CA1097354A - 2,4-dichlorophenyl-triazolyl-ethan-ones and -ols, and their use as fungicides - Google Patents
2,4-dichlorophenyl-triazolyl-ethan-ones and -ols, and their use as fungicidesInfo
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- CA1097354A CA1097354A CA296,582A CA296582A CA1097354A CA 1097354 A CA1097354 A CA 1097354A CA 296582 A CA296582 A CA 296582A CA 1097354 A CA1097354 A CA 1097354A
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- dichlorophenyl
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- 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
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- 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
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- 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
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
?96582 Abstract of the Disclosure 1-Phenoxy-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-ones and -ols of the formula
Description
~L~9735~
The present invention relates to certain new 2,4-dichloro-phenyl-triazolyl-ethan-ones and -ols, to a process for their pre-paration and to their use as fungicides.
It has already been disclosed that certain 3,3-dimethyl-1-phenoxy-l-triazolyl-butan-2-ones and -ols possess a good fungicidal activity (see German Offenlegungsschriften ~German Published Speci-fications~ 2,201,063 and 2,324,010. ~lowever, their action is not always completely satisfactory, in particular when low application amounts and concentrations are used.
The present Invention provides, as new compounds, the 2,4-dichlorophenyl-triazolyl-ethan-ones and -ols of the general formula Cl ~ - O - CH-A-~- Cl ~I) n N
in which A represents a keto group or a CH(OH) grouping, X represents halogen, alkyl or phenyl optionally substituted by halogen, and _ represents 0, 1, 2 or 3, the X substituents being selected independently of one another when n is 2 or 3, and their salts.
The compounds of this invention have powerful fungicidal properties.
Preferably~ X represents fluorine, chlorine, bromine, iodine, straight-chain or branched alkyl with 1 to 4 carbon atoms ~, ~ - 2 _ ~973~
or phenyl which is optionally substituted by halogen (especially chlorine) and n represents 0, 1 or 2.
Those compounds of the formula (I) in which A represents the CH~OH) group possess two asymmetric carbon atoms; they can therefore be present in the form of both geometric isomers (erythro form and threo form), which can be obtained in different proportions. In both cases, they are present as optical isomers.
The formula (I) is intended to include all the isomers.
The invention also provides a process for the prepara-10tion of a 3,4-dichlorophenyl-triazolyl-ethan-one or -ol of the formula (I), in which a l-bromo-2-(2,4-dichlorophenyl)-l-phenoxy-ethan-2-one of the formula Cl ~ o fH - co - ~` - Cl (II), n Br in which X and _ have the meanings stated above, is reacted with 1,2,4-triazole in the presence of a diluent and of an acid binding agent, and, if required, the 1,2,4-triazolyl-ethanone thereby obtained is Teduced with a complex borohydride in a manner which is in itself known, optionally in the presence 20of a diluent.
Furthermore, the 2,4-dichlorophenyl-triazolyl-ethanones-and -ols obtainable accord1ng to the invention can be converted into salts thereof (preferably the non-phytotoxic salts) by re-action with acids.
Surprisingly, the active compounds according to the _.,.
3S~
invention exhibit a considerably higher ~ungicidal a~tivit~, in particular against cereal diseases, than the 3,3-dimethyl-l-phenoxy-l-triazolyl-butan-2-ones and -ols which are known from the state of the art and which are related compounds chemically and from the point of view of their activity. ~he active compounds according to the invention are thus an enrichment of the art.
I~ l-bromo-1-(4-chlorophenoxy)-2-(2,4-dichloro-phenyl)-ethan-2-one and 1~2,4-triazole are u3ed as starting materials, the course of the reaction can be represented by the following equation:
Cl- ~ -O-~H~CO- ~ -Cl ~ ~ NH b~se Br N -HBr Cl- ~ -O-CH-CO- ~ -Cl N
I~ l-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-l~
(1,2,4-triazol-l-yl)-ekhan-2-one is reduced with sodium borohydride, the course of the reaction can be represented by the following equation:
Cl Cl- ~ -O-CH-CO ~ -Cl ~ NaBH~
N _ ~ H~
Le A 17 831 - 4 -~7~5~
Examples ~hich may be mentioned of starting materia~s of the formula (Il) are: l-bromo-l-phenoxy-2-t2,4-dichloro-phenyl)-ethan-2-one, 1-bromo-1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(4-fluorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(4-bromophenoxy)-
The present invention relates to certain new 2,4-dichloro-phenyl-triazolyl-ethan-ones and -ols, to a process for their pre-paration and to their use as fungicides.
It has already been disclosed that certain 3,3-dimethyl-1-phenoxy-l-triazolyl-butan-2-ones and -ols possess a good fungicidal activity (see German Offenlegungsschriften ~German Published Speci-fications~ 2,201,063 and 2,324,010. ~lowever, their action is not always completely satisfactory, in particular when low application amounts and concentrations are used.
The present Invention provides, as new compounds, the 2,4-dichlorophenyl-triazolyl-ethan-ones and -ols of the general formula Cl ~ - O - CH-A-~- Cl ~I) n N
in which A represents a keto group or a CH(OH) grouping, X represents halogen, alkyl or phenyl optionally substituted by halogen, and _ represents 0, 1, 2 or 3, the X substituents being selected independently of one another when n is 2 or 3, and their salts.
The compounds of this invention have powerful fungicidal properties.
Preferably~ X represents fluorine, chlorine, bromine, iodine, straight-chain or branched alkyl with 1 to 4 carbon atoms ~, ~ - 2 _ ~973~
or phenyl which is optionally substituted by halogen (especially chlorine) and n represents 0, 1 or 2.
Those compounds of the formula (I) in which A represents the CH~OH) group possess two asymmetric carbon atoms; they can therefore be present in the form of both geometric isomers (erythro form and threo form), which can be obtained in different proportions. In both cases, they are present as optical isomers.
The formula (I) is intended to include all the isomers.
The invention also provides a process for the prepara-10tion of a 3,4-dichlorophenyl-triazolyl-ethan-one or -ol of the formula (I), in which a l-bromo-2-(2,4-dichlorophenyl)-l-phenoxy-ethan-2-one of the formula Cl ~ o fH - co - ~` - Cl (II), n Br in which X and _ have the meanings stated above, is reacted with 1,2,4-triazole in the presence of a diluent and of an acid binding agent, and, if required, the 1,2,4-triazolyl-ethanone thereby obtained is Teduced with a complex borohydride in a manner which is in itself known, optionally in the presence 20of a diluent.
Furthermore, the 2,4-dichlorophenyl-triazolyl-ethanones-and -ols obtainable accord1ng to the invention can be converted into salts thereof (preferably the non-phytotoxic salts) by re-action with acids.
Surprisingly, the active compounds according to the _.,.
3S~
invention exhibit a considerably higher ~ungicidal a~tivit~, in particular against cereal diseases, than the 3,3-dimethyl-l-phenoxy-l-triazolyl-butan-2-ones and -ols which are known from the state of the art and which are related compounds chemically and from the point of view of their activity. ~he active compounds according to the invention are thus an enrichment of the art.
I~ l-bromo-1-(4-chlorophenoxy)-2-(2,4-dichloro-phenyl)-ethan-2-one and 1~2,4-triazole are u3ed as starting materials, the course of the reaction can be represented by the following equation:
Cl- ~ -O-~H~CO- ~ -Cl ~ ~ NH b~se Br N -HBr Cl- ~ -O-CH-CO- ~ -Cl N
I~ l-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-l~
(1,2,4-triazol-l-yl)-ekhan-2-one is reduced with sodium borohydride, the course of the reaction can be represented by the following equation:
Cl Cl- ~ -O-CH-CO ~ -Cl ~ NaBH~
N _ ~ H~
Le A 17 831 - 4 -~7~5~
Examples ~hich may be mentioned of starting materia~s of the formula (Il) are: l-bromo-l-phenoxy-2-t2,4-dichloro-phenyl)-ethan-2-one, 1-bromo-1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(4-fluorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(4-bromophenoxy)-
2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(4-iodo-phenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(2,4-dichlorophenoxy)-2-(2,4-dichlorophenyl~-ethan-2-one, 1-bromo-1-(2,6-dichlorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(2,5-dichlorophenoxy)-2-(2,4-dichloro-phenyl)-ethan-2-one, 1-bromo-1-(3-rluorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(3-chlorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(3-bromo-phenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, l-bromo-l-(2-chlorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-l-~4-methylphenoxy)-2-(2j4-dichlorophenyl)-ethan-2-one3 1-bromo-1-(4-ethylphenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(3-methylphenoxy)-2-(2,4-dichloro-phenyl)-ethan-2~one, 1-bromo-1-(2-methylphenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(2-isopropylphenoxy)-2-(2,4-dichlorophenyl)-eth~n-2-one3 1-bromo-1-(4-chloro-2-methylphenoxy)-2-(2,4~dichlorophenyl)-ethan-2-one, l-bromo-1-(4-bromo-2-mekhylphenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, l-bromo-1-(4-~luoro-2-methylphenoxy)-2-(2,4-dichloro-phenyl)-ethan-2-one, 1-bromo-1-(4-iodo-2-methylphenoxy)-2-(2,4-dich~orophenyl)-ethan-2-one, 1-bromo-1-(2)3-dimethylphenoxy)-2-(2,4-dichlorophenyl)-ethan-2 one, 1-bromo-1-(4-biphenylyloxy)-2-(2,LI-dichlorophenyl)-ethan-2-one, l-bromo-1-(4~4'-chlorobiphenylyloxy)-2-(2,LI-dichloro-3o phenyl)-ethan-2~one, 1-bromo-1-(4-2',4~-dichlorobiphenylyl-Le A 17 831 - 5 ~
oxy)-2-(2,4-dichlorophenyl)~ethan-2-one, l-bromo-1-(4-~,4'-dichlorophenylyloxy)-2-(2,4-dichlorophenyl)-ethan-2-one, l-bromo-1-(4-4'-bromobiphenylyloxy)-2-(2,4-dichlorophenyl)-ethan-2-one and 1-bromo-1-(4-2-chlorobiphenylyloxy)-2-(2,4-dichlorophenyl)-eth~n-2-one.
The l-bromo-2-(2,4-dichlorophenyl)-l-phenoxy-ethan-2-ones of the formula (II) to be used as starting materials have not yet been described in the l;terature, but can be prepared by known processes, by reacting known phenols of the general ~ormula ~ - OH
Xn (III), in which X and n have the meanings stated above 3 with the bromoacetophenone o~ the formula Cl Br - CH2 ~ CO - ~ -Cl (IV).
The active hydrogen atom which still remains is then replaced by bromine in the customary manner.
Preferred 8alt8 of the compounds of the formula (I) are - for reasons of phytotoxicity - salts with physio-logically acceptable acids. The preferred acids include thehydrogen halide æidæ (for example hydrobromic acid and, in particular, hydrochloric acid), phosphoric acid, nitric acid, mono~unctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetic acid, citric Le A 17 831 - 6 -~73~i4 acid, sorbic acid and lactic acid), and 1,5-naphthalene-disulphonic acid.
Preferred diluents for the reaction accordin~ tc the invention are inert organic solvents, especially ketones, such as diethyl ketone and, in particular, acetone and methyl ethyl ketone; nitriles, such as propionitrile and, in particular, acetonitrile; aaeohols, such as ethanol or iso-propanol; ethers, such as tetrahydrofuran or dioxan;
aromatic hydrocarbons, such as toluene, 1,3-dichloro-benæene and benzene; formamides, such as, in particular, dimethylformamide; and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.
The reaction is carried out in the presence of an acid-binding agent. It is possible to add any of the inorganic or organic acid-binding agents which can be customarily used, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cyclo-alkylamines or ara~kylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylmethylamine and N,N-dimethylbenzylamine, and furthermore pyridine and diazabicyclooctane. Preferably, an appropriate excess of the 1,2,4-triazole is used.
The reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at from 0 to 150C, preferably at from 60 to 120C, in the presence of a solvent, such as acetone or methyl ethyl ketone.
In carrying out the process according to the in-3o vention, 1 to 2 moles of 1,2,4-triazole and 1 to 2 moles Le A 17 B~l - 7 -.
73~
of acid-binding agent are preferably employed per mol~ of the compound of the formula (II). In order to isolate the compound of the ~ormula (I), the solvent is distilled of~, the residue is taken up in an organic solvent and the organic solution is washed with water. ~he organic phase is dried over sodium sulnhate and freed from solvent in vacuo. The residue is purified by dist;llation or recrystallisation.
For the reduction according to the invention, suitable diluents are polar organic solvents, especially alcohols, such as methanol, ethanol, butanol and isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. In general, the reduction reaction is carried out at from 0 to 30C, preferably at from 0 to 20C. For this reaction, about 1 mole of a borohydride, such as sodium borohydride or lithium borohydrîdeS is prererably employed per mole o~
the compound of the ~ormula (II). In order to isolate the compound of the formula (I)~ the residue is taken up, for example, in dilu~e hydrochloric acid and the acid solution is then rendered alkaline and extracted with an organic solvent, or only water is added and the product is ex-tracted by shaking with an organic solvent. Further working up is carried out in the customary manner.
Examples which may be mentioned of particularly active representative~ o~ the active compounds according to the invention are the following: 1-(2-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4 triazol-1-yl)-ethan-2-one or -ol, 1-(2-isopropylphenoxy)-2-(2,4-dichlorophenyl)-1-( 1 9 2,4-triazol-1-yl)-ethan-2-one or -ol~ 1-(2-methyl-phenoxy)~2-(2,4-dichlorophenyl)-1-(1,2,4-triazol~l-yl)-- Le A 17 831 - 8 -
oxy)-2-(2,4-dichlorophenyl)~ethan-2-one, l-bromo-1-(4-~,4'-dichlorophenylyloxy)-2-(2,4-dichlorophenyl)-ethan-2-one, l-bromo-1-(4-4'-bromobiphenylyloxy)-2-(2,4-dichlorophenyl)-ethan-2-one and 1-bromo-1-(4-2-chlorobiphenylyloxy)-2-(2,4-dichlorophenyl)-eth~n-2-one.
The l-bromo-2-(2,4-dichlorophenyl)-l-phenoxy-ethan-2-ones of the formula (II) to be used as starting materials have not yet been described in the l;terature, but can be prepared by known processes, by reacting known phenols of the general ~ormula ~ - OH
Xn (III), in which X and n have the meanings stated above 3 with the bromoacetophenone o~ the formula Cl Br - CH2 ~ CO - ~ -Cl (IV).
The active hydrogen atom which still remains is then replaced by bromine in the customary manner.
Preferred 8alt8 of the compounds of the formula (I) are - for reasons of phytotoxicity - salts with physio-logically acceptable acids. The preferred acids include thehydrogen halide æidæ (for example hydrobromic acid and, in particular, hydrochloric acid), phosphoric acid, nitric acid, mono~unctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetic acid, citric Le A 17 831 - 6 -~73~i4 acid, sorbic acid and lactic acid), and 1,5-naphthalene-disulphonic acid.
Preferred diluents for the reaction accordin~ tc the invention are inert organic solvents, especially ketones, such as diethyl ketone and, in particular, acetone and methyl ethyl ketone; nitriles, such as propionitrile and, in particular, acetonitrile; aaeohols, such as ethanol or iso-propanol; ethers, such as tetrahydrofuran or dioxan;
aromatic hydrocarbons, such as toluene, 1,3-dichloro-benæene and benzene; formamides, such as, in particular, dimethylformamide; and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.
The reaction is carried out in the presence of an acid-binding agent. It is possible to add any of the inorganic or organic acid-binding agents which can be customarily used, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cyclo-alkylamines or ara~kylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylmethylamine and N,N-dimethylbenzylamine, and furthermore pyridine and diazabicyclooctane. Preferably, an appropriate excess of the 1,2,4-triazole is used.
The reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at from 0 to 150C, preferably at from 60 to 120C, in the presence of a solvent, such as acetone or methyl ethyl ketone.
In carrying out the process according to the in-3o vention, 1 to 2 moles of 1,2,4-triazole and 1 to 2 moles Le A 17 B~l - 7 -.
73~
of acid-binding agent are preferably employed per mol~ of the compound of the formula (II). In order to isolate the compound of the ~ormula (I), the solvent is distilled of~, the residue is taken up in an organic solvent and the organic solution is washed with water. ~he organic phase is dried over sodium sulnhate and freed from solvent in vacuo. The residue is purified by dist;llation or recrystallisation.
For the reduction according to the invention, suitable diluents are polar organic solvents, especially alcohols, such as methanol, ethanol, butanol and isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. In general, the reduction reaction is carried out at from 0 to 30C, preferably at from 0 to 20C. For this reaction, about 1 mole of a borohydride, such as sodium borohydride or lithium borohydrîdeS is prererably employed per mole o~
the compound of the ~ormula (II). In order to isolate the compound of the formula (I)~ the residue is taken up, for example, in dilu~e hydrochloric acid and the acid solution is then rendered alkaline and extracted with an organic solvent, or only water is added and the product is ex-tracted by shaking with an organic solvent. Further working up is carried out in the customary manner.
Examples which may be mentioned of particularly active representative~ o~ the active compounds according to the invention are the following: 1-(2-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4 triazol-1-yl)-ethan-2-one or -ol, 1-(2-isopropylphenoxy)-2-(2,4-dichlorophenyl)-1-( 1 9 2,4-triazol-1-yl)-ethan-2-one or -ol~ 1-(2-methyl-phenoxy)~2-(2,4-dichlorophenyl)-1-(1,2,4-triazol~l-yl)-- Le A 17 831 - 8 -
3~i~
ethan-2-one or -ol and 1-(2-chloro-4-methylphenoxy)-2-(2,4-dichlorophenyl)-1-(1,2~4-triazol-1-yl)-ethan-2-one or -ol. Other examples are menticned in the preparative Examples given later in this specification.
The active compounds according to the invention exhibit a powerful fungitoxic action. They do not damage crop plants in the concentrations required for combating fungi. For these reasons~ they are suitable for use as plant protection agents for combating fungi. Fungitoxis agents are employed in plant protection for combating Plasmodiophoromycetes 3 Oomycetes 3 Chytridiomycetes, , ~ , Basidiomycetes and Deuteromycetes.
The active compounds according to the invention have a broad spectrum of action and can be used against parasitic fungi which attack above ground parts of plants or which attack the plants through the soil, as well as against seed-borne pathogens.
They display a particularly good activity against parasitic fungi on above-ground parts of plants.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating powdery mildew fungi, for example for combating powdery mildew of cucumber ( ciohoriaoearum)~ powdery mildew of apples ( leucotricha) and powdery mildew of cereals, as well as other cereal diseases, for example cereal rust.
As plant protection agents, the active compounds according to the invention can be used for the treatment of seed or soil and for the treatment of above-ground parts of plants.
Le A 17 831 - 9 -~7354 The active compounds can be converted into the customary formulationsg such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams~ pastes, soluble powders, ~ranules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very rine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils~ as well as ULV
cold mist and warm mist ~ormulations.
These ~ormulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say li~uid or liquefied gaseous or solid diluents or carriers 9 optionally with the use of surface-active agents, that is to say emulsi~ying agents and/or dispersing agents andtor ~oam-forming agents. In the case of the use of water as a~ extender, organic solvents can, ~or example, also be used as auxiliary solvents.
As liquid solvents diluents or carriers, especially solvents, there are suitable in the main, aromatic hydro-carbons, such as xylene, toluene or alkyl naphthalenes~
chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes~ chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or parafrins; for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and este~s, ketones~ such as acetone~
methyl ethyl ketone, methyl isobutyl ketone or cyclo-hexanone, or strongly polar solvents, such as dimethyl-formamide and dimethylsulphoxide, as well as water.
Le A 17 831 ~ 10 -By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenate~ hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins3 clays, talc, chalk, quartz, attapulgite3 montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers ror granules there may be used crushed and fractionated natural rocks such as calcite, marble 9 pumice, sepiolite and dolomite~ as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust9 coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-rorming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers~ for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphatesj aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, ~or ex~mple, lignin sulphite waste liquors and methylcellulose.
Z5 The active compounds according to the invention can be present in the formulatiorls as a mixture with other acti~e compounds, such as fungicides~ insecticides, acaricides, nematicides, herbicides, bird repellants, growth ~actors, plant nutrients and agent~ ~or improvin~
soil structure.
The ~ormulations in ~eneral contain ~rom 0.1 to Le A 17 831 - 11 -7J3~j4 95 per cent by ~Jeight of active compound, preferably from 0.5 to 90 per cent.
mhe active compounds can be used as such, as their formulations or as the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules.
They may be used in the customary manner, for example by waterin~, spraying~ atomising, dusting, scattering, dry dressing~ moist dressing, wet dressing, slurry dressing or encrusting.
Especially when used as leaf fungicides, the active compound concentrations in the use forms can be varied within a fairly wide range. They are, in general, from 0.1 to 0.00001 per cent by weight, preferably from 0.05 to 0.0001 per cent.
For treatment of seed, amounts Or active compound of from 0.001 to 50 g per kilogram o~ seed, preferably from 0.01 to 10 g, are generally employed.
For the treatment of soil, amounts of from 1 g to 1000 g per cubic metre of soil, preferably of from 10 to 200 g, are generally employed.
The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or lique~ied ga~eous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface--active agent.
The present invention also provides a method o~
combating ~ungi which comprises applying to the fungi~
or to a habitat thereo~, a compound of the present invention alone or in the ~orm o~ a composition containing Le A 17 831 - 12 -~09~3S~
as active ingredlent a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of' providing a harvested crop may be improved by the present invention.
The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.
In these Examples~ the comPounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example~ which will be found later in this specification.
The known comparison compounds are identified as follows:
Cl~ O-CH-CO-C(CH3 )3 (A) =~N N
(B) = ~ - ~ -O-ICH-CO-C(CH3)3 ~ . HCl Cl OH
(C~ =Cl ~ -O-ClH-CH-C(CH3)3 ~N~
Le A 1~ ~31 - 13 -~973~
(D) - Cl- ~ O-CH-CO-C(CH3 )3 N
OH
(E) = ~ O-CH-CH-C(CH3)3 ~`N
N
Example A:
Shoot treatment test/powdery mildew of cereal/protective (leaP destructive mycosis) To produce a suitable preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight o~ dimethylformamide and o.o6 part by weight of alkylaryl polyglycol ether, 975 parts by weight of water were then added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
To test for protective activity, single-leaved young barley plants o~ the Amsel variety were sprayed with the preparation o~ active oompound until dew-moist.
A~ter drying, the barley plants were dusted with spores o~ ~ ~raminis var. hordei.
_ __ A~ter 6 days' dwell time of the plants at a tempera-ture of 21-22 deg.C and 80-90~ atmospheric humidity the ~O occurrence o~ mildew pustule~ on the plants was evaluated.
The degree of in~ection was expressed as a percentage of the inPection of the untreated control plants. 0%
denoted no in~ection and loOZ denoted the same degree Le A 17 831 - 14 -~L~39735~
of infection as in the case of the untreated control.
The active compound was the more active, the lower wa~ the degree of mildew infection.
The active compounds, active compound concentrations in the spray llquor and degrees of infection can be seen from the table which follows:
T a b 1 e A
Shoot treatment te3t~powdery mildew of cereal~protective Active Active compound con- Infection in %
compounds centration in the of the untreated spray liquor in %control by wei~ht _ _ untreated - 100 (A) 0.025 55.0 (2) 0.025 0.~
ethan-2-one or -ol and 1-(2-chloro-4-methylphenoxy)-2-(2,4-dichlorophenyl)-1-(1,2~4-triazol-1-yl)-ethan-2-one or -ol. Other examples are menticned in the preparative Examples given later in this specification.
The active compounds according to the invention exhibit a powerful fungitoxic action. They do not damage crop plants in the concentrations required for combating fungi. For these reasons~ they are suitable for use as plant protection agents for combating fungi. Fungitoxis agents are employed in plant protection for combating Plasmodiophoromycetes 3 Oomycetes 3 Chytridiomycetes, , ~ , Basidiomycetes and Deuteromycetes.
The active compounds according to the invention have a broad spectrum of action and can be used against parasitic fungi which attack above ground parts of plants or which attack the plants through the soil, as well as against seed-borne pathogens.
They display a particularly good activity against parasitic fungi on above-ground parts of plants.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating powdery mildew fungi, for example for combating powdery mildew of cucumber ( ciohoriaoearum)~ powdery mildew of apples ( leucotricha) and powdery mildew of cereals, as well as other cereal diseases, for example cereal rust.
As plant protection agents, the active compounds according to the invention can be used for the treatment of seed or soil and for the treatment of above-ground parts of plants.
Le A 17 831 - 9 -~7354 The active compounds can be converted into the customary formulationsg such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams~ pastes, soluble powders, ~ranules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very rine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils~ as well as ULV
cold mist and warm mist ~ormulations.
These ~ormulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say li~uid or liquefied gaseous or solid diluents or carriers 9 optionally with the use of surface-active agents, that is to say emulsi~ying agents and/or dispersing agents andtor ~oam-forming agents. In the case of the use of water as a~ extender, organic solvents can, ~or example, also be used as auxiliary solvents.
As liquid solvents diluents or carriers, especially solvents, there are suitable in the main, aromatic hydro-carbons, such as xylene, toluene or alkyl naphthalenes~
chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes~ chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or parafrins; for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and este~s, ketones~ such as acetone~
methyl ethyl ketone, methyl isobutyl ketone or cyclo-hexanone, or strongly polar solvents, such as dimethyl-formamide and dimethylsulphoxide, as well as water.
Le A 17 831 ~ 10 -By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenate~ hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins3 clays, talc, chalk, quartz, attapulgite3 montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers ror granules there may be used crushed and fractionated natural rocks such as calcite, marble 9 pumice, sepiolite and dolomite~ as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust9 coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-rorming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers~ for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphatesj aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, ~or ex~mple, lignin sulphite waste liquors and methylcellulose.
Z5 The active compounds according to the invention can be present in the formulatiorls as a mixture with other acti~e compounds, such as fungicides~ insecticides, acaricides, nematicides, herbicides, bird repellants, growth ~actors, plant nutrients and agent~ ~or improvin~
soil structure.
The ~ormulations in ~eneral contain ~rom 0.1 to Le A 17 831 - 11 -7J3~j4 95 per cent by ~Jeight of active compound, preferably from 0.5 to 90 per cent.
mhe active compounds can be used as such, as their formulations or as the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules.
They may be used in the customary manner, for example by waterin~, spraying~ atomising, dusting, scattering, dry dressing~ moist dressing, wet dressing, slurry dressing or encrusting.
Especially when used as leaf fungicides, the active compound concentrations in the use forms can be varied within a fairly wide range. They are, in general, from 0.1 to 0.00001 per cent by weight, preferably from 0.05 to 0.0001 per cent.
For treatment of seed, amounts Or active compound of from 0.001 to 50 g per kilogram o~ seed, preferably from 0.01 to 10 g, are generally employed.
For the treatment of soil, amounts of from 1 g to 1000 g per cubic metre of soil, preferably of from 10 to 200 g, are generally employed.
The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or lique~ied ga~eous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface--active agent.
The present invention also provides a method o~
combating ~ungi which comprises applying to the fungi~
or to a habitat thereo~, a compound of the present invention alone or in the ~orm o~ a composition containing Le A 17 831 - 12 -~09~3S~
as active ingredlent a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of' providing a harvested crop may be improved by the present invention.
The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.
In these Examples~ the comPounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example~ which will be found later in this specification.
The known comparison compounds are identified as follows:
Cl~ O-CH-CO-C(CH3 )3 (A) =~N N
(B) = ~ - ~ -O-ICH-CO-C(CH3)3 ~ . HCl Cl OH
(C~ =Cl ~ -O-ClH-CH-C(CH3)3 ~N~
Le A 1~ ~31 - 13 -~973~
(D) - Cl- ~ O-CH-CO-C(CH3 )3 N
OH
(E) = ~ O-CH-CH-C(CH3)3 ~`N
N
Example A:
Shoot treatment test/powdery mildew of cereal/protective (leaP destructive mycosis) To produce a suitable preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight o~ dimethylformamide and o.o6 part by weight of alkylaryl polyglycol ether, 975 parts by weight of water were then added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
To test for protective activity, single-leaved young barley plants o~ the Amsel variety were sprayed with the preparation o~ active oompound until dew-moist.
A~ter drying, the barley plants were dusted with spores o~ ~ ~raminis var. hordei.
_ __ A~ter 6 days' dwell time of the plants at a tempera-ture of 21-22 deg.C and 80-90~ atmospheric humidity the ~O occurrence o~ mildew pustule~ on the plants was evaluated.
The degree of in~ection was expressed as a percentage of the inPection of the untreated control plants. 0%
denoted no in~ection and loOZ denoted the same degree Le A 17 831 - 14 -~L~39735~
of infection as in the case of the untreated control.
The active compound was the more active, the lower wa~ the degree of mildew infection.
The active compounds, active compound concentrations in the spray llquor and degrees of infection can be seen from the table which follows:
T a b 1 e A
Shoot treatment te3t~powdery mildew of cereal~protective Active Active compound con- Infection in %
compounds centration in the of the untreated spray liquor in %control by wei~ht _ _ untreated - 100 (A) 0.025 55.0 (2) 0.025 0.~
(4) 0.025 0.0 (6) 0,025 16.3 (3) 0.025 7.5 (14) 0.025 Q.0 (15) 0.025 37.5 (16) 0.025 37.5 Example B
Shoot treatment test/cereal rust (leaf-destructive mycosis)/protective To produce a suitable preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight o~ dimethylformamide and 0. o6 part by weight o~ alkylaryl polyglycol ether and then 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
Le A 17 831 - 15 -~7354 To test the protective activity, one-leaved young wheat plants o~ the Michigan Amber variety ~lere inoculated with a uredospore suspenslon of Puccinia recondita in 0.1% strength aqueous agar. After the spore suspension had dried on, the wheat plants were sprayed with the ~reparation of active compound until dew-moist and were placed, for incubation, ill a greenhouse for 24 hours at about 20 deg.C and 100~ relative atmospheric humidity.
After 10 days' dwell time of the plants at a tempera-ture of 20 deg.C and 80-90~ atmospheric humidity, the occurrence of rust pustules on the plant was evaluated.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. 0%
denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control.
The active compound was the more active, the lower was the degree of rust infection.
The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows:
T a b 1 e B
Shoot treatment test/cereal rust/protective Active Active compound con- Infection in compounds centration in the spray % of the un-liquor in % by we;ght treated con-trol untreated ~ 100 (B) 0.025 33.8 (C) 0.025 33 8 (2) 0.02~ 12.5
Shoot treatment test/cereal rust (leaf-destructive mycosis)/protective To produce a suitable preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight o~ dimethylformamide and 0. o6 part by weight o~ alkylaryl polyglycol ether and then 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
Le A 17 831 - 15 -~7354 To test the protective activity, one-leaved young wheat plants o~ the Michigan Amber variety ~lere inoculated with a uredospore suspenslon of Puccinia recondita in 0.1% strength aqueous agar. After the spore suspension had dried on, the wheat plants were sprayed with the ~reparation of active compound until dew-moist and were placed, for incubation, ill a greenhouse for 24 hours at about 20 deg.C and 100~ relative atmospheric humidity.
After 10 days' dwell time of the plants at a tempera-ture of 20 deg.C and 80-90~ atmospheric humidity, the occurrence of rust pustules on the plant was evaluated.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. 0%
denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control.
The active compound was the more active, the lower was the degree of rust infection.
The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows:
T a b 1 e B
Shoot treatment test/cereal rust/protective Active Active compound con- Infection in compounds centration in the spray % of the un-liquor in % by we;ght treated con-trol untreated ~ 100 (B) 0.025 33.8 (C) 0.025 33 8 (2) 0.02~ 12.5
(5) 0~025 10.0 Le A 17 831 - 16 -9~3~4 Example C
Podosphaera test (apple)/protective Solvent: 4.7 parts by weight of acetone Emul~ifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated amount of emulsifier.
Young apple seedlings in the 4 - 6 leaf stage were sprayed with the spray liquid ur.til dripping wet.
The plants remained in a greenhouse for 24 hours at 20 deg.C and at a relative atmospheric humidity of 70%. They were then inoculated by dusting the conidia of the apple powdery mildew causative organism (Podosphaera leucotricha) and placed in a greenhouse at a temperature of 21 - 23 deg. C and at a relative atmospheric humidity of about 70%.
10 days after the inoculation, the infection of the seedlings was determined~ The assessment data were converted to % infection. 0% meant no infection;
100% meant that the plants were completely in~ected.
The active compounds, the concentrations of the active compounds and the results can be seen from the ~ollowing table:
Le A 17 831 - 17 -~3~735~
T a b 1 e C
Podosphaera test (apple)/protective Active Infection in % at an compound active compound con-centration of 0.001%
(D) 42 (2) 25 (3) 0 (14) 0 Example D
Erysi~he test Icucumber)/protective Solvent: 4.7 parts by weight of acetone ~mulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of the active compound required for the desired concentration o~ active compound in the spray liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water containing the stated amount of emulsifier.
Young cucumber plants with about three foliage leaves were sprayed with the spray liquid until dripping wet The cucumber plants remained in a greenhouse for 24 hours to dry. They were then, for the purpose of inoculation, dusted with conidia of the fungus oiohoriacearum. The plants were subsequently placed in a greenhouse at 23-24 degrees C and at a relative atmospheric humidity of about 75%.
After 12 days, the infection of the cucumber plants was determined. The assessment data were con~erted to percent infection 0% meant no infection; 100% meant that the plants were totally infected.
Tne active compounds, the concentrations o~ the Le A 17 831 - 18 -735~
active compounds and the results can be seen from the following table:
T a b 1 e D
Erysiphe test (cucumbers)/protective Active Infection in ~ at an compound active compound con-centration of 0.00025 (E) 62 (2) 12 (~) 6 (14) 16 (15) 12 Preparative Examples Cl Examnle 1 Cl- ~ -0-CH-C0- ~ -Cl N S03H (1) . 1/2 244.6 g (0.62 mol) of 1-bromo-1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one were added dropwise, at the boil, to 149 g (2.13 mol) of lJ2,4-triazole in 1,500 ml of acetonikrile. The mixture was heated under reflux for 40 hours. Thereafter, the solvent was dlstilled off in vacuo, the residue was taken up in 1JOOO ml of methylene chloride and the methylene chloride solution was extracted by shaking with three times 500 ml of water. The aqueous phase was again extracted by shaking with 500 ml of methylene chloride. The combined methylene chloride phases were dried over sodium sulphate and concentrated by distillin~ off the solvent in vacuo. The residue was dissolved in 300 ml of acetone and 100 ~ of 1,5-naphthalenedi3ulphonic acid hexa-Le A 1, 831 - 19 -3~
hydrate in 200 ml of acetone were added. This gave 279 (41.3% Or theory) of 1~(4-chlorophenoxy)-2-(2,4-dichloro-phenyl)-1-(1~2~4-triazol-1-yl)-ethan-2-one naphthalene-1,5-disulphonate of melting point 198C.
Example ?
Cl Cl- ~ O-CH~CO ~ -Cl ~ `N (2) N . HCl The base was liberated from the 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one naphthalene-1,5-disulphonate 3 obtained according to Example 1, by adding sodium bicarbonate solution, and was taken up in ethyl acetate and converted, with ethereal hydrochloric acid, into the hydrochloride, which crystallised out a~ter standing for a long time in ether. l-(4-Chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one hydrochloride of melting point 138-140C was quantitatively obtained.
Example 3 Cl Cl- ~ -O-CH-CH- ~ -Cl N OH (3) N _ . HCl 226 g (0.42 mol) o~ 1-(4-chlorophenoxy)-2-(2,4~
dichlorophenyl)-1~(1,2,4-triazol-1-yl)-ethan-2-one naphtha-lene-1,5-disulphonate (F.xample 1) were suspended in 500 ml o~ methylene chloride, 1,000 ml of saturated sodium bi-Le A 17 831 - 20 -,~
~.397;~
carbonate solution were added and the mixture was stirred for 5 hours. The isolated organic phase was dried over sodium sulphate and concentrated in vacuo. The residue was taken up in 1.5 litres of methanol, 17 g (0.45 mol of sodium borohydride were added in portions of about 1 g at 0 to 5C and the mixture was stirred for 15 hours at room temperature. 200 ml of concen-trated hydrochloric acid were then added dropwise at 0C and the mixture was again stirred for 15 hours at room temperature. The reaction mixture was then stirred into 1,000 ml of saturated sodium bicarbonate solution, the aqueous phase was extracted by shaking with two times 500 ml of methylene chloride and the organic phase was extracted by shaking with two times 200 ml of water. The combined organic phases were dried over sodium sulphate and concentrated by distilling off the solvent in vacuo. The oil which remained was dissolved in 800 ml of ether and dry hydrogen chloride was added in ex-cess. This gave 113.5 g (64% of theory) of 1-~4-chlorophenoxy)-2-(2,4-dichlorophenyl~-1-(1,2,4-triazol-1-yl~-ethan-2-ol hydrochloride as an isomer mixture of melting point 157-172C.
The compounds which are disclosed in Table 1, which follows, were ob-tained analogously to the above-mentioned Examples.
~3~7354 a) a~ 0 r-l h h h h h h V
X X X X X X
~~ r r r r ~ r~
~; h h h ~ h h o a) ~a) a) 0 a~
~ O O O O O O
~r~ r-l r~lr~ r-l r-lr~
~ O
O
r--I r--l Or--I r--I r--i r--~ r--I r I H H H
H ~ C) V {~
a~ ~ ~ X
r~
~ ~ I1 0 1 CO C~ ~ C~ ~ ~ U~
r--I ~ Ir~ 0 1 ~D O I t~J 0 ~D 1 0 crl r-l L~
~ / ~ ~ o ~ r~ ~ 0 ~ ~ ~ ~ U~
r-l ~
~ m_~/ =l ¦ tc tc tc tc c tc ~ O ~1; V V V V V U V VO ~I rr X ~ ~ ~
~X~ " ,~1 V
~J J ~ ~ (\I rr, I ~ ~ ;~ ~\
r ~ z !
Le A 17 831 - 22 -.' ' ' ~
Podosphaera test (apple)/protective Solvent: 4.7 parts by weight of acetone Emul~ifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated amount of emulsifier.
Young apple seedlings in the 4 - 6 leaf stage were sprayed with the spray liquid ur.til dripping wet.
The plants remained in a greenhouse for 24 hours at 20 deg.C and at a relative atmospheric humidity of 70%. They were then inoculated by dusting the conidia of the apple powdery mildew causative organism (Podosphaera leucotricha) and placed in a greenhouse at a temperature of 21 - 23 deg. C and at a relative atmospheric humidity of about 70%.
10 days after the inoculation, the infection of the seedlings was determined~ The assessment data were converted to % infection. 0% meant no infection;
100% meant that the plants were completely in~ected.
The active compounds, the concentrations of the active compounds and the results can be seen from the ~ollowing table:
Le A 17 831 - 17 -~3~735~
T a b 1 e C
Podosphaera test (apple)/protective Active Infection in % at an compound active compound con-centration of 0.001%
(D) 42 (2) 25 (3) 0 (14) 0 Example D
Erysi~he test Icucumber)/protective Solvent: 4.7 parts by weight of acetone ~mulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of the active compound required for the desired concentration o~ active compound in the spray liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water containing the stated amount of emulsifier.
Young cucumber plants with about three foliage leaves were sprayed with the spray liquid until dripping wet The cucumber plants remained in a greenhouse for 24 hours to dry. They were then, for the purpose of inoculation, dusted with conidia of the fungus oiohoriacearum. The plants were subsequently placed in a greenhouse at 23-24 degrees C and at a relative atmospheric humidity of about 75%.
After 12 days, the infection of the cucumber plants was determined. The assessment data were con~erted to percent infection 0% meant no infection; 100% meant that the plants were totally infected.
Tne active compounds, the concentrations o~ the Le A 17 831 - 18 -735~
active compounds and the results can be seen from the following table:
T a b 1 e D
Erysiphe test (cucumbers)/protective Active Infection in ~ at an compound active compound con-centration of 0.00025 (E) 62 (2) 12 (~) 6 (14) 16 (15) 12 Preparative Examples Cl Examnle 1 Cl- ~ -0-CH-C0- ~ -Cl N S03H (1) . 1/2 244.6 g (0.62 mol) of 1-bromo-1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one were added dropwise, at the boil, to 149 g (2.13 mol) of lJ2,4-triazole in 1,500 ml of acetonikrile. The mixture was heated under reflux for 40 hours. Thereafter, the solvent was dlstilled off in vacuo, the residue was taken up in 1JOOO ml of methylene chloride and the methylene chloride solution was extracted by shaking with three times 500 ml of water. The aqueous phase was again extracted by shaking with 500 ml of methylene chloride. The combined methylene chloride phases were dried over sodium sulphate and concentrated by distillin~ off the solvent in vacuo. The residue was dissolved in 300 ml of acetone and 100 ~ of 1,5-naphthalenedi3ulphonic acid hexa-Le A 1, 831 - 19 -3~
hydrate in 200 ml of acetone were added. This gave 279 (41.3% Or theory) of 1~(4-chlorophenoxy)-2-(2,4-dichloro-phenyl)-1-(1~2~4-triazol-1-yl)-ethan-2-one naphthalene-1,5-disulphonate of melting point 198C.
Example ?
Cl Cl- ~ O-CH~CO ~ -Cl ~ `N (2) N . HCl The base was liberated from the 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one naphthalene-1,5-disulphonate 3 obtained according to Example 1, by adding sodium bicarbonate solution, and was taken up in ethyl acetate and converted, with ethereal hydrochloric acid, into the hydrochloride, which crystallised out a~ter standing for a long time in ether. l-(4-Chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one hydrochloride of melting point 138-140C was quantitatively obtained.
Example 3 Cl Cl- ~ -O-CH-CH- ~ -Cl N OH (3) N _ . HCl 226 g (0.42 mol) o~ 1-(4-chlorophenoxy)-2-(2,4~
dichlorophenyl)-1~(1,2,4-triazol-1-yl)-ethan-2-one naphtha-lene-1,5-disulphonate (F.xample 1) were suspended in 500 ml o~ methylene chloride, 1,000 ml of saturated sodium bi-Le A 17 831 - 20 -,~
~.397;~
carbonate solution were added and the mixture was stirred for 5 hours. The isolated organic phase was dried over sodium sulphate and concentrated in vacuo. The residue was taken up in 1.5 litres of methanol, 17 g (0.45 mol of sodium borohydride were added in portions of about 1 g at 0 to 5C and the mixture was stirred for 15 hours at room temperature. 200 ml of concen-trated hydrochloric acid were then added dropwise at 0C and the mixture was again stirred for 15 hours at room temperature. The reaction mixture was then stirred into 1,000 ml of saturated sodium bicarbonate solution, the aqueous phase was extracted by shaking with two times 500 ml of methylene chloride and the organic phase was extracted by shaking with two times 200 ml of water. The combined organic phases were dried over sodium sulphate and concentrated by distilling off the solvent in vacuo. The oil which remained was dissolved in 800 ml of ether and dry hydrogen chloride was added in ex-cess. This gave 113.5 g (64% of theory) of 1-~4-chlorophenoxy)-2-(2,4-dichlorophenyl~-1-(1,2,4-triazol-1-yl~-ethan-2-ol hydrochloride as an isomer mixture of melting point 157-172C.
The compounds which are disclosed in Table 1, which follows, were ob-tained analogously to the above-mentioned Examples.
~3~7354 a) a~ 0 r-l h h h h h h V
X X X X X X
~~ r r r r ~ r~
~; h h h ~ h h o a) ~a) a) 0 a~
~ O O O O O O
~r~ r-l r~lr~ r-l r-lr~
~ O
O
r--I r--l Or--I r--I r--i r--~ r--I r I H H H
H ~ C) V {~
a~ ~ ~ X
r~
~ ~ I1 0 1 CO C~ ~ C~ ~ ~ U~
r--I ~ Ir~ 0 1 ~D O I t~J 0 ~D 1 0 crl r-l L~
~ / ~ ~ o ~ r~ ~ 0 ~ ~ ~ ~ U~
r-l ~
~ m_~/ =l ¦ tc tc tc tc c tc ~ O ~1; V V V V V U V VO ~I rr X ~ ~ ~
~X~ " ,~1 V
~J J ~ ~ (\I rr, I ~ ~ ;~ ~\
r ~ z !
Le A 17 831 - 22 -.' ' ' ~
Claims (23)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. 2,4-Dichlorophenyl-triazolyl-ethan-ones and -ols of the general formula (I) in which A represents a keto group or a CH(OH) grouping, X represents halogen, alkyl or phenyl or optionally substituted by halogen, and n represents 0, 1, 2 or 3, the X substituents being selected independently of one another when n is 2 or 3, and their salts.
2. Compounds according to claim 1, in which X represents fluorine, chlorine, bromine, iodine, straight-chain or branched alkyl with 1 to 4 carbon atoms or phenyl which is optionally substituted by chlorine and n represents 0, 1 or 2.
3. Salts of the compounds of formula (I) according to claim 1 or 2.
4. Salts of the compounds of formula (I) according to claim 1 or 2 that are non-phytotoxic.
5. Hydrochlorides of the compounds of formula (I) according to claim 1 or 2.
6. Compounds of formula (I) according to claim 1 or 2 in the free base form.
7. The compound having the formula
8. The compound having the formula .HCl
9. The compound having the formula .HCl
10. The compound having the formula .HCl
11. The compound having the formula .HCl
12. A process for the preparation of a 2,4-dichlorophenyltriazolyl-ethan-one or -ol as defined in claim 1, in which a 1-bromo-3-(2,4-dichloro-phenyl)-1-phenoxy-ethan-2-one of the general formula (II), in which X and n have the meanings stated above, is reacted with 1,2,4-triazole in the presence of a diluent and of an acid-binding agent, and, where required, the 1,2,4-triazolyl-ethanone thereby obtained is reduced with a com-plex borohydride.
13. A method of combatting fungi which comprises applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound according to claim 1.
14. A method according to claim 13, wherein the compound is applied in the form of a composition comprising said compound as active ingredient in admixture with a diluent or carrier.
15. A method according to claim 14, wherein the composition comprises 0.00001 to 0.1% by weight of said active ingredient.
16, A method according to claim 14, wherein the composition comprises 0.0001 to 0.05% by weight of said active ingredient.
17. A method according to claim 13, 14 or 16, in which the compound is applied to soil in an amount of 1 g to 1 kg per cubic metre of soil.
18. A method according to claim 13, 14 or 16, in which the compound is applied to soil in an amount of 10 g to 200 g per cubic metre of soil.
19. A method according to claim 13, 14 or 16, in which the compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.
20. A method according to claim 13, 14 or 16 in which the compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.
21. A method according to claim 13 or 16, wherein the active in-gredient is a compound as defined according to claim 2.
22. A method for combatting fungi which comprises applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound according to claim 7, 8 or 9.
23. A method for combatting fungi which comprises applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound according to claim 10 or 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2705678.6 | 1977-02-11 | ||
| DE19772705678 DE2705678A1 (en) | 1977-02-11 | 1977-02-11 | 2,4-DICHLORPHENYL-TRIAZOLYL-AETHAN-ONE (-OLE), METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1097354A true CA1097354A (en) | 1981-03-10 |
Family
ID=6000865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA296,582A Expired CA1097354A (en) | 1977-02-11 | 1978-02-09 | 2,4-dichlorophenyl-triazolyl-ethan-ones and -ols, and their use as fungicides |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS5398968A (en) |
| AR (1) | AR221696A1 (en) |
| AU (1) | AU518208B2 (en) |
| BE (1) | BE863852A (en) |
| BR (1) | BR7800789A (en) |
| CA (1) | CA1097354A (en) |
| CH (1) | CH638501A5 (en) |
| CS (1) | CS194198B2 (en) |
| DD (1) | DD136693A5 (en) |
| DE (1) | DE2705678A1 (en) |
| DK (1) | DK61178A (en) |
| FI (1) | FI780432A7 (en) |
| FR (1) | FR2380265A1 (en) |
| GB (1) | GB1566236A (en) |
| HU (1) | HU178436B (en) |
| IL (1) | IL54004A (en) |
| IT (1) | IT7820130A0 (en) |
| NL (1) | NL7801580A (en) |
| NO (1) | NO780316L (en) |
| NZ (1) | NZ186409A (en) |
| PL (1) | PL106362B1 (en) |
| PT (1) | PT67628B (en) |
| SE (1) | SE7801527L (en) |
| TR (1) | TR19678A (en) |
| ZA (1) | ZA78821B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2846038A1 (en) * | 1978-10-23 | 1980-05-08 | Basf Ag | 1,2,4-TRIAZOLE DERIVATIVES, THEIR PRODUCTION AND USE |
| DE3150204A1 (en) * | 1981-12-18 | 1983-06-30 | Basf Ag, 6700 Ludwigshafen | FUNGICIDAL ALPHA AZOLYL GLYCOLES |
| DE19505938A1 (en) * | 1995-02-21 | 1996-08-22 | Bayer Ag | Process for the preparation of 1- (4-chlorophenyl) -4,4-dimethyl-pentan-3-one |
-
1977
- 1977-02-11 DE DE19772705678 patent/DE2705678A1/en not_active Withdrawn
-
1978
- 1978-01-27 NO NO780316A patent/NO780316L/en unknown
- 1978-02-02 CH CH117478A patent/CH638501A5/en not_active IP Right Cessation
- 1978-02-06 PT PT67628A patent/PT67628B/en unknown
- 1978-02-07 GB GB4885/78A patent/GB1566236A/en not_active Expired
- 1978-02-08 AR AR271027A patent/AR221696A1/en active
- 1978-02-08 NZ NZ186409A patent/NZ186409A/en unknown
- 1978-02-08 TR TR19678A patent/TR19678A/en unknown
- 1978-02-09 CA CA296,582A patent/CA1097354A/en not_active Expired
- 1978-02-09 JP JP1304178A patent/JPS5398968A/en active Pending
- 1978-02-09 SE SE7801527A patent/SE7801527L/en unknown
- 1978-02-09 HU HU78BA3628A patent/HU178436B/en unknown
- 1978-02-09 DD DD78203638A patent/DD136693A5/en unknown
- 1978-02-09 IL IL54004A patent/IL54004A/en unknown
- 1978-02-09 FI FI780432A patent/FI780432A7/en not_active Application Discontinuation
- 1978-02-09 CS CS78852A patent/CS194198B2/en unknown
- 1978-02-09 IT IT7820130A patent/IT7820130A0/en unknown
- 1978-02-10 PL PL1978204557A patent/PL106362B1/en unknown
- 1978-02-10 BR BR7800789A patent/BR7800789A/en unknown
- 1978-02-10 BE BE185069A patent/BE863852A/en not_active IP Right Cessation
- 1978-02-10 NL NL7801580A patent/NL7801580A/en not_active Application Discontinuation
- 1978-02-10 FR FR7803834A patent/FR2380265A1/en active Granted
- 1978-02-10 DK DK61178A patent/DK61178A/en unknown
- 1978-02-10 ZA ZA00780821A patent/ZA78821B/en unknown
- 1978-02-13 AU AU33245/78A patent/AU518208B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BE863852A (en) | 1978-08-10 |
| DD136693A5 (en) | 1979-07-25 |
| NZ186409A (en) | 1979-12-11 |
| ZA78821B (en) | 1979-01-31 |
| FI780432A7 (en) | 1978-08-12 |
| AU518208B2 (en) | 1981-09-17 |
| PT67628B (en) | 1979-07-17 |
| CS194198B2 (en) | 1979-11-30 |
| NL7801580A (en) | 1978-08-15 |
| IL54004A0 (en) | 1978-04-30 |
| HU178436B (en) | 1982-05-28 |
| FR2380265A1 (en) | 1978-09-08 |
| FR2380265B1 (en) | 1982-10-22 |
| PT67628A (en) | 1978-03-01 |
| IT7820130A0 (en) | 1978-02-09 |
| PL204557A1 (en) | 1978-10-23 |
| DE2705678A1 (en) | 1978-08-17 |
| AR221696A1 (en) | 1981-03-13 |
| GB1566236A (en) | 1980-04-30 |
| IL54004A (en) | 1982-04-30 |
| JPS5398968A (en) | 1978-08-29 |
| SE7801527L (en) | 1978-08-12 |
| CH638501A5 (en) | 1983-09-30 |
| PL106362B1 (en) | 1979-12-31 |
| TR19678A (en) | 1979-10-05 |
| NO780316L (en) | 1978-08-14 |
| DK61178A (en) | 1978-08-12 |
| BR7800789A (en) | 1979-01-02 |
| AU3324578A (en) | 1979-08-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |