CA2260201A1 - Substituted aromatic carbonyl compounds and their derivatives - Google Patents
Substituted aromatic carbonyl compounds and their derivatives Download PDFInfo
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- CA2260201A1 CA2260201A1 CA002260201A CA2260201A CA2260201A1 CA 2260201 A1 CA2260201 A1 CA 2260201A1 CA 002260201 A CA002260201 A CA 002260201A CA 2260201 A CA2260201 A CA 2260201A CA 2260201 A1 CA2260201 A1 CA 2260201A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
-
- 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
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines 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
- C07D253/075—Two hetero atoms, in positions 3 and 5
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
New substituted aromatic carbonyl compounds and their derivatives have the general formula (I), in which Q stands for oxygen, sulphur or imino (NH); R1 stands for hydrogen or halogen; and R2 stands for the group -A1-A2-A3, in which A1, A2 and A3 have the meanings given in the description. Also disclosed are a process for preparing the same and their use as herbicides.
Description
Le A 31 906 Foreign Countries ~ . L'l.~:~
Sul~liluted an~maac ca~bonyl compounds and denvaaves ~ereof The invention relates to novel substituted aromatic carbonyl compounds and derivatives thereof, to processes for their preparation and to their use as herbicides.
Some substituted aromatic carbonyl compounds having heterocyclyl groups attached via nitrogen are already known (cf. DE-2 102 848, DE-2 119 260, DE-2 166 456, DE-2 342 934). However, a herbicidal activity of these compounds has not been disclosed.
This invention, accordingly, provides novel substituted aromatic carbonyl 10 compounds and their derivatives of the general formula (I) Z~
~,,Q (I) in which Q represents oxygen, sulphur or imino (NH), R' represents hydrogen or halogen, 20 R2 represents the grouping below A' A2 A3 in which A' represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, alkoxy, aryl, alkylsulphonyl and arylsulphonyl, Le A 31 906 Forei~n Countries A' furthermore represents a radical selected from the group consisting of ~lk:~nedjyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted, A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, aryl, alkoxy, alkylsulphonyl and arylsulphonyl, A2 furthermore represents a radical selected from the group consisting of alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted, and A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, IS carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy(thio)phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino, alkinyloxycarbonyl, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl, cycloalkylalkoxycarbonyl, aryl, aryloxy, arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl, heterocyclyl, hetero-cyclylalkyl, heterocyclylalkoxy or heterocyclylalkoxycarbonyl, each of which may optionally be substituted, R3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting ofalkyl, alkoxy, alkylthio and alkylamino, each of which may optionally be substituted, and Z represents a monocyclic or bicyclic, saturated or unsaturated radical selected Le A 31 906 Foreign Countries from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclylamino and heterocyclylimino, each of which may optionally be substituted, except for the prior-art compounds ethyl 5-chloro-4-(1,3-dihydro- 1,3-dioxo-2H-isoindol-2-yl)-2-methoxybenzoate and methyl 5-chloro-4-(1,3-dihydro- 1,3-dioxo-2H-isoindol-2-yl)-2-methoxybenzoate (both known from DE-2 102 848, DE-2 119 260 and DE-2 166 456) and methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 34(1993), 1889-1892).
The novel substituted aromatic carbonyl compounds and their derivatives of the general formula (I) are obtained when substituted aromatic nitriles of the general formula (II) ~ (II) ~--CN
in which Rl, R2 and Z are each as defined above are reacted with water, hydrogen sulphide or ammonia, if appropriate in the presence of reaction auxiliaries, and the resulting substituted aromatic carboxylic acids or their derivatives of the general formula (Ia) Z~
l l l (Ia) ~Q
R QH
Le A 31 906 Foreign Countries in which , Q, Rl, Rl and Z are each as defined above 5 are, if appropriate, converted by customary methods into substituted aromatic carbonyl compounds or their derivatives in accordance with the above definition of the compounds of the formula (I).
The novel substituted aromatic carbonyl compounds of the general formula (I) have 10 strong herbicidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkinyl, are in each case straight-chain or branched, i.e. also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably represents fluorine, chlorine or bromine, and in particular represents fluorine or chlorine.
The invention preferably provides compounds of the formula (I) 20 in which Q represents oxygen, sulphur or imino (NH), Rl represents hydrogen, fluorine, chlorine or bromine, R2 represents the grouping below Al A2 A3 30 in which Al represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the Le A 31 906 Foreign Countries grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of C,-C4-alkyl, C,-C4-alkoxy, phenyl, C,-C4-alkoxysulphonyl and phenylsulphonyl, S A' furthermore represents a radical selected from the group consisting of C ,-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine, 10 A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of C,-C4-alkyl, C,-C4-alkoxy, phenyl, C,-C4-alkylsulphonyl and phenylsulphonyl, I S A2 furthermore represents a radical selected from the group consisting of C,-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine, 20 A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl and dialkoxy(thio)phosphoryl having in each case I to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by halogen, Cl-C4-alkoxy or C,-C4-alkoximino, A3 furthermore represents a radical selected from the group consisting of alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino and alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and being in each caseoptionally substituted by halogen, .
Le A 31 906 Forei~n Countries A3 furthermore represents a radical selected from the group consisting of cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidene-amino, cycloalkyloxycarbonyl and 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 and being in each case optionally substituted by halogen, cyano, carboxyl, Cl-C4-alkyl and/or Cl-C4-alkoxy-carbonyl, A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, phenyl-CI-C4-alkyl, phenyl-C,-C4-alkoxy, phenyloxycarbonyl and phenyl-CI-C4-alkoxycarbonyl, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thia~ 7olyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-CI-C4-alkyl, furyl-CI-C4-alkyl, thienyl-CI-C4-alkyl, oxazolyl-CI-C4-alkyl, isoxazol-CI-C4-alkyl, thiazol-C,-C4-alkyl, pyridinyl-C,-C4-alkyl, pyrimidinyl-CI-C4-alkyl, pyrazolylmethoxy, furylmethoxy, each of which may optionally be substituted by nitro, cyano, carboxyl, halogen, C I -C4-alkyl, C I -C4-halogenoalkyl, C I -C4-alkyloxy, C I -C4-halogenoalkyloxyand/or Cl-C4-alkoxy-carbonyl, represents perhydropyranylmethoxy or pyridylmethoxy, R3 represents hydrogen, hydroxyl, mercapto, amino, (in which case Q does not represent sulphur) or represents a radical selected from the group consisting ofalkyl, alkoxy, alkylthio and alkylamino having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by hydroxyl, cyano, halogen, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl, and Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception:
piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to 6 carbon atoms and 1 to 4 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to three groupings selected from the group consisting of -CO-, Le A 31 906 Foreign Countries -CS-, -SO- and/or SO2- and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, C,-C6-alkyl (which for its part may optionally be substituted by halogen or Cl-C4-alkoxy), C2-C6-alkenyl and S C2-C6-alkinyl (which for their part may each optionally be substituted by halogen), C,-C6-alkoxy and Cl-C6-alkoxy-carbonyl (which for their part may each optionally be substituted by halogen or Cl-C4-alkoxy), C2-C6-alkenyloxy or C2-C6-alkinyloxy (which for their part may each optionally be substituted by halogen), Cl-C6-alkylthio, C2-C6-alkenylthio and C2-C6-alkinylthio (which for their part may each optionally be substituted by halogen), Cl-C6-alkylamino and di-(CI-C4-alkyl)amino, C3-C6-cycloalkyl and C3-C6-cycloalkyl-C,-C4-alkyl (which for their part may each optionally be substituted by halogen and/or C,-C4-alkyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, halogen, C,-C4-alkyl, C,-C4-halogenoalkyl, C,-C4-alkyloxy, C ,-C4-halogenoalkyloxy and/or C ,-C4-alkoxy-carbonyl), where the prior-art compounds ethyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate and methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-20 2-yl)-2-methoxy-benzoate (both known from DE-2 102 848, DE-2 119 260 and DE-2 166 456) and methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 34(1993), 1889- 1892) are excluded by disclaimer.
25 The invention in particular provides compounds of the formula (I) in which Q represents oxygen, sulphur or imino (NH), 30 Rl represents hydrogen, fluorine or chlorine, R2 represents the grouping below - Le A 31 906 Foreign Countries A' A2 A3 in which S A' represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl and ethylsulphonyl, Al furthermore represents a radical selected from the group consisting of methylene, ethane-l,1-diyl, ethane-1,2-diyl, propane-l,l-diyl, propane-I ,2-diyl, propane- I ,3-diyl, ethene- I ,2-diyl, propene- I ,2-diyl, propene-I ,3-diyl, ethine- I ,2-diyl, propine- I ,2-diyl and propine- I ,3-diyl, IS A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl and phenylsulphonyl, A2 furthermore represents a radical selected from the group consisting of methylene, ethane- I, I -diyl, ethane- I ,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 and propine-1,3-diyl, A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, represents a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, Le A 31 906 Foreign Countries ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl and diisopropoxyphosphoryl, each of which may optionally be substituted by fluorine, chlorine, methoxy, ethoxy, methoximino or ethoximino, A3 furthermore represents a radical selected from the group consisting of propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl and butinyloxycarbonyl, each of which may optionally be substituted by fluorine or chlorine, A3 furthermore represents a radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo-propylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl and cyclohexylmethoxycarbonyl, each of which may optionally be substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thier~ylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy and pyridylmethoxy, each of which may - Le A 31 906 Foreign Countries ~ - 10 -optionally be substituted by 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, s R3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting ofmethyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i-propylamino, each of which may optionally be substituted by hydroxyl, cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, and Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception:
piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to S carbon atoms and I to 3 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to two groupings selected from the group consisting of -CO-, -CS-, -SO- and/or SO2-, and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which for their part may optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propinyl and butinyl (which for their part may each optionally be substituted byfluorine or chlorine); methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,methoxycarbonyl and ethoxycarbonyl (which for their part may each optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propinyloxy and butinyloxy (which for their part may optionally be substituted by fluorine or chlorine); methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio and butinylthio (which for their part may each optionally be substituted by fluorine or chlorine);
methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, Le A 31 906 Foreign Countries dimethylamino and diethylamino; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl (which for their part may each optionally be substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, phenylthio,S phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl), 10 where the prior-art compounds ethyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate and methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate (both known from DE-2 102 848, DE-2 119 260 and DE-2 166 456) and methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 3415 (1993), 1889-1892) are excluded by disclaimer.
In the general formula (I), Z in particular represents the heterocyclic groupings listed below R7 N'Q'r~ 6 ~ N--Q
(Zl) (z2) (z3 2'Q' -- R6 N NR_N~Q'N
~= N ~ N = N
z4) (zS) (Z ) CA 0226020l l999-0l-08 Le A 31 906 Foreign Countries ,.S>~ N ~<Q~
(Z7) (z8) (zg) R--N 'Q~ N R--N~-- N~--(Z10) (z11) (z12) R7 N~Q'N Q2 Q'N Q' N--Q R6)~(R6 R6{ N--z13) (z14) (z15 Q--Q N--Q' N--Q
R6~ N~ R6~\ N--Q N--N N--Q
(z16) (Z'7) (z18) ~~Q' R6 R6 R~$Q~
(Z~9) (z20) (z21) Le A 31 906 Foreign Countries N~l N-- R ~N;~,~ R6~;~--(z22) (z23) (z24) R ~Q~ R ~Q'N
N--N N~
(z25) (z26) R--N'Q~N--R Q J~N
\N - Ql R Q
(z27) (z28) 5 where in each case Q' represents a grouping selected from the group consisting of -CO-, -CS-, -CH2-, -CH(OH)-, -CHCI-, -CHBr-, -C(=CH2)-, -C(=CHF)-, -C(=CF2)-, -C(=CHCl)-, -C(=CHBr)-, -C(=CHOCHF2)-, -C(=CHOCF3)-, -C(=CHOCH2CF3)-, Q2 represents oxygen, sulphur or a grouping selected from the group consisting of -CO-, -CS-, -CH2-, -CHF-, -CF2-, -CHCI-, -CHBr-, -CHOCHF2-, -CHOCF3-, -CHOCH2CF3-, 15 R6 represents hydrogen, amino, nitro, cyano, carboxyl, carbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, cyclopropyl, difluoromethyl, , Le A 31 906 Foreign Countries trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difllloromethoxy, trifluoromethoxy, chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, methylamino, ethylamino, n- or i-propylamino, S dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl, and R7 represents hydrogen, hydroxyl, amino, cyano, methyl, ethyl, n- or i-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy, or where, if appropriate, two adjacent groups - R6 and R6 or R7 and R7 or R6 and R7 -together represent alkanediyl or alkenediyl having in each case up to four carbon atoms and being in each case optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and optionally interrupted by oxygen, sulphur or a grouping selected from the group consisting of -SO-, SO2-, -N(CH3)- or N(C2H5)- at the beginning (or at the end) or within the hydrocarbon chain.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other at will, i.e. including combinations between the given ranges of preferred compounds.
Examples of compounds of the formula (I) according to the invention are listed in the groups below.
.
Le A 31 906 Foreign Countries Group I
F3C~N~O
l~N~
O ~Q
5 Q, R', R2 and R3 each have the meanings given in the list below:
Q R' R2 R3 Q R' R2 R3 O H F OH O F F OH
O F Cl OH O Cl F OH
O Cl Cl OH O F Br OH
O F Cl OCH3 O Cl F OCH3 O Cl Cl OCH3 O F Br OCH3 O F Cl SCH3 O Cl F SCH3 O Cl Cl SCH3 O F Br SCH3 S H F OH S F F OH
S F Cl OH S Cl F OH
S Cl Cl OH S F Br OH
S F Cl OCH3 S Cl F OCH3 S Cl Cl OCH3 S F Br OCH3 S F Cl SCH3 S Cl F SCH3 , Le A 31 906 Foreign Countries Q R' R2 R3 Q R' R2 R3 S Cl Cl SCH3 S F Br SCH3 NH F Cl NH2 NH Cl F NH2 NH Cl Cl NH2 NH F Br NH2 NH F Cl SCH3 NH Cl F SCH3 NH Cl Cl SCH3 NH F Br SCH3 O H COOH OH O F COOH OH
O F COOH OH O Cl COOH OH
O Cl COOH OH O F COOH OH
O F COOCH3 OCH3 O Cl COOCH3 OCH3 O Cl COOCH3 OCH3 O F COOCH3 OCH3 O H OH OH O F SH OH
O F OH OH O Cl SH OH
O Cl OH OH O F NH2 OH
O F OH OCH3 O Cl SH OCH3 NH Cl NH2 NH2 NH F NH2 NH2 NH F OH SCH3 NH Cl SH SCH3 NH Cl OH SCH3 NH F NH2 SCH3 O F CH3 OCH3 O Cl OCH3 OCH3 O Cl CH3 OCH3 O F SCH3 OCH3 - Le A 31 906 Foreign Countries R3 Q R' R2 R3 O F SCH3 OCH3 O Cl OC2H5 OCH3 O Cl NHCH3 OCH3 O F SC2H5 OCH3 O F SO2CH3 OCH3 O Cl OCH2CF3 OCH3 O Cl OCH2CH2CN OCH3 O F SCH2CN OCH3 ~ O~CH3 S~ S~CH3 O~ O~CH3 ~~ O~CH3 Il . Il .
Le A 31 906 Foreign Countries R3 Q R' R2 R3 S~ S~CH3 Il 11 O Cl I OCH3 O F I OCH3 S~ SyCH3 O H NHSO2CH3 OCH3 O F NHSO2C2Hs OCH3 O F NHSO2CH3 OCH3 O Cl NHSO2C2Hs OCH3 O Cl NHSO2CH3 OCH3 O F NHSO2c2Hs OCH3 NH H NHSO2CH3 SCH3 NH F NHSO2C2Hs SCH3 NH F NHSO2CH3 SCH3 NH Cl NHSO2C2Hs SCH3 NH Cl NHSO2CH3 SCH3 NH F NHSO2C2Hs SCH3 O H N(SO2CH3)2 OCH3 O F NHSO2C4Hg OCH3 O F N(SO2CH3)2 OCH3 O Cl NHSO2C4H9 OCH3 O F NHSO2C3H7 OCH3 O F NHSO2C5H~ OCH3 NH H N(SO2CH3)2 SCH3 NH F NHSO2C3H7 SCH3 NH F N(SO2CH3)2 SCH3 NH Cl NHSO2C3H7 SCH3 NH Cl NHSO2C4Hg SCH3 NH F NHSO2C5H~ ~ SCH3 --N'So ~q~ l ~2 CH3 C4Hg CH3 Le A 31 906 Forei~n Countries Q R' R2 R3 Q R' R2 R3 N ~ SO ~q~ S~2 CH3 C4Hg CH3 'So ~q~so2 CH3 C4Hg CH3 Group 2 O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
G~up 3 F3C~N~O R' S H3C~ ~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
- Le A 31 906 Foreign Countries Group 4 F3C ~,~ N ~~ R' O ~Q
5 Q, R', R2 and R3 each have, for example, the me~ning.s given above in Group 1.
Gn)up 5 CH3 o N_~ R1 H3C )7~ N ~
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 6 O
,N_~ R
H3C )7~ N ~
O I~Q
R R
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Le A 31 906 Foreign Countries Gn)up 7 ~~_ ,CH3 O ~Q
Q, Rl, R2 and R3 each have, for example, the meanings given above in Group l.
Group 8 ~ CH3 ~N R
N
S F2CH )7~ N ~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Gr~up 9 >=N R
H3C 'h'N'~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group l.
Le A 31 906 Foreign Countries G~up 10 )=N R
H3C 'h' N ~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 11 H3C )7~N~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 12 )= N~ R
F2CH )7~ N ~
O ~Q
R R
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Le A 31 906 Foreign Countries Group 13 O~ N ~O
W
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 14 O~N~O R' W
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 15 O~N~O
H2N N ~
~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Using, forexample, 2-(2-fluoro-4-cyano-5-methoxy-phenyl)-4-methyl-S-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one and water as starting materials, the course of the Le A 31 906 Foreign Countries reaction in the process according to the invention can be illustrated by the following equation: -Y~ H,O
The forrnula (II) provides a general definition of the substituted aromatic nitriles to be used as starting materials in the process according to the invention for preparing compounds of the formula (I).
In the formula (II), R', R2 and Z each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or 10 particularly preferred for R', R2 and Z.
The starting materials of the formula (II) are known and/or can be prepared by known methods (cf. EP-370 332, EP-648 749, DE-4 238 125, DE-4 303 376, US-5 084 084, WO 95/29168).
The process according to the invention for preparing the novel compounds of the 15 formula (I) is preferably carried out in the presence of a reaction auxiliary. These include water and the customary organic diluents, oxidizing agents, such as, forexample, hydrogen peroxide or sodium chlorite, and also amidosulphonic acid.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at 20 temperatures between 0~C and 150~C, preferably between 20~C and 120~C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to theinvention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
.
Le A 31 906 Foreign Countries For carrying out the process according to the invention, the starting materials are generally e~lnployed in approximately equimolar amounts. However, it is also possible to employ one of the components in a relatively large excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction 5 mixture is generally stirred for several hours at the required temperature. 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 weedkillers. By weeds in the broadest sense, there are to be understood all plants which grow in locations where they are undesirable.
10 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, 15 Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, 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 and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus,20 Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and 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, 25 Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Le A 31 906 Foreign Countries Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no wayrestricted to these genera, but also extends in the same manner to other plants.
5 The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea 10 plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns, sports fields and pasture-land. Furthermore, the compounds can also be used for the selective control of weeds in annual cultures.
The compounds of the formula (I) according to the invention are suitable in particular for selectively controlling monocotyledonous and dicotyledonous weeds in 15 monocotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
20 These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersing agents and/or foam-forming agents.
If the extender used is water, it is also possible to use for example organic solvents as 25 auxiliary solvents. Essentially, suitable liquid solvents are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic Le A 31 906 Foreign Countries 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 their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone orS cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also 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 and10 silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-forming agents are: for example nonionic and anionic emulsifiers, such as 15 polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the 20 form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Possible further additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, 25 titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active - Le A 31 906 Foreign Countries compound, preferably between O.S and 90%.
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.
5 Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron (-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, 10 chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, 15 diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop-ethyl, flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, 20 flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam,flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl), hexazinone, im~7~methabenz(-methyl), im:l7~methapyr, im~7~rnox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, 25 isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP,mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metsulfuron(-methyl), metribuzin, molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, 30 piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, . .
Le A 31 906 Foreign Countries propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, 5 tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil 10 structure, are 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 or scattering.
15 The active compounds according to the invention can be applied either before or 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 substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between I g and lO kg of active compound per hectare of soil surface, preferably between 5 g 20 and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples below.
Le A 31 906 Foreign Countries Prepalation FY~ lples:
Example 1 F3C~N~O
N ~
COOH
COOH
At approximately 45~C, a mixture of l.0 g (2.93 mmol) of 1-(4-cyano-2-fluoro-S S-formyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- l (2H)-pyrimidine, lS0 ml of water, 0.58 g (6 mmol) of amidosulphonic acid and 0.54 g (6 mmol) of sodium chlorite is stirred for approximately 24 hours. The mixture is then shaken with ethyl acetate and the organic phase is separated off, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump 1 0 vacuum.
This gives 0.90 g (82% of theory) of 1-(4,5-bis-carboxy-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine as an amorphous residue.
F.Y~ nple 2 F3C ~ N ~;0 N ~
A mixture of 0.80 g (2.24 mmol) of 1-(4,5-bis-carboxy-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine, 0.70 g (5 mmol) of potassium carbonate, 0.64 g (S mmol) of dimethyl sulphate and 20 ml of acetone is heated at the Le A 31 906 Foreign Countries boil under reflux for approximately 20 hours. The mixture is then concentrated under water pump vacuum and the residue is taken up in 50 ml of water, acidified with 2N
hydrochloric acid, then covered with a layer of 4 ml of diethyl ether and slowly diluted with petroleum ether with stirring. The resulting crystalline product is isolated by 5 filtration with suction.
This gives 0.38 g (42% of theory) of 1-(4,5-bis-methoxycarbonyl-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine of melting point 141 ~C.
FYr~rle 3 F3C~N~O
~N~ NH
,SO2 4.5 g ( 1.0 mmol) of I -(3-ethylsulphonylamino-2-fluoro-4-thiocarbamoyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl4-trifluoromethyl-1(2H)-pyrimidine are initially charged in 50 ml of methylene chloride and admixed dropwise with 1.5 g (1.2 mmol) of dimethyl sulphate. The reaction mixture is heated under reflux for approximately 3 15 hours and stirred at room temperature (approximately 20~C) for a further 15 hours.
After addition of a further 0.5 ml of dimethyl sulphate, the mixture is heated under reflux for a further 5 hours and subsequently concentrated under water pump vacuum.
The residue is stirred with diethyl ether and the resulting crystalline product is isolated by filtration with suction.
This gives 4.4 g (94% of theory) of 1-(3-ethylsulphonylamino-2-fluoro-4-(S-methyl-thiocarbonimidoyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-Le A 31 906 Foreign Countries pyrimidine of melting point 212~C.
Similarly to Preparation Examples I to 3, and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below.
~ (1) ~Q
Table 1: Examples of compounds of the formula (I) Ex. Q R' R2 R3 Z Melting No. point (~C) 4 NH F NHSO2C2H5 SCH3 lNH2 'H-NMR
F3C~ N ~~ (DMSO-D6, ~N~ ~): 6.45 ppm H_N~N~O
,~N
6 O H OH OCH3 Cl H3 183 H3C_N'N~O
,~ N
Le A 31 906 Foreign Countries Ex. Q R' R2 R3 Z Melting No. point (~C) H_N~N~O
,~ N
H3C-N'N'~GO
~N
9 O F NHSO2c2H5 SCH3 INH2 182 F3C~N~O
~N~
F3C T~ N ~;0 ~N~
H3C_Nl~N
,~N
Le A 31 906 Foreign Countries Ex. Q Rl R2 R3 Z Melting No. point (~C) o Le A 31 906 Foreign Countries Staltin~ n~ of ~e fonnula (m:
F,Y~ple (II-l) F3C~,~ N~O
~CN
H~O
Step 1 F3C~ N~O
CN
With stirring, 0.17 g (1.2 mmol) of pivaloyl chloride are added to a mixture of O.S0 g ( 1.2 mmol) of 1 -(4-cyano-2-fluoro-S-trifluoroacetylamino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine, 1 ml of triethylamine and S0 ml of acetonitrile, and the reaction mixture is stirred at 20~C for 18 hours and at 10 60~C for a further IS hours. The mixture is then concentrated under water pump vacuum, the residue is shaken with lN hydrochloric acid/ethyl acetate and the organic phase is separated off, dried with sodium sulphate and filtered. The filtrate isconcentrated under water pump vacuum and the residue is worked-up by column chromatography (silica gel, chloroform/ethyl acetate, Vol.: 1:1).
IS In addition to unreacted 1-(4-cyano-2-fluoro-S-trifluoroacetylamino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine (first fraction:
0.30 g), 0.2 g (50% of theory) of 1-(4-cyano-2-fluoro-5-amino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine are obtained as second fraction.
Le A 31 906 Forei~n Countries Melting polnt: 195~C.
step 2 F3C~N~O F
H~N~
~ COOCH3 A mixture of 1.8 g (21 mmol) of methyl acrylate, 1.6 g (15.5 mmol) of t-butyl nitrite, 1.6 g (12 mmol) of copper(II) chloride and 50 ml of acetonitrile is cooled to approximately 0~C, and a solution of 3.3 g (10 mmol) of 1-(5-amino-4-cyano-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine in 20 ml of acetonitrile is added dropwise at this temperature. The reaction mixture is allowed to warm to room temperature and stirred at this temperature for 18 hours. The mixture is 10 subsequently, after addition of 20 ml of IN hydrochloric acid, extracted with ethyl acetate and the organic phase is dried with sodium sulphate and filtered. The filtrate is concentrated and the residue is worked-up by column chromatography. This gives 2.8 g (65% of theory) of 1-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine of melting 15 point 46~C.
0.22 g of sodium hydride (60% strength) are added with stirring to a mixture of 2.0 g (4.6 mmol) of 1-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine and 30 ml ofN,N-dimethylformamide which had been cooled to 0~C, and the ~eaction mixture is 20 stirred initially at 0~C for 15 minutes, then at 20~C for approximately 60 minutes and finally at 60~C for 6 hours. The mixture is then concentrated under water pump vacuum, the residue is stirred with diisopropyl ether and the resulting crystalline product is isolated by filtration with suction.
Le A 31 906 Foreign Countries This gives 1.1 g (60% of theory) of 1 -[4-cyano-2-fluoro-5-(2-methoxycarbonyl-ethenyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine of melting point 154~C.
step 3 F3C~,~ N~O
~CN
H O
Ozone is introduced for 45 minutes into a mixture of 8.7 g (22 mmol) of 1-[4-cyano-2-fluoro-5-(2-methoxycarbonyl-ethenyl)-phenyl] -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H)-pyrimidine and 600 ml of methylene chloride which had been cooled to -70~C. The cooling bath is then removed, and the mixture is admixed with 10 10 ml of dimethyl sulphide. After the mixture has warmed to room temperature (about 20~C), the phases are separated and the organic phase is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by filtration with suction.
This gives 7.4 g (99% of theory) of 1-(4-cyano-2-fluoro-5-formyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine of melting point 177~C.
Le A 31 906 Foreign Countries Use Examples:
FY~ rle A
Prc-e..,e.~ence 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 activecompound 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 preparation 10 of active compound is sprayed onto the soil in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the sprayliquor is chosen so that the amounts of active compound desired in each case areapplied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in 15 comparison with the development of the untreated control.
The figures denote:
0% = no effect (like untreated control) 100% = total destruction In this test, at an application rate of 60 g/ha, for example the compound of Preparation 20 Example 2 exhibits very potent activity against weeds such as Avena fatua (~0%), Setaria (95%), Abutilon (100%), Amaranthus (100%), Galium (95% and Sinapis (100%).
Le A 31 906 Foreign Countries Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To produce a suitable preparation of active compound, I 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.
Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound 10 desired per unit area. The concentration of the spray liquor is chosen so that the amounts of active compound desired in each case are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison with the development of the untreated control.
The figures denote:
15 0% = no effect (like untreated control) 100% = total destruction In this test, at an application rate of 60 g/ha, for example the compound of Preparation Example 2 exhibits very potent activity against weeds such as Abutilon ( 100%), Amaranthus (100%), Galium (90%) and Sinapis (100%).
... .
Sul~liluted an~maac ca~bonyl compounds and denvaaves ~ereof The invention relates to novel substituted aromatic carbonyl compounds and derivatives thereof, to processes for their preparation and to their use as herbicides.
Some substituted aromatic carbonyl compounds having heterocyclyl groups attached via nitrogen are already known (cf. DE-2 102 848, DE-2 119 260, DE-2 166 456, DE-2 342 934). However, a herbicidal activity of these compounds has not been disclosed.
This invention, accordingly, provides novel substituted aromatic carbonyl 10 compounds and their derivatives of the general formula (I) Z~
~,,Q (I) in which Q represents oxygen, sulphur or imino (NH), R' represents hydrogen or halogen, 20 R2 represents the grouping below A' A2 A3 in which A' represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, alkoxy, aryl, alkylsulphonyl and arylsulphonyl, Le A 31 906 Forei~n Countries A' furthermore represents a radical selected from the group consisting of ~lk:~nedjyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted, A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, aryl, alkoxy, alkylsulphonyl and arylsulphonyl, A2 furthermore represents a radical selected from the group consisting of alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted, and A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, IS carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy(thio)phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino, alkinyloxycarbonyl, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl, cycloalkylalkoxycarbonyl, aryl, aryloxy, arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl, heterocyclyl, hetero-cyclylalkyl, heterocyclylalkoxy or heterocyclylalkoxycarbonyl, each of which may optionally be substituted, R3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting ofalkyl, alkoxy, alkylthio and alkylamino, each of which may optionally be substituted, and Z represents a monocyclic or bicyclic, saturated or unsaturated radical selected Le A 31 906 Foreign Countries from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclylamino and heterocyclylimino, each of which may optionally be substituted, except for the prior-art compounds ethyl 5-chloro-4-(1,3-dihydro- 1,3-dioxo-2H-isoindol-2-yl)-2-methoxybenzoate and methyl 5-chloro-4-(1,3-dihydro- 1,3-dioxo-2H-isoindol-2-yl)-2-methoxybenzoate (both known from DE-2 102 848, DE-2 119 260 and DE-2 166 456) and methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 34(1993), 1889-1892).
The novel substituted aromatic carbonyl compounds and their derivatives of the general formula (I) are obtained when substituted aromatic nitriles of the general formula (II) ~ (II) ~--CN
in which Rl, R2 and Z are each as defined above are reacted with water, hydrogen sulphide or ammonia, if appropriate in the presence of reaction auxiliaries, and the resulting substituted aromatic carboxylic acids or their derivatives of the general formula (Ia) Z~
l l l (Ia) ~Q
R QH
Le A 31 906 Foreign Countries in which , Q, Rl, Rl and Z are each as defined above 5 are, if appropriate, converted by customary methods into substituted aromatic carbonyl compounds or their derivatives in accordance with the above definition of the compounds of the formula (I).
The novel substituted aromatic carbonyl compounds of the general formula (I) have 10 strong herbicidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkinyl, are in each case straight-chain or branched, i.e. also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably represents fluorine, chlorine or bromine, and in particular represents fluorine or chlorine.
The invention preferably provides compounds of the formula (I) 20 in which Q represents oxygen, sulphur or imino (NH), Rl represents hydrogen, fluorine, chlorine or bromine, R2 represents the grouping below Al A2 A3 30 in which Al represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the Le A 31 906 Foreign Countries grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of C,-C4-alkyl, C,-C4-alkoxy, phenyl, C,-C4-alkoxysulphonyl and phenylsulphonyl, S A' furthermore represents a radical selected from the group consisting of C ,-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine, 10 A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of C,-C4-alkyl, C,-C4-alkoxy, phenyl, C,-C4-alkylsulphonyl and phenylsulphonyl, I S A2 furthermore represents a radical selected from the group consisting of C,-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine, 20 A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl and dialkoxy(thio)phosphoryl having in each case I to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by halogen, Cl-C4-alkoxy or C,-C4-alkoximino, A3 furthermore represents a radical selected from the group consisting of alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino and alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and being in each caseoptionally substituted by halogen, .
Le A 31 906 Forei~n Countries A3 furthermore represents a radical selected from the group consisting of cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidene-amino, cycloalkyloxycarbonyl and 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 and being in each case optionally substituted by halogen, cyano, carboxyl, Cl-C4-alkyl and/or Cl-C4-alkoxy-carbonyl, A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, phenyl-CI-C4-alkyl, phenyl-C,-C4-alkoxy, phenyloxycarbonyl and phenyl-CI-C4-alkoxycarbonyl, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thia~ 7olyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-CI-C4-alkyl, furyl-CI-C4-alkyl, thienyl-CI-C4-alkyl, oxazolyl-CI-C4-alkyl, isoxazol-CI-C4-alkyl, thiazol-C,-C4-alkyl, pyridinyl-C,-C4-alkyl, pyrimidinyl-CI-C4-alkyl, pyrazolylmethoxy, furylmethoxy, each of which may optionally be substituted by nitro, cyano, carboxyl, halogen, C I -C4-alkyl, C I -C4-halogenoalkyl, C I -C4-alkyloxy, C I -C4-halogenoalkyloxyand/or Cl-C4-alkoxy-carbonyl, represents perhydropyranylmethoxy or pyridylmethoxy, R3 represents hydrogen, hydroxyl, mercapto, amino, (in which case Q does not represent sulphur) or represents a radical selected from the group consisting ofalkyl, alkoxy, alkylthio and alkylamino having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by hydroxyl, cyano, halogen, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl, and Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception:
piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to 6 carbon atoms and 1 to 4 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to three groupings selected from the group consisting of -CO-, Le A 31 906 Foreign Countries -CS-, -SO- and/or SO2- and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, C,-C6-alkyl (which for its part may optionally be substituted by halogen or Cl-C4-alkoxy), C2-C6-alkenyl and S C2-C6-alkinyl (which for their part may each optionally be substituted by halogen), C,-C6-alkoxy and Cl-C6-alkoxy-carbonyl (which for their part may each optionally be substituted by halogen or Cl-C4-alkoxy), C2-C6-alkenyloxy or C2-C6-alkinyloxy (which for their part may each optionally be substituted by halogen), Cl-C6-alkylthio, C2-C6-alkenylthio and C2-C6-alkinylthio (which for their part may each optionally be substituted by halogen), Cl-C6-alkylamino and di-(CI-C4-alkyl)amino, C3-C6-cycloalkyl and C3-C6-cycloalkyl-C,-C4-alkyl (which for their part may each optionally be substituted by halogen and/or C,-C4-alkyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, halogen, C,-C4-alkyl, C,-C4-halogenoalkyl, C,-C4-alkyloxy, C ,-C4-halogenoalkyloxy and/or C ,-C4-alkoxy-carbonyl), where the prior-art compounds ethyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate and methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-20 2-yl)-2-methoxy-benzoate (both known from DE-2 102 848, DE-2 119 260 and DE-2 166 456) and methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 34(1993), 1889- 1892) are excluded by disclaimer.
25 The invention in particular provides compounds of the formula (I) in which Q represents oxygen, sulphur or imino (NH), 30 Rl represents hydrogen, fluorine or chlorine, R2 represents the grouping below - Le A 31 906 Foreign Countries A' A2 A3 in which S A' represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl and ethylsulphonyl, Al furthermore represents a radical selected from the group consisting of methylene, ethane-l,1-diyl, ethane-1,2-diyl, propane-l,l-diyl, propane-I ,2-diyl, propane- I ,3-diyl, ethene- I ,2-diyl, propene- I ,2-diyl, propene-I ,3-diyl, ethine- I ,2-diyl, propine- I ,2-diyl and propine- I ,3-diyl, IS A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl and phenylsulphonyl, A2 furthermore represents a radical selected from the group consisting of methylene, ethane- I, I -diyl, ethane- I ,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 and propine-1,3-diyl, A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, represents a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, Le A 31 906 Foreign Countries ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl and diisopropoxyphosphoryl, each of which may optionally be substituted by fluorine, chlorine, methoxy, ethoxy, methoximino or ethoximino, A3 furthermore represents a radical selected from the group consisting of propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl and butinyloxycarbonyl, each of which may optionally be substituted by fluorine or chlorine, A3 furthermore represents a radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo-propylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl and cyclohexylmethoxycarbonyl, each of which may optionally be substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thier~ylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy and pyridylmethoxy, each of which may - Le A 31 906 Foreign Countries ~ - 10 -optionally be substituted by 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, s R3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting ofmethyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i-propylamino, each of which may optionally be substituted by hydroxyl, cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, and Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception:
piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to S carbon atoms and I to 3 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to two groupings selected from the group consisting of -CO-, -CS-, -SO- and/or SO2-, and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which for their part may optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propinyl and butinyl (which for their part may each optionally be substituted byfluorine or chlorine); methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,methoxycarbonyl and ethoxycarbonyl (which for their part may each optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propinyloxy and butinyloxy (which for their part may optionally be substituted by fluorine or chlorine); methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio and butinylthio (which for their part may each optionally be substituted by fluorine or chlorine);
methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, Le A 31 906 Foreign Countries dimethylamino and diethylamino; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl (which for their part may each optionally be substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, phenylthio,S phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl), 10 where the prior-art compounds ethyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate and methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate (both known from DE-2 102 848, DE-2 119 260 and DE-2 166 456) and methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 3415 (1993), 1889-1892) are excluded by disclaimer.
In the general formula (I), Z in particular represents the heterocyclic groupings listed below R7 N'Q'r~ 6 ~ N--Q
(Zl) (z2) (z3 2'Q' -- R6 N NR_N~Q'N
~= N ~ N = N
z4) (zS) (Z ) CA 0226020l l999-0l-08 Le A 31 906 Foreign Countries ,.S>~ N ~<Q~
(Z7) (z8) (zg) R--N 'Q~ N R--N~-- N~--(Z10) (z11) (z12) R7 N~Q'N Q2 Q'N Q' N--Q R6)~(R6 R6{ N--z13) (z14) (z15 Q--Q N--Q' N--Q
R6~ N~ R6~\ N--Q N--N N--Q
(z16) (Z'7) (z18) ~~Q' R6 R6 R~$Q~
(Z~9) (z20) (z21) Le A 31 906 Foreign Countries N~l N-- R ~N;~,~ R6~;~--(z22) (z23) (z24) R ~Q~ R ~Q'N
N--N N~
(z25) (z26) R--N'Q~N--R Q J~N
\N - Ql R Q
(z27) (z28) 5 where in each case Q' represents a grouping selected from the group consisting of -CO-, -CS-, -CH2-, -CH(OH)-, -CHCI-, -CHBr-, -C(=CH2)-, -C(=CHF)-, -C(=CF2)-, -C(=CHCl)-, -C(=CHBr)-, -C(=CHOCHF2)-, -C(=CHOCF3)-, -C(=CHOCH2CF3)-, Q2 represents oxygen, sulphur or a grouping selected from the group consisting of -CO-, -CS-, -CH2-, -CHF-, -CF2-, -CHCI-, -CHBr-, -CHOCHF2-, -CHOCF3-, -CHOCH2CF3-, 15 R6 represents hydrogen, amino, nitro, cyano, carboxyl, carbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, cyclopropyl, difluoromethyl, , Le A 31 906 Foreign Countries trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difllloromethoxy, trifluoromethoxy, chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, methylamino, ethylamino, n- or i-propylamino, S dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl, and R7 represents hydrogen, hydroxyl, amino, cyano, methyl, ethyl, n- or i-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy, or where, if appropriate, two adjacent groups - R6 and R6 or R7 and R7 or R6 and R7 -together represent alkanediyl or alkenediyl having in each case up to four carbon atoms and being in each case optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and optionally interrupted by oxygen, sulphur or a grouping selected from the group consisting of -SO-, SO2-, -N(CH3)- or N(C2H5)- at the beginning (or at the end) or within the hydrocarbon chain.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other at will, i.e. including combinations between the given ranges of preferred compounds.
Examples of compounds of the formula (I) according to the invention are listed in the groups below.
.
Le A 31 906 Foreign Countries Group I
F3C~N~O
l~N~
O ~Q
5 Q, R', R2 and R3 each have the meanings given in the list below:
Q R' R2 R3 Q R' R2 R3 O H F OH O F F OH
O F Cl OH O Cl F OH
O Cl Cl OH O F Br OH
O F Cl OCH3 O Cl F OCH3 O Cl Cl OCH3 O F Br OCH3 O F Cl SCH3 O Cl F SCH3 O Cl Cl SCH3 O F Br SCH3 S H F OH S F F OH
S F Cl OH S Cl F OH
S Cl Cl OH S F Br OH
S F Cl OCH3 S Cl F OCH3 S Cl Cl OCH3 S F Br OCH3 S F Cl SCH3 S Cl F SCH3 , Le A 31 906 Foreign Countries Q R' R2 R3 Q R' R2 R3 S Cl Cl SCH3 S F Br SCH3 NH F Cl NH2 NH Cl F NH2 NH Cl Cl NH2 NH F Br NH2 NH F Cl SCH3 NH Cl F SCH3 NH Cl Cl SCH3 NH F Br SCH3 O H COOH OH O F COOH OH
O F COOH OH O Cl COOH OH
O Cl COOH OH O F COOH OH
O F COOCH3 OCH3 O Cl COOCH3 OCH3 O Cl COOCH3 OCH3 O F COOCH3 OCH3 O H OH OH O F SH OH
O F OH OH O Cl SH OH
O Cl OH OH O F NH2 OH
O F OH OCH3 O Cl SH OCH3 NH Cl NH2 NH2 NH F NH2 NH2 NH F OH SCH3 NH Cl SH SCH3 NH Cl OH SCH3 NH F NH2 SCH3 O F CH3 OCH3 O Cl OCH3 OCH3 O Cl CH3 OCH3 O F SCH3 OCH3 - Le A 31 906 Foreign Countries R3 Q R' R2 R3 O F SCH3 OCH3 O Cl OC2H5 OCH3 O Cl NHCH3 OCH3 O F SC2H5 OCH3 O F SO2CH3 OCH3 O Cl OCH2CF3 OCH3 O Cl OCH2CH2CN OCH3 O F SCH2CN OCH3 ~ O~CH3 S~ S~CH3 O~ O~CH3 ~~ O~CH3 Il . Il .
Le A 31 906 Foreign Countries R3 Q R' R2 R3 S~ S~CH3 Il 11 O Cl I OCH3 O F I OCH3 S~ SyCH3 O H NHSO2CH3 OCH3 O F NHSO2C2Hs OCH3 O F NHSO2CH3 OCH3 O Cl NHSO2C2Hs OCH3 O Cl NHSO2CH3 OCH3 O F NHSO2c2Hs OCH3 NH H NHSO2CH3 SCH3 NH F NHSO2C2Hs SCH3 NH F NHSO2CH3 SCH3 NH Cl NHSO2C2Hs SCH3 NH Cl NHSO2CH3 SCH3 NH F NHSO2C2Hs SCH3 O H N(SO2CH3)2 OCH3 O F NHSO2C4Hg OCH3 O F N(SO2CH3)2 OCH3 O Cl NHSO2C4H9 OCH3 O F NHSO2C3H7 OCH3 O F NHSO2C5H~ OCH3 NH H N(SO2CH3)2 SCH3 NH F NHSO2C3H7 SCH3 NH F N(SO2CH3)2 SCH3 NH Cl NHSO2C3H7 SCH3 NH Cl NHSO2C4Hg SCH3 NH F NHSO2C5H~ ~ SCH3 --N'So ~q~ l ~2 CH3 C4Hg CH3 Le A 31 906 Forei~n Countries Q R' R2 R3 Q R' R2 R3 N ~ SO ~q~ S~2 CH3 C4Hg CH3 'So ~q~so2 CH3 C4Hg CH3 Group 2 O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
G~up 3 F3C~N~O R' S H3C~ ~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
- Le A 31 906 Foreign Countries Group 4 F3C ~,~ N ~~ R' O ~Q
5 Q, R', R2 and R3 each have, for example, the me~ning.s given above in Group 1.
Gn)up 5 CH3 o N_~ R1 H3C )7~ N ~
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 6 O
,N_~ R
H3C )7~ N ~
O I~Q
R R
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Le A 31 906 Foreign Countries Gn)up 7 ~~_ ,CH3 O ~Q
Q, Rl, R2 and R3 each have, for example, the meanings given above in Group l.
Group 8 ~ CH3 ~N R
N
S F2CH )7~ N ~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Gr~up 9 >=N R
H3C 'h'N'~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group l.
Le A 31 906 Foreign Countries G~up 10 )=N R
H3C 'h' N ~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 11 H3C )7~N~
O ~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 12 )= N~ R
F2CH )7~ N ~
O ~Q
R R
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Le A 31 906 Foreign Countries Group 13 O~ N ~O
W
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 14 O~N~O R' W
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Group 15 O~N~O
H2N N ~
~Q
Q, R', R2 and R3 each have, for example, the meanings given above in Group 1.
Using, forexample, 2-(2-fluoro-4-cyano-5-methoxy-phenyl)-4-methyl-S-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one and water as starting materials, the course of the Le A 31 906 Foreign Countries reaction in the process according to the invention can be illustrated by the following equation: -Y~ H,O
The forrnula (II) provides a general definition of the substituted aromatic nitriles to be used as starting materials in the process according to the invention for preparing compounds of the formula (I).
In the formula (II), R', R2 and Z each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or 10 particularly preferred for R', R2 and Z.
The starting materials of the formula (II) are known and/or can be prepared by known methods (cf. EP-370 332, EP-648 749, DE-4 238 125, DE-4 303 376, US-5 084 084, WO 95/29168).
The process according to the invention for preparing the novel compounds of the 15 formula (I) is preferably carried out in the presence of a reaction auxiliary. These include water and the customary organic diluents, oxidizing agents, such as, forexample, hydrogen peroxide or sodium chlorite, and also amidosulphonic acid.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at 20 temperatures between 0~C and 150~C, preferably between 20~C and 120~C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to theinvention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
.
Le A 31 906 Foreign Countries For carrying out the process according to the invention, the starting materials are generally e~lnployed in approximately equimolar amounts. However, it is also possible to employ one of the components in a relatively large excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction 5 mixture is generally stirred for several hours at the required temperature. 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 weedkillers. By weeds in the broadest sense, there are to be understood all plants which grow in locations where they are undesirable.
10 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, 15 Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, 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 and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus,20 Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and 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, 25 Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Le A 31 906 Foreign Countries Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no wayrestricted to these genera, but also extends in the same manner to other plants.
5 The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea 10 plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns, sports fields and pasture-land. Furthermore, the compounds can also be used for the selective control of weeds in annual cultures.
The compounds of the formula (I) according to the invention are suitable in particular for selectively controlling monocotyledonous and dicotyledonous weeds in 15 monocotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
20 These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersing agents and/or foam-forming agents.
If the extender used is water, it is also possible to use for example organic solvents as 25 auxiliary solvents. Essentially, suitable liquid solvents are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic Le A 31 906 Foreign Countries 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 their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone orS cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also 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 and10 silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-forming agents are: for example nonionic and anionic emulsifiers, such as 15 polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the 20 form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Possible further additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, 25 titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active - Le A 31 906 Foreign Countries compound, preferably between O.S and 90%.
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.
5 Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron (-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, 10 chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, 15 diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop-ethyl, flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, 20 flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam,flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl), hexazinone, im~7~methabenz(-methyl), im:l7~methapyr, im~7~rnox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, 25 isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP,mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metsulfuron(-methyl), metribuzin, molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, 30 piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, . .
Le A 31 906 Foreign Countries propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, 5 tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil 10 structure, are 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 or scattering.
15 The active compounds according to the invention can be applied either before or 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 substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between I g and lO kg of active compound per hectare of soil surface, preferably between 5 g 20 and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples below.
Le A 31 906 Foreign Countries Prepalation FY~ lples:
Example 1 F3C~N~O
N ~
COOH
COOH
At approximately 45~C, a mixture of l.0 g (2.93 mmol) of 1-(4-cyano-2-fluoro-S S-formyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- l (2H)-pyrimidine, lS0 ml of water, 0.58 g (6 mmol) of amidosulphonic acid and 0.54 g (6 mmol) of sodium chlorite is stirred for approximately 24 hours. The mixture is then shaken with ethyl acetate and the organic phase is separated off, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump 1 0 vacuum.
This gives 0.90 g (82% of theory) of 1-(4,5-bis-carboxy-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine as an amorphous residue.
F.Y~ nple 2 F3C ~ N ~;0 N ~
A mixture of 0.80 g (2.24 mmol) of 1-(4,5-bis-carboxy-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine, 0.70 g (5 mmol) of potassium carbonate, 0.64 g (S mmol) of dimethyl sulphate and 20 ml of acetone is heated at the Le A 31 906 Foreign Countries boil under reflux for approximately 20 hours. The mixture is then concentrated under water pump vacuum and the residue is taken up in 50 ml of water, acidified with 2N
hydrochloric acid, then covered with a layer of 4 ml of diethyl ether and slowly diluted with petroleum ether with stirring. The resulting crystalline product is isolated by 5 filtration with suction.
This gives 0.38 g (42% of theory) of 1-(4,5-bis-methoxycarbonyl-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine of melting point 141 ~C.
FYr~rle 3 F3C~N~O
~N~ NH
,SO2 4.5 g ( 1.0 mmol) of I -(3-ethylsulphonylamino-2-fluoro-4-thiocarbamoyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl4-trifluoromethyl-1(2H)-pyrimidine are initially charged in 50 ml of methylene chloride and admixed dropwise with 1.5 g (1.2 mmol) of dimethyl sulphate. The reaction mixture is heated under reflux for approximately 3 15 hours and stirred at room temperature (approximately 20~C) for a further 15 hours.
After addition of a further 0.5 ml of dimethyl sulphate, the mixture is heated under reflux for a further 5 hours and subsequently concentrated under water pump vacuum.
The residue is stirred with diethyl ether and the resulting crystalline product is isolated by filtration with suction.
This gives 4.4 g (94% of theory) of 1-(3-ethylsulphonylamino-2-fluoro-4-(S-methyl-thiocarbonimidoyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-Le A 31 906 Foreign Countries pyrimidine of melting point 212~C.
Similarly to Preparation Examples I to 3, and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below.
~ (1) ~Q
Table 1: Examples of compounds of the formula (I) Ex. Q R' R2 R3 Z Melting No. point (~C) 4 NH F NHSO2C2H5 SCH3 lNH2 'H-NMR
F3C~ N ~~ (DMSO-D6, ~N~ ~): 6.45 ppm H_N~N~O
,~N
6 O H OH OCH3 Cl H3 183 H3C_N'N~O
,~ N
Le A 31 906 Foreign Countries Ex. Q R' R2 R3 Z Melting No. point (~C) H_N~N~O
,~ N
H3C-N'N'~GO
~N
9 O F NHSO2c2H5 SCH3 INH2 182 F3C~N~O
~N~
F3C T~ N ~;0 ~N~
H3C_Nl~N
,~N
Le A 31 906 Foreign Countries Ex. Q Rl R2 R3 Z Melting No. point (~C) o Le A 31 906 Foreign Countries Staltin~ n~ of ~e fonnula (m:
F,Y~ple (II-l) F3C~,~ N~O
~CN
H~O
Step 1 F3C~ N~O
CN
With stirring, 0.17 g (1.2 mmol) of pivaloyl chloride are added to a mixture of O.S0 g ( 1.2 mmol) of 1 -(4-cyano-2-fluoro-S-trifluoroacetylamino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine, 1 ml of triethylamine and S0 ml of acetonitrile, and the reaction mixture is stirred at 20~C for 18 hours and at 10 60~C for a further IS hours. The mixture is then concentrated under water pump vacuum, the residue is shaken with lN hydrochloric acid/ethyl acetate and the organic phase is separated off, dried with sodium sulphate and filtered. The filtrate isconcentrated under water pump vacuum and the residue is worked-up by column chromatography (silica gel, chloroform/ethyl acetate, Vol.: 1:1).
IS In addition to unreacted 1-(4-cyano-2-fluoro-S-trifluoroacetylamino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine (first fraction:
0.30 g), 0.2 g (50% of theory) of 1-(4-cyano-2-fluoro-5-amino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine are obtained as second fraction.
Le A 31 906 Forei~n Countries Melting polnt: 195~C.
step 2 F3C~N~O F
H~N~
~ COOCH3 A mixture of 1.8 g (21 mmol) of methyl acrylate, 1.6 g (15.5 mmol) of t-butyl nitrite, 1.6 g (12 mmol) of copper(II) chloride and 50 ml of acetonitrile is cooled to approximately 0~C, and a solution of 3.3 g (10 mmol) of 1-(5-amino-4-cyano-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine in 20 ml of acetonitrile is added dropwise at this temperature. The reaction mixture is allowed to warm to room temperature and stirred at this temperature for 18 hours. The mixture is 10 subsequently, after addition of 20 ml of IN hydrochloric acid, extracted with ethyl acetate and the organic phase is dried with sodium sulphate and filtered. The filtrate is concentrated and the residue is worked-up by column chromatography. This gives 2.8 g (65% of theory) of 1-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine of melting 15 point 46~C.
0.22 g of sodium hydride (60% strength) are added with stirring to a mixture of 2.0 g (4.6 mmol) of 1-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine and 30 ml ofN,N-dimethylformamide which had been cooled to 0~C, and the ~eaction mixture is 20 stirred initially at 0~C for 15 minutes, then at 20~C for approximately 60 minutes and finally at 60~C for 6 hours. The mixture is then concentrated under water pump vacuum, the residue is stirred with diisopropyl ether and the resulting crystalline product is isolated by filtration with suction.
Le A 31 906 Foreign Countries This gives 1.1 g (60% of theory) of 1 -[4-cyano-2-fluoro-5-(2-methoxycarbonyl-ethenyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidine of melting point 154~C.
step 3 F3C~,~ N~O
~CN
H O
Ozone is introduced for 45 minutes into a mixture of 8.7 g (22 mmol) of 1-[4-cyano-2-fluoro-5-(2-methoxycarbonyl-ethenyl)-phenyl] -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H)-pyrimidine and 600 ml of methylene chloride which had been cooled to -70~C. The cooling bath is then removed, and the mixture is admixed with 10 10 ml of dimethyl sulphide. After the mixture has warmed to room temperature (about 20~C), the phases are separated and the organic phase is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by filtration with suction.
This gives 7.4 g (99% of theory) of 1-(4-cyano-2-fluoro-5-formyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine of melting point 177~C.
Le A 31 906 Foreign Countries Use Examples:
FY~ rle A
Prc-e..,e.~ence 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 activecompound 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 preparation 10 of active compound is sprayed onto the soil in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the sprayliquor is chosen so that the amounts of active compound desired in each case areapplied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in 15 comparison with the development of the untreated control.
The figures denote:
0% = no effect (like untreated control) 100% = total destruction In this test, at an application rate of 60 g/ha, for example the compound of Preparation 20 Example 2 exhibits very potent activity against weeds such as Avena fatua (~0%), Setaria (95%), Abutilon (100%), Amaranthus (100%), Galium (95% and Sinapis (100%).
Le A 31 906 Foreign Countries Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To produce a suitable preparation of active compound, I 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.
Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound 10 desired per unit area. The concentration of the spray liquor is chosen so that the amounts of active compound desired in each case are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison with the development of the untreated control.
The figures denote:
15 0% = no effect (like untreated control) 100% = total destruction In this test, at an application rate of 60 g/ha, for example the compound of Preparation Example 2 exhibits very potent activity against weeds such as Abutilon ( 100%), Amaranthus (100%), Galium (90%) and Sinapis (100%).
... .
Claims (8)
1. Aromatic carbonyl compounds and their derivatives of the general formula (I) in which Q represents oxygen, sulphur or imino (NH), R1 represents hydrogen or halogen, R2 represents the grouping below in which A1 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, alkoxy, aryl, alkylsulphonyl and arylsulphonyl, A1 furthermore represents a radical selected from the group consisting of alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted, A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, aryl, alkoxy, alkylsulphonyl and arylsulphonyl, A2 furthermore presents a radical selected from the group consisting of alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted, and A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy(thio)phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino, alkinyloxycarbonyl, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl, cycloalkylalkoxycarbonyl, aryl, aryloxy, arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl, heterocyclyl, heterocyclylalkyl, heterocyclylalkoxy or heterocyclylalkoxycarbonyl, each of which may optionally be substituted, R3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio and alkylamino, each of which may optionally be substituted, and Z represents a monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclylamino and heterocyclylimino, each of which may optionally be substituted, except for ethyl5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxybenzoate, methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate.
2. Aromatic carbonyl compounds of the general formula (I) according to Claim 1, characterized in that Q represents oxygen, sulphur or imino (NH), R1 represents hydrogen, fluorine, chlorine or bromine, R2 represents the grouping below -A'-A2-A3 in which A1 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkoxysulphonyl and phenylsulphonyl, A1 furthermore represents a radical selected from the group consisting of C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine, A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl and phenylsulphonyl, A2 furthermore represents a radical selected from the group consisting of C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine, A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl and dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by halogen, C1-C4-alkoxy or C1-C4-alkoximino, A3 furthermore represents a radical selected from the group consisting of alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino and alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and being in each case optionally substituted by halogen, A3 furthermore represents a radical selected from the group consisting of cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl and 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 and being in each case optionally substituted by halogen, cyano, carboxyl, C1-C4-alkyl and/or C1-C4-alkoxycarbonyl, A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, phenyl-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenyloxycarbonyl and phenyl-C1-C4-alkoxycarbonyl, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C1-C4-alkyl, furyl-C1-C4-alkyl, thienyl-C1-C4-alkyl, oxazolyl-C1-C4-alkyl, isoxazol-C1-C4-alkyl, thiazol-C1-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy, furylmethoxy, each of which may optionally be substituted by nitro, cyano, carboxyl, halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxy-carbonyl, represents perhydropyranylmethoxy or pyridylmethoxy, R3 represents hydrogen, hydroxyl, mercapto, amino, (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio and alkylamino having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by hydroxyl, cyano, halogen, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl, and Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception:
piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to 6 carbon atoms and 1 to 4 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to three groupings selected from the group consisting of -CO-, -CS-, -SO- and/or SO2- and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, C1-C6-alkyl (which for its part may optionally be substituted by halogen or C1-C4-alkoxy), C2-C6-alkenyl and C2-C6-alkinyl (which for their part may each optionally be substituted by halogen), C1-C6-alkoxy and C1-C6-alkoxy-carbonyl (which for their part may each optionally be substituted by - halogen or C1-C4-alkoxy), C2-C6-alkenyloxy or C2-C6-alkinyloxy (which for their part may each optionally be substituted by halogen), C1-C6-alkylthio, C2-C6-alkenylthio and C2-C6-alkinylthio (which for their part may each optionally be substituted by halogen), C1-C6-alkylamino and di-(C1-C4-alkyl)amino, C3-C6-cycloalkyl and C3-C6-cycloalkyl-C1-C4-alkyl (which for their part may each optionally be substituted by halogen and/or C1-C4-alkyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxy-carbonyl), except for ethyl5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate.
piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to 6 carbon atoms and 1 to 4 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to three groupings selected from the group consisting of -CO-, -CS-, -SO- and/or SO2- and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, C1-C6-alkyl (which for its part may optionally be substituted by halogen or C1-C4-alkoxy), C2-C6-alkenyl and C2-C6-alkinyl (which for their part may each optionally be substituted by halogen), C1-C6-alkoxy and C1-C6-alkoxy-carbonyl (which for their part may each optionally be substituted by - halogen or C1-C4-alkoxy), C2-C6-alkenyloxy or C2-C6-alkinyloxy (which for their part may each optionally be substituted by halogen), C1-C6-alkylthio, C2-C6-alkenylthio and C2-C6-alkinylthio (which for their part may each optionally be substituted by halogen), C1-C6-alkylamino and di-(C1-C4-alkyl)amino, C3-C6-cycloalkyl and C3-C6-cycloalkyl-C1-C4-alkyl (which for their part may each optionally be substituted by halogen and/or C1-C4-alkyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxy-carbonyl), except for ethyl5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate.
3. Aromatic carbonyl compounds of the general formula (I) according to Claim 1, characterized in that Q represents oxygen, sulphur or imino (NH), R1 represents hydrogen, fluorine or chlorine, R2 represents the grouping below in which A1 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R4- in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl and ethylsulphonyl, A1 furthermore represents a radical selected from the group consisting of 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 and propine-1,3-diyl, A2 represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R5- in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl and phenylsulphonyl, A2 furthermore represents a radical selected from the group consisting of 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 and propine-1,3-diyl, A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, represents a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl and diisopropoxyphosphoryl, each of which may optionally be substituted by fluorine, chlorine, methoxy, ethoxy, methoximino or ethoximino, A3 furthermore represents a radical selected from the group consisting of propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl and butinyloxycarbonyl, each of which may optionally be substituted by fluorine or chlorine, A3 furthermore represents a radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo-propylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl and cyclohexylmethoxycarbonyl, each of which may optionally be substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy and pyridylmethoxy, each of which may optionally be substituted by 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, R3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i-propylamino, each of which may optionally be substituted by hydroxyl, cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxy-carbonyl, and Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception:
piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to 5 carbon atoms and 1 to 3 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to two groupings selected from the group consisting of -CO-, -CS-, -SO- and/or SO2-, and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which for their part may optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propinyl and butinyl (which for their part may each optionally be substituted by fluorine or chlorine); methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl and ethoxycarbonyl (which for their part may each optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propinyloxy and butinyloxy (which for their part may optionally be substituted by fluorine or chlorine); methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio and butinylthio (which for their part may each optionally be substituted by fluorine or chlorine);
methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino and diethylamino; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl (which for their part may each optionally be substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl), except for ethyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate.
piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to 5 carbon atoms and 1 to 3 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to two groupings selected from the group consisting of -CO-, -CS-, -SO- and/or SO2-, and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which for their part may optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propinyl and butinyl (which for their part may each optionally be substituted by fluorine or chlorine); methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl and ethoxycarbonyl (which for their part may each optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propinyloxy and butinyloxy (which for their part may optionally be substituted by fluorine or chlorine); methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio and butinylthio (which for their part may each optionally be substituted by fluorine or chlorine);
methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino and diethylamino; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl (which for their part may each optionally be substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl), except for ethyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-2-methoxy-benzoate, methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate.
4. Process for preparing aromatic carbonyl compounds of the general formula (I) in which R1, R2, R3, Q and Z are each as defined in Claim 1, characterized in that aromatic nitriles of the formula (II) in which R1, R2 and Z are each as defined above are reacted with water, hydrogen sulphide or ammonia and the resulting substituted aromatic carboxylic acids or their derivatives of the general formula (Ia) in which Q, R1, R2 and Z are each as defined above are converted by customary methods into substituted aromatic carbonyl compounds or their derivatives in accordance with the above definition of the compounds of the formula (I).
5. Herbicidal compositions, characterized in that they contain at least one aromatic carbonyl compound of the formula (I) according to Claim 1.
6. Method for controlling undesirable plants, characterized in that aromatic carbonyl compounds of the formula (I) according to Claim 1 are allowed to act on undesirable plants and/or their habitat.
7. Use of aromatic carbonyl compounds of the formula (I) according to Claim 1 for controlling undesirable plants.
8. Process for preparing herbicidal compositions, characterized in that aromaticcarbonyl compounds of the formula (I) according to Claim 1 are mixed with extenders and/or surfactants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19627901.1 | 1996-07-11 | ||
| DE19627901A DE19627901A1 (en) | 1996-07-11 | 1996-07-11 | Substituted aromatic carbonyl compounds and their derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2260201A1 true CA2260201A1 (en) | 1998-01-22 |
Family
ID=7799512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002260201A Abandoned CA2260201A1 (en) | 1996-07-11 | 1997-07-01 | Substituted aromatic carbonyl compounds and their derivatives |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0912527A1 (en) |
| JP (1) | JP2000514805A (en) |
| AU (1) | AU3441297A (en) |
| BR (1) | BR9710238A (en) |
| CA (1) | CA2260201A1 (en) |
| DE (1) | DE19627901A1 (en) |
| IL (1) | IL127802A0 (en) |
| WO (1) | WO1998002422A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19929348A1 (en) * | 1999-06-26 | 2000-12-28 | Bayer Ag | Pure 2-heterocyclylmethyl-benzoic acid derivative preparation in high yield, for use as pharmaceutical or agrochemical intermediate, from phthalide compound and nitrogen-containing heterocycle |
| DE19946853A1 (en) | 1999-09-30 | 2001-04-05 | Bayer Ag | Substituted aryl ketones |
| EA005677B1 (en) * | 2000-05-04 | 2005-04-28 | Басф Акциенгезельшафт | Heterocyclyl substituted phenyl sulfamoyl carboxamides |
| HUE027607T2 (en) * | 2002-10-30 | 2016-10-28 | Basf Se | Aminobenzoylsulfonamides and their preparation |
| JP2019535689A (en) | 2016-10-27 | 2019-12-12 | バイエル アクチェンゲゼルシャフトＢａｙｅｒ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ | 4,5-fused 1,2,4-triazolone |
| JOP20190094A1 (en) | 2016-10-27 | 2019-04-25 | Broad Inst Inc | 2,4,5-trisubstituted 1,2,4-triazolones useful as inhibitors of dhodh |
| EP3553052A1 (en) | 2018-04-10 | 2019-10-16 | Bayer AG | 5-oxo-4,5-dihydro-1h-1,2,4-triazol derivatives for the treatment of cancer |
| TW201945346A (en) | 2018-04-10 | 2019-12-01 | 德商拜耳廠股份有限公司 | Method for the preparation of a 2,4,5-trisubstituted 1,2,4-triazolone |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19500439A1 (en) * | 1994-05-04 | 1995-11-09 | Bayer Ag | Substituted aromatic thiocarboxylic acid amides |
| DE19531152A1 (en) * | 1994-12-15 | 1996-06-20 | Bayer Ag | Substituted N-aryl nitrogen heterocycles |
| DE19516785A1 (en) * | 1995-05-08 | 1996-11-14 | Bayer Ag | Substituted aminophenyluracils |
| DE19527570A1 (en) * | 1995-07-28 | 1997-01-30 | Bayer Ag | Substituted aminouracile |
| DE19528186A1 (en) * | 1995-08-01 | 1997-02-06 | Bayer Ag | Substituted phenyluracile |
| DE19528305A1 (en) * | 1995-08-02 | 1997-02-06 | Bayer Ag | Substituted phenyluracile |
-
1996
- 1996-07-11 DE DE19627901A patent/DE19627901A1/en not_active Withdrawn
-
1997
- 1997-07-01 IL IL12780297A patent/IL127802A0/en unknown
- 1997-07-01 CA CA002260201A patent/CA2260201A1/en not_active Abandoned
- 1997-07-01 AU AU34412/97A patent/AU3441297A/en not_active Abandoned
- 1997-07-01 WO PCT/EP1997/003433 patent/WO1998002422A1/en not_active Application Discontinuation
- 1997-07-01 BR BR9710238A patent/BR9710238A/en not_active Application Discontinuation
- 1997-07-01 EP EP97930469A patent/EP0912527A1/en not_active Withdrawn
- 1997-07-01 JP JP10505556A patent/JP2000514805A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0912527A1 (en) | 1999-05-06 |
| BR9710238A (en) | 1999-08-10 |
| WO1998002422A1 (en) | 1998-01-22 |
| AU3441297A (en) | 1998-02-09 |
| DE19627901A1 (en) | 1998-01-15 |
| IL127802A0 (en) | 1999-10-28 |
| JP2000514805A (en) | 2000-11-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |