AU742108B2 - Substituted phenyl pyridazinones - Google Patents
Substituted phenyl pyridazinones Download PDFInfo
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- AU742108B2 AU742108B2 AU37025/99A AU3702599A AU742108B2 AU 742108 B2 AU742108 B2 AU 742108B2 AU 37025/99 A AU37025/99 A AU 37025/99A AU 3702599 A AU3702599 A AU 3702599A AU 742108 B2 AU742108 B2 AU 742108B2
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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
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
- C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
- C07C255/66—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and nitrogen atoms being part of hydrazine or hydrazone groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/08—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D237/14—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D237/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/22—Radicals substituted by singly bound oxygen or sulfur atoms etherified
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Le A 32 986-Foreign Countries Kri/wa/NT Substituted phenylpyridazinones The invention relates to novel substituted phenylpyridazinones, to processes for their preparation and to their use as crop protection agents, in particular as herbicides and as insecticides.
It is already known that certain substituted phenylpyridazinones have herbicidal properties (cf. DE-A-1105232, DE-A-1670309, DE-A-1670315, DE-A-1695840, DE-A-2526643, DE-A-2706700, DE-A-2808193, DE-A-2821809, DE-A-19754348, US-A-5298502, WO-A-96/39392, WO-A-97/07104). The herbicidal activity of these compounds is not entirely satisfactory.
This invention, accordingly, provides the novel substituted phenylpyridazinones of the general formula (I) in which
R
1 represents hydrogen, fluorine, chlorine or bromine, represents cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or represents in each case optionally fluorine- and/or chlorine-substituted alkyl, alkoxy or alkylthio having in each case 1 or 2 carbon atoms, R3 represents the grouping -AI-A 2
-A
3 Le A 32 986-Foreign Countries -2in which Al represents a single bond, represents oxygen, sulphur, -S02-, -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, hydroxyl, C 1
-C
4 -alkyl, C 3
-C
4 -alkenyl, C 3 -C4-alkinyl, C1-C 4 -alkoxy, phenyl, C 1 -C4-alkylsulphonyl or phenylsulphonyl, Al furthermore represents in each case optionally fluorine-, chlorine- or bromine-substituted C 1
-C
6 -alkanediyl, C 2
-C
6 -alkenediyl, C 2
-C
6 -azaalkenediyl, C 2
-C
6 -alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
A
2 represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, hydroxyl, C 1
-C
4 -alkyl, C 1
-C
4 -alkoxy, phenyl, C 1 -C4-alkylsulphonyl or phenylsulphonyl,
A
2 furthermore represents in each case optionally fluorine-, chlorine-, bromine- or Cl -C 4 -alkoxy-substituted C1-C 6 -alkanediyl, C 2
-C
6 alkenediyl, C2-C6-azaalkenediyl, C2-C 6 -alkinediyl, C3-C 6 -cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
A
3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, formyl, carboxyl, carbamoyl, thiocarbamoyl, suipho, chlorosulphonyl, fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, fluorine-, chlorine-, C 1
-C
4 -alkoxy-, C 1
-C
4 -alkylcarbonyloxy- or C -C 4 -alkoxy-carbonyloxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or dialkoxy(thio)phosphoryl having in each case I to 6 carbon atoms in the alkyl groups, represents in each case optionally fluorine- or chlorine-
T
Le A 32 986-Foreip Countries -3substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, represents in each case optionally fluorine-, chlorine-, cyano-, carboxyl-, C 1
-C
4 -alkyl- and/or C 1
-C
4 alkoxy-carbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylamino, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or represents in each case optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, C 1
-C
4 -alkyl-, C 1 -C4-halogenoalkyl,
C
1
-C
4 alkyloxy, C 1
-C
4 -halogenoalkyloxy- and/or C 1 -C4-alkoxy-carbonylsubstituted phenyl, phenyloxy, phenyl-Cl-C 4 -alkyl, phenyl-C 1
-C
4 alkoxy, phenyloxycarbonyl or phenyl-C 1 -C4-alkoxycarbonyl,
A
3 furthermore represents in each case optionally fully or partially hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, dioxanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C 1-C 4 -alkyl, furyl-C 1 -C 4 -alkyl, thienyl-C 1-C 4 -alkyl, oxazolyl-C 1-C 4 -alkyl, isoxazole-C1-C 4 -alkyl, thiazole-C 1-C 4 -alkyl, pyridinyl-C 1-C 4 -alkyl, pyrimidinyl-C l-C 4 -alkyl, pyrazolylmethoxy, furylmethoxy, represents perhydropyranylmethoxy or pyridylmethoxy, R4 represents hydrogen, carboxyl, cyano, carbamoyl, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case optionally- fluorine- and/or chlorine-substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or alkoxycarbonyl having in each case 1 to 4 carbon atoms in the alkyl groups, Le A 32 986-Foreign Countries -4represents hydrogen, carboxyl, cyano, carbamoyl, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case optionally fluorine- and/or chlorine-substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or alkoxycarbonyl having in each case 1 to 4 carbon atoms in the alkyl groups, and R6 represents hydrogen, carboxyl, cyano, carbamoyl, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case optionally fluorine- and/or chlorine-substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or alkoxycarbonyl having in each case 1 to 4 carbon atoms in the alkyl groups.
The novel substituted phenylpyridazinones of the general formula have interesting biological properties, in particular strong herbicidal and insecticidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
R
1 preferably represents hydrogen, fluorine or chlorine;
R
2 preferably represents cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl or trifluoromethyl;
R
3 preferably represents the grouping -A 1
-A
2
-A
3 in which Le A 32 986-Foreign Countries Al represents a single bond, represents oxygen, sulphur, -S02-, -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl, Al furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane- 1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,
A
2 represents a single bond, represents oxygen, sulphur, -S02-, -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl,
A
2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane- 1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,
A
3 represents hydrogen, hydroxyl, amino, cyano, nitro, formyl, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i- Le A 32 986-Foreign Countries -6propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl or dipropoxyphosphoryl, diisopropoxyphosphoryl, represents in each case optionally fluorine- or chlorine- substituted ethenyl, propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, ethinyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, represents in each case optionally fluorine-, chlorine-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonylsubstituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, or represents in each case optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl,
A
3 furthermore represents (in each case optionally fully or partially hydrogenated) dioxolanyl, dioxanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolemethyl, thiazolemethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy; Le A 32 986-Foreign Countries -7-
R
4 preferably represents hydrogen, carboxyl, cyano, carbamoyl, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl;
R
5 preferably represents hydrogen, carboxyl, cyano, carbamoyl, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl; and
R
6 preferably represents hydrogen, carboxyl, cyano, carbamoyl, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl.
R
1 particularly preferably represents hydrogen, fluorine or chlorine;
R
2 particularly preferably represents cyano or thiocarbamoyl;
R
3 particularly preferably represents the grouping -Al-A 2
-A
3 in which
A
1 represents a single bond, represents oxygen, sulphur, -S0 2 -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, methyl, ethyl, n- or i-propyl, methylsulphonyl or ethylsulphonyl, Le A 32 986-Foreign Countries -8- Al furthermore represents methylene, ethane- 1, l-diyl, ethane- 1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl or propene-1,3-diyl,
A
2 represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl,
A
2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1 -diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl or propene-1,3-diyl,
A
3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or ipropoxycarbonyl, represents in each case optionally fluorine- or chlorine-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, represents in each case optionally fluorine-, chlorine-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxy- Le A 32 986-Foreign Countries -9carbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo-propylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylidenamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, or represents in each case optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or ipropyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl or benzyloxycarbonyl,
A
3 furthermore represents pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolemethyl, thiazolemethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy;
R
4 particularly preferably represents hydrogen, cyano, thiocarbamoyl, nitro, fluorine, chlorine, bromine, or represents in each case optionally fluorineand/or chlorine- substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino;
R
5 particularly preferably represents in each case fluorine- and/or chlorinesubstituted methyl, ethyl, n- or i-propyl; and
R
6 particularly preferably represents hydrogen, cyano, thiocarbamoyl, nitro, S T lfluorine, chlorine, bromine, or represents in each case optionally fluorine- Le A 32 986-Foreign Countries and/or chlorine-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl.
The abovementioned general or preferred radical definitions apply both to the end products of the formula and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
Preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.
Particular preference according to the invention is given to the compounds of the formula which contain a combination of the meanings listed above as being particularly preferred.
Very particularly preferred compounds of the formula are listed in the groups below.
Group 1
F
Ar
CF
(IA-1) 0 Ar has here, for example, the meanings listed below: 4-cyano-phenyl, 2-fluoro-4-cyano-phenyl, 2-chloro-4-cyano-phenyl, 3-fluoro-4cyano-phenyl, 3-chloro-4-cyano-phenyl, 2 -fluoro-5-chloro-4-cyano-phenyl, dichloro-4-cyano-phenyl, 2 -chloro-5-fluoro-4-cyano-phenyl, 2-chloro-4,5-dicyanophenyl, 2 -chloro-4-fluoro-5-cyano-phenyl, 2 ,5-difluoro-4-cyano-phenyl, 2-chloro-4- Le A 32 986-Foreign Countries 2-fluoro-4-cyano-5-methyl-phenyl, 2-chloro-4-cyano-5-trifluoromethyl-phenyl, 2-fluoro-4-cyano-5-trifluoromethyl-phenyl, 2,5-difluoro-4-thiocarbamoyl-phenyl, 2-fluoro-4-cyano-5-methoxy-phenyl, 2-fluoro-4-cyano-5-ipro-poxy-phenyl, 2-chloro-4-cyano-5-(2-propinyloxy)-phenyl, 2-fluoro-4-cyano-5-( 1methyl-2-propinyloxy)-phenyl, 2-chloro-4-thiocarbamoyl-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-(2-propenyloxy)-phenyl, 2-chloro-4-cyano-5-methylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-ethylsulphonylamino-phenyl, 2-fluoro-4-thio- 2-chloro-4-cyano-5-ethylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-cyclopropylsulphonylamino-phenyl, 2-fluoro-4cyano-5-i-propylsulphonylamino-phenyl, 2-chloro-4-thiocarbamoyl-5-ethylsuiphonylamino-phenyl, 2-chloro-4-cyano-5-cyanamino-phenyl, 2-fluoro-4-cyano-5trifluoromethylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-(2,2-difluoroethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-phenylsulphonylamino-phenyl, 2- 2-chloro-4-cyano-5-methoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonyl-phenyl, 2-fluoro-4-thio- 2-fluoro-4-cyano-5-( 1-methyl-2-propinylthio)-phenyl, 2-fluoro-4-cyano-5-methylamino-phenyl, 2-chloro-4-thiocarbamoyl-5methoxycarbonylmethyl-phenyl, 2-chloro-4-cyano-5-(N-methyl-ethylsulphonylamino)-phenyl, 2-chloro-4-cyano-5-i-propoxycarbonyl-phenyl, 2-fluoro-4-cyano-5- (bis-ethylsulphonyl-amino)-phenyl, 2-fluoro-4-cyano-5-(N-methylsulphonyl-N-ethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-( 1-methoxycarbonyl-ethoxy)-phenyl, 2- 2-chloro-4-cyano-5-dimethylamino-phenyl, 2-fluoro-4-cyano-5-tetrahydrofurylmethoxy-phenyl, 2-fl uoro-4-cyano-5 -aminophenyl, 2-fluoro-4-cyano-5-methylaminocarbonyl-phenyl, 2-fluoro-4-cyano-5methylsulphonyloxy-phenyl, 2-chloro-4-cyano-5-difluoromethoxy-phenyl, 2-fluoro- 2-fluoro-4-cyano-5-dimethylaminocarbonyl-phenyl, 2-fluoro-4-cyano-5-cyanomethoxy-phenyl, 2-fluoro-4-cyano-5-(2chloro-2-propenyloxy--phenyl, 2-fluoro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4- 2-fluoro-4-cyano-5-diethoxyphosphorylamino-phenyl, 2fluoro-4-cyano-5-chlorosulphonyl-phenyl, 2-fluoro-4-cyano-5-formylamino-phenyl, 2-chloro-4-cyano-5-ethoxycarbonyloxy-phenyl, 2-fluoro-4-cyano-5-diethoxy- Le A 32 986-Foreign Countries -12phosphorylmethoxy-phenyl, 2-chloro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano- 2-fluoro-4-cyano-5-acetylamino-phenyl, 2-chloro-4- 2-fluoro-4-cyano-5-diethylaminooxy-phenyl, 2-fluoro- 2-fluoro-4-cyano-5-ureido-phenyl, 2-fluoro-4cyano-5-dirnethoxymethyleneamino-phenyl, 2-chloro-4-cyano-5-ethoxymethyleneamino-phenyl, 2-fluoro-4-cyano-5-(2-chloro-ethoxycarbonyloxy)-phenyl, 2-chloro-4- 2-chloro-4-cyano-5-(perhydropyran- 4-yloxy)-phenyl, 2-fluoro-4-cyano-5-(2-methoxycarbonyl-ethyl)-phenyl, 2-chloro-4cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-s-butoxycarbonyl)phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-carbamoyl-ethyl)-phenyl, 2-fluoro-4-cyano- 5-(2-chloro-2-methoxycarbonyl- 1 -methyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-( 1,2dibromo-2-methoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-chloro-2-ipropoxy-carbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-carboxy-2-chloro-ethyl)phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl, 2-fluoro- 4-cyano-5-(2-allylaminocarbonyl-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2ethoxycarbonyl-ethenyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-cyclopropylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-dimethylaminocarbonylethyl)-phenyl, 2-chloro-4-cyano-5-(2-chloro-2-ethylsulphonylaminocarbonyl-ethyl)phenyl, 2-fluoro-4-thiocarbamoyl-5-(2-ethylaminocarbonyl-ethenyl)-phenyl, 2- 1 -ethoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-( 1 -ethoxycarbonylethyl)-phenyl, 2-chloro-4-cyano-5-carboxy-phenyl, 2-fluoro-4-cyano-5-ibutoxy-phenyl, 2-chloro-4-cyano-5-i-butoxy-phenyl, 2-chloro-4-cyano-5-(2-methoxyethoxy)-phenyl, 2-fluoro-4-cyano-5-(N-acetyl-N-methylsulphonyl-amino)-phenyl, 2fluoro-4-cyano-5-(N-propionyl-N-methylsulphonyl-amino)-phenyl, 2-fluoro-4-cyano- 2-fluoro-4-cyano-5-(N-pivaloyl- N-methylsulphonyl-amino)-phenyl, 2-fluoro-4-cyano-5-(N-benzoyl-N-methylsulphonyl-amino)-phenyl, 2-fluoro-4-cyano-5-(N-(4-methoxy-benzoyl)-N-methylsulphonyl-amino)-phenyl, 2-fluoro-4-cyano-5-(N-acetyl-N-ethylsulphonyl-amino)phenyl, 2-fluoro- 4 -cyano-5-(N-propionyl-N-ethylsulphonyl-amino)-phenyl, 2-fluoro- 2-fluoro-4-cyano-5-(N- Le A 32 986-Foreign Countries 13 pivaloyl-N-ethylsulphonyl-ainino)-phenyl, 2-fluoro-4-cyano-5-(N-benzoyl-N-ethylsulphonyl-amino)-phenyl, 2-fluoro-4-cyano-5-(N-(4-methoxy-benzoyl)-N-ethylsulphonyl-amino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-acetyl-N-methylsulphonylamino)-phenyl, 2-fluoro-4-thiocarbarnoyl-5-(N-propionyl-N-methylsulphonylamino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-i-butyroyl-N-methylsulphonylam-ino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-pivaloyl-N-methylsulphonyl-amino)phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-benzoyl-N-methylsulphonyl-amino)-phenyl, 2-fluoro-4 thiocarbamoyl-5-(N-(4-methoxy-benzoyl)-N-methylsulphonyl-amino)phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-acetyl-N-ethylsulphonyl-amino)-phenyl, 2fluoro-4-thiocarbamoyl-5-(N-propionyl-N-ethylsulphonyl-amino)-phenyl, 2-fluoro-4- 2-fluoro-4-thio- 2-fluoro-4-thio- 2-fluoro-4-thiocarbamoyl-5-(N-(4-methoxy-benzoyl)-N-ethylsulphonyl-amino)-phenyl.
Group 2
N
Ar-N CF O;D/-CF3(IA-2) Ar has here, for example, the meanings listed above in Group 1.
Group 3 Ar-d
CF
3 (IA-3) 0 CH.
Ar has here, for example, the meanings listed above in Group 1.
Le A 32 986-Foreign Countries -14- Group 4
CH
3
N=
Ar-N
CF
3 O
CH
3 (IA-4) Ar has here, for example, the meanings listed above in Group 1.
Group
N=
A- CHF 3 0 CH 3 Ar has here, for example, the meanings listed above in Group 1.
Group 6 3 (IA-6) Ar has here, for example, the meanings listed above in Group 1.
Group 7 (IA-7) Le A 32 986-Forein Countries Ar has here, for example, the meanings listed above in Group 1.
Group 8 Ar-N
CHF
2 (IA-8) Ar has here, for example, the meanings listed above in Group 1.
Group 9
CI
N F Ar-
CF
3 O0 CH, t 3 (IA-9) Ar has here, for example, the meanings listed above in Group 1.
Group
-CF
3 Ar has here, for example, the meanings listed above in Group 1.
Group 11
N-
Ar- r CHF 2 0
CH
3 (IA-11) Le A 32 986-Foreign Countries -16- Ar has here, for example, the meanings listed above in Group 1.
Group 12
CH
3
N=
Ar-N
CHF
(IA-12)
O
Ar has here, for example, the meanings listed above in Group 1.
Group 13 Ar-N CF 2 CI (IA-13) 0 Ar has here, for example, the meanings listed above in Group 1.
Group 14
N=
Ar-I C CF 2
CI
0
CH
3 (IA-14) Ar has here, for example, the meanings listed above in Group 1.
Group Le A 32 986-Foreign Countries -17-
-CF
2
CI
Ar has here, for example, the meanings listed above in Group 1.
Group 16
N=
Ar-N
CF
3 0 Br (IA-16) Ar has here, for example, the meanings listed above in Group 1.
Group 17
N-
Ar-N CF 3 0 C, (IA-17) Ar has here, for example, the meanings listed above in Group 1.
Group 18 (IA-18) Ar has here, for example, the meanings listed above in Group 1.
Le A 32 986-Foreign Countries -18- Group 19 Ar- (IA-19) Ar has here, for example, the meanings listed above in Group 1.
Group
CH
3
N-
Ar-N
CF
3 O0 CH Ar has here, for example, the meanings listed above in Group 1.
Group 21 Ar-1 (IA-21) Ar has here, for example, the meanings listed above in Group 1.
Group 22
CH
3
/N
Ar-N
CF
2
CI
O
CH,
(IA-22) Le A 32 986-Foreign Countries -19- Ar has here, for example, the meanings listed above in Group 1.
Group 23
CH
3
/N
Ar-N
C
2
F
O
CH,
(IA-23) Ar has here, for example, the meanings listed above in Group 1.
Group 24 (IA-24) Ar has here, for example, the meanings listed above in Group 1.
Group
N-
Ar-N
/CF
3 0
C
2
,H
Ar has here, for example, the meanings listed above in Group 1.
Group 26
COOC
2
H
N
Ar-N
CF
3 O
CH
3 (IA-26) Le A 32 986-Foreign Countries Ar has here, for example, the meanings listed above in Group 1.
Group 27
COOC
2
H
N.
Ar-d
CF
3 (IA-27) 0 Ar has here, for example, the meanings listed above in Group 1.
Group 28
COOH
N Ar-N
CF
3 (IA-28) O
CH
3 Ar has here, for example, the meanings listed above in Group 1.
Group 29
CN
N-
Ar-N
CF
3 (IA-29) 0
CH
3 Ar has here, for example, the meanings listed above in Group 1.
Le A 32 986-Foreign Countries -21- Group Ar has here, for example, the meanings listed above in Group 1.
Group 31
CSNH
2
N-
Ar-d
/-CF
3 O
CH,
(IA-31) Ar has here, for example, the meanings listed above in Group 1.
Group 32 (IA-32) Ar has here, for example, the meanings listed above in Group 1.
The novel substituted phenylpyridazinones of the general formula are obtained when halogenoarenes of the general formula (II) Le A 32 986-Foreign Countries -22-
R
1 X 1 I R 2
R
3 in which Rl, R 2 and R 3 are as defined above and X1 represents halogen are reacted with pyridazinones of the general formula (II)
R
6
R
N
I I R N4H (I) in which
R
4
R
5 and R 6 are as defined above, or with acid adducts or alkali metal salts of compounds of the formula (l) if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or when arylhydrazines of the general formula (IV) Le A 32 986-Foreign Countries -23-
NH
2
R
1
HN
R2
(IV)
R
3 in which
R
1
R
2 and R 3 are as defined above are reacted with B-trihalomethyl-enones of the general formula (V)
R
6
R
Ol (V) R4 'C(X 2 3 in which
R
4
R
5 and R 6 are as defined above and
X
2 represents halogen, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or when hydrazonecarboxylic acids of the general formula (VI)
(VI)
Le A 32 986-Foreign Countries -24in which
R
1
R
2
R
3
R
4
R
5 and R 6 are as defined above are condensed with ring-closure, i.e. reacted with a dehydrating agent, or when 2,4-disubstituted phenylpyridazinones of the general formula (Ia)
R
6
RI
R4 (Ia) in which R1, R 2
R
4
R
5 and R 6 are as defined above are nitrated, i.e. reacted with a nitrating agent, or when hydrazonecarbonyl compounds of the general formula (VII)
R
6
R
N
R'
O HN(v D 02 (VII) in which
R
1
R
2
R
3
R
5 and R 6 are as defined above Le A 32 986-Foreign Countries are reacted with alkoxycarbonylmethylenephosphoranes of the general formula (VIII)
COOR
R4,
P(C
6
H
5 3 (VI) in which
R
4 is as defined above and R represents alkyl having 1 to 6 carbon atoms, or with trialkyl phosphonocarboxylates of the general formula (IX)
COOR
R4
PO(OR)
2 in which
R
4 is as defined above and R represents alkyl having 1 to 6 carbon atoms, in each case optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent.
The compounds of the general formula can also be converted by other customary methods into other compounds of the general formula according to the above definition, for example by nucleophilic substitution R 3 F OH, SH, NH 2
OCH
3
NHSO
2
CH
3 or by further transformations of functional groups R 2 F/Cl/Br -4 CN, CONH 2 CN, CN -4 CSNH 2
NO
2 -4 NH 2
R
3 NO2 NH 2
NH
2 F, Cl, Br, CN, NHSO 2
CH
3
SO
2 C1, OCH 3 OH, OH OCH 2
CH=CH
2 cf. also the Preparation Examples.
Le A 32 986-Foreign Countries -26- Using, for example, 4-fluoro-6-methyl-5-trifluoromethyl-pyridazin-3-one and fluoro-2-methoxy-benzonitrile as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme:
H
3
CH
3 F F 3 N F N F F3C F 1 HF F F NH CN CN 0
CN
OCH
3
OCH,
Using, for example, 4,4,4-trichloro-3-methyl-2-difluoromethyl-crotonaldehyde and 4-cyano-2-fluoro-5-propargyloxy-phenylhydrazine as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme: F H F H FNF N F F- 3 HCI HC -3H CCI
N
H3 0013 CN
ON
CN
Using, for example, 2-chloro-3-chlorodifluoromethyl-4-oxo-2-butenoic acid N-(4as starting material, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme: Le A 32 986-Foreign Countries -27- H H
CIF
2 C ~N F
CIF
2 C N F CI OOH CN H 2 0 CI
CNCN
H o' 2 H NSO2 H3 CH3 Using, for example, 2-(2-chloro-4-cyano-phenyl)-4,6-dichloro-5-pentafluoroethylpyridazin-3-one and nitric acid as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme: CI CI F5C2 N I HNO, 3 FC N CI N N C 0 H20 C 0 NCN
CN
NO
2 Using, for example, 3,3,3-trifluoro-2-oxo-propanal 1-(4-cyano-2,5-difluorophenylhydrazone) and ethyl triphenylphosphoranylidene-acetate as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme:
FFF
N F 1N F
COOC
2
H
5 I I CN 0CN The formula (II) provides a general definition of the halogenoarenes to be used as starting materials in the process according to the invention for preparing the Le A 32 986-Foreign Countries -28compounds of the formula In the formula R 1
R
2 and R 3 preferably or in particular have that meaning which has already been mentioned above, in the description of the compounds of the formula to be prepared according to the invention, as being preferred or as being particularly preferred for R 1
R
2 and R 3
X
I
preferably represents fluorine, chlorine or bromine, in particular fluorine.
The starting materials of the formula (II) are known and/or can be prepared by processes known per se (cf. EP 191181, EP 370332, EP 431373, EP 441004).
The formula (mI) provides a general definition of the pyridazinones further to be used as starting materials in the process according to the invention. In the formula (III),
R
4
R
5 and R 6 preferably have that meaning which has already been mentioned above, in the description of the compounds of the formula to be prepared according to the invention, as being preferred, particularly preferred or very particularly preferred for R 4
R
5 and R 6 The starting materials of the formula (1I) are known and/or can be prepared by processes known per se (cf. J. Chem. Soc. 1947, 239; Angew. Chem. 77 (1965), 282; Monatsh. Chem. 120 (1989), 329).
The formula (IV) provides a general definition of the arylhydrazines to be used as starting materials in the process according to the invention for preparing the compounds of the formula In the formula R 1
R
2 and R 3 preferably have that meaning which has already been mentioned above, in the description of the compounds of the formula to be prepared according to the invention, as being preferred, particularly preferred or very particularly preferred for R 1
R
2 and R 3 The starting materials-of the formula (IV) are known and/or can be prepared by processes known per se (cf. EP 370332).
Le A 32 986-Foreign Countries -29- The formula provides a general definition of the P-trihalogenomethyl-enones further to be used as starting materials in the process according to the invention.
In the formula R 4
R
5 and R 6 preferably have that meaning which has already been mentioned above, in the description of the compounds of the formula to be prepared according to the invention, as being preferred, particularly preferred or very particularly preferred for R 4
R
5 and R 6
X
2 preferably represents fluorine, chlorine or bromine, in particular chlorine.
The starting materials of the formula are known and/or can be prepared by processes known per se (cf. DE 2706700).
The formula (VI) provides a general definition of the hydrazonecarboxylic acids to be used as starting materials in the process according to the invention for preparing the compounds of the formula In the formula R 1
R
2
R
3
R
4
R
5 and R 6 preferably have that meaning which has already been mentioned above, in the description of the compounds of the formula to be prepared according to the invention, as being preferred, particularly preferred or very particularly preferred for R1, R 2
R
3
R
4
R
5 and R 6 The starting materials of the formula (VI) are known and/or can be prepared by processes known per se (cf. WO 9639392).
The hydrazonecarboxylic acids of the general formula (VI) are obtained when arylhydrazines of the general formula (IV) NH, R 1 12
HN
-I
SR 2(IV)
R
3 in which Le A 32 986-Foreign Countries R1, R 2 and R 3 are as defined above are reacted with 3-carboxy-enones of the general formula (X)
R
6 S O (X)
R
4 j COOH in which
R
4
R
5 and R 6 are as defined above, if appropriate in the presence of a diluent, such as, for example, ethanol, and if appropriate in the presence of a reaction auxiliary, such as, for example, p-toluenesulphonic acid, at temperatures between 0°C and 100 0
C.
The formula (Ia) provides a general definition of the 2,4-disubstituted phenylpyridazinones to be used as starting materials in the process according to the invention for preparing compounds of the formula In the formula R 1
R
2
R
4
R
5 and R 6 preferably have that meaning which has already been mentioned above, in the description of the compounds of the formula to be prepared according to the invention, as being preferred, particularly preferred or very particularly preferred for R 1
R
2
R
4
R
5 and R 6 The starting materials of the formula (Ia) are known and/or can be prepared by processes known per se (cf. the processes to according to the invention).
The formula (VII) provides a general definition of the hydrazonecarbonyl compounds to be used as starting materials in the process according to the invention for preparing compounds of the formula In the formula (VII), R 1
R
2
R
3
R
5 and R 6 preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) Le A 32 986-Foreign Countries -31according to the invention, as being preferred, particularly preferred or very particularly preferred for R 1
R
2
R
3
R
5 and R 6 The starting materials of the formula (VII) are known and/or can be prepared by processes known per se (cf. WO 9707104).
Not yet known from the literature and, as novel compounds, part of the subjectmatter of the present application, are the hydrazonecarbonyl compounds of the general formula (VIIa) (VIa) in which
R
1 represents fluorine, chlorine or bromine, R2-1 represents cyano, carbamoyl, thiocarbamoyl, or represents in each case optionally fluorine- and/or chlorine-substituted alkyl, alkoxy or alkylthio having in each case 1 or 2 carbon atoms,
R
3 represents the grouping -A 1
-A
2
-A
3 in which represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, hydroxyl, C 1 -C4-alkyl, C 3 -C4-alkenyl, C 3
-C
4 -alkinyl, C 1 -C4-alkoxy, phenyl, C 1 -C4-alkylsulphonyl or phenylsulphonyl, Le A 32 986-Foreign Countries -32- Al furthermore represents in each case optionally fluorine-, chlorine- or bromine-substituted C1-C6-alkanediyl, C 2
-C
6 -alkenediyl, C2-C 6 -azaalkenediyl, C 2
-C
6 -alkinediyl, C3-C6-cycloalkanediyl, C3-C 6 -cycloalkenediyl or phenylene,
A
2 represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, hydroxyl, C 1
-C
4 -alkyl, C 1
-C
4 -alkoxy, phenyl, C 1 -C4-alkylsulphonyl or phenylsulphonyl,
A
2 furthermore represents in each case optionally fluorine-, chlorine- or bromine-substituted Cl-C6-alkanediyl, C2-C 6 -alkenediyl, C 2
-C
6 -azaalkenediyl, C 2
-C
6 -alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
A
3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, fluorine, chlorine, bromine, represents in each case optionally fluorine-, chlorine- or C 1
-C
4 -alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally fluorine- or chlorine-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, represents in each case optionally fluorine-, chlorine-, cyano-, carboxyl-, C 1
-C
4 -alkyl- and/or C1-C4-alkoxy-carbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxy- 1. carbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 Le A 32 986-Foreign Countries -33carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or represents in each case optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, C 1
-C
4 -alkyl-, C 1 C4-halogenoalkyl-, C 1 -C4-alkyloxy-, C 1 -C4-halogenoalkyloxyand/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-
C
1 -C4-alkyl, phenyl-C1 -C 4 -alkoxy, phenyloxycarbonyl or phenyl-C 1- C4-alkoxycarbonyl,
A
3 furthermore represents in each case optionally fully or partially hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C 1-C 4 -alkyl, furyl-C 1-C 4 -alkyl, thienyl-C 1-C 4 -alkyl, oxazolyl-C 1-C 4 -alkyl, isoxazole-C 1-C 4 -alkyl, thiazole-C 1-C 4 -alkyl, pyridinyl-C 1-C4-alkyl, pyrimidinyl-C 1l-C 4 -alkyl, pyrazolylmethoxy, furylmethoxy, represents perhydropyranylmethoxy or pyridylmethoxy,
R
5 represents hydrogen, cyano, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case optionally fluorineand/or chlorine-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the alkyl groups, and R6 represents hydrogen, cyano, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case optionally fluorineand/or chlorine-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the alkyl groups.
The novel hydrazonecarbonyl compounds of the general formula (VIla) are obtained when arylhydrazines of the general formula (IVa) Le A 32 986-Foreign Countries -34-
NH
2
R
1
HN
R-(
1 (IVa)
R
3 in which R1, R 2 -1 and R 3 are as defined above are reacted with ac-dihalogeno-carbonyl compounds of the general formula (XI)
R
6 R
X
3
(XI)
0 in which
R
5 and R 6 are as defined above and
X
3 represents halogen (in particular chlorine or bromine), if appropriate in the presence of a diluent, such as, for example, water, and if appropriate in the presence of a reaction auxiliary, such as, for example, sodium acetate, at temperatures between 0°C and 100°C (cf. the Preparation Examples), or when in the case that R 6 represents hydrogen arylamines of the general formula (XII)
R
1
HN
R
2 1 R
(XH)
3 Le A 32 986-Foreign Countries in which
R
1
R
2 1 and R 3 are as defined above are diazotized in a customary manner (for example by reaction with sodium nitrite and hydrochloric acid and/or acetic acid), the resulting diazonium compounds are reacted in a customary manner with 1,3-dicarbonyl compounds of the general formula (XII) 0 0 Rs JOR (XIIm) in which
R
5 is as defined above and R represents alkyl (preferably methyl or ethyl) and the resulting compounds of the general formula (XIV) RN R'
I
HN
R2-1 3 in which R, R 1
R
2 -1 R 3 and R 5 are as defined above
(XIV)
are hydrolyzed and decarboxylated in a customary manner.
The formulae (VIII) and (IX) V/ lkoxycarbonylmethylenephosphoranes L F provide general definitions of the and trialkyl phosphonocarboxylates, Le A 32 986-Foreign Countries -36respectively, furthermore required as starting materials in the process according to the invention for preparing compounds of the formula In the formulae (VIII) and
R
4 in each case preferably has that meaning which has already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for R 4 R in each case preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
The starting materials of the formulae (VIII) and (IX) are known chemicals for synthesis.
The processes and according to the invention for preparing the compounds of the formula are preferably carried out in the presence of a diluent.
Suitable diluents are, in general, the customary organic solvents. These preferably include aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons, such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, dichloromethane (methylene chloride), trichloromethane (chloroform) or carbon tetrachloride, dialkyl ethers, such as, for example, diethyl ether, diisopropyl ether, methyl t-butyl ether, ethyl t-butyl ether, methyl t-pentyl ether (MTBE), ethyl t-pentyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethylene glycol dimethyl ether or ethylene glycol diethyl ether, diethylene glycol dimethyl ether or diethylene glycol diethyl ether; dialkyl ketones, such as, for example, acetone, butanone (methyl ethyl ketone), methyl i-propyl ketone or methyl i-butyl ketone, nitriles, such as, for example, acetonitrile, propionitrile, butyronitrile or benzonitrile; amides, such as, for example, N,N-dimethyl-formamide (DMF), N,N-dimethyl-acetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethyl-phosphoric triamide; esters, such as, for example, methyl acetate, ethyl acetate, or -i-propyl acetate, or -s-butyl acetate; sulphoxides, such as, for example, dimethyl sulphoxide; alkanols, such as, for example, methanol, ethanol, n- or i-propanol, s- or t-butanol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol Le A 32 986-Foreign Countries -37monomethyl ether or diethylene glycol monoethyl ether; mixtures thereof with water or pure water. In the process according to the invention it is advantageously also possible to use acetic acid as diluent.
The processes and according to the invention for preparing the compounds of the formula are preferably carried out in the presence of a suitable reaction auxiliary. Suitable reaction auxiliaries are, in general, the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, s- or tbutoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,Ndimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), and 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU).
The process according to the invention for preparing the compounds of the formula is carried out in the presence of a dehydrating agent. Suitable dehydrating agents are the customary dehydrating agents, such as, for example, sulphuric acid, methanesulphonic acid, benzenesulphonic acid, p-toluenesulphonic acid, acetic anhydride and phosphorus oxide.
Le A 32 986-Foreign Countries -38- The process according to the invention for preparing the compounds of the formula is carried out using a nitrating agent. Suitable nitrating agents are the customary nitrating agents, such as, for example, nitric acid and its mixtures with nitrating auxiliaries, such as, for example, sulphuric acid.
When carrying out the processes and according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out at temperatures between -20'C and +200'C, preferably between 0°C and 150'C, in particular between 10°C and 120'C.
The processes according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure in general between 0.1 bar and 10 bar.
For carrying out the processes and according to the invention, the starting materials are generally employed in approximately equimolar amounts.
However, it is also possible to use a relatively large excess of one of the components.
The reaction is generally carried out in a suitable diluent, if appropriate in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for several hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used. The active compounds according to the invention can be used, for example, in connection with the following plants: Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Le A 32 986-Foreign Countries -39- Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.
Le A 32 986-Foreign Countries The compounds of the formula according to the invention have strong herbicidal activity and a broad activity spectrum when applied to the soil and to above-ground parts of plants.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic Le A 32 986-Foreien Countries -41material, such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulphuron, anilofos, asulam, atrazine, azafenidin, azimsulphuron, benazolin(-ethyl), benfuresate, bensulphuron(-methyl), bentazone, benzofenap, N- t benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, V7 Jo) Le A 32 986-Foreign Countries -42 bromofenoxim, bromoxynil, butachior, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chiomethoxyfen, chioramben, chioridazon, chlorimuron(-ethyl), chiomitrofen, chiorsuiphuron, chiortoluron, cinidon(-ethyl), cinmethylin, cinosuiphuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulphuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulphamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachior, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfiuralin, ethametsulphuron(-methyl), ethofumesate, ethoxyfen, ethoxysuiphuron, etobenzanid, fenoxaprop(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasuiphuron, fluazifop(-P-butyl), fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochioridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulphuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosuiphuron, iodosulphron, ioxyni 1, isopropalin, isoproturon, isouron, isoxaben, isoxachiortole, i soxaflutole, i soxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, metamitron, metazachior, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulphuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosuiphuron, norfiurazon, orbencarb, oryzalin, oxadi argyl, oxadiazon, oxasuiphuron, oxaziclomefone, oxy-fluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, preti lachior, primisulphuron(-methyl), prometryn, propachior, propani I, propaquizafop, propisochior, propyzamide, prosulphocarb, prosuiphuron, pyrafl ufen (-ethyl), pyrazolate, pyrazosulphuron(-ethyl), pyrazoxyfen, pyribenzoxi m, Le A 32 986-Foreign Countries -43pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulphuron, sethoxydim, simazine, simetryn, sulcotrione, sulphentrazone, sulphometuron(-methyl), sulphosate, sulphosulphuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulphuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulphuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulphuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.
The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention can Sbe seen from the examples below.
iLe A 32 986-Foreign Countries -44- Preparation Examples: Example 1 F3 N
F
N
CN
F
g (18 mmol) of 3 ,3,3-trifluoro-2-oxo-propanal-lI-(2,5-difluoro-4-cyano-phenylhydrazone) in 150 ml of toluene are admixed with 8.7 g (26 mmol) of methyl (triphenylphosphoranylidene)acetate, and the mixture is stirred at reflux temperature for 3 hours. The mixture is concentrated using a rotary evaporator, and the residue is recrystallized from isopropanol.
This gives 1.3 g (24% of theory) of 2-(2,5-difluoro-4-cyano-phenyl)-5-trifluoromethyl-pyridazin-3-one of melting point 143 0
C.
Example 2
F
3 C
F
H3
C:
~CN
g (18 mmol) of 3 3 ,3-trifluoro-2-oxopropanal-lI-(2,5-difluoro-4-cyano-phenylhydrazone) in 150 ml of toluene are admnixed with 9.4 g (26 mmol) of (1-ethoxycarbonylethylidene)triphenylphosphorane, and the mixture is stirred at reflux I perature for 3 hours. The mixture is concentrated using a rotary evaporator and residue is recrystallized from isopropanol.
Le A 32 986-Foreign Countries This gives 2.41 g (42.5% of theory) of 2-(2,5-difluoro-4-cyano-phenyl)-4-methyl-5trifluoromethyl-pyridazin-3-one of melting point 135 0
C.
Analogously to Example 1 and 2, and in accordance with the general description of the preparation processes according to the invention, it is also possible to prepare the compounds of the formula listed in Table 1 below.
I I R e 0ON R 2 Table 1: Examples of the compounds of the formula (I) Ex.
No. R' R 2
R
3
R
4
R
5
R
6 3 F CN NO 2 H CF 3
H
4 Cl CN NO 2 H CF 3
H
F CN NO 2 H CF 3
CH
3 6 Cl CN NO 2 H CF 3
CH
3 7 F CN NO 2
CH
3
CF
3
H
8 Cl CN NO 2
CH
3
CF
3
H
9 Cl CN OH H CF 3
H
F CN OH CH 3
CF
3
H
11 F CN OCH 3
CH
3
CF
3
H
12 F CN OC 2
H
5
CH
3
CF
3
H
S13 F CN OCH(CH 3 2
CH
3
CF
3
H
Le A 32 986-Foreign Countries -46 Ex.
No. R' R R 3 R4 R 14 F CN OCH 2
CH=CH
2
CH
3
CF
3
H
F CN OCH 2 C=-CH CH 3
CF
3
H
16 F CN OCH(CH 3 )C=-CH CH 3
CF
3
H
17 F CN OCH 2
COOCH
3
CH
3
CF
3
H
18 F CN OCH 2
COOC
2
H
5
CH
3
CF
3
H
19 F CN OCH 2
COOCH(CH
3 2
CH
3
CF
3
H
F CN OCH 2
COOC
5 H, CH 3
CF
3
H
21 F CN OCH(CH 3
)COOC
2
H
5
CH
3
CF
3
H
22 F CN OH H CF 3
H
23 F CN OCH 3 H CF 3
H
24 F CN 0C 2
H
5 H CF 3
H
F CN OCH(CH 3 2 H CF 3
H
26 F CN OCH 2
CH=CH
2 H CF 3
H
27 F CN OCH 2 C-=CH H CF 3
H
28 F CN OCH(CH 3 )C=-CH H CF 3
H
29 F CN OCH 2
COOCH
3 H CF 3
H
F CN OCH 2
COOC
2
H
5 H CF 3
H
31 F CN OCH 2
COOCH(CH
3 2 H CF 3
H
32 F CN OCH 2
COOC
5
H
1 I H CF 3
H
33 F CN OCH(CH 3
)COOC
2
H
5 H CF 3
H
34 F CN COOC 2
H
5
CH
3
CF
3
H
F CN COOC 2
H
5 H CF 3
H
36 F CN CONHCH 3
CH
3
CF
3
H
37 F CN CON(CH 3 2
CH
3
CF
3
H
38 F CN NH 2
CH
3
CF
3
H
39 F CN NH 2 H CF 3
H
F ICN NHSO 2
CH
3
CH
3
CF
3
H
Le A 32 986-Foreign Countries -47- Ex.
No. R' R R 3 R4 R 5 R6 41 F CN NHSO 2
C
2
H
5
CH
3
CF
3
H
42 F CN NIISO 2
CH
2 CI CH 3
CF
3
H
43 F CN NHSO 2
CF
3
CH
3
CF
3
H
44 F CN NHSO 2 CYClopropyl CH 3
CF
3
H
F CN NHSO 2
CH
3 H CF 3
H
46 F CN NH-S0 2
C
2
H
5 H CF 3
H
47 F CN NHSO 2
CH
2 CI H CF 3
H
48 F CN NHSO 2
CF
3 H CF 3
H
49 F CN NHSO 2 Cyclopropyl H CF 3
H
CI CN Nil 2 H CF 3
H
51 CI CN OCH 2 C=-CH H CF 3
H
52 CI CN OCH(CH 3 )C=-CH H CF 3
H
53 CI CN OCH 2
COOCH
3 H CF 3
H
54 Cl CN OCH 2
COOC
2
H
5 H CF 3
H
CI CN OCH 2
COOCH(CH
3 2 H CF 3
H
56 CI CN OCH 2
COOC
5
H
1 H CF 3
H
57 CI CN NHSO 2
CH
3
CH
3
CF
3
H
58 CI CN NIISO 2
C
2
H
5
CH
3
CF
3
H
59 Cl CN OCH 2 C=-CH CH 3
CF
3
H
CI CN OCH(CH 3 )C=-CH CH 3
CF
3
H
61 CI CN OCH 2
COOCH
3
CH
3
CF
3
H
62 CI CN OCH 2
COOC
2
H
5
CH
3
CF
3
H
63 CI CN OCH 2
COOCH(CH
3 2
CH
3
CF
3
H
64 CI CN OCH 2
COOC
5
H
1
CH
3
CF
3
H
F CSNH 2
NHSO
2
CH
3
CH
3
CF
3
H
66 F CSNH 2
NHSO
2
C
2
H
5
CH
3
CF
3
H
671 F CSNII 2
NHSO
2
CH
3 HCF H Le A 32 986-Foreipn Counties -48- Ex.
No. R' R R 3 R R 5 R6 68 F CSNH 2 N7HSO 2
C
2
H
5 H CF 3
H
69 Cl CSNH 2
OCH(CH
3 )C=-CH CH 3
CF
3
H
CI CSNH 2
OCH
2
COOC
5
H
1
CH
3
CF
3
H
71 F CSNH 2
OCH
2
CH=CH
2 H CF 3
H
72 F CSNTI 2
OCH
2 C=-CH H CF 3
H
73 F CSNH 2
OCH(CH
3 )C=-CH H CF 3
H
7 4 CI CSNHi 2
NHSO
2
CH
3 H CF 3
H
CI CSNHi 2 NI{S0 2
C
2
H
5 H CF 3
H
76 F CSNH 2
OCH
2
CH=CH
2
CH
3
CF
3
H
77 F CSNHi 2
OCH
2 C=-CH CH 3
CF
3
H
78 F CSNH 2
OCH(CH
3 )C=-CH CH 3
CF
3
H
79 CI CSNH 2
NHSO
2
CH
3
CH
3
CF
3
H
CI CSNH 2
NHSO
2
C
2
H
5
CH
3
CF
3
H
81 F CN N(SO 2
CH
3 2
CH
3
CF
3
H
82 F CN N(S0 2
C
2
H
5 2
CH
3
CF
3
H
83 F CN N(CH 3
)SO
2
CH
3
CH
3
CF
3
H
84 F CN N(CH 3 )S0 2
C
2
H
5
CH
3
CF
3
H
F CSNHi 2
N(SO
2
CH
3 2
CH
3
CF
3
H
86 F CSNH 2 N(S0 2
C
2
H
5 2
CH
3
CF
3
H
87 F CN SCH 2
COOCH
3
CH
3
CF
3
H
88 F CN SCH 2
COOC
2
H
5
CH
3
CF
3
H
89 F CF 3
NHSO
2
CH
3
CH
3
CF
3
H
F CF 3
NIISO
2
C
2
H
5
CH
3
CF
3
H
91 F CF 3
OCH
2
CH=CH
2
CH
3
CF
3
H
92 F CF 3
OCH
2 C=-CH CH 3
CF
3
H
93 F CF 3
OCH
2
COOC
5
H
1 I CH 3
CF
3
H
94 F CN 2
N(CH
3
)SO
2
CH
3
CH
3
CF
3
H
Le A 32 986-Forei2n Countries -49- Ex.
No. R' R 2R3R4
R
F CSNH 2
N(CH
3 )S0 2
C
2 Hs CH 3
CF
3
H
96 F CSNH 2
N(SO
2
CH
3 2
CH
3
CF
3
H
97 F CSNHi 2 N(S0 2
C
2
H
5 2
CH
3
CF
3
H
98 F CN OCH 2
CH=CH
2 H CF 3
CH
3 99 F CN OCH 2 C=CH H CF 3
CH
3 100 F CN OCH(CH 3 )C=-CH H CF 3
CH
3 101 F CN OCH 2
COOCH
3 H CF 3
CH
3 102 F CN OCH 2
COOC
2
H
5 H CF 3
CH
3 103 F CN OCH 2
COOCH(CH
3 2 H CF 3
CH
3 104 F CN OCH 2
COOC
5
H
1 H CF 3
CH
3 105 F CN OCH(CH 3 )cOOc 2
H
5 H CF 3
CH
3 106 F CN NHSO 2
CH
3 H CF 3
CH
3 107 F CN NHSO 2
C
2
H
5 H CF 3
CH
3 108 F CN NHSO 2
CH
2 CI H CF 3
CH
3 109 F CN NHSO 2
CF
3 H CF 3
CH
3 110 F CSNH 2
NHSO
2
CH
3 H CF 3
CH
3 11I F CSNH 2 NI{S0 2
C
2
H
5 H CF 3
CH
3 112 F CN H H CF 3
H
113 F CSNH 2 H H CF 3
H
114 F CN H CH 3
CF
3
H
115 F CSNH 2 H CH 3
CF
3
H
116 H CN F H CF 3
H
117 H CSNH 2 F H CF 3
H
118 H CN F CH 3
CF
3
H
119 H CSNH 2 F CH 3
CF
3
H
120 tF CSNH 2 F CH 3
CF
3
H
Le A 32 986-Foreign Countries Le A 32 986-Foreign Countries 51 Ex.
No. R' R R 3 R4 R5 R6 128 F CN 0 C3 CH 3
CF
3
H
H C 2
U
129 F CN N7HSO 2
C
2
H
5
CH
3
CF
3
CH
3 130 F CON}{ 2
OCH
3
CH
3
CF
3
H
131 F CN OCH(CH 3
)COOCH(CH
3 2
CH
3
CF
3
H
132 F CN OCH(C 2
H
5
)COOCH(CH
3 2
CH
3
CF
3
H
133 F CN NIISO 2
CH
3
CH
3
CF
3
COOC
2
H
134 F CN NIISO 2
C
2
H
5
CH
3
CF
3
COOC
2
H
135 F CN OCH(C 2
H
5
)COOCH
3
CH
3
CF
3
H
136 F CN OCH(C 2
H
5
)COOC
2
H
5
CH
3
CF
3
H
137 F CN OCH(CH 3
)COOCH
3
CH
3
CF
3
H
138 F CN OCH 2 CN CH 3
CF
3
H
139 F CN 0H CF 3
H
140 F CN 0 CH 3
CF
3
H
141 F CN 0H CF 3
CH
3 142 F CN 0 CH 3
CF
3
CH
3 143 F CN 0 H CF 3
H
144 F CN 0 CH 3
CF
3
H
145 F CN 0 H CF 3
CH
3 2')e Le A 32 986-Foreign Countries -52- Ex.
No. R' R2R3R4 R5 R6 146 F CN
CH
3
CF
3
CH
3 147 F CN H 147 F CN CH CF 3
H
148 F CN CH 3
CF
3
CH
149 F CN H CF 3
CH
3 c 150 F CN 0"a l CH 3
CF
3
CH
3 151 F CN 0 0H CF 3
H
0Nz 153 F CN 0H CF 3
CH
3 Le A 32 986-Foreign Countries 53 Le A 32 986-Foreig-n Countries -54- LeA3 86-ForeigCountiies 55 Ex.
No. R' R R 3 R4 R 5 R6 180 F CN H CF 3
H
181 F CN CH 3
CF
3
H
o 0 182 F CN H CF 3
CH
3 o
D
183 F CN
CH
3
CF
3
CH
3 184 F CN ,CHO H CF 3
H
185 F CN 0O..-CHO CH 3
CF
3
H
186 F CN 0 CHO H CF 3
CH
3 187 F CN 0O--CHO CH 3
CF
3
CH
3 0 188 F CN Ollj1.H H CF 3
H
0 189 F CN CH 3
CF
3
H
190 F CN 0o..JtIO H CF 3
CH
3 0 191 F CN
CH
3
CF
3
CH
3 0 192 F CN 0 H CF 3
H
CH
3 0 193 F CN 0 CH 3
CF
3
H
CH
3
S
.3 0V Q Le A 32 986-Foreign Countries 56 Le A 32 986-Foreign Countries -57 Le A 32 986-Forei~n Countries Ex.
No. R' R2 216 F CN
OI
C
217 F CN 0 N 218 F CN
OI
219 F CN
ON
220 F CN 0..
221 F CN 0-, 222 F CN 0 223 F CN 0 224 F CN 0 225 F CN 0, -58- Le A 32 986-Foreign Countries 59 Le A 32 986-Foreign Countries Le A 32 986-Foreign Countries -61- Le A 32 986-Foreign Countries -62- 0 0 CH 3
OH
3 0N 0
O
Le A 32 986-Foreign Countries -63- The compound listed above in Table 1 as Example 10 can, for example, be prepared as follows: 2.0 g (6.1 mmol) of 2-(4-cyano-2-fluoro-5-methoxy-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one in 100 ml of dichloromethane are admixed with 18.4 g (18.3 mmol) of boron tribromide (1 molar solution in dichloromethane), the mixture is stirred at 25 0 C for 16 hours, 150 ml of water are then added slowly and the organic phase is dried over sodium sulphate and concentrated using a rotary evaporator.
This gives 1.8 g (94% of theory) of 2-(4-cyano-2-fluoro-5-hydroxy-phenyl)-4methyl-5-trifluoromethyl-pyridazin-3-one of melting point 189 0
C.
The compound listed above in Table 1 as Example 11 can, for example, be prepared as follows: 3.9 g (13.5 mmol) of 3,3,3-trifluoro-2-oxopropanal-1-(4-cyano-2-fluoro-5-methoxyphenylhydrazone) in 150 ml of toluene are admixed with 7.0 g (19.3 mmol) of (1-ethoxycarbonyl-ethylidene)-triphenylphosphorane, and the mixture is stirred under argon at reflux temperature for 2 hours. After concentration using a rotary evaporator, the residue is recrystallized from isopropanol.
Le A 32 986-Foreign Countries -64- This gives 2.2 g (50% of theory) of 2-( 4 -cyano-2-fluoro-5-methoxy-phenyl)-4methyl-5-trifluoromethyl-pyridazin-3-one of melting point 178 0
C.
The compound listed above in Table 1 as Example 13 can, for example, be prepared as follows:
F
3 C
F
N F H3 C
CN
'CH(CH
3 2 3.8 g (8 mmol) of 2-(4-bromo-2-fluoro-5-isopropoxy-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one are dissolved in 10 ml of N-methyl-pyrrolidone, admixed with 0.9 g (9.6 mmol) of copper(I) cyanide and heated under reduced pressure (0.1 mbar) at 90 0 C, with distillative removal of 2 ml of solvent. The mixture is then heated under atmospheric pressure (under argon) to 170 0 C and stirred at this temperature for 6 hours. After cooling to 20 0 C, the mixture is stirred with 100 ml of ethyl acetate, admixed with 10% strength ammonia solution and filtered. The filtrate is washed with water, dried with sodium sulphate and carefully concentrated under waterpump vacuum.
This gives 3.0 g (89% of theory) of 2-(4-cyano-2-fluoro-5-isopropoxy-phenyl)-4methyl-5-trifluoromethyl-pyridazin-3-one as crude product (content: 85% according to HPLC).
For further purificatiofi, 2 g of this crude product are chromatographed over silica gel using dichloromethane. This gives the pure product (0.7 g, content: 97% according to /PLC) of melting point 121 0
C.
Le A 32 986-Foreign Countries The compound listed above in Table 1 as Example 15 can, for example, be prepared as follows:
F
3
C.
0.6 g (1.9 mmol) of 2-(4-cyano-2-fluoro-5-hydroxy-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one in 30 ml of N,N-dimethyl-formamide are stirred at 25 0 C with 0.4 g (3 mmol) of potassium carbonate and 0.31 g (2.1 mmol) of propargyl bromide pure) for 60 minutes, and the mixture is then admixed with water and adjusted to pH 6 using conc. hydrochloric acid, and precipitated product is filtered off with suction, washed with water and dried. For purification, the product is recrystallized from isopropanol.
This gives 0.3 g (44% of theory) of 2-(4-cyano-2-fluoro-5-propargyloxy-phenyl)-4methyl-5-trifluoromethyl-pyridazin-3-one of melting point 145°C.
The compound listed above in Table 1 as Example 18 can, for example, be prepared as follows: Le A 32 986-Foreign Countries -66- 0.7 g (2.24 mmol) of 2 4 -cyano-2-fluoro-5-hydroxy-phenyl)-4-methyl-5-trifluoro methyl-pyridazin-3-one in 30 ml of N,N-dimethyl-formamide are stirred at 25 0 C with 0.48 g (3.5 mmol) of potassium carbonate and 0.42 g (2.5 mmol) of ethyl bromoacetate for 60 minutes, the mixture is then admixed with water and adjusted to pH 6 using conc. hydrochloric acid, and precipitated product is filtered off with suction, washed with water and dried.
This gives 0.64 g (71% of theory) of 2-[4-cyano-5-(ethoxycarbonylmethoxy)-2fluoro-phenyl]-4-methyl-5-trifluoromethyl-pyridazin-3-one of melting point 95 0
C.
The compound listed above in Table 1 as Example 41 can, for example, be prepared as follows:
F
3
C
H3C
CN
HC
CN
,NH
H
5 C2-SO 2 5.5 g (15 mmol) of 3,3,3-trifluoro-2-oxo-propanal- 1-(4-cyano-5-ethylsulphonylamino-2-fluoro-phenylhydrazone) in 100 ml of toluene are admixed with 8.2 g (22.5 mmol) of (1 -ethoxycarbonyl-ethylidene)-triphenylphosphorane, and the mixture is stirred under argon at reflux temperature for 2 hours. After concentration using a rotary evaporator, the residue is chromatographed over silica gel using toluene/ethyl acetate 3:1.
This gives 3.6 g (59.5% of theory) of 2-(4-cyano-5-ethanesulphonamino-2-fluorophenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of melting point 198 0
C.
The compound listed above in Table 1 as Example 66 can, for example, be prepared follows: -h IU/ Le A 32 986-Foreign Countries -67-
F
3 C N F HI I H3C'
N
O
.NH NH 2
H
s
C,-SO
2 1.6 g (4 mmol) of 2-(4-cyano-5-ethylsulphonylamino-2-fluoro-phenyl)-4-methyl-5trifluoromethyl-pyridazin-3-one are initially charged in 30 ml of pyridine and 12 ml of triethylamine and, at 60-70 0 C, hydrogen sulphide is introduced underneath the surface of the liquid for 90 minutes. After the reaction has ended, the mixture is flushed with nitrogen for 60 minutes, cooled to 25 0 C and stirred with ice-water, precipitated product is filtered off with suction and the residue is washed with water and dried.
This gives 0.9 g (51% of theory) of 2-(2-fluoro-5-ethylsulphonylamino-4-thiocarbamoyl-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of melting point 88 0
C
The compound listed above in Table 1 as Example 122 can, for example, be prepared as follows:
F
3 C N F
I
H3
CN
N
C-SO
1.2 g (3 mmol) of 2--(4-cyano-5-ethylsulphonylamino-2-fluoro-phenyl)-4-methyl-5trifluoromethyl-pyridazin-3-one in 50 ml of acetonitrile are admixed with 0.6 g (6 mmol) of triethylamine and 0.77 g (6 mmol) of 3-chloro-propionyl chloride, and /the mixture is stirred at 25 0 C for 12 hours. After concentration using a rotary Le A 32 986-Foreign Countries -68evaporator, the residue is stirred with water and acidified with conc. hydrochloric acid, and precipitated product is filtered off with suction, washed with water and dried.
This gives 1.1 g of (2-[5-(N-ethenylcarbonyl-N-ethylsulphonylamino)-4-cyano-2fluoro-phenyl]-4-methyl-5-trifluoromethyl-pyridazin-3-one of melting point 96 0
C.
The compound listed above in Table 1 as Example 129 can, for example, be prepared as follows:
H
3
F
3 0 N
F
I I
N
H
3 0
CN
,NH
H
5 C2-SO 2 1.22 g (3.2 mmol) of 1-[(4-cyano-5-methylsulphonylamino-2-fluoro-phenyl)hydrazono]-3-ethoxycarbonyl-1-chloro-1,1 -difluoro-propan-2-one in 50 ml of toluene are admixed with 1.74 g (4.8 mmol) of (1-ethoxycarbonyl-ethylidene)-triphenylphosphorane, and the mixture is stirred under argon at reflux temperature for 2 hours.
After concentration using a rotary evaporator, the residue is chromatographed over silica gel using toluene/ethyl acetate 3:1.
This gives 0.2 g (15% of theory) of 2-(4-cyano-5-ethanesulphonamino-2-fluorophenyl)-4,6-dimethyl-5-trifluoromethyl-pyridazin-3-one of melting point 191 0
C.
The compound listed above in Table 1 as Example 107 can, forexample, be prepared as follows: Le A 32 986-Foreip-n Countries -69- F3C H 3
F
3 0 F oNO H 5
CF-SO
2 1.22 g (3.2 mmol) of 1-[(4-cyano-5-methylsulphonylamnino-2-fluoro-phenyl)hydrazono]-3-ethoxycarbonyl-l1-chioro- 1,1 -difluoro-propan-2-one in 50 ml of toluene are admixed with 1.7 g (4.8 mmol) of (1-ethoxycarbonyl-methylidene)-triphenylphosphorane, and the mixture is stirred under argon at reflux temperature for 2 hours.
After concentration using a rotary evaporator, the residue is chromatographed over silica gel using toluene/ethyl acetate 3: 1.
This gives 0.2 g (15.5% of theory) of 2-(4-cyano-5-ethylsulphonylamino-2-fluorophenyl)-6-methyl-5-trifluoromethyl-pyridazin-3-one of melting point 143 0
C.
Physical data for compounds listed in Table 1 are listed in Table la below.
Le A 32 986-Foreign Countries 70 Table Ila: Ex. No. Physical data 189'C 2.27 a) I1I 178'C 2.76 a) 12 log.P =3.12 a) 13 121 *C 3.40 a) 14 log.P =3.24 a) NMR(CDCl 3 2.44-2.45; 4.65-4.68; 7.46-7.49; 8.03 ppm 145'C 2.92 a) 18 log.P 3.04 a) 21 11 8'C 23 174'C log.P 2.4 1 a) 24 140'C log.P 2.76 a) 202'C log.P 2.91 a) 41 198'C log.P 2.42 a) 46 174'C 66 88'C log.P 2.44 a) 84 98'C 2.68 a) Le A 32 986-Foreign Countries -71- Ex. No. Physical data 107 143'C 2.3 1 a) 112 160'C 120 183'C 2.43 a) 121 149'C log.P 2.70 a) 122 log.P 2.89 a) 123 220'C 124 135'C log.P 3.3 a) 125 log.P 3.03 a) 126 165'C log.P 3.29 a) 127 116'C Iog.P 2.97 a) 128 131'C 129 189'C log.P 2.65 a) 130 142'C 1.94 a) log.P =3.62 a) 131 -NMR(CDC1 3 1.17-1.19; 1.25-1.27; 1.70-1.72; 2.43; 4.72-4.78; 6.94-6.96; 7.99 ppm log.P 3.9 a) 132 NNM(CDCI 3 1.13-1.26; 2.04-2.13; 2.43; 4.56-4.60; 7.46-7.49 ppm Le A 32 986-Foreipn Countries 72 Ex. No. Physical data 133 134'C 134 135 NMR(CDCl 3 2.43-2.44; 3.77; 4.61-4.63; 8.01 ppm 136 NMR(CDC1 3 2.07-2.12; 2.43-2.44; 4.19-4.24; 7.46- 7.49; 8.00 ppm 137 NMvR(CDCI 3 1.72-1.74; 2.36; 4.77-4.82; 7.47-7.50; 8.01 ppm 138 NMR(CDCl 3 2.44-2.46; 4.93; 7.55-7.58; 8.05 ppm 158 og.P =3.51 NMR(CDC1 3 2.44-2.54; 5.03; 7.26; 8.03 ppm 161 83'C log.P 3.65 256 97'C 257 221'C log.P 4.17 log.P 4.64 258 NNM(CDC1 3 ):1.54-1.55; 1.99-2.09; 2.42-2.44;4.25-4.26; 6.91-6.93 ppm 259 161 'C log.P 3. Iog.P 2.93 260 NNM(CDC1 3 1.49-1.54; 2.01; 2.44-2.46; 4.51-4.52; 7.60-7.63; 8.05 ppm 261M.: log.P 2.91 Le A 32 986-Foreign Countries -73- The logP values given above in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) using a reverse-phase column (C 18). Temperature: 43 0 C. o Mobile phases for the determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile the corresponding test results in Table 1 are labelled a).
Mobile phases for the determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to acetonitrile the corresponding test results in Table 1 are labelled b).
Calibration was carried out using unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones).
The lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.
Le A 32 986-Foreign Countries -74- Starting materials of the formula (IV): Example (IV-1)
F
H
2
N
CN
.NH
H
s C2-SO 2 g (50 mmol) of 81% pure 4 (known from DE-A-4414568) in a mixture with 100 ml of acetic acid and 20 ml of conc. sulphuric acid are cooled to 5 0 C and admixed a little at a time with 12.7 g (100 mmol) of nitrosylsulphuric acid, and the mixture is stirred at from 5°C to 10 0 C for 6 hours; a solution of 33.6 g (140 mmol) of tin(II) chloride dihydrate dissolved in ml of conc. hydrochloric acid is then added dropwise at 10 0 C. The mixture is stirred at 25 0 C for 12 hours, then stirred with ice-water and made alkaline using cone.
ammonia. The precipitated salt is filtered off with suction, the filtrate is made slightly acidic using conc. hydrochloric acid and extracted with ethyl acetate, and the extract is dried over sodium sulphate and concentrated using a rotary evaporator. The residue is recrystallized from isopropanol.
This gives 12.9 g (33% of theory) of 4-cyano-5-ethylsulphonylamino-2-fluorophenylhydrazine.
Example (IV-1)
F
H
2
NA
Le A 32 986-Foreign Countries Step 1
F
H
2
N
CN
'CH
3 9.2 g (0.4 mol) of sodium metal are dissolved in 200 ml of methanol, and the solution is admixed with 30.8 g (0.2 mol) of 2,5-difluoro-4-cyano-aniline. The stirring apparatus is fitted with a distillation head and heated to 90-95°C, and about 4/5 of the amount of metanol is distilled off. After an extra stirring time of 30 minutes at 95 0
C,
heating is removed, the content of the flask is admixed with water, cooled to and adjusted to pH 5 using conc. hydrochloric acid, and precipitated product is filtered off with suction, washed with water and dried.
This gives 31.2 g (94% of theory) of 4-cyano-2-fluoro-5-methoxy-aniline of melting point 99 0 C, purity (method): 99% (HPLC, logP 1.34).
Step 2 Variant a
F
H
2
N
CN
'CH
3 4.7 g (2.8 mmol) of 4-cyano-2-fluoro-5-methoxy-aniline are admixed with 100 ml of conc. hydrochloric acid and 30 ml of water, and the mixture is briefly heated to and then cooled to 0°C. A solution of 2.6 g of sodium nitrite dissolved in 30 ml of water is then added dropwise, and the mixture is stirred at from 5 0 C to 10 0 C for minutes. The mixture is then filtered and the filtrate is, at o0C, added dropwise to a Ssolution of 18 g (8 mmol) of tin(H) chloride dihydrate in 100 ml of conc.
Le A 32 986-Foreign Countries -76hydrochloric acid. The suspension is then stirred at room temperature (20 0 C) for minutes, made alkaline using 45% strength aqueous sodium hydroxide solution and extracted repeatedly with ethyl acetate. The organic phase is dried over sodium sulphate and concentrated under waterpump vacuum using a rotary evaporator.
This gives 3 g (60% of theory) of 4-cyano-2-fluoro-5-methoxy-phenylhydrazine of melting point 160 0
C.
Step 2 Variant b
F
CN
CH
3 g (0.5 mol) of sodium metal are dissolved in 400 ml of methanol, and the solution is admixed with 68 g (0.4 mol) of 2,5-difluoro-4-cyano-phenylhydrazine. The stirring apparatus is fitted with a distillation head and heated at from 80 0 C to 85 0 C, and about 80% of the methanol are distilled off. After an extra stirring time of 3 hours at 85°C, heating is removed, the content of the flask is admixed with water, cooled to 0 C and neutralized using conc. hydrochloric acid, and precipitated product is filtered off with suction, washed with water and dried. For purification, the product is recrystallized from ethanol.
This gives 39 g (54% of theory) of 4-cyano-2-fluoro-5-methoxy-phenylhydrazine of melting point 163 0
C.
Le A 32 986-Foreign Countries -77- Starting materials of the formula (VII): Example (VII-1)
F
3 C N
F
0 HN
CN
F
30 g (370 mmol) of sodium acetate are initially charged in 200 ml of water. With icecooling, 25 g (93 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone are added dropwise, and the mixture is stirred at room temperature (about 20 0 C) for 30 minutes. The reaction mixture is then admixed with 12 g (72 mmol) of 2,5-difluoro-4-cyanophenylhydrazine and stirred at from 40 0 C to 50 0 C for 2 hours. The cold precipitated product is filtered off with suction, washed with water and dried.
This gives 19 g (95.4% of theory) of 3,3,3-trifluoro-2-oxopropanal-l-(2,5-difluoro-4cyano-phenylhydrazone) of melting point 181°C.
Example (VII-2)
F
F3CXN 0 C N
'CH
3 7 g (87 mmol) of sodium acetate in 100 ml of water are admixed with 5.94 g (22 mmol) of 1,1-dibromo-3,3,3-trifluoro-acetone, and the mixture is stirred at room temperature (about 20°C) for 30 minutes, admixed with 3.0 g (17 mmol) of 4-cyanoand stirred at from 40 0 C to 50 0 C for 60 minutes and at 95 0 C for 10 minutes. After cooling to 20 0 C, the precipitated product is filtered off with suction, washed with water and dried.
Le A 32 986-Forei~yn Countries -78- This gives 4.1 g (83% of theory) of 3 3 3 -trifluoro-2-oxo-propanal-1-(4-cyano-2of melting point 168'C.
Example (VII-3)
F
F3C Y -A
H
5
CF-SO
2 4.1 g (50 mmol) of sodium acetate in 50 ml of water are stirred at 80'C with 3.6 g of 1,1-dibromo-3,3,3-trifluoro-acetone, the mixture is admixed at 25'C with 2.58 g mmol) of 4-cyano-5 -ethyl sulphonylamino-2-fluoro-phenylhydrazine, stirred at from to 50'C for 90 minutes and cooled to 10 0 C, and precipitated product is filtered off with suction, washed with water and dried.
This gives 3.03 g (83% of theory) of 3,3,3-trifluoro-2-oxopropanal-1-(4-cyano-5ethyl sulphonylamino-2-fluoro-phenylhydrazone) of melting point 1 27 0
C.
Example (VII-4)
OH
3 H F
F
3 C 'N 0
C
H
5 Ci S0 2 4.1 g (50 mmol) of sodium acetate in 50 ml of water are stirred at 80'C with 3.6 g of 3,3-dibromo- 1,1, 1-trifluoro-2-butanone for 30 minutes, and the mixture is admixed at 0 C with 2.58 g (10 mmol) of 4-cyano-5-ethylsulphonylamino-2-fluoro-phenyl- Le A 32 986-Foreign Countries -79hydrazine, stirred at from 40 0 C to 50 0 C for 2 hours and cooled to 10 0 C. The precipitated product is filtered off with suction, washed with water and dried.
This gives 3.2 g (84.2% of theory) of 1,1,1-trifluoro-2-oxo-butanal-3-(4-cyano-5ethylsulphonylamino-2-fluoro-phenylhydrazone) of melting point 211 C.
Precursors of the formula (XIV): Example (XIV-1)
C
2 Hs
F
F
3
C-CF
2
CN
,NH
H
3 C-SO2 6.87 g (30 mmol) of 4-cyano-5-methylsulphonylamino-2-fluoro-aniline are initially charged in 100 ml of acetic acid, 4.7 g (34 mmol) of nitrosylsulphuric acid (92% strength) are introduced a little at a time at 20 0 C with ice-cooling, and the mixture is stirred at 25 0 C for 2 hours. At 5-10 0 C, the mixture is subsequently added dropwise to a suspension of 10.6 g (45 mmol) of ethyl pentafluoropropinylacetate and 16.4 g (200 mmol) of sodium acetate in 200 ml of ethanol, the mixture is stirred at 25 0 C for 12 hours and stirred into water, and precipitated product is filtered off with suction, washed with water and dried. For purification, the product is recrystallized from isopropanol.
This gives 8.6 g (60.5% of theory) of l-[(4-cyano-5-methylsulphonylamino-2-fluorophenyl)hydrazono]-4-ethoxycarbonyl-1,1,1,2,2-pentafluorobutan-3-one of melting point 165 0
C.
Le A 32 986-Foreign Countries Example (XIV-2) V F
F
2
CIC
CN
,NH
H3C-SO2 10.7 g (47 mmol) of 4-cyano-5-methylsulphonylamino-2-fluoro-aniline are initially charged in 100 ml of acetic acid, 7.3 g (53 mmol) of nitrosylsulphuric acid (92% strength) are introduced at 20 0 C a little at a time with ice-cooling, and the mixture is stirred at 25 0 C for 2 hours. At from 5 0 C to 10 0 C, the mixture is then added dropwise to a suspension of 14.2 g (71 mmol) of ethyl 1,1,1-difluorochloroacetoacetate and 26 g (313 mmol) of sodium acetate in 200 ml of ethanol, the mixture is stirred at 25 0
C
for 12 hours and stirred into water, and precipitated product is filtered off with suction, washed with water and dried.
This gives 13.7 g (66% of theory) of 1-[(4-cyano-5-methylsulphonylamino-2-fluorophenyl)hydrazono]-3-ethoxycarbonyl-l,l-difluoro-l-chloro-propan-2-one of melting point 175 0
C.
Le A 32 986-Foreign Countries -81 Use Examples: In the use examples, the following known compounds are used for comparison: H 3 C N
I
I
N
CI
NH
2
(A)
2-(5-amino-2,4-dichloro-phenyl)-5-methyl-3 (2H)-pyridazinone known from WO 9639392.
H
3 C NN
CI
I I B qN 0 CI
NO
2
(B)
4-bromo-2-(2,4-dichloro-5-nitro-phenyl)-5-methyl-3 (2H)-pynfdazinone known from WO 9639392.
H 3 C NN
CI
I I B
QN
0 C
NH
2
(C)
2-(5-amino-2,4-dichloro-phenyl)-4-bromo-5-methyl-3 (2H)-pyridazinone known from WO 9639392.
Le A 32 986-Foreign Countries 82 H3 N
CI
N
0 C,
NO
2
(D)
2-(2,4-dichloro-5-nitro-phenyl)-5-methyl-3(21{)-pynidazinone known from WO 9639392.
H
3 C' ~N
F
N
O CN F
(E)
2,5-difluoro-4-(4-methyl-6-oxo-1I(6H)-pyridazinyl)-benzonitrile known from WO 9639392.
Le A 32 986-Foreign Countries -83- Example A Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amount of active compound desired is applied per unit area. The concentration of the spray liquor is chosen so that the particular amount of active compound desired is applied in 1000 litres of water per hectare.
After three weeks, the degree of damage to the plants is rated in damage in comparison to the development of the untreated control.
The figures denote: 0% no effect (like untreated control) 100% total destruction In this test, for example, the compounds of Preparation Example 1, 2, 12, 13, 24, t46, 66, 84, 107, 112, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129 and 133 s onsiderably stronger activity against weeds than the known compounds and Le A 32 986-Foreign Countries -84- Example B Post-emergence test Solvent: Emulsifier: To produce a compound is emulsifier is concentration.
5 parts by weight of acetone 1 part by weight of alkylaryl polyglycol ether suitable preparation of active compound, 1 part by weight of active mixed with the stated amount of solvent, the stated amount of added and the concentrate is diluted with water to the desired Test plants of a height of 5-15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in damage in comparison to the development of the untreated control.
The figures denote: 0% 100% no effect (like untreated control) total destruction In this test, for example, the compounds of Preparation Example 1, 2, 12, 13, 24, 41, 46, 66, 84, 107, 112, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129 and 133 show considerably stronger activity against weeds than the known compounds and Le A 32 986-Forein Countries Example C Phaedon larvae test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of S 10 emulsifier, and the concentrate is diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with mustard beetle larvae (Phaedon cochleariae) while the leaves are still moist.
After the desired period of time, the kill in is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
20 In this test, for example, the compounds of Preparation Examples 1 and 2 show good activity.
Note: Amendments have been made to the claims which appear hereafter in order to further define the invention. These amendments are based on preferments of the various groups of the compounds described herein. For integrity of the text, and of the specification as filed, corresponding amendments have not been made to the statement of invention which appears on pages 1 to 4.
The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge in Australia.
Claims (15)
1. Substituted phenylpyridazinones of the general formula (I) in which R 1 represents hydrogen, fluorine or chlorine, R 2 represents cyano or thiocarbamoyl, r r r r r r r R 3 represents the grouping -A 1 -A 2 -A 3 in which A 1 represents a single bond, represents oxygen, sulphur, -SO2-, -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, methyl, ethyl, n- or i-propyl, methyl- sulphonyl or ethylsulphonyl, A 1 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, pro- pane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl or pro- pene-1,3-diyl, A 2 represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, methyl, ethyl, n- or i-propyl, -87- methoxy, ethoxy, n- or i-propoxy, methylsuiphonyl, ethyl- suiphonyl, n- or i-propyl suiphonyl or phenylsuiphonyl, A 2 furthermore represents methylene, ethane-i 1 -diyl, ethane-1,2-diyl, propane-i,1-diyl, propane-i ,2-diyl, pro- pane-i,3-diyl, ethene-1,2-diyl, propene-1,2-diyl or pro- pene-1,3-diyl, A 3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, suipho, fluorine, chlorine, bromine, represents in each case unsubstituted or fluorine-, chlorine-, methoxy- or ethoxy substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, n-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propyl- thio, s- or t-butylthio, methylsulphinyl, ethylsuiphi- nyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsuipho- .:nyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i- propoxycarbonyl, represents in each case unsubstituted or fluorine or chlorine-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycar- bonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycar- bonyl or butinyloxycarbonyl, represents in each case unsubstituted or fluorine-, chlorine-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclo- \S T %qpentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclo- pentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutyl- methyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyl- -88- methoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclo- hexylmethoxy, cyclopentylideneamino, cyclohexylidene- amino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbo- nyl, or represents in each case unsubstituted or nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy, trifluoromethoxy-, methoxycarbonyl- and/or ethoxycarbonyl-substitUted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbofyl or benzyloxycarbonyl, A 3 furthermore represents pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolyl- methyl, isoxazolemethyl, thiazolemethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy, R 4 represents hydrogen or methyl, R 5 represents trifluoromethyl, and R 6 represents hydrogen, cyano, thiocarbamoyl, nitro, fluorine, chlorine, bromine, or represents in each case unsubstituted or fluorine-and/or chlorine-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethyl- amino, dimethylamino, methoxycarbofyl or ethoxycarbonyl. -89-
2. Substituted phenylpyridazinones according to claim 1, in which R 1 represents fluorine, R 2 represents cyano or thiocarbamoyl, R 3 represents the grouping -A 1 -A 2 -A 3 in which A 1 represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, methyl, ethyl, n- or i-propyl, methyl- sulphonyl or ethylsulphonyl, A 1 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, pro- :'pane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl or pro- pene-1,3-diyl, 20 A 2 represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-A 4 in which A 4 <3 represents hydrogen, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethyl- sulphonyl, n- or i-propyl sulphonyl or phenylsulphonyl, •e A 2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, pro- pane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl or pro- pene-1,3-diyl, oST A 3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, j represents in each case unsubstituted or fluorine-, chlorine-, methoxy- or ethoxy substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, n-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propyl- thio, s- or t-butylthio, methylsulphinyl, ethylsulphi- nyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulpho- nyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i- propoxycarbonyl, represents in each case unsubstituted or fluorine or chlorine-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylidenearnino, propenyloxycar- bonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycar- bonyl or butinyloxycarbonyl, represents in each case unsubstituted or fluorine-, chlorine-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclo- butylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo- propylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexyli- deneamino, cyclopentyloxycarbonyl, cyclohexyloxycar- bonyl, cyclopentylmethoxycarbonyl or cyclohexylmeth- oxycarbonyl, or represents in each case unsubstituted or nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy, trifluoro- methoxy-, methoxycarbonyl- and/or ethoxycarbonyl-sub- stituted phenyl, phenyloxy, benzyl, phenylethyl, benzyl- oxy, phenyloxycarbonyl or benzyloxycarbonyl, OI SOF~\~ -91- R 4 represents hydrogen or methyl, R 5 represents trifluoromethyl, and R 6 represents hydrogen, methyl or ethoxycarbonyl. S *5
3. Substituted phenylpyridazinones according to Claim 1, characterized in that R 1 represents fluorine.
4. Substituted phenylpyridazinones according to any of Claims 1 or 2, characterized in that R 2 represents cyano.
Substituted phenylpyridazinones according to any of Claims 1 or 2, characterized in that R 1 represents fluorine and R 2 represents cyano.
6. Substituted phenylpyridazinones according to Claim 5, characterized in that R 4 and R 6 represent hydrogen or methyl.
7. Substituted phenylpyridazinones according to Claim 6, characterized in that R 3 represents A 3
8. Substituted phenylpyridazinones according to Claim 6, characterized in that A 1 represents -NH- and A 2 represents SO 2
9. Substituted phenylpyridazinones according to Claim 6, characterized in that A 1 represents methylsulphonyl or ethylsulphonyl and A 2 represents -CO-.
10. Process for preparing substituted phenylpyridazinones according to YUS any of Claims 1 to 9, characterized in that FFIC halogenoarenes of the general formula (II) F I -92- X' R 3 in which R 1 R 2 and R 3 are as defined in any of Claims 1 or 2 and X 1 represents halogen are reacted with pyridazinones of the general formula (III) R 6 R N R4 'H(I) 0 in which R 4 R 5 and R 6 are as defined in any of Claims 1 or 2, or with acid adducts or alkali metal salts of compounds of the S. formula (III) if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or that C. arylhydrazines of the general formula (IV) H N R' HN R 2 (IV) R C e R 3 -93- in which R 1 R 2 and R 3 are as defined in any of Claims 1 or 2 are reacted with 9I-trihalomethyl-enones of the general formula (V) R 6 R 5 RR 4 O (V R C(X 2 3 in which R 4 R 5 and R 6 are as defined in any of Claims 1 or 2 and X 2 represents halogen, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or that hydrazonecarboxylic acids of the general formula (VI) o o a B a. a a a a S •god p.: o*o eol eooo (VI) in which R 1 R 2 R 3 R 4 R 5 and R 6 are as defined in any of Claims 1or 2 are condensed with ring-closure, i.e. reacted with a dehydrating agent, _b OFFI, 25 I' -94- or that 2 ,4-disubstituted phenylpyridaziflofles of the general formula (la) in which R 1 R 2 R 4 R 5 and R 6 are as defined in any of Claims 1 or 2, are nitrated, i. e. reacted with a nitrating agent, or that 0. S 5 S. S *5 hydrazonecarbonyl compounds of the general formula (VII) R N R' o HN R 3 in which R 1 R 2 R 3 R 5 and R 6 are as defined in any of Claims 1 or 2 reacted with alkoxycarbonylmethylenePhosphoranes of the general f ormula (VIII) CO 2 R R 4,''PC6H53(VI 11) in which R 4 is as defined in any of Claims 1 or 2 and R represents alkyl having 1 to 6 carbon atoms, or with trialkyl phosphonocarboxylates of the general formula (IX) CO 2 R (IX) R4 PO(OR) 2 in which R 4 is as defined in any of Claims 1 or 2 and R represents alkyl having 1 to 6 carbon atoms, in each case optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent.
11. Hydrazonecarbonyl compounds of the general formula (Vlla) SR 6 R. R o. N R R 0 HN R 2 -1 represents cyano, carbamoyl, thiocarbamoyl, or represents in each case unsubstituted or fluorine- and/or chlorine-substituted alkyl, alkoxy or alkylthio having in each case 1 or 2 carbon atoms, R 3 represents the grouping -A 1 -A 2 -A 3 in which -96- Al represents a single bond, represents oxygen, sulphur, -SO 2 -GO- or the grouping -N-A 4 in which A 4 represents hydrogen, hyd roxyl, Cl-C 4 -alkyl, C-4 alkenyl, C 3 -0 4 -alkinyl, C 1 -C 4 -alkoxy, phenyl, C 1 -C 4 -alkyl- sulphonyl or phenylsuiphonyl, A 1 furthermore represents in each case unsubstituted or fluorine-, chlorine- or bromine-substituted C 1 -C 6 -alkane- d jyl, C 2 -C 6 -alkenediyl, C 2 -C 6 -azaalkened iyl, C 2 -C 6 -alki- 0 nediyt, C 3 -C 6 -cycloalkaned iyl, C 3 -C 6 -cycloalkened iyl or phenylene, A 2 represents a single bond, represents oxygen, sulphur, -S02-, -CO- or the grouping -N-A 4 in which A 4 represents hydrogen, hydroxyl, Cl-C 4 -alkyl, 01-04- alkoxy, phenyl, Cl-C 4 -alkylsulphonyl or phenylsulphonyl, A 2 furthermore represents in each case unsubstituted or 20 fluorine-, chlorine- or bromine-substituted C 1 -C 6 alkanediyl, C 2 -0 6 -alkened iyl, C 2 -C 6 -azaalkenediyl, 02- C 6 -alkinediyl, C 3 -C 6 cycloalkanediyl, C 3 -C 6 -cycloalkene- diyl or phenylene, A 3 represents hydrogen, hydroxyl, amino, cyano, isocyano, a: 25 thio cyanato, nitro, carboxyl, carbamoyl, thiocarbamnoyl, sulpho, chlorosulphonyl, fluorine, chlorine, bromine, represents in each case unsubstituted or fluorine-, chlorine- or Cl-C 4 -alkoxy substituted alkyl, alkoxy, alkyl- thio, alkylsulphinyl, alkylsuiphonyl, alkylamino, dialkyl- amino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having L in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case unsubstituted or fluorine- or -97- chlorine-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, represents in each case unsubstituted or fluorine-, chlorine-, cyano-, carboxyl-, Cl-C 4 -alkyl and/or C 1 -C 4 -alkoxy-carbonyl substituted cycloalkyl, cycloalkyl- oxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidene- amino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and unsubstituted or 1 to 4 carbon atoms in the alkyl groups, or represents in each case unsubstituted or nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, Cl-C 4 -alkyl-, Cl-C 4 -halogenoalkyl-, Cl-C 4 -alkyloxy-, C 1 C 4 -halogenoalkyloxy- and/or C 1 -C 4 -alkoxy-carbonyi-sub- stituted phenyl, phenyloxy, phenyl-Cl-C 4 -alkyI, phenyl- 4 -alkoxy, phenyloxycarbonyl or phenyl-C 1 -C 4 alkoxyca rbonyl, see* *0 :0 00 20 A 3 furthermore represents in each case unsubstituted or 5 fully or partially hydrogenated pyrrolyl, pyrazolyl, imida- zolyl, triazolyl, fu ryl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxad iazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-Cl- C 4 -alkyl, furyl-C 1 -C 4 -alkyl, thienyl-C 1 -C 4 -alkyl, oxazolyl- S. C 1 -C 4 -alkyl,isoxazole-C 1 -C 4 -alkyl, thiazole-C 1 -C 4 -alkyl, SS. pyridinyl-C 1 -C 4 -alkyl, pyrimid inyl-C 1 -C 4 -alkyl, pyrazolyl- methoxy, furylmethoxy, represents perhyd ropyranyl- methoxy or pyridylmethoxy, R 5 represents hydrogen, cyano, thiocarbamnoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in r 0 -98- each case unsubstituted or fluorine- and/or chlorine-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the alkyl groups, and R 6 represents hydrogen, cyano, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents in each case unsubstituted or fluorine- and/or chlorine-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the alkyl groups.
12. Crop protection compositions, characterized in that they comprise at least one substituted phenylpyridazinone according to Claim 1 and customary extenders and/or surfactants.
13. Method for controlling undesirable plants, characterized in that at least one substituted phenylpyridazinone according to Claim 1 is allowed to act on undesirable plants and/or their habitat. :0
14. Method for controlling undesirable insects, characterized in that at 20 least one substituted phenylpyridazinone according to Claim 1 is allowed to act on undesirable insects and/or their habitat. :I
15. Substituted phenylpyridazinones of the general formula processes for their preparation, crop protection compositions or methods for 0: controlling involving/containing them, substantially as hereinbefore described with reference to the Examples. I DATED this 28th day of September, 2001 BAYER AKTIENGESELLSCHAFT By its Patent Attorneys DAVIES COLLISON CAVE
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19815947 | 1998-04-09 | ||
| DE19815947 | 1998-04-09 | ||
| DE19859685 | 1998-12-23 | ||
| DE19859685 | 1998-12-23 | ||
| PCT/EP1999/002086 WO1999052878A1 (en) | 1998-04-09 | 1999-03-26 | Substituted phenyl pyridazinones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU3702599A AU3702599A (en) | 1999-11-01 |
| AU742108B2 true AU742108B2 (en) | 2001-12-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU37025/99A Ceased AU742108B2 (en) | 1998-04-09 | 1999-03-26 | Substituted phenyl pyridazinones |
Country Status (8)
| Country | Link |
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| EP (1) | EP1070055A1 (en) |
| JP (1) | JP2002511452A (en) |
| KR (1) | KR20010042411A (en) |
| CN (1) | CN1305466A (en) |
| AU (1) | AU742108B2 (en) |
| BR (1) | BR9909548A (en) |
| CA (1) | CA2327806A1 (en) |
| WO (1) | WO1999052878A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6121201A (en) | 1998-09-11 | 2000-09-19 | Ishihara Sangyo Kaisha, Ltd. | Diaryl ethers and processes for their preparation and herbicidal and desiccant compositions containing them |
| JP3890816B2 (en) * | 1998-12-09 | 2007-03-07 | 住友化学株式会社 | Method for producing pyridazin-3-one derivative |
| CA2406217A1 (en) * | 2000-04-14 | 2001-10-25 | Basf Aktiengesellschaft | 2-phenyl-2h-pyridazine-3-ones |
| CA2406227A1 (en) * | 2000-04-14 | 2001-10-25 | Basf Aktiengesellschaft | 2-phenyl-2h-pyridazine-3-ones |
| DE10034803A1 (en) * | 2000-07-18 | 2002-01-31 | Bayer Ag | Substituted sulfonic acid anilides |
| WO2004089914A1 (en) | 2003-04-08 | 2004-10-21 | Basf Aktiengesellschaft | Benzenesulphonamide derivatives as herbicides or desiccant/defoliant compounds |
| CN101041639B (en) * | 2005-03-17 | 2010-05-26 | 南开大学 | 4-Substituted phenylpyridazines and their herbicidal activity |
| ES2600460T3 (en) | 2005-05-10 | 2017-02-09 | Intermune, Inc. | Pyridone-2-one derivatives as modulators of the stress-activated protein kinase system |
| CN102099036B (en) | 2008-06-03 | 2015-05-27 | 英特芒尼公司 | Compounds and methods for treating inflammatory and fibrotic disorders |
| JP5842594B2 (en) * | 2010-12-27 | 2016-01-13 | 住友化学株式会社 | Pyridazinone compounds, herbicides containing them, and harmful arthropod control agents |
| GB201121317D0 (en) * | 2011-12-09 | 2012-01-25 | Syngenta Ltd | Herbicidal compounds |
| BR112014030284B1 (en) | 2012-07-18 | 2021-11-30 | Sunshine Lake Pharma Co., Ltd | COMPOUND, PHARMACEUTICAL COMPOSITION, AND, USE OF A COMPOUND OR PHARMACEUTICAL COMPOSITION |
| CN103664795B (en) * | 2012-09-06 | 2017-10-03 | 华东理工大学 | Pyridazinone compound and application thereof |
| AR092742A1 (en) | 2012-10-02 | 2015-04-29 | Intermune Inc | ANTIFIBROTIC PYRIDINONES |
| MX382781B (en) | 2014-04-02 | 2025-03-13 | Intermune Inc | ANTI-FIBROTIC PYRIDINONES. |
| CN108884074B (en) * | 2016-04-15 | 2021-07-02 | 先正达参股股份有限公司 | Herbicidal pyridazinone compounds |
| GB201717080D0 (en) | 2017-10-18 | 2017-11-29 | Syngenta Participations Ag | Chemical process |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH373919A (en) * | 1959-02-02 | 1963-12-15 | Ciba Geigy | Method of controlling weeds |
| DE2808193A1 (en) * | 1978-02-25 | 1979-09-06 | Basf Ag | PYRIDAZONE CONNECTIONS |
| DE19520613A1 (en) * | 1995-06-06 | 1996-12-12 | Bayer Ag | Phenylpyridazinones |
| NZ315400A (en) * | 1995-08-21 | 2000-01-28 | Sumitomo Chemical Co | Pyridazin-3-one derivatives, their use, and intermediates for their production |
| AR009380A1 (en) * | 1996-10-21 | 2000-04-12 | Sumitomo Chemical Co | PROCESS OF PREPARATION OF A DERIVATIVE OF PIRIDAZIN-3-ONA, USEFUL AS A HERBICIDE, CARBOXYLIC ACID FOR USE THEREOF, SALE OF THIS LAST AND PROCESS TO PREPARE SUCH CARBOXYLIC ACID |
| ZA978995B (en) * | 1996-10-21 | 1998-08-25 | Sumitomo Chemical Co | Production of pyridazine herbicide |
| DE19754348A1 (en) * | 1996-12-11 | 1998-06-18 | Ciba Geigy Ag | New 2-(hetero)aryl-2(3H)-pyridazinone derivatives |
| IL123339A0 (en) * | 1997-02-19 | 1998-09-24 | Sumitomo Chemical Co | Pyridazin-3-one derivatives and their use |
| IL123340A0 (en) * | 1997-02-20 | 1998-09-24 | Sumitomo Chemical Co | Pyridazin-3-one derivatives and their use |
-
1999
- 1999-03-26 EP EP99919146A patent/EP1070055A1/en not_active Withdrawn
- 1999-03-26 KR KR1020007010988A patent/KR20010042411A/en not_active Withdrawn
- 1999-03-26 WO PCT/EP1999/002086 patent/WO1999052878A1/en not_active Ceased
- 1999-03-26 JP JP2000543440A patent/JP2002511452A/en active Pending
- 1999-03-26 BR BR9909548-3A patent/BR9909548A/en not_active IP Right Cessation
- 1999-03-26 AU AU37025/99A patent/AU742108B2/en not_active Ceased
- 1999-03-26 CA CA002327806A patent/CA2327806A1/en not_active Abandoned
- 1999-03-26 CN CN99807143A patent/CN1305466A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999052878A1 (en) | 1999-10-21 |
| BR9909548A (en) | 2000-12-12 |
| KR20010042411A (en) | 2001-05-25 |
| CN1305466A (en) | 2001-07-25 |
| JP2002511452A (en) | 2002-04-16 |
| EP1070055A1 (en) | 2001-01-24 |
| CA2327806A1 (en) | 1999-10-21 |
| AU3702599A (en) | 1999-11-01 |
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