CA1213592A - Substituted azolylether-ketones and -carbinols - Google Patents
Substituted azolylether-ketones and -carbinolsInfo
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- CA1213592A CA1213592A CA000435968A CA435968A CA1213592A CA 1213592 A CA1213592 A CA 1213592A CA 000435968 A CA000435968 A CA 000435968A CA 435968 A CA435968 A CA 435968A CA 1213592 A CA1213592 A CA 1213592A
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- 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
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- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- 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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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/185—Saturated compounds containing keto groups bound to acyclic carbon atoms containing —CHO groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/213—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C49/217—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings
- C07C49/223—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings polycyclic
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- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
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- 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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- 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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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/26—Radicals substituted by doubly bound oxygen or sulfur atoms or by two such atoms singly bound to the same carbon atom
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Abstract
Substituted azolylether-ketones and -carbinols ABSTRACT OF THE DISCLOSURE
A substituted azolylether-ketone or -carbinol of the formula in which Ar represents optionally substituted aryl, Az represents 1,2,4-triazol-1-yl, 1,2,4-triazol--4-yl or imidazol-1-yl, B represents the keto group or a CH(OH) grouping and R represents substituted cycloalkyl or the groupings -C(CH3)2-R1, -C(CH3)2-CH2-CH2-R2, -C(CH3)2-(CH2)m-R3 and -C(CH3)2-(CH3)2-(CH2)n-R4 wherein R1 represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl or the aldehyde group and its derivatives.
R2 represents optionally substituted phenoxy, R3 represents optionally substituted phenyl, R4 represents halogen, m represents integers from 1 to 4 and n represents integers from 2 to 4, or an addition product thereof with an acid or metal salt for use in combating fungus.
A substituted azolylether-ketone or -carbinol of the formula in which Ar represents optionally substituted aryl, Az represents 1,2,4-triazol-1-yl, 1,2,4-triazol--4-yl or imidazol-1-yl, B represents the keto group or a CH(OH) grouping and R represents substituted cycloalkyl or the groupings -C(CH3)2-R1, -C(CH3)2-CH2-CH2-R2, -C(CH3)2-(CH2)m-R3 and -C(CH3)2-(CH3)2-(CH2)n-R4 wherein R1 represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl or the aldehyde group and its derivatives.
R2 represents optionally substituted phenoxy, R3 represents optionally substituted phenyl, R4 represents halogen, m represents integers from 1 to 4 and n represents integers from 2 to 4, or an addition product thereof with an acid or metal salt for use in combating fungus.
Description
The present invention relates to new substituted azolylether-ketones and -carbino].s several processes for their preparation and their use as fungicides.
It has already been disclosed that certain substi-tuted l-azolyl-3,3-dimethyl-1-phenoxy-butan-2-ones and -ols in general possess good Eungicidal properties ~see the German Offenlegungsschriften (German Published Specifications) 2,632,603 [LeA 17 2731, 2,632,602 [Le~ 17 274~ . 2,635,666 [LeA 17 324]
and 3,021,551 [LeA 20,356].
However, the action of these compounds is not always completely satisfactory in some fields of use, particularly when low amounts and concentrations are used. The same also applies to some 5-aryloxy-5-azolyl-3,3-dimethylpent-1-en-4-ones and -ols which have not been described hitherto (German DE-OS 31 30 435.4 [LeA 21 186]).
New substituted azolylether-ketones and -carbinols of -the formula Ar - O - fH - B - R (I) . Aæ
i.n which
It has already been disclosed that certain substi-tuted l-azolyl-3,3-dimethyl-1-phenoxy-butan-2-ones and -ols in general possess good Eungicidal properties ~see the German Offenlegungsschriften (German Published Specifications) 2,632,603 [LeA 17 2731, 2,632,602 [Le~ 17 274~ . 2,635,666 [LeA 17 324]
and 3,021,551 [LeA 20,356].
However, the action of these compounds is not always completely satisfactory in some fields of use, particularly when low amounts and concentrations are used. The same also applies to some 5-aryloxy-5-azolyl-3,3-dimethylpent-1-en-4-ones and -ols which have not been described hitherto (German DE-OS 31 30 435.4 [LeA 21 186]).
New substituted azolylether-ketones and -carbinols of -the formula Ar - O - fH - B - R (I) . Aæ
i.n which
2~ ~r represents phenyl which is optionally monosubstit~
u-ted or polysubstituted by identical or different substituents sel~cted from: Halogen, alkyl having 1 to 4 carbon atoms, alkoxy and alkylthio each having 1 or 2 carbon atoms; halogenoalkyl, halogenoalkoxy and halogenoalkyl-thio each having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, Le A 21 911 -'J, ~' ~
- la ~
alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl moiety, nitro, cyano or phenyl or phenoxy which is optionally substituted by halogen and/or alkyl having 1 or 2 carbon atoms, or the aldoxime or ketoxime radical or an ether thereof;
Az represents 1,2,4-triazol-1-yl, 1,2,~,-triazol-4-yl or imldazol-l-yl, B represents a keto group or a CH(OH) grouping and R represents substituted cycloalkyl or a grouping of ormula ~(CH3 2-R , -C:(CH3)2-CH2-CH2-R2, -C(CH3)2-(CH2) -R3 or -C(CH3)2~(CH3)2~(CH2)n R , wherein Rl represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl, or the aldehyde group or an oxime, oxime-ether or dialkyl acetal ther~of, R2 represents phenoxy which is optionally monosub-stituted or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case o~ Ar;
R3 represents phenyl which is optionally monosubstituted or polysubstituted by identical or different substituents select-ed from the phenyl substituents mentioned above in the case of Ar;
R4 representshalogen, m represents integers from 1 to 4 and n represents integers from 2 to 4, 5~` Le A 21 911 .~ l3~
or a non-phytotoxic addition product thereof with a hydrohalic acid, phosphoric acid, nitric acid, sulphuric acld, a monofunct-ional or bifunctional carboxylic acid, a hydroxycarboxylic acid or a sulphonic acid salt of copper, zinc, manganese, magnesium, iron or nickel or an anion of a salt derived from a hydrohalic acid, phosphoric acid, nitric acid or sulphuric acid Those compounds of the formula (I) in which B represents the CM(O~) group possess two asymmetric carbon atoms; they can therefore occur in the form of the two geometric isomers (erythro and threo form), which can be obtained in differen-t proportions.
In both cases, they occur as optical isomers. Compounds of the formula (I) in which R represents substituted cycloalkyl can additionally possess an asymmetric carbon atom, with the result that there may be further geometric isomers. All isomers are clai.med according to the invention.
Furthermore, it has been found that the new substituted axolylether-ketones and -carbinols of the formula (I) are obtained if a) halogenoether-ketones of the formula 2~
(II) Ar - O - fH - CO - R (II ) Hal in which Ar and R have the meaning given above and Hal represents chlorine or bromine, Le A 21 911 .~
~ ~3~
- 2a -are reacted with 1,2,4~triazole or imidazole in the presence of an acid-bindiny agent and, if appropriate, in the presence of a diluent; or b) dihalogenoketones of the formula (Hal)2 CH - CO - R (III) in which Hal and R have the meaning given above, are reacted with 1,2,4-triazole or imidazole and with a Le A 21 911 .~
phenol of the formula Ar- OH (IV) ;n wh;ch Ar has the meaning given above, ;n the presence of an acid-b;nding agent and in the pre-sence of a diluent; or, if appropriate, c) the a70lylether-ketones obtained by process (a) or (b), of the formula Ar - O - CH - CO - R
I (Ia) Az 1~ in which Ar, Az and R gave the meaning given above, are reduced in a customary manner by known methods.
The result;ng compounds of the formula (I~ can, if desired, then be subjected to an addition reaction with an acid or a metal salt.
The new substituted azolylether-ketones and -carbinols of the formula (I) possess powerful fungicidal properties. In this respect, the compounds according to the invention surprisingly exhibit better fungicidal activity than the substituted 1-azolyl-3,3-dimethyl-1-phenoxy-butan-2~ones and -ols which are known from the prior art and are similar compounds chemically and in terms of their action. The substances according to the invention thus represent an enrichment of the art.
2~ Formula (I) gives a general definition of the substi~uted azolylether-ketones and -carbinols according to the ;nvention. In this formula, Ar preferably represents phenyl which is mono-substituted or polysubstituted by identical or 3û different substituents, the following preferably being mentioned as substituents: halogen, alkyl having 1 to 4 carbon atoms, alkoxy and alkylthio, each having 1 or 2 carbon atoms; halogenoalkyl, Le A 21 911 ~.3~
halogenoalkoxy and halogenoalkylthio, each having 1 or 2 carbon atoms and 1 to 5 identical or diffexent halogen atoms, such as fluorine atoms and chlorine atoms, alkoxy-carbonyl having 1 to 4 carbon atoms in the alkyl part, nitro, cyano or phenoxy or phenyl which is optionally substituted by halogen and/or alkyl having 1 or 2 carbon atoms, and represents the aldoxime or ketoxime radical and their ethers;
R preferabl.y represents cycloalkyl which has 3 to 7 carbon atoms and is optionally monosubstituted or poly-substituted by identical or different substituents, the followiny pre:Eerably being mentioned as substituents:
halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms, phenyl and chlorophenyl: and furthermore the groupings -C(CH3)2-R , -C(CH3)2-CH2CH2-R
_c(cH3)2_(cH2)rn-R and -C(CH3)2-(CH2)n-R ;
Rl preferably represents straight-chain or branched alkyl having 2 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms and alkinyl having 2 to 4 carbon atoms, and also the aldehyde group and its derivatives, such as oximes, oxirne-ethers and acetals, such as, for example, dialkyl acetals having 1 to 4 carbon atoms in each alkyl part, or represents op-tionally substituted dioxanes and dioxolanes;
R preferably represents phenoxy which is optionally monosubstituted or polysubstituted by identical or different substituents, preferred substituents being the phenyl substituents already mentioned in the case of Ar;
- 4a -R3 preferably represents phenyl which is monosubstituted or polysubstituted by ldentical or different substitu-ents, preferred substituents bei.ng the phenyl substitu-ents already mentioned '~ ?~
in the case of Ar;
~4 preferably represents fluorine, chlorine or bromine; and ~z, e, m and n preferably have the meanings given in the definition of the inventionO
Part;cularly preferred compounds of the formula (I) are those in which Ar represents phenyl which is optionally mono-substituted to trisubstituted by identicaL or different substituents~ the following being men-tioned as substituents~ fluorine, chlorine, bromine, methyl, ethyl, isopropyl, methoxy,methyl-thio, trifluoromethyl, trifluoromethoxy, trifluoro-methylthio, methoxycarbonyl, ethoxycarbonyl, nitro, cyano, phenyl, chlorophenyl, phenoxy, methoximinomethyl, ethoximinomethyl and 1-(methox-imino)-ethyl;
R represents cycloalkyl which has 3 to 6 carbon atoms and is monosubstituted to trisubstituted by ident;cal or different substituents, the follow ing being mentioned as substituents: fluorine, chlorine~ bromine, methyl, ethyl, methoxy, ethoxy, phenyl and chlorophenyl; and also the groupin~s -C(CH~)2-RI, -C~CH3~2-CH2C~l2-R , ~C(c~3)2-(cH2)m R
and -C(CH3)2-(CH2)n R4;
R1 represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl or neo-pentyl, and furthermore represents alkenyl having
u-ted or polysubstituted by identical or different substituents sel~cted from: Halogen, alkyl having 1 to 4 carbon atoms, alkoxy and alkylthio each having 1 or 2 carbon atoms; halogenoalkyl, halogenoalkoxy and halogenoalkyl-thio each having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, Le A 21 911 -'J, ~' ~
- la ~
alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl moiety, nitro, cyano or phenyl or phenoxy which is optionally substituted by halogen and/or alkyl having 1 or 2 carbon atoms, or the aldoxime or ketoxime radical or an ether thereof;
Az represents 1,2,4-triazol-1-yl, 1,2,~,-triazol-4-yl or imldazol-l-yl, B represents a keto group or a CH(OH) grouping and R represents substituted cycloalkyl or a grouping of ormula ~(CH3 2-R , -C:(CH3)2-CH2-CH2-R2, -C(CH3)2-(CH2) -R3 or -C(CH3)2~(CH3)2~(CH2)n R , wherein Rl represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl, or the aldehyde group or an oxime, oxime-ether or dialkyl acetal ther~of, R2 represents phenoxy which is optionally monosub-stituted or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case o~ Ar;
R3 represents phenyl which is optionally monosubstituted or polysubstituted by identical or different substituents select-ed from the phenyl substituents mentioned above in the case of Ar;
R4 representshalogen, m represents integers from 1 to 4 and n represents integers from 2 to 4, 5~` Le A 21 911 .~ l3~
or a non-phytotoxic addition product thereof with a hydrohalic acid, phosphoric acid, nitric acid, sulphuric acld, a monofunct-ional or bifunctional carboxylic acid, a hydroxycarboxylic acid or a sulphonic acid salt of copper, zinc, manganese, magnesium, iron or nickel or an anion of a salt derived from a hydrohalic acid, phosphoric acid, nitric acid or sulphuric acid Those compounds of the formula (I) in which B represents the CM(O~) group possess two asymmetric carbon atoms; they can therefore occur in the form of the two geometric isomers (erythro and threo form), which can be obtained in differen-t proportions.
In both cases, they occur as optical isomers. Compounds of the formula (I) in which R represents substituted cycloalkyl can additionally possess an asymmetric carbon atom, with the result that there may be further geometric isomers. All isomers are clai.med according to the invention.
Furthermore, it has been found that the new substituted axolylether-ketones and -carbinols of the formula (I) are obtained if a) halogenoether-ketones of the formula 2~
(II) Ar - O - fH - CO - R (II ) Hal in which Ar and R have the meaning given above and Hal represents chlorine or bromine, Le A 21 911 .~
~ ~3~
- 2a -are reacted with 1,2,4~triazole or imidazole in the presence of an acid-bindiny agent and, if appropriate, in the presence of a diluent; or b) dihalogenoketones of the formula (Hal)2 CH - CO - R (III) in which Hal and R have the meaning given above, are reacted with 1,2,4-triazole or imidazole and with a Le A 21 911 .~
phenol of the formula Ar- OH (IV) ;n wh;ch Ar has the meaning given above, ;n the presence of an acid-b;nding agent and in the pre-sence of a diluent; or, if appropriate, c) the a70lylether-ketones obtained by process (a) or (b), of the formula Ar - O - CH - CO - R
I (Ia) Az 1~ in which Ar, Az and R gave the meaning given above, are reduced in a customary manner by known methods.
The result;ng compounds of the formula (I~ can, if desired, then be subjected to an addition reaction with an acid or a metal salt.
The new substituted azolylether-ketones and -carbinols of the formula (I) possess powerful fungicidal properties. In this respect, the compounds according to the invention surprisingly exhibit better fungicidal activity than the substituted 1-azolyl-3,3-dimethyl-1-phenoxy-butan-2~ones and -ols which are known from the prior art and are similar compounds chemically and in terms of their action. The substances according to the invention thus represent an enrichment of the art.
2~ Formula (I) gives a general definition of the substi~uted azolylether-ketones and -carbinols according to the ;nvention. In this formula, Ar preferably represents phenyl which is mono-substituted or polysubstituted by identical or 3û different substituents, the following preferably being mentioned as substituents: halogen, alkyl having 1 to 4 carbon atoms, alkoxy and alkylthio, each having 1 or 2 carbon atoms; halogenoalkyl, Le A 21 911 ~.3~
halogenoalkoxy and halogenoalkylthio, each having 1 or 2 carbon atoms and 1 to 5 identical or diffexent halogen atoms, such as fluorine atoms and chlorine atoms, alkoxy-carbonyl having 1 to 4 carbon atoms in the alkyl part, nitro, cyano or phenoxy or phenyl which is optionally substituted by halogen and/or alkyl having 1 or 2 carbon atoms, and represents the aldoxime or ketoxime radical and their ethers;
R preferabl.y represents cycloalkyl which has 3 to 7 carbon atoms and is optionally monosubstituted or poly-substituted by identical or different substituents, the followiny pre:Eerably being mentioned as substituents:
halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms, phenyl and chlorophenyl: and furthermore the groupings -C(CH3)2-R , -C(CH3)2-CH2CH2-R
_c(cH3)2_(cH2)rn-R and -C(CH3)2-(CH2)n-R ;
Rl preferably represents straight-chain or branched alkyl having 2 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms and alkinyl having 2 to 4 carbon atoms, and also the aldehyde group and its derivatives, such as oximes, oxirne-ethers and acetals, such as, for example, dialkyl acetals having 1 to 4 carbon atoms in each alkyl part, or represents op-tionally substituted dioxanes and dioxolanes;
R preferably represents phenoxy which is optionally monosubstituted or polysubstituted by identical or different substituents, preferred substituents being the phenyl substituents already mentioned in the case of Ar;
- 4a -R3 preferably represents phenyl which is monosubstituted or polysubstituted by ldentical or different substitu-ents, preferred substituents bei.ng the phenyl substitu-ents already mentioned '~ ?~
in the case of Ar;
~4 preferably represents fluorine, chlorine or bromine; and ~z, e, m and n preferably have the meanings given in the definition of the inventionO
Part;cularly preferred compounds of the formula (I) are those in which Ar represents phenyl which is optionally mono-substituted to trisubstituted by identicaL or different substituents~ the following being men-tioned as substituents~ fluorine, chlorine, bromine, methyl, ethyl, isopropyl, methoxy,methyl-thio, trifluoromethyl, trifluoromethoxy, trifluoro-methylthio, methoxycarbonyl, ethoxycarbonyl, nitro, cyano, phenyl, chlorophenyl, phenoxy, methoximinomethyl, ethoximinomethyl and 1-(methox-imino)-ethyl;
R represents cycloalkyl which has 3 to 6 carbon atoms and is monosubstituted to trisubstituted by ident;cal or different substituents, the follow ing being mentioned as substituents: fluorine, chlorine~ bromine, methyl, ethyl, methoxy, ethoxy, phenyl and chlorophenyl; and also the groupin~s -C(CH~)2-RI, -C~CH3~2-CH2C~l2-R , ~C(c~3)2-(cH2)m R
and -C(CH3)2-(CH2)n R4;
R1 represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl or neo-pentyl, and furthermore represents alkenyl having
3~ 3 to 6 carbon atoms and alkinyl having 2 ~o 4 carbon atoms, and also represents the aldehyde group and its derivatives, such as ox;mes and oxime-e~hers~ the following being mentîoned in connection with the latter: alkyl ethers having 1 to 4 carbon atoms, alkenyl ethers having 2 to
4 carbon atoms, alkinyl ethers having Z to 4 Le A 21 911 carbon atoms and benzyl ethers which are optionally mono-substituted to trisubstituted by halogen; and acetals, such as, for example, dialkyl acetals having 1 to 4 carbon atoms in each alkyl part, dioxane and dioxolane;
represents phenoxy which is optionally monosub-stituted to trisubstituted by identical or different sub-stituents, preferred substituents being the phenyl sub-stituents already mentioned in the case of Ar;
R represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, preferred substituents being the phenyl substituents already mentioned in the case oE Ar;
R represents fluorine or chlorine;
m represents 1 or 2;
n represents 2; and Az and B have the meanings given in the definition of the invention.
