reaction solution is worked up after the end of the reaction (4 hours) by pouring the reaction solution into ice water and extracting with methylene chloride. Z-1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl)-3-(2-chloro-phenyl)-allyl (compound No. 1) having a melting point of 105-107~C is isolated.
The E isomer is obtained in the same manner by reacting the chromatographically purified E-allyl bromide with triazole and potassium carbonate in dimethylfor mamide.
The compounds listed in the Table below are ob-tained by a similar method:
13~a~~
Table ~~ -C R 2~=C H_R 2 No. R1 R2 Isomer X m.p.
1 4-fluorophenyl 2-chlorophenyl Z N 107C
2 4-fluorophenyl 2-chlorophenyl E N 63-74C
3 4-fluorophenyl 2-chlorophenyl Z CH 104-106C
4 4-fluorophenyl 2-chlorophenyl E CH ?3-81C
5 4-fluorophenyl 4-chlorophenyl Z N
6 4-fluorophenyl 4-chlorophenyl E N
7 4-fluorophenyl 4-chlorophenyl Z CH
8 4-fluorophenyl 4-chlorophenyl E CH
9 4-fluorophenyl 2,4-dichlorophenyl Z N
10 4-fluorophenyl 2,4-dichlorophenyl E N
11 4-fluorophenyl 2,4-dichlorophenyl Z CH
12 4-fluorophenyl 2,4-dichlorophenyl E CH
13 4-fluorophenyl 2-thienyl Z N 106C
14 4-fluorophenyl 2-thienyl E N
15 4-fluorophenyl 2-thienyl Z CH
16 4-fluorophenyl 2-thienyl E N
17 4-fluorophenyl 3-thienyl Z N
18 4-fluorophenyl 3-thienyl E N
19 4-fluorophenyl 3-thienyl Z CH
20 4-fluorophenyl 3-thienyl E CH
21 4-fluorophenyl 2-furanyl Z N 84C
22 4-fluorophenyl 2-furanyl E N
23 4-fluorophenyl 2-furanyl Z CH
24 4-fluorophenyl 2-furanyl E CH
25 4-fluorophenyl 3-furanyl Z N
26 4-fluorophenyl 3-furanyl E N
27 4-fluorophenyl 3-furanyl Z CH
28 4-fluorophenyl 3-furanyl E CH
29 4-fluorophenyl 4-cyclohexenyl Z N 58C
30 4-fluorophenyl 4-cyclohexenyl E N
31 4-fluorophenyl 4-cyclohexenyl Z CH
32 4-fluorophenyl 4-cyclohexenyl E CH
33 4-fluorophenyl 5-(3-methylisoxazolyl)Z N resin 34 4-fluorophenyl 5-(3-methylisoxazolyl)E N
35 4-fluorophenyl 5-(3-methylisoxazolyl)Z CH
No. R1 R2 Isomer X m.p.
No. R1 R2 Isomer X m.p.
36 4-fluorophenyl 5-(3-methylisoxazolyl)E CH
37 2-fluorophenyl 2-chlorophenyl Z N
38 2-fluorophenyl 2-chlorophenyl E N
39 2-fluorophenyl 2-chlorophenyl Z CH
40 2-fluorophenyl 2-chlorophenyl E CH
41 2-fluorophenyl 4-chlorophenyl Z N
42 2-fluorophenyl 4-chlorophenyl E N
43 2-fluorophenyl 4-chlorophenyl Z CH
44 2-fluorophenyl 4-chlorophenyl E CH
45 2-fluorophenyl 2,4-dichlorophenyl Z N
46 2-fluorophenyl 2,4-dichlorophenyl E N
47 2-fluorophenyl 2,4-dichlorophenyl Z CH
48 2-fluorophenyl 2,4-dichlorophenyl E CH
49 2-fluorophenyl 2-thienyl Z N
50 2-fluorophenyl 2-thienyl E N
51 2-fluorophenyl 2-thienyl Z CH
52 2-fluorophenyl 2-thienyl E N
53 2-fluorophenyl 3-thienyl Z N
54 2-fluorophenyl 3-thienyl E N
55 2-fluorophenyl 3-thienyl Z CH
56 2-fluorophenyl 3-thienyl E CH
57 2-fluorophenyl 2-furanyl Z N
58 2-fluorophenyl 2-furanyl E N
59 2-fluorophenyl 2-furanyl Z CH
60 2-fluorophenyl 2-furanyl E CH
61 2-fluorophenyl 3-furanyl Z N
62 2-fluorophenyl 3-furanyl E N
63 2-fluorophenyl 3-furanyl Z CH
64 2-fluorophenyl 3-furanyl E CH
65 2-fluorophenyl 4-cyclohexenyl Z N
66 2-fluorophenyl 4-cyclohexenyl E N
67 2-fluorophenyl 4-cyclohexenyl Z CH
68 2-fluorophenyl 4-cyclohexenyl E CH
69 2-fluorophenyl 5-(3-methylisoxazolyl)Z N
70 2-fluorophenyl 5-(3-methylisoxazolyl)E N
71 2-fluorophenyl 5-(3-methylisoxazolyl)Z CH
72 2-fluorophenyl 5-(3-methylisoxazolyl)E CH
73 3-fluorophenyl 2-chlorophenyl Z N
74 3-fluorophenyl 2-chlorophenyl E N
75 3-fluorophenyl 2-chlorophenyl Z CH
76 3-fluorophenyl 2-chlorophenyl E CH
77 3-fluorophenyl 4-chlorophenyl Z N
13~~~~6 No R1 RZ Isomer X m.p.
13~~~~6 No R1 RZ Isomer X m.p.
78 3-fluorophenyl 4-chlorophenyl E N
79 3-fluorophenyl 4-chlorophenyl Z CH
80 3-fluorophenyl 4-chlorophenyl E CH
5 81 3-fluorophenyl 2,4-dichlorophenyl Z N
82 3-fluorophenyl 2,4-dichlorophenyl E N
83 3-fluorophenyl 2,4-dichlorophenyl Z CH
84 3-fluorophenyl 2,4-dichlorophenyl E CH
85 3-fluorophenyl 2-thienyl Z N
10 86 3-fluorophenyl 2-thienyl E N
87 3-fluorophenyl 2-thienyl Z CH
88 3-fluorophenyl 2-thienyl E N
89 3-fluorophenyl 3-thienyl Z N
90 3-fluorophenyl 3-thienyl E N
91 3-fluorophenyl 3-thienyl Z CH
92 3-fluorophenyl 3-thienyl E CH
93 3-fluorophenyl 2-furanyl Z N
94 3-fluorophenyl 2-furanyl E N
95 3-fluorophenyl 2-furanyl Z CH
96 3-fluorophenyl 2-furanyl E CH
97 3-fluorophenyl 3-furanyl Z N
98 3-fluorophenyl 3-furanyl E N
99 3-fluorophenyl 3-furanyl Z CH
1003-fluorophenyl 3-furanyl E CH
1013-fluorophenyl 4-cyclohexenyl Z N
1023-fluorophenyl 4-cyclohexenyl E N
1033-fluorophenyl 4-cyclohexenyl Z CH
1043-fluorophenyl 4-cyclohexenyl E CH
1053-fluorophenyl 5-(3-methylisoxazolyl)Z N
1063-fluorophenyl 5-(3-methylisoxazolyl)E N
1073-fluorophenyl 5-(3-methylisoxazolyl)Z CH
1083-fluorophenyl 5-(3-methylisoxazolyl)E CH
1092,4-difluorophenyl2-chlorophenyl Z N
1102,4-difluorophenyl2-chlorophenyl E N
1112,4-difluorophenyl2-chlorophenyl Z CH
l122,4-difluorophenyl2-chlorophenyl E CH
1132,4-difluorophenyl4-chlorophenyl Z N
1142,4-difluorophenyl4-chlorophenyl E N
1152,4-difluorophenyl4-chlorophenyl Z CH
1162,4-difluorophenyl4-chlorophenyl E CH
1172,4-difluorophenyl2,4-dichlorophenyl Z N
1182,4-difluorophenyl2,4-difluorophenyl E N
1192,4-difluorophenyl2,4-dichlorophenyl Z CH
1340 ~4b No. R1 R2 Isomer X m.p.
120 2,4-difluorophenyl2,4-dichlorophenyl E CH
121 2,4-difluorophenyl2-thienyl Z N
122 2,4-difluorophenyl2-thienyi E N
123 2,4-difluorophenyl2-thienyl Z CH
124 2,4-difluorophenyl2-thienyl E N
125 2,4-difluorophenyl3-thienyl Z N
126 2,4-difluorophenyl3-thienyl E N
127 2,4-difluorophenyi3-thienyl ~ Z CH
10128 2,4-difluorophenyl3-thienyl E CH
129 2,4-difluorophenyl2-furanyl Z N
130 2,4-difluorophenyl2-furanyl E N
131 2,4-difluorophenyl2-furanyl Z CH
132 2,4-difluorophenyl2-furanyl E CH
15133 2,4-difluorophenyl3-furanyl Z N
134 2,4-difluorophenyl3-furanyl E N
135 2,4-difluorophenyl3-furanyl Z CH
136 2,4-difluorophenyl3-furanyl E CH
137 2,4-difiuorophenyl4-cyclohexenyl Z N
20138 2,4-difluorophenyl4-cyclohexenyi E N
139 2,4-difluorophenyl4-cyclohexenyl Z CH
140 2,4-difluorophenyl4-cyclohexenyl E CH
141 2,4-difluorophenyl5-(3-methylisoxazolyl)Z N
142 2,4-difluorophenyi5-(3-methylisoxazolyi)E N
25143 2,4-difluorophenyl5-(3-methylisoxazolyi)Z CH
144 2,4-difluorophenyi5-(3-methylisoxazolyl)E CH
Compounds 5 to 8 and 113 to 1l6 are excluded from the scope of the claims.
A
In general terms, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large number of fungi in vary~us crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.
The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e. g., xylene), chlorinated aromatics (e. g., chloro-benzenes), paraffins (e. g., crude oil fractions), alcohols (e. g., methanol, butanol), ketones (e. g., cyclohexanone), amines (e. g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e. g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e. g., highly disperse silica and silicates);
emulsifiers such as nonionic and anionic emulsifiers (e. g., polyoxyethyl-ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicides generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt~ of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, e.g., on Paecilomyces variotii.
The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 29 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of compound no. 1 is dissolved in a mixture con-sisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso-butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
134~54~
IV. 20 parts by weight of compound no. 29 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280~C, and parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 5 of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel) and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
VI. 3 parts by weight of compound no. 29 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
vII. 30 parts by weight of compound no. 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of compound no. 29 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.
Ix. 20 parts by weight of compound no. 1 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fun-gicides frequently results in an increase in the fungicidal spectrum.
The following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions.
.. 13454d Examples of fungicides which may be combined with the novel compounds are:
sulfur, dithiocarbamates and their derivatives, such as 5 ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, 10 tetramethylthiuram disulfides, ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithiocarbamate and N,N'-polypropylenebis(thiocarbamyl) disulfide;
nitro derivatives, such as dinitro(1-methylheptyl)-phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonothioate, 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio[4,5-b]quinoxaline, methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(fur-2-yl)-benzimidazole, 2-(thiazol-4-yl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine 1-oxide, 8-hydroxyquinoline and its copper salt, 134~~j~~
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, 2,5-dimethyl-N-cyciohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethyifuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethylacetal, piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide), 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-[3-(p-tert.-butylphenyl)-2-methyipropylJ-cis-2,6-dimethylmorpholine, N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyi]-1H-1,2,4--triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyi]-1H-1,2,4--triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyi-urea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol, 1-(4-phenylphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazoi-1-yl)-2-butanol, a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-(2-dimethylamino-4-hydroxy-6-methytpyrimidine, bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene, 1,2-bis-(3-methoxycarbonyi-2-thioureido)-benzene, and various fungicides, such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyciohexyi)-2-hydroxyethyi]-giutaramide, hexachlorobenzene, DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate, methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyi)-alanate, N-(2,6-dimethylphenyl)-N-chloroacetyt-DL-2-aminobutyrolactone, methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyi)-alanate, 5-methyl-5-vinyl-3-(3,5-dichiorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichiorophenyl)-1-isopropylcarbamylhydantoin, N-(3,5-dichlorophenyi)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximinoJ-acetamide, 1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole, 2,4-difluoro-oc-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, and 1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.
Use examples For comparison purposes, 1-(1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-pentane (A) disclosed in C. A. No. 66246-88-6 was used.
Use Example 1 Action on wheat brown rust Leaves of pot-grown wheat seedlings of the "Friihgold" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20 to 22~C in a high-humidity (90 - 95%) chamber. ouring this period the spores germinated and the germ tubes penetrated the leaf tissue. The infected plants were then sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20 to 22~C and a relative humidity of 65 to 70%. The extent of rust fungus spread on the leaves was assessed after 8 days.
The results show that active ingredient 1, applied as a 0.006wt% spray liquor, has a better fungicidal action (100%) than prior art comparative agent A (60%).
Use Example 2 Action on Pyrenophora teres Barley seedlings of the "Igri" variety were sprayed to runoff at the two-leaf stage with aqueous suspensions containing (dry basis) 80wt% of active ingredient and 20% of emulsifier. After 24 hours, the plants were inoculated with a spore suspension of the fungus Pyrenophora teres and placed for 48 hours in a high-humidity climatic cabinet at 18~C. The plants were then cultivated in the greenhouse at from 20 to 22~C and a relative humidity of 709'o for a further 5 days. The extent of the spread of the symptoms was then assessed.
1340~4ti The results show that active ingredients 1 and 29, applied as 0.025% spray liquors, have a very good fungicidal action (100%).
Use Example 3 Action on Pyricularia oryzae (protective) Leaves of pot-grown rice seedlings of the "Bahia" variety were sprayed to runoff with aqueous emulsions containing (dry basis) 80% of active ingre-dient and 209'0 of emulsifier, and inoculated 24 hours later with an aqueous spore suspension of Pyricularia oryzae. The plants were subsequently placed in a climatic cabinet at 22 to 24~C and a relative humidity of 95 to 99%. The spread of the disease was assessed after 6 days.
The results show that active ingredient 1, applied as a 0.05% spray liquor, has an excellent fungicidal action (97%).
5 81 3-fluorophenyl 2,4-dichlorophenyl Z N
82 3-fluorophenyl 2,4-dichlorophenyl E N
83 3-fluorophenyl 2,4-dichlorophenyl Z CH
84 3-fluorophenyl 2,4-dichlorophenyl E CH
85 3-fluorophenyl 2-thienyl Z N
10 86 3-fluorophenyl 2-thienyl E N
87 3-fluorophenyl 2-thienyl Z CH
88 3-fluorophenyl 2-thienyl E N
89 3-fluorophenyl 3-thienyl Z N
90 3-fluorophenyl 3-thienyl E N
91 3-fluorophenyl 3-thienyl Z CH
92 3-fluorophenyl 3-thienyl E CH
93 3-fluorophenyl 2-furanyl Z N
94 3-fluorophenyl 2-furanyl E N
95 3-fluorophenyl 2-furanyl Z CH
96 3-fluorophenyl 2-furanyl E CH
97 3-fluorophenyl 3-furanyl Z N
98 3-fluorophenyl 3-furanyl E N
99 3-fluorophenyl 3-furanyl Z CH
1003-fluorophenyl 3-furanyl E CH
1013-fluorophenyl 4-cyclohexenyl Z N
1023-fluorophenyl 4-cyclohexenyl E N
1033-fluorophenyl 4-cyclohexenyl Z CH
1043-fluorophenyl 4-cyclohexenyl E CH
1053-fluorophenyl 5-(3-methylisoxazolyl)Z N
1063-fluorophenyl 5-(3-methylisoxazolyl)E N
1073-fluorophenyl 5-(3-methylisoxazolyl)Z CH
1083-fluorophenyl 5-(3-methylisoxazolyl)E CH
1092,4-difluorophenyl2-chlorophenyl Z N
1102,4-difluorophenyl2-chlorophenyl E N
1112,4-difluorophenyl2-chlorophenyl Z CH
l122,4-difluorophenyl2-chlorophenyl E CH
1132,4-difluorophenyl4-chlorophenyl Z N
1142,4-difluorophenyl4-chlorophenyl E N
1152,4-difluorophenyl4-chlorophenyl Z CH
1162,4-difluorophenyl4-chlorophenyl E CH
1172,4-difluorophenyl2,4-dichlorophenyl Z N
1182,4-difluorophenyl2,4-difluorophenyl E N
1192,4-difluorophenyl2,4-dichlorophenyl Z CH
1340 ~4b No. R1 R2 Isomer X m.p.
120 2,4-difluorophenyl2,4-dichlorophenyl E CH
121 2,4-difluorophenyl2-thienyl Z N
122 2,4-difluorophenyl2-thienyi E N
123 2,4-difluorophenyl2-thienyl Z CH
124 2,4-difluorophenyl2-thienyl E N
125 2,4-difluorophenyl3-thienyl Z N
126 2,4-difluorophenyl3-thienyl E N
127 2,4-difluorophenyi3-thienyl ~ Z CH
10128 2,4-difluorophenyl3-thienyl E CH
129 2,4-difluorophenyl2-furanyl Z N
130 2,4-difluorophenyl2-furanyl E N
131 2,4-difluorophenyl2-furanyl Z CH
132 2,4-difluorophenyl2-furanyl E CH
15133 2,4-difluorophenyl3-furanyl Z N
134 2,4-difluorophenyl3-furanyl E N
135 2,4-difluorophenyl3-furanyl Z CH
136 2,4-difluorophenyl3-furanyl E CH
137 2,4-difiuorophenyl4-cyclohexenyl Z N
20138 2,4-difluorophenyl4-cyclohexenyi E N
139 2,4-difluorophenyl4-cyclohexenyl Z CH
140 2,4-difluorophenyl4-cyclohexenyl E CH
141 2,4-difluorophenyl5-(3-methylisoxazolyl)Z N
142 2,4-difluorophenyi5-(3-methylisoxazolyi)E N
25143 2,4-difluorophenyl5-(3-methylisoxazolyi)Z CH
144 2,4-difluorophenyi5-(3-methylisoxazolyl)E CH
Compounds 5 to 8 and 113 to 1l6 are excluded from the scope of the claims.
A
In general terms, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large number of fungi in vary~us crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.
The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e. g., xylene), chlorinated aromatics (e. g., chloro-benzenes), paraffins (e. g., crude oil fractions), alcohols (e. g., methanol, butanol), ketones (e. g., cyclohexanone), amines (e. g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e. g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e. g., highly disperse silica and silicates);
emulsifiers such as nonionic and anionic emulsifiers (e. g., polyoxyethyl-ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicides generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt~ of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, e.g., on Paecilomyces variotii.
The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 29 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of compound no. 1 is dissolved in a mixture con-sisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso-butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
134~54~
IV. 20 parts by weight of compound no. 29 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280~C, and parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 5 of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel) and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
VI. 3 parts by weight of compound no. 29 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
vII. 30 parts by weight of compound no. 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of compound no. 29 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.
Ix. 20 parts by weight of compound no. 1 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fun-gicides frequently results in an increase in the fungicidal spectrum.
The following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions.
.. 13454d Examples of fungicides which may be combined with the novel compounds are:
sulfur, dithiocarbamates and their derivatives, such as 5 ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, 10 tetramethylthiuram disulfides, ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithiocarbamate and N,N'-polypropylenebis(thiocarbamyl) disulfide;
nitro derivatives, such as dinitro(1-methylheptyl)-phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonothioate, 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio[4,5-b]quinoxaline, methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(fur-2-yl)-benzimidazole, 2-(thiazol-4-yl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine 1-oxide, 8-hydroxyquinoline and its copper salt, 134~~j~~
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, 2,5-dimethyl-N-cyciohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethyifuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethylacetal, piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide), 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-[3-(p-tert.-butylphenyl)-2-methyipropylJ-cis-2,6-dimethylmorpholine, N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyi]-1H-1,2,4--triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyi]-1H-1,2,4--triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyi-urea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol, 1-(4-phenylphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazoi-1-yl)-2-butanol, a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-(2-dimethylamino-4-hydroxy-6-methytpyrimidine, bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene, 1,2-bis-(3-methoxycarbonyi-2-thioureido)-benzene, and various fungicides, such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyciohexyi)-2-hydroxyethyi]-giutaramide, hexachlorobenzene, DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate, methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyi)-alanate, N-(2,6-dimethylphenyl)-N-chloroacetyt-DL-2-aminobutyrolactone, methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyi)-alanate, 5-methyl-5-vinyl-3-(3,5-dichiorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichiorophenyl)-1-isopropylcarbamylhydantoin, N-(3,5-dichlorophenyi)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximinoJ-acetamide, 1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole, 2,4-difluoro-oc-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, and 1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.
Use examples For comparison purposes, 1-(1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-pentane (A) disclosed in C. A. No. 66246-88-6 was used.
Use Example 1 Action on wheat brown rust Leaves of pot-grown wheat seedlings of the "Friihgold" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20 to 22~C in a high-humidity (90 - 95%) chamber. ouring this period the spores germinated and the germ tubes penetrated the leaf tissue. The infected plants were then sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20 to 22~C and a relative humidity of 65 to 70%. The extent of rust fungus spread on the leaves was assessed after 8 days.
The results show that active ingredient 1, applied as a 0.006wt% spray liquor, has a better fungicidal action (100%) than prior art comparative agent A (60%).
Use Example 2 Action on Pyrenophora teres Barley seedlings of the "Igri" variety were sprayed to runoff at the two-leaf stage with aqueous suspensions containing (dry basis) 80wt% of active ingredient and 20% of emulsifier. After 24 hours, the plants were inoculated with a spore suspension of the fungus Pyrenophora teres and placed for 48 hours in a high-humidity climatic cabinet at 18~C. The plants were then cultivated in the greenhouse at from 20 to 22~C and a relative humidity of 709'o for a further 5 days. The extent of the spread of the symptoms was then assessed.
1340~4ti The results show that active ingredients 1 and 29, applied as 0.025% spray liquors, have a very good fungicidal action (100%).
Use Example 3 Action on Pyricularia oryzae (protective) Leaves of pot-grown rice seedlings of the "Bahia" variety were sprayed to runoff with aqueous emulsions containing (dry basis) 80% of active ingre-dient and 209'0 of emulsifier, and inoculated 24 hours later with an aqueous spore suspension of Pyricularia oryzae. The plants were subsequently placed in a climatic cabinet at 22 to 24~C and a relative humidity of 95 to 99%. The spread of the disease was assessed after 6 days.
The results show that active ingredient 1, applied as a 0.05% spray liquor, has an excellent fungicidal action (97%).
Claims (7)
1. An azolylalkene of the general formula I
where R1 is fluorophenyl, R2 is C1-C5-alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl, phenyl, biphenyl, naphthyl, a 5-membered or 6-membered heterocycle which contains one or two oxygen, nitrogen or sulfur atoms, these radicals being unsubstituted or substituted by halogen, nitro, amino or phenoxy or by alkyl , alkoxy or haloalkyl , each of 1 to 4 carbon atoms , and X is CH or N, and its plant-tolerated acid addition salts and metal complexes, excluding however the compounds of the general formula I
where:
R1 is 4-fluorophenyl or 2,4-difluorophenyl; and R2 simultaneously denotes 4-fluorophenyl, 4-chloro-phenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl or pyrid-4-yl.
where R1 is fluorophenyl, R2 is C1-C5-alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl, phenyl, biphenyl, naphthyl, a 5-membered or 6-membered heterocycle which contains one or two oxygen, nitrogen or sulfur atoms, these radicals being unsubstituted or substituted by halogen, nitro, amino or phenoxy or by alkyl , alkoxy or haloalkyl , each of 1 to 4 carbon atoms , and X is CH or N, and its plant-tolerated acid addition salts and metal complexes, excluding however the compounds of the general formula I
where:
R1 is 4-fluorophenyl or 2,4-difluorophenyl; and R2 simultaneously denotes 4-fluorophenyl, 4-chloro-phenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl or pyrid-4-yl.
2. A compound of the formula I as set forth in claim 1, where R1 is 4-fluorophenyl, X is N and R2 is 2-chlorophenyl.
3. A compound of the formula I as set forth in claim 1, where R1 is 4-fluorophenyl, X is N and R2 is 2-thienyl.
4. A compound of the formula I as set forth in claim 1, where R1 is 4-fluorophenyl, X is N and R2 is 2-furanyl.
5. A compound of the formula I as set forth in claim 1, where R1 is 4-fluorophenyl, X is N and R2 is 4-cyclohexenyl.
6. A fungicidal composition containing a fungicidally effective amount of an azolylalkene of the formula I as set forth in any one of claims 1 to 5, or a plant-tolerated acid addition salt or metal complex thereof, in admixture with at least one inert carrier.
7. A process for combating fungi, wherein a fungicidally effective amount of an azolylalkene of the formula I as set forth in any one of claims 1 to 5, or a plant-tolerated acid addition salt of metal complex thereof, is allowed to act on the fungi or materials, areas, plants or seed threatened by fungus attack.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3811916A DE3811916A1 (en) | 1988-04-09 | 1988-04-09 | AZOLYLALKENE AND FUNGICIDES CONTAINING THEM |
| DEP3811916.1 | 1988-04-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1340546C true CA1340546C (en) | 1999-05-18 |
Family
ID=6351686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000593771A Expired - Fee Related CA1340546C (en) | 1988-04-09 | 1989-03-15 | Azolylalkenes and fungicides containing these compounds |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0337199B1 (en) |
| JP (1) | JP2851300B2 (en) |
| KR (1) | KR970011280B1 (en) |
| AT (1) | ATE72240T1 (en) |
| CA (1) | CA1340546C (en) |
| DD (1) | DD280462A5 (en) |
| DE (2) | DE3811916A1 (en) |
| ES (1) | ES2029089T3 (en) |
| GR (1) | GR3004231T3 (en) |
| HU (1) | HU202725B (en) |
| NZ (1) | NZ228671A (en) |
| ZA (1) | ZA892544B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2652313A1 (en) * | 1976-11-17 | 1978-05-18 | Basf Ag | TRIAZOLE DERIVATIVES |
| DE2833194A1 (en) * | 1978-07-28 | 1980-02-14 | Basf Ag | TRIAZOLE DERIVATIVES |
| EP0094167A3 (en) * | 1982-05-12 | 1984-07-04 | Fbc Limited | Azolyl fungicide and plant growth regulators and compositions containing them |
| DE3327036A1 (en) * | 1983-07-27 | 1985-02-07 | Bayer Ag, 5090 Leverkusen | 3- (1,2,4-TRIAZOL-1-YL) -L-PROPENE |
| GB8716650D0 (en) * | 1987-07-15 | 1987-08-19 | Ici Plc | Use of olefinic compounds |
-
1988
- 1988-04-09 DE DE3811916A patent/DE3811916A1/en not_active Withdrawn
-
1989
- 1989-03-15 CA CA000593771A patent/CA1340546C/en not_active Expired - Fee Related
- 1989-03-30 AT AT89105586T patent/ATE72240T1/en not_active IP Right Cessation
- 1989-03-30 ES ES198989105586T patent/ES2029089T3/en not_active Expired - Lifetime
- 1989-03-30 DE DE8989105586T patent/DE58900781D1/en not_active Expired - Lifetime
- 1989-03-30 EP EP89105586A patent/EP0337199B1/en not_active Expired - Lifetime
- 1989-04-07 DD DD89327389A patent/DD280462A5/en not_active IP Right Cessation
- 1989-04-07 JP JP1087166A patent/JP2851300B2/en not_active Expired - Fee Related
- 1989-04-07 ZA ZA892544A patent/ZA892544B/en unknown
- 1989-04-07 HU HU891695A patent/HU202725B/en not_active IP Right Cessation
- 1989-04-08 KR KR1019890004676A patent/KR970011280B1/en not_active IP Right Cessation
- 1989-04-10 NZ NZ228671A patent/NZ228671A/en unknown
-
1992
- 1992-04-01 GR GR920400603T patent/GR3004231T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUT50138A (en) | 1989-12-28 |
| DE3811916A1 (en) | 1989-10-19 |
| NZ228671A (en) | 1990-09-26 |
| JP2851300B2 (en) | 1999-01-27 |
| JPH01305066A (en) | 1989-12-08 |
| EP0337199A1 (en) | 1989-10-18 |
| KR890016021A (en) | 1989-11-28 |
| HU202725B (en) | 1991-04-29 |
| ATE72240T1 (en) | 1992-02-15 |
| ZA892544B (en) | 1990-12-28 |
| GR3004231T3 (en) | 1993-03-31 |
| DE58900781D1 (en) | 1992-03-12 |
| EP0337199B1 (en) | 1992-01-29 |
| ES2029089T3 (en) | 1992-07-16 |
| DD280462A5 (en) | 1990-07-11 |
| KR970011280B1 (en) | 1997-07-09 |
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