NZ205485A - Substituted azolylether-ketones and -carbinols and fungicidal compositions - Google Patents

Substituted azolylether-ketones and -carbinols and fungicidal compositions

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Publication number
NZ205485A
NZ205485A NZ205485A NZ20548583A NZ205485A NZ 205485 A NZ205485 A NZ 205485A NZ 205485 A NZ205485 A NZ 205485A NZ 20548583 A NZ20548583 A NZ 20548583A NZ 205485 A NZ205485 A NZ 205485A
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carbon atoms
phenyl
substituted
formula
alkyl
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NZ205485A
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G Jager
H-L Elbe
K Bockmann
A Schulze
K H Buchel
P Reinecke
P-E Frohberger
W Brandes
H Scheinpflug
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Bayer Ag
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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
    • 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
    • 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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    • 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
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C45/63—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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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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    • C07—ORGANIC CHEMISTRY
    • 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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    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
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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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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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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  • Wood Science & Technology (AREA)
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  • Pest Control & Pesticides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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  • Detergent Compositions (AREA)
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  • Investigating Or Analysing Materials By Optical Means (AREA)
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Abstract

1. Substituted azolylether-ketones and -carbinols of the formula see diagramm : EP0102591,P33,F1 in which Ar represents phenyl which is optionally monosubstituted or polysubstituted by identical or different substituents, the following being mentioned as substituents : halogen, alkyl having 1 to 4 carbon atoms, alkoxy and alkylthio, each having 1 to 2 carbon atoms ; halogenoalkyl, halogenoalkoxy and halogenoalkylthio, each having 1 to 2 carbon atoms and 1 to 5 identical or different halogenatoms, alkoxycarbonyl 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 to 2 carbon atoms, 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 cycloalkyl which has 3 to 7 carbon atoms and is monosubstituted or polysubstituted by identical or different substituents, the following being mentioned as substituents : halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 2 carbon atoms and phenyl ; and furthermore represents the groupings -C(CH3 )2 -R**1, -C(CH3 )2 -CH2 CH2 -R**2, -C(CH3 )2 -(CH2 )m -R**3 and -C(CH3 )2 -(CH2 )n -R**4 ; wherein R**1 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 represents the aldehyde group and its derivatives, such as oximes, oxime-ethers and acetals, such as dialkyl acetals having 1 to 4 carbon atoms in each alkyl part, or represents dioxane and dioxolane, R**2 represents phenoxy which is optionally monosubstituted or polysubstituted by identical or different substituents, suitable substituents being the phenyl substituents mentioned above in the case of Ar ; R**3 represents phenyl which is optionally monosubstituted or polysubstituted by identical or different substituents, suitable substituents being the phenyl substituents mentioned above in the case of Ar ; R**4 represents fluorine, chlorine or bromine ; m represents integers from 1 to 4 and n represents integers from 2 to 4, and their acid addition salts and metal salt complexes.

Description

New Zealand Paient Spedficaiion for Paient Number £05485 2054 85 Priority Date(s): 7-S<£P:8A Complete Specification Filed: Class: cs*o?.4-s,chorea,... .0X10^05, BQ!...
Publication Date: . P.O. Journal, No: . 3*0 7«W" NEW ZEALAND Patents Act, 1953 /Cn C0TDZ33/60 ^ COIDIVT/OS COIDk-OSjob N.Z. No.
AOIN 43/50,653 COMPLETE SPECIFICATION "Substituted azolylether-ketones and -carbinols." We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement _1_ (Followed by 1A.) - 1ft- 205485 The present invention relates to new substituted azolylether-ketones and -carbinols, several processes for their preparation and their use as fungicides.
It has already been disclosed that certain substi-5 tuted 1-azolyI-3,3-dimethy1-1-phenoxy-butan-2-ones and -ols in general possess good fungicidal properties (see NZ Patent No. 164658 and US Patent Nos. 4,154,84 2 and 4,406,909).
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-aryIoxy-5-azoly1-3,3-dimethyIpent-1-en-4-ones and -ols which have not been described hitherto 15 (NZ Patent No. 201,576).
New substituted azolylether-ketones and -carbinols of the formula Ar-O-CH-B-R (I) Az in which Ar represents optionally substituted aryl, Az represents 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl or imidazo 1-1-yI, B represents the keto group or a CH(OH) grouping 25 and R represents substituted cycloalkyl or the groupings -CCCH3>2-R1, -C<CH3>2-CH2-CH2-R2, -C(CH3)2-(CH2)m-R3 and -C (CH3)2-(CH2)n-R4 wherein ■i R represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl or the aldehyde group and its derivatives, LL lH Di QH ■ 20548E o R represents optionally substituted phenoxy, R3 represents optionally substituted phenyl, R4 represents halogen, m represents integers from 1 to 4 and 5 n represents integers from 2 to 4, and their acid addition salts and metal salt complexes have been found.
Those compounds of the formula (I) in which B represents the CH(OH) group possess two asymmetric carbon 10 atoms; they can therefore occur in the form of the two geometric isomers (erythro and threo form), which can be obtained in different proportions. In both cases, they occur as optical isomers. Compounds of the formula (I) in which R represents substituted cycloalkyl can addition-15 ally possess an asymmetric carbon atom, with the result that there may be further geometric isomers. All isomers are claimed according to the invention.
Furthermore, it has been found that the new substituted azolylether-ketones and -carbinols of the formula 20 CI) are obtained if a) ha logenoether-ketones of the formula (II) Ar-O-CH-CO-R (II) I Ha I in which Ar and R have the meaning given above and 25 Hal represents chlorine or bromine, are reacted with 1,2,4-triazole or imidazole in the presence of an acid-binding agent and, if appropriate, in the presence of a diluent; or b) diha logenoketones of the formula (Ha I)2 CH - CO - R (III) in which Hal and R have the meaning given above, 205485 phenol of the formula Ar- OH CIV) in which Ar has the meaning given above, in the presence of an acid-binding agent and in the presence of a diluent; or, if appropriate, c) the azolylether-ketones obtained by process Ca) or Cb), of the formula Ar - 0 - CH - CO - R I CI a) Az in which Ar, Az and R gave the meaning given above, are reduced in a customary manner by known methods.
The resulting compounds of the formula CD can, if desired, then be subjected to an addition reaction with 15 an acid or a metal salt.
The new substituted azolylether-ketones and -carbinols of the formula CI) possess powerful fungicidal properties. In this respect, the compounds according to the invention surprisingly exhibit better fungicidal 20 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. 25 Formula CI) gives a general definition of the substituted azolylether-ketones and -carbinols according to the invention. In this formula, Ar preferably represents phenyl which is mono-substituted or polysubstituted by identical or 30 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; ha logenoa Iky I, 205485 halogenoatkoxy and halogenoalkylthio, each having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine atoms and chlorine atoms, alkoxycarbonyl having 1 to 4 5 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 preferably represents cycloalkyl which has 3 to 7 carbon atoms and is optionally monosubstituted or polysubstituted by identical or different substituents, the following preferably being mentioned as substituents: halogen, alkyl having 1 15 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms, phenyl and ehJiopophenyi: and%u<rtehermore the groupi-nqs^ -c(ch3)2-r1, -c(ch3)2-ch2ch2-r2, -C (CH3)2-(CH2)m-R3 and -C(CH3)2~(CH2)n-R4 R preferably represents straight-chain or 20 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, oxime-ethers and acetals, such as, for example, dialkyl acetals 25 having 1 to 4 carbon atoms in each alkyl part, or represents optionally substituted dioxanes and di oxo lanes; •p R preferably represents phenoxy which is optionally monosubstituted or polysubstituted by 30 identical or different substituents, preferred substituents being the phenyl substituents already mentioned in the case of Ar; R 3 preferably represents phenyl which is mono-substituted or polysubstituted by identical or 35 different substituents, preferred substituents being the phenyl substituents already mentioned 205485 in the case of Ar; R 4 preferably represents fluorine, chlorine or bromine; and Az, E, m and n have the meanings given in the definition of the invention.
Particularly preferred compounds of the formula (I) are those i n wh i c h Ar represents phenyl which is optionally mono-10 substituted to trisubstituted by identical or different substituents, the following being mentioned as substituents: fluorine, chlorine, bromine, methyl, ethyl, isopropyl, methoxy,methy I -thio, trif luoromethy I, trif luoromethoxy, trifluoro 15 methylthio, methoxycarbony I , ethoxycarbonyI, nitro, cyano, phenyl, chlorophenyl, phenoxy, methoximinomethyl, ethoximinomethyl and 1-(methox-i mi no)-et h yI; R represents cycloalkyl which has 3 to 6 carbon 20 atoms and is monosubstituted to trisubstituted by identical or different substituents, the following being mentioned as substituents: fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenyl and chlorophenyl; and also the groupings 25 -C(CH3)2-CH2CH2-R2, -C<CH3)2~(CH2)m-R3 and -C (CH3)2-(CH2)n-R4; 4 R represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl or neo-pentyl, and furthermore represents alkenyl having 30 3 to 6 carbon atoms and alkinyl having 2 to 4 carbon atoms, and also represents the aldehyde group and its derivatives, such as oximes and oxime-ethers, the following being mentioned in connection with the latter: alkyl ethers having 35 1 to A carbon atoms, alkenyl ethers having 2 to 4 carbon atoms, alkinyl ethers having 2 to„,j4 ll iii an 5'* jjfsj \\21 l-uuim \c 205485 carbon atoms and benzyl ethers which are optionally monosubstituted to trisubstituted by halogen; and acetals, such as, for example, dialkyl acetals having 1 to 4 carbon atoms in each alkyl part, 5 dioxane and dioxolane; R 2 represents phenoxy which is optionally mono-substituted to trisubstituted by identical or different substituents, preferred substituents being the phenyl substituents already mentioned 10 in the case of of Ar; R3 represents phenyl which is optionally mono-substituted to trisubstituted by identical or different substituents, preferred substituents being the phenyl substituents already mentioned 15 in the case of Ar; 4 R represents fluorine or chlorine; m represents 1 or 2; n represents 2; and Az and B have the meanings given in the defini-20 tion of the invention.
If, for example, 1-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 of the reaction can be represented by the following equation 25 (process a): CH 3 C lN H ' /7^\ ^ i base Cl-<O>-0-CH-C0-C-CH2-<y-Cl ♦ Br CH3 U 3 _ HB(.
C H 3 CI^ C I-^)-0-CH-CO-C - CHj-'v-'"01 CH3 II N N LI 205485 If, for example, 1,1-dichloro-3-(dioxan-2-y I)-3-methyI butan-2-one, 4-ch loropheno I and 1,2,4-triazo le are used as starting materials, the course of the reaction can be represented by the following equation (process b): ^30- h base ci-©-oh + ci2ch-co-c-( ) 1 N ■ II c h 3 ° n []' - 2 h c i c h 3 -> ! /°-\ CL-C/-0-CH-C0-C / ) CH3 0^ N If, for example, 1 - (4-ch lorophenoxy)-4-(2,4-di-chlorophenyl)-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 reaction can be represented by 10 the following equation (process c) : ch3 civ c l-^)-0-CH-C0-C-CH2- <^)-c I NaBH|!> I > s n ^ c h 3 fl n j -oh c h 3 ci N !i 1 ' c i " / - 0- ch-ch - c - c h 2 ~ ~ c i ,fN"N CH3 N [I Formula (II) gives a general definition of the ha logenoether-ketones to be used as starting materials in carrying out process (a) according to the invention.
In this formula, Arand R preferably represent 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 preferred for these substituents.
The ha logenoether-ketones of the formula (II) Jml )l| 01 CM N f - 1 JUL 1986 / JS <. v r- . v! Z.oSQ-SS' 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 - 0 - 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 re-10 quired, be reacted 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 ha logenoketones of the f o rmu I a 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-dimethyIformamide at temperatures between 20 and 120°C.
Some of the ha logenoketones of the formula (VI) are known (see, for example, NZ Patent No. 197789); some of them form the subject of prior patent applications of the applicant, which applications have not yet been published (see European Patent Nos. 0,081,675 and 0,096,801, NZ Patent'No. 204,707 and US Patent No. 4 ,492,795); or they may be prepared by processes which are known in principle.
Formula (III) gives a general definition of -t-h^ fa i .Hi 31 ID11 3 MAR 3987 / 205485 9 dihalogenoketones to be used as starting materials in carrying out'process Cb) according to the invention. In this formula, R preferably represents the radicals which have already been mentioned in connection with the des-5 cription of the substances according to the invention, of the formula (I), as being preferred for these substituents. been unknown hitherto; some of them form the subject of a prior patent application of the applicant, which appli-10 cation has not yet been published (see European Patent may be prepared by processes which are known in principle.
Formula (IV) gives a general definition of the phenols additionally to be used as starting materials for 15 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 preferred for these 20 substituents.
The phenols of the formula (IV) are generally known compounds of organic chemistry.
The azolylether-ketones of the formula (la) which are to be used as starting materials in carrying out pro-25 cess (c) are substances according to the invention. 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 propionitri le, in particular acetonitrile; alcohols, such as ethanol and isopropanol; ethers, such as tetrahydrofuran or dioxane; benzene, toluene, formamides, such as, in particular, dimethylformamide; and halogenated hydrocarbons.
The reaction according to the invention, in accordance with process (a), is carried out in the The dihalogenoketones of the formula (III) have No. 0,09 7,862) ; they Suitable diluents for the reaction according to Li' A CI » H 205485 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, potassium carbonate and sodium 5 bicarbonate, or such as lower tertiary alkylamines, cyclo alkylamines or aralkylamines, for example triethylamine, N,N-dimethyIcyclohexy I amine, dicyclohexyI amine, N,N-di-methyIbenzyI amine and furthermore pyridine and diazabi-cyclooctane. An appropriate excess of triazole or imida-10 zole is preferably used.
In process (a), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at between 20 and 150°C, preferably at 60 to 120°C. When a solvent is pre-15 sent, the reaction is advantageously carried out at the boiling point of the particular solvent.
In carrying out process (a) according to the invention, 1 to 2 mols of triazole or imidazole and 1 to 2 mols of acid-binding agent are preferably employed per 20 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 25 vacuo. The residue is purified by distillation or recrys tallisation or by salt formation and recrysta 11isation.
Suitable diluents for the reaction according to the invention, in accordance with process (b), are polar organic solvents. These preferably include chlorinated 30 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 acetonitriIe.
The reaction according to the invention, in accordance with process (b), is carried out in the l a d 1 q h» 2 0 5485 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 150°C, preferably between 40 and 100°C.
In carrying out process (b) according to the 10 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. 15 The reduction according to the invention, in accordance with process (c), is effected in a customary manner, for example by reaction with complex hydrides, if appropriate in the presence of a diluent, or by reaction with aluminium isopropylate in the presence of a diluent. 20 If complex hydrides are employed, suitable dilu ents for the reaction according to the invention are polar organic solvents. These preferably include alcohols, such as methanol, ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. 25 The reaction is carried out in general at -10 to +30°C, preferably at 0 to 20°C. 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 (la). To isolate the reduced compounds of the formula 30 (I), the residue is taken up in dilute 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 35 diluents for the reaction according to the invention are alcohols, such as isopropanol, or inert hydrocarbons, 20548E such as benzene. The reaction temperatures may once again be varied within a relatively wide range; in general, the reaction is carried out at between 20 and 120°C, preferably at 50 to 10C°C. To carry out the reaction, 5 0.3 to 2 mols of aluminium isopropylate are employed per mol of the ketone of the formula Cla). To isolate the reduced compounds of the formula (I), the excess solvent is removed in vacuo and the aluminium compounds formed are decomposed with dilute sulphuric acid or sod-10 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 compounds of the formula (I). These preferably include 15 hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, and also phosphoric acid, nitric acid, sulphuric acid, monofunctiona I and bifunctional carboxylic acids and hyd-roxycarboxy I ic acids, such as, for example, acetic acid, 20 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 25 be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (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-30 ate purified by washing with an inert organic solvent or by recrystalLisation.
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 35 and IV to VIII, and copper, zinc, manganese, magnesium, iron and nickel may be mentioned as examples. Suitable 2054 85 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 5 sulphuric acid. The metal complexes of the compounds of the formula (I) 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 10 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 15 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-20 mycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deute romycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts 25 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-30 dery mildew diseases, thus, for combating Erysiphe species, such as, for example, against the powdery mildew of barley causative organism (Erysiphe graminis) and the powdery mildew of cucumber causative organism (Spaerotheca fuliginea); and also for combating of 35 brown rust in wheat (Puccini a recondita) and further cereal diseases, such as, for example, Cochliobolus U* iHi ai IPM sativus and Pyrenophora teres for combating rice diseases, such as Pyricularia oryzae and Pellicularia sasakii, as well as for combating apple scab (Venturi a inaequalis) and bean rust (Uromyces appendiculatus). In addition, 5 the substances according to the invention possess a good fungicidal in vitro action.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wet-table powder, suspensions, powders, dusting agents, foams, 10 pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-dressing powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations used with burning 15 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, 20 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 dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, 25 for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aro-matics, such as xylene, toluene or a IkyInaphtha lenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as ch I orobenzenes, ch I oroethy I enes or methylene 30 chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil 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 35 solvents, such as dimethylformamide and dimethyLsuLphoxide, as well as water; by Liquefied gaseous extenders or 2 0 5485 carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid 5 carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmori I lonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid carriers for gran-10 ules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and 15 tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as po lyoxyethylene-fatty acid esters, po lyoxyethyIene-fa11y alcohol ethers, for example alkyl-aryl polyglycol ethers, alkyl sulphonates, alkyl suL-20 phates, aryl sulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethyIce11uIose and natural and synthetic polymers in the form of powders, 25 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 Blue, and organic dyestuffs, such as alizarin 30 dyestuffs, azo dyestuffs and metal phtha locyanine dye- stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably 35 between 0.5 and 90%.
The active compoundsaccording to the invention 54 R5 can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acari-cides, nematicides, herbicides, bird repellants, growth 5 factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solu-10 tions, emulsions, suspensions, powders, pastes and granules. They are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet 15 dressing, slurry dressing or encrusting.
In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. 20 In the treatment of seed, amounts of active com pound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 25 0.0001 to 0.02% by weight, are required at the place of action.
Preparation Examples Examp le 1 and 2 CH 3 ci-<^C/ -0-CH-C0-C-CH2-C( CH3) 3 C -Ex.1) I ! I >N_ ,fN"N CH3 C H 3 ci-^-o- ch-co-c-ch2-c(ch3)3 (Ex.2) 3 0 / N CH 3 N N 2054 85 (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-chIorophenoxy)-3,3,5,5-tetramethylhexan-2-one in 650 ml of acetonitrile 5 is heated at the boil for 5.5 hours. Thereafter, the solution is evaporated down in vacuo, the residue is taken up in 60 0 ml of ethyl acetate and the solution is washed with three times 100 ml of water, dried over sodium sulphate and evaporated down in vacuo. The viscous oil 10 which remains (44 g) is chromatographed over silica gel, using trichloromethane as the mobile phase. 21.8 g (51.9% of theory) of 1-(4-chlorophenoxy)-3,3,5,5-tetramethy 1-1 -(1,2,4-triazoI-1-yI)-hexan-2-one are obtained as colourless crystals of melting point 89-90°C. In addition, 15 7.4 g (17.6% of theory) of the isomeric 1 -(4-chlorophen-oxy)-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 .
Preparation £f_t_he_st_a_rtj_n^ majte_rijal C H 3 C I -/{\ >0-CH-C0-C-CH2-C(CH3)3 ^ i I Br 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-chIorophenoxy)-3,3,5,5-tetramethyI-hexan-2-one in 600 ml of dichloromethane at 25 to 30°C. After 25 the addition of bromine is complete, the mixture is stirred for a further 15 minutes and cooled to 10°C, 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. 30 After the organic phase has been dried over sodium sulphate, the solvent is distilled off in vacuo. 86.8 g (100% of theory) of 1-bromo-1-(4-ch I orop henoxy)-3,3,5,5- 205485 tetramethyl-hexan-2-one are obtained as slightly yellow-coloured crystals of melting point 72-73°C.
C H 3 .
C l-(^J>0-CH 2-CO-C-CH 2-C C CH3 ) 3 CH3 38.6 g (0.3 mol) of 4-ch loropheno I are stirred 5 with 41.4 g (0.3 mol) of potassium carbonate and 57.2 g (0.3 mol) of 1 -ch loro-3,3,5,5-1etramethyI-hexan-2-one in 350 ml of N,N-dimethy I formamide for 16 hours. The mixture is then cooled to 20°C and filtered off from the precipitated inorqanic salt, and the filtrate is evapo-10 rated down in vacuo. The oil which remains (96.2 g) is taken up in 500 ml of ethyl acetate, and the solution is washed with 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 15 evaporated down, and the oily residue (80 g) is stirred with 50 ml of petroleum ether. 68.6 g (81.1% of theory) of 1-(4-chlorophenoxy)-3,3,5,5-tetramethyl-hexan-2-one are obtained as colourless crystals of melting point 47-48°C.
Examp le 3 OH C H 3 C I-<^3-O-ch-CH - C-CH2-C( CH3) 3 /N\ C H 3 i.N 0 N J (Process c) 2 g (0.054 mol) of sodium boronate are introduced in portions into a solution of 9.5 g (0.027 mol) of 25 1-(4-chlorophenoxy)-3,3,5,5-tetramethyl-1-(1,2,4-triazol-1-y l)-hexan-2-one (Example 1) in 95 ml of methanol at 20 to 30°C, while cooling externally. After three hours, the solution is brought to a pH value of 6 by the addition of acetic acid. The solution is then evaporated down in 2054 85 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 v a c uo. 9.5 g (100% of theory) of 1-(4-chlorophenoxy)-5 3,3,5,5-tetramethyl-1-(1,2,4-triazol-1-yl)-hexan-2-ol are obtained as a colourless viscous oil with a refractive index n2^ = 1.5250. £> Example 4 f luoropenten-2-one are added dropwise to a boiling mixture of 4.6 g (C.035 mol) of 4-ch lorophenol, 4.9 g (0.035 mol) of potassium carbonate and 20 ml of acetone. After the 15 mixture has been heated for four hours, it is filtered off from the precipitated potassium chloride, and the filtrate is evaporated down under reduced pressure. The 1-(4-chlorophenoxy)-3,3-dimethyl-5-fluoro-pentan-2-one which remains as a colourless oil (9 g; 100% of theory) is dissolved in 40 ml of dichLoroethane, and 5.9 g (0.037 mol) of bromine 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 of water, and the solvent is distilled off in vacuo. 11.8 g (100% of theory) of 25 1-bromo-1-(4-ch lorophenoxy)-3,3-dimethyl-5-fluoropentan- 2-one remain as the residue, in the form of a slightly yellowish oil. This is taken up in 20 ml of acetonitrile, and the solution is added dropwise, in the course of 20 minutes, to a boiling solution of 14.3 g (0.21 mol) of imidazole in 120 ml of acetonitrile. After the mixture has been heated under reflux for four hours, the solvent / C H 3 (Process a) .9 g (0.035 mol) of 1-ch loro-3,3-dimethy 1-5- is distilled off in vacuo, the residue is taken up in 200 ml of ethyl acetate, and the solution is washed with three times 50 ml of water, dried over sodium sulphate and evaporated down under reduced pressure. After the 5 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-chIorophenoxy)-3,3-dimethy l-5-f I uoro-1-(imidazoI-1-yI)-pentan-2-one are obtained as colourless crystals of melting point 77-78°C by evaporat-10 ing down the eluate.
Examp le 5 43.0 g (0.1 mol) of 1-bromo-5-(4-chlorophenoxy)-3,3-di-methy 1-1-(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 residue is taken up in 400 ml of ethyl acetate, and the solution is 20 washed with 100 ml of water. After the organic phase has been dried over sodium sulphate, it is evaporated down under reduced pressure; and the solid residue which remains is stirred with diethyl ether. 34.3 g (83.5% of theory) of 5- (4-ch lorophenoxy)-3,3-dimethyI-1 -(4-fluoro-25 phenoxy)-1-(imidazol-1-yl)-pentan-2-one are obtained as colourless crystals of melting point 120-121°C.
Preparation of t h.e_s t^a r t i n£ mateH^l (Process a) A solution of 40.2 g (0.591 mol) of imidazole and C H 3 i I 3 r C H 3 2054 85 34.3 g (0.214 mot) of bromine are rapidly added dropwise to a solution of 69.1 g (0.197 mol) of 5-(4-chlorophenoxy)-3,3,-dimethyl-1-(4-fluorophenoxy)-pentan-2-one in 600 ml of dichLoromethane. After the addition 5 of bromine is complete, stirring is continued for a further 15 minutes and 400 ml of ice water are then added to the solution. The organic phase is separated off and washed once with 100 ml of aqueous sodium bisulphite solution and with twice 100 ml of water. The solution is 10 dried over sodium sulphate and then evaporated down in vacuo. 85.9 g (100% of'theory) of 1-bromo-5-(4-chIoro-phenoxy)-3,3-dimethyl-1-(4-fluorophenoxy)-pentan-2-one are obtained as colourless crystals of melting point 92-93°C. 1 5 ch3 fs|^/-o-ch2-co-c-ch2ch2-o- -ci C H 3 68.8 g (0.25 mol) of 1 -ch loro-5-(4-chlorophenoxy)-3 ,3-dimethyIpentan-2-one are heated at the boil for 13 hours with 28 g (0.25 mot) of 4-f luorophenoI and 34.5 g (0.25 mol) of powdered potassium carbonate in 600 ml of 20 acetone. Thereafter, the solution is filtered off from the organic salt, the filtrate is evaporated 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-ch lorophenoxy)-3,3-dimethyl-1-(4-f tuorophenoxy)-pen-25 tan-2-one are obtained as colourless crystals of melting point 71-74°C .
E xa mp le 6 OH C H 3 F-(£ ' - 0-CH-CH- C-CH2CH2-0- '~C L /N\ C H 3 i'/ >■ I N (Process c) 2.6 g (0.068 mol) of sodium boranate are introduced in portions into a solution of 14.2 g (C.034 mol) of 5-(4-chlorophenoxy)-3,3-dimethyl-1-(4-fluorophenoxy)-5 1-(imidazol-1-yl)-pentan-2-one (Example 5) in 140 ml of methanol at 20 to 3 C 0 C , while cooling 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 10 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-1-(4-fluorophen-oxy)-1-(imidazol-1-yl)-pentan-2-ol are obtained as colour-15 less crystals of melting point 88-93°C.
Example 7 C H 3 CI .
C L^>0-CH-C0-C " CH2-(y: "CI CH3 l l N x HCl (Process a) 11 g (0.16 mol) of 1 ,2,4-t ri azo Le and 22 g (0.16 mol) of potassium carbonate in 200 ml of toluene are stirred for 1 hour at 90°C. 35 g (0.078 moL) of 1-bromo-1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-butan-2-one in 100 ml of toluene are added dropwise to 25 the mixture. The reaction mixture is stirred for a further 10 hours at 90°C 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 30 of 1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dime- thy1-1 -(1,2,4-1riazoI-1-yL)-butan-2-one are obtained as a highly viscous oil. 15 ml of saturated ethereal -LL M L I III 2 0 5485 hydrochloric acid are added to 3.9 g of this highly viscous oil. The precipitated salt is filtered off under suction, washed with a little ether and dried in vacuo at 4Q°C. 3.3 g (78.2% of theory) of 1 - (4-ch Iorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one hydrochloride of melting point 130-135°C are obtained.
Hr®.P£r£tjL0H £^_tile_sJLaJltJLniL ro.at.e£.i a.1 CH 3 C U CI- vrN-0-CH-C0-C-CH2-(C) - ci vn7 | i Br C H 3 24.5 g (0.15 mol) of bromine are added to 57 g (0.15 mol) of 1-(4-chlorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-butan-2-one, dissolved in 400 ml of chloroform, at room temperature. After the addition is complete, the reaction mixture is stirred for a further 30 minutes and then evaporated down. 67.6 g (100% of theory) of crude 1-bromo-1-(4-ch Iorophenoxy)-4-(2,4-dich1orophe-nyI)-3,3-dimethyl-butan-2-one are obtained; this product is directly reacted further.
C H 3 C I x C I -^Qy- 0 " C H 2 - C 0 - C - C H 2 - (Q) - C I C H 3 28.2 g (0.22 mol) of 4-ch loropheno I and 30.4 g (0.22 mol) of potassium carbonate in 120 ml of toluene are heated under reflux for 2 hours in a water separator. A solution of 57 g (0.18 mol) of 1-bromo-4-(2,4-dichIoro-phenyl)-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 100°C. The mixture is allowed to cool and filtered off under suction from the inorganic residue, and the toluene phase is washed with 2 0 54 P r> dilute sodium hydroxide solution and then with water, dried over sodium sulphate and evaporated down. 57.4 g (70.2% of theory) of 1 -(4-chIorophenoxy)-4-(2,4-dichIoro-phenyl)-3,3-dimethyl-butan-2-one of refractive index n^ 1.5753 are obtained.
C H 3 CI. i Br-CH2-CO-C-CH2- i C H 3 >-C I 13.4 ml (0.26 mol) of bromine are added dropwise to 64.5 g (0.26 mol) of 4-(2,4-dichIorophenyI)-3,3-dime-thy l-butan-2-one in 600 ml of chloroform at room temperature. The reaction mixture is stirred for a further hour at room temperature and evaporated down. 84 g (100% of theory) of crude 1-bromo-4-(2,4-dichlorophenyI)-3,3-di-methy l-butan-2-one are obtained; this product is directly reacted further.
Example 8 OH CH3 CI f^\ 1 1 CI- - 0- CH-CH - C - CH "CI n y (Process c) 3.5 g (0.008 mol) of 1 -(4-ch lorophenoxy)-4-(2,4-dichlorophenyl)-3,3-dimethyl-1-(1,2,4-triazoL-1-yl)-butan-2-one (see Example 7) are dissolved in 50 ml of methanol at -1 0 0 C , and 0.1 g (0.0026 mol) of sodium borohydride in 2 ml of water is added. The reaction mixture is stirred for a further hour without cooling and is then evaporated down in vacuo. Methylene ch loride/water is then added to the residue. The organic phase is separated off, dried over sodium sulphate and evaporated down. 3.2 g (91.4% of theory) of 1 -(4-ch lorophenoxy)-4-(2,4-dichIorophenyI)-3/3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol of melting In ft 71 f)11i 2 0 54 85 point 60-65°C are obtained. Example 9 C I (Process b) A mixture of 14.4 g (0.21 mol) of 1,2,4-triazo le and 26.9 g (0.21 mol) of 4-chIoropheno 1 in 100 ml of acetone are added to 43 g (0.19 mol) of 1,1-dichloro-3-(di-oxo I an-2-y I)-3-methyl-butan-2-one and 78.4 g (0.57 mol) of potassium carbonate in 300 ml of acetone, under reflux, 10 The reaction mixture is stirred under reflux for a further 10 hours, then cooled and filtered off under suction from the inorganic residue. The filtrate is evaporated down, the residue is taken up in methylene chloride, and the solution is washed with dilute sodium hydroxide solution 15 and with water, dried over sodium sulphate and evaporated down in vacuo. The residue is purified by column chromatography (silica gel/ethyl acetate:cyclohexane = 3:1). 19 g (28.4% of theory) of 1 -(4-chIorophenoxy)-3-(dioxo-lan-2-yl)-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-one of 20 refractive index n?® = 1.4994 are obtained.
P_repa/£t_i_ori £f_t h_e_sjca_rt_i_n_£ mat_e_ri£l 3-ketobutanaI, 13.6 g (0.22 mol) of ethylene glycol and 25 2.2 g of p-toluenesulphonic acid in a mixture of 180 ml of toluene and 160 ml of n-butanol are heated under reflux for 1.5 hours in a water separator. The mixture is C I 2CH-C0- 36.8 g (0.2 mol) of 4,4-d ichloro-2,2-di methyl- 205485 26 allowed to cool, and is evaporated down in vacuo. The residue is taken up methylene chloride, and the solution is washed with water, dried over sodium sulphate and evaporated down. 43.6 g (96% of theory) of 1,1-dichloro-5 3-(dioxoI an-2-yI)-3-methyI-butan-2-one of refractive index n^ = 1 .4631 are obtained. 141 g (1 mol) of 1-(N-morpholino)-isobutene are dissolved- in 470 nl of diethyl ether. 147.5 g (1 mol) of 10 dichloroacetyI 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 15 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 is distilled in vacuo. 155.6 g (85% of 20 theory) of 4,4-dichIoro-2,2-dimethy1-3-keto-butana I of boiling point 118°C/0.2 mbar are obtained.
Example 10 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 C H 3 Cl2CH - CO - C - CH0 CH3 (Proces s c) 7 g (0.02 mol) of 1 - (4-c h I o r op h e noxy)-3-(d i o x olan 2054 85 0.23 g (0.006 mol) of sodium borohydride in 5 ml of water is added. The reaction mixture is stirred for a further 2 hours, the pH value is brought to 6-7 with dilute hydrochloric acid, and the mixture is evaporated down in vacuo. 5 The residue is taken up in methylene chloride, and the solution is washed with water, dried over sodium sulphate and evaporated down. 5.8 g (82.9% of theory) of 1 — C4 — chlorophenoxy)-3-(dio xolan-2-yl )-3-me t hy l-1-(1,2,4-triazol-1-yl)-butan-2-ol of refractive index nj^ = 1.5389 are 10 obtai ned.
The compounds of the general formula Ar - 0- CH - B - R (I) Az are obtained in a corresponding manner and analogously to the processes given: 205485 Ex. Ar No.
Az M.p. (°C) or n 20 11 Cl-<' /- 12 13 CI 14 Cl-v.J/- ■r~>- 16 Cl^O- CL 17 Cl-Q- 18 Cl-(Q)- 19 CL- CL &■ 21 Cl-vQ- 22 CIa0- 23 24 F- Cl-vQ- 26 CL"C.^ 27 Q^Q- — N /^TM -n N -N ^="N -N — N -n -n /=N -n /=N -n -N ,-^N ■n _ : "NV_J /~N -n ! rz: N -n r= n -N _ j /—N -N ! ^ n -N >=N -n CO CO CO CO CO CO CO CO CI- CO -C(CH3) ?-CH2-s >-CL 213(xHCL) CO -C(CH3)2-CH2-, fr~ ch3 , V ch 3 n ch3 \D ch3 ch3 \ ch3 \. A ch3 ^HJ ch 3 V7 CI 'cl CL CL •Br Br ■ 3r Br co -C(CH3)2-n-cjh7 CO -C(CH3)2-i-C3H? CO -C(CH3)2"CH2CH2CL CO -C C CH3) 2- n-C4H9 CO -C(CH3)2- i-C3H? viscous oil CO -C(CH3)2-CH2- )-CL 174-75 ( xHC L) 40 164 viscous oil viscous oil 47 178 viscous oil viscous oil CO -C(CH3)2-n-C3H7 1,5345 65 1,5195 resin 1,5324 127 205485 Ex.
No.
Ar Az M.p. (°C ; or n2u CI / jr. 28 Cl-\ 29 cl-fc - /=N -N /— N -N co -ccch3)2-i-c3h7 co -c(ch3)2-i-c3h7 resin resin cl-c- -N co -c(ch3)2-ch2-c(ch3)3 83-85 31 r~.
-N co -c(ch3)2-ch2-ccch3)3 128 / 32 cl-f,- /-N -N co -c(ch3)2-ch2-ccch3)3 84 33 CL-O/- 34 c l —(t) 36 cl-c.c •ON- 37 cl- /K W ct cl -~C>" 39 f-o- /=-N „ z— /ZM <;OC - -N ! N -N '-n -N /-N 38 Cl-(C_/- -N /rrH -N ! co -c(ch3)2-ch2ch20 co co co co co co Jr V CI ~c(CH3)?-ch2ch2—0 — c l I CL -c(ch3)2-ch2ch2-0 t; CI resin resin -c(ch3)2-ch2ch|0 -c(ch3)2-ch2ch2"9 102-03 "Yl -c(ch3)2-ch2ch2-0 cl resin 1,5822 1,5746 -c(ch3)2-ch2ch2-0 cl 1,5629 tf 40 /t: n )r -n cl co -c(ch3)2-ch2ch2-o Cl cl 1,5950 Ex.
No. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 Ar Az 3 2054 85 M.p. < 0) or ?u n D €■-€>-C I ci-CN- ch3 Ct^ f-S- CLaC)- -N .~n -N cl c- Cl-C- ci /-N /="N -N / - N -N • — N -N i -N -n — N ci^Q- -n n ^ /~=-n -n ; Ci-C'- • /r n -n \ — ' /r-N -N QO- /= "N\=.' a-Q- /=N -N | CL ci^Q,- /= N -n ; CO CO CO CO CO co CO CO CO ■c(ch3) 2-ch2ch2-0^ -cl -c(ch3)2-ch2ch2-0-,q/ -c(ch3)2-ch2ch2-0-<^) ■c ( ch3) 2-ch 2ch 2-0-^/-c l ■c(ch3) ?-ch2ch:>~0—y ■ccch3)2-ch2ch2-o-<^~x/C "ccch3) ?-ch2ch2-0— ~f cl^_ ■:(ch3)2-ch2ch2-0-/C>f: c l --—. -c(ch3)2-ch2ch2-0-ow;>-f cl- ch(oh) -c(ch3)2-ch2-\q-ct ch(oh) -c(ch3)2-ch2-<c/-cl ch(oh) -c(ch3)2-ch2-<^/ ch(oh) ch(oh) ch(oh) ch(oh) CH3 CH3 ch3 Yh ch3 \ /.
XCL cl vCL CL 108-09 95-96 resin resin 88-90 resin viscous oil viscous oil viscous oil 60-65 156-59 144 123 214 145 vi scous oi L 205485 - 3T - Ex. Ar No. 57 CL- 58 CI - (. . 59 CL-<w 68 60 v CL 61 CL-Q- 62 CL-Q- 63 CL-<Q.'- 64 NQ'KQ^" CL 65 CL^>- 66 C L ~ Az B -N CH(OH) "N ; CH(OH) -N_j CH(OH) N -N CH(OH) ,-N -N _ ; CH(OH) /=.N -N CHCOH) /=N ■N _ chcoh) /-N •N CH(OH) /=N -n ch(oh) /- N •n j chcoh) /— N ll.p. C C) or n-'O -ccch3)2- n-c^h^ — C C C H 3)2-CH2CH2Cl -C(CH3)2- n-C4H9 -CCCH3)2~ i_C3H7 -ccch3)2- i_c3h7 -CCCH3)2-ch2ch2cl -ccch3)2-ch2-ccch3)3 -C(CH3)?-CH2-C(CH3)3 -ccch3)2-ch2-ccch3)3 -ccch3)2-ch2ch2-0-\C -Cl 114-16 67 cl-d,--- -n j chcoh) -CCCH3)2-ch2ch2-0-- 69 Cl-Q- CL 70 Cl -n _ j chcoh) /—N -n^_; chcoh) ,-n -N i CHCOH) Civ cl 71 ^ 72 CL-O- 73 •CCCH3) 2-CH2CH2-0-Q^CL a -N ! CHCOH) -CCCH3) 2-CH2CH2-0-O-CL . —N CL /TN -N ! CHCOH) r=u ■N ! CHCOH) -CCCH3)2-CH2CH3-0-<£j-Cl CL X -CCCH3)2-CH2CH2-0-vO-CL 86-90 resin 1,5273 138-40 viscous oil 102-03 137-38 160 resin 118-24 -CCCH3) 2-CH2CH2-0-<Q,-Cl 138-40 -ccch3) 2i;h2ch2crq "cl 147-51 resin 111-13 resin 159-60 - 32 _ ■iX.
No.
Ar Az B 2054 85 PLp. ( C) or — N CH 3 74 8r^. " 75 F -{Q- 76 cl-^_. 77 CL^O- 78 Cl^- 79 ci~'Q~ _/cl 80 Cl<G- 81 Cl^<2>- 82 Cl-C>- 83 CL-vO- -n _! chcoh) -ccch3)2-ch2ch2-0^(_ -cl 138-43 84 /V^\ gc p-/fn- x^y 86 Cl-^- 87 <&"0 88 Cl 89 Cl-O- -n _ ! chcoh) -ccch3)2-ch2ch2-0-v;_j.' -n _ chcoh) -ccch3)2-ch2ch2-o-^v__/-ci — -n _ chcoh) -ccch3)2-ch2ch2-0-^ /"=- N -n chcoh) -ccch3)2-ch2ch2-0-,c__'-f cC -n chcoh) -ccch3)2-ch2ch2-0- 3,'-p n- n c L n- . -n chcoh) -ccch3)2-ch2ch2-0— ^ -f / -N N- ■ N n -■ -N | ' N N — -n i ■=- N /J=, -n i ^=- n ,nh -n i n n ,-N—; ■n ^=-N ,N -■n <N=i -n N— N ,N~; -N CO co CO co co co co CO co n -ccch3)2-ch2-\_ -cl -CCCH3) 2-CH2-.\3' ' -ccch3)2- n-C3H? -ccch3)2- n-c3h? -ccch3)2- i-c3h7 -ccch3)2- n_c4h9 -ccch3)2- i"c3h7 ■ccch3)2- 1_c3h7 ■ccch3)2-i-c3h? resin 64-66 resin resin resin resin 139-41CxHCL) viscous oil 1,5312 75 1,5116 1,5250 121-22 59 67 Ex No 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 2054 85 Ar Az B M.p. ( C) or n20 Cl /—A ci-T > CI .r CL< Cl-v' C1^'Q- <Q-Q- Cl-^I,- y^Ci Cl^O'" XI Cl-O" F-NQ ~ CK> Br-Q> r .
/N — -N i -=jm ,.N — -N | ' —N N — -N N N — -N ' — N N - -N ,N--N N ,N --N ,N--N ,N ~ -N v-^-N ,N~ -N \="N N — -N \= N -N I N /N-j -N < ^ N ,N~ -N \3 N /N-~ •N - N ,N — -N \r N co -c(ch3)2-ch2-c(ch3)3 co -c(ch3)2-ch2-c(ch3)3 co -c(ch3)2-ch0 co co co co co co co CO CO ■c(ch3)2-ch=noch3 0— -c(ch3) 2~\ \ 0- -o-D- ■c(ch3)2-ch2ch2 •C(CH3) 2-CH2CH2-O-,C co -c(ch3)2-ch2ch2-0^_ -cl CLs — c (ch3) 2-ch2 ch 2-0—v^)- c l c -c(ch3)2-ch2ch2-0-.^.'-cl co -c(ch3)2-ch2ch2-0-^.-cl ciw. co -ccch3)2-ch2ch 2-o^C/_c l Clw -c(ch3) 2-ch2ch2-o-<0.1<-cl co -c(ch3)2-ch2ch2-0-\q> / ✓—\ 112 78 1,5350 1,5303 vi scous oi L cl 87-39 resin 103-04 resin 109-10 1,5720 1,5608 88 -c(ch3)2-ch2ch2-0-\c>cl 94-95 86-88 -c(ch3)2-ch2ch2-0-xy cl 107-08 CX. Ar No.
^ -CL 106 Cl-L " Az B CH3 107 ClKjQ 108 Cl-0" 109 C L ~ Ow ^Cl 110 ci KQ- 111 ci-Q- 112 ci-Q.- ^-CL 113 Cl~Q- 114 C/"C 115 Cl-C^ Cl Cl 116 Cl-Q>- 117 Cl-®- 118 QrQ- Cl 119 ci<£- 120 Cl-^>-.fan fli 2 1 DM n = -n co k^rn ,n —, -n co n ,.n- -n co n n — -n co x-^n ,n — -n co n ,n — -n co N__ -n i co n ,.n — -n co nv—:n ,n~ -n co ^ n ,n- -n ! co \^N /n~ -n co ^ n ,n^r- -n co /N- -n co ,N~ -n co ^ n ,n — -n co \_ N 205485 -c(ch3) ?-ch2ch2-q-\v_ -c(ch3)2-ch2ch2-o-<;;7 -ci -c(ch3)2-ch2ch2-0- cu_ -c(ch3)2-ch2ch2-0-fj.-f cu_ -ccch3)2-ch2ch2-o-/q-f C»3/X v Cl Cl ch3 -<2> ch3 ch3 \ ch3 \ 3r 'Br -Br Br ch3 \ Br Br ch3 ch3 ch3 Hi Cl 'ci ch3 ^ Hi M.p. (°C) or ,20 resin 63-65 ; 113-16 1,5581 79-31 1,5555 vi scous oiI vi scous oi L 56 136C xHN03) 125 1,5412 viscous oil vi scous oiI viscous oil - 35 ~ 205485 Ex.
No.
Ar Az M.p.( C) or r.20 121 c KO- 1 22 123 cl-®~ 121* cl<> -Cl 125 cl-o ,—'C L 126 CL^C- 131 cl 132 CL-|l'- 133 cl-®>- 134 cl-<q- ■—c l 135 CL -Q- 1 36 f T n 1 71 H 1 11 N- -N 127 _ 128 129 frc-.^ a-'ch3 130 cl~cv- -N s—N /=-N -N N CO /rN -N '/■=■ N -N N /=N -N | \=N ,-=N -N ! N -N j — N ,~N -N | /=n -n | — N 1 N ,-N -N | CO \=N /=N -N | \=N rz N XL rz N 1 N /="N -N ! /-N co co CO co co co co CO CO co co co co CO ch \ •Br Br CH3)2-CH2CH2-0-/y J-=\ ch3)2-ch2ch2-0-<^_7 -cl ch3)2-ch2ch2-0-®-cl ch3)2-ch2ch2 cly.. ,-o-r - cl cl ch3)2-ch2ch2-o-<_;-cl ch3)2-ch2ch2-0-sq ch3)2-ch2ch2-o-® ch3)2-ch2ch2-o-\T^, cl CLy_ ch3)2-ch2ch2-0-\C/ -F ch3)2- i-c3h7 1,578 ch3)2-ch2ch2-0-^_,>-cl 179-80 resin resin 121-22 110-15 157 ch3)2-ch2ch2-0-®-cl 146-47 ch3)2-ch2ch2-0-®-cl 122-23 ch3)2-ch2ch2-0-®-cl 142-43 154-55 110-111 149-53 ch3)2-ch2ch2-0-^>-f 1,5590 resin { - 6AUGI986 Ex.
No.
Ar 137 Cl-O- -CL 138 CL^l- r 139 _^Cl 140 CL -<£- 141 ClXQ,- CHS" - CL 143 CL -Q- " C L 144 CL 4Q- 145 Cl^jQ/- 146 CL-nQ/- 147 cl-(c/- 148 CL-^QV 149 Cl-Q)- 150 CL-O- 151 CL ^S>- -0 L 152 153 ci -\c/ - 36 Az B -n \="N /-N -N ^N ,<=N ■n V^N /-N -N ^ N / — N -N -N X^N /ziN -N co co co co co co co \=N /J-.
■N chcoh) \=N n — -N | CHCOH) ^ N ,N~ ■N • CHCOH) ^ N ,N~ ■N ! CHCOH) ^N /N- -N | CHCOH) v— N N~, ■N i CHCOH) /N- ■N i CHCOH) 'N^i ■N I CHCOH) v_N ,N-; •N I CHCOH) N— N N - -N CHCOH) CH3, h ; ch 3 -y h -:cch3)2-.i-C3H7 ■cc ch3)2~ i-cjh^ -C(CH3)2~ i_C3H7 -CCCH3)2-CH2-CCCH3)3 -CCCH3)2_CH2_CCCH3)3 -CCCH3)2-CH2-<<2)-CI -CCCH3)2-CH2-<fl)-Cl -CC CH3) 2~CH2"\C) -ccch3)2-ch2-@ -CCCH3)2-CH2-<Q CH3/X ■cl XCL ch3 ch3 -Br Br ch3 •Br Br v \ ch3 Br 'Br \= N -—Cl 'Cl 2 0 54 85 M.p. (C) or n 20 D viscous oil 110-18 224-25 148-49 143 206 138 144CA Form) -37 CB-Form) 157CA Form) viscous oil CB Form) viscous oil viscous oil 168CA Form) 116-19 CB Form) 145 80-85 61-811 13-<Q^O-2H32H3-2 U t S3 J U L S3 J U L S3 J 19- ssl 9Z-0ZI U L S3 J OZl ULS3J £U <70-£0l ol£s'l oil 2££s'l •) LO SnODS LA V8 -id 13-/q)^0-2h32h3-2 ID-/Qv-°-2hd2HD-2 ~^13 13V(^-0-2H32H3-2 £8-18 13-/j*-0-2h32h3-2 13-^Q>-0-2H3-2H3-2 [> £(2h3)3-2h3-2 s:(£:hd)d-2h3-2 ZhS-L -2 ^hS-L -z ZH£3-L -2 Vo-u -2 ZH£D-U -2 ZH£D-U _2 £h3)3-£h3)3-£h3)3-£h3)3-£h3)3-£h3)3-£h3)3-£h3)3-£h3)3- £hd)d' £h3)3- (ho)hd £h3)3' £h3)3- £l 3)3- £h3)3- H ) - _ £"3 h ><-—/£h3 n (h0)h3 j n-•— N (H0)H3 ! N->~bf NZTv (h0)h3 | n-1^-N N=\ (H0)H3 N- ■=■ n' (h0)h3 ! n-^■N/ N:r\ (HO)H3 I N- — n' Nr\ (HO)HD j N- by N^Z\ (HO)HD I N-'~.N' n (h0)h3 i n-'-N' n —, (h0)h3 n- ^n' n r\ N- : — / — n Nrrs (h0)h3 ! n-—■ n' N=\ (h0)h3 n- — N n —x (H0)H3 i N-i=N' 03 n- — NT N^>. ch0)h3 ! n- — N n-="\ (h0)h3 ! n- ■uc li ct ¥ it 0Zl -'2" 13 691 10 rQ-i 891 -Qt13 19 i 991 -4 hi 3 59 l -'3)-13 Wl -''0^13 £9 i 13"" -o-j) 29 l -Or13 L9L - '3)-13 091 13"~ 0/-13 8sl -'^o zst 13 9sl -<3>-13 SSI -< .v-13 <75 i LrN' 13- 02" JO (30)*d*w a zv JV •on ■xg -Z£- £8 V90Z 2Z-9ZI SZLS'l 689S'L (Q^ -0-ZHDZ?D-Z (ho) D- TO TO (o) -0-ZHDZUD-Z (^HD) O-TO 9895' I (d^-0-ZEDZK>-Z (EHD); ID N GO I Jfr- (5)-TD VQL N TD-(0^ -0-3HD3HD-Z(EHD)0- 00 N^N- - (0)-T3 E81 TO 00 • Pn- -@-T0 Z81 00 -(d)-TD 181 Ilo snoosLA ei£D0-(^-O-3H0-3HD-3(eHD)O- 00 - (§>~T0 081 8Z.CS * I £o}-0-ZHD-ZHD-Z(CHD) O- "J3 OO | jp- -<0)-T0 6LI 06^5 i'T tJOS (o)-°p5g^-Z (£HD)D- __OD ^N- -(d)~TD 8Z.I HO 82L c(cHD)D-2H3-2(jHD)D- SO-^OL lD-/Q^-0-2HD2HD-2(£HD)D- ulssj i-<Q)-0-2HD2H3-2C£HD)D-VTD uisaj /O>,'.1)-0-2H32H3-2 (£HD)0-.
U L S3 J U L S3 J 1D-v^-0-2HD2HD-2(£HD)3-!D-(|2rO-2HD2HD-2(fHD)D- Zt-Sll 13~0"° ?h:)2h:)-2(£h35D- f^r\ HO)HD N-N=/ Nr\ (HO)HD . N-N=/ (HO)HD N--l/ N^r\ (HO)HD | N- — NX (HO)HD | N- N'' (HO)HD I N- — N' N=\ (HO)HD I N-t= N' III 3 V** -Q-1D 9ZI -<^1D SZl *lL I -0"-lD £Zl £hd-- -Q-J Zll -Qr-J a LZl 02 jo (oo) -d-w a z v J\/ "on • -xa smog - 8£ - m CO Ki- in ■--% o ouN^ o CM a • L. £ o o 1*1 Pi m % ■ • x O LLl| Z. cr> CN m ro b tol CM .
CM ro s v EC O 0 d LO 00 00 ro I ro ro ? (N 0 CN f V EC o $ d 00 (/) a; L. (0 a) L CN O CN CN (N 8 § d oo O t (N s CN 9 CN n s v 8 p—s V u oo 00 en o 0 o T— 1 a> CT> CO 0) L.
\D ro I in ro V) a> (» 0) L.
W a; L.
CM Ol © (N O ? CN 0 tT tT CN s CM <N s CN 8 CM T CN T CM T CN T CM ET m M 0 V V V V T 0. <7 CN ro b v u CN b f (N ro § v rH u d-l*J ? CN 0, ? (N ro 0 V § § § 8 8 . 8 8 0 0 0 (o) d Ch 00 „ !z n v d o <T> O ? a o :z_ 2: V H u CN CTi <? Co) a m <n Co) d rf cn $ $ d in cr> 205485 Ex. Ar Az No.
B M.p. (°C) 196 Cl-©- CH(OH) 197 Cl -®- -Ci CH(CH) °^0 123 104-07 (A Form) 198 C1^0> -ifjj CH(OH) Cl 199 d-<c£- -nQj CH(CH) 200 201 .Ci N_ Cl-(o}- jjj CH(CH) Cl Cl-<0>- -H CO 202 Cl Cl M ■-& "Cl Cl 203 206 CO > /=■ N ClHo) N I CO W WN 204 Cl-(o)- CO 205 Cl-®- -N^ CO ci<o>- -n'J, CO ■CH, CjHS CH H sa C6H5 °H (B Form) oi I 94 oi I oi t 175 91 156-58 107 2054 85 Ex. Ar No.
Az B Cl 207 Cl-^oS- -*n 2C8 209 Cl N &-<s>- -<Q 210 Cl-®- -N*H n -N Cl 211 Cl -N Cl 212 Cl-{g/- -l/Tf . "~N 01 N 213 Cl^Oy- "Ol" 214 Cl-®- 215 Cl-^V -oTV ^=N 216 Cl-®- -N^Jj CH (OH) Cl ~Oi CH (OH) CH (OH) CH(OH) CO CO CO CO OO OO C2H5 X3 C?5 H5 xa C6H5 C6H5 C6H ^3 % C6H' C6H5 ■KEl C^H, C..H, C6H5 217 ©"®~~ 00 XJ M.p. (°c; °D 107-10 oi I oi L oi I oi L 138-40 102-03 98-100 160-61 oi L oi L 2 0 54 85 Ex. No.
Ar Az B R M.p. ( C) 20 N 218 <0><G}- -N^ CO 219 Cl-(o>- 220 Cl r-<C1 221 Cl^o}- 222 d-®- 223 C1-<S>-224- Cl-<§)- -/I.
-N :N a a -N h/H \=.N CH(OH) CH (OH) CH(OH) CH (OH) CH(OH) C6H5 Xi C6H5 X3 C6H5 C,H^ 6 D X3 C6H5 XI 103-09 oi L 111 (A Foot) oi I 114 (A Form) oi L CO -C(CH3)2-CH2CH2CH2C1 1,54-12 225 Cl-^ 226 Cl-®- 227 Cl-@— -N \—N -nH =H -a CH(0H) -C(CH3)2-CH2CH2-0-<O)-SCF3 oil CO CO 4-C1C.H 6 »-clcA- X3 oil oil A and B form: the two possible geometric isomers 2054 85 Use Examples In the examples which follow, the compounds shown below are employed as comparative substances: C^h3 ch3 ^o-ch-co-c-ch2c i CH3 I! • N <?H CH3 /?=*. (3) c i 0-ch-ch- c- chg-o 8 r -N> C H 3 N a--cl |h3 (C) Cl-<^.;/-0-CH-C0-C-CH2Cl C N^> C H 3 U m .Cl C H 3 (D) C l-^^-0-CH-C0-C-CH2-0-C0CH3 I /NN C H 3 (l ' -N ch3 (£) Cl-^w//-0-CH-C0-C-CH2-0-C0CH3 * CH3 G CH ( F) c i-^^/-o-ch-co-c-ch2oh ch3 ch 3 (G) C l-<^j>-0-CH-C0-C-CH2-0-<Q>- 7" c I CH 3 (I) ( J ) c t c h 3 (H) CL-;' — 0 - C H - C 0 - C - C H ? - 0 - ( . -CL (I n ^ CH .CL OH t c h 3 C L~Y\_/"O-CH-CH - C-CH2 -0^,-Br 1L—N oh /T- 1 -o-ch-l /N -s (lJn c h 3 c h 3 C L^C/-O-CH-CH - C-CH2-OVC ~CL C H 3 2 0 54 8 5 c h 3 _ (K) CL^oC-?-0-CH-CO-i-CH2-S-C \_y | I rfN'-N iH3 N li c h 3 (l) cl-'^2^-o-ch-co-c-ch2-o-c2h5 ch3 a_3 (M) C H 3 C H 3 C L -(C)- 0- CH-C0-C-CH?CL n_ n' n Ij ! CH3 - 45 _ oh ch3 cp) clko-o-chx-ch - c-ch2-o-/©-ci v—' I I CH- l| N N I? j.h3 oh ch3 CQ) c i-(^)-o-ch-ch - c-ch2cl ff^N "3 • » I N L (r) OH C H 5 I l //-O-CH-CH - C-CH2Sr N_ I! oh ch3 (s) '\Qx-o-ch-ch - c-ch2cl (f^V ^H, n 1! (T) Cl cl oh c h 3 cl I I x '/-o-ch-ch - c-ch2-o~/ov;-ci I I v—V r, n"n CH; N U xi oh ch3 /—1 I (u) c i^Q/-o-ch-ch - c-ch2ci rr^N c H 3 N 2 0 54 8 5 Example A Puccinia test (wheat) / protective Solvent: 100 parts by weight of dimethyLformamide Fmulsifier: 0.25 parts by weight of alkylaryl poly-5 glycol ether To produce a suitable preparation of active compound, 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 concentration, 10 To test for protective activity, young plants are inoculated with a spore suspension of Puccinia recondita in a 0.1% 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 15 plants remain in an incubation cabin at 20°C and 100% relative atmospheric humidity for 24 hours.
The plants are placed in a greenhouse at a temperature of about 20°C and a relative atmospheric humidity of about 80% in order to promote the development of rust 20 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 25 according to the following preparation examples: 13, 12, 22, 16, 17, 33, 34, 4, 36, 24, 38, 39, 40, 41, 42, 43, 5, 44, 45, 145, 147, 169, 171 and 172. 2054 85 Example E? Cochliobolus sativus test (barley) / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl poly-5 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 con-10 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 15 Cochliobolus sativus. The plants remain in an incubation cabinet for 48 hours at 2 0 0 C and 100% relative atmospheric humidity.
The plants are placed in a greenhouse at a temperature of about 20°C and a relative atmospheric 20 humidity of about 80%.
Evaluation is carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the 25 compounds according to the following Preparation Examples 13, 12, 22, 17, 45, 68, 58 and 75. 2054 85 Example C Sphaerotheca test (cucumber) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl poly-5 glycol ether To produce a suitable preparation of active compound, 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 10 concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are dusted with conidia of the fungus Sphaerotheca 15 fuliginea.
The plants are then placed in a greenhouse at 23 to 24°C and at a relative atmospheric humidity of about 75%.
Evaluation is carried out 10 days after the 20 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, 85, 100, 103, 150, 169, 156, 152 and 83. 205485 Example D Erysiphe test (barley) / protective Solvent: 100 parts by weight of dimethyLformamide Emulsifier: 0.25 parts by weight of alkylaryl poly-5 glycolether To produce a suitable preparation of active compound, 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-10 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 15 f.sp. hordei.
The plants are placed in a greenhouse at a temperature of about 20°C and a relative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules.
Evaluation is carried out 7 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: 50, 52, 25 66, 67, 68, 70, 71, 72, 58, 73, 6, 75, 82, 83, 93, 112, 113 and 106. 205485 Example E Erysiphe test (barley) / 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 finely pulverulent 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 20°C and a relative atmospheric humidity of about 80% in order to promote the development of powdery mildew pustules.
Evaluation is carried out 7 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: 150. 2 0 54 85 Example F PyricuLaria test Cri ce)/protective Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl poly-5 glycolether To produce a suitable preparation of active compound, 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, 10 to the desired concentration.
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 in a greenhouse at 100% relative atmospheric humidity and 25°C.
Evaluation of the disease infestation is carried out 4 days after the inoculation.
In this test, a clearly superior activity compared 20 with the prior art is shown, for example, by the compounds according to the following preparation examples: 156, 169, 152, 24 and 43. 205485 Example G Pellicular!a test (rice) Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl poly-5 glycol ether To produce a suitable preparation of active compound, 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, 10 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 in a greenhouse until they have dried off. The plants are then inoculated with Pellicularia sasakii 15 and are placed at 25°C and 100% relative atmospheric humi di ty.
The evaluation of the disease infestation is carried out 5 to 8 days after the inoculation.
In this test, a clearly superior activity com-20 pared with the prior art is shown, for example, by the compounds according to the following preparation examples: 12, 22, 14, 23, 16, 17, 18, 33, 4, 37, 24, 38, 25-, 41 , 42, 43 and 44.

Claims (13)

205485 - 53 - Example H Agar plate test Nutrient medium used 39 parts by weight of potato glucose agar 5 parts by weight of agar-agar 10 parts by weight of peptone 5 parts by weight of malt are dissolved in 1,000 ml of distilled water and the solution is kept in an autoclave at 121°C for 30 minutes. Solvent: 2 parts by weight of water-acetone (97.5 : 2.5) Ratio of the amounts of solvent to nutrient medium: 2 : 100. To produce a suitable preparation of active compound, 1 part by weight of active 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 mixture is then poured into Petri dishes. When the nutrient medium has cooled and solidified, the plates are inoculated with the following microorganisms and are incubated at about 21°C: Cochliobolus mi yabeanus Evaluation is carried out after 2 to 8 days, depending on the speed of growth of the microorganisms, the inhibition of growth being used as a measure of the action of the preparations. In this test, a clear superiority compared with the prior art is shown by the compounds according to the following preparation examples: 145, 147, 156, 157, 167, 168 and 173. 205485 whai We claim |Sv. - 54 -
1) Substituted azolylether-ketones and -carbinols of the formula Ar-0-CH-B-R (I) i A z in which Ar represents phenyl which is optionally monosubstituted or polysubstituted by identical or different substituents chosen from the group consisting of: 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 part, nitro, cyano or phenoxy or phenyl which is optionally substituted by halogen and/or alkyl having 1 or 2 carbon atoms, Az represents 1,2,4-1riazoI-1-yI, 1,2,4-1riazo I --4-yl or imidazol-1-yI, B represents the keto group or a CH(OH) grouping and R represents •substituted cycloalkyl or one of the groupings -C(CH3>2-R1, -C(CH3>2-CH2-CH2-R2, -C(CH3)2-(CH2)m-R3 L and -CCCH3)2-(CH2)n-R 9 wherein 1 R represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl or the aldehyde group or a derivative thereof, R represents optionally substituted phenoxy, R represents optionally substituted phenyl, R represents halogen, m represents an integer from 1 to 4 and n represents an integer frcm 2 to 4, and their acid addition salts and metal salt complexes. 2) Compounds of the general formula (I) in Claim 1, wherei n 205485 - 55 - R represents cycloalkyl which has 3 to 7 carbon atoms and is monosubstituted or polysubstituted by identical or different substituents chosen from the group consisting of: ^ a I o g e n , alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms and phenyl; or represents one of the groupings -CCCH^^-R1, -C(CH^)^-CH^CH^-R^, -C(CH,)-,-(CH_) -R3 and -C(CH,)_-(CH_) -R4; 32 2m 32 2 n ' wherein 1 R 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 itsderivatives, or represents optionally substituted dioxanes or dioxolanes;
2 R represents phenoxy which is optionally mono-substituted or polysubstituted by identical or different suDstituents chosen from the phenyl substituents mentioned in the case of Arin claim 1; R3 represents phenyl which is optionally monosubstituted or polysubstituted by identical or different substituents chosen from the phenyl substituents mentioned in the case of Ar -in claim 1; 4 R represents fluorine, chlorine or bromine; and Ar, Az, B, m and n have the meaning given in Claim 1.
3) A compound of the general formula (I) of claim 1 wherein R^" represents the aldehyde group derivatives chosen from oximes, oxime ethers and acetals.
4) A compound according to claim 3 wherein R"*" represents a dialkyl acetal having 1 to 4 carbon atoms in each alkyl part.
5) Compounds of the general formula (I) in Claim 1, wherein 205485 - 56 - Ar represents phenyl which is optionally mono-substituted to trisubstituted by identical or different substituents chosen from the group consisting of: fluorine, chlorine, bromine, methyl, ethyl, isopropyl, methoxy, methylthio, trif I uoromethyI, trifluoromethoxy, trif Iuoromethy11hio, methoxycarbonyI, ethoxycar-bonyl, nitro, cyano, phenyl, chlorophenyl, phenoxy, methoximinomethyI, ethoximinomethyI and 1-(methox-i m i no)-et hy I; R represents cycloalkyl which has 3 to 6 carbon atoms and is monosubstituted to trisubstituted by identical or different substituents, chosen from the group consisting of: fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy 1 and phenyl; or one of the groupings -C(CH3)2~R /> -C (CH3>2-CH2CH2-R2, -CC C H 3)2-(CH2)m-R3 and -C(CH3)2-(CH2)n-R4; wherein 1 R represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl or neopentyl, or represents one of alkenyl having 3 to 6 carbon atoms or alkinyl having 2 to 4 carbon atoms, or represents the aldehyde group or its derivatives; 2 R represents phenoxy which is optionally mono-substituted to trisubstituted by identical or 205485 - 57 - different substituents chosen from the phenyl substituents mentioned above in the case of Ar; R3 represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, chosen from the phenyl substituents mentioned above in the case of Ar; L R represents fluorine or chlorine; m represents 1 or 2; n represents 2; Az and B have the meaning given in Claim 1.
6) A compound according to claim 5 wherein an R^" represents joxime or oxime-ether, the latter being chosen 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 monosubstituted to trisubstituted by halogen; and dialkyl acetals having 1 to 4 carbon atoms in each alkyl part, dioxane and dioxolane
7) Process for the preparation of substituted azolylether-ketones and -carbinols of the formula Ar-0-CH-B-R (I) I A z i n wh i ch Ar has the meaning given in claim 1, Az represents 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl or imidazo 1-1-y I, B represents the keto group or a CH(OH) grouping and R represents substituted cycloalkyl or one of the groupings -C(CH3)2-R1, -C(CH3)2-CH2-CH2-R2, -C(CH,),-(CH-) -R and -C(CH-),-(CH,> -R 32 2m 32 2n wherein - 58 - 205485 R^ represents alkyl having more than 1 carbon atom, alkenyl having more than 2 carbon atoms, alkinyl or the aldehyde group or a derivative thereof, R2 represents optionally substituted phenoxy, R3 represents optionally substituted phenyl, 4 R represents halogen, an m rep resents>integer from 1 to 4 and n represent^>integer from 2 to 4, or their acid addition salts or metal salt ootiplexes, characterised in that. a) halogenoether-ketones of the formula Ar-O-CH-CO-R (II) Ha I in which Ar and R have the meaning given above and Hal represents chlorine or bromine, are reacted with 1,2,4-triazoIe or imidazole in the presence of an acid-binding agent and, if appropriate, in the presence of a diluent; or b) dihalogenoketones of the formula (Ha I)^ CH-CO-R (III) in which Hal and R have the meaning given above, are reacted with 1,2,4-triazoIe or imidazole and with a phenol of the formula Ar-°H (IV) in which Ar has the meaning given above, in the presence of an acid-binding agent and in the presence of a diluent; or, if appropriate, c) the azolylether-ketones obtained by process (a) or (b), of the formula Ar-O-CH-CO-R (la) I Az in which Ar, Az and R have the meaning given above, are reduced in a customary manner by known methods, and, if desired, the resulting compounds of the formula (I) 205485 - 59 - are then subjected to an addition reaction with an acid or a metal salt to prepare acid addition salts and metal salt comp lexe s.
8) Fungicidal agents characterised in that they contain at least one substituted azoIyIether-ketone or -car-binol of the formula (I) in Claims 1 and 6'?'
9) Method of combating fungi, characterised in that substituted azolylether-ketones or -carbinols of the formula (I) in Claims 1 and,#/' are allowed to act on fungi or their habitat.
10) Use of substituted azolylether-ketones and -carbinols of the formula (I) in Claims 1 and/6^for combating fungi.
11) Use of substituted azolylether-ketones and -carbinols of the formula (1) in Claims 1 and^as plant protection agents.
12) Process for the preparation of fungicidal agents, characterised in that substituted azolylether-ketones and -carbinols of the fcr-r.ula (I) in Claims 1 and ^are mixed with extenders and/or surface-active agents.
13) A compound according to claim 1 substantially as he: described or exemplified. BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By: L _.
NZ205485A 1982-09-07 1983-09-05 Substituted azolylether-ketones and -carbinols and fungicidal compositions NZ205485A (en)

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