If, for example, l-bromo-1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl) 3,3-dimethylbutan-2-one and 1,2,4-triazole are used as starting materials, the course o-E the reaction can be represented by the following e~uation (process a):
fH3 Cl ~r CH3 Cl ~ O-CH-CO-C - CH2 ~ Cl ~ H3 3~
If, for example, 1,1-dichloro-3-(dioxan-2-yl)-3-methyl-butan-2-one, 4-chlorophenol and 1,2,4-triazole are used as start-ing ma-terials, the course of the reaction can be represented by the following equation (process b):
CH3 H base Cl ~ OH + Cl CH-CO-C ~ ~ + N~ - 2 HCl CH3 N~ ~ N
cl~-~H~C~T- g-~
~ ~ CH3 If, for example, l-(A~chlorophenoxy)-4-(2,4-dichloro-phenyl)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one and sodium borohydride are used as starting materials, the course of the reac-tion can be represented by the following equation (process c):
CH3 Cl Cl ~ O-ICH CO T CH2 ~ CH NaslI4 `N CH3 OH CEi3 Cl ~ Cl ~ N~ CH3 Formula (II) gives a general definition of the halogeno-ether-ketones to be used as starting materials .in carrying out pro-cess (a) according to the invention. In this formula, A and R pre-ferably represent the radicals which have already been men-tioned in connection with the description of the substances according to - 7a -the invention, of the formula (I~, as being preferred for these substituents.
The halogenoether~ketones of the formula (II) " ~
35~3~
have been unknown hitherto; however, they can be obtained in a generally known manner by a process in which, for example in ether-ketones of the formula Ar - O - CH2 - CO - R (V) in which Ar and R have the meaning given above, one of the two active hydrogen atoms is exchanged in a customary manner for chlorine or bromine. The resulting halogenoether-ketones of the formula (II) can, if required, be reac-ted further without isolation.
The ether-ketones of the formula (V) have also been unknown hitherto; they, too, can be obtained in a generally known manner, by reacting halogenoketones of the formula Hal - CH2 - CO - R (VI) in which Hal and R have the meaning given above, with phenols of the formula (IV), in the presence of a strong base, such as, for example, potassium carbonate, and in the presence of an inert organic solvent, such as, for example, acetone or N,N-dimethyl-formamide at temperatures between 20 and 120C.
Some of the halogenoketones of the formula (VI) are known (see, for example, DE-OS (German Published 5pecification) 3,028,330 ~Le A 20 458]; some of them form the subject of prior patent applications of the applicant, which applications have not '~ I,e A 21 911 ~3~
~ 8a -yet been published (see German DE-OS 31 45 857 [Le A 21 383], 31 45 858 [I.e A 21 400], 32 09 431 [Le A 21 585], or they may be prepared by processes which are known in principle.
Formula (III) gives a general definition of the Le A 21 911 ~ :P~3~ 2 dihalogenoketones to be used as staxting materials in carrying out process (b) accordiny to the invention. In this formula, R preferably represents the radicals which have already been mentioned in connection with the description of the substances according to the invention, of the formula (I), as being pref-erred for these substituents.
The dihalogenoketones of the formula (III) have been unknown hitherto; they may be prepared by processes which are known in principle.
Formula (IV) gives a general definition of the phenols additionally to be used as startin~ materials for carrying out process (b) according to the invention. In this formula, Ar preferably represents those radicals which have already been mentioned in connection with the description of the substances according to the invention, of the formula (I), as being pref-erred for these substituents.
The phenols of the formula (IV) are generally known compounds of organic chemistry.
The azolylether-ketones of the formula (Ia) which are ~0 to be used as starting materials in carrying out process (c) are substances according to the invention.
Suitable diluen-ts for the reaction according to the invention, in accordance with process ~a), are inert organic solvents. These preferably include ketones, such as diethyl ketone and in particular acetone and methyl ethyl ketone;
nitriles, such as propionitrile, in particular acetonitrile;
Le A 21 911 j. ., 3~
- 9a -alcohols, such as ethanol and isopropanol; ethers, such as tetrahydrofuran or dioxane; benzene, toluene, formamides, such as, in particular, dimethylformamide, and halogenated hydrocarh-ons.
The reaction according to the lnvention, in accordance with process (a), is carried out in the Le A 21 911 ~ .
~3~
presence of an acid-binding agent. It is possible to add all customarily usable inorganic or organic acid-binding agents, such as alkali metal carbonates, for example sodium carbonate, potassiu~ carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cyclo-alkylamines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, N,N-di-methylbenzylamine and furthermore pyridine and diazabi cyclooctane. An appropriate excess of triazole or imida-zole is preferably used.
In process ta), the reaction temperatures can bevaried within a relatively wide range. In general, the reaction is carried out at between about 20 and about 15QC, preferably at 60 to 120C. When a solvent is pre-sent, the reaction is advantageously carried out at theboiling point of the particular solvent.
In carrying out process (a~ according to the invent;on, 1 to 2 mols of triazole or imidazole and 1 to 2 mols of acid-binding agent are preferably employed per 2Q mol of the compounds of the formula (II). To isolate the compounds of the formula ~I), the solvent is distilled off, the residue is taken up with an organic solvent and the solution is washed with water. The organic phase is dried over sodium sulphate and freed from solvent in vacuo. The residue is purified by distillation or recrys-tallisation or by salt formation and recrystallisation.
Suitable diluents for the reaction according to the invention, in accordance with process (b), are polar organic solvents. These preferably include chlorinated hydrocarbons, such as methylene chloride or chloroform;
alcohols, such as ethanol, propanol, n-butanol or tert.-butanol; ketones, such as methyl ethyl ketone or acetone;
ethers, such as tetrahydrofuran or dioxane; and nitriles, such as acetonitrile~
The reaction according to the invention, in accordance with process (b), is carried out in the Le A 21 ~11 35~
presence of an acid-binding agent. All customarily usable inorganic and organic acid-binding agents can be added.
These preferably include the solvents already mentioned in the case of process (a).
In process (b), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at between 0 and 150C, prefer-ably between 40 and 100C.
In carrying out process (b) according to the invention, 1 to 1.2 mols of phenol of the formula (IV) and 1 to 1.2 mols of triazole or imidazole as well as 2 to 3 mols of an acid-binding agent are preferably employed per mol of dihalogenoketone of the formula (III)~ The end products are isolated in a generally customary manner.
The reduction according to the invention, in accordance with process (c), is effected in a customary manner, for example by react;on with complex hydrides, if appropriate in the presence of a diluent, or by reaction with aluminium isopropylate in the presence of a diluent.
If complex hydrides are employed, suitable dilu-ents for the reaction according to the invent;on are polar organic solvents. These preferably include alco-hols, such as methanol, ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetrahydrofuran.
The rèaction is carried out in general at -10 to +3ûC, preferably at 0 to 20C. For this purpose, about 1 mol of a complex hydride~ such as sodium borohydride or lithium alanate, is employed per mol of the ketone of the formula (Ia). To isolate the reduced compounds of the formula (I), the residue is taken up in dilu~e hydrochloric acid, and the solution is then rendered alkaline, and extracted with an organic solvent~ Further working-up is effected in a customary manner.
If aluminium isopropylate is employed, preferred diluents for the reaction according to the invention are alcohols, such as isopropanol, or inert hydrocarbons, Le A 21 911 ~3~
such as benzene. The reaction temp~ratures may once again be varied within a relatively wide range; in general, the reaction is carried out at between 20 and 120C, preferably at 50 to 100CA To carry out the reaction, abou~ 0.3 ~o 2 mols of aluminium isopropylate are employed per mol of the ketone of the formula (Ia)~ To ;solate the reduced compounds of the formula (I), the excess sol-vent is removed in vacuo and the aluminium compounds formed are decomposed with dilute sulphuric acid or sod-1n ium hydroxide solution. Further working-up is effected in a customary manner.
All physiologically tolerated acids are suitable for the preparation of acid addition salts of the com-pounds of the formula (I). These preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobrom;c acid, in particular hydrochloric acid, and also phosphoric acid~ nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hyd-roxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and sulphonic acids, such as, for example, p~toluenesul-phonic acid and naphthalene-1,5-disulphonic acid.
The salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for e~ample by dissolving a compound of the for-mula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and can be isolated in a known manner, for example by filtration, and if appropri-ate purifled by washing with an inert organic solvent orby recrystall;sation.
Preferred salts for the preparation of metal salt complexes of compounds of the formula (I) are salts of metals of main groups II to IV and sub-groups I and II
and IV to VIII, and copper, zinc, manganese, magnesium, iron and nickel may be mentioned as examples. Suitable Le A 21 911 s~
anions of the salts are those which are derived from physiological acids. These preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydro-bromic acid, and also phosphoric acid, nitric acid and sulphuric acid. The metal complexes of the compounds of the formula tI) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (I). Metal 1Q salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystallisation.
The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are employed for combating Plasmodiphoromycetes, Oomycetes, Chytridio-mycetes, Zygomycetes, Ascomycetes, Basidiomycetes andDeuteromycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating those fungi which cause pow-dery mildew diseases, ~hus, for combating Erysiphespecies, such as, for example, against the powdery m;ldew of barley causative organism (Erysiphe graminis) and the powdery mildew of cucumber causative or0anism (Spaerotheca fuliginea); and also for combating oF
brown rust in wheat (Puccinia recondita) and furlher cereal diseases, such as, for example, Cochliobolus Le A 21 911 35~
sativus and Pyrenophora ~eres for combating rice dis-eases, such as Pyricularia oryzae and ~ell;cularia sasakii, as well as for combating apple scab (Venturia inaequalis) and bean rust (Uromyces appendiculatus). In addi~ion, the substançes according to the invention possess a good fungicidal ;n vitro action.
The active compounds can be converted to the cus-tomary formulations, such as solutions~ emulsions, wet-table powder, suspensions, powders, dusting agents, foams~
pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-dress;ng powders, natural and synthetic materials impregnated with active compound, very fine rapsules in polymeric substances and in coating compositions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.
These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dis-persing agents, and/or foam-forming agents~ In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solventsr there are suitable in the main: aro-matics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocar-bons, such as chlorobenzenes, chloroethylenes or methylene ~0 chloride, aliphatic hydrocarbons, such as cyclohexane or paraff;ns, for example mineral o;l fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide~
as well as water; by liquefied gaseous extenders or Le A 21 911 3~
carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aero-sol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide, as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and around synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid carriers for gran-1n ules there are suitable: for example crushed and frac-tionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic mat-erial such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ion~ic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkyl aryl polyglycol ethers, alkyl sulphonates, alkyl sul-2~ phates, aryl sulphonates as well as albumin hydrolysationproducts; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of oowders, granules or latices, such as gum arabic, polyvinyL alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian ~lue, and organic dyestuffs, such as alizarin 3n dyestuffs, azo dyestuffs and metal phthalocyanine dye~
stuffs, and trace nutrients such as salts of iron, manga-nese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0~5 and 90~.
The active compoundsaccording to the invention Le A 21 911 can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bacterlcides, insecticides, acaricides, nematicides, herbicides, blrd repellants, growth factors, plant nutrients and agents for improvlng soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by ~urther dilutlon, such as ready-to~use solutions, emulsions, sus-pensions, powders, pastes and granules. They are used ln the customary manner, for example by watering, immersion, spraying atomising, misting, vaporising, injecting, forming a slurry, brush-ing on, dusting, scattering, dry dressing, moist dressing~ wet dressing, slurry aressing or encrusting.
ln the treatment o~ parts cf plants, the active compound concentrations in the use forms can be varied within a substantial range. They are/ in general, between l and o.ooOl~ by weight, pre-ferably ~etween 0.5 and 0.001%.
In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to lO g, are generally required.
For the treatment of soil, active compound concentrations ot 0.~)0001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight are required at the place of action.
3~
Preparation Examples Example 1 and 2_ l~3 Cl ~ O-CH-CO-C-CH2-C(CH3)3 (Ex.l) ~ N~ CH3 Cl ~ O- CH-co-c-cH2-c(cH3)3 (Ex.2) ~ N 3 (Process a) A solution of 49.7 g (0.72 mol) of 1,2,4-triazole and 43.4 g (0.12 mol) of 1-bromo-1-(4-chlorophenoxy) 3,3,5,5--tetra-methylhexan-2-one in 650 ml of acetonitrile is hea-ted at the boil for 5.5 hours~ Thereafter, the solution is evaporated down in vacuo, the residue is ta~en up in 600 ml of ethyl acetate and the solution is washed with three times 100 ml of water, dried over sodium sulphate and evapora-ted down in vacuo. The viscous oil which remains (44 g) is chromatographed over silica gel, using tri-chloromethane as the mobile phase. 21.8 g (51.9% of theory) of 1-(4-chlorophenoxy)-3,3,5,5-tetramethyl-1-(1,2,4-triazol-1-yl)-hexan-2-one are obtained as colourless crystals of melting point 89-90 C. In addition, 7.4 g (17.6~ of theory) of the isomeric 1-(4-chlorophenoxy)-3,3,5,5-tetramethyl-1-(1,2,4-triazol-4-yl)-hexan-2-one are obtained as colourless crystals of melting point 146-148 C.
Pr~paration of the startin~ material Cl ~ O-CH-CO-C-CH2-C(CH3)3 ~r CH3 42.2 g (0.264 mol) of bromine are rapidly added dropwise to a vigorously stirred solution of 67.9 g (0.24 mol) of 1-(4-chlorophenoxy~-3,3,5,5-tetramethyl-hexan-2-one in 600 ml of dichloromethane at 25 to 30C. After the addition of bromine is complete, the mixture is stirred for a further 15 minutes and cooled to 10C, and 500 ml of ice-cold water are added. The organic phase is separated off, and washed once with 100 ml of aqueous sodium bisulphite solution and then with twice 100 ml of water. After the organic phase has been dried over sodium sul-phate, the solvent is distilled off in vacuo. 86.8 g (100% of theory) of l-bromo-l-(4-chlorophenoxy)-3,3,5,5-tetramethyl-he~an-2-one are obtained as slightly yellow-coloured crystals of melting point 72-73C.
fH3 Cl~o-CH2 -Co-f -cH2-c(cH3)3 38.6 g (0.3 mol) of 4-chlorophenol are stirred with 41.4 g (0.3 mol) of potassium carbonate and 57.2 g (0.3 mol) of l-chloro-3,3,5,5-tetramethyl-hexan-2-one in 350 ml of N,N-dimethyl-
represents phenoxy which is optionally monosub-stituted to trisubstituted by identical or different sub-stituents, preferred substituents being the phenyl sub-stituents already mentioned in the case of Ar;
R represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, preferred substituents being the phenyl substituents already mentioned in the case oE Ar;
R represents fluorine or chlorine;
m represents 1 or 2;
n represents 2; and Az and B have the meanings given in the definition of the invention.
If, for example, l-bromo-1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl) 3,3-dimethylbutan-2-one and 1,2,4-triazole are used as starting materials, the course o-E the reaction can be represented by the following e~uation (process a):
fH3 Cl ~r CH3 Cl ~ O-CH-CO-C - CH2 ~ Cl ~ H3 3~
If, for example, 1,1-dichloro-3-(dioxan-2-yl)-3-methyl-butan-2-one, 4-chlorophenol and 1,2,4-triazole are used as start-ing ma-terials, the course of the reaction can be represented by the following equation (process b):
CH3 H base Cl ~ OH + Cl CH-CO-C ~ ~ + N~ - 2 HCl CH3 N~ ~ N
cl~-~H~C~T- g-~
~ ~ CH3 If, for example, l-(A~chlorophenoxy)-4-(2,4-dichloro-phenyl)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one and sodium borohydride are used as starting materials, the course of the reac-tion can be represented by the following equation (process c):
CH3 Cl Cl ~ O-ICH CO T CH2 ~ CH NaslI4 `N CH3 OH CEi3 Cl ~ Cl ~ N~ CH3 Formula (II) gives a general definition of the halogeno-ether-ketones to be used as starting materials .in carrying out pro-cess (a) according to the invention. In this formula, A and R pre-ferably represent the radicals which have already been men-tioned in connection with the description of the substances according to - 7a -the invention, of the formula (I~, as being preferred for these substituents.
The halogenoether~ketones of the formula (II) " ~
35~3~
have been unknown hitherto; however, they can be obtained in a generally known manner by a process in which, for example in ether-ketones of the formula Ar - O - CH2 - CO - R (V) in which Ar and R have the meaning given above, one of the two active hydrogen atoms is exchanged in a customary manner for chlorine or bromine. The resulting halogenoether-ketones of the formula (II) can, if required, be reac-ted further without isolation.
The ether-ketones of the formula (V) have also been unknown hitherto; they, too, can be obtained in a generally known manner, by reacting halogenoketones of the formula Hal - CH2 - CO - R (VI) in which Hal and R have the meaning given above, with phenols of the formula (IV), in the presence of a strong base, such as, for example, potassium carbonate, and in the presence of an inert organic solvent, such as, for example, acetone or N,N-dimethyl-formamide at temperatures between 20 and 120C.
Some of the halogenoketones of the formula (VI) are known (see, for example, DE-OS (German Published 5pecification) 3,028,330 ~Le A 20 458]; some of them form the subject of prior patent applications of the applicant, which applications have not '~ I,e A 21 911 ~3~
~ 8a -yet been published (see German DE-OS 31 45 857 [Le A 21 383], 31 45 858 [I.e A 21 400], 32 09 431 [Le A 21 585], or they may be prepared by processes which are known in principle.
Formula (III) gives a general definition of the Le A 21 911 ~ :P~3~ 2 dihalogenoketones to be used as staxting materials in carrying out process (b) accordiny to the invention. In this formula, R preferably represents the radicals which have already been mentioned in connection with the description of the substances according to the invention, of the formula (I), as being pref-erred for these substituents.
The dihalogenoketones of the formula (III) have been unknown hitherto; they may be prepared by processes which are known in principle.
Formula (IV) gives a general definition of the phenols additionally to be used as startin~ materials for carrying out process (b) according to the invention. In this formula, Ar preferably represents those radicals which have already been mentioned in connection with the description of the substances according to the invention, of the formula (I), as being pref-erred for these substituents.
The phenols of the formula (IV) are generally known compounds of organic chemistry.
The azolylether-ketones of the formula (Ia) which are ~0 to be used as starting materials in carrying out process (c) are substances according to the invention.
Suitable diluen-ts for the reaction according to the invention, in accordance with process ~a), are inert organic solvents. These preferably include ketones, such as diethyl ketone and in particular acetone and methyl ethyl ketone;
nitriles, such as propionitrile, in particular acetonitrile;
Le A 21 911 j. ., 3~
- 9a -alcohols, such as ethanol and isopropanol; ethers, such as tetrahydrofuran or dioxane; benzene, toluene, formamides, such as, in particular, dimethylformamide, and halogenated hydrocarh-ons.
The reaction according to the lnvention, in accordance with process (a), is carried out in the Le A 21 911 ~ .
~3~
presence of an acid-binding agent. It is possible to add all customarily usable inorganic or organic acid-binding agents, such as alkali metal carbonates, for example sodium carbonate, potassiu~ carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cyclo-alkylamines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, N,N-di-methylbenzylamine and furthermore pyridine and diazabi cyclooctane. An appropriate excess of triazole or imida-zole is preferably used.
In process ta), the reaction temperatures can bevaried within a relatively wide range. In general, the reaction is carried out at between about 20 and about 15QC, preferably at 60 to 120C. When a solvent is pre-sent, the reaction is advantageously carried out at theboiling point of the particular solvent.
In carrying out process (a~ according to the invent;on, 1 to 2 mols of triazole or imidazole and 1 to 2 mols of acid-binding agent are preferably employed per 2Q mol of the compounds of the formula (II). To isolate the compounds of the formula ~I), the solvent is distilled off, the residue is taken up with an organic solvent and the solution is washed with water. The organic phase is dried over sodium sulphate and freed from solvent in vacuo. The residue is purified by distillation or recrys-tallisation or by salt formation and recrystallisation.
Suitable diluents for the reaction according to the invention, in accordance with process (b), are polar organic solvents. These preferably include chlorinated hydrocarbons, such as methylene chloride or chloroform;
alcohols, such as ethanol, propanol, n-butanol or tert.-butanol; ketones, such as methyl ethyl ketone or acetone;
ethers, such as tetrahydrofuran or dioxane; and nitriles, such as acetonitrile~
The reaction according to the invention, in accordance with process (b), is carried out in the Le A 21 ~11 35~
presence of an acid-binding agent. All customarily usable inorganic and organic acid-binding agents can be added.
These preferably include the solvents already mentioned in the case of process (a).
In process (b), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at between 0 and 150C, prefer-ably between 40 and 100C.
In carrying out process (b) according to the invention, 1 to 1.2 mols of phenol of the formula (IV) and 1 to 1.2 mols of triazole or imidazole as well as 2 to 3 mols of an acid-binding agent are preferably employed per mol of dihalogenoketone of the formula (III)~ The end products are isolated in a generally customary manner.
The reduction according to the invention, in accordance with process (c), is effected in a customary manner, for example by react;on with complex hydrides, if appropriate in the presence of a diluent, or by reaction with aluminium isopropylate in the presence of a diluent.
If complex hydrides are employed, suitable dilu-ents for the reaction according to the invent;on are polar organic solvents. These preferably include alco-hols, such as methanol, ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetrahydrofuran.
The rèaction is carried out in general at -10 to +3ûC, preferably at 0 to 20C. For this purpose, about 1 mol of a complex hydride~ such as sodium borohydride or lithium alanate, is employed per mol of the ketone of the formula (Ia). To isolate the reduced compounds of the formula (I), the residue is taken up in dilu~e hydrochloric acid, and the solution is then rendered alkaline, and extracted with an organic solvent~ Further working-up is effected in a customary manner.
If aluminium isopropylate is employed, preferred diluents for the reaction according to the invention are alcohols, such as isopropanol, or inert hydrocarbons, Le A 21 911 ~3~
such as benzene. The reaction temp~ratures may once again be varied within a relatively wide range; in general, the reaction is carried out at between 20 and 120C, preferably at 50 to 100CA To carry out the reaction, abou~ 0.3 ~o 2 mols of aluminium isopropylate are employed per mol of the ketone of the formula (Ia)~ To ;solate the reduced compounds of the formula (I), the excess sol-vent is removed in vacuo and the aluminium compounds formed are decomposed with dilute sulphuric acid or sod-1n ium hydroxide solution. Further working-up is effected in a customary manner.
All physiologically tolerated acids are suitable for the preparation of acid addition salts of the com-pounds of the formula (I). These preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobrom;c acid, in particular hydrochloric acid, and also phosphoric acid~ nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hyd-roxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and sulphonic acids, such as, for example, p~toluenesul-phonic acid and naphthalene-1,5-disulphonic acid.
The salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for e~ample by dissolving a compound of the for-mula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and can be isolated in a known manner, for example by filtration, and if appropri-ate purifled by washing with an inert organic solvent orby recrystall;sation.
Preferred salts for the preparation of metal salt complexes of compounds of the formula (I) are salts of metals of main groups II to IV and sub-groups I and II
and IV to VIII, and copper, zinc, manganese, magnesium, iron and nickel may be mentioned as examples. Suitable Le A 21 911 s~
anions of the salts are those which are derived from physiological acids. These preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydro-bromic acid, and also phosphoric acid, nitric acid and sulphuric acid. The metal complexes of the compounds of the formula tI) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (I). Metal 1Q salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystallisation.
The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are employed for combating Plasmodiphoromycetes, Oomycetes, Chytridio-mycetes, Zygomycetes, Ascomycetes, Basidiomycetes andDeuteromycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating those fungi which cause pow-dery mildew diseases, ~hus, for combating Erysiphespecies, such as, for example, against the powdery m;ldew of barley causative organism (Erysiphe graminis) and the powdery mildew of cucumber causative or0anism (Spaerotheca fuliginea); and also for combating oF
brown rust in wheat (Puccinia recondita) and furlher cereal diseases, such as, for example, Cochliobolus Le A 21 911 35~
sativus and Pyrenophora ~eres for combating rice dis-eases, such as Pyricularia oryzae and ~ell;cularia sasakii, as well as for combating apple scab (Venturia inaequalis) and bean rust (Uromyces appendiculatus). In addi~ion, the substançes according to the invention possess a good fungicidal ;n vitro action.
The active compounds can be converted to the cus-tomary formulations, such as solutions~ emulsions, wet-table powder, suspensions, powders, dusting agents, foams~
pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-dress;ng powders, natural and synthetic materials impregnated with active compound, very fine rapsules in polymeric substances and in coating compositions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.
These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dis-persing agents, and/or foam-forming agents~ In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solventsr there are suitable in the main: aro-matics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocar-bons, such as chlorobenzenes, chloroethylenes or methylene ~0 chloride, aliphatic hydrocarbons, such as cyclohexane or paraff;ns, for example mineral o;l fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide~
as well as water; by liquefied gaseous extenders or Le A 21 911 3~
carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aero-sol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide, as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and around synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid carriers for gran-1n ules there are suitable: for example crushed and frac-tionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic mat-erial such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ion~ic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkyl aryl polyglycol ethers, alkyl sulphonates, alkyl sul-2~ phates, aryl sulphonates as well as albumin hydrolysationproducts; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of oowders, granules or latices, such as gum arabic, polyvinyL alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian ~lue, and organic dyestuffs, such as alizarin 3n dyestuffs, azo dyestuffs and metal phthalocyanine dye~
stuffs, and trace nutrients such as salts of iron, manga-nese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0~5 and 90~.
The active compoundsaccording to the invention Le A 21 911 can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bacterlcides, insecticides, acaricides, nematicides, herbicides, blrd repellants, growth factors, plant nutrients and agents for improvlng soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by ~urther dilutlon, such as ready-to~use solutions, emulsions, sus-pensions, powders, pastes and granules. They are used ln the customary manner, for example by watering, immersion, spraying atomising, misting, vaporising, injecting, forming a slurry, brush-ing on, dusting, scattering, dry dressing, moist dressing~ wet dressing, slurry aressing or encrusting.
ln the treatment o~ parts cf plants, the active compound concentrations in the use forms can be varied within a substantial range. They are/ in general, between l and o.ooOl~ by weight, pre-ferably ~etween 0.5 and 0.001%.
In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to lO g, are generally required.
For the treatment of soil, active compound concentrations ot 0.~)0001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight are required at the place of action.
3~
Preparation Examples Example 1 and 2_ l~3 Cl ~ O-CH-CO-C-CH2-C(CH3)3 (Ex.l) ~ N~ CH3 Cl ~ O- CH-co-c-cH2-c(cH3)3 (Ex.2) ~ N 3 (Process a) A solution of 49.7 g (0.72 mol) of 1,2,4-triazole and 43.4 g (0.12 mol) of 1-bromo-1-(4-chlorophenoxy) 3,3,5,5--tetra-methylhexan-2-one in 650 ml of acetonitrile is hea-ted at the boil for 5.5 hours~ Thereafter, the solution is evaporated down in vacuo, the residue is ta~en up in 600 ml of ethyl acetate and the solution is washed with three times 100 ml of water, dried over sodium sulphate and evapora-ted down in vacuo. The viscous oil which remains (44 g) is chromatographed over silica gel, using tri-chloromethane as the mobile phase. 21.8 g (51.9% of theory) of 1-(4-chlorophenoxy)-3,3,5,5-tetramethyl-1-(1,2,4-triazol-1-yl)-hexan-2-one are obtained as colourless crystals of melting point 89-90 C. In addition, 7.4 g (17.6~ of theory) of the isomeric 1-(4-chlorophenoxy)-3,3,5,5-tetramethyl-1-(1,2,4-triazol-4-yl)-hexan-2-one are obtained as colourless crystals of melting point 146-148 C.
Pr~paration of the startin~ material Cl ~ O-CH-CO-C-CH2-C(CH3)3 ~r CH3 42.2 g (0.264 mol) of bromine are rapidly added dropwise to a vigorously stirred solution of 67.9 g (0.24 mol) of 1-(4-chlorophenoxy~-3,3,5,5-tetramethyl-hexan-2-one in 600 ml of dichloromethane at 25 to 30C. After the addition of bromine is complete, the mixture is stirred for a further 15 minutes and cooled to 10C, and 500 ml of ice-cold water are added. The organic phase is separated off, and washed once with 100 ml of aqueous sodium bisulphite solution and then with twice 100 ml of water. After the organic phase has been dried over sodium sul-phate, the solvent is distilled off in vacuo. 86.8 g (100% of theory) of l-bromo-l-(4-chlorophenoxy)-3,3,5,5-tetramethyl-he~an-2-one are obtained as slightly yellow-coloured crystals of melting point 72-73C.
fH3 Cl~o-CH2 -Co-f -cH2-c(cH3)3 38.6 g (0.3 mol) of 4-chlorophenol are stirred with 41.4 g (0.3 mol) of potassium carbonate and 57.2 g (0.3 mol) of l-chloro-3,3,5,5-tetramethyl-hexan-2-one in 350 ml of N,N-dimethyl-
5~
formamide for 16 hours. The mixture is then cooled to 20 C and filtered off from the precipi-tated inorganic salt, and the fil-trate is evaporated down in vacuo. The oil which remains (96.2 g) is taken up in 500 ml of ethyl acetate, and the solution is washed wi-th three times 100 ml of 10% strength sodium carbonate solution and with -twice 100 ml of water. After the solution has been dried over sodium sulphate, it is evaporated down, and the oily residue (80 g) is stirred with 50 ml of petroleum ether. 68.6 g (81~1% of theory) of l-(4-chlorophenoxy)-3,3,5,5-tetramethyl-hexan-2-one are obtained as colourless crystals of melting point 47-48C.
Example 3 _ Cl ~ O-fH-lH - f-CH2-C(CH3)3 ~N~N CH3 N
(Process c) 2 g (0.054 mol) of sodium boronate are introduced in por-tions into a solution oE 9.5 g (0.027 mol) of 1-(4-chlorophenoxy)-3,3,5,5-tetramethyl-l-(1,2,4-triazol-l-yl)-hexan-2-one (Example l) in 95 ml of methanol at 20 to 30 C, while cooling externally.
After three houxs, the solution is brought to a pH value of 6 by the addition of acetic acid. The solution is then evaporated down in vacuo, the residue is taken up in 100 ml of ethyl acetate and the solution is washed with three times 20 ml of water, dried over sodium sulphate and evaporated down in vacuo. 9~5 g (100% of theory) of l-(4-chlorophenoxy)-3,3,5,5-tetramethyl-l-(1,2,4-tri-s-~
azol-l-yl)-hexan-2-ol are obtained as a colourless viscous oil with a refractive index nD = 1.5250.
Example 4 _ .
fH3 c].~o-T~-C-f CH2CH2 ~ N
(Process a) 5.9 g (0.035 mol) of 1-chloro-3,3-dimethyl-5-fluoro-penten-2-one are added dropwise to a boiling mixture of 4.6 g (0.035 mol) of 4-chlorophenol, 4.9 g (0.035 mol) of potassium carbonate and 20 ml of acetone. After the mixture has been heated for four hours, it is filtered off from the precipitated potassium chloride, and the filtrate is evaporated down under reduced pres sure. The 1-(4-chlorophenoxy)-3,3-dimethyl-5-fluoro-pentan-2-one which remains as a colourless oil (9 g; 100% of theory) is dis-solved in 40 ml of dichloroethane, and 5O9 g (0.037 mol) of bro-mine are added in the course of 20 minutes at 20 C. The solution is stirred for two hours at 20 C and washed with three times 20 ml oE water, and the solvent is distilled oEf in vacuo. 11.8 g (100%
oE theory) of l-bromo-1-(4-chlorophenoxy)-3,3-dimethyl-5-fluoro-pentan-2-one remain as the residue, in the form of a slightly yellowish oil. This is ta~en up in 20 ml of acetonitrile, and the solution is added dropwise, in -the course of 20 minutes, to a boil-ing solution of 14.3 g (0.21 mol) of imidazole in 120 ml of aceto-nitrile. After the mixture has been heated under reflux for four 5~
- 21 ~
hours, the solvent is distilled off in vacuo, -the residue is taken up in 200 ml of ethyl acetate, and the solution is washed wlth three times 50 ml of water, dried over sodium sulphate and evapor-ated down under reduced pressure. After the oil which remains (10.8 g) has been filtered over a silica gel column (ethyl acetate:
trichloroethane, 1:1), 8.0 g (70.2% of theory) of 1-(4-chloro-phenoxy)-3~3-dimethyl-5-fluoro-l-(imidazol-l-yl)-pentan-2-one are obtained as colourless crystals of melting point 77-78C ~y evapor-ating down the eluate.
Example 5 fH3 F ~ O-CH-CO-C-CH2CH2-O ~ Cl ~ N
(Process a) A solution of 40.2 g (0.591 mol) of imidazole and 43.0 g (0.1 mol) of 1-bromo-5-(4-chlorophenoxy)-3,3-dimethyl-1-(4-fluorophenoxy)-pentan-2-one in 600 ml of acetonitrile is heated at the boil for 4 hours. The solution is then evaporated down in vacuo, the xesidue is taken up in 400 ml of ethyl acetate, and the solution is washed with 100 ml of water. After the organic phase has been dried over sodium sulphate, it is evaporated dcwn under reduced pressure, and the solid residue which remains is stirred with dlethyl ether. 34.3 g (83.5% of theory) of 5-(4-chloro phenoxy)-3,3-dimethyl 1-(4-fluorophenoxy)-1-(imidazol-1-yl)-pentan-2-one are obtained as colourless crystals of melting point 120-121C.
5~3~
Preparation of the starting material C~I3 -CH-C-f~CH2CH2- ~ Cl Br CH3 34.3 y (0.214 mol) of bromine are rapidly added dropwise to a solution of 69.1 g (0.197 mol) of 5-(4-chlorophenoxy)-3,3-dimethyl-l-(4-fluorophenoxy)-pentan-2-one in 600 ml of dichloro-methane. After the addition of bromine is complete, stirring is continued for a further 15 minutes and 400 ml of ice water are then added to the ~olution. The organic phase is separa-ted off and washed once with 100 ml of aqueous sodium bisulphite solution and with twice 100 ml of water. The solution is dried over sodium sulphate and then evaporated down in vacuo. 85.9 g (100% of theory) of l-bromo-5-(4-chlorophenoxy)-3,3-dimethyl-1-(4-fluoro-phenoxy)-pentan-2-one are obtained as colourless crystals of melt-ing point 92-93 C
fH3 CH2-CO-I-CH2CH2-O ~ Cl 68.8 g (0.25 mol) of 1 chloro-5-(4-chlorophenoxy~-3,3-dimethylpentan-2-one are heated at the boil for 13 hours with 28 g (0.25 mol) of 4-fluorophenol and 34.5 g (0.25 mol) of powdered potassium carbonate in 600 ml of acetone. Thereafter, the solu-tion is filtered off from the organic salt, the filtrate is evapor-ated down in vacuo and the residue is taken up in diethyl ether.
After petroleum ether has been added, 69.3 g (79% of theory) of 5-(4-chlorophenoxy~-3~3-dimethyl-l-(4-fluorophenoxy)-pentan-2-one are obtained as colourless crystals of melting point 71-74 C.
Example 6 F~o_cH_cH_ C_cH2cH2_o~Cl ~ N
(Process c) 2.6 g (0.068 mol) of sodium boranate are introduced in portions into a solution of 14.2 y (0.034 mol) of 5-(4-chloro-phenoxy)-3,3-dimethyl-1-(4-fluorophenoxy)-1-(imidazol-1-yl)-pentan-2~one (Example 5) in 140 ml of methanol at 20 to 30C, while cool-ing externally~ After two hours, the solution is brought to a pH
value of 6 by the addition of acetic acid~ and is evaporated down in vacuo. The residue is taken up in 200 ml of ethyl acetate, washed with twice 50 ml of water, dried over sodium sulphate and evaporated down. By triturating the solid residue with petroleum ether, 12.3 g (86.6% of theory) of 5-(4-chlorophenoxy)-3,3-dimethyl-l-(4-fluorophenoxy)-1-(imidazol-1-yl)-pentan-2-ol are ob-tained as colourless crystals of melting point 88-93 C.
Example 7 fH3 Cl Cl~o_fH_Co lC CH2~
~N CH3 N I I x HCl 3 ~
- 23~ -(Process aj 11 g (0.16 mol) of 1,2,4-triazole and 22 g (0.16 mol) of potassium carbonate in 200 ml of toluene are stirre~ for 1 hour at 90 C. 35 g (0.078 mol) of l-bromo-l (4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-butan-2-one in 100 ml of toluene are added dropwise ~o the mixture. The reaction mixture is stirred for a further 10 hours at 90C and then cooled to room temperature and 200 ml of water added. The organic phase is separated off, dried over sodium sulphate and evaporated down. The residue is purified by column chromatography. 7.8 g of 1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3~dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one are obtained as a highly viscous oil. 15 ml of saturated ethereal hydrochloric acid are added to 3.9 g of this highly vis-cous oil. The precipitated salt is filtered off under suction, washed with a little ether and dried in vacuo at 40 C. 3.3 g (78.2% of theory) of 1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-l-(1,2,4--triazol-1-yl)-butan-2-one hydrochloride of melt-ing point 130-135 C are obtained.
Preparation of the startin~ material Cl ~ O-ICH-CO-C - CHz ~ Cl Br CH3 24.5 g (0.15 mol) of bromine are added to 57 g (0.15 mol) of l-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)~3,3-dimethyl-butan-2-one, dissolved in 400 ml of chloroform, at room temperature.
- 23b -After the addition is complete, the reaction mix-ture is stirred for a further 30 minutes and then evaporated down. 67.6 g (100% of theory) of crude 1-bromo-1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl butan-2-one are ob~ained; this product is directly reacted further.
~l_ ~ O-CH2-CO-C - CH2- ~ Cl 28.2 g (0.22 mol) of 4-chlorophenol and 30.4 g (0.22 mol) of potassium carbonate in 120 ml of toluene are heated under re-flux for 2 hours in a water separator. A solution of 57 g (0.18 mol) of 1-bromo-4-(2,4-dichlorophenyl)-3,3-dimethyl-butan-2-one in 200 ml of toluene is added dropwise at 60 C. The reaction mixture is then stirred for a further 5 hours at 100C. The mixture is allowed to cool and filtered off under suction from the inorganic residue, and the toluene phase is washed with ~3~
dilute sodium hydroxide solution and then with water, dr;ed over sodium sulphate and evaporated down. 57.4 g (7n.2~ of theory) of 1-(4-chlorophenoxy)-4-(2,4-dichloro-phenyl)-3,3-dimethyl-buta~-2-one of refractive index n20 =
1.5753 are obtained.
CH3 C~
Br-CH2-CO-C-CHz- ~-Cl c~3 13.4 ml (0.26 mol) of bromine are added dropw;se to 64.5 9 (C.26 mol) of 4-(2,4-dichlorophenyl)-3,3-d;me-thyl-butan-2-one in 600 ml of chloroform at room tempera-1û ture. The reaction mixture is stirred for a further hourat room temperature and evaporated down. 84 g (1Q0% of ~heory) of crude 1-bromo-4-(~,4-dichlorophenyl)-3,3-di-methyl-butan 2-one are obtained; this product is directly reacted furtherO
Example ~
OH CH3 Cl Cl- ~ -O-CH-CH - C-CH2 ~ -Cl ~ N~N CH3 N l¦
(Process c) 3.5 9 (0.008 mol) of 1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2n 2-one ~see Example 7) are dissolved in 50 ml of methanol at -1QC, and 0.1 9 ~0.0026 mol) of sodium borohydride in 2 ml of water is added. The reaction mixture is stirred for a further hour w;thout cooling and ;s then evaporated down in vacuo. Methylene chloride/water is then added ~o the res;due~ The organic phase ;s separated off, dried over sodium sulphate and evaporated down. 3L2 9 ~91.4%
of theory) of 1-~4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-1-(1,2,4-tr;azol-1-yl)-butan-2-ol of melting Le A 21 911 ~ 3~
po;nt 60-65C are obta;ned.
Example 9 -C~
Cl ~ 0-CH-C0-C
~N CH3 (Process b) A mixture of 14.4 9 (0.21 mol~ of 1,2,4 triazole and 26.9 9 ~0.21 mol~ of 4 chlorophenol in 1QG ml of ace-tone are added to 43 9 (0.19 mol) of 1,1-dichloro-3-(di-oxolan-2-yl)-3-methyl-butan-2-one and 78.4 g (0.57 mol) of potassium carbonate in 300 ml of acetone, under reflux.
1Q The reaction mixture is stirred under reflux for a further 10 hours, then cooled and filtered off under suction from the inorganic residueA The filtra~e is evaporated down, the residue is taken up in methylene chloride, and the solution is washed with dilute sodium hydroxide solution and with water, dr;ed over sod;um sulphate and evaporated down in vacuo. The residue is purified by column chroma-tography (silica gel/ethyl acetate:cyclohexane = 3:1).
19 g (28~4% of theory) of 1-(4-chlorophenoxy)-3-(dioxo-lan-2-yl~-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-one of refract;ve index n20 = 1.4994 are obtained.
_reparation of the start;ng material_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ CjH3,o C l 2CH-CO-C -\ ~
C~3 36.8 g (0.2 mol) of 4,4-d;chloro-2,2-d;methyl-3-ketobutanal, 13.~ 9 (0.22 mol) of echylene glycol and 2.2 g of p-toluenesulphonic ac;d ;n a mixture of 180 ml of toluene and 16C ml of n-butanol are heated under reflux for 1.5 hours in a water separator. The mixture is Le A 21 911 3~
- 26 ~
allowed ~o cool~ and ;s evaporated do~Jn in vacuo. The residue is taken up methylene chloride, and the solution is washed with water, dried over sodium sulphate and evaporated down. 43.~ 0 (96' of theory) of 1,1 dichloro~
5 3-(dioxolan-2-yl) 3-me~hyl butan-Z-one of refractive index n2n = 1~4631 are obtained.
Cl2CH - CO - C - CHO
~ CH3 141 9 (1 mol~ of 1-(N-morpholino)-isobutene are dissolved in 470 ml of diethyl ether~ 147.5 9 (1 mol) of dichloroacetyl chloride are slowly added dropwise, while cooling with ice. The reaction mixture is then stirred for 24 hours at room temperature~ after which 150 ml of water are added and sodium bicarbonate solution is added until a pH value of 5 to 6 is reached. The mixture is stirred for a further hour and the ether phase is then separated off. The aqueous phase is extracted with ether and then with methylene chloride. The combined organic phases are dried over sodium sulphate and evaporated down, and the residue ;s dist;lled in vacuo. 155.6 9 (85% of theory) of 4,4-dichloro-2,2-dimethyl-3-keto-butanal of boiling point 118C/0.2 mbar are obtained~
Example 10 OH CH3 0 _ Cl ~ -O-CH-CH - C -~ N N CH3 N , ~Process c) 7 9 (Q~02 mol) of 1-~4-chlorophenoxy)-3-(dioxolan 2-yl)-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-one (Example 9) are dissolved in 70 ml of methanol, and a solution of Le A 21_911 ~ 3~3~
n.23 9 (0.006 mol) of sodium borohydride in 5 ml of water is added. The reaction mixture is stirred for a further 2 hours, the p~l value is brought to 6-7 with dilute hydro-chloric acid, and the mixture is evaporated down in vacuo.
The residue is taken up in methylene chloride, and the solution is washed with water, dried over sodium sulphate and evaporated down. 5.8 9 (~2.9% of theory) of 1-(4-chlorophenoxy) 3-(dioxo1an-2-yl)-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-ol of refractive index n20 = 1.5389 are obtained.
The compounds of the general formula Ar - O- CH ~ i3 ~ R (I) A z are obtained in a corresponding manner and analogously to the processes given:
Le A 21 911 NoX Ar Az B R D
.
~ N Cl 11 Cl ~ - -N ¦ CO -C(CH~)2-CH~ ~ C1 213(xHCl) 12 C1 ~-N ~ N CO C(C 3)2 2 ~ viscous oil ~N
13 C1 ~ -N ¦ CO C( 3)2 2 ~ C1 174-75(xHC1) /==N \3 A
14 C1 ~ - -N ¦ CO CH Cl 15 ~ -N ~ CO ~ Ccl 164 16 Cl ~ -N ~ CO ~ ~iscous oil 17 Cl ~ -N ~ CO ~ viscous oil 18 C1 ~ ~N CH Br 19 ~ -N ~ CO ~ BBr 178 C1 ~ -N ~ CO ~ viscous oil 21 C1 ~ ~ N ~ viscous oil 22 C1 ~ -N ~N CO -C~CH3)2-n-C3H7 1,5345 ~=~N
~3 ~ -N ~ CO -C~CH3)2-n-C3ll7 65 /=~N
24 ~ ~ _ -N ~ ~O -C~CH3)2-i-C3~l7 1,5195 ~=~N
C1 ~ -N J CO -C~CH3)2-CH2CH2C1 resin 26 Cl ~ ~ ~C~cH3~~n~c4~9 1,5324 r=N
27 ~ - -N ~ CO C~CH3)2 3 7 127 ~3~
_ 29 -NXo Ar Az B R M.p. ( C) or Cl~=~N
28 Cl ~ -N ~ C0 c(CH3)2 i C3H7 resin f=~N
29 Cl ~ -N ~ C0 C(CH3)2 i C3H7 resin Cl ~ - -N ~ N C0 -C(CH3)2-CH2-c~cH3)3 83-85 31 ~ -N ~ N C0 -C~cH3)2-cH2-c~cH3)3 128 ~ Cl ~ N C0 -C(cH3)2-cH2-c~cH3)3 84 33 Cl ~ -N ~ N C0 -C(CH3)2-CH2CH20 ~ resin 34 Cl ~ _-N ~ N C0 -C~CH3)2-CH2CH2-0 resin N g ~ -N ~ C0 -C~CH3) -CH2CH2-0 102-03 36 ~ N C0 -C~CH3)2-CH2CH2 ~ Cl resin f=~N Cl 37 Cl ~ -N ~ C0 -C~CH3)2-ci~2cH2 ~ Cl 1~5822 ClN Cl 38 Cl ~ -N ~ C0 -C(CH3)2-C~l2cH2 ~ 1,5746 r N Cl 39 F ~ -N ~ C0 -C(CH3)2-CH2cH2 ~ Cl 1,5629 l$Jl 3~
E M.p. ( C) or NXoAr Az B R nDO
~N
40 ~ -N~=¦ C0 -C(CH3)2-CH2CH2~Cl 1,5950 41Br~-N~JN C0 -C(cH3)2-cH2cH2-o~cl 108-09 42 ~ -N~NI C0 -C (CH3) 2-CH2CH2 ~) 95-96 _~Cl ~N C0 -C(cH~)2-cH2cH2 ~) resin _~$CH3 ~N C0 -C (CH3) 2-CH2CH2-~Cl resin 45F~ -N~Nl C0 -C(CH3)2-CH2cH2 ~) 88-90 46Cl~ -N~N C0 -C (CH3) 2-CH2CH2 ~ resin 47Cl ~-N ~ C0 -C~CH3)2-CH2CH2 O ~ viscous oil 48 ~-N ~ N CO -C(CH3)2-CEl2cH2 ~ viscous oil 49Cl ~-N ~ N CO -C~CH3)2-CH2CH2-0 ~ F viscous oil FN
Cl ~ -N ¦ CH~OH)-C~cH3)2-cEl2 ~ Cl 60-65 /=~N
Sl Cl ~ -N ~ CEI(OH) C(CH3)2 C~l2 ~ 156-59 /=~N
52 Cl ~ -N ~ CH~OH)-C~CH3)2-CH2 ~ 144 53 Cl ~ -N ~ CEI~OH)C~l Ccl 123 54 ~ -N ~ CH~OH)~ ~ Ccl 214 F N ~ 3,-~
Cl ~ - -N ~ CH~OH) ~ 145 5~
No Ar Az B R 20 ~ ~ ~ viscous oil 57 Cl ~ -N ~ CH(OH) c(CH3)2 n C3 7 86-90 58 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2CH2Cl resin 59 Cl ~ -N ¦ CH(OEI) C(CH3)2 4 9 1,5273 ~=~N
~ 1 -N ~ CEI(OH) C(CH3) 2 i C3 7 138-40 61 Cl ~ -N ~ CH(OH) C(CH3)2 i C3H7 viscous oil 62 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2CH2C1 102-03 63 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2-c(cH3)3 137-38 ~=N
64 ~ 1 /=,N -C(CH3)2-CH2-c(cH3)3 160 Cl ~ -N ~ CH(OE-I) -C(CH3)2-CH2-c(cH3)3 resin ~P~
66 Cl ~ -NJ CH (OH) -C (CH3) 2 -CH2CH2 -o~Cl 1 14 - 16 67 Cl -~ -N~ CH (OEI) -C (CH3) 2 -CH2CE12-O~ 118-24 68 ~_ -N~J CH (OH) -C (CH3) 2-CH2CH2-0~)-C1 138-40 69 Cl~ -N~j CH(OH) _C(cH3)2_cH2cH2_o~cl 147-51 Cl~ -N~ CH (OEI) -C (CH3) 2 _CH2cEl2_o~Cl resin 71 F~ ~N -C (CH~;) 2_cH2cH2 o~C1 111-13 72 Cl ~ -N~ CH (OH) -C (CH3) 2 -CH2CE-13-O~Cl resin 5~
No Ar Az B R 20 ~ Cl 73 ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-O ~ Cl 159-60 ~ N
74 Br ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-o- ~ -Cl 138-43 ~ N
F ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-O ~ resin ,CH3 /=~N
76 Cl ~ _ -N ~ CH(~H) -C(CH3)2-~H2CH2-O ~ Cl 64-66 77 Cl ~ -N ~ ~H(~H) -C~H3)2-~H2~H2 ~ resin /--N
78 Cl ~ -N~ CH(OH) -C(CH3)2-CH~CH~-O ~ F resin /=~N Cl 79 Cl ~ -l~ ~ CH(OH) -C(cH3)2-cH~cH~-o ~ F resin Cl /=~N Cl Cl ~ -N ~ CH~OH) -C(CH3)2-CH~CH~-O ~ -F resin ,N~
81 Cl ~ -N I CO -C(CH3)2-CH2 ~ Cl 13J-41(xHCl) N
S2 Cl ~ ~N\ l ~ -C(C~I3)~-CH2 ~ viscous oil ,N
83 ~1 ~ _ -N 1 CO -C(CH3)2-n-C3ll7 1,5312 ~, 84 ~ -N ~ CO -C(CH3)2-n-C3H7 ~5 F ~ -N~N CO -C(~H3)2-1-C~H7 1,5116 N
86 Cl ~ -N ~ COC(CH3)2 4 9 1,5250 P~
87 ~ -N ¦ CO-C(~H3)2-i-C3H7 121-22 _~/ClNL~
88 Cl ~ _ -N I CO-C(CH~)2-i-C3H7 59 ,N~
89 Cl ~ -N\=~N CO-C(CH3)2-i-C3~17 67 ~ ~?J ~ ~3 r~
NXo Ar Az B R M.p. ( C) or ~ ~ -N ~ C0 -C~CH3)2-CH2-c(cH3)3 112 91 C1 ~ -N 1 C0 -C~cH3)2-cH2-c(cH3)3 78 92 C1. ~ -N ~N C0 -C~CH3)2-CH0 1,5350 P~
93 C1 ~ ~N\==l C0 _C(CH3)2-C~l=NOcH3 1,5303 ,N Q
9'1 Cl ~ -N ~ C0 -C~CH3)2 ~ ~ viscous oil Cl ~ ~ N C0 _-C(CH3)2-CH2c~l2 ~ Cl 87-89 96 C1 ~ ,N l C0 --C(CH3)2-Cll2cH2 ~ resin 97 ~ -N ~ C0 C(CH3)2 CH2CH2 0 ~ 103-04 Cl C0 -C(CH3)2-CH2cH2 ~ Cl resin N ~
Cl ~ C0 -C(CH3)2-CH2CH2-0 ~ Cl 109-10 100 C1 ~ -N ~ CO C(CH3)2 C 2 2 ~ 1,5720 101 F ~ -N~N~N CO -C(CH3)2-CH2CH2-O ~ C1 1,5608 102 ~ ~ ~ N CO -clCll3)2-CH2CH2-O ~ C1 88 103 Br ~ -N ~ N CO -C(CH3)2-CH2CH2-O ~ C1 9'-l-95 104 ~ - -N ~ N CO -C(CH3)2-CH2cH2 ~ 86-88 N
105 F ~ -N l CO -C(CH )2-CH2CH2-O ~ C1 107-08 ~ C1 ~ CO -C(CH3)2-CH2cll2 ~ resin 3~ ?~
- 3~ -Ex. Ar Az B R M (C) or No. nD
__ Cl-l -c(cH3)2-cH2cH2-O ~ Cl 63-65 108 Cl ~ -N~N l C0-C(CH )2-CH2CH2-0 ~ 113-16 \~N Cl 109 Cl ~ -N ~N CO-c(cH3)2-cH2cH2 ~ 1,5581 ~ Cl ~ CO-C~C1~3)2-CH2CH2-O ~ F 79-81 111 Cl ~ -N ~ CO~ Cl 1,5555 112 Cl ~ -N l C0 ~ viscous oil ~ Cl ~N l; C ~ viscous oil 114 ~ 1 N CH3 Br 5~
115 Cl ~ ~ N \ Br 136(xHNO3) 116 Cl ~ -N ~ CO~ BBrr 125 117 Cl ~ -N ~ CO ~ 1,5412 118 ~ ~ N \ Cl viscous oil 119 Cl ~ -N 1 COC ~ viscous oil 120 Cl ~ -N ~ CO ~ viscous oil 121 Cl ~ -N -lN CO~ BBrr 1,578 122 ~ -N~=~X CO-C~CH3)2-CH2CH2-O ~ C1 179-80 123 Cl ~ ~¦ CO-C~CH3)2-C~12CH2 ~ resin , ~
q:~q~
Ex M . p . ( C) or Ar Az ~ R 20 No. ~_ Cl nD
124 Cl~ -N~7 C0 -C (CH ) 2-CH2CH2-O~Cl resin \~N
125 Cl~Cl ~N C0 -C(CI-I3)2-CH2CH2 ~Cl 121-22 126 Cl~ -N ¦ C0 C~CH3)2 Cll2C 2 ~ ~ 110-15 Cl 127 ~ -N/=~7 C0 _C(cH3)2_cH2cH2_o~-cl 157 \=N
128 Br~ -N N CO -C (CH ) 2-CH2CH2-O~C1 146-47 129 E-~ ~ ¦ CO -C~cH3)2-cH2cH2 ~Cl 122~23 130 Cl~ -N ¦ CO -C (CH3) 2_cH2cH2_o~C1 142-43 \==N
131 ~ 1 -N~N¦ C0 -C(CH )2-CH2CH3-0~ 154-55 /C ~N
132 Cl~ -N ¦ C0 -C(cH3)2-cH2cH2 ~ 110-111 133 Cl ~ /==N -C(CH3)2-CH2CH2-0 ~ 149-53 134 Cl ~ -N ~ CO -C(CH3)2-CH2cH2 ~ F 1,5590 / ~ N ~ __ l35 Cl ~ -N\=~N C0 -C(CH3)2-CH2CH2-0 ~ F resin 136 F~ /=~N CO -C(CI-I3)2-i-c3H7 122-25 :L37 Cl ~ -N ¦ C0 ~ viscous oil 138 C1~ -N ¦ C0 ~ 110-18 139 ~ Cl-N r NNI CO C(CH3)2 C3 7 224-25 /= N
140 Cl ~ -N\=~N C0 c(CH3)2 i C3 7 148-49 ~3~
NXo Ar A~ B R M . p . ( C) or 141 Cl ~ -N~ CO C (CH3) 2 C3 7 143 142 ~ -N\==7CO -C ~CH3) 2-CH2-C (CH3) 3 206 Cl f~N
143 Cl~ -N ¦ CO -C(cH3)2-cH2-c(cH3)3 138 ~, N
144 Cl~ -N~ CH(OH) C(CH3)2 CH2~ 144(A Form) 145 Cl~ -N~ CH(OH) -C(CH3)2-CH2~-Cl (B Form) 146 Cl~ -N ~CH(OH) -C(CH3)2-cH2~ 157(A Form) N
147 Cl~ -N~ CH(OH)-C(cH3)2-cH2~ viscous oil 148 Cl~ -N~ CH(OH)-C(CH3)2-CH2~ viscous oil 149 Cl~ -N 1 CH(OH)~Cl viscous oil 150 Cl~ -N~ CH(OH) ~Br 168(A Form) 151 Cl~ -N ~ CH(OH)~Br 116-19 \=~N Br (B Form) 152 Cl~ -N~ C~l(OH)~Br 145 153 ~ -N 1 CH(O~I)~Cl 80-85 ~ ~ - N ~ Cl 84 155 Cl~ -N~ CH(OH) ~ viscous oil 156 Cl~ ~N C(C 3)2 3 7 1~5332 NXo Ar Az B R M.p. ( C) or __ _ 157 ~ -N ~ Cll(OH~ C(C 3)2 3 7 110 N
158 Cl ~ -N ~ CH(OH) C(CH3)2 n C4 9 1,5310 N
159 ~ -N ~ CH(OH) C(C 3)2 3 7 103-04 Cl N
160Cl ~ -N ~ CH(OH) C(CH3)2 i C3 7 113 161Cl ~ -N ~ CH(OH) C(C 3)2 3 7 resin N~
162 ~ -N ¦ CH(OH) -ClcH3)2-cH2-c(cH3)3 120 Cl N
~ /N~
163Cl ~ -N ¦ CH(OH) -c(cH3)2-cH2-c~cH3)3 resin 164Cl ~ -N ~ CH(OH) -C(CH3)2 ~ 120-26 N
165 Cl ~ --N ~ CH(OH) -C(cH3)2-cH2-cH2-o ~ Cl 155-63 166 ~ ~ N -C(C113)2-CH2CH2-0 ~ Cl 81-83 167 Cl ~ -N ~ CH(OH) -C(C~-13)2-CH2CH2-0 ~ Cl resin 168 P ~ Cl -N ~ CH(OH) -C(CH3)2-CH2CH2-0 ~ -Cl resin 169 Cl ~ -N ~ Cll(OH) -c(cH3)2-c~l2cH2 ~ resin 17~ -C(CH3)2-CH2C,H2-0 ~ Cl 118-19 N
171 Br ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-0 ~ Cl 115-17 172 F ~ ~ N -C(CH3)2-CH2CH2-0 ~ Cl resin 173 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-0 ~ Cl resin Ex Ar Az B R 20 174 Cl ~ -N ~ CH(OH) -C(CH3)2-Cll2cH2 ~ ~ resin 175 Cl ~ -N 1 CH(OH) -C(cH3)2-cH2cH2 O ~ F resin ~=N
176 Cl ~ -N ¦ CH(OH) -C(CH )2-CH2CH2-O ~ Cl 104-05 177 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2-c(cH3)3 128 ~=~N
178 Cl ~ -N ~ N CO -C(cH3)2-cH2- ~ SC 3 1,5490 179 Cl ~ -N ~ N CO -C(CH3)2-CH2-cH2 ~ 1,5378 180 Cl ~ -N ~ N CO ( 3)2 CH2-CH2-O ~ OCF3 viscous oil 181 Cl ~ -N ~ CO -C(C~I3)2-cH2cll2 ~ 1,5686 N Cl 182 Cl ~ -N ~ N CO -C(CH3)2-CH2CH2-O ~ 1,5689 183 Cl ~ -N ~ N CO C(CH3)2 CH2CH2 ~ 1,5738 184 Cl ~ -N~=X CO -c~CH3)2-CH2cH2-O ~ 126-28 Ex.Ar ~Z B R M.p. ( C j No. or ~
_ 185Cl~ H(OH) { (CH3)2-CH2cH2 o4~ 1,5291 186Cl~ -N/~lN CH(OH) ~(CH3)2{EI~!c~2-O~-(xF3 187Cl~ t ~- N ~ ~(CH3) 2{~H2CH2~ ~> resin 188 C1~ -N 1N CO ~ (CH3 ) 2{ H2C~2~ . r~s i n 189 Cl ~ ~ C(CH3)2 {~H2CH2~ o2 :resir, 190 Cl ~ -N~ N CO -C(C ~ )2-CH2C~2 ~ NO 99 100 NO
191 Cl ~ -N~Nl -C(CH3)2-CH2CH2-0 ~ ~resin f~N
192 Cl~ -N I CO -C(CH3)2 CH2CH2 ~)2 135-36 Cl 193 Cl~ ~N CH(OH) ~C(CH3)2~H2CH2~) resin 194 Cl ~ ~N~ CH(OH~ -C(CH3) 2-CH2CH2~ resin 195 Cl~- ~ CH(OH) -C(CH3)2-CH2CH2 ~ resin Le A 21 911 ~ ~o -Ex. Ar AZ B R M~p. ( C ) No. nDO
196 Cl{~ -N~CH(O~) ~1 123 197 Cl~ -N~CH(OH)~1 104-07 (A For~) :~H
198Cl~ -N 1CH(O~) ~ i l (B Form) Cl CH~
199Cl~ -N~Cq(CH) Y~l i l OEI
200 Cl~ -~ 94 C~H~
Cl C oi l :~q~
202 Cl~ ~ ~N CO ~ oi l 203 Cl~~ ~ 175 C 1~_ 204Cl~ -N~ CO ~ 91 C6H~
205 Cl~ -N~ CO ~ 156-58 N~ ~l 206 C1{~-N,~ CO \~J 107 Le A 21 911 Ex. Ar Az B R M.p. ( C ) No. ~0 ___ _ .
207 Cl~ ~ CH (OH) ~ 107-10 Cl N 2 5 208 Cl~ ~ ~CH (OH~ ~ o i l 209 C~ CH (CH) ~ i l 210 C:L~ ~NCH (OH~ ~ ~i l 21 1 Cl~ ~ oi l \= N
Cl C6~ 138-40 Cl N 6 5 213 Cl~ ~ CO ~ 102-03 214 Cl~ ~ O ~ 98-1 00 215 C1~ ~ CO ~ 160-61 216 Cl~ ~ i 217 ~} -N~ CO -\~ oi l Le A 21 911 3~
42 ~
~x. Ar Az B R M.p (~C ) No~
218 <~ ~ ~ CO ~ 103-09 219 Cl~ ~cN OEI(OH) Y~l oi l C6~5 220 Cl~ ~ l(OH) ~ 111 (A Farm) C~
221 Cl ~ -N ~ CH(OH) ~ oil C6~3 222 Cl ~ -N ~N CH(OH) ~ 114 (A Form) 223 Cl ~ ~ N CH(OH) ~ oil 224 Cl~ -~ CO-c(cH3~2-cH2cH2cH2cl 1,54l2 225 Cl ~ -N\~ N CH(OH) -C(CH3)2-CH2CH2-0- ~ -SCF3 oil 226 Cl ~ -N ~N CO 4-ClC6~ oil 227 Cl ~ -N ~ CO 4-ClC6H~ ~ oil A and B ~orm: the two possible geometric isomers Le A 21 911 3~
Use E_amples In the examples which follow, the compounds shown below are employed as comparative substances:
CH3 fH3 (A) C1 ~ O-fH-CO-f-CH2C
~ N
Cl OH CH3 (B) Cl ~ O-fH-CH-C-CH2-O ~ Br ~ N
Cl fH3 (C) Cl~-O-fH-CO-f-CH2Cl ~ N
Cl CIH3 (D) Cl ~ O-fH-CO-C-CH2-O-COCH3 N
~E) Cl ~ O-fH-CO-f-CH2-O-COCH3 N
CH
(F) Cl ~ -O-CH-CO-f-CH20H
~ ~ CH~
.
~3~
(G) C1~ O~CH-CO-C-CH2-0-~3 C1 ~ N
(H) C1~ 5-O-CH-CO-C-CH2-O~ -C1 ~ N
(I) C1~ -O-fH-CH C-CH2-O-~ -Br C ~N CH3 (J) C1-~ O-CH-CH - i-CH2-0-~ -CH3 K) C1--~-O-CH-CO-C-CH2-S~
~N~N CH3 (L) C1-~ -O-CH-CO-¢-CH2-O C2H5 N~- ~N CH3 (M) ~ 5-O-CH-CO-C-CH2C1 ~ ~ CH3 .3~
Cl CH3 r~ I
(N) Cl ~ -O-CH-CO-C-CH2-OH
~N CH3 OH CH~
(O) Cl ~ O-fH-CH - C-CH2-S ~ -Cl (P) Cl ~ -O-CH-CH - C-CH2-O ~ Cl ~ N~N CH3 (Q) Cl ~ O-CH-CH - C-CH2Cl N~N CH3 OH CH
(R) ~ ~ -O-CH-CH - C-CH2Br ~ N~N CH3 OFl CH
(S) ~ O-CH-CH - C-CH2Cl ~N CH3 - 45a -(T) Cl- ~ -O-CH-CH - C-CH2-O- ~ Cl ~N~N CH3 Cl OH CH3 (U) Cl ~ -O-CH-CH - C-CH2Cl ~ N~N CH3 ~3~
Example A
Puccinia ~est (wheat) / protective Solvent: 1CC parts oy weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl poly-glycol ether To produce a suitable preparation of active com pound~ 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the con~
centrate is diluted with water to the desired concentration.
To test for protective activity~ young plants are inoculated with a spore suspension of Puccinia recondita in a 0.17~ strength aqueous agar solution. After the spore suspension has dried on, the plants are sprayed with the preparation of active compound until dew-moist~ The plants remain in an incubation cabin at 20C and 100%
relative atmospheric humidity for 24 hours.
The plants are placed in a greenhouse at a tempera-ture of about 20C and a relative atmospheric humidity of about 80% in order to promote the development of rust pustules.
Evaluation is carried out 10 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 13, 12, 22, 16, 17, 33, 34, 4, 36, 24, 38, 39, 40, 41, ~t2, 43, 5, 44, 45, 145, 147, 169, 171 and 172.
Le A 21 ~11 _xample e Cochliobolus sativus tes~ (barley) / protective ~olvent: 100 par~s by weight of dimethylformamide Emulsifier: 0~25 parts by weight of alkylaryl poly-glycol ether ~o produce a suitable preparation of ac~ive com-pound, 1 part by weight of active compound is mixed w;th the stated amounts of solvent and emulsifier~ and the concentrate is diluted with water to the deslred con-centration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Cochliobolus sativus. The plants remain in an 1ncuba-tion cabinet for 48 hours at 20C and 100% relative atmospheric hum;dity.
The plants are placed in a greenhouse at a temperature of about 2QC and a relative atmospheric humidity of about 8~o~
Evaluation is carried out 7 days after the inoculat;on.
In this test~ a clearly superior activity com-pared with the prior art is shown, for example, by the compounds according to the following Preparat;on Examples:
13, 12, 22, 17, ~5, 68, 58 and 75.
Le A 21 S11 i.3~
- ~8 -Example C
Sphaerotheca test (cucumber) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl poly-glycol ether To produce a suitable preparation of active com-pound, 1 part by we;ght of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparatlon of act;ve compound until dripping wet. After the spray coating has dried on, ~he plants are dusted with conidia o-f the fungus Sphaerotheca fulig;nea.
The plants are then placed in a greenhouse at 23 to 2~C and at a relat;ve atmospheric humidity of about 75%.
Evaluation is carried out 10 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples:
98, ~5~ 10Q, 1Q3, 15û, 169, 156, 152 and 83.
Le ~ 21 911 3~
Example D
Erysiphe test (barley) / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl poly~
glycoL ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concen-tration~
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.
The plan~s are placed in a greenhouse at a tem-perature of about 20C and a reLative atmospher;c hum-id;ty of about 80~, in order to promote the development of powdery mildew pustules.
Evaluation ;s carr1ed out 7 days after the inoculation.
In this test, a clearly superior act;vity compared with the pr;or art is shown, for example, by the compounds according to the follow;ng preparation examples: 50, 52, 66, 67, 68, 70, 71, 72, 58, 73, 6, 75, 82, 83, 93, 112, 113 and 106.
Le A 21 911 z Example E
Erysiphe test tbarley) / seed treatment The active compounds are used as dry dressings.
These are prepared by extending the particular active compound with a ground mineral to give a f;nely pulveru-lent mixture, which ensures uniform distribution on the seed surface.
To apply the dressing, the seed is shaken with the dressing in a closed glass flask for 3 minutes.
3 batches of 12 grains of the barley are sown 2 cm deep in standard soil. 7 days after sowing, when the young plants have unfolded their first leaf, they are dusted with spores of Erysiphe graminis f. sp. hordei.
The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humid-;ty of about 8û% in order to promote the development of pow-dery mildew pustules.
Evaluation is carried out 7 days after the inoculationv 2n In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the compounds accord;ng to the following preparation examples:
1 5 0 .
Le A 21 911 ~ ~35~2 Example F
-Pyricularia test (rice)/protective Solvent: 12.5 parts by weig'nt of acetone Emulsifier: 0.3 parts by weight of alkylaryL poly glycol ether To produce a su;table preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the sta-:ed amount of emulsifier, 1~ to the desired concentrat;on.
To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried off, the plants are inoculated with an aqueous spore suspension 15 of Pyricularia oryzae. The plants are then placed ;n a greenhouse at 10~% reLative atmospheric humidity and 25C.
Evaluat;on of the disease infestation is carried out 4 days after the inoculation.
In this test, a clearly superior activity compared 2~ with the prior art is shown, for example, by the compounds according to the following preparation examples:
156, 169, 152, 24 and 43O
Le A 21 911 .3~)?~
~xample C
Pellicularia test (rice~
Solvent: 12.5 parts by we;ght of acetone Emulsifier 0.3 parts by weight of alkylaryl poly-glycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, to the desired concentration.
To test for activity, young rice plants in the 3 to 4 leaf stage are sprayed until dripping wet. The plants remain ;n a greenhouse until they have dried off.
The plants are then inoculated with Pellicularia sasakii and are placed at 25C and 100% relative atmospher;c humidity.
The evaluation of the disease infestation is carried out 5 tO 8 days after the inoculation.
In this test, a clearly superior activity com-2Q pared with the prior art is shown, for example, by thecompounds according to the following preparation examples: 12, 22, 14, 23, 16, 17, 1~, 33, 4, 37, 24, 38, 25, 41, 429 43 and 44.
Le ~ 21 11 Example l-l ~gar plate test ~!utrient medium used 39 parts by weight of potato glucose agar 5 parts by weight of agar-agar 1Q parts by weight of peptone 5 parts by we;ght of malt are dissolved in 1,0nO ml of distilled water and the sol-ution is kept in an autoclave at 121C for 30 minu~es.
Solvent: 2 parts by weight of water-acetone (97.5 : 2.5) Ratio of the amounts of solvent to nutrient medium:
Z : 100.
To produce a suitable preparation of active com pound, 1 part by weight of ac~ive compound is mixed with the stated amount of solvent.
The concentrate is thoroughly mixed, in the stated proportion, with the liquid nutrient medium and the mix-ture is then poured into Petri d;shes~
When the nutrient medium has cooled and solidi-fied, the plates are inoculated with the follow;ng micro-organisms and are incubated at about 21C: Cochliobolus miyabeanus Evaluat;on ;s carr;ed out after Z to 8 days, depending on the speed of arowth of the microorganisms, the ;nh;bit;on of growth be;ng used as a measure of the action of the preparations.
In this test, a clear superiority compared with the pr;or art ;s shown by the compounds according to the following preparation examples: 145, 147, 156, 157, 167, 168 and 173 Le A 21 911
formamide for 16 hours. The mixture is then cooled to 20 C and filtered off from the precipi-tated inorganic salt, and the fil-trate is evaporated down in vacuo. The oil which remains (96.2 g) is taken up in 500 ml of ethyl acetate, and the solution is washed wi-th three times 100 ml of 10% strength sodium carbonate solution and with -twice 100 ml of water. After the solution has been dried over sodium sulphate, it is evaporated down, and the oily residue (80 g) is stirred with 50 ml of petroleum ether. 68.6 g (81~1% of theory) of l-(4-chlorophenoxy)-3,3,5,5-tetramethyl-hexan-2-one are obtained as colourless crystals of melting point 47-48C.
Example 3 _ Cl ~ O-fH-lH - f-CH2-C(CH3)3 ~N~N CH3 N
(Process c) 2 g (0.054 mol) of sodium boronate are introduced in por-tions into a solution oE 9.5 g (0.027 mol) of 1-(4-chlorophenoxy)-3,3,5,5-tetramethyl-l-(1,2,4-triazol-l-yl)-hexan-2-one (Example l) in 95 ml of methanol at 20 to 30 C, while cooling externally.
After three houxs, the solution is brought to a pH value of 6 by the addition of acetic acid. The solution is then evaporated down in vacuo, the residue is taken up in 100 ml of ethyl acetate and the solution is washed with three times 20 ml of water, dried over sodium sulphate and evaporated down in vacuo. 9~5 g (100% of theory) of l-(4-chlorophenoxy)-3,3,5,5-tetramethyl-l-(1,2,4-tri-s-~
azol-l-yl)-hexan-2-ol are obtained as a colourless viscous oil with a refractive index nD = 1.5250.
Example 4 _ .
fH3 c].~o-T~-C-f CH2CH2 ~ N
(Process a) 5.9 g (0.035 mol) of 1-chloro-3,3-dimethyl-5-fluoro-penten-2-one are added dropwise to a boiling mixture of 4.6 g (0.035 mol) of 4-chlorophenol, 4.9 g (0.035 mol) of potassium carbonate and 20 ml of acetone. After the mixture has been heated for four hours, it is filtered off from the precipitated potassium chloride, and the filtrate is evaporated down under reduced pres sure. The 1-(4-chlorophenoxy)-3,3-dimethyl-5-fluoro-pentan-2-one which remains as a colourless oil (9 g; 100% of theory) is dis-solved in 40 ml of dichloroethane, and 5O9 g (0.037 mol) of bro-mine are added in the course of 20 minutes at 20 C. The solution is stirred for two hours at 20 C and washed with three times 20 ml oE water, and the solvent is distilled oEf in vacuo. 11.8 g (100%
oE theory) of l-bromo-1-(4-chlorophenoxy)-3,3-dimethyl-5-fluoro-pentan-2-one remain as the residue, in the form of a slightly yellowish oil. This is ta~en up in 20 ml of acetonitrile, and the solution is added dropwise, in -the course of 20 minutes, to a boil-ing solution of 14.3 g (0.21 mol) of imidazole in 120 ml of aceto-nitrile. After the mixture has been heated under reflux for four 5~
- 21 ~
hours, the solvent is distilled off in vacuo, -the residue is taken up in 200 ml of ethyl acetate, and the solution is washed wlth three times 50 ml of water, dried over sodium sulphate and evapor-ated down under reduced pressure. After the oil which remains (10.8 g) has been filtered over a silica gel column (ethyl acetate:
trichloroethane, 1:1), 8.0 g (70.2% of theory) of 1-(4-chloro-phenoxy)-3~3-dimethyl-5-fluoro-l-(imidazol-l-yl)-pentan-2-one are obtained as colourless crystals of melting point 77-78C ~y evapor-ating down the eluate.
Example 5 fH3 F ~ O-CH-CO-C-CH2CH2-O ~ Cl ~ N
(Process a) A solution of 40.2 g (0.591 mol) of imidazole and 43.0 g (0.1 mol) of 1-bromo-5-(4-chlorophenoxy)-3,3-dimethyl-1-(4-fluorophenoxy)-pentan-2-one in 600 ml of acetonitrile is heated at the boil for 4 hours. The solution is then evaporated down in vacuo, the xesidue is taken up in 400 ml of ethyl acetate, and the solution is washed with 100 ml of water. After the organic phase has been dried over sodium sulphate, it is evaporated dcwn under reduced pressure, and the solid residue which remains is stirred with dlethyl ether. 34.3 g (83.5% of theory) of 5-(4-chloro phenoxy)-3,3-dimethyl 1-(4-fluorophenoxy)-1-(imidazol-1-yl)-pentan-2-one are obtained as colourless crystals of melting point 120-121C.
5~3~
Preparation of the starting material C~I3 -CH-C-f~CH2CH2- ~ Cl Br CH3 34.3 y (0.214 mol) of bromine are rapidly added dropwise to a solution of 69.1 g (0.197 mol) of 5-(4-chlorophenoxy)-3,3-dimethyl-l-(4-fluorophenoxy)-pentan-2-one in 600 ml of dichloro-methane. After the addition of bromine is complete, stirring is continued for a further 15 minutes and 400 ml of ice water are then added to the ~olution. The organic phase is separa-ted off and washed once with 100 ml of aqueous sodium bisulphite solution and with twice 100 ml of water. The solution is dried over sodium sulphate and then evaporated down in vacuo. 85.9 g (100% of theory) of l-bromo-5-(4-chlorophenoxy)-3,3-dimethyl-1-(4-fluoro-phenoxy)-pentan-2-one are obtained as colourless crystals of melt-ing point 92-93 C
fH3 CH2-CO-I-CH2CH2-O ~ Cl 68.8 g (0.25 mol) of 1 chloro-5-(4-chlorophenoxy~-3,3-dimethylpentan-2-one are heated at the boil for 13 hours with 28 g (0.25 mol) of 4-fluorophenol and 34.5 g (0.25 mol) of powdered potassium carbonate in 600 ml of acetone. Thereafter, the solu-tion is filtered off from the organic salt, the filtrate is evapor-ated down in vacuo and the residue is taken up in diethyl ether.
After petroleum ether has been added, 69.3 g (79% of theory) of 5-(4-chlorophenoxy~-3~3-dimethyl-l-(4-fluorophenoxy)-pentan-2-one are obtained as colourless crystals of melting point 71-74 C.
Example 6 F~o_cH_cH_ C_cH2cH2_o~Cl ~ N
(Process c) 2.6 g (0.068 mol) of sodium boranate are introduced in portions into a solution of 14.2 y (0.034 mol) of 5-(4-chloro-phenoxy)-3,3-dimethyl-1-(4-fluorophenoxy)-1-(imidazol-1-yl)-pentan-2~one (Example 5) in 140 ml of methanol at 20 to 30C, while cool-ing externally~ After two hours, the solution is brought to a pH
value of 6 by the addition of acetic acid~ and is evaporated down in vacuo. The residue is taken up in 200 ml of ethyl acetate, washed with twice 50 ml of water, dried over sodium sulphate and evaporated down. By triturating the solid residue with petroleum ether, 12.3 g (86.6% of theory) of 5-(4-chlorophenoxy)-3,3-dimethyl-l-(4-fluorophenoxy)-1-(imidazol-1-yl)-pentan-2-ol are ob-tained as colourless crystals of melting point 88-93 C.
Example 7 fH3 Cl Cl~o_fH_Co lC CH2~
~N CH3 N I I x HCl 3 ~
- 23~ -(Process aj 11 g (0.16 mol) of 1,2,4-triazole and 22 g (0.16 mol) of potassium carbonate in 200 ml of toluene are stirre~ for 1 hour at 90 C. 35 g (0.078 mol) of l-bromo-l (4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-butan-2-one in 100 ml of toluene are added dropwise ~o the mixture. The reaction mixture is stirred for a further 10 hours at 90C and then cooled to room temperature and 200 ml of water added. The organic phase is separated off, dried over sodium sulphate and evaporated down. The residue is purified by column chromatography. 7.8 g of 1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3~dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one are obtained as a highly viscous oil. 15 ml of saturated ethereal hydrochloric acid are added to 3.9 g of this highly vis-cous oil. The precipitated salt is filtered off under suction, washed with a little ether and dried in vacuo at 40 C. 3.3 g (78.2% of theory) of 1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-l-(1,2,4--triazol-1-yl)-butan-2-one hydrochloride of melt-ing point 130-135 C are obtained.
Preparation of the startin~ material Cl ~ O-ICH-CO-C - CHz ~ Cl Br CH3 24.5 g (0.15 mol) of bromine are added to 57 g (0.15 mol) of l-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)~3,3-dimethyl-butan-2-one, dissolved in 400 ml of chloroform, at room temperature.
- 23b -After the addition is complete, the reaction mix-ture is stirred for a further 30 minutes and then evaporated down. 67.6 g (100% of theory) of crude 1-bromo-1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl butan-2-one are ob~ained; this product is directly reacted further.
~l_ ~ O-CH2-CO-C - CH2- ~ Cl 28.2 g (0.22 mol) of 4-chlorophenol and 30.4 g (0.22 mol) of potassium carbonate in 120 ml of toluene are heated under re-flux for 2 hours in a water separator. A solution of 57 g (0.18 mol) of 1-bromo-4-(2,4-dichlorophenyl)-3,3-dimethyl-butan-2-one in 200 ml of toluene is added dropwise at 60 C. The reaction mixture is then stirred for a further 5 hours at 100C. The mixture is allowed to cool and filtered off under suction from the inorganic residue, and the toluene phase is washed with ~3~
dilute sodium hydroxide solution and then with water, dr;ed over sodium sulphate and evaporated down. 57.4 g (7n.2~ of theory) of 1-(4-chlorophenoxy)-4-(2,4-dichloro-phenyl)-3,3-dimethyl-buta~-2-one of refractive index n20 =
1.5753 are obtained.
CH3 C~
Br-CH2-CO-C-CHz- ~-Cl c~3 13.4 ml (0.26 mol) of bromine are added dropw;se to 64.5 9 (C.26 mol) of 4-(2,4-dichlorophenyl)-3,3-d;me-thyl-butan-2-one in 600 ml of chloroform at room tempera-1û ture. The reaction mixture is stirred for a further hourat room temperature and evaporated down. 84 g (1Q0% of ~heory) of crude 1-bromo-4-(~,4-dichlorophenyl)-3,3-di-methyl-butan 2-one are obtained; this product is directly reacted furtherO
Example ~
OH CH3 Cl Cl- ~ -O-CH-CH - C-CH2 ~ -Cl ~ N~N CH3 N l¦
(Process c) 3.5 9 (0.008 mol) of 1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2n 2-one ~see Example 7) are dissolved in 50 ml of methanol at -1QC, and 0.1 9 ~0.0026 mol) of sodium borohydride in 2 ml of water is added. The reaction mixture is stirred for a further hour w;thout cooling and ;s then evaporated down in vacuo. Methylene chloride/water is then added ~o the res;due~ The organic phase ;s separated off, dried over sodium sulphate and evaporated down. 3L2 9 ~91.4%
of theory) of 1-~4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-1-(1,2,4-tr;azol-1-yl)-butan-2-ol of melting Le A 21 911 ~ 3~
po;nt 60-65C are obta;ned.
Example 9 -C~
Cl ~ 0-CH-C0-C
~N CH3 (Process b) A mixture of 14.4 9 (0.21 mol~ of 1,2,4 triazole and 26.9 9 ~0.21 mol~ of 4 chlorophenol in 1QG ml of ace-tone are added to 43 9 (0.19 mol) of 1,1-dichloro-3-(di-oxolan-2-yl)-3-methyl-butan-2-one and 78.4 g (0.57 mol) of potassium carbonate in 300 ml of acetone, under reflux.
1Q The reaction mixture is stirred under reflux for a further 10 hours, then cooled and filtered off under suction from the inorganic residueA The filtra~e is evaporated down, the residue is taken up in methylene chloride, and the solution is washed with dilute sodium hydroxide solution and with water, dr;ed over sod;um sulphate and evaporated down in vacuo. The residue is purified by column chroma-tography (silica gel/ethyl acetate:cyclohexane = 3:1).
19 g (28~4% of theory) of 1-(4-chlorophenoxy)-3-(dioxo-lan-2-yl~-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-one of refract;ve index n20 = 1.4994 are obtained.
_reparation of the start;ng material_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ CjH3,o C l 2CH-CO-C -\ ~
C~3 36.8 g (0.2 mol) of 4,4-d;chloro-2,2-d;methyl-3-ketobutanal, 13.~ 9 (0.22 mol) of echylene glycol and 2.2 g of p-toluenesulphonic ac;d ;n a mixture of 180 ml of toluene and 16C ml of n-butanol are heated under reflux for 1.5 hours in a water separator. The mixture is Le A 21 911 3~
- 26 ~
allowed ~o cool~ and ;s evaporated do~Jn in vacuo. The residue is taken up methylene chloride, and the solution is washed with water, dried over sodium sulphate and evaporated down. 43.~ 0 (96' of theory) of 1,1 dichloro~
5 3-(dioxolan-2-yl) 3-me~hyl butan-Z-one of refractive index n2n = 1~4631 are obtained.
Cl2CH - CO - C - CHO
~ CH3 141 9 (1 mol~ of 1-(N-morpholino)-isobutene are dissolved in 470 ml of diethyl ether~ 147.5 9 (1 mol) of dichloroacetyl chloride are slowly added dropwise, while cooling with ice. The reaction mixture is then stirred for 24 hours at room temperature~ after which 150 ml of water are added and sodium bicarbonate solution is added until a pH value of 5 to 6 is reached. The mixture is stirred for a further hour and the ether phase is then separated off. The aqueous phase is extracted with ether and then with methylene chloride. The combined organic phases are dried over sodium sulphate and evaporated down, and the residue ;s dist;lled in vacuo. 155.6 9 (85% of theory) of 4,4-dichloro-2,2-dimethyl-3-keto-butanal of boiling point 118C/0.2 mbar are obtained~
Example 10 OH CH3 0 _ Cl ~ -O-CH-CH - C -~ N N CH3 N , ~Process c) 7 9 (Q~02 mol) of 1-~4-chlorophenoxy)-3-(dioxolan 2-yl)-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-one (Example 9) are dissolved in 70 ml of methanol, and a solution of Le A 21_911 ~ 3~3~
n.23 9 (0.006 mol) of sodium borohydride in 5 ml of water is added. The reaction mixture is stirred for a further 2 hours, the p~l value is brought to 6-7 with dilute hydro-chloric acid, and the mixture is evaporated down in vacuo.
The residue is taken up in methylene chloride, and the solution is washed with water, dried over sodium sulphate and evaporated down. 5.8 9 (~2.9% of theory) of 1-(4-chlorophenoxy) 3-(dioxo1an-2-yl)-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-ol of refractive index n20 = 1.5389 are obtained.
The compounds of the general formula Ar - O- CH ~ i3 ~ R (I) A z are obtained in a corresponding manner and analogously to the processes given:
Le A 21 911 NoX Ar Az B R D
.
~ N Cl 11 Cl ~ - -N ¦ CO -C(CH~)2-CH~ ~ C1 213(xHCl) 12 C1 ~-N ~ N CO C(C 3)2 2 ~ viscous oil ~N
13 C1 ~ -N ¦ CO C( 3)2 2 ~ C1 174-75(xHC1) /==N \3 A
14 C1 ~ - -N ¦ CO CH Cl 15 ~ -N ~ CO ~ Ccl 164 16 Cl ~ -N ~ CO ~ ~iscous oil 17 Cl ~ -N ~ CO ~ viscous oil 18 C1 ~ ~N CH Br 19 ~ -N ~ CO ~ BBr 178 C1 ~ -N ~ CO ~ viscous oil 21 C1 ~ ~ N ~ viscous oil 22 C1 ~ -N ~N CO -C~CH3)2-n-C3H7 1,5345 ~=~N
~3 ~ -N ~ CO -C~CH3)2-n-C3ll7 65 /=~N
24 ~ ~ _ -N ~ ~O -C~CH3)2-i-C3~l7 1,5195 ~=~N
C1 ~ -N J CO -C~CH3)2-CH2CH2C1 resin 26 Cl ~ ~ ~C~cH3~~n~c4~9 1,5324 r=N
27 ~ - -N ~ CO C~CH3)2 3 7 127 ~3~
_ 29 -NXo Ar Az B R M.p. ( C) or Cl~=~N
28 Cl ~ -N ~ C0 c(CH3)2 i C3H7 resin f=~N
29 Cl ~ -N ~ C0 C(CH3)2 i C3H7 resin Cl ~ - -N ~ N C0 -C(CH3)2-CH2-c~cH3)3 83-85 31 ~ -N ~ N C0 -C~cH3)2-cH2-c~cH3)3 128 ~ Cl ~ N C0 -C(cH3)2-cH2-c~cH3)3 84 33 Cl ~ -N ~ N C0 -C(CH3)2-CH2CH20 ~ resin 34 Cl ~ _-N ~ N C0 -C~CH3)2-CH2CH2-0 resin N g ~ -N ~ C0 -C~CH3) -CH2CH2-0 102-03 36 ~ N C0 -C~CH3)2-CH2CH2 ~ Cl resin f=~N Cl 37 Cl ~ -N ~ C0 -C~CH3)2-ci~2cH2 ~ Cl 1~5822 ClN Cl 38 Cl ~ -N ~ C0 -C(CH3)2-C~l2cH2 ~ 1,5746 r N Cl 39 F ~ -N ~ C0 -C(CH3)2-CH2cH2 ~ Cl 1,5629 l$Jl 3~
E M.p. ( C) or NXoAr Az B R nDO
~N
