CA1175844A - Azolylpropyl-oximino derivatives, processes for their preparation, and their use as fungicides and plant growth regulators - Google Patents
Azolylpropyl-oximino derivatives, processes for their preparation, and their use as fungicides and plant growth regulatorsInfo
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- CA1175844A CA1175844A CA000401712A CA401712A CA1175844A CA 1175844 A CA1175844 A CA 1175844A CA 000401712 A CA000401712 A CA 000401712A CA 401712 A CA401712 A CA 401712A CA 1175844 A CA1175844 A CA 1175844A
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- compound
- oximino
- propane
- dichlorophenyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- Health & Medical Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Abstract
ABSTRACT
The invention relates to new azolylpropyloximino derivatives, to several processes for their preparation and to their use as fungicides and plant growth regulators.
The compounds of the general formula (I) ln which A, R1 and R2 have the meaning given in the descrip-tion, are obtained if azolyl-ketones are reacted with substitu-ted hydroxylamines, in the presence of a diluent: in addition, there are also other processes.
The active compounds are suitable for use as plant protection agents, and can be employed with particularly good success for combating diseases of cereals and disea-ses of rice, and for combating bacteria. In addition, the active compounds intervene in the metabolism of the plants and can be used as growth regulators.
The invention relates to new azolylpropyloximino derivatives, to several processes for their preparation and to their use as fungicides and plant growth regulators.
The compounds of the general formula (I) ln which A, R1 and R2 have the meaning given in the descrip-tion, are obtained if azolyl-ketones are reacted with substitu-ted hydroxylamines, in the presence of a diluent: in addition, there are also other processes.
The active compounds are suitable for use as plant protection agents, and can be employed with particularly good success for combating diseases of cereals and disea-ses of rice, and for combating bacteria. In addition, the active compounds intervene in the metabolism of the plants and can be used as growth regulators.
Description
2~189-533~ ``~
The present inven-tion rela-tes to certain new azolylpropyl-oximino derivatives, to several processes for their procluction and to their use as fungicides and plant qrowth regulators.
It has already been di.scl.osed -tha-t subs~.i-tu-ted 2-azolyl-1-benzyloximino-1-phenyl-ethanes exhibit good -Eunglcidal propert:ie~s (see ~E-OS (German Published Specifica-tion) 2,657,578, DE-OS
(German Published Specification) 2,723,924 and DE-OS (German Published Specification) 2,816,817). However, the action of -these compounds is not always completely satisfactory, particularly when low quanti-ties and concentrations are used.
The present lnvention now p:rovicles, as new comE~o~lllcls, the azolylpropyl-oximino derivatives oE the general :Eormula ~ -N
R2 _ C - CH2 - C~l2 - N ¦ (I) --o _ Rl in which A is a nitrogen atom or a CH group, Rl is an alkyl, alkenyl or alkinyl group, a benzyl or phenyl group which is optionally substituted by halogen, cyano/ nitro, Cl to C4-alkyl, Cl to C4-alkoxy, methylenedioxo, phenyl, phenoxy or Cl to C2 halogenoalkyl having up to 3 carbon atoms, or Rl is a cycloalkyl, cycloalkylalkyl or cycloalkenyl group optionally substituted by Cl to C4-alkyl and R2 is a phenyl group substituted by one or more substituents selected from halogen, nitro, cyano, Cl to C4-alkyl, Cl to C~-alkoxy, Cl to C4-alkylmercapto,Cl to C4-halogenoalkyl, Cl to C4-halogeno-alkoxy, C1 to C4-halogenoalkylmercapto (each halvgenoalkyl moiety having up to 5 halogen atoms), mono- and di-(Cl to C4-alkyl)amino, Le A 20 992-CA -1-~ ~t7~
and phenyl, phenoxy, phenylmercapto, benzyl, benzyloxy and benzyl-mercapto in which each phenyl nucleus is optionally substituted by halogen, cyano, nitro or halo~enoalkyl having up -to 2 c:arbon atoms and up to 3 halogen a-toms, or a non-phytotoxic acid addition salt or metal salt complex thereof in which the metal is selected from main group II to IV o:r sub-groups I, II and IV to VIII of the Periodic Table.
The compounds of the formula (I~ can be present in the syn or anti form; they are predominantly produced as mixtures o~
the two forms.
According to the present inven-tion we ~urther provide a process for the production oE a compound of the presen-t :inv~tltion, characterised in that, -la-.
5~344 ~a) an azolyl-ketone o the general or~ula R2 _ C ~ ctl2 ~ CH2 ~ N~
in which A and R2 have the meaning given above, is reacted with a substituted hydroxylamine of the general formula H2N - O - R ~III) in which Rl has the meaning given above, in the presence o a diluentl or tb) an azolyl-oxime o the general formula ~ N
: R ll Ctl2 Ctl2 N\ ¦ ~IV) N \
OH
in which A and R2 have the meaning given above, is reacted with a halide of the:general formula ~al - Rl ~V) in which R has the meaning given above and Hal represents a chlorine or bromine atom, if appropriate in the presence o a strong base, and in the presence of a dilu-ent, or (c) a halogenopropyl-oximino derivative of the general formula - r :~ ~
S~
R - C - CH - CH2 - Hal' ~VI) \o _ in which Rl and R2 have the meaning given above and Hal' represents a chlorine or bromine atom, is reacted with 1,2,4-triazole or imidazole, in the - 2a -~, presence of an acid-binding agent and in the presence of a diluent~
and an acid or a metal salt is then added, i:E desired onto the compound of the formula (I) which is obtained by raaction variant ~a), tb) or (c).
Finally, it has been Eound -that the new azolyl-p.ropyl-oximino derivatives of the formula ~I) and the acid addition salts and metal salt complexes thereof exhibit powerful fungicidal and plant growth-regulating properties.
Surprisingly, the compounds according to the present invention, of the formula (I), exhibit a better fung.icidal activity than the substi~utcd 2-a~olyl-1-benzyl-oximino~l-phen~l-ethancs known from the state of the art, which are similar compouncls chemically and in ~erms o:E their action. In adclition, -the compounds according to the invention/ of the ~ormula (I), exhibit a surpris-ingly good plant growth-regulating action. The active compounds according to the invention thus represent an enrichment of the art.
Preferred compounds according to the invention are those in which Rl represents an alkyl group having 1 to 12 carbon atoms, an alkenyl or alkinyl group, each having 2 to 1:2 carbon atoms; a cycloalkyl, cycloalkylalkyl or cycloalkenyl group, each having 5 to 7 carbon atoms in the cycloalkyl or cycloa1kenyl part and 1 or 2 carbon atoms in the alkyl part, it being possible for the cycloalkyl or cycloalkenyl part to be optionally substituted by alkyl having 1 to 4 carbon atoms; or a benzyl or phenyl group which is optionally monosubstituted or polysubstituted by identical or different substituents, as defined above for Rl.
The present inven-tion rela-tes to certain new azolylpropyl-oximino derivatives, to several processes for their procluction and to their use as fungicides and plant qrowth regulators.
It has already been di.scl.osed -tha-t subs~.i-tu-ted 2-azolyl-1-benzyloximino-1-phenyl-ethanes exhibit good -Eunglcidal propert:ie~s (see ~E-OS (German Published Specifica-tion) 2,657,578, DE-OS
(German Published Specification) 2,723,924 and DE-OS (German Published Specification) 2,816,817). However, the action of -these compounds is not always completely satisfactory, particularly when low quanti-ties and concentrations are used.
The present lnvention now p:rovicles, as new comE~o~lllcls, the azolylpropyl-oximino derivatives oE the general :Eormula ~ -N
R2 _ C - CH2 - C~l2 - N ¦ (I) --o _ Rl in which A is a nitrogen atom or a CH group, Rl is an alkyl, alkenyl or alkinyl group, a benzyl or phenyl group which is optionally substituted by halogen, cyano/ nitro, Cl to C4-alkyl, Cl to C4-alkoxy, methylenedioxo, phenyl, phenoxy or Cl to C2 halogenoalkyl having up to 3 carbon atoms, or Rl is a cycloalkyl, cycloalkylalkyl or cycloalkenyl group optionally substituted by Cl to C4-alkyl and R2 is a phenyl group substituted by one or more substituents selected from halogen, nitro, cyano, Cl to C4-alkyl, Cl to C~-alkoxy, Cl to C4-alkylmercapto,Cl to C4-halogenoalkyl, Cl to C4-halogeno-alkoxy, C1 to C4-halogenoalkylmercapto (each halvgenoalkyl moiety having up to 5 halogen atoms), mono- and di-(Cl to C4-alkyl)amino, Le A 20 992-CA -1-~ ~t7~
and phenyl, phenoxy, phenylmercapto, benzyl, benzyloxy and benzyl-mercapto in which each phenyl nucleus is optionally substituted by halogen, cyano, nitro or halo~enoalkyl having up -to 2 c:arbon atoms and up to 3 halogen a-toms, or a non-phytotoxic acid addition salt or metal salt complex thereof in which the metal is selected from main group II to IV o:r sub-groups I, II and IV to VIII of the Periodic Table.
The compounds of the formula (I~ can be present in the syn or anti form; they are predominantly produced as mixtures o~
the two forms.
According to the present inven-tion we ~urther provide a process for the production oE a compound of the presen-t :inv~tltion, characterised in that, -la-.
5~344 ~a) an azolyl-ketone o the general or~ula R2 _ C ~ ctl2 ~ CH2 ~ N~
in which A and R2 have the meaning given above, is reacted with a substituted hydroxylamine of the general formula H2N - O - R ~III) in which Rl has the meaning given above, in the presence o a diluentl or tb) an azolyl-oxime o the general formula ~ N
: R ll Ctl2 Ctl2 N\ ¦ ~IV) N \
OH
in which A and R2 have the meaning given above, is reacted with a halide of the:general formula ~al - Rl ~V) in which R has the meaning given above and Hal represents a chlorine or bromine atom, if appropriate in the presence o a strong base, and in the presence of a dilu-ent, or (c) a halogenopropyl-oximino derivative of the general formula - r :~ ~
S~
R - C - CH - CH2 - Hal' ~VI) \o _ in which Rl and R2 have the meaning given above and Hal' represents a chlorine or bromine atom, is reacted with 1,2,4-triazole or imidazole, in the - 2a -~, presence of an acid-binding agent and in the presence of a diluent~
and an acid or a metal salt is then added, i:E desired onto the compound of the formula (I) which is obtained by raaction variant ~a), tb) or (c).
Finally, it has been Eound -that the new azolyl-p.ropyl-oximino derivatives of the formula ~I) and the acid addition salts and metal salt complexes thereof exhibit powerful fungicidal and plant growth-regulating properties.
Surprisingly, the compounds according to the present invention, of the formula (I), exhibit a better fung.icidal activity than the substi~utcd 2-a~olyl-1-benzyl-oximino~l-phen~l-ethancs known from the state of the art, which are similar compouncls chemically and in ~erms o:E their action. In adclition, -the compounds according to the invention/ of the ~ormula (I), exhibit a surpris-ingly good plant growth-regulating action. The active compounds according to the invention thus represent an enrichment of the art.
Preferred compounds according to the invention are those in which Rl represents an alkyl group having 1 to 12 carbon atoms, an alkenyl or alkinyl group, each having 2 to 1:2 carbon atoms; a cycloalkyl, cycloalkylalkyl or cycloalkenyl group, each having 5 to 7 carbon atoms in the cycloalkyl or cycloa1kenyl part and 1 or 2 carbon atoms in the alkyl part, it being possible for the cycloalkyl or cycloalkenyl part to be optionally substituted by alkyl having 1 to 4 carbon atoms; or a benzyl or phenyl group which is optionally monosubstituted or polysubstituted by identical or different substituents, as defined above for Rl.
3-~.
Particularly preferred compounds of -the present invention are those in which any halogen atoms presen-t are fluorine or chlorine, and espec.ially those in which Rl represents an alkyl group havincJ 1 to 8 carbon atoms, an alkenyl or alkinyl group, each having 2 to 6 carbon atoms; a cyclopentyl, cyclohexyl~ cyclohexylmethyl or cyclohexenyl group; or a benzyl or phenyl group which is optionally monosubstituted to trisubstituted by identical or different substituents selected fromo lQ fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methyl.enedioxo, phenyl, phenoxy and trifluoromethyl; and R2 represents a phenyl group which :Ls monosubs-ti.tuted or disubstituted by identical or difEerent substituents selected from: fluorine, chlorine, bromine, methyl, phenyl and phenoxy, the phenyl and phenoxy substituents themselves being optionally substituted by chlorine, bromine or nitro.
In addition to the compounds mentioned in the preparative Examples, the following compounds of the formula (I) may be mentioned individually ~ N
R2 _ C - CH - CH - N ~ (I) O _ Rl (A= N, CH) ~ 4 _ 5~
R2 Rl ~ __ __ _. _____ _ _ _ . , ........ .. .......... ., .. , .. , , .. ... ., . _, _ _ _ , C1~ CH;,--~ ~- F
Cl~Cl -CH~ ~ ~2 C 1--~C 1 CH 2 C~
Cl ~ C1~12~CH=CH2 C 1 ~ -CH 2 -C--C~l Cl CH3 Cl~ 2~ CH3 ~,, R 2 . . . . . . . . . . R 1 Cl~ cl~
C 1~ 1 - C H 2 - ~ _ C H 3 C l ~i;- 2 ~ >
C1-~ ~ -C1 Cl~ C~cl Cl~; C~l C.l~
Cl~- -CH
H 3 C -~ - - C H 2 C
C 1~, - C 1 Le~- A ~C~ 9~2 R2 ' R
fC~3 C1 Br~ CH2-,CH3 -CH2- ~
If, for example~ 4,4'-chlorobiphenyl-yl-2-imidazol-1-yl-ethyl ketone and 0-(2,6-dichlorobenzy:L)-hyclroxylamine hydrochloride are used as the starting materials, the course o~ the r-eaction varlant (a) according to the present invention is illus~rated by the following equation:
Cl ~ C-CH2-CH2-N ~ ~ H2N-0 CH2 ~ x HCl Base Cl ~ -C-CH2CH2-N
N Cl~-~
O CH
Cl If, for example, 1-(2,4-dichlorophenyl~ oximino-3-(1,2,4-triazol-l-yl)-propane and 2,4-dichlorobenzyl chlGride are used ~s the starting materials, the course of the reaction variant (b) according to the present invention is illustrated by the following equatlon:
Le A 2~ 992 ~ .
l~ S~
Cl~ 1 2 C 2 ~ Cl-CH2~ Cl OH
,Cl J-- N
- H C 1 C 1- ~ - C - C H - C H
O-CH2- ~ -Cl If, for example, 3-chloro-1-(2,4-dichlorophenyl)-: l-methyloximino-propane and 1,2,4-triazole are used as ; the startin~ materials, the course of the reaction variant tc) according to t~e pre~ent i.nVention i~ illust-rated by the followin~ equation:
C 1~)- C - C H 2 ' ~ H 2 - C 1 + H N~
2 2 `,~
N ~
Preferrëd~azolyl-ketones of the formula (II) ~ required as the~starting materials in carrying out the : 10 reaction variant (a) according to the invention are those . in which A and R;2:have those meanings which have already I been mentioned in connection:with the description of the preferred and particul~arly p~referred compounds of ~ormula ~- (I) according to the~:invention.
1~ 15 Some of thè azolyl-ketones of the formula (II) ~ ~ have been descrlb~ed (see DE-OS (German.Published Specific-`:
:
Le A 20 9-G2 ': ' `
ation) 2,633,492 or U.S. Patent Specification 4~045,568).
Howe~7er, those derivatives are new in which A represents nitro~en. They can be obtained by the processes given in the references~ ~y reactlng~ for example, a vinyl ketone of the ger.eral formula R2 C - CH = CH2 (VII3 Il .
o in which R2 has the meaning gi~7en abcve, with 1,2,4-triazole or imidazole, in the presence of an inert organic solvent (such as climethylformamide~) at a temperature between 0 and lC0C, or by reacting a halogeno-methyl-ketone of the general formula R2 _ C - CH2--CH2- Hal' (VIII) in which R2 and Hal' have the meanings given above, with 1,2,4-triazole or imidazole, in the presence of an acid-binding agent ~such as potasslum carbonate) and in the presence of an inert organic solvent (such as dimethyl-formamide) at a temperature between 40 and 120C.
~ Preferred substituted hydroxylamines of the formula (III) additionally required as starting materials for reaction variant (a) according to the inYention are those in which Rl represents those radicals which ha~e been men-tioned for this substituent in connection with the des-cription of the preferred and particularly preferred com-pounds of the formula (I) according to the in~7ention.
The substituted hydroxylamines of the formula (III) are generally krown compounds of organic chemistry.
Preferred azolyl-oximes of the formula (III) 3 required as starting materials in carrying QUt reaction Le A 20 992 variant (b) according to the invention are those in which A and R2 ha~e those meanings ~hich have already been rren-tioned in connection with the description of the pre~erred and particularly preferred co~pounds of the formula (I) according to the invention.
~ he azolyl-oximes of the ~ormula (IV) are novel.
However, they can be obtained in a generally known manner, by reacting an azolyl-l~etone of the formula (II) with hydroxylamine, in the presence of a solvent, preferably an alcohol, at 50C to 100C, the hydroxylamine preferably being employed as the hydrochloride, in the presence of an acid-binding agent.
Preferred halides of formula (V) additionally required as starting materials ~or reaction variant (b) according to the inventlon are those in which Rl represents those radicals which have already been mentioned for this substituent in connection with the description of the pre~erred and particularly preferred compounds of the formula (I) according to the invention.
The halides of the formula (V) are generally known compounds of organic chemistry.
Preferred halogenopropyl-oximino derivatives of formula (~I) required as starting materials in carrying out reaction variant (c) according to the invention are those in which Rl and R2 represent those radicals which have already been mentioned for these su~s.tituents in connection with the description of the preferred and particularly preferred compounds of the formula (I) according to the invention.
3 The halogenopropyl-oximino derivatives of the formula (~-I) are novel. However, they can be obtained in a generally ~nown manner3 by reacting a halogenoethyl-ketone of the formula (~III) with a substituted hydroxyl-amine of the formula (III), in the presence of a solvent ~5 (preferably an alcohol) at a temperature between 50 and , . . . . . . . . .
Le ~ 20 992 100C, the substituted hydrcxylamines being preferab'y employed as the hydrochlori.des, in the presence of an acid-binding agent.
Alcohols ancl~ater, or mixtures of the two3 are pre~erred suitable diluents ~or reactior! ~ariant (a) according to the ~`nvention.
In reaction variant (a), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at a terperature lG between 20 and 120~, preferably between 5C and 100C.
In carrying out reaction varlant (a), 1 to 1.3 mol of hydroxylamlne of the formula (III) ls preferably employed per mol of azolyl-ketone o~ the formula (II).
The isolation of the compounds of the f'ormula (I) is effected according to customary methods.
According to a pre~erred embodiment of reaction varlant (a), the hydroxylamines of the formula ~III) are employed in the form of their salts (particularly as hydrochlorides) if appropriate in the presence of an acid-binding agent (such as sodium acetate) (see, also, the preparative Examples).
Inert organic solvents are suitable diluents for the reaction variant (b) according to the inventlon.
These preferably includeethers (such as tetrahydrofuran and dioxane), aromatic hydrocarbons (such as toluene and benzene), in individual cases, also chlorinated hydro-carbons (such as chloroform, methylene chloride or carbon tetrachloride), and hexamethylphosphoric acid tria~.ide, acld amides (such as dimethylformamide) and sulphoxides ~o (such as dimethyl sulphoxide).
The reaction variant (b) is carried out, if appropriate, in the presence of a strong base. These preferably include alkali metal amides, alkali metal hyd-rides, alkali metal hydroxides and alkali metal carbonates (such as sodiu~ ~mide, car~onate; hydroxide or hydride, .
Le A 20 992 and potassium amide, carbonate, hydroxide or hydride), and quaternary am~cnium hydroxides and phosphonium hydroxides (such as tetramethylammoniun: hydroxide, benzyl-trimethyl-ammonium hydroxide, dibenzyl-dimethyl-an~oniu~, hydroxide, tetraphenylphosphonium hydroxide and methyl-triphenylphosphonium hydroxide).
In reaction variant (b), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at a temperature bet-ween 20 and 15CC, preferably at room temperature. Inindividual cases, it is advantageous to carry out the reaction at the boiling point of the solvent1 for example between 60 and 100C.
In carrying out reaction variant (b), 1 to 3 mol of halide of the formula (V) are preferably emplcyed per mol of oxime of the formula tIV~. To isolate the er.d produc~s, the reaction mixture is freed from the solvent, and water and an or~anic solvcnt are added to the residue.
The organic phase is separated off, worked up in the custom-ary manner, and purified.
In a pre~erred embodiment of reaction variant (b),the reaction according to the lnvention is carried out in a two-phase system ~such as aqueous sodium hydroxide solution or potassium hydroxide solution/toluene or methylene chlcride~ with the addition of 0.01 to 1 mol of a ~hase-transfer catalyst per mol of oxime of formula (I~) (such as am~onium or phosphoniu~ compounds), the ethylates bein~ formed in the or~anic phase or at the boundary surface and being reacted with the halides present in the or~anic 3 phase~
Inert organic solvents are preferred diluents for the reaction variant (c) according to the invention.
These include nitriles (such as acetonitrile), alcohols (such as ethanol), ethers (such as tetrahydrofuran or dioxane)~ aro~atic hydrocarbon~ Csuch as toluene and Le A 20 992 .
~-~'75~
benzene), formamides (such as di~ethylfor~amide), and halogenated hydrocarbons, (such as ~ethylene chloride, carbon tetrachloride cr chloroform).
The reaction variant (c) is carried o~t in the presence of an acid-binding agent. Any of the inorganic or organic acid-binding agents which can customarily be used can be added, such as alkali ~eta:l carbonates (for example sodium carbonate and potassium carbonate), or such as tertiary Cl to C~ alkyla~.ines~ cycloalkylamines or aralkylamines (for example triethylamine, N,N-dimethyl-cyclohex~-lamine and N,N-dimethylbenzyla~ine). An appro-priate excess of 1,2,4-tria~ole or i~.ldazole is also possible, In reaction varian~ (c), the reacticn temperatures can be varied within a relatively wide ran~e. In ~eneral, the reaction is carried out at a te~pera-ture betweerl 0 and 150C, pre~era~ly between 60 and 120G.
For carrying out reaction variant (c) according to t~e invention, 1 to 2 mol of 1,2,4-triazole or imidazole and 1 to 2 mol of acid-bindin~ agent are preferably employed per mol of the compounds of the formula (VI). The isolation of the compounds of the formula (I) is effected according to customary methods.
According to a particular embodiment of reaction variant (c), the process can also be carried out in such a manner that the intermedlate products of the ~ormula (VI) are first prepared~ as described previously, and, without isolatin~ these intermediate products and without a change of solvent, the further reaction is carried out and the end products of the formula (I) are cbtained in one operation, within the scope of a "one pot process".
The following are preferred acids which are suitable for the preparation of physiologically tolerated acid addition salts of the compounds of the formula hydrohalic acids (such as hydrobromic acid and~ preferably~
.. . . . . ... . . . . . . . . . . .
Le A 20 992 hydrochloric acid), phosphoric acld, nitIi( acid~ sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (such as acetic acid, m~leic acid, succinic acid, fum~ric acid, tartaric acid, citric acid, salicylic acld, sorbic acicl and lactic acid) and sulphonic acids, (such as p~toluenesulphonic acid and 1~5-naphthalene-disulphonic acid). The acid addition salts of the com-pounds of the formula (I) can be obtained in a simple manner by customary methods o~ salt formation~ for example by dissolving a compound of the formula (I) in a suitable org-anic solvent and adding the acid (for example hydrochloric acid), and can be isolated in a kncwn manner, for example by filterirlg off, and can be purified, if appropriate, by washing with an inert organic solvent.
Salts of metals of the IIncl to I~th main group and of the Ist and IInd and ~th to VIIIth sub-groups are pre~erably 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 exa~.ples.
Sui-table anions of the salts are those which are derived preferably from the following acids: hydrohalic acids (such a~ hydrochloric acid and hydrobromic acid) and also phosphoric acid, nitric acid and sulphuric acid.
The metal salt complexes of compounds of the-formula (I) can be obtained in a simple manner, according to customary processes, that is to say, for example, by dissolving the metal salt in alcohol ~for example ethanol) and adding the solution to the compound of the formula (I) Metal salt complexes can be isolated in a known manner, for example by filtering off, and car be purified, if appropriate, by recrystallisation.
The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for co~.batin~ undesired ~.icroorgan~sms, ~e .
Le A 20 992 active compounds are suitable for use as plant prctectlon agents.
Fungicidal agents in plant protection are employed fo. combating Plasmodiophoromycetes, Oom~cetes, Ghytridiomycetes, ~ygomycetes, ~scomycetes, Basidio-mycetes and ~euterom.y~etes.
~ actericidal agents are employed in plant pro-tection for combating Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacterlaceae and ~trepto-mycetaceae.
~ e good toleration, by plants, cf the activecompounds 3 at the concentratior.s required for co~hatirg plant diseases, permits treatmen~ of abc~e-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agen-ts, the active compounds according to the invention can be used with partlcu.larly good success for combating cereal diseases, for example 2gainst the powdery mildew of barley causative organism (Erysiphe graminis), rice diseases, for example, Pyricularia oryzae, Venturia species, for example, against the apple scab causative organism (Venturia inaequalis), as well as for combating bacteria.
The active compounds which can be used according to the invention engage in the metabolism of the plants and can therefore be employed as growth regulators.
Experience to date of the mode of action o4 plant growth regulators has shGwn that an active compound can also exert several different actions on plants~ Ihe 3 actions of the compounds depend essentially on the point in time at which they 2re used, relative to the stage of development of the pl2nt, and on the amounts of active ccmpound applied to the plants or their environment and the way in which the compounds are applied. In every case, -35 growth regulators are intended to influence the c~op pl~nts Le A 20-992 j L~ L ?J, in the particular ~anner desired.
Plant growth regulating compounds can be employed, for example, to inhibit vegetatlve growth of the plar.ts.
Such inhibition of growth is inter alia of econo~,ic interest in the case of grasses, since it is the~eby possible to reduce the f`requency of cutting the grass in ornamental gardens, parks, and sports&rounds, at verges, at airports or in fruit orchards. ~he inhibition of growth of herbaceous and woody plants at verges and in the vicinity of pipellnes or overland lines or, quite general~, in areas in which hea~y additional growth of plants is undesired, is also of importance.
The use of growth regulators to inhibit the growth in length of cereals is also inlportant~ The danger of lodging of the plants before harvesting is thereby reduced or completely eliminated. Further-more, growth regulators can strengthen the stem of cereals, which again counteracts lodging. Use of ærowth regulators for shortening and 5 trengthening the stem enables higher amounts of fertiliser to be applied to increase the yield, without danger of the cereal lo~ging.
In the case of many crop plants, inhibition of the vegetative growth makes denser planting possible~ so that greater yields per area of ground can be achieved.
An advantage of the smaller plants thus produced is also that the crop can ~e worked and har~ested more easily.
Inhibition of the vegetative growth of plants can also lead to increases in yield, since the nutrients and assimilates benefit blossoming and fruit formation 3 to a greater extent than they benefit the vegetative parts of plants.
Promotion of vegetative growth can also fre-quently be achieved with growth regulators. This is of great utility if it is the vegetatlve parts of the plarts which ~re harYested. PromQting the ~egetat}Ye growth .
Le A 20-9-92 L ~
can, howe~er, also simultaneously lead to a promotion of generative growth, since ~ore assimilates are formed, so that more fruit~ or larger fruit, is obtained.
Increases in yield can in some cases be achieved by affecting the plant metabolism, withoul, noticeable char.ges in vegetative growth. A chan~e in the compos-ition of plants, which in turn can lead to a better quality of the harvested products, can furthermore be achieved with growth regulators. Thus it is possible, for example, to increase the content of sugar in sugar beet, sugar cane, pineapples and citrus fruit or to increase the protein content in soya or cereals. Using growth regulators it is also possible, for exa~.ple, to inhibit the degradation of desired constituents, such as sugar in sugar beet or sugar cane, before or sfter harvesting. It is also possible favourably to influence the production or the efflux of seccndary plant constit-uents. The stimu}ation of latex flux in rubber trees may be mentioned as an example.
Parthenocarpous fruit can be formed under the influence of growth regulators. Furthermore, the gender of the flowers can be influenced. Sterility of the pollen can also be produced, which is of great importance in the breeding and preparation of hybrid seed.
Branching of plants can be controlled by using growth regulators. On the one hand, by breaking the spical dominance the development of side shoots can be prcmoted, which can be very desirable, especially in the cultivation of ornamental plants, also in connection with growth inhibition. On the other hand, however, it is also possible to inhibit the growth of side shoots.
There is great interest in this action, for example, in the cultivation of tobacco or in the planting of tomatoes.
The amount of leaf on plants can be controlled, under the nfluence o~ grcw.~th re~ulators~ so that Le A 20 992 defoliation cf the plar.ts at a desired point in tirne is achieved. Such defoliation is of great i~portance ir the mechanical harvesting of cotton, but is also of interest for facilitating harvestinc in other cro~ps, such as, for example, in viticulture. Defoliation of the plants can also be carried out to lower the transpiration of plants before they are transplanted.
The shedding of fruit can also be controlled with growth regulators. On the one hand, it is possible lC to prevent premature shedding of fruit, or even the fall of blossom, can be promoted up to a certain degree (thinning out) in order to interrupt the alternance. By alternance there is understood the peculiarity of some varietles of fruit to produce very dif~erent yields from year to ~ear, for endogenic reasons. Finally, using growth regu1ators it is possihle to reduce the force required to detacl~ ~he fruik at har~est` time so as to permit mechanical har~esking or facilitate ~lanual harvestlng.
Using growth regulators, it is furthermore poss-ible to achieve an acceleration or retardation of ripeningof the harvest product, before or after harvesting.
This is of particular advantage, since it is thereby poss-ible to achieve optimum adaptation to market requirernents~
Furthermore, growth regulators can at times improve the coloraticn of fruit. In addition, concentrating the ripening within a certain period of time is also achievable with the aid of growth regulators. This provides the preconditions for being able to carry out complete mechan-ical or manual harvesting in only a single pass~ for example in the case of tobacco, tomatoes or coffee~
Using growth regulators, it is furthermore Foss-ible to influence the latent period of seeds or buds of plants, so that the plants, such as pineapple or ornamental plants in nurseries, germinate, shoot or blosso~. at a time at which they normally show no readiness to do so~
.
- Le A 2C 992 r ~etarding the shooting of buds or the ~ermination of seeds with the aid of growth regulatcrs car. be desirable in regions ~here frost is a hazard, in order to avoid damage by late frosts.
Finally, the resistance of plants to frost~
drought or a high salt content in the soil can be induced with growth regulators. Cultl~ation of plants in regions which are usually unsuitable for this purpose thereby becomes possible.
~he preferred time of application of the growth regulators depends on the climatic and vegetative circu~-stances.
The foregoing description should not be talcen as i.mplying that eac~l of the compounds can e~chibit all of the described effects on plants. The effect exhibitecl by a compcund in any particular set of circumstances must be determinecl empirically.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, sus~ensions, powders, foams, pastes, granules; aerosols, very fine capsules in polymeric substances and in coating compositions for seed, as well as UL~ 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 diluents or carriers, optionally with the use of surface-active agents, that is to say emulsi~ying agents and~or dispersing agents and/or foam-forming ager.ts.
In the case of the use of ~ater as an extender 3 organic solvents can~ for example, also be used as auxiliary solvents.
As liquid diluents cr carriers, especially solverts, there are suitable in the main, aromatic hydro-carbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, Le A 2C 92 such as chlorobenzenes, chloroethyler.es cr methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fract-ions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, ~.ethyl ethyl ketone, ~ethyl isobutyl };etone cr cyclohexanone, or strongly polar solvents, such as dimethylforma~.ide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ~round natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, ~ontmorillonite or diatomaceous eart;h, and ground synthetic minerals, such as highl~~dispersed silicic acid, alumina and silicates. As solid carriers rOr granules there may be used crushed and fractionated - .~0 r~tural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of ~norganic 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 emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcokol ethers, for example alkylaryl polyglycol ethers 3 alky- 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, polyYinyl alcohol and poly~inyl acetate~ can be used in the for~.ula~ions, Le A 20 992 5'~3~
- 21 ~
It is possible to use colorants such as inorganic pigments, for exa~.ple iron oxide, titanium oxide and Frussian Blue, and organic dyestuffs, such as alizarin dyestu~fs~ azo dyestuf~s or ~etal phthalocyanine dyestufls 3 and trace nutrients, such as salts of iron, ~anganese, boron~ copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0 1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weightO
The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds~ such as fungicldes, insecticides, acaricides and herbicides, and also as mixtur&s wit~
fertilisers and other growth regulators~
The active compounds can be used as such ~ in the fcrm of their formulatiorls or as the ~se for~s prepared therefrom, such as ready-to-use solutions, eml1lsifiable concentrates, emulsions, foams, suspensions, wettable pow-ders, pastes, soluble powders, dusting agents and~granules..
They are used in the customary ~ann~r, for example by watering, spraying, atomising, scattering, dusting, foaming and coating. Furthermore, it is possible to a~ply the active compounds in accordance with the ultra-low ~olume process or to inject the active compound preparation or the active compound itself into the soil. It is also possible to treat the seeds of plants.
When the compounds according to the invention are used as plant growth regulators, the quantities can be varied within a relatively wide range. In general, C.01 to 50 kg, preferably 0.05 to lO kg, are used per hectare of soil surface.
Even when the compounds according to the invention are used as fungicides, the quantity used can be varied within a relatively wide range, depending on the type of application. ~hils, especially in the treatment of parts .. . . .
Le A 20 992 3 Ll ~
of plants, the active Goncentrations in the use for~is are, in general, between 1 and O.C001% by weight, pre-ferably between 0.5 and 0.001% by weight. In the treatment of seed, quantities of~ active compound of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 ~, are generally required. In the treatment cf soil, active compound conce~trations of C.00001 to 0.1% by welght, preferably of 0.0001 to 0.02%3 are required at the place of action.
The present invention also provides a plant growth regulant or 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 carrler co~tainin~
a surface-acti~e agent.
The present invention also provldes a method of combati~ lngi which comprises applying to the tungi~
or to a habita-t thereof~ a compound of the present invention alone or in the ~orm of a composition containin~ as ac-tive ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention also provides a method of regulating the growth of plants which comprises applying to the plants, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing 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.
The present invention further provides plants, the growth of which has been regulated by their being grown in areas in which immediately prior to and/or during .. .. . . . . ..
Le ~ 2C 92 7~
the time of the gro~ing a compOund of the present invention was applied alone or in admixture with a diluerIt or carrier.
It will be seen that the usual ~ethods of providing a harvested crop may be improved by the present invention.
Preparative ~xamples Example 1 , _ Cl ~ ~ _ C ~ C~l2 ~ CH2 ~ ~
N\ C ~ (1) O CH
(Reaction variant (a)) 12.4 g (0~04 mol) of 4,4'-chlorobip~len~lyl 2-imidazol-l-yl-ethyl Icetone were stirred with 1,.7 g (O.o6 molj o~ 0-(2,6 dichlorobenzyl)-hydroxylamine hydrochloride and 3,9 g ~0 048 mol) o~ sodlum ace~tate in 40 ml of water for 1 hour at 60C The reaction mixture was allowed to cool and was extracted~with ethyl acetate.
The organic phase was washed with water, dried over sodium sulphate and concentrated. The residue was purified by column chromatography. 3.9 g (70% of theory) of 1-(4,4'-chlorobiphenylyl)-1-(2,6-dichlorobenzyl-oximino)-3-(imidazol-l-yl)-propane of melting point 110 to 111C were obtained.
Pre~aration of the starting material C1- ~ - ~ _ C- CH2 - CH2 - N ~
~ 20 g (0.43 mol) of 4,4'-chlorobiphenylyl 2-chloro-ethyl ketone in 500 ml of acetQne were added drop-wlse to 32.4 g (0.47 mol) of imidazole and 178 g (1.29 mol)of potassium carbonate in 500 ml of acetone at room tem-perature, whilst stirring, the temperature of the mixture increasing to approx. 35C. The mixture was stirred under reflux for 8 hour~ and was thereafter cooled, ~he - Le A 20 992 -- 21~ --reaction mi~ture W2~ filtered. The filtrate ~ras concen-trated, and the residue was ta~en up in methylene chloride, washed with water, dried over sodiu~ sulphate and again concentrated. The residue was recrystallised frc~
5 toluene. 60 g (45~ of theory) of 4,4'-chloro~ipherlyl~L
2-imidazol-1-yl-ethyl i~etone of melting point 132-134C
ware obtained.
~1- ~ ~ - C - H~ - CH2- Cl 117 g (0.92 mol) of 3-chloropropionyl chloride were added dropwise to 170 G (O, 9 mol) of 4-chloro-biphenyl and 144 g (1.08 mol) of anhydrous aluminium chloride in 1~000 ml of ethylene chloride at roor temper-ature, whilst cocling. The mixture was furt,her stirred for one hour at 25C, and the reaction mixture was ~hen added to 3 litres of ice water. The or~anic phase was separated off, dried over sodium sulphate and concentrated.
The residue was recrystallised from diisopropyl ether.
242 g (96.3% of theory) of 4,4'-chlorobiphenylyl 2-chloro-ethyl ketone of melting point 90 to 94C were obtained.
The following compounds of the general formula / - N
R2 _ C - CH2 - CH2 \A~
N
O _ Rl were obtained in a corresponding manner and according to the processes indicated previously:
Le A 20 992 .
3 ~
Melting point Example Rl R2 racti~/e lnaex No. r~2(~
. . . _ D
2 CH ~> Cl~)- N 1, ~937 -CH2~-Cl Cl~- N 1~ 5902
Particularly preferred compounds of -the present invention are those in which any halogen atoms presen-t are fluorine or chlorine, and espec.ially those in which Rl represents an alkyl group havincJ 1 to 8 carbon atoms, an alkenyl or alkinyl group, each having 2 to 6 carbon atoms; a cyclopentyl, cyclohexyl~ cyclohexylmethyl or cyclohexenyl group; or a benzyl or phenyl group which is optionally monosubstituted to trisubstituted by identical or different substituents selected fromo lQ fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methyl.enedioxo, phenyl, phenoxy and trifluoromethyl; and R2 represents a phenyl group which :Ls monosubs-ti.tuted or disubstituted by identical or difEerent substituents selected from: fluorine, chlorine, bromine, methyl, phenyl and phenoxy, the phenyl and phenoxy substituents themselves being optionally substituted by chlorine, bromine or nitro.
In addition to the compounds mentioned in the preparative Examples, the following compounds of the formula (I) may be mentioned individually ~ N
R2 _ C - CH - CH - N ~ (I) O _ Rl (A= N, CH) ~ 4 _ 5~
R2 Rl ~ __ __ _. _____ _ _ _ . , ........ .. .......... ., .. , .. , , .. ... ., . _, _ _ _ , C1~ CH;,--~ ~- F
Cl~Cl -CH~ ~ ~2 C 1--~C 1 CH 2 C~
Cl ~ C1~12~CH=CH2 C 1 ~ -CH 2 -C--C~l Cl CH3 Cl~ 2~ CH3 ~,, R 2 . . . . . . . . . . R 1 Cl~ cl~
C 1~ 1 - C H 2 - ~ _ C H 3 C l ~i;- 2 ~ >
C1-~ ~ -C1 Cl~ C~cl Cl~; C~l C.l~
Cl~- -CH
H 3 C -~ - - C H 2 C
C 1~, - C 1 Le~- A ~C~ 9~2 R2 ' R
fC~3 C1 Br~ CH2-,CH3 -CH2- ~
If, for example~ 4,4'-chlorobiphenyl-yl-2-imidazol-1-yl-ethyl ketone and 0-(2,6-dichlorobenzy:L)-hyclroxylamine hydrochloride are used as the starting materials, the course o~ the r-eaction varlant (a) according to the present invention is illus~rated by the following equation:
Cl ~ C-CH2-CH2-N ~ ~ H2N-0 CH2 ~ x HCl Base Cl ~ -C-CH2CH2-N
N Cl~-~
O CH
Cl If, for example, 1-(2,4-dichlorophenyl~ oximino-3-(1,2,4-triazol-l-yl)-propane and 2,4-dichlorobenzyl chlGride are used ~s the starting materials, the course of the reaction variant (b) according to the present invention is illustrated by the following equatlon:
Le A 2~ 992 ~ .
l~ S~
Cl~ 1 2 C 2 ~ Cl-CH2~ Cl OH
,Cl J-- N
- H C 1 C 1- ~ - C - C H - C H
O-CH2- ~ -Cl If, for example, 3-chloro-1-(2,4-dichlorophenyl)-: l-methyloximino-propane and 1,2,4-triazole are used as ; the startin~ materials, the course of the reaction variant tc) according to t~e pre~ent i.nVention i~ illust-rated by the followin~ equation:
C 1~)- C - C H 2 ' ~ H 2 - C 1 + H N~
2 2 `,~
N ~
Preferrëd~azolyl-ketones of the formula (II) ~ required as the~starting materials in carrying out the : 10 reaction variant (a) according to the invention are those . in which A and R;2:have those meanings which have already I been mentioned in connection:with the description of the preferred and particul~arly p~referred compounds of ~ormula ~- (I) according to the~:invention.
1~ 15 Some of thè azolyl-ketones of the formula (II) ~ ~ have been descrlb~ed (see DE-OS (German.Published Specific-`:
:
Le A 20 9-G2 ': ' `
ation) 2,633,492 or U.S. Patent Specification 4~045,568).
Howe~7er, those derivatives are new in which A represents nitro~en. They can be obtained by the processes given in the references~ ~y reactlng~ for example, a vinyl ketone of the ger.eral formula R2 C - CH = CH2 (VII3 Il .
o in which R2 has the meaning gi~7en abcve, with 1,2,4-triazole or imidazole, in the presence of an inert organic solvent (such as climethylformamide~) at a temperature between 0 and lC0C, or by reacting a halogeno-methyl-ketone of the general formula R2 _ C - CH2--CH2- Hal' (VIII) in which R2 and Hal' have the meanings given above, with 1,2,4-triazole or imidazole, in the presence of an acid-binding agent ~such as potasslum carbonate) and in the presence of an inert organic solvent (such as dimethyl-formamide) at a temperature between 40 and 120C.
~ Preferred substituted hydroxylamines of the formula (III) additionally required as starting materials for reaction variant (a) according to the inYention are those in which Rl represents those radicals which ha~e been men-tioned for this substituent in connection with the des-cription of the preferred and particularly preferred com-pounds of the formula (I) according to the in~7ention.
The substituted hydroxylamines of the formula (III) are generally krown compounds of organic chemistry.
Preferred azolyl-oximes of the formula (III) 3 required as starting materials in carrying QUt reaction Le A 20 992 variant (b) according to the invention are those in which A and R2 ha~e those meanings ~hich have already been rren-tioned in connection with the description of the pre~erred and particularly preferred co~pounds of the formula (I) according to the invention.
~ he azolyl-oximes of the ~ormula (IV) are novel.
However, they can be obtained in a generally known manner, by reacting an azolyl-l~etone of the formula (II) with hydroxylamine, in the presence of a solvent, preferably an alcohol, at 50C to 100C, the hydroxylamine preferably being employed as the hydrochloride, in the presence of an acid-binding agent.
Preferred halides of formula (V) additionally required as starting materials ~or reaction variant (b) according to the inventlon are those in which Rl represents those radicals which have already been mentioned for this substituent in connection with the description of the pre~erred and particularly preferred compounds of the formula (I) according to the invention.
The halides of the formula (V) are generally known compounds of organic chemistry.
Preferred halogenopropyl-oximino derivatives of formula (~I) required as starting materials in carrying out reaction variant (c) according to the invention are those in which Rl and R2 represent those radicals which have already been mentioned for these su~s.tituents in connection with the description of the preferred and particularly preferred compounds of the formula (I) according to the invention.
3 The halogenopropyl-oximino derivatives of the formula (~-I) are novel. However, they can be obtained in a generally ~nown manner3 by reacting a halogenoethyl-ketone of the formula (~III) with a substituted hydroxyl-amine of the formula (III), in the presence of a solvent ~5 (preferably an alcohol) at a temperature between 50 and , . . . . . . . . .
Le ~ 20 992 100C, the substituted hydrcxylamines being preferab'y employed as the hydrochlori.des, in the presence of an acid-binding agent.
Alcohols ancl~ater, or mixtures of the two3 are pre~erred suitable diluents ~or reactior! ~ariant (a) according to the ~`nvention.
In reaction variant (a), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at a terperature lG between 20 and 120~, preferably between 5C and 100C.
In carrying out reaction varlant (a), 1 to 1.3 mol of hydroxylamlne of the formula (III) ls preferably employed per mol of azolyl-ketone o~ the formula (II).
The isolation of the compounds of the f'ormula (I) is effected according to customary methods.
According to a pre~erred embodiment of reaction varlant (a), the hydroxylamines of the formula ~III) are employed in the form of their salts (particularly as hydrochlorides) if appropriate in the presence of an acid-binding agent (such as sodium acetate) (see, also, the preparative Examples).
Inert organic solvents are suitable diluents for the reaction variant (b) according to the inventlon.
These preferably includeethers (such as tetrahydrofuran and dioxane), aromatic hydrocarbons (such as toluene and benzene), in individual cases, also chlorinated hydro-carbons (such as chloroform, methylene chloride or carbon tetrachloride), and hexamethylphosphoric acid tria~.ide, acld amides (such as dimethylformamide) and sulphoxides ~o (such as dimethyl sulphoxide).
The reaction variant (b) is carried out, if appropriate, in the presence of a strong base. These preferably include alkali metal amides, alkali metal hyd-rides, alkali metal hydroxides and alkali metal carbonates (such as sodiu~ ~mide, car~onate; hydroxide or hydride, .
Le A 20 992 and potassium amide, carbonate, hydroxide or hydride), and quaternary am~cnium hydroxides and phosphonium hydroxides (such as tetramethylammoniun: hydroxide, benzyl-trimethyl-ammonium hydroxide, dibenzyl-dimethyl-an~oniu~, hydroxide, tetraphenylphosphonium hydroxide and methyl-triphenylphosphonium hydroxide).
In reaction variant (b), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at a temperature bet-ween 20 and 15CC, preferably at room temperature. Inindividual cases, it is advantageous to carry out the reaction at the boiling point of the solvent1 for example between 60 and 100C.
In carrying out reaction variant (b), 1 to 3 mol of halide of the formula (V) are preferably emplcyed per mol of oxime of the formula tIV~. To isolate the er.d produc~s, the reaction mixture is freed from the solvent, and water and an or~anic solvcnt are added to the residue.
The organic phase is separated off, worked up in the custom-ary manner, and purified.
In a pre~erred embodiment of reaction variant (b),the reaction according to the lnvention is carried out in a two-phase system ~such as aqueous sodium hydroxide solution or potassium hydroxide solution/toluene or methylene chlcride~ with the addition of 0.01 to 1 mol of a ~hase-transfer catalyst per mol of oxime of formula (I~) (such as am~onium or phosphoniu~ compounds), the ethylates bein~ formed in the or~anic phase or at the boundary surface and being reacted with the halides present in the or~anic 3 phase~
Inert organic solvents are preferred diluents for the reaction variant (c) according to the invention.
These include nitriles (such as acetonitrile), alcohols (such as ethanol), ethers (such as tetrahydrofuran or dioxane)~ aro~atic hydrocarbon~ Csuch as toluene and Le A 20 992 .
~-~'75~
benzene), formamides (such as di~ethylfor~amide), and halogenated hydrocarbons, (such as ~ethylene chloride, carbon tetrachloride cr chloroform).
The reaction variant (c) is carried o~t in the presence of an acid-binding agent. Any of the inorganic or organic acid-binding agents which can customarily be used can be added, such as alkali ~eta:l carbonates (for example sodium carbonate and potassium carbonate), or such as tertiary Cl to C~ alkyla~.ines~ cycloalkylamines or aralkylamines (for example triethylamine, N,N-dimethyl-cyclohex~-lamine and N,N-dimethylbenzyla~ine). An appro-priate excess of 1,2,4-tria~ole or i~.ldazole is also possible, In reaction varian~ (c), the reacticn temperatures can be varied within a relatively wide ran~e. In ~eneral, the reaction is carried out at a te~pera-ture betweerl 0 and 150C, pre~era~ly between 60 and 120G.
For carrying out reaction variant (c) according to t~e invention, 1 to 2 mol of 1,2,4-triazole or imidazole and 1 to 2 mol of acid-bindin~ agent are preferably employed per mol of the compounds of the formula (VI). The isolation of the compounds of the formula (I) is effected according to customary methods.
According to a particular embodiment of reaction variant (c), the process can also be carried out in such a manner that the intermedlate products of the ~ormula (VI) are first prepared~ as described previously, and, without isolatin~ these intermediate products and without a change of solvent, the further reaction is carried out and the end products of the formula (I) are cbtained in one operation, within the scope of a "one pot process".
The following are preferred acids which are suitable for the preparation of physiologically tolerated acid addition salts of the compounds of the formula hydrohalic acids (such as hydrobromic acid and~ preferably~
.. . . . . ... . . . . . . . . . . .
Le A 20 992 hydrochloric acid), phosphoric acld, nitIi( acid~ sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (such as acetic acid, m~leic acid, succinic acid, fum~ric acid, tartaric acid, citric acid, salicylic acld, sorbic acicl and lactic acid) and sulphonic acids, (such as p~toluenesulphonic acid and 1~5-naphthalene-disulphonic acid). The acid addition salts of the com-pounds of the formula (I) can be obtained in a simple manner by customary methods o~ salt formation~ for example by dissolving a compound of the formula (I) in a suitable org-anic solvent and adding the acid (for example hydrochloric acid), and can be isolated in a kncwn manner, for example by filterirlg off, and can be purified, if appropriate, by washing with an inert organic solvent.
Salts of metals of the IIncl to I~th main group and of the Ist and IInd and ~th to VIIIth sub-groups are pre~erably 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 exa~.ples.
Sui-table anions of the salts are those which are derived preferably from the following acids: hydrohalic acids (such a~ hydrochloric acid and hydrobromic acid) and also phosphoric acid, nitric acid and sulphuric acid.
The metal salt complexes of compounds of the-formula (I) can be obtained in a simple manner, according to customary processes, that is to say, for example, by dissolving the metal salt in alcohol ~for example ethanol) and adding the solution to the compound of the formula (I) Metal salt complexes can be isolated in a known manner, for example by filtering off, and car be purified, if appropriate, by recrystallisation.
The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for co~.batin~ undesired ~.icroorgan~sms, ~e .
Le A 20 992 active compounds are suitable for use as plant prctectlon agents.
Fungicidal agents in plant protection are employed fo. combating Plasmodiophoromycetes, Oom~cetes, Ghytridiomycetes, ~ygomycetes, ~scomycetes, Basidio-mycetes and ~euterom.y~etes.
~ actericidal agents are employed in plant pro-tection for combating Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacterlaceae and ~trepto-mycetaceae.
~ e good toleration, by plants, cf the activecompounds 3 at the concentratior.s required for co~hatirg plant diseases, permits treatmen~ of abc~e-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agen-ts, the active compounds according to the invention can be used with partlcu.larly good success for combating cereal diseases, for example 2gainst the powdery mildew of barley causative organism (Erysiphe graminis), rice diseases, for example, Pyricularia oryzae, Venturia species, for example, against the apple scab causative organism (Venturia inaequalis), as well as for combating bacteria.
The active compounds which can be used according to the invention engage in the metabolism of the plants and can therefore be employed as growth regulators.
Experience to date of the mode of action o4 plant growth regulators has shGwn that an active compound can also exert several different actions on plants~ Ihe 3 actions of the compounds depend essentially on the point in time at which they 2re used, relative to the stage of development of the pl2nt, and on the amounts of active ccmpound applied to the plants or their environment and the way in which the compounds are applied. In every case, -35 growth regulators are intended to influence the c~op pl~nts Le A 20-992 j L~ L ?J, in the particular ~anner desired.
Plant growth regulating compounds can be employed, for example, to inhibit vegetatlve growth of the plar.ts.
Such inhibition of growth is inter alia of econo~,ic interest in the case of grasses, since it is the~eby possible to reduce the f`requency of cutting the grass in ornamental gardens, parks, and sports&rounds, at verges, at airports or in fruit orchards. ~he inhibition of growth of herbaceous and woody plants at verges and in the vicinity of pipellnes or overland lines or, quite general~, in areas in which hea~y additional growth of plants is undesired, is also of importance.
The use of growth regulators to inhibit the growth in length of cereals is also inlportant~ The danger of lodging of the plants before harvesting is thereby reduced or completely eliminated. Further-more, growth regulators can strengthen the stem of cereals, which again counteracts lodging. Use of ærowth regulators for shortening and 5 trengthening the stem enables higher amounts of fertiliser to be applied to increase the yield, without danger of the cereal lo~ging.
In the case of many crop plants, inhibition of the vegetative growth makes denser planting possible~ so that greater yields per area of ground can be achieved.
An advantage of the smaller plants thus produced is also that the crop can ~e worked and har~ested more easily.
Inhibition of the vegetative growth of plants can also lead to increases in yield, since the nutrients and assimilates benefit blossoming and fruit formation 3 to a greater extent than they benefit the vegetative parts of plants.
Promotion of vegetative growth can also fre-quently be achieved with growth regulators. This is of great utility if it is the vegetatlve parts of the plarts which ~re harYested. PromQting the ~egetat}Ye growth .
Le A 20-9-92 L ~
can, howe~er, also simultaneously lead to a promotion of generative growth, since ~ore assimilates are formed, so that more fruit~ or larger fruit, is obtained.
Increases in yield can in some cases be achieved by affecting the plant metabolism, withoul, noticeable char.ges in vegetative growth. A chan~e in the compos-ition of plants, which in turn can lead to a better quality of the harvested products, can furthermore be achieved with growth regulators. Thus it is possible, for example, to increase the content of sugar in sugar beet, sugar cane, pineapples and citrus fruit or to increase the protein content in soya or cereals. Using growth regulators it is also possible, for exa~.ple, to inhibit the degradation of desired constituents, such as sugar in sugar beet or sugar cane, before or sfter harvesting. It is also possible favourably to influence the production or the efflux of seccndary plant constit-uents. The stimu}ation of latex flux in rubber trees may be mentioned as an example.
Parthenocarpous fruit can be formed under the influence of growth regulators. Furthermore, the gender of the flowers can be influenced. Sterility of the pollen can also be produced, which is of great importance in the breeding and preparation of hybrid seed.
Branching of plants can be controlled by using growth regulators. On the one hand, by breaking the spical dominance the development of side shoots can be prcmoted, which can be very desirable, especially in the cultivation of ornamental plants, also in connection with growth inhibition. On the other hand, however, it is also possible to inhibit the growth of side shoots.
There is great interest in this action, for example, in the cultivation of tobacco or in the planting of tomatoes.
The amount of leaf on plants can be controlled, under the nfluence o~ grcw.~th re~ulators~ so that Le A 20 992 defoliation cf the plar.ts at a desired point in tirne is achieved. Such defoliation is of great i~portance ir the mechanical harvesting of cotton, but is also of interest for facilitating harvestinc in other cro~ps, such as, for example, in viticulture. Defoliation of the plants can also be carried out to lower the transpiration of plants before they are transplanted.
The shedding of fruit can also be controlled with growth regulators. On the one hand, it is possible lC to prevent premature shedding of fruit, or even the fall of blossom, can be promoted up to a certain degree (thinning out) in order to interrupt the alternance. By alternance there is understood the peculiarity of some varietles of fruit to produce very dif~erent yields from year to ~ear, for endogenic reasons. Finally, using growth regu1ators it is possihle to reduce the force required to detacl~ ~he fruik at har~est` time so as to permit mechanical har~esking or facilitate ~lanual harvestlng.
Using growth regulators, it is furthermore poss-ible to achieve an acceleration or retardation of ripeningof the harvest product, before or after harvesting.
This is of particular advantage, since it is thereby poss-ible to achieve optimum adaptation to market requirernents~
Furthermore, growth regulators can at times improve the coloraticn of fruit. In addition, concentrating the ripening within a certain period of time is also achievable with the aid of growth regulators. This provides the preconditions for being able to carry out complete mechan-ical or manual harvesting in only a single pass~ for example in the case of tobacco, tomatoes or coffee~
Using growth regulators, it is furthermore Foss-ible to influence the latent period of seeds or buds of plants, so that the plants, such as pineapple or ornamental plants in nurseries, germinate, shoot or blosso~. at a time at which they normally show no readiness to do so~
.
- Le A 2C 992 r ~etarding the shooting of buds or the ~ermination of seeds with the aid of growth regulatcrs car. be desirable in regions ~here frost is a hazard, in order to avoid damage by late frosts.
Finally, the resistance of plants to frost~
drought or a high salt content in the soil can be induced with growth regulators. Cultl~ation of plants in regions which are usually unsuitable for this purpose thereby becomes possible.
~he preferred time of application of the growth regulators depends on the climatic and vegetative circu~-stances.
The foregoing description should not be talcen as i.mplying that eac~l of the compounds can e~chibit all of the described effects on plants. The effect exhibitecl by a compcund in any particular set of circumstances must be determinecl empirically.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, sus~ensions, powders, foams, pastes, granules; aerosols, very fine capsules in polymeric substances and in coating compositions for seed, as well as UL~ 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 diluents or carriers, optionally with the use of surface-active agents, that is to say emulsi~ying agents and~or dispersing agents and/or foam-forming ager.ts.
In the case of the use of ~ater as an extender 3 organic solvents can~ for example, also be used as auxiliary solvents.
As liquid diluents cr carriers, especially solverts, there are suitable in the main, aromatic hydro-carbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, Le A 2C 92 such as chlorobenzenes, chloroethyler.es cr methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fract-ions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, ~.ethyl ethyl ketone, ~ethyl isobutyl };etone cr cyclohexanone, or strongly polar solvents, such as dimethylforma~.ide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ~round natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, ~ontmorillonite or diatomaceous eart;h, and ground synthetic minerals, such as highl~~dispersed silicic acid, alumina and silicates. As solid carriers rOr granules there may be used crushed and fractionated - .~0 r~tural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of ~norganic 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 emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcokol ethers, for example alkylaryl polyglycol ethers 3 alky- 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, polyYinyl alcohol and poly~inyl acetate~ can be used in the for~.ula~ions, Le A 20 992 5'~3~
- 21 ~
It is possible to use colorants such as inorganic pigments, for exa~.ple iron oxide, titanium oxide and Frussian Blue, and organic dyestuffs, such as alizarin dyestu~fs~ azo dyestuf~s or ~etal phthalocyanine dyestufls 3 and trace nutrients, such as salts of iron, ~anganese, boron~ copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0 1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weightO
The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds~ such as fungicldes, insecticides, acaricides and herbicides, and also as mixtur&s wit~
fertilisers and other growth regulators~
The active compounds can be used as such ~ in the fcrm of their formulatiorls or as the ~se for~s prepared therefrom, such as ready-to-use solutions, eml1lsifiable concentrates, emulsions, foams, suspensions, wettable pow-ders, pastes, soluble powders, dusting agents and~granules..
They are used in the customary ~ann~r, for example by watering, spraying, atomising, scattering, dusting, foaming and coating. Furthermore, it is possible to a~ply the active compounds in accordance with the ultra-low ~olume process or to inject the active compound preparation or the active compound itself into the soil. It is also possible to treat the seeds of plants.
When the compounds according to the invention are used as plant growth regulators, the quantities can be varied within a relatively wide range. In general, C.01 to 50 kg, preferably 0.05 to lO kg, are used per hectare of soil surface.
Even when the compounds according to the invention are used as fungicides, the quantity used can be varied within a relatively wide range, depending on the type of application. ~hils, especially in the treatment of parts .. . . .
Le A 20 992 3 Ll ~
of plants, the active Goncentrations in the use for~is are, in general, between 1 and O.C001% by weight, pre-ferably between 0.5 and 0.001% by weight. In the treatment of seed, quantities of~ active compound of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 ~, are generally required. In the treatment cf soil, active compound conce~trations of C.00001 to 0.1% by welght, preferably of 0.0001 to 0.02%3 are required at the place of action.
The present invention also provides a plant growth regulant or 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 carrler co~tainin~
a surface-acti~e agent.
The present invention also provldes a method of combati~ lngi which comprises applying to the tungi~
or to a habita-t thereof~ a compound of the present invention alone or in the ~orm of a composition containin~ as ac-tive ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention also provides a method of regulating the growth of plants which comprises applying to the plants, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing 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.
The present invention further provides plants, the growth of which has been regulated by their being grown in areas in which immediately prior to and/or during .. .. . . . . ..
Le ~ 2C 92 7~
the time of the gro~ing a compOund of the present invention was applied alone or in admixture with a diluerIt or carrier.
It will be seen that the usual ~ethods of providing a harvested crop may be improved by the present invention.
Preparative ~xamples Example 1 , _ Cl ~ ~ _ C ~ C~l2 ~ CH2 ~ ~
N\ C ~ (1) O CH
(Reaction variant (a)) 12.4 g (0~04 mol) of 4,4'-chlorobip~len~lyl 2-imidazol-l-yl-ethyl Icetone were stirred with 1,.7 g (O.o6 molj o~ 0-(2,6 dichlorobenzyl)-hydroxylamine hydrochloride and 3,9 g ~0 048 mol) o~ sodlum ace~tate in 40 ml of water for 1 hour at 60C The reaction mixture was allowed to cool and was extracted~with ethyl acetate.
The organic phase was washed with water, dried over sodium sulphate and concentrated. The residue was purified by column chromatography. 3.9 g (70% of theory) of 1-(4,4'-chlorobiphenylyl)-1-(2,6-dichlorobenzyl-oximino)-3-(imidazol-l-yl)-propane of melting point 110 to 111C were obtained.
Pre~aration of the starting material C1- ~ - ~ _ C- CH2 - CH2 - N ~
~ 20 g (0.43 mol) of 4,4'-chlorobiphenylyl 2-chloro-ethyl ketone in 500 ml of acetQne were added drop-wlse to 32.4 g (0.47 mol) of imidazole and 178 g (1.29 mol)of potassium carbonate in 500 ml of acetone at room tem-perature, whilst stirring, the temperature of the mixture increasing to approx. 35C. The mixture was stirred under reflux for 8 hour~ and was thereafter cooled, ~he - Le A 20 992 -- 21~ --reaction mi~ture W2~ filtered. The filtrate ~ras concen-trated, and the residue was ta~en up in methylene chloride, washed with water, dried over sodiu~ sulphate and again concentrated. The residue was recrystallised frc~
5 toluene. 60 g (45~ of theory) of 4,4'-chloro~ipherlyl~L
2-imidazol-1-yl-ethyl i~etone of melting point 132-134C
ware obtained.
~1- ~ ~ - C - H~ - CH2- Cl 117 g (0.92 mol) of 3-chloropropionyl chloride were added dropwise to 170 G (O, 9 mol) of 4-chloro-biphenyl and 144 g (1.08 mol) of anhydrous aluminium chloride in 1~000 ml of ethylene chloride at roor temper-ature, whilst cocling. The mixture was furt,her stirred for one hour at 25C, and the reaction mixture was ~hen added to 3 litres of ice water. The or~anic phase was separated off, dried over sodium sulphate and concentrated.
The residue was recrystallised from diisopropyl ether.
242 g (96.3% of theory) of 4,4'-chlorobiphenylyl 2-chloro-ethyl ketone of melting point 90 to 94C were obtained.
The following compounds of the general formula / - N
R2 _ C - CH2 - CH2 \A~
N
O _ Rl were obtained in a corresponding manner and according to the processes indicated previously:
Le A 20 992 .
3 ~
Melting point Example Rl R2 racti~/e lnaex No. r~2(~
. . . _ D
2 CH ~> Cl~)- N 1, ~937 -CH2~-Cl Cl~- N 1~ 5902
4 -CH2~)-Cl ~ N 1, 5912 S -C4H9-n Cl~;- N L,~491 6 -CH2~Cl ~j N :l~ 5937 7 -C~2~ ~ 1J 5814 8 - C H 3 ~ N 1~, 5 6 6 S
9 -C4Hg-n Cl~-0~- N 1, 576a lo -CH2~ N viscous 11 -CH2Cl~ Cl~>- N 138-40 12 -CH2-~>-Cl Cl~ )- N 130-31 Le- A 2~ g-a2 ~.elting point Example Rl F~2 __ ~x _. _. _ , . _. . ~ .__ ~, . _ 13 -CH2~-cl Cl~0~- N 1,6100 14 CH2 ~ Cl~-0~- N l, 6134 15 -C4H9-n Cl~- N 72-73 16 -C~ H ~-n C1~ N vlscous oil 17-CH2~Cl C1~ CH 1,,616:~
18 Cl~ Cl~ CH 154-1~6 19-CH2-(~ ~- CH l90 ,Cl 20-C7Hl5-n Cl~ CH l~ 5390 Le ~. 2C~ 992 li7~ 4 Melting point Examp le 1 2 ( G ) or ref -No. R R A ractive index nco Cl 21 - ~ Cl~- CH 1,5684 Cl 22 -C4H9-n Cl~- CH 1,5601 23 -C4Hg-n Cl~-0~ CH 1,5756 24 -C4H9-n C~ CH 1, 6088 : ' -C4H9-n ~ CH l t 5923 . ~ 26 -CH~CH3~C2H5 ~ CH 1,5880 : ~ :
27 - ~ Cl~-O~ CH 1,5972 28 -CH2~-~1 ~: CH 1,6244 :
29 C7 15 ~ CH 1,5710 Le A 2 0 9 9 2 : : :
: .
' r~ LlL '~
Meltin~ point E~am~le 1 2 ( C) or ref-No. R R A ractive inde~
n2o .
-CH3 Cl ~ CH 1,5842 31 Cl ~ Cl ~ CH 1,5992 32 CH2 ~ Cl ~- CH 1,5992 / c~l3 33 -CH2 ~ Cl ~ - - CH 1J 5878 ,-~CI
34 -CH2 ~ Cl Cl ~ CH 1,5878 Cl Cl -CH2 ~ -Cl Cl ~ - CH 1~5920 36 CH2 ~ Cl ~ 0 ~ - CH 17 6200 37 -CH ~ ~ Cl (x CuC12) .*Forms A and. B~ the two possible geometrical isomers .. . . . . ..
Le A 20-992 The fungioidal a~d plant growth regularlt activity of the compounds of this inventior is i.llustrated by the followi~g biotest Examples.
In these Examples~ the compounds according to the present invention are each identified ~y the number (given in brackets) of the corresponding preparative Exa~.ple.
The known comparison co~.pounds are identified as follows:
\
O -- C~12~Cl Cl Cl~_~ ~ N
( B ) Cl~)-lCI -CH2 N\N--N
C1 ~=
( C ) C 1-~ C - C H 2 x HN03 syn-Form Cl j_ (D) Cl~C-CH2-N
N x HN03 anti-Form O-CH2-~Cl Le A 20 992 r~ f,~
Example A
Erysiphe test (barley)~protective/
Solvent: 100 parts by weight of di~ethylformamide Ernulsifier: C. 25 part by weight of al};ylaryl polyglycol ether To produce a ~uitable preparatlon of active com-pound3 1 part by weight of active compound was ~ixed ~Tith the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concen-10 tration.
To test for protective activlty, young plants were sprayed with the preparation of active compouncl until dew-moist. After the spray coating had dried on, the plants were dusted with spores of Erysiphe ~raminis f. sp.
15 hordei-The plants were placed in a greenhouse at a ter~-perature of about 20C and a reLative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules.
Evaluation was carried out 7 days after the inoculation.
In this test, a clearly superior activity co~pared with the prior art was shown, for example, by the compounds:
(2), (3), (4)3 (5), (6), (7), (8), (9), (10), (11), (15), 25 (16), (32), (30), (22), (:~i1)3 (33), (34), (35), (24), (25), (26), (21~, (20) and (18), Example B
Venturia test (apple)/protective/
Solvent: 4 . 7 parts by weight of acetone 3 Emulsifier: C.3 part by weight of-alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by wei~ht of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was dilutea with water to the desired concen--35 . tration, Le A 20 9-92 .
>~
To test for protective activity, ycung plants ~ere sprayed with the preparation of active compound until drioping wet. After the spray coating had dried on, the plants were inoculated with an aqueous conidia sus-pension of the apple scab causative organism (Venturiainaequalis) and then remained in an incubation cabin at 20C and 100~ relative atmospheric humidity fcr 1 day.
The plants were then placed in a greenhouse at 20C
and a relative atmospheric humidity of about 70%.
Evaluation was carried out 12 days after the inoculation.
In this test, a clearly superior activity co~
pared with the prior art is shown, for exar~ple, by the compounds: (2), (3), (4)~ (32), (31) and (30).
Exam Inhibition of gro~th of sugar beet Solvent: 30 parts by weight of dimeth~lfor~amide Emulsifier: 1 part by wei~ht of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active com-pound, 1 part by weight of active co~pound was mixed with the stated amounts of solvent and e~uls fier and the mix-ture was made up to the desired concentration with water.
Sugar beet was grown in a greenhouse until for-mation of the co-tyledons was complete. In this stage, the plants were sprayed with the preparation of active compound until dripping wet. After 14 d~ys~ the additional growth of the plants was measured and the inhibition of growth in per cent of the additional growth of the control pl~nts was calculated. 0% inhibition of growth denoted a growth which corresponded to that of the control plants. 100%
inhibition of growth meant that grDwth had stopped.
In this test, the active compounds (9), (14), (15) and (17~ exhibited a good. effect on growth, in co~parison to the control, Le A 20 9-92 -
9 -C4Hg-n Cl~-0~- N 1, 576a lo -CH2~ N viscous 11 -CH2Cl~ Cl~>- N 138-40 12 -CH2-~>-Cl Cl~ )- N 130-31 Le- A 2~ g-a2 ~.elting point Example Rl F~2 __ ~x _. _. _ , . _. . ~ .__ ~, . _ 13 -CH2~-cl Cl~0~- N 1,6100 14 CH2 ~ Cl~-0~- N l, 6134 15 -C4H9-n Cl~- N 72-73 16 -C~ H ~-n C1~ N vlscous oil 17-CH2~Cl C1~ CH 1,,616:~
18 Cl~ Cl~ CH 154-1~6 19-CH2-(~ ~- CH l90 ,Cl 20-C7Hl5-n Cl~ CH l~ 5390 Le ~. 2C~ 992 li7~ 4 Melting point Examp le 1 2 ( G ) or ref -No. R R A ractive index nco Cl 21 - ~ Cl~- CH 1,5684 Cl 22 -C4H9-n Cl~- CH 1,5601 23 -C4Hg-n Cl~-0~ CH 1,5756 24 -C4H9-n C~ CH 1, 6088 : ' -C4H9-n ~ CH l t 5923 . ~ 26 -CH~CH3~C2H5 ~ CH 1,5880 : ~ :
27 - ~ Cl~-O~ CH 1,5972 28 -CH2~-~1 ~: CH 1,6244 :
29 C7 15 ~ CH 1,5710 Le A 2 0 9 9 2 : : :
: .
' r~ LlL '~
Meltin~ point E~am~le 1 2 ( C) or ref-No. R R A ractive inde~
n2o .
-CH3 Cl ~ CH 1,5842 31 Cl ~ Cl ~ CH 1,5992 32 CH2 ~ Cl ~- CH 1,5992 / c~l3 33 -CH2 ~ Cl ~ - - CH 1J 5878 ,-~CI
34 -CH2 ~ Cl Cl ~ CH 1,5878 Cl Cl -CH2 ~ -Cl Cl ~ - CH 1~5920 36 CH2 ~ Cl ~ 0 ~ - CH 17 6200 37 -CH ~ ~ Cl (x CuC12) .*Forms A and. B~ the two possible geometrical isomers .. . . . . ..
Le A 20-992 The fungioidal a~d plant growth regularlt activity of the compounds of this inventior is i.llustrated by the followi~g biotest Examples.
In these Examples~ the compounds according to the present invention are each identified ~y the number (given in brackets) of the corresponding preparative Exa~.ple.
The known comparison co~.pounds are identified as follows:
\
O -- C~12~Cl Cl Cl~_~ ~ N
( B ) Cl~)-lCI -CH2 N\N--N
C1 ~=
( C ) C 1-~ C - C H 2 x HN03 syn-Form Cl j_ (D) Cl~C-CH2-N
N x HN03 anti-Form O-CH2-~Cl Le A 20 992 r~ f,~
Example A
Erysiphe test (barley)~protective/
Solvent: 100 parts by weight of di~ethylformamide Ernulsifier: C. 25 part by weight of al};ylaryl polyglycol ether To produce a ~uitable preparatlon of active com-pound3 1 part by weight of active compound was ~ixed ~Tith the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concen-10 tration.
To test for protective activlty, young plants were sprayed with the preparation of active compouncl until dew-moist. After the spray coating had dried on, the plants were dusted with spores of Erysiphe ~raminis f. sp.
15 hordei-The plants were placed in a greenhouse at a ter~-perature of about 20C and a reLative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules.
Evaluation was carried out 7 days after the inoculation.
In this test, a clearly superior activity co~pared with the prior art was shown, for example, by the compounds:
(2), (3), (4)3 (5), (6), (7), (8), (9), (10), (11), (15), 25 (16), (32), (30), (22), (:~i1)3 (33), (34), (35), (24), (25), (26), (21~, (20) and (18), Example B
Venturia test (apple)/protective/
Solvent: 4 . 7 parts by weight of acetone 3 Emulsifier: C.3 part by weight of-alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by wei~ht of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was dilutea with water to the desired concen--35 . tration, Le A 20 9-92 .
>~
To test for protective activity, ycung plants ~ere sprayed with the preparation of active compound until drioping wet. After the spray coating had dried on, the plants were inoculated with an aqueous conidia sus-pension of the apple scab causative organism (Venturiainaequalis) and then remained in an incubation cabin at 20C and 100~ relative atmospheric humidity fcr 1 day.
The plants were then placed in a greenhouse at 20C
and a relative atmospheric humidity of about 70%.
Evaluation was carried out 12 days after the inoculation.
In this test, a clearly superior activity co~
pared with the prior art is shown, for exar~ple, by the compounds: (2), (3), (4)~ (32), (31) and (30).
Exam Inhibition of gro~th of sugar beet Solvent: 30 parts by weight of dimeth~lfor~amide Emulsifier: 1 part by wei~ht of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active com-pound, 1 part by weight of active co~pound was mixed with the stated amounts of solvent and e~uls fier and the mix-ture was made up to the desired concentration with water.
Sugar beet was grown in a greenhouse until for-mation of the co-tyledons was complete. In this stage, the plants were sprayed with the preparation of active compound until dripping wet. After 14 d~ys~ the additional growth of the plants was measured and the inhibition of growth in per cent of the additional growth of the control pl~nts was calculated. 0% inhibition of growth denoted a growth which corresponded to that of the control plants. 100%
inhibition of growth meant that grDwth had stopped.
In this test, the active compounds (9), (14), (15) and (17~ exhibited a good. effect on growth, in co~parison to the control, Le A 20 9-92 -
Claims (33)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An azolylpropyl-oximino derivative of the formula in which A is a nitrogen atom or a CH group, Rl is an alkyl, alkenyl or alkinyl group, a benzyl or phenyl group which is optionally substituted by halogen, cyano, nitro, Cl to C4-alkyl, Cl to C4-alkoxy, methylenedioxo, phenyl, phenoxy or Cl to C2 halogenonlkyl having up to 3 halogen atoms, or Rl is a cycloalkyl, cycloalkylalkyl or cycloalkenyl group optionally substituted by Cl to C4-alkyl and R2 is a phenyl group substituted by one or more substituents selected from halogen, nitro, cyano, Cl to C4-alkyl, Cl to C4-alkoxy, Cl to C4-alkyl-mercapto, Cl to C4-halogenoalkyl, Cl to C4-halogenoalkoxy, Cl to C4-halogenoalkylmercapto (each halogenoalkyl moiety having up to 5 halogen atoms), mono- and di-(Cl to C4-alkyl)amino, and phenyl, phenoxy, phenylmercapto, benzyl, benzyloxy and benzylmercapto in which each phenyl nucleus is optionally substituted by halogen, cyano, nitro or halogenoalkyl having up to 2 carbon atoms and up to 3 halogen atoms, or a non-phytotoxic acid addition salt or metal salt complex thereof in which the metal is selected from main group II to IV or sub-groups I, II and IV to VIII
of the Periodic Table.
of the Periodic Table.
2. A compound, according to claim 1, in which Rl represents an alkyl group having 1 to 12 carbon atoms, an alkenyl or alkinyl group, each having 2 to 12 carbon atoms; a cycloalkyl, cycloalkylalkyl or cycloalkenyl group, each having 5 to 7 carbon atoms in the cycloalkyl or cycloalkenyl part and 1 or 2 carbon atoms in the alkyl part, it being possible for the cycloalkyl or cycloalkenyl part to be optionally substituted by alkyl having 1 to 4 carbon atoms; or a benzyl or phenyl group which is optionally substituted by identical or different substituents as defined in claim 1 for Rl, but wherein any halogen atoms present in Rl and R2 are fluorine or chlorine.
3. A compound according to claim l, in which Rl represents an alkyl group having 1 to 8 carbon atoms, an alkenyl or alkinyl group, each having 2 to 6 carbon atoms, a cyclopentyl, cyclohexyl, cyclo-hexylmethyl or cyclohexenyl group, or a benzyl or phenyl group which is optionally monosubstituted to trisubstituted by identical or different substituents selected from fluorine, chlorine, bromine, cycmo, nitro, methyl, ethyl, methoxy, methylene-dioxo, phenyl, phenoxy and trifluoromethyl, and R2 represents a phenyl group which is monosubstituted or disubstitutod by identical or different substituents selected from fluorine, chlorine, bromine and methyl, phenyl and phenoxy, the phenyl and phenoxy substituents themselves being optionally substituted by chlorine, bromine or nitro.
4. 1-(2,4-Dichlorophenyl)-1-(2,6-dichlorobenzyl-oximino)-3-(1,2,4-tri-azol-l-yl)-propane of the formula
5. 1-(2,4-Dichlorophenyl)-1-(4-chlorobenzyl-oximino)-3-(1,2,4-triazol-l-yl)-propane of the formula
6. 1-(2,4-Dichlorophenyl)-1-(2,4-dichlorobenzyl-oximino)-3-(1,2,4-tri-azol-l-yl)-propane of the formula
7. 1-(2,4-Dichlorophenyl)-1-(2,6-dichlorobenzyl-oximino)-3-(imidazol-1-yl)-propane of the formula
8. 1-(2,4-Dichlorophenyl)-1-(3-methylbenzyl-oximino)-3-(imidazol-1-yl)-propane of the formula
9. A non-phytotoxic acid addition salt, or metal salt complex in which the metal is selected from main group II to IV or sub-groups I, II and IV to VIII
of the Periodic Table, of the compound of claim 4, 5 or 6.
of the Periodic Table, of the compound of claim 4, 5 or 6.
10. A non-phytotoxic acid addition salt, or motal salt complox in which the metal is selected from main group II to IV or sub-groups I, II and IV to VIII
of the Periodic Table, of the compound of claim 7 or 8.
of the Periodic Table, of the compound of claim 7 or 8.
11. A process for the production of a compound according to claim 1, characterised in that (a) an azolyl-ketone of the general formula (II) in which A and R2 have the same meanings as in claim 1, is reacted with a substituted hydroxylamine of the general formula H2N - O - Rl (III) in which Rl has the same meaning as in claim 1, in the presence of a diluent, or (b) an azolyl-oxime of the general formula (IV) in which A and R2 have the same meanings as in claim 1, is reacted with a halide of the general formula Hal - R1 (V) in which R1 has the same meaning as in claim 1 and Hal represents a chlorine or bromine atom, in the presence of a diluent, or (c) a halogenopropyl-oximino derivative of the general formula (VI) in which R1 and R2 have the same meanings as in claim 1 and Hal' represents a chlorine or bromine atom, is reacted with 1,2,4-triazole or imidazole, in the presence of an acid-binding agent and in the presence of a diluent, and where required, a suitable acid or a suitable metal salt is then added onto the compound of the formula (I) which is obtained by reaction variant (a), (b) or (c).
12. 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.
13. A method of regulating the growth of plants comprising applying to the plants, or to a habitat thereof, a plant-growth regulating effective amount of a compound according to claim 1.
14. A method according to claim 12 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.
15. A method according to claim 13 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.
16. A method according to claim 12 or 14, wherein a composition is used containing from 1 to 0.0001 % of snid compound, by weight.
17. A method according to claim 12 or 14, wherein a composition is used containing from 0.5 to 0.001 % of said compound, by weight.
18. A method according to claim 13 or 15, wherein said compound is applied to an area of agriculture in an amount of 0.01 to 50 kg per hectare.
19. A method according to claim 13 or 15, wherein said compound is applied to an area of agriculture in an amount of 0.05 to 10 kg per hectare.
20. A method according to claim 12 or 14, wherein said compound is applied to soil in an amount of 0.00001 to 0.1 per cent by weight.
21. A method according to claim 12 or 14, wherein said compound is applied to soil in an amount of 0.0001 to 0.02 per cent by weight.
22. A method according to claim 12 or 14, wherein said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.
23. A method accorcling to claim 12 or 14, wherein said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.
24. The method according to claim 12 or 14, wherein such compound is 1-(2,4-dichlorophenyl)-1-)2,6-dichlorobenzyl-oximino)-3-(l,2,4-triazol-l-yl)-propane.
25. The method according to claim 12 or 14, wherein such compound is 1-(2,4-dichlorophenyl)-1-(4-chlorobenzyl-oximino)-3-(1,2,4-triazol-1-yl)-propane.
26. The method according to claim 12 or 14, wherein such compound is 1-(2,4-dichlorophenyl)-1-(2,4-dichlorobenzyl-oximino)-3-(1,2,4-triazol-l-yl)-propane.
27. The method according to claim 12 or 14, wherein such compound is 1(2,4-dichlorophenyl)-1-(2,6-dichlorobenzy-l-oximino)-3-(imidazol-1-yl)-propane.
28. The method according to claim 12 or 14, wherein such compound is 1-(2,4-dichlorophenyl)-1-(methylbenzyl-oximino)-3-(imidazol-1-yl)-propane.
29. The method according to claim 13 or 15, wherein such compound is 1-(2,4-dichlorophenyl)-1-(2,6-dichlorobenzyl-oximino)-3-(1,2,4-triazol-1-yl)-propane.
30. The method according to claim 13 or 15, wherein such compound is 1-(2,4-dichlorophenyl)-1-(4-chlorobenzyl-oximino)-3-(1,2,4-triazol-1-yl)-propane.
31. The method according to claim 13 or 15, wherein such compound is 1-(2,4-dichlorophenyl)-1-(2,4-dichlorobenzyl-oximino)-3-(1,2,4-triazol-1-yl)-propane.
32. The method according to claim 13 or 15, wherein such compound is 1-(2,4-dichlorophenyl)-1-(2,6-dichlorobenzyl-oximino)-3-(imidazol-1-yl)-propane.
33. The method according to claim 13 or 15, wherein such compound is 1-(2,4-dichlorophenyl)-1-(methylbenzyl-oximino)-3-(imidazol-1-yl)-propane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813116888 DE3116888A1 (en) | 1981-04-28 | 1981-04-28 | "AZOLYLPROPYL-OXIMINO DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES AND PLANT GROWTH REGULATORS" |
| DEP3116888.4 | 1981-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1175844A true CA1175844A (en) | 1984-10-09 |
Family
ID=6131012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000401712A Expired CA1175844A (en) | 1981-04-28 | 1982-04-27 | Azolylpropyl-oximino derivatives, processes for their preparation, and their use as fungicides and plant growth regulators |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0065107B1 (en) |
| JP (1) | JPS57181065A (en) |
| AT (1) | ATE15666T1 (en) |
| BR (1) | BR8202418A (en) |
| CA (1) | CA1175844A (en) |
| DE (2) | DE3116888A1 (en) |
| DK (1) | DK188382A (en) |
| HU (1) | HU186926B (en) |
| IL (1) | IL65612A (en) |
| ZA (1) | ZA822853B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3407005A1 (en) * | 1983-09-26 | 1985-04-04 | Bayer Ag, 5090 Leverkusen | HYDROXYETHYLAZOLYL OXIME DERIVATES |
| IL97144A (en) * | 1990-02-27 | 1994-11-28 | Erba Carlo Spa | Substituted 1-(alkoxy-iminoalkyl)imidazole derivatives, their preparation and pharmaceutical compositions containing them |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH617427A5 (en) * | 1975-12-24 | 1980-05-30 | Siegfried Ag | |
| DE2820361A1 (en) * | 1978-05-10 | 1979-11-15 | Bayer Ag | SUBSTITUTED ALKANYL-AZOLYL-OXIMCARBAMATE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES, ACARICIDES AND NEMATOCIDS |
| DE2842801A1 (en) * | 1978-09-30 | 1980-04-10 | Basf Ag | BETA TRIAZOLYLOXIME |
-
1981
- 1981-04-28 DE DE19813116888 patent/DE3116888A1/en not_active Withdrawn
-
1982
- 1982-04-16 DE DE8282103202T patent/DE3266306D1/en not_active Expired
- 1982-04-16 EP EP82103202A patent/EP0065107B1/en not_active Expired
- 1982-04-16 AT AT82103202T patent/ATE15666T1/en not_active IP Right Cessation
- 1982-04-26 HU HU821312A patent/HU186926B/en unknown
- 1982-04-26 JP JP57068861A patent/JPS57181065A/en active Pending
- 1982-04-26 IL IL65612A patent/IL65612A/en unknown
- 1982-04-27 CA CA000401712A patent/CA1175844A/en not_active Expired
- 1982-04-27 DK DK188382A patent/DK188382A/en not_active Application Discontinuation
- 1982-04-27 ZA ZA822853A patent/ZA822853B/en unknown
- 1982-04-27 BR BR8202418A patent/BR8202418A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR8202418A (en) | 1983-04-12 |
| IL65612A0 (en) | 1982-07-30 |
| DK188382A (en) | 1982-10-29 |
| DE3116888A1 (en) | 1982-11-11 |
| HU186926B (en) | 1985-10-28 |
| EP0065107B1 (en) | 1985-09-18 |
| IL65612A (en) | 1985-04-30 |
| ATE15666T1 (en) | 1985-10-15 |
| EP0065107A3 (en) | 1983-01-05 |
| EP0065107A2 (en) | 1982-11-24 |
| ZA822853B (en) | 1983-03-30 |
| DE3266306D1 (en) | 1985-10-24 |
| JPS57181065A (en) | 1982-11-08 |
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