CA1187084A - Phenoxyphenyl azolylmethyl ketones and carbinols, processes for their preparation, and their use as fungicides and as intermediate products - Google Patents
Phenoxyphenyl azolylmethyl ketones and carbinols, processes for their preparation, and their use as fungicides and as intermediate productsInfo
- Publication number
- CA1187084A CA1187084A CA000413102A CA413102A CA1187084A CA 1187084 A CA1187084 A CA 1187084A CA 000413102 A CA000413102 A CA 000413102A CA 413102 A CA413102 A CA 413102A CA 1187084 A CA1187084 A CA 1187084A
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- carbon atoms
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- cycloalkyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—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
-
- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
Novel compounds of the formula
Novel compounds of the formula
Description
3'7~
The present invention relates to certain new phenoxy-phenyl azolylmethyl ketones and carbinols, to a process for their preparation and to their use as fungicides and as intermediate products for the synthesis of further plant protection agents.
It has already been disclosed that phenyl azolylmethyl ketones and carbinols possess fungicidal properties (see DE-OS
(German Published Specification) 2,431,407). However, the action of these azolyl derivatives is not always completely satisfactory in many areas of indication, in particular when small amounts and low concentrations are used.
The present invention now provides, as new compounds, the phenoxyphenyl azolylmethyl ketones and carbinols of the general formula X - O ~ A - CH - R
y in which Az is 1,2,4 -triazol-l-yl or -4-yl or imidazol-l-yl, A is the keto group or the -CH(OH)- or -C(OH)R
grouping, R is alkyl, cycloalkyl, cycloalkylalkyl, alkenyl or alkynyl, or is phenyl or phenalkyl optionally substituted in the phenyl ring by halogen or alkyl, X is phenyl optionally substituted by halogen, alkyl, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, ~ Le A 21 322-CA -1-:~:
7~
nitro, cyano or methylenedioxy, yl~ y2 and Y3 each independently is hydrogen, halogen, or alkyl, and Rl is alkyl, cycloalkyl, cycloa]kylalkyl, alkenyl, alkynyl, halogenoalkyl, alkoxyalkyl, halogenoalkoxyalkyl, alkylthioalkyl, halogeno-substituted phenalkyl, or may be hydrogen provided (a) X is not unsubstitu-ted phenyl while at the same time each of yl~ y2 and Y3 is hydrogen, or (b) R is not alkyl, cycloalkyl, or cycloalkylalkyl, and their plant-tolerated acid addition salts and metal salt complexes.
The compounds of the formula (I) rnay possess two asymmetric carbon atoms, they can then be present as the two geometrical isomers (threo form and erythro form), which can occur in varyin~ proportions. In both cases, they are present as optical isomers.
The present invention also provides a process for the preparation of a phenoxyphenyl azolylmethyl ketone or carbinol of the formula (I), in which (a) a halogenoketone of the general formula X - O ~ ~ ~CO - CH2 - Hal (II), in which Hal represents halogen, preferably chlorine or bromine, and ....
~87~
X, yl~ y2 and Y3 have the meanings given above, is reacted with an azole of the general formula H - Az (III), in which Az has the meaning given above, in the presence of a diluent and in the presence of an acid-binding agent; or (b) an azolyl ketone of the general formula -2a-.
1~37~
X _ 0 ~ ~ C0 - CH2 - Az (Ia~
y1 y2 y3 in which Az, X, y1~ y2 and Y3 have the meanings given above, is reacted with an alkylating agent of the general formula R1 z (IV), in which R1 has the meaning given above and Z represents an electron-attracting leaving grouping, in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in -the presence of a phase transfer catalyst; or (c) an azolyl ketone of the general formula X - 0 - ~ - C0 - CH - R2 (Ib), in which Az, X, y1~ y2 and Y3 have the meanings given above and R2 represents hydrogen or R1j where R1 has the : meaning given above, is reduced by reaction with a complex hydride or alumin-ium isopropylate in the presence of a diluent, or is reacted with an organometallic compound of the general formula M - R (V), in which R has the meaning given above and ,1 ~
, Le A 21 322 I
'' '' :
;
-~8i7~
M represents an alkaii metal or the radical Hal' Mg, wherein ~al' represents chlorine, bromine or iodine, in the presence of a diluent.
An acid or a metal salt can then be added onto the compound of the formula (I) obtained by process variant (a), (b) or (c), if appropriate. In some cases it proves to be advantageous to obtain the compounds of the formula (I) in pure form via their salts.
Iû The phenoxyphenyl azolylmethyl ketones and carbinols of the formula (I) and their deri~atives possess powerful fungicidal properties. Surprisingly, the com-pounds according to the invention exhibit a better fung-icidal action than the phenyl azolylmethyl ketones and carbinols which are known from the state of the art and are chemically similar compounds with a similar action.
In addition, the phenoxyphenyl azolylrnethyl ketones and carbinols of the formula (I) are interesting inter-mediate products for the preparation of further plantprotection agents. In the keto derivatives, the keto group can be reduced to a -CH(OH) group or to a -CR(OH) group (see process variant (c)). Furthermore, functional derivatives oF the keto group, for example oximes, oxime ethers, hydrazones and ketals, can be obtained by appro-priate reactions. The carbinol derivatives can be converted into the corresponding ethers in the customary rnanner, at the hydroxyl group. Furthermore, acyl or carbamoyl derivatives of the compounds of the formula (I) can be obtained by reaction with, for example, acyl halides or carbamoyl chlorides in a manner which is known in principle.
The substances according to the invention thus represent a valuable enrichment of the art.
Le ~ 21 322 ~87~
Formula (I) gives a ge-neral definition of the phenoxyphenyl azolylmethyl ketones and carbinols according to the invention. PreFerred compounds are thase of the general formula ~3 ~ - O ; ~ ; A - CH - R (IA) in which Az represents 1,2,4-triazol-l-yl or -4-yl or imidazol-1-yl, A represents the keto group, or the -CH(OH) or -C(OI~)R grouping, R represents straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part, alkenyl or alkynyl each having 2 to 6 carbon atoms, optionally sub-stituted phenyl or optionally subs-tituted phen-alkyl having 1 to 4 carbon atoms in the alkyl part, preferred substituents on the phenyl in either case being halogen and alkyl having 1 to 4 carbon atoms, R1 represents straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkyl-alkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part, alkenyl or alkynyl, each having 2 to 6 carbon atoms, alkoxyalkyl or alkylthioalkyl, each having 1 to
The present invention relates to certain new phenoxy-phenyl azolylmethyl ketones and carbinols, to a process for their preparation and to their use as fungicides and as intermediate products for the synthesis of further plant protection agents.
It has already been disclosed that phenyl azolylmethyl ketones and carbinols possess fungicidal properties (see DE-OS
(German Published Specification) 2,431,407). However, the action of these azolyl derivatives is not always completely satisfactory in many areas of indication, in particular when small amounts and low concentrations are used.
The present invention now provides, as new compounds, the phenoxyphenyl azolylmethyl ketones and carbinols of the general formula X - O ~ A - CH - R
y in which Az is 1,2,4 -triazol-l-yl or -4-yl or imidazol-l-yl, A is the keto group or the -CH(OH)- or -C(OH)R
grouping, R is alkyl, cycloalkyl, cycloalkylalkyl, alkenyl or alkynyl, or is phenyl or phenalkyl optionally substituted in the phenyl ring by halogen or alkyl, X is phenyl optionally substituted by halogen, alkyl, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, ~ Le A 21 322-CA -1-:~:
7~
nitro, cyano or methylenedioxy, yl~ y2 and Y3 each independently is hydrogen, halogen, or alkyl, and Rl is alkyl, cycloalkyl, cycloa]kylalkyl, alkenyl, alkynyl, halogenoalkyl, alkoxyalkyl, halogenoalkoxyalkyl, alkylthioalkyl, halogeno-substituted phenalkyl, or may be hydrogen provided (a) X is not unsubstitu-ted phenyl while at the same time each of yl~ y2 and Y3 is hydrogen, or (b) R is not alkyl, cycloalkyl, or cycloalkylalkyl, and their plant-tolerated acid addition salts and metal salt complexes.
The compounds of the formula (I) rnay possess two asymmetric carbon atoms, they can then be present as the two geometrical isomers (threo form and erythro form), which can occur in varyin~ proportions. In both cases, they are present as optical isomers.
The present invention also provides a process for the preparation of a phenoxyphenyl azolylmethyl ketone or carbinol of the formula (I), in which (a) a halogenoketone of the general formula X - O ~ ~ ~CO - CH2 - Hal (II), in which Hal represents halogen, preferably chlorine or bromine, and ....
~87~
X, yl~ y2 and Y3 have the meanings given above, is reacted with an azole of the general formula H - Az (III), in which Az has the meaning given above, in the presence of a diluent and in the presence of an acid-binding agent; or (b) an azolyl ketone of the general formula -2a-.
1~37~
X _ 0 ~ ~ C0 - CH2 - Az (Ia~
y1 y2 y3 in which Az, X, y1~ y2 and Y3 have the meanings given above, is reacted with an alkylating agent of the general formula R1 z (IV), in which R1 has the meaning given above and Z represents an electron-attracting leaving grouping, in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in -the presence of a phase transfer catalyst; or (c) an azolyl ketone of the general formula X - 0 - ~ - C0 - CH - R2 (Ib), in which Az, X, y1~ y2 and Y3 have the meanings given above and R2 represents hydrogen or R1j where R1 has the : meaning given above, is reduced by reaction with a complex hydride or alumin-ium isopropylate in the presence of a diluent, or is reacted with an organometallic compound of the general formula M - R (V), in which R has the meaning given above and ,1 ~
, Le A 21 322 I
'' '' :
;
-~8i7~
M represents an alkaii metal or the radical Hal' Mg, wherein ~al' represents chlorine, bromine or iodine, in the presence of a diluent.
An acid or a metal salt can then be added onto the compound of the formula (I) obtained by process variant (a), (b) or (c), if appropriate. In some cases it proves to be advantageous to obtain the compounds of the formula (I) in pure form via their salts.
Iû The phenoxyphenyl azolylmethyl ketones and carbinols of the formula (I) and their deri~atives possess powerful fungicidal properties. Surprisingly, the com-pounds according to the invention exhibit a better fung-icidal action than the phenyl azolylmethyl ketones and carbinols which are known from the state of the art and are chemically similar compounds with a similar action.
In addition, the phenoxyphenyl azolylrnethyl ketones and carbinols of the formula (I) are interesting inter-mediate products for the preparation of further plantprotection agents. In the keto derivatives, the keto group can be reduced to a -CH(OH) group or to a -CR(OH) group (see process variant (c)). Furthermore, functional derivatives oF the keto group, for example oximes, oxime ethers, hydrazones and ketals, can be obtained by appro-priate reactions. The carbinol derivatives can be converted into the corresponding ethers in the customary rnanner, at the hydroxyl group. Furthermore, acyl or carbamoyl derivatives of the compounds of the formula (I) can be obtained by reaction with, for example, acyl halides or carbamoyl chlorides in a manner which is known in principle.
The substances according to the invention thus represent a valuable enrichment of the art.
Le ~ 21 322 ~87~
Formula (I) gives a ge-neral definition of the phenoxyphenyl azolylmethyl ketones and carbinols according to the invention. PreFerred compounds are thase of the general formula ~3 ~ - O ; ~ ; A - CH - R (IA) in which Az represents 1,2,4-triazol-l-yl or -4-yl or imidazol-1-yl, A represents the keto group, or the -CH(OH) or -C(OI~)R grouping, R represents straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part, alkenyl or alkynyl each having 2 to 6 carbon atoms, optionally sub-stituted phenyl or optionally subs-tituted phen-alkyl having 1 to 4 carbon atoms in the alkyl part, preferred substituents on the phenyl in either case being halogen and alkyl having 1 to 4 carbon atoms, R1 represents straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkyl-alkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part, alkenyl or alkynyl, each having 2 to 6 carbon atoms, alkoxyalkyl or alkylthioalkyl, each having 1 to
2 carbon atoms in each alkyl part, halogenoalkyl having 1 to 8 carbon atoms and 1 to 5 halogen Ie_A 21 322 7~
atoms (preferably fluorine atoms and chlorine atoms), halogenoalkoxyalkyl or halogenoalkyl-thioalkyl, each having 1 to 4 carbon atoms in each alkyl part and 1 to 5 halogen atoms (preferably fluorine atorns and chlorine atoms), dialkylaminoalkyl having 1 to 4 carbon atoms in each`alkyl part, or optionally substituted ---pnenylalkyl having 1 to 4 carbon atoms in the alkyl part 7 the radicals mentioned for X1 being suitable phenyl substituents, or R1 may represent hydrogen provided that a-t the same time X1, x2 X3 y1 y2 d Y3 d represent hydrogen, or provided that R does not represent alkyl, cycloalkyl or cycloalkylalkyl, X1 represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms, halogenoalkyl, halogenoalkoxy or halogenoalkylthio, each having 1 to 4 carbon atoms and 1 to 5 halogen atoms (preferably fluorine atoms and chlorine atoms), alkoxy or alkylthio, each havi.ng 1 to 4 carbon atoms, arnino, alkyl-amino or dialkylamino, each having 1 to 4 carbon atoms in each alkyl part, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl part, nitro or cyano, x2 represents hydrogen, halogen or alkyl or alkoxy, each having 1 to 4 carbon atoms, or x1 and x2 together, in the o-position to one another, represent methylenedioxo, X3 represents hydrogen, halogen or alKyl ~ralkoxy~
each having 1 to 4 carbon atoms, Y represents hydrogen, halogen or alkyl having 1 to 4 carbon atoms, y2 represents hydrogen or halogen, and Y3 represents hydrogen.
Le A 21 322 ~_ ., .
~87~
Particularly preferred compounds are those of the formula (IA), in which A and Az have the meanings given above, R represents straight-chain or branched alkyl having 1 to 4 carbon atoms, cycloalkyl or cyclo-alkylmethyl, each having 5 or 6 carbon atoms in -the cycloalkyl par-t, alkenyl or alkynyl, each having 2 to 4 carbon atoms, or optionally sub stituted phenyl or benzyl, the following being mentioned as possible substituents: fluorine, chlorine, bromine and methyl, R represents straight-chain or branched alkyl having 1 to 8 carbon atoms, cyc~oalkyl or cyclo-alkylmethyl, each having 5 or 6 carbon atoms in the cycloalkyl part, alkenyl having 2 to 6 carbon atoms, alkynyl having 2 to 4 carbon atoms, alkoxy-alkyl or alkylthioalkyl, each having 1 to 2 carbon atoms in each alkyl part, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms (especially fluorine atoms and chlorine atoms), halogenoalkoxyalkyl or halogenoalkylthioalkyl1 each haviny 1 to 2 carbon atoms in each alkyl part and 1 to 5 halogen atoms (especially fluorine atoms and chlorine atoms), dialkylaminoalkyl having 1 to 2 carbon atoms in each alkyl part, or optionally substituted benzyl, the radicals mentioned for X
being suitable phenyl substituents, or R1 may represent hydrogen provided that at the ti X1 x2 X3 y1 y2 and Y3 do not represent hydrogen, or provided that R does not represent alkyl, cycloalkyl or cycloalkyla].kyl, ; x1 represents hydrogen, fluorine, chlorine, Le A 21 322 ., ;: ~
-~ :' 7~
bromine, methyl, trifluoromethyl, trifluoro-methoxy, trifluoromethylthio, methoxy, methyl-thio, amino, dlmethylamino, methoxycarbonyl, nitro or cyano, x2 represents hydrogen, fluorine, chlorine, methyl or methoxy, or x1 and x2 together, in the o-position to one another, represent methylenedioxo, X3 represents hydrogen, fluorine, chlorine, methyl or methoxy, y1 represents hydrogen, fluorine, chlorine or methyl, y2 represents hydrogen, fluorine or chlorine, and Y3 represents hydrogen.
In addition to the compounds mentioned in the preparative examples, the following compounds of the general formula (IA) may be mentioned individually (Az representiny 1,2,4-triazol-1--yl or imidazol~1-yl):
X1 (IA) - A - C~ -y1 y2 y3 . Le A 21 322 -~8~8~
Xl x2 X3 y1 y2 y3 A R
4-Cl H H H H H -C(OH) ~ H
4-Cl H H H H H -C(CH)-CH2 ~ H
4-Cl H H H H H -C(OH)-CH2CH=CHCH3 H
4-Cl H H H H H -C(OH)-C4Hg H
4-Cl H H H H H -C(OH) -CH2-C -CH H
4-F H H H H H -C(OH) ~ H
4-F H H H H H -C(OH)-CH2 ~ H
4-F H H H H H -C(OH)-CH2CH-CHCH3 H
4-F H H H H H -C(OH)-C4Hg H
4-F H H H H H -C(OH)-CH2-C - CH H
4-F . H H H H H -CO- CH3 15 4-F H H H H H -CO- C4Hg 4-F H H H H H CO- C5Hll 4-F H H H H H -CO- i-C~H7 4-F H H H H H -CH(OH)- CH3 4-F H H H H H -CH(OH)- C2H5 20 4-F H H H H H -CH(OH)- C3H7 4-F H H H H H -CH(OH)- C4Hg : 4-F H H H H H -CH(OH)- C5H11 4-F H H H H H -CH(OH)- i~C}H7 , .
Le A 21 322 ~7~8~
Xl x2 X3 y1 y2 y3 A R
. ~
4-N(CH3)2 H H H H H -CO- C3H7 -O-CH2-a- H H H H -CO- C3H7
atoms (preferably fluorine atoms and chlorine atoms), halogenoalkoxyalkyl or halogenoalkyl-thioalkyl, each having 1 to 4 carbon atoms in each alkyl part and 1 to 5 halogen atoms (preferably fluorine atorns and chlorine atoms), dialkylaminoalkyl having 1 to 4 carbon atoms in each`alkyl part, or optionally substituted ---pnenylalkyl having 1 to 4 carbon atoms in the alkyl part 7 the radicals mentioned for X1 being suitable phenyl substituents, or R1 may represent hydrogen provided that a-t the same time X1, x2 X3 y1 y2 d Y3 d represent hydrogen, or provided that R does not represent alkyl, cycloalkyl or cycloalkylalkyl, X1 represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms, halogenoalkyl, halogenoalkoxy or halogenoalkylthio, each having 1 to 4 carbon atoms and 1 to 5 halogen atoms (preferably fluorine atoms and chlorine atoms), alkoxy or alkylthio, each havi.ng 1 to 4 carbon atoms, arnino, alkyl-amino or dialkylamino, each having 1 to 4 carbon atoms in each alkyl part, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl part, nitro or cyano, x2 represents hydrogen, halogen or alkyl or alkoxy, each having 1 to 4 carbon atoms, or x1 and x2 together, in the o-position to one another, represent methylenedioxo, X3 represents hydrogen, halogen or alKyl ~ralkoxy~
each having 1 to 4 carbon atoms, Y represents hydrogen, halogen or alkyl having 1 to 4 carbon atoms, y2 represents hydrogen or halogen, and Y3 represents hydrogen.
Le A 21 322 ~_ ., .
~87~
Particularly preferred compounds are those of the formula (IA), in which A and Az have the meanings given above, R represents straight-chain or branched alkyl having 1 to 4 carbon atoms, cycloalkyl or cyclo-alkylmethyl, each having 5 or 6 carbon atoms in -the cycloalkyl par-t, alkenyl or alkynyl, each having 2 to 4 carbon atoms, or optionally sub stituted phenyl or benzyl, the following being mentioned as possible substituents: fluorine, chlorine, bromine and methyl, R represents straight-chain or branched alkyl having 1 to 8 carbon atoms, cyc~oalkyl or cyclo-alkylmethyl, each having 5 or 6 carbon atoms in the cycloalkyl part, alkenyl having 2 to 6 carbon atoms, alkynyl having 2 to 4 carbon atoms, alkoxy-alkyl or alkylthioalkyl, each having 1 to 2 carbon atoms in each alkyl part, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms (especially fluorine atoms and chlorine atoms), halogenoalkoxyalkyl or halogenoalkylthioalkyl1 each haviny 1 to 2 carbon atoms in each alkyl part and 1 to 5 halogen atoms (especially fluorine atoms and chlorine atoms), dialkylaminoalkyl having 1 to 2 carbon atoms in each alkyl part, or optionally substituted benzyl, the radicals mentioned for X
being suitable phenyl substituents, or R1 may represent hydrogen provided that at the ti X1 x2 X3 y1 y2 and Y3 do not represent hydrogen, or provided that R does not represent alkyl, cycloalkyl or cycloalkyla].kyl, ; x1 represents hydrogen, fluorine, chlorine, Le A 21 322 ., ;: ~
-~ :' 7~
bromine, methyl, trifluoromethyl, trifluoro-methoxy, trifluoromethylthio, methoxy, methyl-thio, amino, dlmethylamino, methoxycarbonyl, nitro or cyano, x2 represents hydrogen, fluorine, chlorine, methyl or methoxy, or x1 and x2 together, in the o-position to one another, represent methylenedioxo, X3 represents hydrogen, fluorine, chlorine, methyl or methoxy, y1 represents hydrogen, fluorine, chlorine or methyl, y2 represents hydrogen, fluorine or chlorine, and Y3 represents hydrogen.
In addition to the compounds mentioned in the preparative examples, the following compounds of the general formula (IA) may be mentioned individually (Az representiny 1,2,4-triazol-1--yl or imidazol~1-yl):
X1 (IA) - A - C~ -y1 y2 y3 . Le A 21 322 -~8~8~
Xl x2 X3 y1 y2 y3 A R
4-Cl H H H H H -C(OH) ~ H
4-Cl H H H H H -C(CH)-CH2 ~ H
4-Cl H H H H H -C(OH)-CH2CH=CHCH3 H
4-Cl H H H H H -C(OH)-C4Hg H
4-Cl H H H H H -C(OH) -CH2-C -CH H
4-F H H H H H -C(OH) ~ H
4-F H H H H H -C(OH)-CH2 ~ H
4-F H H H H H -C(OH)-CH2CH-CHCH3 H
4-F H H H H H -C(OH)-C4Hg H
4-F H H H H H -C(OH)-CH2-C - CH H
4-F . H H H H H -CO- CH3 15 4-F H H H H H -CO- C4Hg 4-F H H H H H CO- C5Hll 4-F H H H H H -CO- i-C~H7 4-F H H H H H -CH(OH)- CH3 4-F H H H H H -CH(OH)- C2H5 20 4-F H H H H H -CH(OH)- C3H7 4-F H H H H H -CH(OH)- C4Hg : 4-F H H H H H -CH(OH)- C5H11 4-F H H H H H -CH(OH)- i~C}H7 , .
Le A 21 322 ~7~8~
Xl x2 X3 y1 y2 y3 A R
. ~
4-N(CH3)2 H H H H H -CO- C3H7 -O-CH2-a- H H H H -CO- C3H7
3-OCH34-OCH3 5-CCH3 H - H H -CO- C3H7
4-CO-OCt3 H H H H H -CO- C3H7 4-CN H H H H H ~CO- C3H7 4-8r H H H H H -CO- C3H7 4-N(CH3)2 H H H H H -CH(OH)- C3H7 -O-CH2-a- H H H H -CH(OH)- C3H7 4-CH3 H H H H H -CH~OH)- C3H7 3-OCH3 4-CCH3 5-CCH3 H H H -CH(OH)- C3H7 4-CO-OCH3 H H H H H -CH(OH)- C3H7 4-SCF3 H H H H H -CH(OH)- C3H7 4-N02 H H H H H -CH(OH)- C3H7 4-CN H H H H H -CH(OH)- C3H7 4-8r H H H H H -CH(OH)- C3H7 4-OCF3 H H H H H -CH(OH) C3H7 4-F H H H H H -CO- -CH2CH20C~l3 4-F H H H H H -CO- -cH2cH2scH3 4-F H H H H H ~-CO- -CH2CH2N(CH3)2 Le A 21 322 .. ..
~ ~ ~7~}8~
X1 x2 X3 y1 y2 y3 A R1 4-F H H H H H -CH(OH)- -CH2CH20CH3 4-F H H H- H H -CH(OH)- -CH2cH2scH3 4-F H H H H H -CH(OH)- -CH2CH2N(CH3)2
~ ~ ~7~}8~
X1 x2 X3 y1 y2 y3 A R1 4-F H H H H H -CH(OH)- -CH2CH20CH3 4-F H H H- H H -CH(OH)- -CH2cH2scH3 4-F H H H H H -CH(OH)- -CH2CH2N(CH3)2
5 4-Cl H H H H H -CH(OH)- -cH2cH2ocH3 4-Cl H H H H H -CH(OH)- -cH2cH2scH3 4-Cl H H H H H -CH(OH)- -CH2CH2N(CH3)2 4-Cl H H H H H -CO- -CH2CH20CH3 4-Cl H H H H H -CO- -CH2CH25CH3 4-Cl H H H H H -CO- -CH2CH2N(CH3)2 4-Cl H H 3-Cl H H -CO- C3H7 4-Cl H H 3-Cl H H -CH(OH)- C3H7 4-Cl H H 3-CH3 H H -CO- C3H7 4-Cl H H 3-CH3 H H CH(OH)- C3H7 15 4-Cl H H H H H -C(OH)CH3 C3H7 `
4-Cl H H H H H -C(OH)-C3H7 C3H7 4-Cl H H H H H -CO- -CH
4-Cl H H H H H -CH(OH)- -CH
.. . . ..
Le A 21 322 ~ ~, .
' 37t~
If, for example, ~-chloro-4-(4'-chlorophenoxy)-acetophenone and 1,2,4-triazole are used as starting materials in process variant (a) 9 the course of the reaction can be represented by the following equation:
Cl- ~ o ~ -CO-CH2Cl x H ~ - > Cl ~ O ~ CO-CH2N
If, for example, 4-(4'--chlorophenoxy)- ~-(1,2,4-triazol-1-yl)-acetophenone and 4-chlorobenzyl chloride are used as starting materials in process variant (b) the course of the reaction can be represented by the following equation:
Cl-<~>-O~CO-CH2 clcH2~-cl ->
N~ Cl-<~O~CO-CIH-c~l2~C
~N`N
N Jl If, for example, 4-(4'-chlorophenoxy)-~ -(1,2,4-triazol-1-yl)-acetophenone and sodium borohydride are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation:
-Cl ~ O- ~ CO CH2-N\=~l + NaBH~ ->
Cl-~O~CH-CH2-N =1 2û If, for example, 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-Le A 21 322 ~Q 87~
one and methyl-magnesium bromide are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation:
Cl~-O-<~CO-CH-CH2~-Cl + CH3MgBr-->
N ~ ~H3 ~
Formula (II) gives a general definition of the halogenoketones required as starting materials for carry-ing out process variant (a). In this formula, X, y1 y2 and Y3 preferably have the meanings given in the preferred definition of the invention.
The halogenoketones of the formula (II) have not hitherto been disclosed in the literature; however, they can be prepared in a generally known manner by reacting, for example, diphenyl ethers of general formula X - 0 - ~ (VI), y1 y2 y3 in which X, y1~ y2 and Y3 have the meaning given above, with chloro(bromo)acetyl chloride (bromide) under the conditions of a Friedel-Crafts acylation (see also the preparative examples).
Formula (III) gives a general definition of the azoles additionally to be used as starting materials for process variant (a). In this formula Az has the meanings given in the definition of the invention.
Le A 21 322 ~87;3~
The azoles of the formula (III) are generall~
known compounds oF organic chemistry.
Formula (Ia) gives a general definition of the azolyl ketones -to be used as starting materials for carrying ou-t process variant (b). The compounds of the formula (Ia) are themselves compounds according to the ; invention: they are prepared by process variant (a).
; Formula (IV) gives a general definition of the alkylating agents additionally to be used as starting materials for process variant (b) according to the invention. In this formula, R1 preFerably has the meanings given in the preferred definition of the invention. Z preferably represents an electron-attract-ing leaving grouping, such as, for example, halogen, p-methylphenyl-sulphonyloxy or the grouping -0-502-OR' or -~R3,whereas R' represents, for example, alkyl with l to 4 carbon atoms.
The alkylating agents of the formula (IV) are generally known compounds of organic chemistry.
Formula (Ib) gives a general definition of the azolyl ketones to be used as starting materials for carrying out process variant (c). The compounds of the formula (Ib) are themselves compounds according to the invention: they are prepared by process variant (a) or (b).
Formula (V) gives a general definition of the organometallic compounds additionally to be used, inter alia, as starting materials for process variant (c). In this formula, R preferably has the meanings given in the preferred definition of the invention.
M preferably represents lithium, sodium or the so-called Grignard grouping Hal'-Mg, wherein Hal' represents chlor-ine, bromine or iodine.
The organometallic compounds of the formula (V) are generally known compounds of organic chemistry.
Le A 21 322 ~ - - .
8~
Suitable diluents for process variant (a) are inert organic solvents. These include, as preferences ketones, such as diethyl ketone or, in particular, acetone or methyl ethyl ketone; nitriles, such as pro-pionitrile or, in particular, acetonitrile; alcohols,such as ethanol or isopropanol; ethers~ such as tetra-hydrofuran or dioxan; aromatic hydrocarbons, such as toluene, benzene or chlorobenzene; formamides, such as, in particular, dimethylformamide; and halogenated hydro-carbons.
Process variant (a) is carried out in the presenceof an acid-binding agent. Any of the inorganic or organic acid-binding agents which can customarily be used can be added, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate or sodium bicarb-onate, or such as lower tertiary alkylamines, cycloalkyl-amines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine and N,N-dimethylbenzylamine, and furthermore pyridine or diazabicyclooctane. An appropriate excess of azole is preferably employed.
In process variant (a), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at between20 and 150C, pr~ferably at 60 to 120C. In the presence of a solvent, the reaction is advantageously carried out at the boiling point of the particular solvent.
In carrying out process variant (a), 2 to 4 moles of azole and 1 to 4 moles of acid-binding agent are preferably employed par mole of the compound of the formula (II). To isolate the compounds of the formula (I), the solvent is distilled off and the residue is worked up in the customary manner.
Le A 2? 3?2 ~8~
Suitable diluents for process variant (b) of the invention are inert organic solvents. These include, as preferences, aromatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride,~carbon tetrachloride, chloroform or chlorobenzerle; esters, such as ethyl acetate; form-amides, such as dimethylformamide; and dimethylsulphoxide.
Process variant (b) is carried out in the presence of a base. In this process~ any of the customary organic and in particular inorganic bases can be employed, especially alkali metal hydroxides or alkali metal carbonates, sodium hydroxide and potassium hydroxide being mentioned as examples.
In carrying out process variant (b), the reaction temperatures can be varied within a relatively wide range.
In general, the reaction is carried out at between 0 and 100C, preferably between 20 and 100C.
In carrying out the process variant (b), 1 to 1.2 moles of alkylating agent are preferably employed per mole of the compound of the formula (Ia). The isolation of the end products of the formula (I~ can be effected in a generally customary manner.
Process variant (b) can alternatively be carried out in a two-phase system, for example aqueous sodium hydroxide solution or potassium hydroxide solution/tolu-ene or rnethylene chloride, if appropriate with the add-ition of 0.1 to 1 mol of a phase-transfer catalyst, for example an ammonium or phosphonium compound, benzyl-dodecyl-dimethyl-ammonium chloride and triethyl-benzyl-ammonium chloride being mentioned as examples.
The reduction according to process variant (c), can be effected in a customary manner.
If the reaction is carried out using a complex Le A 21 322 _.
... .
~87~
hydride, suitable diluents for the reaction are polar organic solvents. These include, as preferences, alcohols, such as methanol, ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetra-hydrofuran. The reaction is carried out in general at 0 to 3ûC, preferably at û to 2ûC. In this reaction, about 1 reaction equivalent of a complex hydride, such as sodium borohydride or lithium alanate, is employcd per mole of the ketone of the formula (Ib). To isolate 1û the resultant compound of the formula (I), the residue is taken up in dilute hydrochloric acid, and the sol~
ution is then rendered alkaline and is extracted with an organic solvent. Further working-up may be effected in the customary manner.
If the reaction is carried out using aluminium isopropylate, preferred diluents for the reaction according to the invention are alcohols, such as iso-propanol, or inert hydrocarbons, such.as benzene.
ûnce again, the reaction temperatures can be varied within a relatively wide range; in general the reaction is carried out at between 20 and 120C, preferably at 50 to 100C. To carry out the reaction, about 1 to 2 moles of aluminium isopropylate are employ-ed per mole of the ketone oF the formula (Ib). To isolate the resultant compound of the formula (I), the excess solvent is removed by distillation in vacuo, andthe resulting aluminium compound is decomposed with dilute sulphuric acid or sodium hydroxide solution.
Further working-up may be effected in the customary 3û manner.
If the reaction is carried out using an organo-metallic compound, preferred diluents are anhydrous ethers, such as diethyl ether, dibutyl ether or tetra-hydrofuran. The reaction is carried out in general at 0 to 80C, preferably at the boiling poin-t of the Le A 21 322 ~8'~
solvent used. In this reaction, about 1 to 3 moles of the organometallic compound of the formula (V) are employed per mole of the compound of the formula (Ib).
Working-up of the mixtures obtained by organometallic reactions can be effected in a customary and generally known manner.
The following acids are preferably used for the preparation of physiologically tolerated acid addition salts of the compounds of the formula (I): hydrogen halide acids (for example hydrobromic acid and, in particular, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for ex-ample acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid) and sulphonic acids (for example p-toluenesulphonic acid and naphthalene-1,5-disulphonic acid). The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by custom-ary salt formation methods, for example by dissolving acompound 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 filtra-tion, and if appropriate purified by washing wlth an inert organic solvent.
Salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII are preferably used for the preparation of metal salt complexes of the compounds of the formula (I), copper, zinc, manganese, magnesium, tin, iron and nickel being mentioned as examples of such metals. Preferred anions of the salts are those which are derived from the following acids:
hydrogen halide acids (for example hydrochloric acid Le A 21 322 ~8~7~
and hydrobromic acid), phosphoric acid, nitric acid and sulphuric acid. The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (I). The metal salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystallisation.
1~ The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organlsms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are emp-loyed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomyc~tes, Zygomycetes, Ascomyce-tes, 8asidiomy-cetes and Deuteromycetes.
Bactericidal agents are employed in plant protec-~ tion for combating Pseudomonadaceae, Rhizobiaceae,Enterobacteriaceae, Corynebacteriaceae and Streptomycet-aceae.
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 powdery mildew diseases, hence for combating Erysiphe species, such as the powdery mildew of barley or powdery mildew of cereal causative organism (Erysiphe graminis), Le A 21 322 . .
~87~8~
for combating Venturia species, for example the apple scab causative organism (Venturia inaequalis), or for combating rice diseases, for example Pyricularia oryzae and Pellicularia sasakii. It should be emphasised that the substances according to the invention also possess good bactericidal propertiesO
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, solwble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment 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 equipment, such as fumigating cart-ridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid dil-uents or carriers, optionally with the use of surface active agents, that is to say 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, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or al~yl naphthalenes, chlorin-ated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well Le A 21 322 as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo-hexanone, or strongly polar solvents, such as dimethyl-formamide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temper-ature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxlde.
As solid carriers -there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed sili-cic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated nat-ural 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 tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic ernulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example all<ylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the form-ulations.
It is possible to use colorants such as inorganic ~37~
pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dye-stuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 55 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth 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 J such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They may be used in the customary manner~ for example by watering, imrnersion, spraying, atomising, mistlng, vaporising, injecting, forming a slurry, brush-ing on, dusting, scattering, dry dressing, moist dress-ing, wet dressing, slurry dressing or encrusting.
Especially 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~o by weight, preferably between 0.5 and 0.001o.
In the treatment of seed, amounts of active com-pound of in general 0.001 to 50 9, preferably 0.01 to 10 9, are required per kilogram of seed.
~ or the treatment of soil, active compound concentrations of in general 0.00001 to 0.1o by weight, , Le A 21 322 ~ 37~8~
preferably O.nO01 to 0. 2o by weight, are required at the place of action.
The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agen-t.
The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present invention alone or in the form of a composition contain~
ing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time oF
the growing a.compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of provi-ding a harvested crop may be improved by the present invention.
The preparative process is illustrated by the following Examples.
Preparative Examples Example 1 Cl ~ 0 ~ C0-CH2-Le A 21 322 . _ _ _ .
~' .
: ' ~8~7a~84 Process variant (a) 100 g (O.36 mol) oF ~J-chloro-4-(4'-chlorophenoxy)-acetophenone, 31.1 9 (0.45 mol) of 1,2,4-triazole and 124 g (0.9 mol) of ground potassium carbonate were heated under reflux for 20 hours, while stirring. There-after, the mixture was allowed to cool, the inorganic salts were filtered- aff under suction, and the filtrate was concentrated. The residue was stirred in methylene chloride, and dilute hydrochloric acid was added. The resulting hydrochloride was separated off, washed with methylene chloride and converted into the free base in the customary manner by the addition of all~alis and subsequent extraction. 41.5 9 (36.8o of theory) of 4-(4'-chlorophenoxy)-1,~ -(1,2,4-triazol-1-yl)-acetophenone of melting point 148-150C were obtained.
Preparation of_the starting material Cl - ~-l)~CO-CH2-Cl 86.6 9 (0.77 mol) of chloroacetyl chloride were added dropwise to 150 g (0.73 mol) of 4-chlorobiphenyl 2n ether and 117 9 (0.88 mol) of aluminium trichloride in 1,000 ml of methylene chloride at room temperature. The reaction solution was stirred for a further hour, and was then introduced onto 3 litres oF ice-water. The organic phase was separated off, washed with water, dried over sodium sulphate and concentrated. The residue was tri-turated with petroleum ether, filtered off under suction and dried. '168.7 9 (82.3o of theory) of l~)-chloro-4-(4'-chlorophenoxy)-acetophenone of melting point 59-61C
were obtained.
Example 2 Cl~-O~-CO-CH-CH2~>-Cl (2) .
:~87~
Process variant (b) 31.4 9 (0.1 mol) of 4-(4'-chlorophenoxy)- ~J-(1,2, 4-triazol-1-yl)-acetophenone (Example 1), 16.1 9 of 4-chlorobenzyl chloride and 5.6 9 (0.1 mol) of potassium 5 hydroxide in 200 ml of dimethylsulphoxide were stirred for 20 hours at 40C. The reaction mixture was then introduced onto 700 ml of water and extracted with ethyl acetate. The organic phase was washed with water, dried over sodium sulphate and concentrated. The residue was 10 purified by boiling it with isopropyl ether. 26.1 9 (59.6o of theory) of 1-(4-chlorophenyl)-3-[4-(4'-chloro-phenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan~3-one of melting point 132C were obtained.
Example 3 OH
Cl~-O~-C--CH-CH2~Cl N i Process variant (c) ._ 7 9 (O.016 mol) of 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-one (l~xample 2) and 4.8 9 (0.04 mol) of methyl-magnesium 20 bromide, dissolved in 50 ml of ether, were stirred under reflux in 100 ml of tetrahydrofuran for 1 hour. The mixture was allowed to cool, and dilute hydrochloric acid was added. The organic phase was separated off, washed with water, dried over sodium sulphate and concentrated.
25 The residue was stirred in diisopropyl ether, filtered off under suction and dried. 5.3 9 (73~0 of theory) of 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-butan-3-ol of melting point 159C
were obtained.
Le A 21 322 ~8~7~
Example 4 OH
Cl~-O-~CH-CH-CH2- ~ Cl ~ LI
N
Process variant (c) 0.38 9 (0.01 mol) of sodium borohydricle, dissolved in 10 ml of water, was added to 14 9 (0.032 mol) of 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-one (Example 2) in 400 ml of methanol. The mixture was stirred for 2 hours at 25C, and the pH value was then adjus-ted to 6-7 by the addition of dilute hydrochloric acid. The reaction solution was concentrated and the residue was taken up with methylene chloride/water. The organic phase was separated ofF, dried over sodium sulphate and concent-rated. The solid residue was recrystallised from diiso-propyl ether. 10.5 9 (75O of theory) of 1-(4-chloro-phenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-ol of melting point 112C were obtained.
The compounds of the general formula x2 ~ o ~ _ A - C~ - R1 (IA) y1 y2 y3 which are listed in the table below were obtained in a manner analogous to those described in the above Ex-amples and by means of the processes according to the invention.
In this table, the references to "A form" and "B form" relate to the two possible geometrical isomers.
Le A 21 322 _ _ .... ~.
1~8~
E~- X1 x2 X3 y1 y2 y3 A Az R1 m-p-( C~
mple or nD
/N--~ 5 H H H H H H ~ca- -N n-C3H7 66-68
4-Cl H H H H H -C(OH)-C3H7 C3H7 4-Cl H H H H H -CO- -CH
4-Cl H H H H H -CH(OH)- -CH
.. . . ..
Le A 21 322 ~ ~, .
' 37t~
If, for example, ~-chloro-4-(4'-chlorophenoxy)-acetophenone and 1,2,4-triazole are used as starting materials in process variant (a) 9 the course of the reaction can be represented by the following equation:
Cl- ~ o ~ -CO-CH2Cl x H ~ - > Cl ~ O ~ CO-CH2N
If, for example, 4-(4'--chlorophenoxy)- ~-(1,2,4-triazol-1-yl)-acetophenone and 4-chlorobenzyl chloride are used as starting materials in process variant (b) the course of the reaction can be represented by the following equation:
Cl-<~>-O~CO-CH2 clcH2~-cl ->
N~ Cl-<~O~CO-CIH-c~l2~C
~N`N
N Jl If, for example, 4-(4'-chlorophenoxy)-~ -(1,2,4-triazol-1-yl)-acetophenone and sodium borohydride are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation:
-Cl ~ O- ~ CO CH2-N\=~l + NaBH~ ->
Cl-~O~CH-CH2-N =1 2û If, for example, 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-Le A 21 322 ~Q 87~
one and methyl-magnesium bromide are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation:
Cl~-O-<~CO-CH-CH2~-Cl + CH3MgBr-->
N ~ ~H3 ~
Formula (II) gives a general definition of the halogenoketones required as starting materials for carry-ing out process variant (a). In this formula, X, y1 y2 and Y3 preferably have the meanings given in the preferred definition of the invention.
The halogenoketones of the formula (II) have not hitherto been disclosed in the literature; however, they can be prepared in a generally known manner by reacting, for example, diphenyl ethers of general formula X - 0 - ~ (VI), y1 y2 y3 in which X, y1~ y2 and Y3 have the meaning given above, with chloro(bromo)acetyl chloride (bromide) under the conditions of a Friedel-Crafts acylation (see also the preparative examples).
Formula (III) gives a general definition of the azoles additionally to be used as starting materials for process variant (a). In this formula Az has the meanings given in the definition of the invention.
Le A 21 322 ~87;3~
The azoles of the formula (III) are generall~
known compounds oF organic chemistry.
Formula (Ia) gives a general definition of the azolyl ketones -to be used as starting materials for carrying ou-t process variant (b). The compounds of the formula (Ia) are themselves compounds according to the ; invention: they are prepared by process variant (a).
; Formula (IV) gives a general definition of the alkylating agents additionally to be used as starting materials for process variant (b) according to the invention. In this formula, R1 preFerably has the meanings given in the preferred definition of the invention. Z preferably represents an electron-attract-ing leaving grouping, such as, for example, halogen, p-methylphenyl-sulphonyloxy or the grouping -0-502-OR' or -~R3,whereas R' represents, for example, alkyl with l to 4 carbon atoms.
The alkylating agents of the formula (IV) are generally known compounds of organic chemistry.
Formula (Ib) gives a general definition of the azolyl ketones to be used as starting materials for carrying out process variant (c). The compounds of the formula (Ib) are themselves compounds according to the invention: they are prepared by process variant (a) or (b).
Formula (V) gives a general definition of the organometallic compounds additionally to be used, inter alia, as starting materials for process variant (c). In this formula, R preferably has the meanings given in the preferred definition of the invention.
M preferably represents lithium, sodium or the so-called Grignard grouping Hal'-Mg, wherein Hal' represents chlor-ine, bromine or iodine.
The organometallic compounds of the formula (V) are generally known compounds of organic chemistry.
Le A 21 322 ~ - - .
8~
Suitable diluents for process variant (a) are inert organic solvents. These include, as preferences ketones, such as diethyl ketone or, in particular, acetone or methyl ethyl ketone; nitriles, such as pro-pionitrile or, in particular, acetonitrile; alcohols,such as ethanol or isopropanol; ethers~ such as tetra-hydrofuran or dioxan; aromatic hydrocarbons, such as toluene, benzene or chlorobenzene; formamides, such as, in particular, dimethylformamide; and halogenated hydro-carbons.
Process variant (a) is carried out in the presenceof an acid-binding agent. Any of the inorganic or organic acid-binding agents which can customarily be used can be added, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate or sodium bicarb-onate, or such as lower tertiary alkylamines, cycloalkyl-amines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine and N,N-dimethylbenzylamine, and furthermore pyridine or diazabicyclooctane. An appropriate excess of azole is preferably employed.
In process variant (a), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at between20 and 150C, pr~ferably at 60 to 120C. In the presence of a solvent, the reaction is advantageously carried out at the boiling point of the particular solvent.
In carrying out process variant (a), 2 to 4 moles of azole and 1 to 4 moles of acid-binding agent are preferably employed par mole of the compound of the formula (II). To isolate the compounds of the formula (I), the solvent is distilled off and the residue is worked up in the customary manner.
Le A 2? 3?2 ~8~
Suitable diluents for process variant (b) of the invention are inert organic solvents. These include, as preferences, aromatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride,~carbon tetrachloride, chloroform or chlorobenzerle; esters, such as ethyl acetate; form-amides, such as dimethylformamide; and dimethylsulphoxide.
Process variant (b) is carried out in the presence of a base. In this process~ any of the customary organic and in particular inorganic bases can be employed, especially alkali metal hydroxides or alkali metal carbonates, sodium hydroxide and potassium hydroxide being mentioned as examples.
In carrying out process variant (b), the reaction temperatures can be varied within a relatively wide range.
In general, the reaction is carried out at between 0 and 100C, preferably between 20 and 100C.
In carrying out the process variant (b), 1 to 1.2 moles of alkylating agent are preferably employed per mole of the compound of the formula (Ia). The isolation of the end products of the formula (I~ can be effected in a generally customary manner.
Process variant (b) can alternatively be carried out in a two-phase system, for example aqueous sodium hydroxide solution or potassium hydroxide solution/tolu-ene or rnethylene chloride, if appropriate with the add-ition of 0.1 to 1 mol of a phase-transfer catalyst, for example an ammonium or phosphonium compound, benzyl-dodecyl-dimethyl-ammonium chloride and triethyl-benzyl-ammonium chloride being mentioned as examples.
The reduction according to process variant (c), can be effected in a customary manner.
If the reaction is carried out using a complex Le A 21 322 _.
... .
~87~
hydride, suitable diluents for the reaction are polar organic solvents. These include, as preferences, alcohols, such as methanol, ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetra-hydrofuran. The reaction is carried out in general at 0 to 3ûC, preferably at û to 2ûC. In this reaction, about 1 reaction equivalent of a complex hydride, such as sodium borohydride or lithium alanate, is employcd per mole of the ketone of the formula (Ib). To isolate 1û the resultant compound of the formula (I), the residue is taken up in dilute hydrochloric acid, and the sol~
ution is then rendered alkaline and is extracted with an organic solvent. Further working-up may be effected in the customary manner.
If the reaction is carried out using aluminium isopropylate, preferred diluents for the reaction according to the invention are alcohols, such as iso-propanol, or inert hydrocarbons, such.as benzene.
ûnce again, the reaction temperatures can be varied within a relatively wide range; in general the reaction is carried out at between 20 and 120C, preferably at 50 to 100C. To carry out the reaction, about 1 to 2 moles of aluminium isopropylate are employ-ed per mole of the ketone oF the formula (Ib). To isolate the resultant compound of the formula (I), the excess solvent is removed by distillation in vacuo, andthe resulting aluminium compound is decomposed with dilute sulphuric acid or sodium hydroxide solution.
Further working-up may be effected in the customary 3û manner.
If the reaction is carried out using an organo-metallic compound, preferred diluents are anhydrous ethers, such as diethyl ether, dibutyl ether or tetra-hydrofuran. The reaction is carried out in general at 0 to 80C, preferably at the boiling poin-t of the Le A 21 322 ~8'~
solvent used. In this reaction, about 1 to 3 moles of the organometallic compound of the formula (V) are employed per mole of the compound of the formula (Ib).
Working-up of the mixtures obtained by organometallic reactions can be effected in a customary and generally known manner.
The following acids are preferably used for the preparation of physiologically tolerated acid addition salts of the compounds of the formula (I): hydrogen halide acids (for example hydrobromic acid and, in particular, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for ex-ample acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid) and sulphonic acids (for example p-toluenesulphonic acid and naphthalene-1,5-disulphonic acid). The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by custom-ary salt formation methods, for example by dissolving acompound 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 filtra-tion, and if appropriate purified by washing wlth an inert organic solvent.
Salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII are preferably used for the preparation of metal salt complexes of the compounds of the formula (I), copper, zinc, manganese, magnesium, tin, iron and nickel being mentioned as examples of such metals. Preferred anions of the salts are those which are derived from the following acids:
hydrogen halide acids (for example hydrochloric acid Le A 21 322 ~8~7~
and hydrobromic acid), phosphoric acid, nitric acid and sulphuric acid. The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (I). The metal salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystallisation.
1~ The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organlsms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are emp-loyed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomyc~tes, Zygomycetes, Ascomyce-tes, 8asidiomy-cetes and Deuteromycetes.
Bactericidal agents are employed in plant protec-~ tion for combating Pseudomonadaceae, Rhizobiaceae,Enterobacteriaceae, Corynebacteriaceae and Streptomycet-aceae.
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 powdery mildew diseases, hence for combating Erysiphe species, such as the powdery mildew of barley or powdery mildew of cereal causative organism (Erysiphe graminis), Le A 21 322 . .
~87~8~
for combating Venturia species, for example the apple scab causative organism (Venturia inaequalis), or for combating rice diseases, for example Pyricularia oryzae and Pellicularia sasakii. It should be emphasised that the substances according to the invention also possess good bactericidal propertiesO
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, solwble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment 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 equipment, such as fumigating cart-ridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid dil-uents or carriers, optionally with the use of surface active agents, that is to say 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, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or al~yl naphthalenes, chlorin-ated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well Le A 21 322 as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo-hexanone, or strongly polar solvents, such as dimethyl-formamide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temper-ature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxlde.
As solid carriers -there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed sili-cic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated nat-ural 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 tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic ernulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example all<ylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the form-ulations.
It is possible to use colorants such as inorganic ~37~
pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dye-stuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 55 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth 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 J such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They may be used in the customary manner~ for example by watering, imrnersion, spraying, atomising, mistlng, vaporising, injecting, forming a slurry, brush-ing on, dusting, scattering, dry dressing, moist dress-ing, wet dressing, slurry dressing or encrusting.
Especially 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~o by weight, preferably between 0.5 and 0.001o.
In the treatment of seed, amounts of active com-pound of in general 0.001 to 50 9, preferably 0.01 to 10 9, are required per kilogram of seed.
~ or the treatment of soil, active compound concentrations of in general 0.00001 to 0.1o by weight, , Le A 21 322 ~ 37~8~
preferably O.nO01 to 0. 2o by weight, are required at the place of action.
The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agen-t.
The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present invention alone or in the form of a composition contain~
ing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time oF
the growing a.compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of provi-ding a harvested crop may be improved by the present invention.
The preparative process is illustrated by the following Examples.
Preparative Examples Example 1 Cl ~ 0 ~ C0-CH2-Le A 21 322 . _ _ _ .
~' .
: ' ~8~7a~84 Process variant (a) 100 g (O.36 mol) oF ~J-chloro-4-(4'-chlorophenoxy)-acetophenone, 31.1 9 (0.45 mol) of 1,2,4-triazole and 124 g (0.9 mol) of ground potassium carbonate were heated under reflux for 20 hours, while stirring. There-after, the mixture was allowed to cool, the inorganic salts were filtered- aff under suction, and the filtrate was concentrated. The residue was stirred in methylene chloride, and dilute hydrochloric acid was added. The resulting hydrochloride was separated off, washed with methylene chloride and converted into the free base in the customary manner by the addition of all~alis and subsequent extraction. 41.5 9 (36.8o of theory) of 4-(4'-chlorophenoxy)-1,~ -(1,2,4-triazol-1-yl)-acetophenone of melting point 148-150C were obtained.
Preparation of_the starting material Cl - ~-l)~CO-CH2-Cl 86.6 9 (0.77 mol) of chloroacetyl chloride were added dropwise to 150 g (0.73 mol) of 4-chlorobiphenyl 2n ether and 117 9 (0.88 mol) of aluminium trichloride in 1,000 ml of methylene chloride at room temperature. The reaction solution was stirred for a further hour, and was then introduced onto 3 litres oF ice-water. The organic phase was separated off, washed with water, dried over sodium sulphate and concentrated. The residue was tri-turated with petroleum ether, filtered off under suction and dried. '168.7 9 (82.3o of theory) of l~)-chloro-4-(4'-chlorophenoxy)-acetophenone of melting point 59-61C
were obtained.
Example 2 Cl~-O~-CO-CH-CH2~>-Cl (2) .
:~87~
Process variant (b) 31.4 9 (0.1 mol) of 4-(4'-chlorophenoxy)- ~J-(1,2, 4-triazol-1-yl)-acetophenone (Example 1), 16.1 9 of 4-chlorobenzyl chloride and 5.6 9 (0.1 mol) of potassium 5 hydroxide in 200 ml of dimethylsulphoxide were stirred for 20 hours at 40C. The reaction mixture was then introduced onto 700 ml of water and extracted with ethyl acetate. The organic phase was washed with water, dried over sodium sulphate and concentrated. The residue was 10 purified by boiling it with isopropyl ether. 26.1 9 (59.6o of theory) of 1-(4-chlorophenyl)-3-[4-(4'-chloro-phenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan~3-one of melting point 132C were obtained.
Example 3 OH
Cl~-O~-C--CH-CH2~Cl N i Process variant (c) ._ 7 9 (O.016 mol) of 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-one (l~xample 2) and 4.8 9 (0.04 mol) of methyl-magnesium 20 bromide, dissolved in 50 ml of ether, were stirred under reflux in 100 ml of tetrahydrofuran for 1 hour. The mixture was allowed to cool, and dilute hydrochloric acid was added. The organic phase was separated off, washed with water, dried over sodium sulphate and concentrated.
25 The residue was stirred in diisopropyl ether, filtered off under suction and dried. 5.3 9 (73~0 of theory) of 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-butan-3-ol of melting point 159C
were obtained.
Le A 21 322 ~8~7~
Example 4 OH
Cl~-O-~CH-CH-CH2- ~ Cl ~ LI
N
Process variant (c) 0.38 9 (0.01 mol) of sodium borohydricle, dissolved in 10 ml of water, was added to 14 9 (0.032 mol) of 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-one (Example 2) in 400 ml of methanol. The mixture was stirred for 2 hours at 25C, and the pH value was then adjus-ted to 6-7 by the addition of dilute hydrochloric acid. The reaction solution was concentrated and the residue was taken up with methylene chloride/water. The organic phase was separated ofF, dried over sodium sulphate and concent-rated. The solid residue was recrystallised from diiso-propyl ether. 10.5 9 (75O of theory) of 1-(4-chloro-phenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-ol of melting point 112C were obtained.
The compounds of the general formula x2 ~ o ~ _ A - C~ - R1 (IA) y1 y2 y3 which are listed in the table below were obtained in a manner analogous to those described in the above Ex-amples and by means of the processes according to the invention.
In this table, the references to "A form" and "B form" relate to the two possible geometrical isomers.
Le A 21 322 _ _ .... ~.
1~8~
E~- X1 x2 X3 y1 y2 y3 A Az R1 m-p-( C~
mple or nD
/N--~ 5 H H H H H H ~ca- -N n-C3H7 66-68
6 4-Cl H H H H H -C0- -N~ n~C3H7 64-66 ~N~
7 4-Cl H H H H H -C0- -N ¦ -C2H5 91-92 \~=N
~N -
~N -
8 H H H H H H -C0~ -C2Hs 62-63 /N_
9 4-Cl H H H H H -C0- -N -CH3 1, 6061 ,N - .
104~Cl H H H H H -C0- -N n-C4H9 88 ll 4-Cl H H H H H -C0- -N ~ ~ 126 ~N I
124-Cl H H H H . H -C0- -N ¦ n-CsH11 64 \~N
,N=
134-Cl H H H H H -C0- -N i -C3H7 92-93 144-Cl H H H H H -C0- -N ¦ -CH2C _ CH 116 ~N~
154-Cl H H H H H -C0- -N ¦ -CH2CH=CH2 87 ~N
~N_ I
164-Cl H H H H H -C0- -N I -C7H1s 67 ~N I
174-Cl H H H H H -C0- -N I -CH2CH~CHCH3 87 N
184-Cl H H H H H -C0- -N ~ -CH2CH20CH3 1,5940 ,N_I
l94-Cl H H H H H -C0- -N I -CH=CHC3H7 1,5840 /N _ 202-Cl 4-Cl H H H H -C0- -N ¦ -C3H7 106 Le A 21 322 ... ..
~ 28 -Ex- XZ X3 yl y2 y3 AAz Rl m P2~C) No. or nD
_. _ _ _ ~N_ 21 2-CH3 6-Cl H H H H -CO--1~ ¦ H 93-97 22 2-Cl 4-Cl H H H H -CO--N 1 H 100 \==N
23 4-Br H H H H H-CO- -N ~ H 150 \=N
24 4-Cl H H H H H -CO- -~ C,Hs 1,6092 4-Cl H H H H H -CO-N\== ¦ n -C3H7 1, 6040 26 4-Cl H H H H H -CO- -N~ -CH3 1,5990 27 4-Cl H H H H H -CO--N ¦ n -C4H9 1 J 5959 28 4-Cl H H H H H -ca -N~ i-C3H7 114-116 \=N
104~Cl H H H H H -C0- -N n-C4H9 88 ll 4-Cl H H H H H -C0- -N ~ ~ 126 ~N I
124-Cl H H H H . H -C0- -N ¦ n-CsH11 64 \~N
,N=
134-Cl H H H H H -C0- -N i -C3H7 92-93 144-Cl H H H H H -C0- -N ¦ -CH2C _ CH 116 ~N~
154-Cl H H H H H -C0- -N ¦ -CH2CH=CH2 87 ~N
~N_ I
164-Cl H H H H H -C0- -N I -C7H1s 67 ~N I
174-Cl H H H H H -C0- -N I -CH2CH~CHCH3 87 N
184-Cl H H H H H -C0- -N ~ -CH2CH20CH3 1,5940 ,N_I
l94-Cl H H H H H -C0- -N I -CH=CHC3H7 1,5840 /N _ 202-Cl 4-Cl H H H H -C0- -N ¦ -C3H7 106 Le A 21 322 ... ..
~ 28 -Ex- XZ X3 yl y2 y3 AAz Rl m P2~C) No. or nD
_. _ _ _ ~N_ 21 2-CH3 6-Cl H H H H -CO--1~ ¦ H 93-97 22 2-Cl 4-Cl H H H H -CO--N 1 H 100 \==N
23 4-Br H H H H H-CO- -N ~ H 150 \=N
24 4-Cl H H H H H -CO- -~ C,Hs 1,6092 4-Cl H H H H H -CO-N\== ¦ n -C3H7 1, 6040 26 4-Cl H H H H H -CO- -N~ -CH3 1,5990 27 4-Cl H H H H H -CO--N ¦ n -C4H9 1 J 5959 28 4-Cl H H H H H -ca -N~ i-C3H7 114-116 \=N
10 29 4-Cl H H H H H -CO- -N~ H 212 \=N ( xCuC12 ) 30 4-Cl H H H H H -CH(OH)- -N~ -C2H5 (A-Form) 31 4-Cl H H H H H -CH( OH )--N ¦ -C2H5 161-62 \;~ N ( B-Form) /N~T
32, 4-Cl H H H H H -CH(OH)--N\~= I n-C3H7 150(A Form) 33 4-Cl H H H H H -CH( OH ) - -N ¦ n -C3H7 106-07 . \:=N (B-Form) 15 34 4-Cl H H H H H -CH(OH)- -N~ n-C4Hg 90(A-Form) ,N _ 35 4-Cl H H H HH -(CH(OH)- -N I n_C4Hg 116 \~ N (B-Form) 36 4-CL H- H H HH -CH( OH )- -N 1 -CH3 90-100 ~N
Le A 21 322 ~7~
Ex 1 x2 X3 yl y2 y3 A Az Rl m.p.(C) ~o. or n20 /N:l 37 H H H H H H -CH(OH)~ -CH3 1,5842 ,N
38 H H H H H H -CH(OH)- -N\==l n-C3H7 96(A-Form) 39 HH H H H H -CH(OH)- -N 1 n-C3H7 102 ~N (B-Form) 5 40 HH H H H H -CH(OH)- -N ~ i-C3H7 114-117 41 4-ClH H H H H -CH(OH)- -N ~ ~ 158 ,N=~
42 HH H H H H -CH(OH)- -N I -C2Hs 121 \~N- (A-Form) ~N=~
43 H H H H H H -CH(OH)- -N ¦ -C2H5 120 \==N (B-Form) 44 4-Cl HH H HH-CH( OH)- -N 1 n -CsH1l 84 ~=~N (A-Form) 10 454-Cl , H H HH H -CH(OH)--N ¦ n -CsHll 102 \:= (B-Form) ,N ~
464-Cl H H HHH -CH(3H)--N I i -C3H7 161-63 N (A-Form) ~N.=l 474-Cl H H H H H -CH(OH)--N I i -C3H7 74-76 \~N (B-Form) /N~ -484-Cl H H H H H -CH(OH)--N I i -C4Hg 110-14 ~= N
494-Cl H HHHH -CH(OH)--N 1 i-C4Hg 107 \==N (A-Form) 15 504-Cl HHHHH -CH(OH)- ~ C4Hg 151 ~;N (B-Form) /N~ .
514-Cl H H H H H -CH(OH)--N ¦ i-C3H7 160-62 ~N
524-Cl H H H H H -CH(OH)- -~ -CH2C--CH 90 ,1\l _1 534-Cl H H HH H -CH(OH)- -N ¦ -CH2CH=CH2 107 ~_N
Le A 21_ 322 ... ..
~8~7~
~x ~mP1e X1 X2 ~3 Y1 Y2 Y3 A AZ R1 m.~ C) ~- . r nD
54 4-Cl H H H H H -CH(OH)- -N 1n~C7H~5 74 \~N
55 4-C1 H H H H H -CH( OH)--N 1 -CH2CH-CHCH3 109 \~: N
56 4-C1 H H H H H -CH(OH)--N ~ -CH=CHC3H7 1,5608 /N -I
S 57 4-C1 H H H H H -CH( OH)--N I -CH2CH20CH3 95-lOO
58 2-C14-C1 H H H H -CH(OH)--N 1 n C3H7 ViSCOUS Oi1 \~N
59 2-C14-C1 H H H H -CH(OH)--l~ ~ -CH3 20G(XHC1) \=N
60 4-C1 H H H H H -C ( OH )-N ¦ n-C3H7 Oi1 ~N
61 4-C1 H H H H H -C(OH)CH3~ n_C3H7 145 ~: ~N~= .
62 4-C1 H H H H H -C(OH)CH3 -N _CH3 128 63 4-C1 H H H H H -C(OH) ,N ~ -CH3 142 CH2 ~C l 64 4-C1 H H H H H -Cl(OH)-N ~ n -C3H7 128 ,N -65 2-CH3 6-C1 H H H H -CH(OH)- -N H 125-26 662-C14-C1 HH H H -CH(OH)--l~ 1 H viscous oil : \~=N
674-C1 H HH H H -CH( OH ) - -l~ 1N H 114 68 4-BrH H H H H -CH( OH )- _N ¦ H 106 \=~l Le A 21 322 :
1~8t7~8~
~mpl~ X1 x2 X3 y1 y2 y3 A Az R1 m.~.(C) o. . or n.20 69 H H H H H H -CH(OH)- -N ¦n-C3H7 l,5600 \~:N
70 H H H H H H -CH(OH)- -N ~ i-C3H7 128 714-Cl H H H H H -CH(OH)~ -N ~ -C2Hs 48-52 5 72 4-ClH H H H H -CH(OH) -N ¦ -CH3 viscous oil \~\1 734-Cl H H H H H -CH(OH)- -N ~ n-C~Hg 120-30 ~=~N
744-Cl H H H H H -CH(OH)- - ~ i-C3H7 50-55 754-Cl H H H H H -CH(OH)- -N ~ n-C3H7 44-48 Le_A 21 322 . . .
:
3'7~4 Use Examples . The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example.
The known comparison compounds are identified as n follows:
/=~N
(A) - ~ CO CH2-N
(B) = CH3 ~ _CO-CH2~
( C )- ~CO-CH2-N
(D)= Cl- ~ C -CHz~N
Example_A
Venturia test (apple) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed Le A 21 322 , ~, ., ~t7~8~
with the stated amounts of-solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
To test for protective activity, young plants were sprayed with t-he preparation of active compound until dripping wet. After the spray coating had dried on, the plants were inoculated with an aqueous conidia suspension of the apple scab causative organism (Venturia inaequalis) and were then left in an incub-ation cabin at 20C and 100o relative atmospherichumidity for 1 day.
The plants were then placed in a greenhouse at 20C and a relative atmospheric humidity of about 70O.
Evaluation was carried out 12 days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art was shown, for example, by -the compounds (9), (10), (41), (5), (7), (6), (8), (40) and (13).
Exampl_ B
Erysiphe test (barley)/protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl poly glycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
To test for protective activity, young plants were sprayed with the preparation of active compound until dew-moist. After the spray coating had dried on, the plants were dusted with spores of Erysiphe graminis Le A 21 322 ;
:
~ ' : ' ~::
37~
f.sp. hordei.
The plants were placed in a greenhouse at a tem-perature oF about 20C ancl a relative atmospheric humidity of about 80o~ in order to promote the develop-ment of powdery mildew pustules.
Evaluation was carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art was shown, for example, by the com-pounds (69), (9), (10), (36), (41), (4), (37), (5), (7), (6), (8), (~0) and (13).Example C
Pyricularia test (rice) / protective Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a ~uitable preparation of active com-pound, 1 part by weight of active compound was mixed with the stated amount of solvent, and the concentrate was diluted with water and the stated amount of emulsi-fier, to the desired concentration.
To test for protective activity, young rice plantswere sprayed with the preparation of active compound until dripping wet. After the spray coating had dried off, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants were then placed in a greenhouse at 100, relative atmospheric humidity and 25aC.
Evaluation of the disease infestation was carried out 4 days after the inoculation.
In this test, a clearly superior activity compared with the prior art was shown, for example, by the com-pounds (36), (7) and (74).
Le A_21 322 ' ' '7~
Example D
Pellicularia test (rice) Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol - ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound was mixed with the stated amount of solvent, and the concentrate was diluted with water and the stated amount of emulsif-ier, to the desired concentration.
To test for activity, young rice plants in the 3 to 4 leaf stage were sprayed until dripping wet.
The plants remained in a greenhouse until they had dried off. The plants were then inoculated with Pelli-cularia sasakii and were kept at Z5C and 100~ relative atmospheric humidity.
The evaluation of the disease infestation was carried out 5 to 8 days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art was shown, for example, by the compounds (36), (7) and (74).
~' ~ Le A 21 322 .
32, 4-Cl H H H H H -CH(OH)--N\~= I n-C3H7 150(A Form) 33 4-Cl H H H H H -CH( OH ) - -N ¦ n -C3H7 106-07 . \:=N (B-Form) 15 34 4-Cl H H H H H -CH(OH)- -N~ n-C4Hg 90(A-Form) ,N _ 35 4-Cl H H H HH -(CH(OH)- -N I n_C4Hg 116 \~ N (B-Form) 36 4-CL H- H H HH -CH( OH )- -N 1 -CH3 90-100 ~N
Le A 21 322 ~7~
Ex 1 x2 X3 yl y2 y3 A Az Rl m.p.(C) ~o. or n20 /N:l 37 H H H H H H -CH(OH)~ -CH3 1,5842 ,N
38 H H H H H H -CH(OH)- -N\==l n-C3H7 96(A-Form) 39 HH H H H H -CH(OH)- -N 1 n-C3H7 102 ~N (B-Form) 5 40 HH H H H H -CH(OH)- -N ~ i-C3H7 114-117 41 4-ClH H H H H -CH(OH)- -N ~ ~ 158 ,N=~
42 HH H H H H -CH(OH)- -N I -C2Hs 121 \~N- (A-Form) ~N=~
43 H H H H H H -CH(OH)- -N ¦ -C2H5 120 \==N (B-Form) 44 4-Cl HH H HH-CH( OH)- -N 1 n -CsH1l 84 ~=~N (A-Form) 10 454-Cl , H H HH H -CH(OH)--N ¦ n -CsHll 102 \:= (B-Form) ,N ~
464-Cl H H HHH -CH(3H)--N I i -C3H7 161-63 N (A-Form) ~N.=l 474-Cl H H H H H -CH(OH)--N I i -C3H7 74-76 \~N (B-Form) /N~ -484-Cl H H H H H -CH(OH)--N I i -C4Hg 110-14 ~= N
494-Cl H HHHH -CH(OH)--N 1 i-C4Hg 107 \==N (A-Form) 15 504-Cl HHHHH -CH(OH)- ~ C4Hg 151 ~;N (B-Form) /N~ .
514-Cl H H H H H -CH(OH)--N ¦ i-C3H7 160-62 ~N
524-Cl H H H H H -CH(OH)- -~ -CH2C--CH 90 ,1\l _1 534-Cl H H HH H -CH(OH)- -N ¦ -CH2CH=CH2 107 ~_N
Le A 21_ 322 ... ..
~8~7~
~x ~mP1e X1 X2 ~3 Y1 Y2 Y3 A AZ R1 m.~ C) ~- . r nD
54 4-Cl H H H H H -CH(OH)- -N 1n~C7H~5 74 \~N
55 4-C1 H H H H H -CH( OH)--N 1 -CH2CH-CHCH3 109 \~: N
56 4-C1 H H H H H -CH(OH)--N ~ -CH=CHC3H7 1,5608 /N -I
S 57 4-C1 H H H H H -CH( OH)--N I -CH2CH20CH3 95-lOO
58 2-C14-C1 H H H H -CH(OH)--N 1 n C3H7 ViSCOUS Oi1 \~N
59 2-C14-C1 H H H H -CH(OH)--l~ ~ -CH3 20G(XHC1) \=N
60 4-C1 H H H H H -C ( OH )-N ¦ n-C3H7 Oi1 ~N
61 4-C1 H H H H H -C(OH)CH3~ n_C3H7 145 ~: ~N~= .
62 4-C1 H H H H H -C(OH)CH3 -N _CH3 128 63 4-C1 H H H H H -C(OH) ,N ~ -CH3 142 CH2 ~C l 64 4-C1 H H H H H -Cl(OH)-N ~ n -C3H7 128 ,N -65 2-CH3 6-C1 H H H H -CH(OH)- -N H 125-26 662-C14-C1 HH H H -CH(OH)--l~ 1 H viscous oil : \~=N
674-C1 H HH H H -CH( OH ) - -l~ 1N H 114 68 4-BrH H H H H -CH( OH )- _N ¦ H 106 \=~l Le A 21 322 :
1~8t7~8~
~mpl~ X1 x2 X3 y1 y2 y3 A Az R1 m.~.(C) o. . or n.20 69 H H H H H H -CH(OH)- -N ¦n-C3H7 l,5600 \~:N
70 H H H H H H -CH(OH)- -N ~ i-C3H7 128 714-Cl H H H H H -CH(OH)~ -N ~ -C2Hs 48-52 5 72 4-ClH H H H H -CH(OH) -N ¦ -CH3 viscous oil \~\1 734-Cl H H H H H -CH(OH)- -N ~ n-C~Hg 120-30 ~=~N
744-Cl H H H H H -CH(OH)- - ~ i-C3H7 50-55 754-Cl H H H H H -CH(OH)- -N ~ n-C3H7 44-48 Le_A 21 322 . . .
:
3'7~4 Use Examples . The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example.
The known comparison compounds are identified as n follows:
/=~N
(A) - ~ CO CH2-N
(B) = CH3 ~ _CO-CH2~
( C )- ~CO-CH2-N
(D)= Cl- ~ C -CHz~N
Example_A
Venturia test (apple) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed Le A 21 322 , ~, ., ~t7~8~
with the stated amounts of-solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
To test for protective activity, young plants were sprayed with t-he preparation of active compound until dripping wet. After the spray coating had dried on, the plants were inoculated with an aqueous conidia suspension of the apple scab causative organism (Venturia inaequalis) and were then left in an incub-ation cabin at 20C and 100o relative atmospherichumidity for 1 day.
The plants were then placed in a greenhouse at 20C and a relative atmospheric humidity of about 70O.
Evaluation was carried out 12 days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art was shown, for example, by -the compounds (9), (10), (41), (5), (7), (6), (8), (40) and (13).
Exampl_ B
Erysiphe test (barley)/protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl poly glycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
To test for protective activity, young plants were sprayed with the preparation of active compound until dew-moist. After the spray coating had dried on, the plants were dusted with spores of Erysiphe graminis Le A 21 322 ;
:
~ ' : ' ~::
37~
f.sp. hordei.
The plants were placed in a greenhouse at a tem-perature oF about 20C ancl a relative atmospheric humidity of about 80o~ in order to promote the develop-ment of powdery mildew pustules.
Evaluation was carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art was shown, for example, by the com-pounds (69), (9), (10), (36), (41), (4), (37), (5), (7), (6), (8), (~0) and (13).Example C
Pyricularia test (rice) / protective Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a ~uitable preparation of active com-pound, 1 part by weight of active compound was mixed with the stated amount of solvent, and the concentrate was diluted with water and the stated amount of emulsi-fier, to the desired concentration.
To test for protective activity, young rice plantswere sprayed with the preparation of active compound until dripping wet. After the spray coating had dried off, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants were then placed in a greenhouse at 100, relative atmospheric humidity and 25aC.
Evaluation of the disease infestation was carried out 4 days after the inoculation.
In this test, a clearly superior activity compared with the prior art was shown, for example, by the com-pounds (36), (7) and (74).
Le A_21 322 ' ' '7~
Example D
Pellicularia test (rice) Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol - ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound was mixed with the stated amount of solvent, and the concentrate was diluted with water and the stated amount of emulsif-ier, to the desired concentration.
To test for activity, young rice plants in the 3 to 4 leaf stage were sprayed until dripping wet.
The plants remained in a greenhouse until they had dried off. The plants were then inoculated with Pelli-cularia sasakii and were kept at Z5C and 100~ relative atmospheric humidity.
The evaluation of the disease infestation was carried out 5 to 8 days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art was shown, for example, by the compounds (36), (7) and (74).
~' ~ Le A 21 322 .
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A phenoxyphenyl azolylmethyl ketone or carbinol of the formula in which Az is 1,2,4-triazol-1-yl or -4-yl or imidazol-1-yl, A is the keto group or the -CH(OH)- or-C(OH)R grouping, R is alkyl, cycloalkyl, cycloalkylalkyl, alkenyl or alkynyl, or is phenyl or phenalkyl optionally substituted in the phenyl ring by halogen or alkyl, X is phenyl optionally substituted by halogen, alkyl, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, nitro, cyano or methylenedioxy, Y1, Y2 and Y3 each independently is hydrogen, halogen, or alkyl, and R1 is alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, halogenoalkyl, alkoxyalkyl, halogenoalkoxyalkyl, alkylthioalkyl, halogeno-substituted phenalkyl, or may be hydrogen provided (a) X is not unsubstituted phenyl while at the same time each of Y1, Y2 and Y3 is hydrogen, or (b) R is not alkyl, cycloalkyl or cycloalkylalkyl, or a plant-tolerated acid addition salt or metal salt complex thereof.
2. A compound according to claim 1, in which X is a group of the formula R is alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part, alkenyl or alkynyl each having 2 to 6 carbon atoms, optionally substituted phenyl or optionally substituted phenalkyl having 1 to 4 carbon atoms in the alkyl part, each phenyl substituent in either case being selected independently from halogen and alkyl having 1 to 4 carbon atoms, X1 is hydrogen, halogen, alkyl having 1 to 4 carbon atoms, halogeno-alkyl, halogenoalkoxy or halogenoalkylthio each having 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy or alkylthio each having 1 to 4 carbon atoms, amino, alkylamino or dialkylamino each having 1 to 4 carbon atoms, in each alkyl part, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl part, nitro or cyano, X2 is hydrogen, halogen, or alkyl or alkoxy each having 1 to 4 carbon atoms, or X1 and X2 together, in the o-position to one another, are methylene-dioxy, X3 is hydrogen, halogen, or alkyl or alkoxy each having 1 to 4 carbon atoms, Y1 is hydrogen, halogen, or alkyl having 1 to 4 carbon atoms, Y2 is hydrogen or halogen, Y3 is hydrogen, and R1 is alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part, alkenyl or alkynyl each having 2 to 6 carbon atoms, alkoxyalkyl or alkylthioalkyl each having 1 to 2 carbon atoms in each alkyl part, halogenoalkyl having 1 to 8 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxyalkyl or halogenoalkylthioalkyl each having 1 to 4 carbon atoms in each alkyl part and 1 to 5 halogen atoms, dialkylaminoalkyl having 1 to 4 carbon atoms in each alkyl part, or optionally substituted phenylalkyl having 1 to 4 carbon atoms in the alkyl part, each phenyl substituent being selected independently from the radicals mentioned for X1, or may be hydrogen provided (a) that at the same time X1, X2, X3, Y1, Y2, and Y3 are not a hydro-gen, or (b) R is not alkyl, cycloalkyl or cycloalkylalkyl.
3. A compound according to claim 2, in which R is alkyl having 1 to 4 carbon atoms, cycloalkyl or cycloalkyl-methyl each having 5 or 6 carbon atoms in the cycloalkyl part, alkenyl or alkynyl each having 2 to 4 carbon atoms, or phenyl or benzyl either of which may optionally carry one or more substituents each selected independently from fluorine, chlorine, bromine and methyl, X1 is hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxy, methylthio, amino, dimethyl-amino, methoxycarbonyl, nitro or cyano, X2 is hydrogen, fluorine, chlorine, methyl or methoxy, or X1 and X2 together, in the o-position to one another, are methylene-dioxy, X3 is hydrogen, fluorine, chlorine, methyl or methoxy, Y1 is hydrogen, fluorine, chlorine or methyl, Y2 is hydrogen, fluorine or chlorine, Y3 is hydrogen, and R1 is alkyl having 1 to 8 carbon atoms, cycloalkyl or cycloalkyl-methyl each having 5 or 6 carbon atoms in the cycloalkyl part, alkenyl having 2 to 6 carbon atoms, alkynyl having 2 to 4 carbon atoms, alkoxyalkyl or alkyl-thioalkyl each having 1 to 2 carbon atoms in each alkyl part, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxyalkyl or halogenoalkylthioalkyl each having 1 to 2 carbon atoms in each alkyl part and 1 to 5 halogen atoms, dialkylaminoalkyl having 1 to 2 carbon atoms in each alkyl part, or optionally substituted benzyl, each phenyl sub-stituent being selected independently from the radicals mentioned for X1, or may be hydrogen provided (a) that at the same time X1, X2, X3, Y1, Y2 and Y3 are not hydrogen, or (b) R is not alkyl, cycloalkyl or cycloalkylalkyl.
4. A compound according to claim 1 in the form of a salt of an acid selected from hydrogen halide acids, phosphoric acid, sulphuric acid, nitric acid, sulphonic acids, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, or in the form of a metal salt, the metal of which is selected from copper, zinc, manganese, magnesium, tin, iron and nickel and the anion of which is selected from halide, phosphate, sulphate or nitrate.
5. 1-(4-Chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-ol of the formula
6. 4-[(4'-Chlorophenoxy)-phenyl]-3-(1,2,4-triazol-1-yl)-butan-4-one of the formula
7. A method of combating fungi comprising applying to the fungi, or to a habitat thereof, a fungicidally effective amount of a compound according to claim 1.
8. A method according to claim 7 wherein the compound is applied in the form of a composition containing said compound as active ingredient, in admixture with a suitable diluent or carrier.
9. A method according to claim 8, characterised in that a composition is used containing from 0.0001 to 1% of said compound, by weight.
10. A method according to claim 8, characterised in that a composition is used containing from 0.001 to 0.5% of said compound, by weight.
11. A method according to claim 7, 8 or 10, characterised in that said compound is applied to soil in an amount of 0.00001 to 0.1 percent by weight.
12. A method according to claim 7, 8 or 10, characterised in that said compound is applied to soil in an amount of 0.0001 to 0.02 percent by weight.
13. A method according to claim 7, 8 or 10, characterised in that said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.
14. A method according to claim 7, 8 or 10, characterised in that said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.
15. A process according to claim 7, 8 or 10 wherein such compound is 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-ol.
16. A process according to claim 7, 8 or 10 wherein such compound is 4-[(4'-chlorophenoxy)-phenyl]-(1,2,4-triazol-1-yl)-butan-4-one.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813140276 DE3140276A1 (en) | 1981-10-10 | 1981-10-10 | PHENOXYPHENYL-AZOLYLMETHYL-KETONE AND CARBINOLS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES AND AS INTERMEDIATE PRODUCTS |
| DEP3140276.3 | 1981-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1187084A true CA1187084A (en) | 1985-05-14 |
Family
ID=6143812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000413102A Expired CA1187084A (en) | 1981-10-10 | 1982-10-08 | Phenoxyphenyl azolylmethyl ketones and carbinols, processes for their preparation, and their use as fungicides and as intermediate products |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0077479A3 (en) |
| JP (1) | JPS5872568A (en) |
| AU (1) | AU8922382A (en) |
| BR (1) | BR8205929A (en) |
| CA (1) | CA1187084A (en) |
| CS (1) | CS235964B2 (en) |
| DD (1) | DD206728A5 (en) |
| DE (1) | DE3140276A1 (en) |
| DK (1) | DK447082A (en) |
| ES (1) | ES8307004A1 (en) |
| GR (1) | GR77014B (en) |
| IL (1) | IL66942A0 (en) |
| NZ (1) | NZ202107A (en) |
| PL (1) | PL134646B1 (en) |
| PT (1) | PT75638B (en) |
| ZA (1) | ZA827370B (en) |
Cited By (9)
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|---|---|---|---|---|
| AU2011246088B2 (en) * | 2010-04-27 | 2014-09-04 | Nippon Paper Industries Co., Ltd. | Cell differentiation promoter and use of same |
| US10212934B2 (en) | 2014-06-25 | 2019-02-26 | BASF Agro B.V. | Pesticidal compositions |
| US10512267B2 (en) | 2013-07-08 | 2019-12-24 | BASF Agro, B.V. | Compositions comprising a triazole compound and a biopesticide |
| US10519122B2 (en) | 2013-01-09 | 2019-12-31 | BASF Agro B.V. | Process for the preparation of substituted oxiranes and triazoles |
| US10759767B2 (en) | 2012-12-20 | 2020-09-01 | BASF Agro B.V. | Compositions comprising a triazole compound |
| US10779536B2 (en) | 2014-11-07 | 2020-09-22 | Basf Se | Pesticidal mixtures |
| US10905122B2 (en) | 2016-03-16 | 2021-02-02 | Basf Se | Use of tetrazolinones for combating resistant phytopathogenic fungi on cereals |
| US11241012B2 (en) | 2016-03-16 | 2022-02-08 | Basf Se | Use of tetrazolinones for combating resistant phytopathogenic fungi on soybean |
| US11425909B2 (en) | 2016-03-16 | 2022-08-30 | Basf Se | Use of tetrazolinones for combating resistant phytopathogenic fungi on fruits |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2143815B (en) * | 1983-05-19 | 1988-01-20 | Ciba Geigy Ag | Process for the preparation of micro biocidal 1-triazolylethyl ether derivatives |
| DE3322526A1 (en) * | 1983-06-23 | 1985-01-10 | Basf Ag, 6700 Ludwigshafen | FUNGICIDAL AZOL COMPOUNDS, THEIR PRODUCTION AND USE |
| HUT36990A (en) * | 1983-07-08 | 1985-11-28 | Sandoz Ag | Fungicide preparates containing azole derivatives as active ingredient and method for producing azole derivates and medicine preparates containing these compunds |
| US4690942A (en) * | 1983-12-20 | 1987-09-01 | Ciba-Geigy Corporation | 1-aryl-2-fluoro-2-azolyl alkanones, alkanols, esters, and ethers, composition containing them, and use of them to control phytopathogenic microorganisms |
| DE3501370A1 (en) * | 1985-01-17 | 1986-07-17 | Bayer Ag, 5090 Leverkusen | 1-ARYL-2,2-DIALKYL-2- (1,2,4-TRIAZOL-1-YL) ETHANOLE |
| GB8511344D0 (en) * | 1985-05-03 | 1985-06-12 | Ici Plc | Heterocyclic compounds |
| ES2016660B3 (en) * | 1987-01-21 | 1990-11-16 | Ciba-Geigy Ag | MICROBICIDE AGENT. |
| MD36C2 (en) * | 1988-08-04 | 1995-03-31 | Циба-Гейги АГ | Fungi controlling method |
| EP2928873A1 (en) * | 2012-11-27 | 2015-10-14 | Basf Se | Substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides |
| WO2014082879A1 (en) | 2012-11-27 | 2014-06-05 | Basf Se | Substituted [1,2,4]triazole compounds |
| US20150307459A1 (en) * | 2012-11-27 | 2015-10-29 | Basf Se | Substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol Compounds and Their Use as Fungicides |
| EP2925732A1 (en) | 2012-11-27 | 2015-10-07 | Basf Se | Substituted [1,2,4]triazole compounds |
| BR112015012003A2 (en) * | 2012-11-27 | 2018-05-15 | Basf Se | compounds of formula I, composition, use of a compound, method for combating harmful fungi, seed, process for preparing the compounds and intermediate compounds |
| EP2735563A1 (en) * | 2012-11-27 | 2014-05-28 | Basf Se | Meta substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides |
| WO2014095547A1 (en) | 2012-12-19 | 2014-06-26 | Basf Se | New substituted triazoles and imidazoles and their use as fungicides |
| EP2746274A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Substituted [1,2,4]triazole compounds |
| EP2746263A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Alpha-substituted triazoles and imidazoles |
| EP2746278A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Substituted [1,2,4]triazole and imidazole compounds |
| EP2746262A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Substituted [1,2,4]triazole and imidazole compounds for combating phytopathogenic fungi |
| EP2745691A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Substituted imidazole compounds and their use as fungicides |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2832234A1 (en) * | 1978-07-21 | 1980-01-31 | Bayer Ag | ALPHA -AZOLYL-KETO DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE2832233A1 (en) * | 1978-07-21 | 1980-01-31 | Bayer Ag | ALPHA -AZOLYL- BETA -HYDROXY-KETONE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
-
1981
- 1981-10-10 DE DE19813140276 patent/DE3140276A1/en not_active Withdrawn
-
1982
- 1982-09-29 EP EP82108991A patent/EP0077479A3/en not_active Withdrawn
- 1982-10-01 PT PT75638A patent/PT75638B/en unknown
- 1982-10-07 IL IL66942A patent/IL66942A0/en unknown
- 1982-10-07 CS CS827177A patent/CS235964B2/en unknown
- 1982-10-07 NZ NZ202107A patent/NZ202107A/en unknown
- 1982-10-07 JP JP57175430A patent/JPS5872568A/en active Pending
- 1982-10-08 PL PL1982238571A patent/PL134646B1/en unknown
- 1982-10-08 GR GR69481A patent/GR77014B/el unknown
- 1982-10-08 CA CA000413102A patent/CA1187084A/en not_active Expired
- 1982-10-08 AU AU89223/82A patent/AU8922382A/en not_active Abandoned
- 1982-10-08 DK DK447082A patent/DK447082A/en not_active Application Discontinuation
- 1982-10-08 BR BR8205929A patent/BR8205929A/en unknown
- 1982-10-08 DD DD82243875A patent/DD206728A5/en unknown
- 1982-10-08 ES ES516368A patent/ES8307004A1/en not_active Expired
- 1982-10-08 ZA ZA827370A patent/ZA827370B/en unknown
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| AU2011246088B2 (en) * | 2010-04-27 | 2014-09-04 | Nippon Paper Industries Co., Ltd. | Cell differentiation promoter and use of same |
| US10759767B2 (en) | 2012-12-20 | 2020-09-01 | BASF Agro B.V. | Compositions comprising a triazole compound |
| US10519122B2 (en) | 2013-01-09 | 2019-12-31 | BASF Agro B.V. | Process for the preparation of substituted oxiranes and triazoles |
| US10981883B2 (en) | 2013-01-09 | 2021-04-20 | BASF Agro B.V. | Process for the preparation of substituted oxiranes and triazoles |
| US10512267B2 (en) | 2013-07-08 | 2019-12-24 | BASF Agro, B.V. | Compositions comprising a triazole compound and a biopesticide |
| US10212934B2 (en) | 2014-06-25 | 2019-02-26 | BASF Agro B.V. | Pesticidal compositions |
| US10779536B2 (en) | 2014-11-07 | 2020-09-22 | Basf Se | Pesticidal mixtures |
| US10905122B2 (en) | 2016-03-16 | 2021-02-02 | Basf Se | Use of tetrazolinones for combating resistant phytopathogenic fungi on cereals |
| US11241012B2 (en) | 2016-03-16 | 2022-02-08 | Basf Se | Use of tetrazolinones for combating resistant phytopathogenic fungi on soybean |
| US11425909B2 (en) | 2016-03-16 | 2022-08-30 | Basf Se | Use of tetrazolinones for combating resistant phytopathogenic fungi on fruits |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA827370B (en) | 1983-08-31 |
| PL134646B1 (en) | 1985-08-31 |
| PT75638A (en) | 1982-11-01 |
| GR77014B (en) | 1984-09-04 |
| EP0077479A3 (en) | 1983-05-25 |
| DE3140276A1 (en) | 1983-04-28 |
| CS235964B2 (en) | 1985-05-15 |
| ES516368A0 (en) | 1983-06-16 |
| EP0077479A2 (en) | 1983-04-27 |
| BR8205929A (en) | 1983-09-13 |
| DD206728A5 (en) | 1984-02-08 |
| NZ202107A (en) | 1985-07-12 |
| JPS5872568A (en) | 1983-04-30 |
| ES8307004A1 (en) | 1983-06-16 |
| AU8922382A (en) | 1983-04-21 |
| IL66942A0 (en) | 1983-02-23 |
| PL238571A1 (en) | 1983-05-23 |
| DK447082A (en) | 1983-04-11 |
| PT75638B (en) | 1985-01-11 |
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