40 ~ -N~=¦ C0 -C(CH3)2-CH2CH2~Cl 1,5950 41Br~-N~JN C0 -C(cH3)2-cH2cH2-o~cl 108-09 42 ~ -N~NI C0 -C (CH3) 2-CH2CH2 ~) 95-96 _~Cl ~N C0 -C(cH~)2-cH2cH2 ~) resin _~$CH3 ~N C0 -C (CH3) 2-CH2CH2-~Cl resin 45F~ -N~Nl C0 -C(CH3)2-CH2cH2 ~) 88-90 46Cl~ -N~N C0 -C (CH3) 2-CH2CH2 ~ resin 47Cl ~-N ~ C0 -C~CH3)2-CH2CH2 O ~ viscous oil 48 ~-N ~ N CO -C(CH3)2-CEl2cH2 ~ viscous oil 49Cl ~-N ~ N CO -C~CH3)2-CH2CH2-0 ~ F viscous oil FN
Cl ~ -N ¦ CH~OH)-C~cH3)2-cEl2 ~ Cl 60-65 /=~N
Sl Cl ~ -N ~ CEI(OH) C(CH3)2 C~l2 ~ 156-59 /=~N
52 Cl ~ -N ~ CH~OH)-C~CH3)2-CH2 ~ 144 53 Cl ~ -N ~ CEI~OH)C~l Ccl 123 54 ~ -N ~ CH~OH)~ ~ Ccl 214 F N ~ 3,-~
Cl ~ - -N ~ CH~OH) ~ 145 5~
No Ar Az B R 20 ~ ~ ~ viscous oil 57 Cl ~ -N ~ CH(OH) c(CH3)2 n C3 7 86-90 58 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2CH2Cl resin 59 Cl ~ -N ¦ CH(OEI) C(CH3)2 4 9 1,5273 ~=~N
~ 1 -N ~ CEI(OH) C(CH3) 2 i C3 7 138-40 61 Cl ~ -N ~ CH(OH) C(CH3)2 i C3H7 viscous oil 62 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2CH2C1 102-03 63 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2-c(cH3)3 137-38 ~=N
64 ~ 1 /=,N -C(CH3)2-CH2-c(cH3)3 160 Cl ~ -N ~ CH(OE-I) -C(CH3)2-CH2-c(cH3)3 resin ~P~
66 Cl ~ -NJ CH (OH) -C (CH3) 2 -CH2CH2 -o~Cl 1 14 - 16 67 Cl -~ -N~ CH (OEI) -C (CH3) 2 -CH2CE12-O~ 118-24 68 ~_ -N~J CH (OH) -C (CH3) 2-CH2CH2-0~)-C1 138-40 69 Cl~ -N~j CH(OH) _C(cH3)2_cH2cH2_o~cl 147-51 Cl~ -N~ CH (OEI) -C (CH3) 2 _CH2cEl2_o~Cl resin 71 F~ ~N -C (CH~;) 2_cH2cH2 o~C1 111-13 72 Cl ~ -N~ CH (OH) -C (CH3) 2 -CH2CE-13-O~Cl resin 5~
No Ar Az B R 20 ~ Cl 73 ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-O ~ Cl 159-60 ~ N
74 Br ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-o- ~ -Cl 138-43 ~ N
F ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-O ~ resin ,CH3 /=~N
76 Cl ~ _ -N ~ CH(~H) -C(CH3)2-~H2CH2-O ~ Cl 64-66 77 Cl ~ -N ~ ~H(~H) -C~H3)2-~H2~H2 ~ resin /--N
78 Cl ~ -N~ CH(OH) -C(CH3)2-CH~CH~-O ~ F resin /=~N Cl 79 Cl ~ -l~ ~ CH(OH) -C(cH3)2-cH~cH~-o ~ F resin Cl /=~N Cl Cl ~ -N ~ CH~OH) -C(CH3)2-CH~CH~-O ~ -F resin ,N~
81 Cl ~ -N I CO -C(CH3)2-CH2 ~ Cl 13J-41(xHCl) N
S2 Cl ~ ~N\ l ~ -C(C~I3)~-CH2 ~ viscous oil ,N
83 ~1 ~ _ -N 1 CO -C(CH3)2-n-C3ll7 1,5312 ~, 84 ~ -N ~ CO -C(CH3)2-n-C3H7 ~5 F ~ -N~N CO -C(~H3)2-1-C~H7 1,5116 N
86 Cl ~ -N ~ COC(CH3)2 4 9 1,5250 P~
87 ~ -N ¦ CO-C(~H3)2-i-C3H7 121-22 _~/ClNL~
88 Cl ~ _ -N I CO-C(CH~)2-i-C3H7 59 ,N~
89 Cl ~ -N\=~N CO-C(CH3)2-i-C3~17 67 ~ ~?J ~ ~3 r~
NXo Ar Az B R M.p. ( C) or ~ ~ -N ~ C0 -C~CH3)2-CH2-c(cH3)3 112 91 C1 ~ -N 1 C0 -C~cH3)2-cH2-c(cH3)3 78 92 C1. ~ -N ~N C0 -C~CH3)2-CH0 1,5350 P~
93 C1 ~ ~N\==l C0 _C(CH3)2-C~l=NOcH3 1,5303 ,N Q
9'1 Cl ~ -N ~ C0 -C~CH3)2 ~ ~ viscous oil Cl ~ ~ N C0 _-C(CH3)2-CH2c~l2 ~ Cl 87-89 96 C1 ~ ,N l C0 --C(CH3)2-Cll2cH2 ~ resin 97 ~ -N ~ C0 C(CH3)2 CH2CH2 0 ~ 103-04 Cl C0 -C(CH3)2-CH2cH2 ~ Cl resin N ~
Cl ~ C0 -C(CH3)2-CH2CH2-0 ~ Cl 109-10 100 C1 ~ -N ~ CO C(CH3)2 C 2 2 ~ 1,5720 101 F ~ -N~N~N CO -C(CH3)2-CH2CH2-O ~ C1 1,5608 102 ~ ~ ~ N CO -clCll3)2-CH2CH2-O ~ C1 88 103 Br ~ -N ~ N CO -C(CH3)2-CH2CH2-O ~ C1 9'-l-95 104 ~ - -N ~ N CO -C(CH3)2-CH2cH2 ~ 86-88 N
105 F ~ -N l CO -C(CH )2-CH2CH2-O ~ C1 107-08 ~ C1 ~ CO -C(CH3)2-CH2cll2 ~ resin 3~ ?~
- 3~ -Ex. Ar Az B R M (C) or No. nD
__ Cl-l -c(cH3)2-cH2cH2-O ~ Cl 63-65 108 Cl ~ -N~N l C0-C(CH )2-CH2CH2-0 ~ 113-16 \~N Cl 109 Cl ~ -N ~N CO-c(cH3)2-cH2cH2 ~ 1,5581 ~ Cl ~ CO-C~C1~3)2-CH2CH2-O ~ F 79-81 111 Cl ~ -N ~ CO~ Cl 1,5555 112 Cl ~ -N l C0 ~ viscous oil ~ Cl ~N l; C ~ viscous oil 114 ~ 1 N CH3 Br 5~
115 Cl ~ ~ N \ Br 136(xHNO3) 116 Cl ~ -N ~ CO~ BBrr 125 117 Cl ~ -N ~ CO ~ 1,5412 118 ~ ~ N \ Cl viscous oil 119 Cl ~ -N 1 COC ~ viscous oil 120 Cl ~ -N ~ CO ~ viscous oil 121 Cl ~ -N -lN CO~ BBrr 1,578 122 ~ -N~=~X CO-C~CH3)2-CH2CH2-O ~ C1 179-80 123 Cl ~ ~¦ CO-C~CH3)2-C~12CH2 ~ resin , ~
q:~q~
Ex M . p . ( C) or Ar Az ~ R 20 No. ~_ Cl nD
124 Cl~ -N~7 C0 -C (CH ) 2-CH2CH2-O~Cl resin \~N
125 Cl~Cl ~N C0 -C(CI-I3)2-CH2CH2 ~Cl 121-22 126 Cl~ -N ¦ C0 C~CH3)2 Cll2C 2 ~ ~ 110-15 Cl 127 ~ -N/=~7 C0 _C(cH3)2_cH2cH2_o~-cl 157 \=N
128 Br~ -N N CO -C (CH ) 2-CH2CH2-O~C1 146-47 129 E-~ ~ ¦ CO -C~cH3)2-cH2cH2 ~Cl 122~23 130 Cl~ -N ¦ CO -C (CH3) 2_cH2cH2_o~C1 142-43 \==N
131 ~ 1 -N~N¦ C0 -C(CH )2-CH2CH3-0~ 154-55 /C ~N
132 Cl~ -N ¦ C0 -C(cH3)2-cH2cH2 ~ 110-111 133 Cl ~ /==N -C(CH3)2-CH2CH2-0 ~ 149-53 134 Cl ~ -N ~ CO -C(CH3)2-CH2cH2 ~ F 1,5590 / ~ N ~ __ l35 Cl ~ -N\=~N C0 -C(CH3)2-CH2CH2-0 ~ F resin 136 F~ /=~N CO -C(CI-I3)2-i-c3H7 122-25 :L37 Cl ~ -N ¦ C0 ~ viscous oil 138 C1~ -N ¦ C0 ~ 110-18 139 ~ Cl-N r NNI CO C(CH3)2 C3 7 224-25 /= N
140 Cl ~ -N\=~N C0 c(CH3)2 i C3 7 148-49 ~3~
NXo Ar A~ B R M . p . ( C) or 141 Cl ~ -N~ CO C (CH3) 2 C3 7 143 142 ~ -N\==7CO -C ~CH3) 2-CH2-C (CH3) 3 206 Cl f~N
143 Cl~ -N ¦ CO -C(cH3)2-cH2-c(cH3)3 138 ~, N
144 Cl~ -N~ CH(OH) C(CH3)2 CH2~ 144(A Form) 145 Cl~ -N~ CH(OH) -C(CH3)2-CH2~-Cl (B Form) 146 Cl~ -N ~CH(OH) -C(CH3)2-cH2~ 157(A Form) N
147 Cl~ -N~ CH(OH)-C(cH3)2-cH2~ viscous oil 148 Cl~ -N~ CH(OH)-C(CH3)2-CH2~ viscous oil 149 Cl~ -N 1 CH(OH)~Cl viscous oil 150 Cl~ -N~ CH(OH) ~Br 168(A Form) 151 Cl~ -N ~ CH(OH)~Br 116-19 \=~N Br (B Form) 152 Cl~ -N~ C~l(OH)~Br 145 153 ~ -N 1 CH(O~I)~Cl 80-85 ~ ~ - N ~ Cl 84 155 Cl~ -N~ CH(OH) ~ viscous oil 156 Cl~ ~N C(C 3)2 3 7 1~5332 NXo Ar Az B R M.p. ( C) or __ _ 157 ~ -N ~ Cll(OH~ C(C 3)2 3 7 110 N
158 Cl ~ -N ~ CH(OH) C(CH3)2 n C4 9 1,5310 N
159 ~ -N ~ CH(OH) C(C 3)2 3 7 103-04 Cl N
160Cl ~ -N ~ CH(OH) C(CH3)2 i C3 7 113 161Cl ~ -N ~ CH(OH) C(C 3)2 3 7 resin N~
162 ~ -N ¦ CH(OH) -ClcH3)2-cH2-c(cH3)3 120 Cl N
~ /N~
163Cl ~ -N ¦ CH(OH) -c(cH3)2-cH2-c~cH3)3 resin 164Cl ~ -N ~ CH(OH) -C(CH3)2 ~ 120-26 N
165 Cl ~ --N ~ CH(OH) -C(cH3)2-cH2-cH2-o ~ Cl 155-63 166 ~ ~ N -C(C113)2-CH2CH2-0 ~ Cl 81-83 167 Cl ~ -N ~ CH(OH) -C(C~-13)2-CH2CH2-0 ~ Cl resin 168 P ~ Cl -N ~ CH(OH) -C(CH3)2-CH2CH2-0 ~ -Cl resin 169 Cl ~ -N ~ Cll(OH) -c(cH3)2-c~l2cH2 ~ resin 17~ -C(CH3)2-CH2C,H2-0 ~ Cl 118-19 N
171 Br ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-0 ~ Cl 115-17 172 F ~ ~ N -C(CH3)2-CH2CH2-0 ~ Cl resin 173 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2CH2-0 ~ Cl resin Ex Ar Az B R 20 174 Cl ~ -N ~ CH(OH) -C(CH3)2-Cll2cH2 ~ ~ resin 175 Cl ~ -N 1 CH(OH) -C(cH3)2-cH2cH2 O ~ F resin ~=N
176 Cl ~ -N ¦ CH(OH) -C(CH )2-CH2CH2-O ~ Cl 104-05 177 Cl ~ -N ~ CH(OH) -C(CH3)2-CH2-c(cH3)3 128 ~=~N
178 Cl ~ -N ~ N CO -C(cH3)2-cH2- ~ SC 3 1,5490 179 Cl ~ -N ~ N CO -C(CH3)2-CH2-cH2 ~ 1,5378 180 Cl ~ -N ~ N CO ( 3)2 CH2-CH2-O ~ OCF3 viscous oil 181 Cl ~ -N ~ CO -C(C~I3)2-cH2cll2 ~ 1,5686 N Cl 182 Cl ~ -N ~ N CO -C(CH3)2-CH2CH2-O ~ 1,5689 183 Cl ~ -N ~ N CO C(CH3)2 CH2CH2 ~ 1,5738 184 Cl ~ -N~=X CO -c~CH3)2-CH2cH2-O ~ 126-28 Ex.Ar ~Z B R M.p. ( C j No. or ~
_ 185Cl~ H(OH) { (CH3)2-CH2cH2 o4~ 1,5291 186Cl~ -N/~lN CH(OH) ~(CH3)2{EI~!c~2-O~-(xF3 187Cl~ t ~- N ~ ~(CH3) 2{~H2CH2~ ~> resin 188 C1~ -N 1N CO ~ (CH3 ) 2{ H2C~2~ . r~s i n 189 Cl ~ ~ C(CH3)2 {~H2CH2~ o2 :resir, 190 Cl ~ -N~ N CO -C(C ~ )2-CH2C~2 ~ NO 99 100 NO
191 Cl ~ -N~Nl -C(CH3)2-CH2CH2-0 ~ ~resin f~N
192 Cl~ -N I CO -C(CH3)2 CH2CH2 ~)2 135-36 Cl 193 Cl~ ~N CH(OH) ~C(CH3)2~H2CH2~) resin 194 Cl ~ ~N~ CH(OH~ -C(CH3) 2-CH2CH2~ resin 195 Cl~- ~ CH(OH) -C(CH3)2-CH2CH2 ~ resin Le A 21 911 ~ ~o -Ex. Ar AZ B R M~p. ( C ) No. nDO
196 Cl{~ -N~CH(O~) ~1 123 197 Cl~ -N~CH(OH)~1 104-07 (A For~) :~H
198Cl~ -N 1CH(O~) ~ i l (B Form) Cl CH~
199Cl~ -N~Cq(CH) Y~l i l OEI
200 Cl~ -~ 94 C~H~
Cl C oi l :~q~
202 Cl~ ~ ~N CO ~ oi l 203 Cl~~ ~ 175 C 1~_ 204Cl~ -N~ CO ~ 91 C6H~
205 Cl~ -N~ CO ~ 156-58 N~ ~l 206 C1{~-N,~ CO \~J 107 Le A 21 911 Ex. Ar Az B R M.p. ( C ) No. ~0 ___ _ .
207 Cl~ ~ CH (OH) ~ 107-10 Cl N 2 5 208 Cl~ ~ ~CH (OH~ ~ o i l 209 C~ CH (CH) ~ i l 210 C:L~ ~NCH (OH~ ~ ~i l 21 1 Cl~ ~ oi l \= N
Cl C6~ 138-40 Cl N 6 5 213 Cl~ ~ CO ~ 102-03 214 Cl~ ~ O ~ 98-1 00 215 C1~ ~ CO ~ 160-61 216 Cl~ ~ i 217 ~} -N~ CO -\~ oi l Le A 21 911 3~
42 ~
~x. Ar Az B R M.p (~C ) No~
218 <~ ~ ~ CO ~ 103-09 219 Cl~ ~cN OEI(OH) Y~l oi l C6~5 220 Cl~ ~ l(OH) ~ 111 (A Farm) C~
221 Cl ~ -N ~ CH(OH) ~ oil C6~3 222 Cl ~ -N ~N CH(OH) ~ 114 (A Form) 223 Cl ~ ~ N CH(OH) ~ oil 224 Cl~ -~ CO-c(cH3~2-cH2cH2cH2cl 1,54l2 225 Cl ~ -N\~ N CH(OH) -C(CH3)2-CH2CH2-0- ~ -SCF3 oil 226 Cl ~ -N ~N CO 4-ClC6~ oil 227 Cl ~ -N ~ CO 4-ClC6H~ ~ oil A and B ~orm: the two possible geometric isomers Le A 21 911 3~
Use E_amples In the examples which follow, the compounds shown below are employed as comparative substances:
CH3 fH3 (A) C1 ~ O-fH-CO-f-CH2C
~ N
Cl OH CH3 (B) Cl ~ O-fH-CH-C-CH2-O ~ Br ~ N
Cl fH3 (C) Cl~-O-fH-CO-f-CH2Cl ~ N
Cl CIH3 (D) Cl ~ O-fH-CO-C-CH2-O-COCH3 N
~E) Cl ~ O-fH-CO-f-CH2-O-COCH3 N
CH
(F) Cl ~ -O-CH-CO-f-CH20H
~ ~ CH~
.
~3~
(G) C1~ O~CH-CO-C-CH2-0-~3 C1 ~ N
(H) C1~ 5-O-CH-CO-C-CH2-O~ -C1 ~ N
(I) C1~ -O-fH-CH C-CH2-O-~ -Br C ~N CH3 (J) C1-~ O-CH-CH - i-CH2-0-~ -CH3 K) C1--~-O-CH-CO-C-CH2-S~
~N~N CH3 (L) C1-~ -O-CH-CO-¢-CH2-O C2H5 N~- ~N CH3 (M) ~ 5-O-CH-CO-C-CH2C1 ~ ~ CH3 .3~
Cl CH3 r~ I
(N) Cl ~ -O-CH-CO-C-CH2-OH
~N CH3 OH CH~
(O) Cl ~ O-fH-CH - C-CH2-S ~ -Cl (P) Cl ~ -O-CH-CH - C-CH2-O ~ Cl ~ N~N CH3 (Q) Cl ~ O-CH-CH - C-CH2Cl N~N CH3 OH CH
(R) ~ ~ -O-CH-CH - C-CH2Br ~ N~N CH3 OFl CH
(S) ~ O-CH-CH - C-CH2Cl ~N CH3 - 45a -(T) Cl- ~ -O-CH-CH - C-CH2-O- ~ Cl ~N~N CH3 Cl OH CH3 (U) Cl ~ -O-CH-CH - C-CH2Cl ~ N~N CH3 ~3~
Example A
Puccinia ~est (wheat) / protective Solvent: 1CC parts oy weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl poly-glycol ether To produce a suitable preparation of active com pound~ 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the con~
centrate is diluted with water to the desired concentration.
To test for protective activity~ young plants are inoculated with a spore suspension of Puccinia recondita in a 0.17~ strength aqueous agar solution. After the spore suspension has dried on, the plants are sprayed with the preparation of active compound until dew-moist~ The plants remain in an incubation cabin at 20C and 100%
relative atmospheric humidity for 24 hours.
The plants are placed in a greenhouse at a tempera-ture of about 20C and a relative atmospheric humidity of about 80% in order to promote the development of rust pustules.
Evaluation is carried out 10 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 13, 12, 22, 16, 17, 33, 34, 4, 36, 24, 38, 39, 40, 41, ~t2, 43, 5, 44, 45, 145, 147, 169, 171 and 172.
Le A 21 ~11 _xample e Cochliobolus sativus tes~ (barley) / protective ~olvent: 100 par~s by weight of dimethylformamide Emulsifier: 0~25 parts by weight of alkylaryl poly-glycol ether ~o produce a suitable preparation of ac~ive com-pound, 1 part by weight of active compound is mixed w;th the stated amounts of solvent and emulsifier~ and the concentrate is diluted with water to the deslred con-centration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Cochliobolus sativus. The plants remain in an 1ncuba-tion cabinet for 48 hours at 20C and 100% relative atmospheric hum;dity.
The plants are placed in a greenhouse at a temperature of about 2QC and a relative atmospheric humidity of about 8~o~
Evaluation is carried out 7 days after the inoculat;on.
In this test~ a clearly superior activity com-pared with the prior art is shown, for example, by the compounds according to the following Preparat;on Examples:
13, 12, 22, 17, ~5, 68, 58 and 75.
Le A 21 S11 i.3~
- ~8 -Example C
Sphaerotheca test (cucumber) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl poly-glycol ether To produce a suitable preparation of active com-pound, 1 part by we;ght of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparatlon of act;ve compound until dripping wet. After the spray coating has dried on, ~he plants are dusted with conidia o-f the fungus Sphaerotheca fulig;nea.
The plants are then placed in a greenhouse at 23 to 2~C and at a relat;ve atmospheric humidity of about 75%.
Evaluation is carried out 10 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples:
98, ~5~ 10Q, 1Q3, 15û, 169, 156, 152 and 83.
Le ~ 21 911 3~
Example D
Erysiphe test (barley) / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl poly~
glycoL ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concen-tration~
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.
The plan~s are placed in a greenhouse at a tem-perature of about 20C and a reLative atmospher;c hum-id;ty of about 80~, in order to promote the development of powdery mildew pustules.
Evaluation ;s carr1ed out 7 days after the inoculation.
In this test, a clearly superior act;vity compared with the pr;or art is shown, for example, by the compounds according to the follow;ng preparation examples: 50, 52, 66, 67, 68, 70, 71, 72, 58, 73, 6, 75, 82, 83, 93, 112, 113 and 106.
Le A 21 911 z Example E
Erysiphe test tbarley) / seed treatment The active compounds are used as dry dressings.
These are prepared by extending the particular active compound with a ground mineral to give a f;nely pulveru-lent mixture, which ensures uniform distribution on the seed surface.
To apply the dressing, the seed is shaken with the dressing in a closed glass flask for 3 minutes.
3 batches of 12 grains of the barley are sown 2 cm deep in standard soil. 7 days after sowing, when the young plants have unfolded their first leaf, they are dusted with spores of Erysiphe graminis f. sp. hordei.
The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humid-;ty of about 8û% in order to promote the development of pow-dery mildew pustules.
Evaluation is carried out 7 days after the inoculationv 2n In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the compounds accord;ng to the following preparation examples:
1 5 0 .
Le A 21 911 ~ ~35~2 Example F
-Pyricularia test (rice)/protective Solvent: 12.5 parts by weig'nt of acetone Emulsifier: 0.3 parts by weight of alkylaryL poly glycol ether To produce a su;table preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the sta-:ed amount of emulsifier, 1~ to the desired concentrat;on.
To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried off, the plants are inoculated with an aqueous spore suspension 15 of Pyricularia oryzae. The plants are then placed ;n a greenhouse at 10~% reLative atmospheric humidity and 25C.
Evaluat;on of the disease infestation is carried out 4 days after the inoculation.
In this test, a clearly superior activity compared 2~ with the prior art is shown, for example, by the compounds according to the following preparation examples:
156, 169, 152, 24 and 43O
Le A 21 911 .3~)?~
~xample C
Pellicularia test (rice~
Solvent: 12.5 parts by we;ght of acetone Emulsifier 0.3 parts by weight of alkylaryl poly-glycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, to the desired concentration.
To test for activity, young rice plants in the 3 to 4 leaf stage are sprayed until dripping wet. The plants remain ;n a greenhouse until they have dried off.
The plants are then inoculated with Pellicularia sasakii and are placed at 25C and 100% relative atmospher;c humidity.
The evaluation of the disease infestation is carried out 5 tO 8 days after the inoculation.
In this test, a clearly superior activity com-2Q pared with the prior art is shown, for example, by thecompounds according to the following preparation examples: 12, 22, 14, 23, 16, 17, 1~, 33, 4, 37, 24, 38, 25, 41, 429 43 and 44.
Le ~ 21 11 Example l-l ~gar plate test ~!utrient medium used 39 parts by weight of potato glucose agar 5 parts by weight of agar-agar 1Q parts by weight of peptone 5 parts by we;ght of malt are dissolved in 1,0nO ml of distilled water and the sol-ution is kept in an autoclave at 121C for 30 minu~es.
Solvent: 2 parts by weight of water-acetone (97.5 : 2.5) Ratio of the amounts of solvent to nutrient medium:
Z : 100.
To produce a suitable preparation of active com pound, 1 part by weight of ac~ive compound is mixed with the stated amount of solvent.
The concentrate is thoroughly mixed, in the stated proportion, with the liquid nutrient medium and the mix-ture is then poured into Petri d;shes~
When the nutrient medium has cooled and solidi-fied, the plates are inoculated with the follow;ng micro-organisms and are incubated at about 21C: Cochliobolus miyabeanus Evaluat;on ;s carr;ed out after Z to 8 days, depending on the speed of arowth of the microorganisms, the ;nh;bit;on of growth be;ng used as a measure of the action of the preparations.
In this test, a clear superiority compared with the pr;or art ;s shown by the compounds according to the following preparation examples: 145, 147, 156, 157, 167, 168 and 173 Le A 21 911
Claims (25)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A substituted azolylether-ketone or -carbinol of the formula in which Ar represents phenyl which is optionally monosubstit-uted or polysubstituted by identical or different substituents selected from: Halogen, alkyl having 1 to 4 carbon atoms, alkoxy and alkylthio each having 1 or 2 carbon atoms; halogenoalkyl, halogenoalkoxy and halogenoalkylthio each having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl moiety, nitro, cyano or phenyl or phenoxy which is optionally substituted by halogen and/or alkyl having 1 or 2 carbon atoms, or the aldoxime or ketoxime radical or an ether thereof;
Az represents 1,2,4-triazol-1-yl, 1,2,4,-triazol-4-yl or imidazol-1-yl, B represents a keto group or a CH(OH) grouping and R represents substituted cycloalkyl or a grouping of the formula -C(CH3)2-R1 , -C(CH3)2-CH2-CH2-R2, -C(CH3)2-(CH2)m-R3 or -C(CH3)2-(CH3)2-(CH2)n-R4, wherein R1 represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl, or the aldehyde group or an oxime, oxime-ether or dialkyl acetal thereof, R2 represents phenoxy which is optionally monosub-stituted or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R3 represents phenyl which is optionally monosub-stituted or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R4 represents halogen, m represents integers from 1 to 4 and n represents integers from 2 to 4, or a non-phytotoxic addition product thereof with a hydrohalic acid, phosphoric acid, nitric acid, sulphuric acid, a monofunct-ional or bifunctional carboxylic acid, a hydroxycarboxylic acid or a sulphonic acid salt of copper, zinc, manganese, magnesium, iron or nickel or an anion of a salt derived from a hydrohalic acid, phosphoric acid, nitric acid or sulphuric acid.
Az represents 1,2,4-triazol-1-yl, 1,2,4,-triazol-4-yl or imidazol-1-yl, B represents a keto group or a CH(OH) grouping and R represents substituted cycloalkyl or a grouping of the formula -C(CH3)2-R1 , -C(CH3)2-CH2-CH2-R2, -C(CH3)2-(CH2)m-R3 or -C(CH3)2-(CH3)2-(CH2)n-R4, wherein R1 represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl, or the aldehyde group or an oxime, oxime-ether or dialkyl acetal thereof, R2 represents phenoxy which is optionally monosub-stituted or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R3 represents phenyl which is optionally monosub-stituted or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R4 represents halogen, m represents integers from 1 to 4 and n represents integers from 2 to 4, or a non-phytotoxic addition product thereof with a hydrohalic acid, phosphoric acid, nitric acid, sulphuric acid, a monofunct-ional or bifunctional carboxylic acid, a hydroxycarboxylic acid or a sulphonic acid salt of copper, zinc, manganese, magnesium, iron or nickel or an anion of a salt derived from a hydrohalic acid, phosphoric acid, nitric acid or sulphuric acid.
2. A compound or addition product according to claim 1 wherein Ar represents phenyl which is optionally monosub-stituted or polysubstituted by identical or different substituents selected from: halogen, alkyl having 1 to 4 carbon atoms, alkoxy and alkylthio each having 1 or 2 carbon atoms; halogenoalkyl, halogenoalkoxy and halogenoalkylthio each having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl moiety, nitro, cyano or phenyl or phenoxy which is option-ally substituted by halogen and/or alkyl having 1 or 2 carbon atoms, or the aldoxime or ketoxime radical or an ether thereof;
and R represents cycloalkyl which has 3 to 7 carbon atoms and is monosubstituted or polysubstituted by identical or differ-ent substituents selected from: halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms and phenyl; or R represents the grouping -C(CH3)2-R1, -C(CH3)2-CH2CH2-R2, -C(CH3)2-(CH2)m-R3 or -C(CH3)2-(CH2)n-R4 wherein R1 represents straight-chain or branched alkyl having 2 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms or alkinyl having 2 to 4 carbon atoms, or represents the aldehyde group or an oxime, oxime-ether or dialkyl acetal thereof, said dialkyl acetal having 1 to 4 carbon atoms in each alkyl moiety, or R1 represents a dioxane ordioxolane group;
R2 represents phenoxy which is optionally monosubstit-uted or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R3 represents phenyl which is optionally monosubstitut-ed or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar; and R4 represents fluorine, chlorine or bromine.
and R represents cycloalkyl which has 3 to 7 carbon atoms and is monosubstituted or polysubstituted by identical or differ-ent substituents selected from: halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms and phenyl; or R represents the grouping -C(CH3)2-R1, -C(CH3)2-CH2CH2-R2, -C(CH3)2-(CH2)m-R3 or -C(CH3)2-(CH2)n-R4 wherein R1 represents straight-chain or branched alkyl having 2 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms or alkinyl having 2 to 4 carbon atoms, or represents the aldehyde group or an oxime, oxime-ether or dialkyl acetal thereof, said dialkyl acetal having 1 to 4 carbon atoms in each alkyl moiety, or R1 represents a dioxane ordioxolane group;
R2 represents phenoxy which is optionally monosubstit-uted or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R3 represents phenyl which is optionally monosubstitut-ed or polysubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar; and R4 represents fluorine, chlorine or bromine.
3. A compound according to Claim 1, Ar represents phenyl which is optionally monosubstituted to trisub-stituted by identical or different substituents selected from: fluorine, chlorine, bromine, methyl, ethyl, isopropyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, nitro, cyano, phenyl, chlorophenyl, phenoxy, methoximinomethyl, ethoximinomethyl and 1-(methoximino)-ethyl;
R represents cycloalkyl which has 3 to 6 carbon atoms and is mono-substituted to trisubstituted by identical or different substituents selected from: fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy and phenyl;
or represents the grouping -C(CH3)2-R1, -C(CH3)2-CH2CH2-R2, -C(CH3)2-(CH2)m-R3 or -C(CH3)2-(CH2)n-R4;
wherein R1 represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl or neopentyl, or represents alkenyl having 3 to 6 carbon atoms or alkinyl having 2 to 4 carbon atoms, or represents the aldehyde group or an oxime thereof or an oxime-ether thereof selected from: alkyl ethers having 1 to 4 carbon atoms, alkenyl ethers having 2 to 4 carbon atoms, alkinyl ethers having 2 to 4 carbon atoms and benzyl ethers which are optionally monosub-stituted to trisubstituted by halogen, or represents a dialkyl acetal thereof having 1 to 4 carbon atoms in each alkyl moiety, or represents a dioxanyl or dioxolanyl group;
R2 represents phenoxy which is optionally monosubstituted to trisubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R3 represents phenyl which is optionally monosubstituted to trisub-stituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R4 represents fluorine or chlorine;
m represents 1 or 2; and n represents 2.
R represents cycloalkyl which has 3 to 6 carbon atoms and is mono-substituted to trisubstituted by identical or different substituents selected from: fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy and phenyl;
or represents the grouping -C(CH3)2-R1, -C(CH3)2-CH2CH2-R2, -C(CH3)2-(CH2)m-R3 or -C(CH3)2-(CH2)n-R4;
wherein R1 represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl or neopentyl, or represents alkenyl having 3 to 6 carbon atoms or alkinyl having 2 to 4 carbon atoms, or represents the aldehyde group or an oxime thereof or an oxime-ether thereof selected from: alkyl ethers having 1 to 4 carbon atoms, alkenyl ethers having 2 to 4 carbon atoms, alkinyl ethers having 2 to 4 carbon atoms and benzyl ethers which are optionally monosub-stituted to trisubstituted by halogen, or represents a dialkyl acetal thereof having 1 to 4 carbon atoms in each alkyl moiety, or represents a dioxanyl or dioxolanyl group;
R2 represents phenoxy which is optionally monosubstituted to trisubstituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R3 represents phenyl which is optionally monosubstituted to trisub-stituted by identical or different substituents selected from the phenyl substituents mentioned above in the case of Ar;
R4 represents fluorine or chlorine;
m represents 1 or 2; and n represents 2.
4. 1-(2,4-Dichlorophenoxy)-1-(imidazol-1-yl)-3,3,4-trimethyl-pentan-2-one of the formula
5. 1-(4-Chlorophenoxy)-1-(imidazol-1-yl)-3,3,4-trimethyl-pentan-2-one of the formula
6. 3,3-Dimethyl-1-(4-fluorophenoxy)-1-(imidazol-1-yl)-5-phenoxy-pentan-2-ol of the formula
7. 1-(2,2-dibromo-1-Methylcyclopropyl)-2-(2,4-dichlorophenoxy)-2-(1,2,4-triazol-1-yl)ethanol of the formula
8. 1-(4-Chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-hexan-2-one of the formula
9. 1-(4-Chlorophenoxy)-1-(1,2,4-triazol-1-yl)-3,3,4-trimethyl-pentan-2-ol of the formula
10. 1,5-Bis-(2,4-dichlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-pentan-2-ol of the formula
11. A method of combating fungi which comprises applying to a fungus or a fungus habitat a fungicidally effective amount of a compound according to Claim 1.
12. A method according to Claim 11 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.
13. A method according to Claim 12 wherein the active ingredient concentration in said composition is between 0.0001 and 1 % by weight.
14. A method according to Claim 12 wherein the active ingredient concentration in said composition is between 0.001 and 0.5 % by weight.
15. A method according to Claim 11, 12 or 14 wherein the compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.
16. A method according to Claim 11, 12 or 14 wherein the compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.
17. A method according to Claim 11, 12 or 14 wherein the compound is applied to soil in an amount to give a soil concentration of 0.00001 to 0.1 % by weight at the place of action.
18. A method according to Claim 11, 12 or 14 wherein the compound is applied to soil in an amount to give a soil concentration of 0.001 to 0.02 %
by weight at the place of action.
by weight at the place of action.
19. A method according to Claim 11, 12 or 14 wherein each compound is 1-(2,4-dichlorophenoxy)-1-(imidazol-1-yl)-3,3,4-trimethyl-pentan-2-one.
20. A method according to Claim 11, 12 or 14 wherein such compound is 1-(4-chlorophenoxy)-1-(imidazol-1-yl)-3,3,4-trimethyl-pentan-2-one.
21. A method according to Claim 11, 12 or 14 wherein such compound is 3,3-dimethyl-1-(4-fluorophenoxy)-1-(imidazol-1-yl)-5-phenoxy-pentan-2-ol.
22. A method according to Claim 11, 12 or 14 wherein such compound is 1-(2,2-dibromo-1-methylcyclopropyl)-2-(2,4-dichlorophenoxy)-2-(1,2,4-triazol-1-yl)ethanol.
23. A method according to Claim 11, 12 or 14 wherein such compound is 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-hexan-2-one.
24. A method according to Claim 11, 12 or 14 wherein such compound is 1-(4-chlorophenoxy)-1-(1,2,4-triazol-1-yl)-3,3,4-trimethyl-pentan-2-ol.
25. A method according to Claim 11, 12 or 14 wherein such compound is 1,5-bis-(2,4-dichlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-pentan-2-ol.
62.
62.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3233173.8 | 1982-09-07 | ||
| DE19823233173 DE3233173A1 (en) | 1982-09-07 | 1982-09-07 | SUBSTITUTED AZOLYL ETHER KETONES AND CARBINOLS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1213592A true CA1213592A (en) | 1986-11-04 |
Family
ID=6172632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000435968A Expired CA1213592A (en) | 1982-09-07 | 1983-09-02 | Substituted azolylether-ketones and -carbinols |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0102591B1 (en) |
| JP (1) | JPS5965080A (en) |
| AT (1) | ATE24493T1 (en) |
| AU (2) | AU564478B2 (en) |
| BR (1) | BR8304843A (en) |
| CA (1) | CA1213592A (en) |
| DE (2) | DE3233173A1 (en) |
| DK (1) | DK404483A (en) |
| ES (1) | ES525402A0 (en) |
| GR (1) | GR78935B (en) |
| HU (1) | HU192157B (en) |
| IL (1) | IL69663A0 (en) |
| NZ (1) | NZ205485A (en) |
| PT (1) | PT77262B (en) |
| TR (1) | TR21634A (en) |
| ZA (1) | ZA836603B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60177967U (en) * | 1984-05-01 | 1985-11-26 | 小倉 熊雄 | Foil mounting slide stand for flat foil thread cutting and separation device with double ears |
| DE3436452A1 (en) * | 1984-10-05 | 1986-04-10 | Bayer Ag, 5090 Leverkusen | ANTIMYCOTIC AGENT |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2926280A1 (en) * | 1979-06-29 | 1981-01-08 | Basf Ag | FUNGICIDAL ALPHA -TRIAZOLYL GLYCOLE DERIVATIVES, THEIR PRODUCTION AND USE |
| DE3021551A1 (en) * | 1980-06-07 | 1981-12-24 | Bayer Ag, 5090 Leverkusen | 4-SUBSTITUTED 1-AZOLYL-1-PHENOXY-3,3-DIMETHYL-BUTAN-2-ONE AND -OLE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| JPS5758671A (en) * | 1980-09-25 | 1982-04-08 | Ishihara Sangyo Kaisha Ltd | Phenoxyalkylazole type compound and agricultural and gardening fungicide comprising it |
-
1982
- 1982-09-07 DE DE19823233173 patent/DE3233173A1/en not_active Withdrawn
-
1983
- 1983-08-25 AT AT83108365T patent/ATE24493T1/en not_active IP Right Cessation
- 1983-08-25 EP EP83108365A patent/EP0102591B1/en not_active Expired
- 1983-08-25 DE DE8383108365T patent/DE3368613D1/en not_active Expired
- 1983-08-29 PT PT77262A patent/PT77262B/en unknown
- 1983-09-02 JP JP58160599A patent/JPS5965080A/en active Pending
- 1983-09-02 CA CA000435968A patent/CA1213592A/en not_active Expired
- 1983-09-05 NZ NZ205485A patent/NZ205485A/en unknown
- 1983-09-05 GR GR72385A patent/GR78935B/el unknown
- 1983-09-05 IL IL69663A patent/IL69663A0/en unknown
- 1983-09-06 AU AU18731/83A patent/AU564478B2/en not_active Ceased
- 1983-09-06 HU HU833101A patent/HU192157B/en unknown
- 1983-09-06 TR TR21634A patent/TR21634A/en unknown
- 1983-09-06 ZA ZA836603A patent/ZA836603B/en unknown
- 1983-09-06 BR BR8304843A patent/BR8304843A/en unknown
- 1983-09-06 DK DK404483A patent/DK404483A/en not_active Application Discontinuation
- 1983-09-06 ES ES525402A patent/ES525402A0/en active Granted
-
1987
- 1987-04-09 AU AU71404/87A patent/AU7140487A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| PT77262B (en) | 1986-02-04 |
| GR78935B (en) | 1984-10-02 |
| EP0102591A2 (en) | 1984-03-14 |
| TR21634A (en) | 1985-01-21 |
| DK404483A (en) | 1984-03-08 |
| JPS5965080A (en) | 1984-04-13 |
| BR8304843A (en) | 1984-04-24 |
| AU1873183A (en) | 1984-03-15 |
| NZ205485A (en) | 1987-04-30 |
| DK404483D0 (en) | 1983-09-06 |
| EP0102591B1 (en) | 1986-12-30 |
| ES8405588A1 (en) | 1984-06-16 |
| IL69663A0 (en) | 1983-12-30 |
| DE3233173A1 (en) | 1984-03-08 |
| EP0102591A3 (en) | 1984-08-22 |
| AU564478B2 (en) | 1987-08-13 |
| PT77262A (en) | 1983-09-01 |
| DE3368613D1 (en) | 1987-02-05 |
| ATE24493T1 (en) | 1987-01-15 |
| ZA836603B (en) | 1984-05-30 |
| AU7140487A (en) | 1987-08-06 |
| ES525402A0 (en) | 1984-06-16 |
| HU192157B (en) | 1987-05-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |