CA2332443A1 - Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes - Google Patents
Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes Download PDFInfo
- Publication number
- CA2332443A1 CA2332443A1 CA002332443A CA2332443A CA2332443A1 CA 2332443 A1 CA2332443 A1 CA 2332443A1 CA 002332443 A CA002332443 A CA 002332443A CA 2332443 A CA2332443 A CA 2332443A CA 2332443 A1 CA2332443 A1 CA 2332443A1
- Authority
- CA
- Canada
- Prior art keywords
- chlorine
- fluorine
- optionally substituted
- cyano
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
- C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D239/08—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms directly attached in position 2
- C07D239/10—Oxygen or sulfur atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/20—N-Aryl derivatives thereof
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
- C07D233/36—One oxygen atom with hydrocarbon radicals, substituted by nitrogen atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D233/30—Oxygen or sulfur atoms
- C07D233/42—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
- C07D243/04—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The invention relates to new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of general formula (I), in which n is 1, 2 or 3, Q is oxygen or sulphur, R1 is alkyl, alkoxy, alkylamino, dialkylamino, alkenyl, alkinyl, cycloalkyl or cycloalkylalkyl, whereby each of these groups is possibly substituted, and R2 is a monocyclic or bicyclic aromatic grouping which is possibly substituted and possibly heterocyclically anellated. The invention also relates to a method for producing these compounds and to their use as herbicides.
Description
Le A 33 025-Foreign Countries / Kri/li/Ke/NT
Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes The invention relates to new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes, to processes for their preparation and to their use as herbicides.
Some substituted 1,3-diaza-2-(thi)oxo-cycloalkanes are already known from the literature (cf. J. Chem. Eng. Data 13 (1968), 582-585 - cited in Chem.
Abstracts 69:106613). However, nothing has been disclosed about the biological properties of these compounds.
There have now been found the new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (I) Q
' ~ Rz RAN N~ (I) ~(CHZ)~
in which n represents I, 2 or 3, Q represents oxygen or sulphur, RI represents hydrogen, formyl or in each case optionally substituted alkyl, alkoxy, alkylamino, dialkylamino, alkenyl, alkinyl, cycloalkyl or cycloalkyl-alkyl, and R2 represents an optionally substituted monocyclic or bicyclic aromatic group which is optionally fused to a heterocycle.
Le A 33 025-Foreign Countries In the definitions, the hydrocarbon chains such as alkyl - also in connection with hetero atoms such as in alkoxy - are in each case straight-chain or branched.
n preferably represents 1, 2 or 3;
Q preferably represents oxygen or sulphur;
RI preferably represents hydrogen, formyl, or represents alkyl, alkoxy, alkylamino, dialkylamino, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, halogen, Cl-C4-alkoxy, Cl-C4-alkyl-carbonyl, Cl-C4-alkoxy-carbonyl or morpholinyl, or represents alkenyl or alkinyl, each of which has 2 to 6 carbon atoms, and each of which is optionally substituted by cyano, halogen or C1-C4-alkoxy-carbonyl, or represents cycloalkyl or cycloalkylalkyl, each of which has 3 to carbon atoms in the cycloalkyl groups and, if appropriate, 1 to 4 carbon atoms in the alkyl moiety and each of which is optionally substituted by cyano, halogen or C 1-C4-alkyl;
R2 preferably represents the aromatic group defined hereinbelow R~ / Rs Rs \ ~ Ra where 2~ R3 represents hydrogen, vitro, amino, cyano, formylamino, halogen, or represents alkyl, alkoxy, alkylcarbonylamino, alkoxycarbonylamino, alkylaminocarbonylamino, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, Le A 33 025-Foreign Countries halogen or C1-C4-alkoxy, or represents cycloalkylcarbonylamino which has 3 to 6 carbon atoms in the cycloalkyl moiety and which is optionally substituted by cyano, halogen, C 1-C4-alkyl or C 1-C4-halogenoalkyl, or represents phenylcarbonylamino which is optionally substituted by cyano, nitro, C 1-C4-alkyl, C 1-C4-halogenoalkyl, C 1-C4-alkoxy or C1-C4-halogenoalkoxy;
R4 represents hydrogen, nitro, cyano, fluorine, chlorine or bromine;
RS represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, fluorine, chlorine, bromine, or represents alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl, each of which has up to 4 carbon atoms and each of which is optionally substituted by fluorine and/or chlorine;
R~ represents the group hereinbelow:
_A 1 _A2_~,3 in which Al represents a single bond, or represents oxygen, sulphur, -SO-, -S02-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, C 1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C 1-C4-alkoxy, phenyl, C 1-C4-alkyl-carbonyl, phenylcarbonyl, C 1-C4-alkyl-sulphonyl or phenylsulphonyl, Al furthermore represents Cl-C~-alkanediyl, C2-C~-alkenediyl, C2-Cb-azaalkenediyl, C2-C~-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, each of which is optionally substituted by fluorine, chlorine or bromine, Le A 33 025-Foreign Countries A2 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenyl-sulphonyl, A2 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-G~-cycloalkenediyl or phenylene, each of which is optionally substituted by fluorine, chlorine or bromine, A3 represents hydrogen, hydroxyl, mercapto, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, fluorine, chlorine, bromine, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkyl-I S amino, alkoxycarbonyl or dialkoxy(thio)phosphoryl, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by fluorine, chlorine or C1-C4-alkoxy, or represents alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxy-carbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl, each of which has 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and each of which is optionally substituted by fluorine or chlorine, or represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl, each of which has 3 to 6 carbon atoms in the cycloalkyl groups and, if appropriate, I to 4 carbon atoms in the alkyl groups and each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, CI-C4-alkyl and/or CI-C4-alkoxy-carbonyl, or represents phenyl, phenoxy, phenyl-CI-C4-alkyl, phenyl-C I -C4-alkoxy, phenoxycarbonyl or phenyl-C 1-C,1-alkoxycarbonyl, each of which is optionally substituted by nitro, cyano, carboxyl, Le A 33 025-Foreign Countries fluorine, chlorine, bromine, Cl-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxy-carbonyl, A3 furthermore represents (in each case optionally fully or partially S hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C 1-C4-alkyl, furyl-C 1-C4-alkyl, thienyl-C 1-C4-alkyl, oxazolyl-Cl-C4-alkyl, isoxazol-C1-C4-alkyl, thiazol-C1-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy, furylmethoxy, perhydropyranylmethoxy or pyridylmethoxy, R~ represents hydrogen, fluorine or chlorine, or in each case two adjacent radicals - R3 and R4, R4 and R5, RS and Rb or R6 and R~ - together represent one of the following groups -Q3-CQ4-> -Q3-CQ4-QS-> -Q3-C(Rg>R9)-QS-> -C(Rg>R9)-CQ4->
-C(Rg~R9)-Q3-CQ4-> -Q3-C(R$>R9)-C(Rg>R9)->
-Q3-C(Rg,R~)-C(Rg,R9)-QS-, -C(Rg,R9)-C(Rg,R9)-CQ4-, -Q3-C(Rg)-C(Rg)-~ -C(Rg)-C(Rg)-CQ4-> -Q3-C(Rg>R9)-CQ4->
_N(R10)_C(R8~R9)_CQ4_, _C(R8)-N_, _Q3_CQ4-C(R8~R9)->
-Q3-CQ4_N(R10)_, -Q3_C(R8~R9)-CQ4_N(R10)-_C(R8,R9)_Q3_CQ4-N(R10)-~ -C(R8,R9)_C(R8,R9)-N(R10)-_C(R8>R9)_C(R8>R9)_CQ4_N(R10)_> _C(R8)-C(R8)-N(R10)_>
-C(R8)_C(R8)_CQ4-N(R10)_, -C(R8,R9)_CQ4-N(R10)-, _N(R10~_C~R8;R9~_CQ4_N~R10~-> _C(R8~-N_N~R10)_, _Q3-CQ4_C(RS.R9)_N(R10~_, Q3_C(R8>R9~_C(R8>R9)_CQ4-N(R10)_ where Le A 33 025-Foreign Countries Q3~ Q4 ~d QS ~-a identical or different and represent in each case oxygen or sulphur, Rg and R9 are identical or different and individually represent hydrogen, fluorine, chlorine, bromine or Cl-C4-alkyl or together represent C2-CS-alkanediyl, and R10 represents hydrogen, hydroxyl or represents alkyl, alkylcarbonyl, alkoxy-carbonyl or alkylsulphonyl, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, fluorine, chlorine, C 1-C4-alkoxy, C 1-C4-alkyl-carbonyl or C 1-C4-alkoxy-carbonyl, or represents alkenyl or alkinyl, each of which has 2 to 6 carbon atoms and each of which is optionally substituted by fluorine, chlorine or bromine, or represents cycloalkyl or cycloalkylalkyl, each of which has 3 to 6 carbon atoms in the cycloalkyl groups and, if appropriate, 1 to 3 atoms in the alkyl moiety and each of which is optionally substituted by fluorine, chlorine, bromine or Cl-C4-alkyl, or represents alkoxy or alkenyloxy, each of which has up to 6 carbon atoms and each of which is optionally substituted by fluorine and/or chlorine, or represents benzyl or benzyloxy, each of which is optionally substituted by cyano, fluorine, chlorine, Cl-C4-alkyl, C1-C4-halogenoalkyl, C 1-C4-alkoxy or C 1-C4-halogenoalkoxy.
n especially preferably represents 1, 2 or 3;
Q especially preferably represents oxygen or sulphur;
R 1 especially preferably represents hydrogen, formyl, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexyl-Le A 33 025-Foreign Countries methyl, each of which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl;
R3 preferably represents hydrogen, nitro, amino, cyano, formylamino, fluorine, chlorine, or represents methyl, trifluoromethyl, acetylamino, propionylamino, butyroylamino, i-butyroylamino, trifluoroacetylamino, methoxycarbonyl-amino, ethoxycarbonylamino, methylaminocarbonylamino, ethylamino-carbonylamino, cyclopropylcarbonylamino or phenylcarbonylamino (benzoyl-amino);
R4 preferably represents hydrogen, fluorine or chlorine;
RS preferably represents cyano, thiocarbamoyl, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy or trifluoromethoxy;
R~ especially preferably represents the group hereinbelow:
-A1-A2_A3 in which A1 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl, A 1 furthermore represents methylene, ethane- I ,1-diyl, ethane-1,2-diyl, propane- l , l -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, propinc-1,2-diyl or propinc-1,3-diyl, Le A 33 025-Foreign Countries _g_ A2 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl, A2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl, A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents 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, methyl-amino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl or dipropoxyphosphoryl, diisopropoxyphosphoryl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propenyloxy, butenyloxy, propenyl-amino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxy-carbonyl or butinyloxycarbonyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyl, cyclo-3O butyl, cyclopcntyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclo-pentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, Le A 33 025-Foreign Countries cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclo-butylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclo-pentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclo-hexylmethoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, or represents phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxy-carbonyl, each of which is optionally substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, tri-fluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, tri-fluoromethoxy, methoxycarbonyl and/or ethoxycarbonyl, A3 furthermore represents (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, thienyl-methyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinyl methyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy;
R~ preferably represents hydrogen, fluorine or chlorine.
Two adjacent radicals - R3 and R4, R4 and R5, RS and Rb or R6 and R~ -together preferably represent one of the following groups:
-Q3-CQ4-~ -Q3-CQ4-QS-~ -Q3-C(Rg>R9)-QS-, -C(Rg~R9)-CQ4-, -C(R8,R9~-Q3_CQ4_, _Q3_C~R8,R9~_C(R8,R9~_, -Q3_C~R8,R9)_C(R8,R9)_QS_, _C(R8,R9)_C(R8>R9)-CQ4_, -Q3-C(Rg)=C(Rg)-, _C(R8~-C(R8~_CQ4_, -Q3-C~R8,R9~_CQ4-, -N~R10~_C(R8~R9~_CQ4_, _C(R8~-N_, _Q3_CQ4_C(R8,R9~_>
Le A 33 025-Foreign Countries -Q3_CQ4_N(R10)_~ _Q3_C(R8~R9)-CQ4_N(R10)-_C(R8~R9)_Q3_CQ4_N~R10)-~ _C(R8~R9)-C~R8~R9)-N(R10)_ _C(R8~R9)-C~R8~R9)-CQ4_N(R10)_~ _C(R8)=C(R8)_N(R10)-_C(R8)-C(R8)_CQ4_N~R10)-~ _C(R8~R9)-CQ4-N(R10)-_N(R10)_C(R8~R9)_CQ4_N(R10)_~ _C(R8)-N_N(R10)_~
-Q3_CQ4_C(R8~R9)-N(R10)_~ Q3_C(R8~R9)-C(R8~R9)-CQ4_N(R10)_ where Q3, Q4 and QS are identical or different and in each case represent oxygen or sulphur, R8 and R9 are identical or different and individually represent hydrogen, fluorine, chlorine, methyl or ethyl or together represent ethane-1,2-diyl (dimethylene), and R 10 represents hydrogen, hydroxyl, or represents methyl, ethyl, n- or i-propyl, n-, i-,s or t-butyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl or ethoxy-carbonyl, or represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by fluorine, chlorine or bromine, or represents cyclo-propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutyl-methyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or represents methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyl-oxy, each of which is optionally substituted by fluorine and/or chlorine, or represents benzyl or benzyloxy, each of which is optionally substituted by cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy;
n very especially preferably represents 1 or 2;
Le A 33 025-Foreign Countries Q very especially preferably represents oxygen or sulphur;
R1 very especially preferably represents methyl, ethyl, n- or i-propyl, each of S which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy;
R3 especially preferably represents hydrogen, fluorine or chlorine;
R4 especially preferably represents hydrogen;
RS especially preferably represents cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl;
Rf especially preferably represents the group hereinbelow:
_A 1 _A2_A3 in which A 1 represents a single bond, A2 represents a single bond, 2~ A3 represents hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-prop-oxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethyl-thio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, cthylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n-Le A 33 025-Foreign Countries or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethyl-amino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyl-oxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyloxy, cyclobutyloxy, cyclopentyl-oxy, cyclohexyloxy, cyclopropylmethoxy, cyclobutylmethoxy, cyclo-pentylmethoxy, cyclohexylmethoxy, cyclopentyloxycarbonyl, cyclo-hexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexyl-methoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxy-carbonyl or ethoxycarbonyl, or represents phenoxy, benzyloxy, phenyloxycarbonyl or benzyloxycarbonyl, each of which is optionally 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;
R~ especially preferably represents hydrogen.
Preferred in accordance with the invention are the compounds of the formula (I) which contain a combination of the meanings mentioned above as being preferred.
Especially preferred in accordance with the invention are the compounds of the formula (I) which contain a combination of the meanings mentioned above as being especially preferred.
Le A 33 025-Foreign Countries Very especially preferred in accordance with the invention are the compounds of the formula (I) which contain a combination of the meanings mentioned above as being especially preferred.
A very especially preferred group are those compounds of the formula (I) in which n represents 1 or 2, Q represents oxygen or sulphur, R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy and R2 represents the aromatic group defined hereinbelow R~ / Rs Rs \ ~ R4 Rs where R3 represents hydrogen, fluorine or chlorine, R4 represents hydrogen, RS represents cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl, R~' rrpresents the group hereinbclow Le A 33 025-Foreign Countries _A 1 _A2_A3 in which A 1 represents the group -N-A4- where A4 represents hydrogen, methylsulphonyl or ethylsulphonyl, A2 represents a single bond or -CO-, A3 represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s-or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s-or t-butylthio, methylsulphonyl, ethylsulphonyl, n- or i-propyl-sulphonyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents cyclopropyl, cyclo-butyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutyl-methyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyl-methoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexyl-methoxy, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, or represents phenyl, phenoxy, benzyl or benzyloxy, each of which is optionally substituted by vitro, cyano, carboxyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, meth-oxy, ethoxy, n- or i-propoxy, difluoromethoxy, tri-fluoromethoxy, methoxycarbonyl and/or ethoxycarbonyl, and R~ represents hydrogen.
Le A 33 025-Foreign Countries A further very especially preferred group are those compounds of the formula (I) in which n represents 1 or 2, Q represents oxygen or sulphur, R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, and R2 represents the aromatic group defined hereinbelow R~ / Rs Rs \ ~ R4 Rs where R3 represents hydrogen, fluorine or chlorine, R4 represents hydrogen, R5 represents cyano, thiocarbamoyl, chlorine, bromine, methyl or tri fluoromethyl, Rb represents the group hereinbelow in which Le A 33 025-Foreign Countries A1 represents the group -N-A4- where A4 represents hydrogen, methylsulphonyl or ethylsulphonyl, A2 represents -S02-, A3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally substituted by fluorine, chlorine, cyano or methyl, or represents phenyl or benzyl, each of which is optionally substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, tri-fluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoro-methoxy, methoxycarbonyl or ethoxycarbonyl, and R~ represents hydrogen.
The definitions of radicals mentioned above in general terms or in preferred ranges apply not only to the end products of the formula (I), but also accordingly to the starting materials or intermediates required in each case for the preparation.
These definitions of radicals can be combined with each other as desired, that is to say combinations between the stated ranges of preferred compounds are also possible.
The new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (I) are distinguished by a potent and selective herbicidal activity.
The new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (I) are obtained when 3t) 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (II) Le A 33 025-Foreign Countries Q
R~N~N~H (II) ~(CHz)~
in which n, Q and R1 are as defined above are reacted with halogen compounds of the general formula (III) X 1-R2 (III) in which R2 is as defined above and X 1 represents halogen, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and, if appropriate, electrophilic or nucleophilic substitution reactions are subsequently carried out in the customary manner within the definition of the substituents.
In principle, the compounds of the general formula (I) can also be synthesized as shown schematically hereinbelow:
Reaction of diamines of the general formula (IV) with (thio)carbonic acid derivatives of the general formula (V) Le A 33 02S-Foreign Countries R ~ Rz + Q
(I) (CH2)n (N) (V) where S
n, Q, R1 and R2 are as defined above and Y1 and Y2 are identical or different and in each case represent halogen (in particular chlorine), alkoxy (in particular methoxy or ethoxy), alkoxyalkoxy (in particular (methoxyethoxy or ethoxyethoxy), phenoxy or imidazolyl, if appropriate in the presence of a reaction auxiliary such as, for example, pyridine and if appropriate in the presence of a diluent such as, for example, toluene.
1 S Reaction of 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (VI) with halogen compounds of the general formula (VII) Q
H\N~N~R + R~ z (I) -(CHZ)~ X --(VI) (VII) where n, Q, R 1 and R2 are as defined above and 2S ~-' represents halogen (in particular chlorine, bromine or iodine), Le A 33 025-Foreign Countries if appropriate in the presence of a reaction auxiliary such as, for example, ethyl-diiso-propylamine and if appropriate in the presence of a diluent such as, for example, acetonitrile.
Reaction of (thio)ureas of the general formula (VIII) with a,w-disubstituted alkanes of the general formula (IX) Q
Ei R\H H/R + E2~(CH2)~ --~ (I) ( V III) (IX) where n, Q, R1 and R2 are as defined above, and E1 and E2 represent leaving groups which can be substituted by a nucleophile, such as halogen (in particular chlorine or bromine or alkylsulphonyloxy (in particular methylsulphonyloxy), if appropriate in the presence of a reaction auxiliary such as, for example, potassium carbonate and if appropriate in the presence of a diluent such as, for example, acetone.
If, for example, 1-methyl-imidazolidin-2-one and 2,4,5-trifluorobenzonitrile are used as starting materials, the course of the reaction in the process according to the ?5 invention can be outlined by the following formulaic scheme:
Le A 33 025-Foreign Countries F
O
II CN
HsC.N~N.H + O / I
-' ~ \
- HF H3C~N~N
L--J F
Formula (II) provides a general definition of the 1,3-diaza-2-(thi)oxo-cycloalkanes to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I). In formula (II), n, Q and RI
preferably, or in particular, have those meanings which have already been stated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or particularly prefered, for n, Q and R I .
The starting materials of the general formula (II) are known and/or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 80 (1958), 6409-6412; J.
Chem.
Soc. Perkin Trans. 1, 1981, 2499-2503; J. Org. Chem. 22 (1957), 1581; J. Org.
Chem. 28 ( 1992), 7339-7342; Synth. Commun. 27 (1997), 3565-3571 ).
Formula (III) provides a general definition of the halogen compounds furthermore to be used as starting materials in the process according to the invention. In formula (III), R2 preferably, or in particular, has that meaning which has already been stated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, especially preferred or very especially preferred for R2; X2 preferably represents fluorine or chlorine, in particular fluorine.
The starting materials of the general formula (III) are known and/or can be prepared by processes known per se (cf EP-A-191181, EP-A-370332, EP-A-431373, EP-A-441004, EP-A-597360).
The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent. Suitable dilucnts are, above all, inert organic solvents. These include, in particular, aliphatic, alicyclic or Le A 33 02S-Foreign Countries aromatic, optionally halogenated hydrocarbons such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl S ether or ethylene glycol diethyl ether; ketones such as acetone, butanone or methyl isobutyl ketone; nitrites such as acetonitrile, propionitrile or butyronitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethyl phosphoric tr-iamide; esters such as methyl acetate or ethyl acetate, sulphoxides such as dimethyl sulphoxide.
The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a reaction auxiliary.
Suitable reaction auxiliaries are generally the customary inorganic or organic bases or acid acceptors. These preferably include the acetates, amides, carbonates, 1 S hydrogencarbonates, hydrides, hydroxides or alkoxides of alkali metals or alkaline earth metals such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or calcium hydrogencarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or -i-propoxide or potassium n- or i-propoxide, sodium n-, -i-, -s- or -t-butoxide, or potassium n-, -i-, -s- or -t-butoxide; furthermore also basic organic nitrogen 2S compounds such as, for example, tr-imethylamine, triethylamine, tripropylamine, tri-butylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclo-hexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,S-dimethyl-pyridine, S-ethyl-2-methyl-pyridine, 4-dimethyl-amino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2Joctane (DABCO), l,S-diazabicyclo[4,3,OJnon-S-ene (DBN), or 1,8-diazabicyclo[S,4,OJundec-7-ene (DBU).
Le A 33 025-Foreign Countries When carrying out the process according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 1 SO°C, preferably between 20°C and 120°C.
S
The process according to the invention is generally earned out under atmospheric pressure. However, it is also possible for the process according to the invention to be carried out under elevated or reduced pressure, in general between 0.1 bar and 10 bar.
To carry out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the temperature required.
1 S 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 undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, 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.
Le A 33 025-Foreign Countries Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
S
Monocotyledonous weeds of the enera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
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 way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks, and on paths and areas with or without tree stands. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pastures, and for selective weed control in annual crops.
The compounds of the formula (I) according to the invention arc particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous crops, both pre- and post-emergence.
Le A 33 025-Foreign Countries The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric S substances.
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 dispersants and/or foam formers.
If water is used as an extender, organic solvents can, for example, also be used as cosolvents. Liquid solvents which are mainly suitable are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic I S 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 as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else 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 formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylenc fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, Le A 33 025-Foreign Countries arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colourants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention, as such or in their formulations, can also be used for controlling weeds as a mixture with known herbicides, ready-mixes or tank mixes being possible.
Herbicides which are suitable for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromo-fenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlor-imuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulf=
Le A 33 025-Foreign Countries uron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfam-uron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, di-allate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethen-S amid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epo-prodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, florasulam, fluazi-fop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumet-sulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, meto-benzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propa-chlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulf uron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenz-oxim, pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quin-chlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rim-sulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfo-meturon(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, ter-butryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), 3(1 thiobencarb, tiocarbazil, tralkoxydim, tri-allate, triasulfuron, tribenuron(-methyl), tri-clopyr, tridiphane, trifluralin and triflusulfuron.
Le A 33 025-Foreign Countries Mixtures with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners, 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 spreading.
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 1 S essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and S kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples which follow.
Le A 33 025-Foreign Countries Preparation Examples:
Example 1 F
CN
H3C~N~N \
F
A mixture of 5.8 g (50 mmol) of 1-methyl-imidazolidine-2-thione, 8.6 g (SS
mmol) of 2,4,5-trifluoro-benzonitrile, 7.6 g (SS mmol) of potassium carbonate and 50 ml of dimethyl sulphoxide is stirred for 16 hours at 80°C. When cold, the mixture is poured into a stirred mixture of approximately equal volumes of methylene chloride and water and acidified with 2N hydrochloric acid. The organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated in a water pump vacuum, the residue is digested with diethyl ether, and the product which is obtained as crystals is isolated by filtration with suction.
This gives 9.5 g (75% of theory) of 1-methyl-3-(4-cyano-2,5-difluoro-phenyl)-imida-zolidine-2-thione of melting point 143°C.
Example 2 C2Hs HN~SO2 CN
H3C~N~N \
F
(subsequent reaction) Le A 33 025-Foreign Countries A mixture of 2.0 g (8 mmol) of 1-methyl-3-(4-cyano-2,5-difluoro-phenyl)-imida-zolidine-2-thione, 1.8 g (16 mmol) of ethanesulphonamide, 2.2 g (16 mmol) of potassium carbonate and 50 ml of dimethyl sulphoxide is stirred for 16 hours at 100°C. When cold, the mixture is poured into a stirred mixture of approximately equal volumes of methylene chloride and water and acidified with 2N
hydrochloric acid. The organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated in a water pump vacuum, the residue is digested with isopropanol, and the product which is obtained as crystals is isolated by filtration with suction.
This gives 1.9 g (68% of theory) of 1-methyl-3-(4-cyano-2-fluoro-5-ethylsulphonyl-amino-phenyl)-imidazolidine-2-thione of melting point 174°C.
Other examles of compounds of the formula (I) which can be prepared analogously to the Preparation Examples 1 to 2 and in accordance with the general description of the preparation processes according to the invention are those listed in Table 1 below.
Q
Rz RU-N~ (I) (CHz)~
Le A 33 025-Foreign Countries Table 1: Examples of the compounds of the formula (I) Ex. Melting No. n Q R1 R2 point (°C) ~O
F
CN
/
F
CN
F
6 1 O CH3 ~ CI 98 7 1 S CH3 ~ CI 166 O
CN
/
F
Le A 33 025-Foreign Countries Ex. Melting No. n Q R1 R2 point (°C) 9 1 S CH3 ~ 164 CN
/
F
Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes The invention relates to new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes, to processes for their preparation and to their use as herbicides.
Some substituted 1,3-diaza-2-(thi)oxo-cycloalkanes are already known from the literature (cf. J. Chem. Eng. Data 13 (1968), 582-585 - cited in Chem.
Abstracts 69:106613). However, nothing has been disclosed about the biological properties of these compounds.
There have now been found the new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (I) Q
' ~ Rz RAN N~ (I) ~(CHZ)~
in which n represents I, 2 or 3, Q represents oxygen or sulphur, RI represents hydrogen, formyl or in each case optionally substituted alkyl, alkoxy, alkylamino, dialkylamino, alkenyl, alkinyl, cycloalkyl or cycloalkyl-alkyl, and R2 represents an optionally substituted monocyclic or bicyclic aromatic group which is optionally fused to a heterocycle.
Le A 33 025-Foreign Countries In the definitions, the hydrocarbon chains such as alkyl - also in connection with hetero atoms such as in alkoxy - are in each case straight-chain or branched.
n preferably represents 1, 2 or 3;
Q preferably represents oxygen or sulphur;
RI preferably represents hydrogen, formyl, or represents alkyl, alkoxy, alkylamino, dialkylamino, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, halogen, Cl-C4-alkoxy, Cl-C4-alkyl-carbonyl, Cl-C4-alkoxy-carbonyl or morpholinyl, or represents alkenyl or alkinyl, each of which has 2 to 6 carbon atoms, and each of which is optionally substituted by cyano, halogen or C1-C4-alkoxy-carbonyl, or represents cycloalkyl or cycloalkylalkyl, each of which has 3 to carbon atoms in the cycloalkyl groups and, if appropriate, 1 to 4 carbon atoms in the alkyl moiety and each of which is optionally substituted by cyano, halogen or C 1-C4-alkyl;
R2 preferably represents the aromatic group defined hereinbelow R~ / Rs Rs \ ~ Ra where 2~ R3 represents hydrogen, vitro, amino, cyano, formylamino, halogen, or represents alkyl, alkoxy, alkylcarbonylamino, alkoxycarbonylamino, alkylaminocarbonylamino, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, Le A 33 025-Foreign Countries halogen or C1-C4-alkoxy, or represents cycloalkylcarbonylamino which has 3 to 6 carbon atoms in the cycloalkyl moiety and which is optionally substituted by cyano, halogen, C 1-C4-alkyl or C 1-C4-halogenoalkyl, or represents phenylcarbonylamino which is optionally substituted by cyano, nitro, C 1-C4-alkyl, C 1-C4-halogenoalkyl, C 1-C4-alkoxy or C1-C4-halogenoalkoxy;
R4 represents hydrogen, nitro, cyano, fluorine, chlorine or bromine;
RS represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, fluorine, chlorine, bromine, or represents alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl, each of which has up to 4 carbon atoms and each of which is optionally substituted by fluorine and/or chlorine;
R~ represents the group hereinbelow:
_A 1 _A2_~,3 in which Al represents a single bond, or represents oxygen, sulphur, -SO-, -S02-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, C 1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C 1-C4-alkoxy, phenyl, C 1-C4-alkyl-carbonyl, phenylcarbonyl, C 1-C4-alkyl-sulphonyl or phenylsulphonyl, Al furthermore represents Cl-C~-alkanediyl, C2-C~-alkenediyl, C2-Cb-azaalkenediyl, C2-C~-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, each of which is optionally substituted by fluorine, chlorine or bromine, Le A 33 025-Foreign Countries A2 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenyl-sulphonyl, A2 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-G~-cycloalkenediyl or phenylene, each of which is optionally substituted by fluorine, chlorine or bromine, A3 represents hydrogen, hydroxyl, mercapto, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, fluorine, chlorine, bromine, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkyl-I S amino, alkoxycarbonyl or dialkoxy(thio)phosphoryl, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by fluorine, chlorine or C1-C4-alkoxy, or represents alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxy-carbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl, each of which has 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and each of which is optionally substituted by fluorine or chlorine, or represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl, each of which has 3 to 6 carbon atoms in the cycloalkyl groups and, if appropriate, I to 4 carbon atoms in the alkyl groups and each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, CI-C4-alkyl and/or CI-C4-alkoxy-carbonyl, or represents phenyl, phenoxy, phenyl-CI-C4-alkyl, phenyl-C I -C4-alkoxy, phenoxycarbonyl or phenyl-C 1-C,1-alkoxycarbonyl, each of which is optionally substituted by nitro, cyano, carboxyl, Le A 33 025-Foreign Countries fluorine, chlorine, bromine, Cl-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxy-carbonyl, A3 furthermore represents (in each case optionally fully or partially S hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C 1-C4-alkyl, furyl-C 1-C4-alkyl, thienyl-C 1-C4-alkyl, oxazolyl-Cl-C4-alkyl, isoxazol-C1-C4-alkyl, thiazol-C1-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy, furylmethoxy, perhydropyranylmethoxy or pyridylmethoxy, R~ represents hydrogen, fluorine or chlorine, or in each case two adjacent radicals - R3 and R4, R4 and R5, RS and Rb or R6 and R~ - together represent one of the following groups -Q3-CQ4-> -Q3-CQ4-QS-> -Q3-C(Rg>R9)-QS-> -C(Rg>R9)-CQ4->
-C(Rg~R9)-Q3-CQ4-> -Q3-C(R$>R9)-C(Rg>R9)->
-Q3-C(Rg,R~)-C(Rg,R9)-QS-, -C(Rg,R9)-C(Rg,R9)-CQ4-, -Q3-C(Rg)-C(Rg)-~ -C(Rg)-C(Rg)-CQ4-> -Q3-C(Rg>R9)-CQ4->
_N(R10)_C(R8~R9)_CQ4_, _C(R8)-N_, _Q3_CQ4-C(R8~R9)->
-Q3-CQ4_N(R10)_, -Q3_C(R8~R9)-CQ4_N(R10)-_C(R8,R9)_Q3_CQ4-N(R10)-~ -C(R8,R9)_C(R8,R9)-N(R10)-_C(R8>R9)_C(R8>R9)_CQ4_N(R10)_> _C(R8)-C(R8)-N(R10)_>
-C(R8)_C(R8)_CQ4-N(R10)_, -C(R8,R9)_CQ4-N(R10)-, _N(R10~_C~R8;R9~_CQ4_N~R10~-> _C(R8~-N_N~R10)_, _Q3-CQ4_C(RS.R9)_N(R10~_, Q3_C(R8>R9~_C(R8>R9)_CQ4-N(R10)_ where Le A 33 025-Foreign Countries Q3~ Q4 ~d QS ~-a identical or different and represent in each case oxygen or sulphur, Rg and R9 are identical or different and individually represent hydrogen, fluorine, chlorine, bromine or Cl-C4-alkyl or together represent C2-CS-alkanediyl, and R10 represents hydrogen, hydroxyl or represents alkyl, alkylcarbonyl, alkoxy-carbonyl or alkylsulphonyl, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, fluorine, chlorine, C 1-C4-alkoxy, C 1-C4-alkyl-carbonyl or C 1-C4-alkoxy-carbonyl, or represents alkenyl or alkinyl, each of which has 2 to 6 carbon atoms and each of which is optionally substituted by fluorine, chlorine or bromine, or represents cycloalkyl or cycloalkylalkyl, each of which has 3 to 6 carbon atoms in the cycloalkyl groups and, if appropriate, 1 to 3 atoms in the alkyl moiety and each of which is optionally substituted by fluorine, chlorine, bromine or Cl-C4-alkyl, or represents alkoxy or alkenyloxy, each of which has up to 6 carbon atoms and each of which is optionally substituted by fluorine and/or chlorine, or represents benzyl or benzyloxy, each of which is optionally substituted by cyano, fluorine, chlorine, Cl-C4-alkyl, C1-C4-halogenoalkyl, C 1-C4-alkoxy or C 1-C4-halogenoalkoxy.
n especially preferably represents 1, 2 or 3;
Q especially preferably represents oxygen or sulphur;
R 1 especially preferably represents hydrogen, formyl, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexyl-Le A 33 025-Foreign Countries methyl, each of which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl;
R3 preferably represents hydrogen, nitro, amino, cyano, formylamino, fluorine, chlorine, or represents methyl, trifluoromethyl, acetylamino, propionylamino, butyroylamino, i-butyroylamino, trifluoroacetylamino, methoxycarbonyl-amino, ethoxycarbonylamino, methylaminocarbonylamino, ethylamino-carbonylamino, cyclopropylcarbonylamino or phenylcarbonylamino (benzoyl-amino);
R4 preferably represents hydrogen, fluorine or chlorine;
RS preferably represents cyano, thiocarbamoyl, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy or trifluoromethoxy;
R~ especially preferably represents the group hereinbelow:
-A1-A2_A3 in which A1 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl, A 1 furthermore represents methylene, ethane- I ,1-diyl, ethane-1,2-diyl, propane- l , l -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, propinc-1,2-diyl or propinc-1,3-diyl, Le A 33 025-Foreign Countries _g_ A2 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl, A2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl, A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents 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, methyl-amino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl or dipropoxyphosphoryl, diisopropoxyphosphoryl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propenyloxy, butenyloxy, propenyl-amino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxy-carbonyl or butinyloxycarbonyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyl, cyclo-3O butyl, cyclopcntyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclo-pentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, Le A 33 025-Foreign Countries cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclo-butylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclo-pentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclo-hexylmethoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, or represents phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxy-carbonyl, each of which is optionally substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, tri-fluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, tri-fluoromethoxy, methoxycarbonyl and/or ethoxycarbonyl, A3 furthermore represents (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, thienyl-methyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinyl methyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy;
R~ preferably represents hydrogen, fluorine or chlorine.
Two adjacent radicals - R3 and R4, R4 and R5, RS and Rb or R6 and R~ -together preferably represent one of the following groups:
-Q3-CQ4-~ -Q3-CQ4-QS-~ -Q3-C(Rg>R9)-QS-, -C(Rg~R9)-CQ4-, -C(R8,R9~-Q3_CQ4_, _Q3_C~R8,R9~_C(R8,R9~_, -Q3_C~R8,R9)_C(R8,R9)_QS_, _C(R8,R9)_C(R8>R9)-CQ4_, -Q3-C(Rg)=C(Rg)-, _C(R8~-C(R8~_CQ4_, -Q3-C~R8,R9~_CQ4-, -N~R10~_C(R8~R9~_CQ4_, _C(R8~-N_, _Q3_CQ4_C(R8,R9~_>
Le A 33 025-Foreign Countries -Q3_CQ4_N(R10)_~ _Q3_C(R8~R9)-CQ4_N(R10)-_C(R8~R9)_Q3_CQ4_N~R10)-~ _C(R8~R9)-C~R8~R9)-N(R10)_ _C(R8~R9)-C~R8~R9)-CQ4_N(R10)_~ _C(R8)=C(R8)_N(R10)-_C(R8)-C(R8)_CQ4_N~R10)-~ _C(R8~R9)-CQ4-N(R10)-_N(R10)_C(R8~R9)_CQ4_N(R10)_~ _C(R8)-N_N(R10)_~
-Q3_CQ4_C(R8~R9)-N(R10)_~ Q3_C(R8~R9)-C(R8~R9)-CQ4_N(R10)_ where Q3, Q4 and QS are identical or different and in each case represent oxygen or sulphur, R8 and R9 are identical or different and individually represent hydrogen, fluorine, chlorine, methyl or ethyl or together represent ethane-1,2-diyl (dimethylene), and R 10 represents hydrogen, hydroxyl, or represents methyl, ethyl, n- or i-propyl, n-, i-,s or t-butyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl or ethoxy-carbonyl, or represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by fluorine, chlorine or bromine, or represents cyclo-propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutyl-methyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or represents methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyl-oxy, each of which is optionally substituted by fluorine and/or chlorine, or represents benzyl or benzyloxy, each of which is optionally substituted by cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy;
n very especially preferably represents 1 or 2;
Le A 33 025-Foreign Countries Q very especially preferably represents oxygen or sulphur;
R1 very especially preferably represents methyl, ethyl, n- or i-propyl, each of S which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy;
R3 especially preferably represents hydrogen, fluorine or chlorine;
R4 especially preferably represents hydrogen;
RS especially preferably represents cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl;
Rf especially preferably represents the group hereinbelow:
_A 1 _A2_A3 in which A 1 represents a single bond, A2 represents a single bond, 2~ A3 represents hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-prop-oxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethyl-thio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, cthylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n-Le A 33 025-Foreign Countries or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethyl-amino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyl-oxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyloxy, cyclobutyloxy, cyclopentyl-oxy, cyclohexyloxy, cyclopropylmethoxy, cyclobutylmethoxy, cyclo-pentylmethoxy, cyclohexylmethoxy, cyclopentyloxycarbonyl, cyclo-hexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexyl-methoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxy-carbonyl or ethoxycarbonyl, or represents phenoxy, benzyloxy, phenyloxycarbonyl or benzyloxycarbonyl, each of which is optionally 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;
R~ especially preferably represents hydrogen.
Preferred in accordance with the invention are the compounds of the formula (I) which contain a combination of the meanings mentioned above as being preferred.
Especially preferred in accordance with the invention are the compounds of the formula (I) which contain a combination of the meanings mentioned above as being especially preferred.
Le A 33 025-Foreign Countries Very especially preferred in accordance with the invention are the compounds of the formula (I) which contain a combination of the meanings mentioned above as being especially preferred.
A very especially preferred group are those compounds of the formula (I) in which n represents 1 or 2, Q represents oxygen or sulphur, R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy and R2 represents the aromatic group defined hereinbelow R~ / Rs Rs \ ~ R4 Rs where R3 represents hydrogen, fluorine or chlorine, R4 represents hydrogen, RS represents cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl, R~' rrpresents the group hereinbclow Le A 33 025-Foreign Countries _A 1 _A2_A3 in which A 1 represents the group -N-A4- where A4 represents hydrogen, methylsulphonyl or ethylsulphonyl, A2 represents a single bond or -CO-, A3 represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s-or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s-or t-butylthio, methylsulphonyl, ethylsulphonyl, n- or i-propyl-sulphonyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents cyclopropyl, cyclo-butyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutyl-methyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyl-methoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexyl-methoxy, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, or represents phenyl, phenoxy, benzyl or benzyloxy, each of which is optionally substituted by vitro, cyano, carboxyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, meth-oxy, ethoxy, n- or i-propoxy, difluoromethoxy, tri-fluoromethoxy, methoxycarbonyl and/or ethoxycarbonyl, and R~ represents hydrogen.
Le A 33 025-Foreign Countries A further very especially preferred group are those compounds of the formula (I) in which n represents 1 or 2, Q represents oxygen or sulphur, R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, and R2 represents the aromatic group defined hereinbelow R~ / Rs Rs \ ~ R4 Rs where R3 represents hydrogen, fluorine or chlorine, R4 represents hydrogen, R5 represents cyano, thiocarbamoyl, chlorine, bromine, methyl or tri fluoromethyl, Rb represents the group hereinbelow in which Le A 33 025-Foreign Countries A1 represents the group -N-A4- where A4 represents hydrogen, methylsulphonyl or ethylsulphonyl, A2 represents -S02-, A3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally substituted by fluorine, chlorine, cyano or methyl, or represents phenyl or benzyl, each of which is optionally substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, tri-fluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoro-methoxy, methoxycarbonyl or ethoxycarbonyl, and R~ represents hydrogen.
The definitions of radicals mentioned above in general terms or in preferred ranges apply not only to the end products of the formula (I), but also accordingly to the starting materials or intermediates required in each case for the preparation.
These definitions of radicals can be combined with each other as desired, that is to say combinations between the stated ranges of preferred compounds are also possible.
The new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (I) are distinguished by a potent and selective herbicidal activity.
The new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (I) are obtained when 3t) 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (II) Le A 33 025-Foreign Countries Q
R~N~N~H (II) ~(CHz)~
in which n, Q and R1 are as defined above are reacted with halogen compounds of the general formula (III) X 1-R2 (III) in which R2 is as defined above and X 1 represents halogen, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and, if appropriate, electrophilic or nucleophilic substitution reactions are subsequently carried out in the customary manner within the definition of the substituents.
In principle, the compounds of the general formula (I) can also be synthesized as shown schematically hereinbelow:
Reaction of diamines of the general formula (IV) with (thio)carbonic acid derivatives of the general formula (V) Le A 33 02S-Foreign Countries R ~ Rz + Q
(I) (CH2)n (N) (V) where S
n, Q, R1 and R2 are as defined above and Y1 and Y2 are identical or different and in each case represent halogen (in particular chlorine), alkoxy (in particular methoxy or ethoxy), alkoxyalkoxy (in particular (methoxyethoxy or ethoxyethoxy), phenoxy or imidazolyl, if appropriate in the presence of a reaction auxiliary such as, for example, pyridine and if appropriate in the presence of a diluent such as, for example, toluene.
1 S Reaction of 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (VI) with halogen compounds of the general formula (VII) Q
H\N~N~R + R~ z (I) -(CHZ)~ X --(VI) (VII) where n, Q, R 1 and R2 are as defined above and 2S ~-' represents halogen (in particular chlorine, bromine or iodine), Le A 33 025-Foreign Countries if appropriate in the presence of a reaction auxiliary such as, for example, ethyl-diiso-propylamine and if appropriate in the presence of a diluent such as, for example, acetonitrile.
Reaction of (thio)ureas of the general formula (VIII) with a,w-disubstituted alkanes of the general formula (IX) Q
Ei R\H H/R + E2~(CH2)~ --~ (I) ( V III) (IX) where n, Q, R1 and R2 are as defined above, and E1 and E2 represent leaving groups which can be substituted by a nucleophile, such as halogen (in particular chlorine or bromine or alkylsulphonyloxy (in particular methylsulphonyloxy), if appropriate in the presence of a reaction auxiliary such as, for example, potassium carbonate and if appropriate in the presence of a diluent such as, for example, acetone.
If, for example, 1-methyl-imidazolidin-2-one and 2,4,5-trifluorobenzonitrile are used as starting materials, the course of the reaction in the process according to the ?5 invention can be outlined by the following formulaic scheme:
Le A 33 025-Foreign Countries F
O
II CN
HsC.N~N.H + O / I
-' ~ \
- HF H3C~N~N
L--J F
Formula (II) provides a general definition of the 1,3-diaza-2-(thi)oxo-cycloalkanes to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I). In formula (II), n, Q and RI
preferably, or in particular, have those meanings which have already been stated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or particularly prefered, for n, Q and R I .
The starting materials of the general formula (II) are known and/or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 80 (1958), 6409-6412; J.
Chem.
Soc. Perkin Trans. 1, 1981, 2499-2503; J. Org. Chem. 22 (1957), 1581; J. Org.
Chem. 28 ( 1992), 7339-7342; Synth. Commun. 27 (1997), 3565-3571 ).
Formula (III) provides a general definition of the halogen compounds furthermore to be used as starting materials in the process according to the invention. In formula (III), R2 preferably, or in particular, has that meaning which has already been stated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, especially preferred or very especially preferred for R2; X2 preferably represents fluorine or chlorine, in particular fluorine.
The starting materials of the general formula (III) are known and/or can be prepared by processes known per se (cf EP-A-191181, EP-A-370332, EP-A-431373, EP-A-441004, EP-A-597360).
The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent. Suitable dilucnts are, above all, inert organic solvents. These include, in particular, aliphatic, alicyclic or Le A 33 02S-Foreign Countries aromatic, optionally halogenated hydrocarbons such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl S ether or ethylene glycol diethyl ether; ketones such as acetone, butanone or methyl isobutyl ketone; nitrites such as acetonitrile, propionitrile or butyronitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethyl phosphoric tr-iamide; esters such as methyl acetate or ethyl acetate, sulphoxides such as dimethyl sulphoxide.
The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a reaction auxiliary.
Suitable reaction auxiliaries are generally the customary inorganic or organic bases or acid acceptors. These preferably include the acetates, amides, carbonates, 1 S hydrogencarbonates, hydrides, hydroxides or alkoxides of alkali metals or alkaline earth metals such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or calcium hydrogencarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or -i-propoxide or potassium n- or i-propoxide, sodium n-, -i-, -s- or -t-butoxide, or potassium n-, -i-, -s- or -t-butoxide; furthermore also basic organic nitrogen 2S compounds such as, for example, tr-imethylamine, triethylamine, tripropylamine, tri-butylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclo-hexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,S-dimethyl-pyridine, S-ethyl-2-methyl-pyridine, 4-dimethyl-amino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2Joctane (DABCO), l,S-diazabicyclo[4,3,OJnon-S-ene (DBN), or 1,8-diazabicyclo[S,4,OJundec-7-ene (DBU).
Le A 33 025-Foreign Countries When carrying out the process according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 1 SO°C, preferably between 20°C and 120°C.
S
The process according to the invention is generally earned out under atmospheric pressure. However, it is also possible for the process according to the invention to be carried out under elevated or reduced pressure, in general between 0.1 bar and 10 bar.
To carry out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the temperature required.
1 S 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 undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, 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.
Le A 33 025-Foreign Countries Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
S
Monocotyledonous weeds of the enera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
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 way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks, and on paths and areas with or without tree stands. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pastures, and for selective weed control in annual crops.
The compounds of the formula (I) according to the invention arc particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous crops, both pre- and post-emergence.
Le A 33 025-Foreign Countries The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric S substances.
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 dispersants and/or foam formers.
If water is used as an extender, organic solvents can, for example, also be used as cosolvents. Liquid solvents which are mainly suitable are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic I S 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 as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else 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 formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylenc fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, Le A 33 025-Foreign Countries arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colourants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention, as such or in their formulations, can also be used for controlling weeds as a mixture with known herbicides, ready-mixes or tank mixes being possible.
Herbicides which are suitable for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromo-fenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlor-imuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulf=
Le A 33 025-Foreign Countries uron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfam-uron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, di-allate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethen-S amid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epo-prodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, florasulam, fluazi-fop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumet-sulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, meto-benzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propa-chlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulf uron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenz-oxim, pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quin-chlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rim-sulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfo-meturon(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, ter-butryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), 3(1 thiobencarb, tiocarbazil, tralkoxydim, tri-allate, triasulfuron, tribenuron(-methyl), tri-clopyr, tridiphane, trifluralin and triflusulfuron.
Le A 33 025-Foreign Countries Mixtures with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners, 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 spreading.
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 1 S essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and S kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples which follow.
Le A 33 025-Foreign Countries Preparation Examples:
Example 1 F
CN
H3C~N~N \
F
A mixture of 5.8 g (50 mmol) of 1-methyl-imidazolidine-2-thione, 8.6 g (SS
mmol) of 2,4,5-trifluoro-benzonitrile, 7.6 g (SS mmol) of potassium carbonate and 50 ml of dimethyl sulphoxide is stirred for 16 hours at 80°C. When cold, the mixture is poured into a stirred mixture of approximately equal volumes of methylene chloride and water and acidified with 2N hydrochloric acid. The organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated in a water pump vacuum, the residue is digested with diethyl ether, and the product which is obtained as crystals is isolated by filtration with suction.
This gives 9.5 g (75% of theory) of 1-methyl-3-(4-cyano-2,5-difluoro-phenyl)-imida-zolidine-2-thione of melting point 143°C.
Example 2 C2Hs HN~SO2 CN
H3C~N~N \
F
(subsequent reaction) Le A 33 025-Foreign Countries A mixture of 2.0 g (8 mmol) of 1-methyl-3-(4-cyano-2,5-difluoro-phenyl)-imida-zolidine-2-thione, 1.8 g (16 mmol) of ethanesulphonamide, 2.2 g (16 mmol) of potassium carbonate and 50 ml of dimethyl sulphoxide is stirred for 16 hours at 100°C. When cold, the mixture is poured into a stirred mixture of approximately equal volumes of methylene chloride and water and acidified with 2N
hydrochloric acid. The organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated in a water pump vacuum, the residue is digested with isopropanol, and the product which is obtained as crystals is isolated by filtration with suction.
This gives 1.9 g (68% of theory) of 1-methyl-3-(4-cyano-2-fluoro-5-ethylsulphonyl-amino-phenyl)-imidazolidine-2-thione of melting point 174°C.
Other examles of compounds of the formula (I) which can be prepared analogously to the Preparation Examples 1 to 2 and in accordance with the general description of the preparation processes according to the invention are those listed in Table 1 below.
Q
Rz RU-N~ (I) (CHz)~
Le A 33 025-Foreign Countries Table 1: Examples of the compounds of the formula (I) Ex. Melting No. n Q R1 R2 point (°C) ~O
F
CN
/
F
CN
F
6 1 O CH3 ~ CI 98 7 1 S CH3 ~ CI 166 O
CN
/
F
Le A 33 025-Foreign Countries Ex. Melting No. n Q R1 R2 point (°C) 9 1 S CH3 ~ 164 CN
/
F
10 1 O CH3 ~ 2Hs 188 HN'S02 CN
F
F
O
CN
/
F
CN
/
F
CN
/
F
/
F
13 1 S CH3 ~ C~ 105 H~N~O
''Of~CH3 Le A 33 025-Foreign Countries Ex. Melting No. n Q R1 R2 point (°C) 14 1 S CH3 ~ CI 187 H~N~O
'N~HCH3 15 1 S CH3 ~ ~I 142 H~N~(O
'C~H(CH3)2 16 1 S CH3 ~ CI 1 SO
H~N O
''Of~CH3 Le A 33 025-Foreign Countries Ex. Melting No. n Q R1 R2 point (°C) 14 1 S CH3 ~ CI 187 H~N~O
'N~HCH3 15 1 S CH3 ~ ~I 142 H~N~(O
'C~H(CH3)2 16 1 S CH3 ~ CI 1 SO
H~N O
17 1 S CH3 ~ CI
H~N~O
'C~s H s 18 1 S CH3 ~ CI 162 H~N~O
C~F3 19 1 O CHI ~ CI 127 H~N~O
'C~f~F3 Le A 33 025-Foreign Countries Ex. Melting No. n Q R1 R2 point (°C) 20 1 O CH3 ~ C~ 144 /
H~N~O
'C~H(CH3)2 21 1 O CH3 ~ C~ 149 H~N~O
'C~sHs 22 1 O CH3 ~ C~ 220 H~N~O
'N~HCH3 23 1 S CH3 ~ C~ 1 gg H~N~O
'~H
H~N~O
'C~s H s 18 1 S CH3 ~ CI 162 H~N~O
C~F3 19 1 O CHI ~ CI 127 H~N~O
'C~f~F3 Le A 33 025-Foreign Countries Ex. Melting No. n Q R1 R2 point (°C) 20 1 O CH3 ~ C~ 144 /
H~N~O
'C~H(CH3)2 21 1 O CH3 ~ C~ 149 H~N~O
'C~sHs 22 1 O CH3 ~ C~ 220 H~N~O
'N~HCH3 23 1 S CH3 ~ C~ 1 gg H~N~O
'~H
24 1 S CH3 C~ 150 CN
25 1 S CHFz F 143 CN
/
F
Le A 33 025-Foreign Countries Ex. Melting No. n Q R1 R2 point (°C) 26 1 S CHFZ ~ 2H5 90 HN'S02 \ CN
/
F
/
F
Le A 33 025-Foreign Countries Ex. Melting No. n Q R1 R2 point (°C) 26 1 S CHFZ ~ 2H5 90 HN'S02 \ CN
/
F
27 1 O ~N~ F 165 O ~ \ CN
F
F
28 I O CHFz F loge = 2.23 CN b>
F
F
29 1 S CHFZ C3H~-i 138 HN'SOZ
\ CN
/
F
\ CN
/
F
30 1 S CHFz ~ H3 130 HN'SOz \ CN
/
F
/
F
31 1 S C~HS F 117 \ CN
/
F
Le A 33 02S-Forei~rt Countries Ex. Melting No. n Q R1 R2 point (°C) 32 1 O CHO F loge = 1.42 CN b>
F
/
F
Le A 33 02S-Forei~rt Countries Ex. Melting No. n Q R1 R2 point (°C) 32 1 O CHO F loge = 1.42 CN b>
F
CN
/
F
/
F
34 1 S H ~zHs 1S7 HN'S02 \ CN
F
The loge values stated in Table 1 were determined by HPLC (high performance liquid chromatography) on a reversed phase column (C 18) in accordance with EEC
Directive 79/831 Annex V.AB. Temperature: 43°C.
S
(a) Eluents for the determination in the acidic range: 0.1 % aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile -the relevant readings are marked with a) in Table 1.
(b) Eluents for the determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - the relevant readings arc marked with b) in Table 1.
Standardization was done with unbranched alkan-2-ones (with 3 to 16 carbon atoms) 1 S whose loge values are known (determination of the loge values with the aid of the retention times by linear interpolation between two subsequent alkanones).
Le A 33 025-Foreign Countries The lambda-max values were determined with the aid of the I1V spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
Le A 33 025-Foreign Countries Use Examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After approx. 24 hours, the soil is sprayed with the active compound preparation in such a way that the amounts of active compound desired in each case are applied per unit area. The concentration of the spray mixture is chosen in such a way that the amounts of active compound desired in each case are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is scored in % damage in comparison with the development of the untreated control.
The figures denote:
0 % - no action (like untreated control) 100 % - total destruction In this test, a potent action against weeds combined in some cases with good tolerance by crop plants such as, for example, maize is shown, for example, by the compounds of Preparation Example 2, S, 8, 9, 10, 1 1 and 12.
Le A 33 025-Foreign Countries Example B
Post-emergence test S Solvent: S parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted' with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the active compound preparation in such a way that the amounts of active compound desired in each case are applied per unit area. The concentration of the spray mixture is chosen in such a way that the amounts of active compound desired in each case are applied in of water/ha.
After three weeks, the degree of damage to the plants is scored in % damage in comparison with the development of the untreated control.
The figures denote:
0 % - no action (like untreated control) 100 % - total destruction In this test, a potent action against weeds combined in some cases with good tolerance by crop plants such as, for example, barley is shown, for example, by the compounds of Preparation Example 2, 8, 9, 10 and 12.
F
The loge values stated in Table 1 were determined by HPLC (high performance liquid chromatography) on a reversed phase column (C 18) in accordance with EEC
Directive 79/831 Annex V.AB. Temperature: 43°C.
S
(a) Eluents for the determination in the acidic range: 0.1 % aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile -the relevant readings are marked with a) in Table 1.
(b) Eluents for the determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - the relevant readings arc marked with b) in Table 1.
Standardization was done with unbranched alkan-2-ones (with 3 to 16 carbon atoms) 1 S whose loge values are known (determination of the loge values with the aid of the retention times by linear interpolation between two subsequent alkanones).
Le A 33 025-Foreign Countries The lambda-max values were determined with the aid of the I1V spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
Le A 33 025-Foreign Countries Use Examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After approx. 24 hours, the soil is sprayed with the active compound preparation in such a way that the amounts of active compound desired in each case are applied per unit area. The concentration of the spray mixture is chosen in such a way that the amounts of active compound desired in each case are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is scored in % damage in comparison with the development of the untreated control.
The figures denote:
0 % - no action (like untreated control) 100 % - total destruction In this test, a potent action against weeds combined in some cases with good tolerance by crop plants such as, for example, maize is shown, for example, by the compounds of Preparation Example 2, S, 8, 9, 10, 1 1 and 12.
Le A 33 025-Foreign Countries Example B
Post-emergence test S Solvent: S parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted' with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the active compound preparation in such a way that the amounts of active compound desired in each case are applied per unit area. The concentration of the spray mixture is chosen in such a way that the amounts of active compound desired in each case are applied in of water/ha.
After three weeks, the degree of damage to the plants is scored in % damage in comparison with the development of the untreated control.
The figures denote:
0 % - no action (like untreated control) 100 % - total destruction In this test, a potent action against weeds combined in some cases with good tolerance by crop plants such as, for example, barley is shown, for example, by the compounds of Preparation Example 2, 8, 9, 10 and 12.
Claims (9)
1. Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (I) in which n represents 1, 2 or 3, Q represents oxygen or sulphur, R1 represents hydrogen, formyl or in each case optionally substituted alkyl, alkoxy, alkylamino, dialkylamino, alkenyl, alkinyl, cycloalkyl or cycloalkylalkyl, and R2 represents an optionally substituted monocyclic or bicyclic aromatic group which is optionally fused to a heterocycle.
2. Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes according to Claim 1, characterized in that n represents 1, 2 or 3, Q represents oxygen or sulphur, R1 represents hydrogen, formyl, or represents alkyl, alkoxy, alkylamino, dialkylamino, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, halogen, C1-C4-alkoxy, C1-C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl or morpholinyl, or represents alkenyl or alkinyl, each of which has 2 to 6 carbon atoms, and each of which is optionally substituted by cyano, halogen or C1-C4-alkoxy-carbonyl, or represents cycloalkyl or cycloalkylalkyl, each of which has 3 to 6 carbon atoms in the cycloalkyl groups and, if appropriate, 1 to 4 carbon atoms in the alkyl moiety and each of which is optionally substituted by cyano, halogen or C1-C4-alkyl, and R2 represents the aromatic group defined hereinbelow where R3 represents hydrogen, nitro, amino, cyano, formylamino, halogen, or represents alkyl, alkoxy, alkylcarbonylamino, alkoxycarbonylamino, alkylaminocarbonylamino, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, halogen or C1-C4-alkoxy, or represents cycloalkylcarbonylamino which has 3 to 6 carbon atoms in the cycloalkyl moiety and which is optionally substituted by cyano, halogen, C1-C4-alkyl or C1-C4-halogenoalkyl, or represents phenylcarbonylamino which is optionally substituted by cyano, nitro, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, R4 represents hydrogen, nitro, cyano, fluorine, chlorine or bromine, R5 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, fluorine, chlorine, bromine, or represents alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl, each of which has up to 4 carbon atoms and each of which is optionally substituted by fluorine and/or chlorine, R6 represents the group hereinbelow in which A1 represents a single bond, or represents oxygen, sulphur, -SO-, -SO2-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C1-C4-alkoxy, phenyl, C1-C4-alkyl-carbonyl, phenyl-carbonyl, C1-C4.-alkyl-sulphonyl or phenylsulphonyl, A1 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, each of which is optionally substituted by fluorine, chlorine or bromine, A2 represents a single bond, or represents oxygen, sulphur, -SO-, -SO2-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl, A2 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cyclo-alkanediyl, C3-C6-cycloalkenediyl or phenylene, each of which is optionally substituted by fluorine, chlorine or bromine, A3 represents hydrogen, hydroxyl, mercapto, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, fluorine, chlorine, bromine, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by fluorine, chlorine or C1-C4-alkoxy, or represents alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyl-oxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxy-carbonyl, each of which has 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and each of which is optionally substituted by fluorine or chlorine, or represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cyclo-alkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxy-carbonyl, each of which has 3 to 6 carbon atoms in the cycloalkyl groups and, if appropriate, 1 to 4 carbon atoms in the alkyl groups and each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkyl and/or C1-C4-alkoxy-carbonyl, or represents phenyl, phenoxy, phenyl-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenoxycarbonyl or C1-C4-alkoxycarbonyl, each of which is optionally substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxy-carbonyl, A3 furthermore represents (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-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, perhydropyranylmethoxy or pyridylmethoxy, and R7 represents hydrogen, fluorine or chlorine, or in each case two adjacent radicals - R3 and R4, R4 and R5, R5 and R6 or R6 and R7 - together represent one of the following groups -Q3-CQ4- -Q3-CQ4-Q5-, -Q3-C(R8,R9)-Q5-, -C(R8,R9)-CQ4-, -C(R8,R9)-Q3-CQ4-, -Q3-C(R8,R9)-C(R8,R9)-, -Q3-C(R8,R9)-C(R8,R9)-Q5-, -C(R8,R9)-C(R8,R9)-CQ4-, -Q3-C(R8)=C(R8)-, -C(R8)=C(R8)-CQ4-, -Q3-C(R8,R9)-CQ4-, -N(R10)-C(R8,R9)-CQ4-, -C(R8)=N-, -Q3-CQ4-C(R8,R9)-, -Q3-CQ4-N(R10)-, -Q3-C(R8,R9)-CQ4-N(R10)-, -C(R8,R9)-Q3-CQ4-N(R10)-, -C(R8,R9)-C(R8,R9)-N(R10)-, -C(R8,R9)-C(R8,R9)-CQ4-N(R10)-, -C(R8)=C(R8)-N(R10)-, -C(R8)=C(R8)-CQ4-N(R10)-, -C(R8,R9)-CQ4-N(R10)-, -N(R10)-C(R8,R9)-CQ4-N(R10)-, -C(R8)=N-N(R10)-, -Q3-CQ4-C(R8,R9)-N(R10)-, Q3-C(R8,R9)-C(R8,R9)-CQ4-N(R10)-where Q3, Q4 and Q5 are identical or different and represent in each case oxygen or sulphur, R8 and R9 are identical or different and individually represent hydrogen, fluorine, chlorine, bromine or C1-C4-alkyl or together represent C2-C5-alkanediyl, and R10 represents hydrogen, hydroxyl or represents alkyl, alkyl-carbonyl, alkoxycarbonyl or alkylsulphonyl, each of which has 1 to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by cyano, fluorine, chlorine, C1-C4-alkoxy, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or represents alkenyl or alkinyl, each of which has 2 to 6 carbon atoms and each of which is optionally substituted by fluorine, chlorine or bromine, or represents cycloalkyl or cycloalkylalkyl, each of which has 3 to 6 carbon atoms in the cycloalkyl groups and, if appropriate, 1 to 3 atoms in the alkyl moiety and each of which is optionally substituted by fluorine, chlorine, bromine or C1-C4-alkyl, or represents alkoxy or alkenyloxy, each of which has up to 6 carbon atoms and each of which is optionally substituted by fluorine and/or chlorine, or represents benzyl or benzyloxy, each of which is optionally substituted by cyano, fluorine, chlorine, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy.
3. Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes according to Claim 1, characterized in that n represents 1, 2 or 3, Q represents oxygen or sulphur, R1 represents hydrogen, formyl, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyl, cyclobutyl, cyclo-pentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentyl-methyl or cyclohexylmethyl, each of which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl, and R2 represents the aromatic group defined hereinbelow where R3 represents hydrogen, nitro, amino, cyano, formylamino, fluorine, chlorine, or represents methyl, trifluoromethyl, acetyl-amino, propionylamino, butyroylamino, i-butyroylamino, tri-fluoroacetylamino, methoxycarbonylamino, ethoxycarbonyl-amino, methylaminocarbonylamino, ethylaminocarbonylamino, cyclopropylcarbonylamino or phenylcarbonylamino (benzoyl-amino), R4 represents hydrogen, fluorine or chlorine, R5 represents cyano, thiocarbamoyl, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy or tri-fluoromethoxy, R6 represents the group hereinbelow in which A1 represents a single bond, or represents oxygen, sulphur, -SO-, -SO2-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl, A1 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl, A2 represents a single bond, or represents oxygen, sulphur, -SO-, -SO2-, -CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl, A2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl, A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents 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 or dipropoxyphosphoryl, diisopropoxyphosphoryl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, or represents phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, each of which is optionally 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 ethoxy-carbonyl, A3 furthermore represents (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 or pyridylmethoxy, and R7 represents hydrogen, fluorine or chlorine, or in each case two adjacent radicals - R3 and R4, R4 and R5, R5 and R6 or R6 and R7 - together represent one of the following groups -Q3-CQ4-, -Q3-CQ4-Q5-, -Q3-C(R8,R9)-Q5-, -C(R8,R9)-CQ4-, -C(R8,R9)-Q3-CQ4-, -Q3-C(R8,R9)-C(R8,R9)-, -Q3-C(R8,R9)=C(R8=R9)-Q5-, -C(R8,R9)-C(R8,R9)-CQ4-, -Q3-C(R8)=C(R8)-, -C(R8)=C(R8)-CQ4-, -Q3-C(R8,R9)-CQ4-, -N(R10)-C(R8,R9)-CQ4-, -C(R8)=N-, -Q3-CQ4-C(R8,R9)-, -Q3-CQ4-N(R10)-, -Q3-C(R8,R9)-CQ4-N(R10)-, -C(R8,R9)-Q3-CQ4-N(R10)-, -C(R8,R9)-C(R8,R9)-N(R10)-, -C(R8,R9)-C(R8,R9)-CQ4-N(R10)-, -C(R8)=C(R8)-N(R10)-, -C(R8)=C(R8)-CQ4-N(R10)-, -C(R8,R9)-CQ4-N(R10)-, -N(R10)-C(R8,R9)-CQ4-N(R10)-, -C(R8)=N-N(R10)-, -Q3-CQ4-C(R8,R9)-N(R10)-, Q3-C(R8,R9)-C(R8,R9)-CQ4-N(R10)-where Q3, Q4 and Q5 are identical or different and in each case represent oxygen or sulphur, R8 and R9 are identical or different and individually represent hydrogen, fluorine, chlorine, methyl or ethyl or together represent ethane-1,2-diyl (dimethylene), and R10 represents hydrogen, hydroxyl, or represents methyl, ethyl, n- or i-propyl, n-, i-,s or t-butyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl or ethoxy-carbonyl, or represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by fluorine, chlorine or bromine, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or represents methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents benzyl or benzyloxy, each of which is optionally substituted by cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy.
4. Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes according to Claim 1, characterized in that n represents 1 or 2, Q represents oxygen or sulphur, R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, and R2 represents the aromatic group defined hereinbelow where R3 represents hydrogen, fluorine or chlorine, R4 represents hydrogen, R5 represents cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl, R6 represents the group hereinbelow in which A1 represents a single bond, A2 represents a single bond, A3 represents hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents 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-propyl-amino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, each of which is optionally substituted by fluorine or chlorine, or represents cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentyl-methoxycarbonyl or cyclohexylmethoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, or represents phenoxy, benzyloxy, phenyloxycarbonyl or benzyloxycarbonyl, each of which is optionally 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, and R7 represents hydrogen.
5. Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes according to Claim 1, characterized in that n represents 1 or 2, Q represents oxygen or sulphur, R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy and R2 represents the aromatic group defined hereinbelow where R3 represents hydrogen, fluorine or chlorine, R4 represents hydrogen, R5 represents cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl, R6 represents the group hereinbelow in which A1 represents the group -N-A4- where A4 represents hydrogen, methylsulphonyl or ethylsulphonyl, A2 represents a single bond or -CO-, A3 represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutyl-methyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyl-methoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexyl-methoxy, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, or represents phenyl, phenoxy, benzyl or benzyloxy, each of which is optionally 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, and R7 represents hydrogen.
6. Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes according to Claim 1, characterized in that n represents 1 or 2, Q represents oxygen or sulphur, R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, and R2 represents the aromatic group defined hereinbelow where R3 represents hydrogen, fluorine or chlorine, R4 represents hydrogen, R5 represents cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl, R6 represents the group hereinbelow in which A1 represents the group -N-A4- where A4 represents hydrogen, methylsulphonyl or ethylsulphonyl, A2 represents -SO2-, A3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally substituted by fluorine, chlorine, cyano or methyl, or represents phenyl or benzyl, each of which is optionally substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl, and R7 represents hydrogen.
7. Process for the preparation of substituted 1,3-diaza-2-(thi)oxo-cycloalkanes according to one of Claims 1 to 6, characterized in that 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (II) in which n, Q and R1 are as defined in one of Claims 1 to 6 are reacted with halogen compounds of the general formula (III) X1-R2 (III) in which R2 is as defined in one of Claims 1 to 6 and X1 represents halogen, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and, if appropriate, electrophilic or nucleophilic substitution reactions are subsequently carried out in a customary manner within the definition of the substituents.
8. Herbicidal composition, characterized in that it comprises at least one substituted 1,3-diaza-2-(thi)oxo-cycloalkane according to one of Claims 1 to 6.
9. Use of at least one substituted 1,3-diaza-2-(thi)oxo-cycloalkane according to one of Claims 1 to 6 for controlling undesired plants.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19822678.0 | 1998-05-20 | ||
| DE19822678A DE19822678A1 (en) | 1998-05-20 | 1998-05-20 | New 1,3-diaza-2-oxo-cycloalkane derivatives, useful as pre- or post-emergence, total or selective herbicides |
| PCT/EP1999/003422 WO1999059977A1 (en) | 1998-05-20 | 1999-05-18 | Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2332443A1 true CA2332443A1 (en) | 1999-11-25 |
Family
ID=7868439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002332443A Abandoned CA2332443A1 (en) | 1998-05-20 | 1999-05-18 | Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1080077A1 (en) |
| JP (1) | JP2002515492A (en) |
| KR (1) | KR20010043505A (en) |
| CN (1) | CN1301257A (en) |
| AU (1) | AU4263999A (en) |
| BR (1) | BR9910610A (en) |
| CA (1) | CA2332443A1 (en) |
| DE (1) | DE19822678A1 (en) |
| WO (1) | WO1999059977A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017002201A1 (en) * | 2015-06-30 | 2017-01-05 | 株式会社エス・ディー・エス バイオテック | Cyclopropane carboxylic acid amide compound and herbicide containing same |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2596742A (en) * | 1950-03-22 | 1952-05-13 | Eastman Kodak Co | Nu-substituted ethylene thioureas |
| US2985663A (en) * | 1958-04-16 | 1961-05-23 | Du Pont | Substituted imidazolidinone and method for the control of undesired vegetation |
| DE1126392B (en) * | 1959-10-15 | 1962-03-29 | Bayer Ag | Process for making cyclic ureas and thioureas |
| FR1394708A (en) * | 1962-10-19 | 1965-04-09 | American Cyanamid Co | Process for the preparation of substituted imidazolidinones and imidazolidinethiones |
| CH427827A (en) * | 1961-11-07 | 1967-01-15 | Bayer Ag | Process for the preparation of imidazolidine derivatives |
| FR1516714A (en) * | 1962-11-07 | 1968-02-05 | Bayer Ag | Process for preparing imidazolidine derivatives |
| DE1226589B (en) * | 1963-09-12 | 1966-10-13 | Asta Werke Ag Chem Fab | Process for the preparation of imidazolidones |
| GB1108918A (en) * | 1966-01-15 | 1968-04-10 | Bayer Ag | 2-imidazolidone derivatives |
| FR1531143A (en) * | 1966-07-16 | 1968-06-28 | Bayer Ag | Process for the production of 2-imidazolidone derivatives with basic substituents |
| US3702327A (en) * | 1970-12-28 | 1972-11-07 | Aldrich Chem Co Inc | N-beta-1-(3-phenylimidazolidin-2-one)ethyl 4,4-ethylene dioxypiperidines |
| US3876657A (en) * | 1971-06-03 | 1975-04-08 | Ashland Oil Inc | Preparation of 1-substituted-2-imidazolidinones |
| AT311956B (en) * | 1971-06-07 | 1973-12-10 | Boehringer Sohn Ingelheim | Process for the preparation of new phenylimidazolidinone derivatives and their salts |
| CH547288A (en) * | 1971-06-23 | 1974-03-29 | Ciba Geigy Ag | PROCESS FOR MANUFACTURING NEW HETEROCYCLIC SUBSTANCES. |
| DK529378A (en) * | 1978-01-09 | 1979-07-10 | Shell Int Research | anilide |
| EP0011693A1 (en) * | 1978-10-03 | 1980-06-11 | Ciba-Geigy Ag | N-trifluoromethane-sulfonylaminophenyl-substituted N-heterocycles, their preparation, compositions containing them and their use in regulating plant growth |
| AU526579B2 (en) * | 1981-02-25 | 1983-01-20 | Boehringer Ingelheim International Gmbh | N-aminoalkylimidazolidines |
| US4642351A (en) * | 1983-01-20 | 1987-02-10 | The Dow Chemical Company | Preparation of N-substituted imidazolidinones and N-substituted 2-thionimidazolidinones |
| US4619931A (en) * | 1983-02-28 | 1986-10-28 | Janssen Pharmaceutica, N.V. | [[4-[4-(4-phenyl-1-piperazinyl)phenoxymethyl]-1,3-dioxolan-2-yl]methyl]-1H-imidazoles and 1H-1,2,4-triazoles |
| DE3324903A1 (en) * | 1983-07-09 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF SUBSTITUTED ETHYLENE UREAS AND NEW N-VINYLETHYLENE UREAS |
| DE3325875A1 (en) * | 1983-07-18 | 1985-01-31 | Boehringer Ingelheim KG, 6507 Ingelheim | NEW 1-PHENYLIMIDAZOLIDIN-2-ON DERIVATIVES, THEIR PRODUCTION AND USE |
| CA1331757C (en) * | 1988-02-29 | 1994-08-30 | Janssen Pharmaceutica Naamloze Vennootschap | 5-lipoxygenase inhibiting 4-(4-phenyl-1-piperazinyl)phenols |
| EP0536279A1 (en) * | 1990-06-29 | 1993-04-14 | The Upjohn Company | Substituted 1-(alkoxyphenyl)piperazines with cns and antihypertensive activity |
| DE4425696A1 (en) * | 1994-07-20 | 1996-01-25 | Basf Ag | Process for the preparation of 1,3-disubstituted imidazolidinones |
-
1998
- 1998-05-20 DE DE19822678A patent/DE19822678A1/en not_active Withdrawn
-
1999
- 1999-05-18 EP EP99952091A patent/EP1080077A1/en not_active Withdrawn
- 1999-05-18 CN CN99806393A patent/CN1301257A/en active Pending
- 1999-05-18 CA CA002332443A patent/CA2332443A1/en not_active Abandoned
- 1999-05-18 JP JP2000549596A patent/JP2002515492A/en active Pending
- 1999-05-18 BR BR9910610-8A patent/BR9910610A/en not_active Application Discontinuation
- 1999-05-18 WO PCT/EP1999/003422 patent/WO1999059977A1/en not_active Application Discontinuation
- 1999-05-18 KR KR1020007012595A patent/KR20010043505A/en not_active Application Discontinuation
- 1999-05-18 AU AU42639/99A patent/AU4263999A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU4263999A (en) | 1999-12-06 |
| EP1080077A1 (en) | 2001-03-07 |
| DE19822678A1 (en) | 1999-11-25 |
| JP2002515492A (en) | 2002-05-28 |
| KR20010043505A (en) | 2001-05-25 |
| BR9910610A (en) | 2001-01-09 |
| WO1999059977A1 (en) | 1999-11-25 |
| CN1301257A (en) | 2001-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MXPA01011213A (en) | Substituted benzoylisoxazoles and the use thereof as herbicides. | |
| MXPA01011357A (en) | Substituted benzoyl ketones, methods for producing them and their use as herbicides. | |
| US6399541B1 (en) | Substituted 2,4-diamino-1,3,5-triazines as herbicides | |
| CA2274119A1 (en) | 3-amino-1-cyanophenyl-uracils | |
| AU718868B2 (en) | Substituted p-trifluoromethylphenyluracils | |
| US6559102B1 (en) | Substituted 3-aryl-pyrazoles | |
| US6187716B1 (en) | Heterocyclyluracil | |
| CA2373665C (en) | Substituted thienocycloalk(en)ylamino-1,3,5-triazine | |
| CA2260201A1 (en) | Substituted aromatic carbonyl compounds and their derivatives | |
| US6548449B1 (en) | Substituted phenyluracils with herbicidal effect | |
| US6617281B1 (en) | Substituted acylamino phenyl uracils | |
| US6608004B2 (en) | Substituted 2-aryl-1,2,4-triazine-3,5-di(thi)ones | |
| AU734598B2 (en) | Heterocyclyluracils | |
| AU735744B2 (en) | Substituted iminoalkoxy-phenyluracils, their preparation and their use as herbicides | |
| AU765922B2 (en) | Substituted N-cyano amidines | |
| CA2319053A1 (en) | Substituted heteroarylmethyl compounds used as herbicides | |
| CA2332443A1 (en) | Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes | |
| US6602827B1 (en) | Herbicidal 5-chlorodifluoromethyl-1,3,4-thiadiazol-2-yl-oxyacetanilides | |
| AU740818B2 (en) | Substituted phenyl uracils | |
| US6420313B1 (en) | Thienylalkylamino-1,3,5-triazines and the use thereof as herbicides | |
| CA2278584A1 (en) | Substituted phenyltriazolin(thi)ones and their use as herbicides | |
| CA2307344A1 (en) | Substituted n-aryl-o-aryloxyalkyl carbamates and their use as herbicides | |
| CA2302709A1 (en) | Substituted phenyluracils | |
| MXPA00010774A (en) | Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes | |
| CA2322482A1 (en) | Optically active substituted 2,4-diamino-1,3,5-triazines as herbicides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |