CA1132580A - 1,2,4-triazol-1-yl compounds, their manufacture, and use thereof as fungicides - Google Patents
1,2,4-triazol-1-yl compounds, their manufacture, and use thereof as fungicidesInfo
- Publication number
- CA1132580A CA1132580A CA338,144A CA338144A CA1132580A CA 1132580 A CA1132580 A CA 1132580A CA 338144 A CA338144 A CA 338144A CA 1132580 A CA1132580 A CA 1132580A
- Authority
- CA
- Canada
- Prior art keywords
- compound
- carbon atoms
- formula
- absence
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/20—N-Aryl derivatives thereof
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention relates to new 1,2,4-triazol-1-yl compounds of the formule (I):
(I) where R1 denotes phenyl substituted by cyclohexyl, phenyl, 1 to 3 halogen atoms or alkyl of 1 to 4 carbon atoms, and Y denotes OR2 or
The present invention relates to new 1,2,4-triazol-1-yl compounds of the formule (I):
(I) where R1 denotes phenyl substituted by cyclohexyl, phenyl, 1 to 3 halogen atoms or alkyl of 1 to 4 carbon atoms, and Y denotes OR2 or
Description
~3;~8~
The present invention relates to new 1,2,4-triazole derivatives, processes for the manufacture thereof, and their use as fungicides.
It has been disclosed that t-butyl 2-(1',2',4'-triazol-l'-yl)-2-phenylacetate has a fungicidal action (German Laid-Open Application DE-OS 2,638,470). However, its action, particularly on mildews and rusts, is unsatisactory. It is therefore hardly suitable for use as a crop protection agent for combating injurious fungi.
We have now found new compounds having a superior herbicidal action. The object of the invention was to provide new 1,2,4-triazol-1-yl compounds of the formula R O-CH-CO-Y
~ ~ (I) where Rl denotes phenyl substituted by cyclohexyl, phenyl, 1 to 3 halogen atoms or alkyl of 1 to 4 carbon atoms, and Y denotes oR2 or N
\ R4 R2 denoting alkynyl of 3 to 15 carbon atoms, R denoting hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 15 carbon atoms, phenyl or cyanoethyl, and R4 denoting phenyl, benzyl or phenyl or benzyl substituted by 1 or 2 halogen atoms, trifluoromethyl or alkyl of 1 to 4 carbon atoms, or alkenyl or alkynyl of 3 to 15 carbon carbon atoms, phenylethyl, naphthyl or cyanoethyl, and their plant-compatible salts and metal complexes.
3Z5~30 In formule I, R preferably denotes l-chlorobutyn-
The present invention relates to new 1,2,4-triazole derivatives, processes for the manufacture thereof, and their use as fungicides.
It has been disclosed that t-butyl 2-(1',2',4'-triazol-l'-yl)-2-phenylacetate has a fungicidal action (German Laid-Open Application DE-OS 2,638,470). However, its action, particularly on mildews and rusts, is unsatisactory. It is therefore hardly suitable for use as a crop protection agent for combating injurious fungi.
We have now found new compounds having a superior herbicidal action. The object of the invention was to provide new 1,2,4-triazol-1-yl compounds of the formula R O-CH-CO-Y
~ ~ (I) where Rl denotes phenyl substituted by cyclohexyl, phenyl, 1 to 3 halogen atoms or alkyl of 1 to 4 carbon atoms, and Y denotes oR2 or N
\ R4 R2 denoting alkynyl of 3 to 15 carbon atoms, R denoting hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 15 carbon atoms, phenyl or cyanoethyl, and R4 denoting phenyl, benzyl or phenyl or benzyl substituted by 1 or 2 halogen atoms, trifluoromethyl or alkyl of 1 to 4 carbon atoms, or alkenyl or alkynyl of 3 to 15 carbon carbon atoms, phenylethyl, naphthyl or cyanoethyl, and their plant-compatible salts and metal complexes.
3Z5~30 In formule I, R preferably denotes l-chlorobutyn-
2-yl-4, 3-chlorobutyn-1-yl-4, 1-chlorpentyn-2-yl-4, butyn-2-yl-l, butyn-l-yl-3, butyn-1-yl-4, 3-methylbutyn-1-yl-3 and l-ethynylcyclohexyl.
Exemples of salts tolerated by crop plants are hydrochlorides, hydrobromides, sulfates, nitrates, phosphates, oxalates and dodecylbenzene sulfonates.
Metal complexes are compounds of the formula 10~ R10-CH--CO-~ \ ~
Me ~ ~ ~ ) Zk IX, where Rl and Y have the above meanings, Me denotes a metal cation, e.g., of copper, zinc, thin, manganese, iron, cobalt or nickel, Z denotes the anion of an inorganic acid, e.g., hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or hydrobromic acid, and k and m denote one of the integers 1, 2, 3 and 4.
A further object of the invention is to provide a process for the manufacture of 1,2,4-triazolyl compounds of the formula I wherein a) a compound of the formula R2-C ~ II, where R2 and Y have the~above meanings and Ll and L2 are identical or different and are nucleophilically displaceable leaving groups, is reacted with a compound of the formula RlOH III, 113~
where Rl has the above meanings, or a salt thereof, and with 1,2,4-triazole, or a salt thereof, in the presence or absence of a solvent or diluent and/or of an inorganic or organic base and in the presence or absence of a reaction accelerator at from O to ].80C, or b) a compound of the formula H ~
RlO-C-C-OM IV, N
~
where Rl has the above meaning and M denotes hydrogen, one equivalent of a metal cation or a substituted or unsubstituted ammonium ion, is reacted with a compound of the formula HY V, where Y has the above meanings, after or ~ith simultaneous addition of reagents suitable for derivatizing acids, in the presence or absence of a solvent or diluent and/or of an inorganic or organic base and in the presence or absence of a reaction accelerator at from -20 to +180C, or c) a compound of the formula V is reacted with a compound of the formula L3Y VI, where Y has the above meanings and L3 is a nucleophilically displaceable leaving group, in the presence or absence of a solvent or diluent and/or an acid binder and in the presence or absence of a reaction accelerator at from -20 to +180C, or d) a compound of the formula H_C ~ O
L VII, where Rl, Y and L2 have the above meanings, is reacted with 1,2,4-triazole in the presence or absence of a solvent or diluent and/or an inorganic or organic base and in the presence or absence of a reaction accelerator at from -20 to +180C
and/ if desired, the compounds obtained according to a) to d) are converted into salts and metal complexes tolerated by plants.
Examples of nucleophilically displaceable leaving groups Ll and L2 mentioned in processes a) and d) are halogen, such as chlorine, bromine and iodine; bisulfate; hydrogen sulfonate; and unsubstituted or substituted alkylsulfonyloxy, arylsulfonyloxy, alkylsulfate, phenoxy, phenylthio, oxonium, sulfonium or ammonium radicals. Suitable inorganic or organic bases which may if desired also be used as acid binders in reaction a) are, for example, alkali metal and alkaline earth metal hyd~oxides, such as sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal carbonates, such as potassium and sodium carbonate; alkali metal hydrides, such as sodium hydride; alkali metal and alkaline earth metal alcoholates, such as sodium methylate, magnesium ethylate and sodium isopropylate; tertiary amines, such as trimethylamine, triethylamine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine, N-methylpiperidine and pyridine; and azoles, such as 1,2,4-triazole and imidazole. However, other bases usually employed30 may also be used.
Examples of suitable salts of compounds of the formulae III and salts of 1,2,4-triazol are their alkali metal, 1~L3Z5l30 alkaline earth metal, and substituted or unsubstituted ammonium salts.
The preferred solvents or diluents include halo-hydrocarbons, such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene; aliphatic or aromatic hydrocarbons, such as cyclohexane, petroleum ether, benzene, toluene and xylenes; alcohols, such as methanol, ethanol, isopropanol and n-butanol; esters, such as ethyl acetate;
amides, such as dimethylformamide; nitriles, such as acetronitrile; sulfoxides, such as dimethylsulfoxide; ketones, such as acetone and methyl ethyl ketone; ethers, such as diethyl ether, tetrahydrofuran and dioxane, and mixtures of the above. Advantageously, the solvent or diluent is used in an amount of from 100 to 2,000 wt~, preferably from 100 to 1,000 wt~, based on starting materials II or III.
Preferred reaction accelerators are metal halides such as sodium bromide and potassium iodide, crown ethers, quaternary ammonium compounds, such as tetrabutylammonium iodide, acids, or combinations of these compounds.
The process according to the invention is in general carried out at from 40 to 150C, for from 1 to 60 hours, under atmospheric or superatmospheric pressure, and continuously or batchwise.
In carrying out the process according to the invention, the amounts employed per mole of compound II are in general from 0.5 to 2 moles of compound III and 1,2,4-triazole, preferably from 0.9 to 1.3 moles of III and 1,2,4-triazole, from 1 to 4 moles, preferably from 1.8 to 2.3 moles, of base, and, if a reaction accelerator is used, from 0.01 to 0.1 mole thereof.
In a preferred form of process a) according to the invention, the starting materials III and 1,2,4-triazole are 1132~3V
mixed, in optional sequence, with a base and a diluent, the starting material II, with or without a reaction accelerator, is then added and the reaction is carried out at from 40 to 150C, for from 0.5 to 120, preferably from 1 to 60, hours.
To isolate the compounds according to the invention, the diluent is, if desired, removed, and the residue is taken up in a suitable solvent and washed with water to remove excess base and unreacted starting materials of the formula III and 1,2,4-triazole. In general, the products remaining after removal of the solvent do not require any further purification, but if necessary they can be additionally purified by conven-tional methods, such as recrystallization, extraction and chromatography.
The following are - without restricting the invention - to them - examples of conventional reagents suitable for derivatizing acids for process b): proton or Lewis acids, inorganic and organic acid halides, such as thionyl chloride, phosphorus pentachloride and acetyl chloride; chlorocarbonic acid esters, such as the ethyl, tert~butyl and benzyl esters;
anhydrides, such as ketene; diimides, such as N,N'-dicyclohexyl-carbodiimide; and carbonyl or sulfonyl diazoles, such as carbonyldiimidazole, carbonylditriazole, sulfonyldiimidazole and sulfonylditriazole.
For process c), particularly suitable compounds of the formula VI are those in which L3 is a nucleophilically displaceable leaving group, such as halogen, e.g., chlorine, bromine and iodine; substituted or unsubstituted alkyl- or arylsulfonyloxy, such as mesyloxy, trifluoromethylsulfonyloxy,`
brosyloxy and tosyloxy; an alkyl sulfate, such as methyl sulfate; and the diazo group.
Preferred solvents or diluents and acid binders preferably used for processes b), c) and d) are those given '3~
J~ --6--1:~3ZS8~
for process a).
The reactions according to processes b), c) and d) described in general terms and the isolation of the compounds according to the invention are carried out in conventional manner (cf. Houben-Weyl, 8, 508 et seq., and 653 et seq., Stuttgart, 1952, and 15, 2, Stuttgart, 1974).
The starting materials of the formula IV may be produced by reaction of a compound of the formula Ll R2-C~ X, where R2, Ll, L2 and M have the ahove meanlngs, with a hydroxy compound of the formula R OH III, where Rl has the above meanings, or a salt thereof, and with 1,2,4-triazole or a salt thereof, in the presence or absence of a diluent and/or an acid binder and in the presence or absence of a reaction accelerator, at from O to 180C.
The starting materials of the formula VII may be prepared by conventional methods~ e.g., by halogenation of the corresponding aryl- or heteroaryloxyalkanoic acid derivatives (c.f. German Laid-Open Application DE-OS 1,808,034).
The compounds of the formula I have one or more chiral centers; pure isomers can be obtained from the mixtures, obtained by synthesis, in accordance with prior art methods.
The pure isomers anZ also mixtures thereof may be used.
The following examples illustrate the production of the new compounds.
. ,, Manufacture of the starting materlals a) 90 parts of a technical-grade sodium methylate solution in methanol (30 parts of sodium methylate in 100 parts of solution) is added to 81.5 parts of 2,4-dichlorophenol and 34.S parts of 1,2,4-triazote in 300 parts of ethanol and after brief stirring 109 parts of dibromoacetic acid is introduced. The mixture is refluxed for 14 hours, the solvent is stripped off and the residue is dissolved in about 1,000 parts of water. While cooling, the pH is brought to 1 by adding concentrated hydrochloric acid, and the precipitate which has formed is filtered off and washed with isopropanol.
After drying, 121 parts of 2-(2',4'-dichlorophenoxy)-2-(1', 2',4'-triazol-1'-yl)-acetic acid, of melting point 211-213C
(with decomposition), is obtained.
b) 771 parts of 4-chlorophenol and 414 parts of 1,2,4-triazole are added to 1,080 parts of a technical-grade sodium methylate solution in methanol (30 parts of sodium methylate in 100 parts of solution). After briefly stirring the mixturet 774 parts of dichloroacetic acid is run in, during which addition the temperature rises to about 60C. The methanol is then distilled off and isopropanol is run in at the same time in such amount that the reaction mixture can be stirred without difficulty. When the internal temperature has reached 80C, boiling is continued for 10 hours, the solvent is then distilled off, ice water is added and the mixture is acidified with concentrated hydrochloric acid. The precipitate formed is filtered off, washed with isopropanol and dried. 676 parts (58~ of theory) of 2-(4'-chlorophenoxy)-2-(1',2',4'-triazol-l'-yl)-acetic acid of melting point 205-207C (with decom-position) is obtained.
Manufacture of the end products 25 parts of 2-(4'-chlorophenoxy)-2-(1',2',4'-triazol-l'-yl)-acetic acid was introduced into 100 parts of methylene chloride, and 0.5 part of dimethylformamide and 15 parts of triethylamine were added. The reaction mixture was cooled to -10C, and 15 parts of thionyl chloride was dripped in while stirring. The mixture was then stirred overnight at room temperature. A solution of 12 parts of triethylamine and 12 parts of aniline in 20 parts of methylene chloride was dripped in at +10C with cooling. The mixture was then refluxed for 1 hour. After the mixture had cooled, the precipitate was filtered off and washed with methylene chloride, and the organic phase was concentrated. The oil which remained was filtered through silica gel using methylene chloride as eluant, and 18 parts of a uniform oil was obtained which crystallized after standing overnight in ether.
The yield was 15 parts of 2-(4'-chlorophenoxy)-2-(1',2',4'-triazol-1'-yl)-acetic acid anilide of melting point 134 to 136C.
23 parts of 2-(4'-phenylphenoxy)-2-(1',2',4'-triazol-l'-yl)-acetic acid was suspended in 150 parts of tetrahydrofuran, 13 parts of N,N' carbonyldiimidazole was added in portions to this suspension. After the mixture had been stirred for 1 hour at room temperature, a solution of 9 parts of 4-fluoro-aniline in 20 parts of tetrahydrofuran was dripped in. The mixture was stirred for 12 hours and then stirred into 1,000 parts of ice water, and the precipitate was filtered and dried.
There was obtained 26 parts of 2-(4'-phenylphenoxy)-2-(1',2',4'-triazol-1'-yl)-acetic acid-p-fluoroanilide of melting point 92 to 96C.
1~3Z5~30 Table No. Rl R2 R R4 X y Fp/nD20
Exemples of salts tolerated by crop plants are hydrochlorides, hydrobromides, sulfates, nitrates, phosphates, oxalates and dodecylbenzene sulfonates.
Metal complexes are compounds of the formula 10~ R10-CH--CO-~ \ ~
Me ~ ~ ~ ) Zk IX, where Rl and Y have the above meanings, Me denotes a metal cation, e.g., of copper, zinc, thin, manganese, iron, cobalt or nickel, Z denotes the anion of an inorganic acid, e.g., hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or hydrobromic acid, and k and m denote one of the integers 1, 2, 3 and 4.
A further object of the invention is to provide a process for the manufacture of 1,2,4-triazolyl compounds of the formula I wherein a) a compound of the formula R2-C ~ II, where R2 and Y have the~above meanings and Ll and L2 are identical or different and are nucleophilically displaceable leaving groups, is reacted with a compound of the formula RlOH III, 113~
where Rl has the above meanings, or a salt thereof, and with 1,2,4-triazole, or a salt thereof, in the presence or absence of a solvent or diluent and/or of an inorganic or organic base and in the presence or absence of a reaction accelerator at from O to ].80C, or b) a compound of the formula H ~
RlO-C-C-OM IV, N
~
where Rl has the above meaning and M denotes hydrogen, one equivalent of a metal cation or a substituted or unsubstituted ammonium ion, is reacted with a compound of the formula HY V, where Y has the above meanings, after or ~ith simultaneous addition of reagents suitable for derivatizing acids, in the presence or absence of a solvent or diluent and/or of an inorganic or organic base and in the presence or absence of a reaction accelerator at from -20 to +180C, or c) a compound of the formula V is reacted with a compound of the formula L3Y VI, where Y has the above meanings and L3 is a nucleophilically displaceable leaving group, in the presence or absence of a solvent or diluent and/or an acid binder and in the presence or absence of a reaction accelerator at from -20 to +180C, or d) a compound of the formula H_C ~ O
L VII, where Rl, Y and L2 have the above meanings, is reacted with 1,2,4-triazole in the presence or absence of a solvent or diluent and/or an inorganic or organic base and in the presence or absence of a reaction accelerator at from -20 to +180C
and/ if desired, the compounds obtained according to a) to d) are converted into salts and metal complexes tolerated by plants.
Examples of nucleophilically displaceable leaving groups Ll and L2 mentioned in processes a) and d) are halogen, such as chlorine, bromine and iodine; bisulfate; hydrogen sulfonate; and unsubstituted or substituted alkylsulfonyloxy, arylsulfonyloxy, alkylsulfate, phenoxy, phenylthio, oxonium, sulfonium or ammonium radicals. Suitable inorganic or organic bases which may if desired also be used as acid binders in reaction a) are, for example, alkali metal and alkaline earth metal hyd~oxides, such as sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal carbonates, such as potassium and sodium carbonate; alkali metal hydrides, such as sodium hydride; alkali metal and alkaline earth metal alcoholates, such as sodium methylate, magnesium ethylate and sodium isopropylate; tertiary amines, such as trimethylamine, triethylamine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine, N-methylpiperidine and pyridine; and azoles, such as 1,2,4-triazole and imidazole. However, other bases usually employed30 may also be used.
Examples of suitable salts of compounds of the formulae III and salts of 1,2,4-triazol are their alkali metal, 1~L3Z5l30 alkaline earth metal, and substituted or unsubstituted ammonium salts.
The preferred solvents or diluents include halo-hydrocarbons, such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene; aliphatic or aromatic hydrocarbons, such as cyclohexane, petroleum ether, benzene, toluene and xylenes; alcohols, such as methanol, ethanol, isopropanol and n-butanol; esters, such as ethyl acetate;
amides, such as dimethylformamide; nitriles, such as acetronitrile; sulfoxides, such as dimethylsulfoxide; ketones, such as acetone and methyl ethyl ketone; ethers, such as diethyl ether, tetrahydrofuran and dioxane, and mixtures of the above. Advantageously, the solvent or diluent is used in an amount of from 100 to 2,000 wt~, preferably from 100 to 1,000 wt~, based on starting materials II or III.
Preferred reaction accelerators are metal halides such as sodium bromide and potassium iodide, crown ethers, quaternary ammonium compounds, such as tetrabutylammonium iodide, acids, or combinations of these compounds.
The process according to the invention is in general carried out at from 40 to 150C, for from 1 to 60 hours, under atmospheric or superatmospheric pressure, and continuously or batchwise.
In carrying out the process according to the invention, the amounts employed per mole of compound II are in general from 0.5 to 2 moles of compound III and 1,2,4-triazole, preferably from 0.9 to 1.3 moles of III and 1,2,4-triazole, from 1 to 4 moles, preferably from 1.8 to 2.3 moles, of base, and, if a reaction accelerator is used, from 0.01 to 0.1 mole thereof.
In a preferred form of process a) according to the invention, the starting materials III and 1,2,4-triazole are 1132~3V
mixed, in optional sequence, with a base and a diluent, the starting material II, with or without a reaction accelerator, is then added and the reaction is carried out at from 40 to 150C, for from 0.5 to 120, preferably from 1 to 60, hours.
To isolate the compounds according to the invention, the diluent is, if desired, removed, and the residue is taken up in a suitable solvent and washed with water to remove excess base and unreacted starting materials of the formula III and 1,2,4-triazole. In general, the products remaining after removal of the solvent do not require any further purification, but if necessary they can be additionally purified by conven-tional methods, such as recrystallization, extraction and chromatography.
The following are - without restricting the invention - to them - examples of conventional reagents suitable for derivatizing acids for process b): proton or Lewis acids, inorganic and organic acid halides, such as thionyl chloride, phosphorus pentachloride and acetyl chloride; chlorocarbonic acid esters, such as the ethyl, tert~butyl and benzyl esters;
anhydrides, such as ketene; diimides, such as N,N'-dicyclohexyl-carbodiimide; and carbonyl or sulfonyl diazoles, such as carbonyldiimidazole, carbonylditriazole, sulfonyldiimidazole and sulfonylditriazole.
For process c), particularly suitable compounds of the formula VI are those in which L3 is a nucleophilically displaceable leaving group, such as halogen, e.g., chlorine, bromine and iodine; substituted or unsubstituted alkyl- or arylsulfonyloxy, such as mesyloxy, trifluoromethylsulfonyloxy,`
brosyloxy and tosyloxy; an alkyl sulfate, such as methyl sulfate; and the diazo group.
Preferred solvents or diluents and acid binders preferably used for processes b), c) and d) are those given '3~
J~ --6--1:~3ZS8~
for process a).
The reactions according to processes b), c) and d) described in general terms and the isolation of the compounds according to the invention are carried out in conventional manner (cf. Houben-Weyl, 8, 508 et seq., and 653 et seq., Stuttgart, 1952, and 15, 2, Stuttgart, 1974).
The starting materials of the formula IV may be produced by reaction of a compound of the formula Ll R2-C~ X, where R2, Ll, L2 and M have the ahove meanlngs, with a hydroxy compound of the formula R OH III, where Rl has the above meanings, or a salt thereof, and with 1,2,4-triazole or a salt thereof, in the presence or absence of a diluent and/or an acid binder and in the presence or absence of a reaction accelerator, at from O to 180C.
The starting materials of the formula VII may be prepared by conventional methods~ e.g., by halogenation of the corresponding aryl- or heteroaryloxyalkanoic acid derivatives (c.f. German Laid-Open Application DE-OS 1,808,034).
The compounds of the formula I have one or more chiral centers; pure isomers can be obtained from the mixtures, obtained by synthesis, in accordance with prior art methods.
The pure isomers anZ also mixtures thereof may be used.
The following examples illustrate the production of the new compounds.
. ,, Manufacture of the starting materlals a) 90 parts of a technical-grade sodium methylate solution in methanol (30 parts of sodium methylate in 100 parts of solution) is added to 81.5 parts of 2,4-dichlorophenol and 34.S parts of 1,2,4-triazote in 300 parts of ethanol and after brief stirring 109 parts of dibromoacetic acid is introduced. The mixture is refluxed for 14 hours, the solvent is stripped off and the residue is dissolved in about 1,000 parts of water. While cooling, the pH is brought to 1 by adding concentrated hydrochloric acid, and the precipitate which has formed is filtered off and washed with isopropanol.
After drying, 121 parts of 2-(2',4'-dichlorophenoxy)-2-(1', 2',4'-triazol-1'-yl)-acetic acid, of melting point 211-213C
(with decomposition), is obtained.
b) 771 parts of 4-chlorophenol and 414 parts of 1,2,4-triazole are added to 1,080 parts of a technical-grade sodium methylate solution in methanol (30 parts of sodium methylate in 100 parts of solution). After briefly stirring the mixturet 774 parts of dichloroacetic acid is run in, during which addition the temperature rises to about 60C. The methanol is then distilled off and isopropanol is run in at the same time in such amount that the reaction mixture can be stirred without difficulty. When the internal temperature has reached 80C, boiling is continued for 10 hours, the solvent is then distilled off, ice water is added and the mixture is acidified with concentrated hydrochloric acid. The precipitate formed is filtered off, washed with isopropanol and dried. 676 parts (58~ of theory) of 2-(4'-chlorophenoxy)-2-(1',2',4'-triazol-l'-yl)-acetic acid of melting point 205-207C (with decom-position) is obtained.
Manufacture of the end products 25 parts of 2-(4'-chlorophenoxy)-2-(1',2',4'-triazol-l'-yl)-acetic acid was introduced into 100 parts of methylene chloride, and 0.5 part of dimethylformamide and 15 parts of triethylamine were added. The reaction mixture was cooled to -10C, and 15 parts of thionyl chloride was dripped in while stirring. The mixture was then stirred overnight at room temperature. A solution of 12 parts of triethylamine and 12 parts of aniline in 20 parts of methylene chloride was dripped in at +10C with cooling. The mixture was then refluxed for 1 hour. After the mixture had cooled, the precipitate was filtered off and washed with methylene chloride, and the organic phase was concentrated. The oil which remained was filtered through silica gel using methylene chloride as eluant, and 18 parts of a uniform oil was obtained which crystallized after standing overnight in ether.
The yield was 15 parts of 2-(4'-chlorophenoxy)-2-(1',2',4'-triazol-1'-yl)-acetic acid anilide of melting point 134 to 136C.
23 parts of 2-(4'-phenylphenoxy)-2-(1',2',4'-triazol-l'-yl)-acetic acid was suspended in 150 parts of tetrahydrofuran, 13 parts of N,N' carbonyldiimidazole was added in portions to this suspension. After the mixture had been stirred for 1 hour at room temperature, a solution of 9 parts of 4-fluoro-aniline in 20 parts of tetrahydrofuran was dripped in. The mixture was stirred for 12 hours and then stirred into 1,000 parts of ice water, and the precipitate was filtered and dried.
There was obtained 26 parts of 2-(4'-phenylphenoxy)-2-(1',2',4'-triazol-1'-yl)-acetic acid-p-fluoroanilide of melting point 92 to 96C.
1~3Z5~30 Table No. Rl R2 R R4 X y Fp/nD20
3 4-Cl-C H - H H H O OC (CH3) 2C--CH 91--94
4 2,4-DiBr-C6H3- H H H O OC (CH3) 2C--CH
2-Br-4-Cl-C H3- H H H O OC (CH3) 2C-CH
6 2,4-DiCl-C6ll3- H H H O OC (CH3) 2C~CH 60-63 7 2,4-DiCl-C6H3- H H H O NHC(CH3)2C--CH 112-115 8 2,4-DiCH3C6H3-- H H H O NHC (CH3) 2C--CH
4-Cl-C6H4- H H H O NHC (CH3) 2C-CH 74-82 3-F-C6H4- H H H O NHC (CH3) 2CH--CH2 11 2,4-DiCl-C6H3- H H H O NHC6H5 92--95 12 2,4-DiCH3-C6H3 H H H O NHC6H5 114-116 13 2,4-DiCl-C6H3- H H H O NH-2-F-C6H4 99-101 14 4-Br-C6H4- H H H O NH-2-F-C6H4 4-Cl-C6H4 H H H- O NH-3-F-C6H4 102-105 16 2,4-DiCl-C6H3-- H H H O NH--3-F-C6H4 80-84 18 4-Cl-C6H4- H H H O NH-4-C6H4 138-142 20- 19 2,4,5-TriCl-C6H2-H H H o NH-4-F-C6H4 136-140 2,9-DiCl-C6H3- 1l ll H o N~l-4--F-C6H4139-142 21 4-Cl-C6H4-- H H H O NH-4-Cl-C6H4 146-149 22 2-Br-4Cl-C6H3- H H H O NH-4-Cl-C6H4 23 3-F-C6H4- H H H O NH-4-Cl-C6H4 24 2,4-DiCl-C6H3- H H H O NH-2,4-DiF-C6H3122-124 3,4-DiCl--C6H3-- H H H O NH--3,4-DiF-C6H3 26 2,4 DiCH3 C6H3 H H o NH-3Cl-4F-C6H3 27 2,4--DiCl--C6H3-- H H H O NH-3,5-DiCl-C6EI3 170-173 28 3 CHF2 CF2 C6H4 H H H O NH-3,5--DiCl-C6H3 2,4-DiCl-C6H3- H H H O ~I 2 i C3H7 C6H4 90 9 31 4-Cl-C6H4- H H H O NH-3-tert-C4Hg-1~32580 -Table No. Rl R2 R3 R4 X y Fp/nD
32 2,4-DiC1~6H3- H H H O NH-3-tert 4 9 154-155 33 4-Cl-C6H4- H H H O NH-3-CF3~6H4 121-124 34 4-tert-C4H9-C6H4 H H H O NH-3-CF3-C6H4 2,4-DiC1-C6H3~ H ll H O NH-3CF3-C6H4 115-122 36 4-C1-C6H4- H H H O N(CH3)C6H5 oil 37 3-F-C6H4- H H H S N(CH3)C6H5 10 38 4-Cl-C6H4- H H H O N (CH3) -4-Cl-C6H4 125--127 39 2,4-DiCl-C3H3- H H H O N~l-CH2-C6H5 72-75 4-C1-C6H4- H H H O N(CH3)CH2C6H5 1,5652 41 4-Cl-C6H4- H H H O NH-~ 144-146 42 2,4-DiC1-C6H3-- H H H O N 106-108 .. 1/(0 43 4-Cl-C6H4-- H H H O NE~ 152-156 20 44 4-C1-C6H4- H H H O N~ 1, 526 4-Cl-C6H4- H H H O N ~ F 1,530 CH3 Cl 46 4-F-C6H4-- H H H O N~ 102--110 47 2,4-DiCl-C6H3- H H H O N(~H3)C6H5 145-148 48 2,4-DiC1-C6H3- H H H O N-CH2 CH~12 76-77 49 3,5-DiCH3-C6H3- H H H o N(CH3)C6H5 101-103 4-tert-C4HgH4- H H H O NH-4F-C6H4 123-125 :113Z5~30 Table No. Rl R2 R3 R X Y Fp/~
, _ .
51 2,4-DiCl-C6H3- H H H O N-2,4-DiCl-C6H3 109-111 52 4-Cl-C6H4- H H H O N(CH2CH2CN) 2 1,529 53 ~ H H H O NH-C6H5 120-123 54 4-Cl-C H4- H H H O N-C6H5 74-76 4-Cl-C6H4- H H H O N(CH2-CH=CH2) 2 1,5280 56 ~ H H H O NH-C6H5 110-113 57 2,4,5-TriCl-C6H2- H H H O NHC (CH3) 2C=CH 176-185 59 ~ H H H O ~ 105-111 ~) .
2,4,5-TriCl-C6H2 H H H O NHCH~ - ~ 168-172 20 61 ~ H H H O NH-C6H5 158-163 62 ~ H H H O ( 3)C6H5 69-74 63 2,4-DiCl-C6H3 H H H NH-CH-C6H5 102-103 64 2,4-DiCl-C6H3- H H H O NH-CH2 - 2Cl - C6H~ 102-105 3-tert-C4Hg-C6H3- H H H O NHC6H5 103-106 66 ~ H H H O NH-4Cl-C6H4 120-125 67 ~ H H H O NHCH2C6H5 71-76 113ZSt30 Table No. Rl R2 R3 R4 X Y Ep/~0 _ 68 ~_ H H H O N (CH2-CH=CH2) 2 49~54 69 (~_ H H H O NH--3CF3~6H4120-12S
, "
,, 1~ 3;~0 The manufacture of the metal complexes is illustrated by the following non limitative example.
17 parts of 2-(4'-phenylphenoxy)-2-(1',2',4'-triazol-l'-yl)-acetic acid-4-fluoroanilide was dissolved in 200 parts of ethanol at 35C; a solution of14 parts of copper (II) chloride in 100 parts of ethanol was then added.
The mixture was stirred for 2 hours and cooled to 15C, and the precipitate filtered.
There was obtained 13 parts of bis-~2-(~'-phenyl-phenoxy)-2-(1',2',4'-triazol-1'-yl)-acetic acid-4-fluoro-anilid~ -copper (II) chloride of melting point 176 to 180C.
The other compounds can be converted into their metal complexes in analogous manner.
The compounds according to the invention and their salts and metal complexes have an excellent action on a broad spectrum of fungi, expecially plant-pathogenic fungi, particul-arly from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and may be used as foliar and soil fungicides.
The fungicides according-to the invention are of particular interest for combatting numerous fungi in various crop plants or their seed.
By " crop plants" , we mean in the connection in particular wheat, rye, barley, oats, rice, Indian corn, cotton soybeans, coffee, sugarcane, fruit and ornamentals in horticulture, and vegetables such as cucumbers, beans and Cucurbitaceae.
The new compounds are especially su~itable for combatting the following diseases: Erysiphe graminis in cereals, Erysiphe cichoriacearum in Cucurbitaceae, Posdosphaera leucotricha in apples, Uncinula necator in grapes, ErYsiphe polygoni in beans, Sphaerotheca pannosa in roses, Puccinia species in cereals, Rhizoctonia solani in cotton, ~3Z58() Helminthosphorium species in cerials, Ustilago species in cereals and sugarcane, Rhynchosporium secale in cereals, and Venturia inaequalis (apple scab).
The compounds are applied by spraying or dusting the plants with the activc inc3redients or treating their sced with them. They may be applied before or after infection of the plants or seed by the fungi.
The compounds of the invention can be converted into the conventional formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends entirely on the purpose for which the agents are being used; it should, however, ensure a fine and uniform distribution of the active ingredient. The formul-ations are prepared in the conventional manner, for example by diluting the active ingredient with solvent and/or carriers, with or without the addition of emulsifiers and dispersants and, where water is used as the diluent, with or without organic auxiliary solvents. Suitable auxiliaries are, essentially, solvents for example aromatics, e.g., xylene and benzene, chloroaromatics, e.g. chlorobenzene, paraffins, e.g. petroleum fractions, alcohols, e.g. methanol and butanol, amines, e.g., ethanolamine, dimethylformamide, and water; solid carriers, for example natural rock powders, e.g. kaolin, alumina, talc and chalk, and synthetic rock powders, e.g. highly disperse silica and silicates; emulsifiers, for example non~ionic and anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates, and dispersants, for example lignin, sulfite waste liquors and methylcellulose.
The agents in general contain from 0.1 to 95%
by weight of active ingredient, preferably from 0.5 to 90~.
The application rates depend on the type of effect desired, and are from 0.01 to 3, but preferably from 0.01 to ~3Z580 l, kg of active ingredient per hectare.
The agents, and the ready-to-use preparations obtained therefrom, e.g., solutions, emulsions, suspensions, powders, dust, pastes or granules, are applied in conventional manner, e.g. by spraying, atomizing, dusting, broadcasting, dressing seed, or watering.
Examples of such formulations are as follows.
I. 90 parts by weight of the compound of Example 6 is mixed with 10 parts by weight of N-methyl-~-pyrrolidone. A
mixture is obtained which is suitable for application in the form of very fine drops.-II. 20 parts by weight of the compound of Example 32 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 with 1 mole of oleic acid-N-monoethanolamide,
2-Br-4-Cl-C H3- H H H O OC (CH3) 2C-CH
6 2,4-DiCl-C6ll3- H H H O OC (CH3) 2C~CH 60-63 7 2,4-DiCl-C6H3- H H H O NHC(CH3)2C--CH 112-115 8 2,4-DiCH3C6H3-- H H H O NHC (CH3) 2C--CH
4-Cl-C6H4- H H H O NHC (CH3) 2C-CH 74-82 3-F-C6H4- H H H O NHC (CH3) 2CH--CH2 11 2,4-DiCl-C6H3- H H H O NHC6H5 92--95 12 2,4-DiCH3-C6H3 H H H O NHC6H5 114-116 13 2,4-DiCl-C6H3- H H H O NH-2-F-C6H4 99-101 14 4-Br-C6H4- H H H O NH-2-F-C6H4 4-Cl-C6H4 H H H- O NH-3-F-C6H4 102-105 16 2,4-DiCl-C6H3-- H H H O NH--3-F-C6H4 80-84 18 4-Cl-C6H4- H H H O NH-4-C6H4 138-142 20- 19 2,4,5-TriCl-C6H2-H H H o NH-4-F-C6H4 136-140 2,9-DiCl-C6H3- 1l ll H o N~l-4--F-C6H4139-142 21 4-Cl-C6H4-- H H H O NH-4-Cl-C6H4 146-149 22 2-Br-4Cl-C6H3- H H H O NH-4-Cl-C6H4 23 3-F-C6H4- H H H O NH-4-Cl-C6H4 24 2,4-DiCl-C6H3- H H H O NH-2,4-DiF-C6H3122-124 3,4-DiCl--C6H3-- H H H O NH--3,4-DiF-C6H3 26 2,4 DiCH3 C6H3 H H o NH-3Cl-4F-C6H3 27 2,4--DiCl--C6H3-- H H H O NH-3,5-DiCl-C6EI3 170-173 28 3 CHF2 CF2 C6H4 H H H O NH-3,5--DiCl-C6H3 2,4-DiCl-C6H3- H H H O ~I 2 i C3H7 C6H4 90 9 31 4-Cl-C6H4- H H H O NH-3-tert-C4Hg-1~32580 -Table No. Rl R2 R3 R4 X y Fp/nD
32 2,4-DiC1~6H3- H H H O NH-3-tert 4 9 154-155 33 4-Cl-C6H4- H H H O NH-3-CF3~6H4 121-124 34 4-tert-C4H9-C6H4 H H H O NH-3-CF3-C6H4 2,4-DiC1-C6H3~ H ll H O NH-3CF3-C6H4 115-122 36 4-C1-C6H4- H H H O N(CH3)C6H5 oil 37 3-F-C6H4- H H H S N(CH3)C6H5 10 38 4-Cl-C6H4- H H H O N (CH3) -4-Cl-C6H4 125--127 39 2,4-DiCl-C3H3- H H H O N~l-CH2-C6H5 72-75 4-C1-C6H4- H H H O N(CH3)CH2C6H5 1,5652 41 4-Cl-C6H4- H H H O NH-~ 144-146 42 2,4-DiC1-C6H3-- H H H O N 106-108 .. 1/(0 43 4-Cl-C6H4-- H H H O NE~ 152-156 20 44 4-C1-C6H4- H H H O N~ 1, 526 4-Cl-C6H4- H H H O N ~ F 1,530 CH3 Cl 46 4-F-C6H4-- H H H O N~ 102--110 47 2,4-DiCl-C6H3- H H H O N(~H3)C6H5 145-148 48 2,4-DiC1-C6H3- H H H O N-CH2 CH~12 76-77 49 3,5-DiCH3-C6H3- H H H o N(CH3)C6H5 101-103 4-tert-C4HgH4- H H H O NH-4F-C6H4 123-125 :113Z5~30 Table No. Rl R2 R3 R X Y Fp/~
, _ .
51 2,4-DiCl-C6H3- H H H O N-2,4-DiCl-C6H3 109-111 52 4-Cl-C6H4- H H H O N(CH2CH2CN) 2 1,529 53 ~ H H H O NH-C6H5 120-123 54 4-Cl-C H4- H H H O N-C6H5 74-76 4-Cl-C6H4- H H H O N(CH2-CH=CH2) 2 1,5280 56 ~ H H H O NH-C6H5 110-113 57 2,4,5-TriCl-C6H2- H H H O NHC (CH3) 2C=CH 176-185 59 ~ H H H O ~ 105-111 ~) .
2,4,5-TriCl-C6H2 H H H O NHCH~ - ~ 168-172 20 61 ~ H H H O NH-C6H5 158-163 62 ~ H H H O ( 3)C6H5 69-74 63 2,4-DiCl-C6H3 H H H NH-CH-C6H5 102-103 64 2,4-DiCl-C6H3- H H H O NH-CH2 - 2Cl - C6H~ 102-105 3-tert-C4Hg-C6H3- H H H O NHC6H5 103-106 66 ~ H H H O NH-4Cl-C6H4 120-125 67 ~ H H H O NHCH2C6H5 71-76 113ZSt30 Table No. Rl R2 R3 R4 X Y Ep/~0 _ 68 ~_ H H H O N (CH2-CH=CH2) 2 49~54 69 (~_ H H H O NH--3CF3~6H4120-12S
, "
,, 1~ 3;~0 The manufacture of the metal complexes is illustrated by the following non limitative example.
17 parts of 2-(4'-phenylphenoxy)-2-(1',2',4'-triazol-l'-yl)-acetic acid-4-fluoroanilide was dissolved in 200 parts of ethanol at 35C; a solution of14 parts of copper (II) chloride in 100 parts of ethanol was then added.
The mixture was stirred for 2 hours and cooled to 15C, and the precipitate filtered.
There was obtained 13 parts of bis-~2-(~'-phenyl-phenoxy)-2-(1',2',4'-triazol-1'-yl)-acetic acid-4-fluoro-anilid~ -copper (II) chloride of melting point 176 to 180C.
The other compounds can be converted into their metal complexes in analogous manner.
The compounds according to the invention and their salts and metal complexes have an excellent action on a broad spectrum of fungi, expecially plant-pathogenic fungi, particul-arly from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and may be used as foliar and soil fungicides.
The fungicides according-to the invention are of particular interest for combatting numerous fungi in various crop plants or their seed.
By " crop plants" , we mean in the connection in particular wheat, rye, barley, oats, rice, Indian corn, cotton soybeans, coffee, sugarcane, fruit and ornamentals in horticulture, and vegetables such as cucumbers, beans and Cucurbitaceae.
The new compounds are especially su~itable for combatting the following diseases: Erysiphe graminis in cereals, Erysiphe cichoriacearum in Cucurbitaceae, Posdosphaera leucotricha in apples, Uncinula necator in grapes, ErYsiphe polygoni in beans, Sphaerotheca pannosa in roses, Puccinia species in cereals, Rhizoctonia solani in cotton, ~3Z58() Helminthosphorium species in cerials, Ustilago species in cereals and sugarcane, Rhynchosporium secale in cereals, and Venturia inaequalis (apple scab).
The compounds are applied by spraying or dusting the plants with the activc inc3redients or treating their sced with them. They may be applied before or after infection of the plants or seed by the fungi.
The compounds of the invention can be converted into the conventional formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends entirely on the purpose for which the agents are being used; it should, however, ensure a fine and uniform distribution of the active ingredient. The formul-ations are prepared in the conventional manner, for example by diluting the active ingredient with solvent and/or carriers, with or without the addition of emulsifiers and dispersants and, where water is used as the diluent, with or without organic auxiliary solvents. Suitable auxiliaries are, essentially, solvents for example aromatics, e.g., xylene and benzene, chloroaromatics, e.g. chlorobenzene, paraffins, e.g. petroleum fractions, alcohols, e.g. methanol and butanol, amines, e.g., ethanolamine, dimethylformamide, and water; solid carriers, for example natural rock powders, e.g. kaolin, alumina, talc and chalk, and synthetic rock powders, e.g. highly disperse silica and silicates; emulsifiers, for example non~ionic and anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates, and dispersants, for example lignin, sulfite waste liquors and methylcellulose.
The agents in general contain from 0.1 to 95%
by weight of active ingredient, preferably from 0.5 to 90~.
The application rates depend on the type of effect desired, and are from 0.01 to 3, but preferably from 0.01 to ~3Z580 l, kg of active ingredient per hectare.
The agents, and the ready-to-use preparations obtained therefrom, e.g., solutions, emulsions, suspensions, powders, dust, pastes or granules, are applied in conventional manner, e.g. by spraying, atomizing, dusting, broadcasting, dressing seed, or watering.
Examples of such formulations are as follows.
I. 90 parts by weight of the compound of Example 6 is mixed with 10 parts by weight of N-methyl-~-pyrrolidone. A
mixture is obtained which is suitable for application in the form of very fine drops.-II. 20 parts by weight of the compound of Example 32 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 with 1 mole of oleic acid-N-monoethanolamide,
5 parts by weight of the calcium salts of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained con-taining 0.02~ by weight of the active ingredient.
III. 20 parts by weight of the compound of Example 17 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02~ by weight of the active ingredient.
IV 20 parts by weight of compound of Example 56 is dissolved in a mixture consisting of 25 parts by weight of 58~;) cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with l mole of castor oil. By pouring the solution into lO0,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
V. 20 parts by weight of the compound of Example 58 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distrib-uting the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1~ by weight of the active ingredient.
VI. 3 parts by weight of the compound of Example 30 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 the compound of Example 2 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 the compound of Example 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-ureà-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in lO0,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active 113;2~8~
ingredient.
IX. 20 parts of the compound of Example 2 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A
stable oily dispersion is obtained.
The above ready-to-use preparations may contain other active ingredients together with those according to the invention, e.g., herbicides, insecticides, growth regulators and other fungicides or may be mixed with fertilizers and applied together with these. When the active ingredients are mixed with other fungicides, the fungicidal spectrum of action is in many cases broadened.
The list of fungicides given below, with which the compounds according to the invention can be combined, is intended to illustrate the possible combinations, but the invention is in no way limited to these.
Examples of fungicides which may be combined with the compounds according to the invention are as follows.
~ ithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate zinc dimethyldithiocarbamate manganese ethylenebisdithiocarbamate zinc ethylenebisthiocarbamate tetramethylthiuram disulfide manganese-zinc ethylenediamine-bisdithiocarbamate zinc-(N,N'-propylene-bisdithiocarbamate) ammonia complex of zinc-(N,N'-ethylene)-bisdithiocarbamate and N,N'-polyethylene-bis-(thiocarbamoyl)-disulfide ammonia complex of zinc-(N,N'-propylene-bisdithiocarbamate) ll~Z580 and N,N'-polypropylene-bis-(thiocarbamoyl)-disulfide nitro derivatives, such as dinitro-(l-methylheptyl J -phenylcrotonate 2-sec-butyl-4,6-dinitrophenyl-3,5-dimethylacrylate 2-sec-butyl-4,6-dinitrophenylisopropylcarbonate heterocyclic structures, such as N-trichloromethylthiotetrahydrophthalimide N-trichloromethylthiophthalimide 2-heptadecyl-2-imidazoline acetate 2,4-dichloro-6-(o-chloroanilino)-s-triazine 0,0-diethylphthalimidophosphorothionate 5-amino-1-rbis-(dimethylamino)-phosphinyl~-3-phenyl-1,2,4-triazole 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole 2,3-dicyano-1,4-dithiaanthraquinone 2-thio-1,3-dithio-(4,5b)-quinoxaline methyl l-(butylcarbamoyl)-2-benzimidazole carbamate ~2-methoxycarbonylaminobenzimidazole 2-thiocyanomethylthiobenzothiazole 4-(2-chlorophenyl~ydrazono)-3-methyl-5-isooxazolone pyridine-2-thiol-1-oxide 8-hydroxyquinoline and its copper salt 2,3-dihydro-5-carboxanilido-6-methyl-1,4,-oxathin-4,4-dioxide 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 2-~furyl-(2 U-benzimidazole piperazine-1,4-diyl-biS~1-(2,2,2-trichloroethyl)-formamide~
2-Lthiazolyl-(4)~-benzimidazole 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine bis-(p-chlorophenyl)-3-pyridinemethanol 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene 1,2-bis-(3-methoxycarbonyl)-2-thioureido)-benzene - lg -1~32580 and various fungicides, such as dodecylguanidine acetate 3-l2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl~7-glutarimide hexachlorobenzene N-dichlorofluoromethylthio-N,N'-dimet]lyl-N-phenylsulEurlc acld diamide 2,5-dimethyl-furan-3-carboxylic acid anilide 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide 2-methyl-benzoic acid anilide 2-iodo-benzoic acid anilide 1-(3,4-dichloroanilino)-1-formy~amino-2,2,2-trichloroethane 2,6-dimethyl-N-tridecyl-morpholine and its salts 2,6-dimethyl-N-cyclododecyl-morpholine and its salts DL-methyl-N-(2,6-dimethylphenyl)-N-furoyl-(2)-alaninate DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl-alanine methyl ester diisopropyl 5-nitroisophthalate 1-(1',2',4'-triazolyl 1')-~1-(4'-chlorophenoxy)~-3,3-dimethyl-butan-2-one 1-(1',2',4'-triazolyl-1')-~1-(4'-chlorophenoxy)_7-3,3-dimethyl-butane-2-ol N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone and N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolylurea.
The following examples demonstrate the biological action of the new compounds. The agent used for comparison purposes was t-butyl 2-phenyl-2-(1',2',4'-triazol-1'-yl)-acetate (N) disclosed in German Laid-Open Application DE-OS 2,638,470.
EXAMPLE A
Leaves of pot-grown wheat seedlings of the " Caribo"
variety are sprayed with aqueous emulsions consisting of 80 ~3~,58~
(by weight) of active ingredient and 20% of emulsifier, and dusted, 2 days after the sprayed-on layer has dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants are then placed in a greenhouse at 18 to 24C. The extent of mildew spread is determined after 10 days.
113;~580 Compound from Leaf attack after spraying with liquor Example No. containing active ingredient in amounts of 0.025~ O.Oi2% 0.006 61 ~ 0 0 : 1~3'~580 Compound from Leaf attack after spraying with liquor Example No. containing active ingredient in amounts of 0.025 0.012% 0.006%
66 0 ~ 2 Control (untreated) 5 0 = no fungus growth, graduated down to 5 = leaf surface totally covered with fungus EXAMPLE B
Leaves of wheat plants grown in pots are artificially infected with spores of Puccinia recondita, and placed for 48 hours in a steam-saturated chamber at 20 to 25C. The plants are then sprayed with aqueous liquor containing, as a solution or emulsion in the water, a mixture of 80% of the compound to be investigated and 20% of sodium ligninsulfonate.
The plants are then set up in the greenhouse at from 20 to .
22C and a relative humidity of 75 to 80%. The e~tent of fungus spread is assessed after 10 days.
Compound from Leaf attack after spraying with liquor con-Example No. taining active ingr~dient in amounts of 0.025% 0.01~% 0.006%
Control (untreated) 5 0 = no fungus growth, graduated down to 5 = leaf surface totally covered with fungus~
III. 20 parts by weight of the compound of Example 17 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02~ by weight of the active ingredient.
IV 20 parts by weight of compound of Example 56 is dissolved in a mixture consisting of 25 parts by weight of 58~;) cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with l mole of castor oil. By pouring the solution into lO0,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
V. 20 parts by weight of the compound of Example 58 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distrib-uting the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1~ by weight of the active ingredient.
VI. 3 parts by weight of the compound of Example 30 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 the compound of Example 2 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 the compound of Example 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-ureà-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in lO0,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active 113;2~8~
ingredient.
IX. 20 parts of the compound of Example 2 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A
stable oily dispersion is obtained.
The above ready-to-use preparations may contain other active ingredients together with those according to the invention, e.g., herbicides, insecticides, growth regulators and other fungicides or may be mixed with fertilizers and applied together with these. When the active ingredients are mixed with other fungicides, the fungicidal spectrum of action is in many cases broadened.
The list of fungicides given below, with which the compounds according to the invention can be combined, is intended to illustrate the possible combinations, but the invention is in no way limited to these.
Examples of fungicides which may be combined with the compounds according to the invention are as follows.
~ ithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate zinc dimethyldithiocarbamate manganese ethylenebisdithiocarbamate zinc ethylenebisthiocarbamate tetramethylthiuram disulfide manganese-zinc ethylenediamine-bisdithiocarbamate zinc-(N,N'-propylene-bisdithiocarbamate) ammonia complex of zinc-(N,N'-ethylene)-bisdithiocarbamate and N,N'-polyethylene-bis-(thiocarbamoyl)-disulfide ammonia complex of zinc-(N,N'-propylene-bisdithiocarbamate) ll~Z580 and N,N'-polypropylene-bis-(thiocarbamoyl)-disulfide nitro derivatives, such as dinitro-(l-methylheptyl J -phenylcrotonate 2-sec-butyl-4,6-dinitrophenyl-3,5-dimethylacrylate 2-sec-butyl-4,6-dinitrophenylisopropylcarbonate heterocyclic structures, such as N-trichloromethylthiotetrahydrophthalimide N-trichloromethylthiophthalimide 2-heptadecyl-2-imidazoline acetate 2,4-dichloro-6-(o-chloroanilino)-s-triazine 0,0-diethylphthalimidophosphorothionate 5-amino-1-rbis-(dimethylamino)-phosphinyl~-3-phenyl-1,2,4-triazole 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole 2,3-dicyano-1,4-dithiaanthraquinone 2-thio-1,3-dithio-(4,5b)-quinoxaline methyl l-(butylcarbamoyl)-2-benzimidazole carbamate ~2-methoxycarbonylaminobenzimidazole 2-thiocyanomethylthiobenzothiazole 4-(2-chlorophenyl~ydrazono)-3-methyl-5-isooxazolone pyridine-2-thiol-1-oxide 8-hydroxyquinoline and its copper salt 2,3-dihydro-5-carboxanilido-6-methyl-1,4,-oxathin-4,4-dioxide 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 2-~furyl-(2 U-benzimidazole piperazine-1,4-diyl-biS~1-(2,2,2-trichloroethyl)-formamide~
2-Lthiazolyl-(4)~-benzimidazole 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine bis-(p-chlorophenyl)-3-pyridinemethanol 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene 1,2-bis-(3-methoxycarbonyl)-2-thioureido)-benzene - lg -1~32580 and various fungicides, such as dodecylguanidine acetate 3-l2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl~7-glutarimide hexachlorobenzene N-dichlorofluoromethylthio-N,N'-dimet]lyl-N-phenylsulEurlc acld diamide 2,5-dimethyl-furan-3-carboxylic acid anilide 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide 2-methyl-benzoic acid anilide 2-iodo-benzoic acid anilide 1-(3,4-dichloroanilino)-1-formy~amino-2,2,2-trichloroethane 2,6-dimethyl-N-tridecyl-morpholine and its salts 2,6-dimethyl-N-cyclododecyl-morpholine and its salts DL-methyl-N-(2,6-dimethylphenyl)-N-furoyl-(2)-alaninate DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl-alanine methyl ester diisopropyl 5-nitroisophthalate 1-(1',2',4'-triazolyl 1')-~1-(4'-chlorophenoxy)~-3,3-dimethyl-butan-2-one 1-(1',2',4'-triazolyl-1')-~1-(4'-chlorophenoxy)_7-3,3-dimethyl-butane-2-ol N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone and N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolylurea.
The following examples demonstrate the biological action of the new compounds. The agent used for comparison purposes was t-butyl 2-phenyl-2-(1',2',4'-triazol-1'-yl)-acetate (N) disclosed in German Laid-Open Application DE-OS 2,638,470.
EXAMPLE A
Leaves of pot-grown wheat seedlings of the " Caribo"
variety are sprayed with aqueous emulsions consisting of 80 ~3~,58~
(by weight) of active ingredient and 20% of emulsifier, and dusted, 2 days after the sprayed-on layer has dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants are then placed in a greenhouse at 18 to 24C. The extent of mildew spread is determined after 10 days.
113;~580 Compound from Leaf attack after spraying with liquor Example No. containing active ingredient in amounts of 0.025~ O.Oi2% 0.006 61 ~ 0 0 : 1~3'~580 Compound from Leaf attack after spraying with liquor Example No. containing active ingredient in amounts of 0.025 0.012% 0.006%
66 0 ~ 2 Control (untreated) 5 0 = no fungus growth, graduated down to 5 = leaf surface totally covered with fungus EXAMPLE B
Leaves of wheat plants grown in pots are artificially infected with spores of Puccinia recondita, and placed for 48 hours in a steam-saturated chamber at 20 to 25C. The plants are then sprayed with aqueous liquor containing, as a solution or emulsion in the water, a mixture of 80% of the compound to be investigated and 20% of sodium ligninsulfonate.
The plants are then set up in the greenhouse at from 20 to .
22C and a relative humidity of 75 to 80%. The e~tent of fungus spread is assessed after 10 days.
Compound from Leaf attack after spraying with liquor con-Example No. taining active ingr~dient in amounts of 0.025% 0.01~% 0.006%
Control (untreated) 5 0 = no fungus growth, graduated down to 5 = leaf surface totally covered with fungus~
Claims (3)
1. A 1,2,4-Triazol-1-yl compound of the formula I, where R1 denotes phenyl substituted by cyclohexyl, phenyl, 1 to 3 halogen atoms or alkyl of 1 to 4 carbon atoms, and Y denotes OR2 or R2 denoting alkynyl of 3 to 15 carbon atoms, R3 denoting hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 15 carbon atoms, phenyl or cyanoethyl, and R4 denoting phenyl, benzyl or phenyl or benzyl substituted by 1 or 2 halogen atoms, trifluoromethyl or alkyl of 1 to 4 carbon atoms, or alkenyl or alkynyl of 3 to 15 carbon atoms, phenylethyl, naphthyl or cyanoethyl, and their plant-compatible salts and metal complexes.
2. A compound selected from the group consisting of 2-(1',2',4'-triazol-1'-yl)-2-(4'-chlorophenoxy)-acetic acid anilide, 2-(1',2',4'-triazol-1'-yl)-2-(4'-phenylphenoxy)-acetic acid-p- fluoroanilide, and 2-(1',2',4'-triazol-1'-yl)-2-(4'-chlorophenoxy)-acetic acid-.alpha.-naphthylamide.
3. A process for manufacturing a compound as claimed in claim 1, wherein a) a compound of the formula II, where R2 and Y have the above meanings and L1 and L2 are identical or different and are nucleophilically displaceable leaving groups, is reacted with a compound of the formula R1OH III, where R1 has the above meanings, or a salt thereof, and with 1,2,4-triazole, or a salt thereof, in the presence or absence of a solvent or diluent and/or of an inorganic or organic base and in the presence or absence of a reaction accelerator at from 0° to 180°C, or b) a compound of the formula IV, where R1 has the above meaning and M denotes hydrogen, one equivalent of a metal cation or a substituted or unsubstituted ammonium ion, is reacted with a compound of the formula HY V, where Y has the above meanings, after or with simultaneous addition of reagents suitable for derivatizing acids, in the presence or absence of a solvent or diluent and/or of an inorganic or organic base and in the presence or absence of a reaction accelerator at from -20° to +180°C, or c) a compound of the formula V is reacted with a compound of the formula VI, where Y has the above meanings and L3 is a nucleophilically displaceable leaving group, in the presence or absence of a solvent or diluent and/or an acid binder and in the presence or absence of a reaction accelerator at from -20° to +180°C, or d) a compound of the formula VII, where R1, Y and L2 have the above meanings, is reacted with 1,2,4-triazole in the presence or absence of a solvent or diluent and/or an inorganic or organic base and in the presence or absence of a reaction accelerator at from -20° to +180°C
and, if desired, the compounds obtained according to a) to d) are converted into salts and metal complexes tolerated by plants.
and, if desired, the compounds obtained according to a) to d) are converted into salts and metal complexes tolerated by plants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782846127 DE2846127A1 (en) | 1978-10-23 | 1978-10-23 | 1,2,4-TRIAZOL-1-YL COMPOUNDS, THEIR PRODUCTION AND USE AS FUNGICIDES |
| DEP2846127.0 | 1978-10-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1132580A true CA1132580A (en) | 1982-09-28 |
Family
ID=6052910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA338,144A Expired CA1132580A (en) | 1978-10-23 | 1979-10-22 | 1,2,4-triazol-1-yl compounds, their manufacture, and use thereof as fungicides |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0010298B1 (en) |
| JP (1) | JPS5557573A (en) |
| AT (1) | ATE470T1 (en) |
| CA (1) | CA1132580A (en) |
| CS (1) | CS221276B2 (en) |
| DD (1) | DD146686A5 (en) |
| DE (2) | DE2846127A1 (en) |
| DK (1) | DK444379A (en) |
| HU (1) | HU183082B (en) |
| IE (1) | IE48969B1 (en) |
| IL (1) | IL58506A (en) |
| PL (1) | PL118865B2 (en) |
| SU (1) | SU1055313A3 (en) |
| ZA (1) | ZA795629B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7271130B2 (en) | 2002-11-26 | 2007-09-18 | Syngenta Limited | N-alkynyl-2-(substituted phenoxy) alkylamides and their use as fungicides |
| US7371764B2 (en) | 2002-11-26 | 2008-05-13 | Syngenta Limited | Quinolin-isoquinolin-and quinazolin-oxyalkylamides and their use as fungicides |
| US7420090B2 (en) | 2002-11-26 | 2008-09-02 | Syngenta Limited | Fungicides |
| US7511151B2 (en) | 2002-11-26 | 2009-03-31 | Syngenta Limited | Substituted pyridyloxyalkylamides and their use as fungicides |
| US8067592B2 (en) | 2003-06-04 | 2011-11-29 | Syngenta Limited | N-alkyny-2-(substituted aryloxy) alkylthioamine derivatives as fungicides |
| US8969248B2 (en) | 2010-08-26 | 2015-03-03 | Bayer Intellectual Property Gmbh | 5-iodotriazole derivatives |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3041702A1 (en) * | 1980-11-05 | 1982-06-09 | Basf Ag, 6700 Ludwigshafen | METHOD FOR CONTROLLING UNWANTED PLANT GROWTH WITH 2-ARYLOXY-2-AZOLYL ALKANICARBONIC ACID AMIDES, HERBICIDES CONTAINING THEM, AND METHOD FOR THE PRODUCTION THEREOF |
| CA1179678A (en) * | 1981-03-27 | 1984-12-18 | Elmar Sturm | Antimicrobial triazole derivatives |
| GB2104065B (en) * | 1981-06-04 | 1985-11-06 | Ciba Geigy Ag | Heterocyclyl-substituted mandelic acid compounds and mandelonitriles and their use for combating microorganisms |
| US4515623A (en) * | 1981-10-09 | 1985-05-07 | Basf Aktiengesellschaft | Control of unwanted plant growth with 2-aryloxy-2-azolylalkanecarboxamides |
| DE3216301A1 (en) * | 1982-04-26 | 1983-10-27 | Schering AG, 1000 Berlin und 4709 Bergkamen | 1,2,4-TRIAZOL-1-YL-PROPIONITRILE, METHOD FOR PRODUCING THESE COMPOUNDS AND THE BIOCIDES CONTAINING THEM |
| US4729986A (en) * | 1986-04-24 | 1988-03-08 | E. I. Du Pont De Nemours And Company | Fungicidal triazoles and imidazoles |
| AU2560300A (en) * | 1999-02-20 | 2000-09-04 | Astrazeneca Ab | Acetamido acetonitrile derivatives as inhibitors of cathepsin l and/or cathepsins |
| WO2013182433A1 (en) | 2012-06-05 | 2013-12-12 | Basf Se | A process using grignard reagents |
| CN110746375B (en) * | 2018-07-23 | 2022-11-29 | 南京农业大学 | Acetylphenylhydrazine compound containing thiadiazinethione group, preparation method and application |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912752A (en) * | 1972-01-11 | 1975-10-14 | Bayer Ag | 1-Substituted-1,2,4-triazoles |
| DE2324010C3 (en) * | 1973-05-12 | 1981-10-08 | Bayer Ag, 5090 Leverkusen | 1-Substituted 2-triazolyl-2-phenoxyethanol compounds, process for their preparation and their use for combating fungi |
| DE2406665C3 (en) * | 1974-02-12 | 1978-11-16 | Bayer Ag, 5090 Leverkusen | Process for the preparation of 1,2,4-triazole derivatives |
| DE2535332A1 (en) * | 1975-08-07 | 1977-02-17 | Bayer Ag | FUNGICIDALS |
| DE2552967A1 (en) * | 1975-11-26 | 1977-06-08 | Bayer Ag | FUNGICIDALS |
| DE2713777C3 (en) * | 1977-03-29 | 1979-10-31 | Bayer Ag, 5090 Leverkusen | Process for the preparation of l-azolyl-33-dimethyl-l-phenoxy-butan-2-ones |
-
1978
- 1978-10-23 DE DE19782846127 patent/DE2846127A1/en active Pending
-
1979
- 1979-10-18 SU SU792830605A patent/SU1055313A3/en active
- 1979-10-18 DE DE7979104020T patent/DE2961558D1/en not_active Expired
- 1979-10-18 EP EP79104020A patent/EP0010298B1/en not_active Expired
- 1979-10-18 AT AT79104020T patent/ATE470T1/en not_active IP Right Cessation
- 1979-10-19 DD DD79216344A patent/DD146686A5/en unknown
- 1979-10-19 IL IL58506A patent/IL58506A/en unknown
- 1979-10-20 PL PL1979219083A patent/PL118865B2/en unknown
- 1979-10-22 IE IE2013/79A patent/IE48969B1/en unknown
- 1979-10-22 CS CS797154A patent/CS221276B2/en unknown
- 1979-10-22 DK DK444379A patent/DK444379A/en not_active Application Discontinuation
- 1979-10-22 CA CA338,144A patent/CA1132580A/en not_active Expired
- 1979-10-22 ZA ZA00795629A patent/ZA795629B/en unknown
- 1979-10-22 HU HU79BA3871A patent/HU183082B/en unknown
- 1979-10-23 JP JP13600079A patent/JPS5557573A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7271130B2 (en) | 2002-11-26 | 2007-09-18 | Syngenta Limited | N-alkynyl-2-(substituted phenoxy) alkylamides and their use as fungicides |
| US7371764B2 (en) | 2002-11-26 | 2008-05-13 | Syngenta Limited | Quinolin-isoquinolin-and quinazolin-oxyalkylamides and their use as fungicides |
| US7420090B2 (en) | 2002-11-26 | 2008-09-02 | Syngenta Limited | Fungicides |
| US7511151B2 (en) | 2002-11-26 | 2009-03-31 | Syngenta Limited | Substituted pyridyloxyalkylamides and their use as fungicides |
| US8067592B2 (en) | 2003-06-04 | 2011-11-29 | Syngenta Limited | N-alkyny-2-(substituted aryloxy) alkylthioamine derivatives as fungicides |
| US8969248B2 (en) | 2010-08-26 | 2015-03-03 | Bayer Intellectual Property Gmbh | 5-iodotriazole derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| PL219083A2 (en) | 1980-08-11 |
| IE792013L (en) | 1980-04-23 |
| ATE470T1 (en) | 1981-12-15 |
| DE2961558D1 (en) | 1982-02-04 |
| DE2846127A1 (en) | 1980-04-30 |
| PL118865B2 (en) | 1981-11-30 |
| DD146686A5 (en) | 1981-02-25 |
| EP0010298A1 (en) | 1980-04-30 |
| DK444379A (en) | 1980-04-24 |
| IL58506A (en) | 1984-02-29 |
| IL58506A0 (en) | 1980-01-31 |
| JPS5557573A (en) | 1980-04-28 |
| HU183082B (en) | 1984-04-28 |
| ZA795629B (en) | 1980-11-26 |
| SU1055313A3 (en) | 1983-11-15 |
| EP0010298B1 (en) | 1981-12-09 |
| CS221276B2 (en) | 1983-04-29 |
| IE48969B1 (en) | 1985-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4380546A (en) | Azole compounds, their preparation, their use for crop treatment, and agents for this purpose | |
| CA1271764A (en) | Azolylmethyloxiranes, their preparation and their use as crop protection agents | |
| CA1132580A (en) | 1,2,4-triazol-1-yl compounds, their manufacture, and use thereof as fungicides | |
| US4104399A (en) | Triazole derivatives | |
| US4331674A (en) | Combating fungi with 4-phenoxy-4-(azolyl-1-yl)-butanoic acid derivatives | |
| EP0000752A2 (en) | Alpha-azolylsulphides, sulphoxides and sulphones, their salts and metal complexes, method for their production and fungizides containing them | |
| CA1151181A (en) | .alpha.-AZOLYL-GLYCOL DERIVATIVES, THEIR PREPARATION, FUNGICIDAL AND PLANT GROWTH-REGULATING AGENTS CONTAINING THESE COMPOUNDS, PROCESSES FOR CONTROLLING FUNGI AND REGULATING PLANT GROWTH, AND USE OF THE COMPOUNDS AS FUNGICIDES AND PLANT GROWTH REGULATORS | |
| CA1092128A (en) | Combatting fungi with 1-(azol-1-yl)-4-halo-1-phenoxy- butan-2-ones and -ols | |
| CA1098820A (en) | B-imidazolyl alcohols | |
| US4431812A (en) | Pyridinecarbinols | |
| US4154842A (en) | Fungicidally and bactericidally active 1-azolyl-4-hydroxy-1-phenoxy-butane derivatives | |
| US4456608A (en) | Azole compounds, their preparation, and fungicides which contain these compounds | |
| CA1127154A (en) | .alpha.-AZOLYL-.alpha.-PHENYLACETIC ACID DERIVATIVES | |
| GB1580389A (en) | azolyl ketones and their use as fungicides | |
| CA1274521A (en) | Benzyloxyalkylazoles and fungicides containing these compounds | |
| EP0021327A1 (en) | Beta-triazolyl ethers, their preparation, fungicides containing them, process for combating fungi and for producing fungicides | |
| US4626544A (en) | Azole compounds and fungicides containing these compounds | |
| US4822889A (en) | Triazolyl alcohols, their preparation and their use as fungicides | |
| US4532234A (en) | Neopentyl-phenethyltriazoles, their preparation and fungicides containing these compounds | |
| US4199503A (en) | Phenylazophenyloxytriazolyl compounds | |
| CA1184182A (en) | Fungicidal alpha-azolylglycols | |
| US4496738A (en) | Process for preparing 1,2,4-triazole derivatives | |
| US4330535A (en) | Fungicidal azolyl-silyl-glycol ethers, their use for combating fungi, and agents therefor | |
| US4921870A (en) | Fungicidal novel substituted phenethyl-triazolyl derivatives | |
| EP0071095B1 (en) | Phenylketene acetals, process for their preparation and fungicides containing them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |