CA2409142A1 - Substituted iminoazines - Google Patents
Substituted iminoazines Download PDFInfo
- Publication number
- CA2409142A1 CA2409142A1 CA002409142A CA2409142A CA2409142A1 CA 2409142 A1 CA2409142 A1 CA 2409142A1 CA 002409142 A CA002409142 A CA 002409142A CA 2409142 A CA2409142 A CA 2409142A CA 2409142 A1 CA2409142 A1 CA 2409142A1
- Authority
- CA
- Canada
- Prior art keywords
- substituted
- methyl
- chlorine
- fluorine
- cyano
- 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
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/61—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D237/20—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention relates to novel substituted iminoazines of general formula (I), in which R1, R2, R3, R4, Z1, Z2 and Z3 are defined as cited in the description. The invention also relates to several methods and intermediate compounds for producing said substituted iminoazines and to their use as herbicides.
Description
Le A 34 486-Foreign Countries Hor/klu/NT
, .:
Substituted iminoazines The invention relates to novel substituted iminoazines, to processes for their prepara-tion and to their use as plant treatment agents, in particular as herbicides.
It is already known that certain substituted iminopyridines have herbicidal properties (cf. EP-A-432 600). However, the activity of these compounds is not entirely satis-factory.
This invention, accordingly, provides the novel substituted aminoazines of the gen-eral formula (I) R Z\
Z\N~N~R~
R3 ~ I (I)~
in which R1 represents nitro, cyano or one of the groupings -R5, -CQ1-QZ-R5, -NH-CQ1_ Q2-RS or -SOZ-R6, Rz represents nitro, cyano, SFS, halogen or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl or alkylsulphonyloxy, R3 represents hydrogen or halogen, or together with RZ represents optionally sub-stituted alkylenedioxy, R4 represents hydrogen, cyano, carboxyl, carbamoyl, halogen or optionally sub-stituted alkyl, Le A 34 486-Foreign Countries ~ -2-Q1 represents O (oxygen), S (sulphur) or N-Rs, QZ represents a single bond or represents O (oxygen), S (sulphur) or N-Rs, Rs represents hydrogen, amino or in each case optionally substituted alkyl, alk-oxy, alkylamino, dialkylamino, alkylideneamino, alkenyl, alkenyloxy, alk-inyl, cycloalkyl, cycloalkylamino, cycloalkylalkyl, aryl, arylamino, arylalkyl, heterocyclyl or heterocyclylalkyl, R6 represents in each case optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl, Z1 represents N (nitrogen) or C-R4, 1 S ZZ represents N (nitrogen) or C-R4, and Z3 represents N (nitrogen) or C-R4.
In the definitions, the hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched - including in combination with heteroatoms, such as in alkylamino. R3 is preferably located in the meta or para position on the phenyl ring.
Preferred substituents or preferred ranges of the radicals which are present in the formulae listed above and below are defined below.
R1 preferably represents cyano or one of the groupings -Rs, -CQ1-QZ-Rs, -NH-CQ1-Q2-RS or -SOZ-R6.
RZ preferably represents nitro, cyano, SFs, halogen or in each case optionally cyano-, halogen- or C~-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkyl-Le A 34 486-Foreign Countries ~ -3-sulphinyl, alkylsulphonyl or alkylsulphonyloxy having in each case 1 to carbon atoms.
R3 preferably represents hydrogen or halogen, or together with RZ represents 5 optionally halogen-substituted alkylenedioxy having 1 to 3 carbon atoms.
R4 preferably represents hydrogen, cyano, carboxyl, carbamoyl, halogen or op-tionally cyano-, halogen- or CI-C4-alkoxy-substituted alkyl having 1 to S carbon atoms.
Q1 preferably represents O (oxygen) or S (sulphur).
RS preferably represents hydrogen or amino, represents in each case optionally cyano-, halogen- or C,-C4-alkoxy-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, represents alkylamino having 1 to 6 carbon atoms, represents dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents alkylideneamino having up to 6 carbon atoms, represents in each case optionally cyano- or halogen-substituted alkenyl, alkenyloxy or alkinyl having in each case 2 to 6 carbon atoms, represents in each case op-tionally cyano-, halogen- or C1-Ca-alkyl-substituted cycloalkyl, cycloalkyl-amino or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, rep-resents in each case optionally nitro-, cyano-, phenyl-, phenoxy-, phenylthio-, halogen-, CI-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C,-C4-haloge-noalkoxy-, Cl-Ca-alkylthio-, Ci-C4-halogenoalkylthio-, C1-C4-alkylsulph-inyl-, C,-C4-halogenoalkylsulphinyl-, C~-C4-alkylsulphonyl-, C,-C4-halo-genoalkylsulphonyl- or di-(C1-C4-alkyl)-aminosulphonyl-substituted aryl, arylamino or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, phenyl-, phenoxy-, phenylthio-, halogen-, C~-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, Le A 34 486-Foreign Countries ~ -4-C,-Ca-alkylthio-, C,-Ca-halogenoalkylthio-, C1-Ca-alkylsulphinyl-, C,-C4-halogenoalkylsulphinyl-, C~-C4-alkylsulphonyl-, C1-C4-halogenoalkyl-sulphonyl- or di-(CI-C4-alkyl)-amino-sulphonyl-substituted monocyclic or bi-cyclic heterocyclyl or heterocyclylalkyl having in each case up to 10 carbon atoms and up to 4 nitrogen atoms and/or 1 or 2 oxygen or sulphur atoms in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety.
R6 preferably represents optionally halogen-substituted alkyl having 1 to 6 carbon atoms, represents optionally halogen-substituted alkenyl having 2 to 6 carbon atoms, represents optionally halogen- or C1-C4-alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, represents in each case optionally nitro-, cyano-, halogen-, C~-C4-alkyl-, C1-C4-halogeno-alkyl-, C~-C4-alkoxy-, C~-C4-halogenoalkoxy-, C,-C4-alkylthio-, C1-C4-halo-genoalkylthio-, C~-C4-alkylsulphinyl-, C,-C4-halogenoalkylsulphinyl-, C,-C4-alkylsulphonyl-, C,-C4-halogenoalkylsulphonyl- or di-(C1-C4-alkyl)-amino-sulphonyl-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, halogen-, C,-C4-alkyl-, C,-C4-halogenoalkyl-, C~-C4-alkoxy-, C1-C4-halogenoalkoxy-, C,-C4-alkylthio-, C,-Ca-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C,-C4-halogenoalkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-halogenoalkyl-sulphonyl- or di-(C1-C4-alkyl)-amino-sulphonyl-substituted monocyclic or bicyclic heterocyclyl or heterocyclylalkyl having in each case up to 10 carbon atoms and up to 4 nitrogen atoms and/or 1 or 2 oxygen or sulphur atoms in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety.
Z1 preferably represents C-R4.
Zz preferably represents C-R4.
Le A 34 486-Foreign Countries Z3 preferably represents C-R4.
R2 particularly preferably represents vitro, cyano, SFS, fluorine, chlorine or bro-mine, or represents in each case optionally cyano-, fluorine-, chlorine-, meth-oxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n-or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethyl-sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylsulphonyloxy, ethylsulphonyloxy, n- or i-propyl-sulphonyloxy.
R3 particularly preferably represents hydrogen, fluorine, chlorine or bromine, or together with RZ represents in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy.
R4 particularly preferably represents hydrogen, cyano, carboxyl, carbamoyl, fluo-rine, chlorine, bromine or represents optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl.
Q' particularly preferably represents O (oxygen).
RS particularly preferably represents hydrogen or amino, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents dimethylamino or diethylamino, represents propylideneamino or butylideneamino, represents in each case optionally cyano-, fluorine-, chlorine- and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substi-tuted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, Le A 34 486-Foreign Countries cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, represents in each case optionally nitro-, cyano-, phenyl-, phenoxy-, phenylthio-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, di-chloromethyl-, difluoromethyl-, trichloromethyl-, trifluoromethyl-, chlorodi-S fluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, eth-ylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted phenyl, naphthyl, phenylamino, benzyl or phenylethyl, or represents in each case op-tionally cyano-, phenyl-, phenoxy-, phenylthio-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichlo-romethyl-, difluoromethyl-, trichloromethyl-, trifluoromethyl-, chlorodifluo-romethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, di-fluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, eth-ylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted hetero-cyclyl or heterocyclylalkyl from the group consisting of furyl, tetrahydro-furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzopyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, quinolinyl, pyrimidinyl, furylmethyl, thi-enylmethyl, pyrrolylmethyl, pyrazolylmethyl, oxazolylmethyl, thiazolylmeth-yl, pyridinylmethyl, pyrimidinylmethyl.
R6 particularly preferably represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, repre-sents in each case optionally fluorine-, chlorine- and/or bromine-substituted propenyl or butenyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentyl-Le A 34 486-Foreign Countries methyl or cyclohexylmethyl, represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-or t-butyl-, dichloromethyl-, difluoromethyl- trichloromethyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n-or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethyl-sulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted phenyl or naphthyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, di-chloromethyl-, difluoromethyl-, trichloromethyl-, trifluoromethyl-, chlorodi-fluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluorornethylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethyl-sulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted heterocyclyl or heterocyclylalkyl from the group consisting of furyl, benzo-furyl, thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzopyr-azolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzothiazolyl, pyr-idinyl, quinolinyl, pyrimidinyl, furylmethyl, thienylmethyl, pyrrolylmethyl, pyrazolylmethyl, oxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyr-imidinylmethyl.
Z' particularly preferably represents CH.
ZZ particularly preferably represents CH.
Z3 particularly preferably represents CH.
RZ very particularly preferably represents cyano, fluorine, chlorine or bromine, or represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-Le A 34 486-Foreign Countries . _8_ substituted methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, methylsul-phinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylsulphonyloxy or ethylsulphonyloxy.
R4 very particularly preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or represents optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl or ethyl.
RS very particularly preferably represents hydrogen or amino, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methylamino, ethylamino, n- or i-propylamino, represents dimethylamino, represents in each case optionally fluorine-, chlorine- and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl- or 1 S ethyl-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluorometh-oxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoro-methylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoro-methylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethyl-sulphonyl- or dimethylaminosulphonyl-substituted phenyl, phenylamino, benzyl or phenylethyl.
R6 very particularly preferably represents in each case optionally fluorine-and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, repre-sents in each case optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclopentyl or cyclohexyl, or represents optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, di-Le A 34 486-Foreign Countries fluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propyl-thio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethyl-sulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, tri-fluoromethylsulphonyl- or dimethylaminosulphonyl-substituted phenyl.
RZ most preferably represents trifluoromethyl.
R4 most preferably represents methyl.
A very particularly preferred group are those compounds of the formula (I) in which Rl represents cyano or one of the groupings -CQ1-Qz-RS or -SOZ-R6, R2 represents trifluoromethyl, difluoromethoxy or trifluoromethoxy, R3 represents hydrogen, fluorine or chlorine, or together with RZ - in the ortho position - represents difluoromethylenedioxy or tetrafluoroethylenedioxy, R4 represents hydrogen, fluorine, chlorine, bromine or methyl, Q1 represents O (oxygen) or S (sulphur), QZ represents a single bond or represents O (oxygen), S (sulphur) or N-R5, RS represents hydrogen, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, repre-sents in each case optionally fluorine-, chlorine- and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluo-rine-, chlorine- or methyl-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, Le A 34 486-Foreign Countries ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, eth-oxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methyl-sulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethylamino-sulphonyl-substituted phenyl or benzyl, R6 represents in each case optionally fluorine-, and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case op-tionally fluorine-, chlorine- or methyl-substituted cyclopropyl, cyclopentyl or cyclohexyl, or represents optionally nitro-, cyano-, fluorine-, chlorine-, bro-mine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluo-romethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethyl-aminosulphonyl-substituted phenyl, Z' represents CH, ZZ represents CH, and Z3 represents CH.
Preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.
Particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings given above as being par-ticularly preferred.
Le A 34 486-Foreign Countries Very particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings given above as being very particularly preferred.
The general or preferred radical definitions listed above apply both to the end prod-ucts of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation.
These radical definitions can be combined with one another as desired, i.e.
including combinations between the given preferred ranges.
The novel substituted iminoazines of the general formula (I) have interesting biologi-cal properties. In particular, they have strong herbicidal activity.
1 S The novel substituted iminoazines of the general formula (I) are obtained when (a) iminoazines of the general formula (II) R4~Z
Z~N~N~H
Rs ~ ~ (II)~
in which RZ, R3, R4, Z', ZZ and Z3 are each as defined above - or acid adducts of iminoazines of the general formula (II), - such as, for ex-ample, the hydrochlorides are reacted with compounds of the general formula (III) Le A 34 486-Foreign Countries X'-R' (III) in which R' is as defined above, X' represents halogen, -S02CH3, -O-CO-RS or -O-S02-R6 and RS and R6 are each as defined above, or with iso(thio)cyanates of the general formula (IV) Q'=C=N-RS (IV) in which Q' and RS are each as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or when (b) azinethiones of the general formula (V) (V), Le A 34 486-Foreign Countries in which R2, R3, R4, Z1, ZZ and Z3 are each as defined above are reacted with compounds of the general formula (VI) M+ Cl-N-SO2-R6 (VI) in which R6 is as defined above and M represents a metal equivalent, if appropriate in the presence of one or more diluents, or when (c) chloroazinium compounds of the general formula (VII) Ra 2 ~z.z3 z, i .~ Y
~N+ CI
(VII), in which R2, R3, R4, Z', ZZ and Z3 are each as defined above, and Y represents Cl, PC14, POC14 or PC16 Le A 34 486-Foreign Countries are reacted with amino compounds of the general formula (VIII) H2N-Rl (VIII) in which RI is as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or when (d) iminoazines of the general formula (II) R4~Z
Z~N~N~H
Rs ~ I (II)~
in which R2, R3, R4, Z1, ZZ and Z3 are each as defined above - or acid adducts of iminoazines of the general formula (II), such as, for ex-ample, the hydrochlorides -are reacted with nitric acid, if appropriate in the presence of a reaction auxili-ary and/or diluent.
Le A 34 486-Foreign Countries Using, for example, 5-chloro-1-(3-cyano-phenyl)-2(1H)-pyridineimine and acetyl chloride as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following formula scheme:
CI \
C
N NH + CI-CO-CH3 - HCI
/ CN
Using, for example, 1-(3-chloro-phenyl)-5-ethyl-2(1H)-pyridinethione and N-chloro-benzenesulphonamide sodium salt as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following formula scheme:
H5C2 \
H5C2 ( \
CsHs N S + ~ ~SOZ
Na CI-N-SOZC6Hs N N
\ \
/ CI ~ /
CI
Using, for example, 1-(3-bromo-phenyl)-2-chloro-5-trifluoromethyl-pyridinium chloride and dimethylhydrazine as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following formula scheme:
Le A 34 486-Foreign Countries CI~ F3C ~ \
N+ CI H2N-N(CHs)2 N~N~N(CH3)2 / /
\ Br \ I Br Using, for example, 5-bromo-1-(3-chlorodifluoromethyl-phenyl)-2(1H)-pyridine-imine and nitric acid as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following formula scheme:
Br \
H HN~ ~ N~ ~N02 N
\
~F2CI /
The formula (II) provides a general definition of the iminoazines to be used as start-ing materials in the processes (a) and (d) according to the invention for preparing compounds of the general formula (I). In the general formula (II), R2, R3, R4, Z', Zz and Z3 each preferably have those meanings which have already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very par-ticularly preferred for R2 , R3, R4, ZI, Zz and Z3.
The starting materials of the general formula (II) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel iminoazines of the general formula (II), are obtained when Le A 34 486-Foreign Countries ' - 17-(a) azinones of the general formula (IX) R4 Z:
Z1 ~, ~N~O
R3 ~
RZ (IX), in which R2, R3, R4, Z', Z2 and Z3 are each as defined above are reacted, in a first step, with chlorinating agents, such as, for example, phosgene, diphosgene, oxalyl chloride, thionyl chloride, phosphorus(III) chloride, phosphoryl chloride or phosphorus(V) chloride, if appropriate in the presence of reaction auxiliaries, such as, for example, N,N-dimethyl-form-amide, and if appropriate in the presence of diluents, such as, for example, 1,2-dichloro-ethane, at temperatures between 0°C and 150°C (cf.
the Prepara-tion Examples) and the resulting chloroazinium compounds of the general formula (VII) I Zs R4~Z
Y
~N+ CI
R3 ~ ~ (VII), in which RZ, R3, R4, Z', ZZ and Z3 are each as defined above and Le A 34 486-Foreign Countries Y represents Cl, PCl4, POCl4 or PC16 are, in a second step, reacted with ammonia, if appropriate in the presence of a diluent, such as, for example, methanol, and if appropriate in the presence of S an acid acceptor, such as, for example, sodium methoxide, at temperatures between 0°C and 80°C (cf. the preparation examples), or when ((3) substituted iminoazines of the general formula (Ia) Ra 72_ ~~Zs Rs I I
Z~N~N~S02 Rs ~ I (Ia)~
in which Rz, R3, R4, R6, Z1, Z2 and Z3 are each as defined above are reacted with a strong acid, such as, for example, sulphuric acid, which is optionally diluted with water, at temperatures between 0°C and 100°C (cf. the Preparation Examples).
The starting materials of the general formula (IX) are partly known and/or can be prepared by known processes (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A-1900947, DE-A-2362958, DE-A-2555411, cf. also the Preparation Examples).
The starting materials of the general formula (IXa) Le A 34 486-Foreign Countries Ra N ~O
(IXa) wherein R2, R3 and R4 are each as defined above, S are novel compounds according to the invention for preparing compounds of the general formula (II). In the general formula (IXa), R2, R3 and R4 each preferably have those meanings which have already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for R2, R3 and R4.
The starting materials of the general formula (IXa) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject matter of the present application.
The novel compounds of the general formula (IXa) can be prepared by known processes (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A-1900947, DE-A-2362958, DE-A-2555411, cf. also the Preparation Examples).
The compounds of the general formula (IX) as well as the compounds of the formula (IXa) also have interesting biological properties. In particular, they show a strong herbicidal activity.
The substituted iminoazines of the general formula (Ia) are novel compounds ac-cording to the invention; they are preferably prepared by the process (b) according to the invention.
Le A 34 486-Foreign Countries The formulae (III) and (IV) provide general definitions of the compounds further to be used as starting materials in the process (a) according to the invention for prepar-ing compounds of the general formula (I). In the general formulae (III) and (IV), Rl preferably has that meaning which has already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for Rl; X' preferably represents fluorine, chlorine, bromine or the grouping -0-CO-Rl, in particular chlorine or bromine; Q' preferably represents O or S.
The starting materials of the general formulae (III) and (IV) are known organic chemicals for synthesis.
The formula (V) provides a general definition of the azinethiones to be used as start-ing materials in the process (b) according to the invention for preparing compounds 1 S of the general formula (I). In the general formula (V), R2, R3, R4, Zi, ZZ
and Z3 each preferably have those meanings which have already been mentioned above, in con-nection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for RZ, R3, R4, Z1, ZZ and Z3.
The starting materials of the general formula (V) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel azinethiones of the general formula (V) are obtained when azinones of the general formula (IX) Le A 34 486-Foreign Countries (IX), in which R2, R3, R4, Z1, ZZ and Z3 are each as defined above are reacted with a sulphurizing agent, such as, for example, phosphorus(V) sulphide (PzSs or P4S~o), if appropriate in the presence of a reaction auxiliary, such as, for ex-ample, pyridine, at temperatures between 10°C and 150°C (cf.
Preparation Ex-amples).
The starting materials of the general formula (IX) are known and/or can be prepared by processes known per se (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A-1 900 947, DE-A-2 362 958, DE-A-2 555 411, cf. also the Preparation Ex-amples).
The azinones of the general formula (IX) are obtained when azinones of the general formula (X) R~Z
I
(X)~
I
H
in which R4, Zl, ZZ and Z3 are each as defined above are reacted with halogenoarenes of the general formula (XI) Le A 34 486-Foreign Countries Rs ~ (XI), in which RZ and R3 are each as defined above and XZ represents fluorine, chlorine, bromine or iodine, if appropriate in the presence of a catalyst, such as, for example, copper(I) iodide, if appropriate in the presence of an acid acceptor, such as, for example, potassium carbonate, and if appropriate in the presence of a diluent, such as, for example, N,N-dimethyl-formamide, at temperatures between 20°C and 200°C
(cf. the Prepa-ration Examples).
The formula (VII) provides a general definition of the chloroazinium compounds to be used as starting materials in the process (c) according to the invention for prepar-ing compounds of the general formula (I). In the general formula (VII), R2, R3, R4, Zl, ZZ and Z3 each preferably have those meanings which have already been men-boned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for RZ, R3, R4, Z1, ZZ and Z3.
The starting materials of the general formula (VII) have hitherto not being disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel chloroazinium compounds of the general formula (VII) are obtained when azinones of the general formula (IX) Le A 34 486-Foreign Countries R Z~
~Z3 Z ~
~N~O
Rs ~ I (IX)~
Rz in which R2, R3, R4, Z1, ZZ and Z3 are each as defined above are reacted with chlorinating agents, such as, for example, phosgene, diphosgene, oxalyl chloride, thionyl chloride, phosphorus(III) chloride, phosphoryl chloride or phosphorus(V) chloride, if appropriate in the presence of reaction auxiliaries, such as, for example, N,N-dimethyl-formamide, and if appropriate in the presence of diluents, such as, for example, 1,2-dichloro-ethane, at temperatures between 0°C
and 150°C
(cf. the Preparation Examples).
The formula (VIII) provides a general definition of the amino compounds further to be used as starting materials in the process (c) according to the invention for prepar-ing compounds of the general formula (I). In the general formula (VIII), Rl prefer-ably has that meaning which has already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the inven-tion, as being preferred, particularly preferred or very particularly preferred for R'.
The starting materials of the general formula (VIII) are known chemicals for synthe-sis.
Suitable reaction auxiliaries for the processes (a) and (c) according to the invention are, in general, the customary inorganic or organic bases or acid acceptors.
These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium ace-Le A 34 486-Foreign Countries ' -24-tate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbon-ate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, S sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohex-ylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzyl-amine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2.2.2]-octane (DABCO), 1,5-di-azabicyclo[4.3.0)-non-5-ene (DBN), or 1,8-diazabicyclo[5.4.0)-undec-7-ene (DBU).
Further reaction auxiliaries suitable for the processes (a) and (c) according to the in-vention are phase-transfer catalysts. Examples of such catalysts which may be men-tioned are:
tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium chloride, tetrabutylammonium hydrogen sulphate, methyl-trioctylammonium chloride, hexadecyl-trimethylammonium chloride, hexadecyl-trimethylammonium bromide, benzyl-trimethylammonium chloride, benzyl-triethylammonium chloride, benzyl-trimethylammonium hydroxide, benzyl-triethylammonium hydroxide, benzyl-tributylammonium chloride, benzyl-tributylammonium bromide, tetrabutylphos-phonium bromide, tetrabutylphosphonium chloride, tributyl-hexadecylphosphonium bromide, butyl-triphenylphosphonium chloride, ethyl-trioctylphosphonium bromide, tetraphenylphosphonium bromide.
Le A 34 486-Foreign Countries _, Suitable reaction auxiliaries and/or diluents for the process (d) according to the in-vention are substances which are generally used for nitrations. These preferably in-clude sulphuric acid, acetic acid and acetic anhydride.
The processes (a), (b) and (c) for preparing the compounds of the general formula (I) are preferably carried out using one or more diluents. Suitable diluents for carrying out the processes (a), (b) and (c) according to the invention are, in addition to water, especially inert organic solvents. These include, in particular, aliphatic, alicyclic or 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 di-ethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitriles, amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene gly col monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono ethyl ether, mixtures thereof with water or pure water.
When carrying out the processes (a), (b), (c) and (d) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carned out at temperatures between -30 C and 150°C, preferably be tween -10°C and 120°C.
The processes according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the in-vention under elevated or reduced pressure - in general between 0.1 bar and 10 bar.
Le A 34 486-Foreign Countries For carrying out the processes according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possi-ble to use a relatively large excess of one of the components. The reaction is gener-ally carried out in a suitable diluent, in the presence of an appropriate reaction auxil-iary, and the reaction mixture is generally stirred at the required temperature for sev-eral hours. Work-up is carried out by customary methods (cf. the Preparation Ex-amples).
The active compounds according to the invention can be used as defoliants, desic-cants, haulm killers and, especially, as weed killers. Weeds in the broadest sense are understood to mean 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 con-nection with the following plants:
Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, An-themis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.
Le A 34 486-Foreign Countries ', Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dac-tyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Monocotyledonous crops of the genera: Album, Ananas, Asparagus, Avena, Hor-deum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
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.
The active compounds according to the invention are suitable, depending on the con-centration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and areas with and without tree plantings. Similarly, the active compounds according to the invention can be employed for controlling weeds in per-ennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns, turf and pastureland, and for the selective control of weeds in annual crops.
The compounds of the formula (I) and the compounds of the formulae (IX) and (IXa) according to the invention have strong herbicidal activity and a broad activity spec-trum when used on the soil or on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledonous and dicotyle-donous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.
Le A 34 486-Foreign Countries _28_ At certain concentrations or application rates, the active compounds according to the invention can also be employed for controlling animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.
According to the invention, it is possible to treat all plants and parts of plants. Plants are to be understood here as meaning all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurnng crop plants).
Crop plants can be plants which can be obtained by conventional breeding and opti-mization methods or by biotechnological and genetic engineering methods or combi-nations of these methods, including the transgenic plants and including plant culti-vars which can or cannot be protected by plant breeders' certificates. Parts of plants are to be understood as meaning all above-ground and below-ground parts and or-gans of plants, such as shoot, leaf, flower and root, examples which may be men-boned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
The treatment of the plants and parts of plants according to the invention with the active compounds is carned out directly or by action on their environment, habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one-or multi-layer coating.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric sub-stances.
Le A 34 486-Foreign Countries These formulations are produced in a known manner, for example by mixing the ac tive compounds with extenders, that is to say liquid solvents and/or solid Garners, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are:
aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated ali-phatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid Garners are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoma-ceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid Garners for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic gran-ules of inorganic and organic meals, and granules of organic material, such as saw-dust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polygly-col ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydroly-sates; suitable dispersants are: for example lignosulphite waste liquors and methyl-cellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or lattices, such as gum arabic, polyvinyl alcohol and Le A 34 486-Foreign Countries ' -30-polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
S It is possible to use colorants, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in their formulations, can also be used as mixtures with known herbicides and/or sub-stances which improve the compatibility with crop plants ("safeners"), finished for-mulations or tank mixes being possible. Also possible are mixtures with weed-killers comprising one or more known herbicides and a safener.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzfendizone, benzobicyclon, benzofenap, benzoyl-prop(-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben, chlo-ridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop Le A 34 486-Foreign Countries (-butyl), 2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (-P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxy-sulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide, flamprop(-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluri-done, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate (-ammonium), glypho-sate (-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl, -P-methyl), hexazi-none, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (al-pha-) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (-methyl), moli-nate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluor-fen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedi-pham, picolinafen, piperophos, pretilachlor, primisulfuron (-methyl), profluazol, prometryn, propachlor, propanil, propaquizafop, propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyri-date, pyridatol, pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlo-rac, quinmerac, quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron, seth-oxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sul-fosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thioben-Le A 34 486-Foreign Countries carb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, sus-pensions, emulsions, powders, pastes and granules. They are used in a customary manner, for example by watering, spraying, atomizing or broadcasting.
The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It de-pends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention is illustrated by the examples below.
Le A 34 486-Foreign Countries Preparation Examples:
Example 1 HsC \
I
N N O
/I
\ CFs (Process (a)) A mixture of 2.3 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridineimine, 2.1 g (10 mmol) of trifluoroacetic anhydride, 1.0 g (10 mmol) of tri-ethylamine and 50 ml of ethyl acetate is stirred at room temperature (about 20°C) for 60 minutes. The reaction mixture is then washed with water, dried with sodium sul-phate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diisopropyl ether and the resulting crystalline product is isolated by filtration with suction.
This gives 0.5 g (14% of theory) of 2,2,2-trifluoro-N-[S-methyl-1-(3-trifluoromethyl-phenyl)-2( 1 H)-pyridinylidene]-acetamide of melting point 11 S°C.
Example 2 HsC \ O~CsH~_i IN~~
N O
/) (Process (a)) Le A 34 486-Foreign Countries A mixture of 1.1 g (4 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyri-dineimine, 5 ml (5 mmol) of isopropyl chloroformate, 0.5 g (5 mmol) of triethyl-amine and 50 ml of ethyl acetate is stirred at room temperature (about 20°C) for 60 minutes. The reaction mixture is then washed with water, the aqueous phase is S reextracted with methylene chloride and the combined organic phases are dried with sodium sulphate and filtered. From the filtrate, the solvents are carefully distilled off under reduced pressure.
This gives 0.6 g (46% of theory) of O-methyl N-[5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-carbamate as an amorphous residue.
loge = 1.59 (determination of log P values see page 40).
Example 3 ~CN
.,F3 (Process (a)) A mixture of 1.1 g (4 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridineimine, 0.6 g (5 mmol) of cyanogen bromide, 0.5 g (5 mmol) of triethylamine and 50 ml of ethyl acetate and stirred at room temperature (about.
20°C) for minutes. The reaction mixture is then washed with water, the aqueous phase is reextracted with methylene chloride and the combined organic phases are dried with sodium sulphate and filtered. From the filtrate, the solvents are carefully distilled off 25 under reduced pressure.
Le A 34 486-Foreign Countries This gives 0.35 g (32% of theory) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidenecyanamide of melting point 165°C.
Example 4 (Process (a)) m 3 A mixture of 2.6 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridineimine, 0.6 g (10 mmol) of methyl isocyanate and 100 ml of acetonitrile is allowed to stand at room temperature (about 20°C) for two hours. The mixture is then concentrated under water pump vacuum, the residue is digested with diisopropyl ether and the resulting crystalline product is isolated by filtration with suction.
This gives 2.1 g (68% of theory) of N-methyl-N'-[5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-urea of melting point 114°C.
Example 5 H
SOZ
(Process (a)) Le A 34 486-Foreign Countries 2.9 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinimine hydrochloride, 3.1 g (30 mmol) of triethylamine and 100 ml of acetonitrile is, at room temperature (about 20°C) and with stirnng, admixed dropwise with 2.9 g (10 mmol) of trifluoromethanesulphonic anhydride. The reaction mixture is stirred at room temperature for 60 minutes and then concentrated under water pump vacuum.
The crude product obtained as residue is purified by column chromatography (silica gel, ethyl acetate/hexane, 9:1 ).
This gives 0.40 g (10% of theory) of N-[5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-trifluoromethanesulphonamide of melting point 206°C.
Example 6 ~~'wCF3 m 3 (Process (a)) A mixture of 2.9 g (10 mmol) of S-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinimine hydrochloride, 2.3 g (10 mmol) of 2-methylsulphonyl-5-trifluorometh-yl-1,3,4-thiadiazole, 4.2 g (30 mmol) of calcium carbonate and 30 ml of dimethyl sulphoxide is stirred at 100°C for 60 minutes and, after cooling, poured into about the same volume of methylene chloride. The organic phase is washed with water and saturated aqueous sodium chloride solution and then dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diethyl ether and the resulting crystalline product is isolated by filtration with suction.
Le A 34 486-Foreign Countries This gives 2.3 g (57% of theory) of N-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-S-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinimine of melting point 179°C.
Example 7 ~SOz N N
/
(Process (b)) 2.7 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinethione are initially charged in 50 ml of chloroform and, at room temperature (about 20°C) and with stirring, admixed dropwise with a solution of 2.9 g (10 mmol) of N-chloro-p-toluenesulphonamide sodium salt hydrate (chloramine T hydrate) in 50 ml of ethanol.
The reaction mixture is stirred at room temperature for 1 S hours and then concentrated under water pump vacuum, and the residue is taken up in chloroform, washed with water and then with saturated aqueous sodium bicarbonate solution, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum and the residue is kept under high vacuum at 180°C for 15 minutes.
After cooling and digestion with diisopropyl ether, the resulting crystalline product is isolated by filtration with suction.
This gives 1.8 g (49% of theory) of 4-methyl-N-[S-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-benzenesulphonamide of melting point 174°C.
Le A 34 486-Foreign Countries Example 8 ~ N~ ~
N
x HCI
(Process (c)) A mixture of 1.6 g (5 mmol) of 2-chloro-5-methyl-1-(3-trifluoromethyl-phenyl)-pyridinium chloride, 0.9 g (15 mmol) of cyclopropylamine and 50 ml of methanol is allowed to stand at room temperature (about 20°C) for 15 hours and then concentrated under water pump vacuum. The residue is taken up in methylene chloride, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is taken up in methanol and hydrochloric acid and the volatile components are carefully distilled off under reduced pressure. The crude product obtained as residue is purified by column chromatography (silica gel, ethyl acetate/hexane, 5:1 ).
This gives 1.5 g (91% of theory) of N-cyclopropyl-5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridineimine as an oily product.
loge = 1.51 (determination of log P values see page 40).
Analogously to Examples 1 to 8, and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the general formula (I) listed in Table 1 below.
Le A 34 486-Foreign Countries R' Table: Examples of compounds of the formula (I) Ex. (Position) Physical No. R' RZ R3 R4 ZI ZZ Z3 data 9 F F CF3 CH3 CH CH CH m.p.: 121 °C
'F
O
I ~ CF3 CH3 CH CH CH m.p.:175°C
~O
11 S~CzHs CF3 CH3 CH CH CH m.p.:124°C
O
12 HN~C(CH3)3 CF3 CH3 CH CH CH m.p.: 156°C
O
13 HN~CaHi ~ CF3 CH3 CH CH CH m.p.: 139°C
~S
14 SiC3H7 ~ CF3 CH3 CH CH CH m.p.: 140°C
-CO-CF3 CF3 CH3 N CH CH m.p.:128°C
Le A 34 486-Foreign Countries 16 -CHZ-C6H5 CF3 CH3 CH CH CH m.p.:253°C
17 -CO-C3H~-i CF3 CH3 CH CH CH m.p.:93°C
18 CF3 CH3 CH CH CH m.p.:98°C
O
19 -CO-CHF2 CF3 CH3 CH CH CH m.p.:137°C
20 ~"3 CF3 CH3 CH CH CH m.p.:165°C
NI \~
~ i ' _N OCH3 21 I ~ CF3 CH3 CH CH CH m.p.:148°C
22 ~Hz CF3 CH3 CH CH CH loge = 1,58 ,CH a) /O
23 O~C3H~ i CF3 CH3 CH CH CH m.p.: 188°C
/NH
24 -CO-CF3 CF3 H CH CH CH m.p.:150°C
25 -CO-CF3 CF3 (4) F CH3 CH CH CH m.p.: 180°C
26 -CO-CF3 CF3 (5) F CH3 CH CH CH m.p.: 158°C
Le A 34 486-Foreign Countries 27 N-N ~H3 CF3 CH3 CH CH CH m.p.: 179°C
H3C / ~ F
~O
28 ~e"3 CF3 CH3 CH CH CH m.p.: 201 °C
N-F~C \ S
~O
29 -CN CF3 CH3 N CH CH m.p.:148°C
30 -CO-CH3 CF3 CH3 CH CH CH m.p.: 101 °C
31 -CO-CZHS CF3 CH3 CH CH CH m.p.:113°C
32 -CO-C3H~-n CF3 CH3 CH CH CH m.p.:103°C
33 ~~H3 CF3 CH3 CH CH CH m.p.:133°C
O
34 O.CZHs CF3 CH3 CH CH CH m.p.:150°C
O
35 O~C3H~ n CF3 CH3 CH CH CH m.p.: 85°C
O
36 CHs CF3 CH3 CH CH CH m.p.:103°C
O
37 CI CF3 CH3 CH CH CH m.p.: 181 °C
CI
~O
Le A 34 486-Foreign Countries 38 -CO-C4H9-t CF3 CH3 CH CH CH m.p.:77°C
39 O~C4H9 t CF3 CH3 CH CH CH m.p.: 108°C
O
40 ~CH3 CF3 CH3 N CH CH m.p.:148°C
O
41 O~CZHs CF3 CH3 N CH CH m.p.:146°C
O
42 ~CsHi ~ CF3 CH3 N CH CH m.p.: 98°C
O
43 OiC3H7 ~ CF3 CH3 N CH CH m.p.: 123°C
O
44 .C3H; I CF3 CH3 N CH CH m.p.: 83°C
O
45 CF3 CH3 N CH CH m.p.:108°C
O
46 I CF3 CH3 N CH CH m.p.:164°C
CI
O
47 FZ CF3 CH3 N CH CH m.p.:85°C
'F
O
48 F ~ ~ F CF3 CH3 N CH CH m.p.: 157°C
HNI
' 'O
Le A 34 486-Foreign Countries Loge values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.AB by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18). Temperature: 43°C.
S
(a) Mobile phases for the determination in the acidic range: 0.1 % aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile -the corresponding data in Table 1 are labelled a).
(b) Mobile phases for the determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90%
acetonitrile - the corresponding data in Table 1 are labelled b).
The calibration was carried out using unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known loge values (determination of the loge values by the retention times using linear interpolation between two successive alkanones).
The lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.
Le A 34 48fi-Foreign Countries .2 Starting materials of the formula (II):
Example (II-1) I ~ .H
N N
/
(Process (a)) Step 1 CI_ N CI
A mixture of 2.5 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridone, 3.9 g (30 mmol) of oxalyl chloride, 40 ml of 1,2-dichloro-ethane and 2 drops of N,N-dimethyl-formamide is heated at the boil under reflux until the evolution of gas has ceased. After cooling to room temperature, the resulting crystalline product is isolated by filtration with suction.
This gives 2.1 g (65% of theory) of 2-chloro-5-methyl-1(3-trifluoromethyl-phenyl)-pyridinium chloride of melting point 194°C.
Le A 34 486-Foreign Countries Step 2 H
J
, .:
Substituted iminoazines The invention relates to novel substituted iminoazines, to processes for their prepara-tion and to their use as plant treatment agents, in particular as herbicides.
It is already known that certain substituted iminopyridines have herbicidal properties (cf. EP-A-432 600). However, the activity of these compounds is not entirely satis-factory.
This invention, accordingly, provides the novel substituted aminoazines of the gen-eral formula (I) R Z\
Z\N~N~R~
R3 ~ I (I)~
in which R1 represents nitro, cyano or one of the groupings -R5, -CQ1-QZ-R5, -NH-CQ1_ Q2-RS or -SOZ-R6, Rz represents nitro, cyano, SFS, halogen or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl or alkylsulphonyloxy, R3 represents hydrogen or halogen, or together with RZ represents optionally sub-stituted alkylenedioxy, R4 represents hydrogen, cyano, carboxyl, carbamoyl, halogen or optionally sub-stituted alkyl, Le A 34 486-Foreign Countries ~ -2-Q1 represents O (oxygen), S (sulphur) or N-Rs, QZ represents a single bond or represents O (oxygen), S (sulphur) or N-Rs, Rs represents hydrogen, amino or in each case optionally substituted alkyl, alk-oxy, alkylamino, dialkylamino, alkylideneamino, alkenyl, alkenyloxy, alk-inyl, cycloalkyl, cycloalkylamino, cycloalkylalkyl, aryl, arylamino, arylalkyl, heterocyclyl or heterocyclylalkyl, R6 represents in each case optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl, Z1 represents N (nitrogen) or C-R4, 1 S ZZ represents N (nitrogen) or C-R4, and Z3 represents N (nitrogen) or C-R4.
In the definitions, the hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched - including in combination with heteroatoms, such as in alkylamino. R3 is preferably located in the meta or para position on the phenyl ring.
Preferred substituents or preferred ranges of the radicals which are present in the formulae listed above and below are defined below.
R1 preferably represents cyano or one of the groupings -Rs, -CQ1-QZ-Rs, -NH-CQ1-Q2-RS or -SOZ-R6.
RZ preferably represents nitro, cyano, SFs, halogen or in each case optionally cyano-, halogen- or C~-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkyl-Le A 34 486-Foreign Countries ~ -3-sulphinyl, alkylsulphonyl or alkylsulphonyloxy having in each case 1 to carbon atoms.
R3 preferably represents hydrogen or halogen, or together with RZ represents 5 optionally halogen-substituted alkylenedioxy having 1 to 3 carbon atoms.
R4 preferably represents hydrogen, cyano, carboxyl, carbamoyl, halogen or op-tionally cyano-, halogen- or CI-C4-alkoxy-substituted alkyl having 1 to S carbon atoms.
Q1 preferably represents O (oxygen) or S (sulphur).
RS preferably represents hydrogen or amino, represents in each case optionally cyano-, halogen- or C,-C4-alkoxy-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, represents alkylamino having 1 to 6 carbon atoms, represents dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents alkylideneamino having up to 6 carbon atoms, represents in each case optionally cyano- or halogen-substituted alkenyl, alkenyloxy or alkinyl having in each case 2 to 6 carbon atoms, represents in each case op-tionally cyano-, halogen- or C1-Ca-alkyl-substituted cycloalkyl, cycloalkyl-amino or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, rep-resents in each case optionally nitro-, cyano-, phenyl-, phenoxy-, phenylthio-, halogen-, CI-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C,-C4-haloge-noalkoxy-, Cl-Ca-alkylthio-, Ci-C4-halogenoalkylthio-, C1-C4-alkylsulph-inyl-, C,-C4-halogenoalkylsulphinyl-, C~-C4-alkylsulphonyl-, C,-C4-halo-genoalkylsulphonyl- or di-(C1-C4-alkyl)-aminosulphonyl-substituted aryl, arylamino or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, phenyl-, phenoxy-, phenylthio-, halogen-, C~-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, Le A 34 486-Foreign Countries ~ -4-C,-Ca-alkylthio-, C,-Ca-halogenoalkylthio-, C1-Ca-alkylsulphinyl-, C,-C4-halogenoalkylsulphinyl-, C~-C4-alkylsulphonyl-, C1-C4-halogenoalkyl-sulphonyl- or di-(CI-C4-alkyl)-amino-sulphonyl-substituted monocyclic or bi-cyclic heterocyclyl or heterocyclylalkyl having in each case up to 10 carbon atoms and up to 4 nitrogen atoms and/or 1 or 2 oxygen or sulphur atoms in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety.
R6 preferably represents optionally halogen-substituted alkyl having 1 to 6 carbon atoms, represents optionally halogen-substituted alkenyl having 2 to 6 carbon atoms, represents optionally halogen- or C1-C4-alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, represents in each case optionally nitro-, cyano-, halogen-, C~-C4-alkyl-, C1-C4-halogeno-alkyl-, C~-C4-alkoxy-, C~-C4-halogenoalkoxy-, C,-C4-alkylthio-, C1-C4-halo-genoalkylthio-, C~-C4-alkylsulphinyl-, C,-C4-halogenoalkylsulphinyl-, C,-C4-alkylsulphonyl-, C,-C4-halogenoalkylsulphonyl- or di-(C1-C4-alkyl)-amino-sulphonyl-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, halogen-, C,-C4-alkyl-, C,-C4-halogenoalkyl-, C~-C4-alkoxy-, C1-C4-halogenoalkoxy-, C,-C4-alkylthio-, C,-Ca-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C,-C4-halogenoalkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-halogenoalkyl-sulphonyl- or di-(C1-C4-alkyl)-amino-sulphonyl-substituted monocyclic or bicyclic heterocyclyl or heterocyclylalkyl having in each case up to 10 carbon atoms and up to 4 nitrogen atoms and/or 1 or 2 oxygen or sulphur atoms in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety.
Z1 preferably represents C-R4.
Zz preferably represents C-R4.
Le A 34 486-Foreign Countries Z3 preferably represents C-R4.
R2 particularly preferably represents vitro, cyano, SFS, fluorine, chlorine or bro-mine, or represents in each case optionally cyano-, fluorine-, chlorine-, meth-oxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n-or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethyl-sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylsulphonyloxy, ethylsulphonyloxy, n- or i-propyl-sulphonyloxy.
R3 particularly preferably represents hydrogen, fluorine, chlorine or bromine, or together with RZ represents in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy.
R4 particularly preferably represents hydrogen, cyano, carboxyl, carbamoyl, fluo-rine, chlorine, bromine or represents optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl.
Q' particularly preferably represents O (oxygen).
RS particularly preferably represents hydrogen or amino, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents dimethylamino or diethylamino, represents propylideneamino or butylideneamino, represents in each case optionally cyano-, fluorine-, chlorine- and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substi-tuted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, Le A 34 486-Foreign Countries cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, represents in each case optionally nitro-, cyano-, phenyl-, phenoxy-, phenylthio-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, di-chloromethyl-, difluoromethyl-, trichloromethyl-, trifluoromethyl-, chlorodi-S fluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, eth-ylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted phenyl, naphthyl, phenylamino, benzyl or phenylethyl, or represents in each case op-tionally cyano-, phenyl-, phenoxy-, phenylthio-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichlo-romethyl-, difluoromethyl-, trichloromethyl-, trifluoromethyl-, chlorodifluo-romethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, di-fluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, eth-ylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted hetero-cyclyl or heterocyclylalkyl from the group consisting of furyl, tetrahydro-furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzopyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, quinolinyl, pyrimidinyl, furylmethyl, thi-enylmethyl, pyrrolylmethyl, pyrazolylmethyl, oxazolylmethyl, thiazolylmeth-yl, pyridinylmethyl, pyrimidinylmethyl.
R6 particularly preferably represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, repre-sents in each case optionally fluorine-, chlorine- and/or bromine-substituted propenyl or butenyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentyl-Le A 34 486-Foreign Countries methyl or cyclohexylmethyl, represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-or t-butyl-, dichloromethyl-, difluoromethyl- trichloromethyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n-or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethyl-sulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted phenyl or naphthyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, di-chloromethyl-, difluoromethyl-, trichloromethyl-, trifluoromethyl-, chlorodi-fluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluorornethylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethyl-sulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted heterocyclyl or heterocyclylalkyl from the group consisting of furyl, benzo-furyl, thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzopyr-azolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzothiazolyl, pyr-idinyl, quinolinyl, pyrimidinyl, furylmethyl, thienylmethyl, pyrrolylmethyl, pyrazolylmethyl, oxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyr-imidinylmethyl.
Z' particularly preferably represents CH.
ZZ particularly preferably represents CH.
Z3 particularly preferably represents CH.
RZ very particularly preferably represents cyano, fluorine, chlorine or bromine, or represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-Le A 34 486-Foreign Countries . _8_ substituted methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, methylsul-phinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylsulphonyloxy or ethylsulphonyloxy.
R4 very particularly preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or represents optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl or ethyl.
RS very particularly preferably represents hydrogen or amino, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methylamino, ethylamino, n- or i-propylamino, represents dimethylamino, represents in each case optionally fluorine-, chlorine- and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl- or 1 S ethyl-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluorometh-oxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoro-methylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoro-methylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethyl-sulphonyl- or dimethylaminosulphonyl-substituted phenyl, phenylamino, benzyl or phenylethyl.
R6 very particularly preferably represents in each case optionally fluorine-and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, repre-sents in each case optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclopentyl or cyclohexyl, or represents optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, di-Le A 34 486-Foreign Countries fluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propyl-thio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethyl-sulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, tri-fluoromethylsulphonyl- or dimethylaminosulphonyl-substituted phenyl.
RZ most preferably represents trifluoromethyl.
R4 most preferably represents methyl.
A very particularly preferred group are those compounds of the formula (I) in which Rl represents cyano or one of the groupings -CQ1-Qz-RS or -SOZ-R6, R2 represents trifluoromethyl, difluoromethoxy or trifluoromethoxy, R3 represents hydrogen, fluorine or chlorine, or together with RZ - in the ortho position - represents difluoromethylenedioxy or tetrafluoroethylenedioxy, R4 represents hydrogen, fluorine, chlorine, bromine or methyl, Q1 represents O (oxygen) or S (sulphur), QZ represents a single bond or represents O (oxygen), S (sulphur) or N-R5, RS represents hydrogen, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, repre-sents in each case optionally fluorine-, chlorine- and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluo-rine-, chlorine- or methyl-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, Le A 34 486-Foreign Countries ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, eth-oxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methyl-sulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethylamino-sulphonyl-substituted phenyl or benzyl, R6 represents in each case optionally fluorine-, and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case op-tionally fluorine-, chlorine- or methyl-substituted cyclopropyl, cyclopentyl or cyclohexyl, or represents optionally nitro-, cyano-, fluorine-, chlorine-, bro-mine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluo-romethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethyl-aminosulphonyl-substituted phenyl, Z' represents CH, ZZ represents CH, and Z3 represents CH.
Preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.
Particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings given above as being par-ticularly preferred.
Le A 34 486-Foreign Countries Very particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings given above as being very particularly preferred.
The general or preferred radical definitions listed above apply both to the end prod-ucts of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation.
These radical definitions can be combined with one another as desired, i.e.
including combinations between the given preferred ranges.
The novel substituted iminoazines of the general formula (I) have interesting biologi-cal properties. In particular, they have strong herbicidal activity.
1 S The novel substituted iminoazines of the general formula (I) are obtained when (a) iminoazines of the general formula (II) R4~Z
Z~N~N~H
Rs ~ ~ (II)~
in which RZ, R3, R4, Z', ZZ and Z3 are each as defined above - or acid adducts of iminoazines of the general formula (II), - such as, for ex-ample, the hydrochlorides are reacted with compounds of the general formula (III) Le A 34 486-Foreign Countries X'-R' (III) in which R' is as defined above, X' represents halogen, -S02CH3, -O-CO-RS or -O-S02-R6 and RS and R6 are each as defined above, or with iso(thio)cyanates of the general formula (IV) Q'=C=N-RS (IV) in which Q' and RS are each as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or when (b) azinethiones of the general formula (V) (V), Le A 34 486-Foreign Countries in which R2, R3, R4, Z1, ZZ and Z3 are each as defined above are reacted with compounds of the general formula (VI) M+ Cl-N-SO2-R6 (VI) in which R6 is as defined above and M represents a metal equivalent, if appropriate in the presence of one or more diluents, or when (c) chloroazinium compounds of the general formula (VII) Ra 2 ~z.z3 z, i .~ Y
~N+ CI
(VII), in which R2, R3, R4, Z', ZZ and Z3 are each as defined above, and Y represents Cl, PC14, POC14 or PC16 Le A 34 486-Foreign Countries are reacted with amino compounds of the general formula (VIII) H2N-Rl (VIII) in which RI is as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or when (d) iminoazines of the general formula (II) R4~Z
Z~N~N~H
Rs ~ I (II)~
in which R2, R3, R4, Z1, ZZ and Z3 are each as defined above - or acid adducts of iminoazines of the general formula (II), such as, for ex-ample, the hydrochlorides -are reacted with nitric acid, if appropriate in the presence of a reaction auxili-ary and/or diluent.
Le A 34 486-Foreign Countries Using, for example, 5-chloro-1-(3-cyano-phenyl)-2(1H)-pyridineimine and acetyl chloride as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following formula scheme:
CI \
C
N NH + CI-CO-CH3 - HCI
/ CN
Using, for example, 1-(3-chloro-phenyl)-5-ethyl-2(1H)-pyridinethione and N-chloro-benzenesulphonamide sodium salt as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following formula scheme:
H5C2 \
H5C2 ( \
CsHs N S + ~ ~SOZ
Na CI-N-SOZC6Hs N N
\ \
/ CI ~ /
CI
Using, for example, 1-(3-bromo-phenyl)-2-chloro-5-trifluoromethyl-pyridinium chloride and dimethylhydrazine as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following formula scheme:
Le A 34 486-Foreign Countries CI~ F3C ~ \
N+ CI H2N-N(CHs)2 N~N~N(CH3)2 / /
\ Br \ I Br Using, for example, 5-bromo-1-(3-chlorodifluoromethyl-phenyl)-2(1H)-pyridine-imine and nitric acid as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following formula scheme:
Br \
H HN~ ~ N~ ~N02 N
\
~F2CI /
The formula (II) provides a general definition of the iminoazines to be used as start-ing materials in the processes (a) and (d) according to the invention for preparing compounds of the general formula (I). In the general formula (II), R2, R3, R4, Z', Zz and Z3 each preferably have those meanings which have already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very par-ticularly preferred for R2 , R3, R4, ZI, Zz and Z3.
The starting materials of the general formula (II) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel iminoazines of the general formula (II), are obtained when Le A 34 486-Foreign Countries ' - 17-(a) azinones of the general formula (IX) R4 Z:
Z1 ~, ~N~O
R3 ~
RZ (IX), in which R2, R3, R4, Z', Z2 and Z3 are each as defined above are reacted, in a first step, with chlorinating agents, such as, for example, phosgene, diphosgene, oxalyl chloride, thionyl chloride, phosphorus(III) chloride, phosphoryl chloride or phosphorus(V) chloride, if appropriate in the presence of reaction auxiliaries, such as, for example, N,N-dimethyl-form-amide, and if appropriate in the presence of diluents, such as, for example, 1,2-dichloro-ethane, at temperatures between 0°C and 150°C (cf.
the Prepara-tion Examples) and the resulting chloroazinium compounds of the general formula (VII) I Zs R4~Z
Y
~N+ CI
R3 ~ ~ (VII), in which RZ, R3, R4, Z', ZZ and Z3 are each as defined above and Le A 34 486-Foreign Countries Y represents Cl, PCl4, POCl4 or PC16 are, in a second step, reacted with ammonia, if appropriate in the presence of a diluent, such as, for example, methanol, and if appropriate in the presence of S an acid acceptor, such as, for example, sodium methoxide, at temperatures between 0°C and 80°C (cf. the preparation examples), or when ((3) substituted iminoazines of the general formula (Ia) Ra 72_ ~~Zs Rs I I
Z~N~N~S02 Rs ~ I (Ia)~
in which Rz, R3, R4, R6, Z1, Z2 and Z3 are each as defined above are reacted with a strong acid, such as, for example, sulphuric acid, which is optionally diluted with water, at temperatures between 0°C and 100°C (cf. the Preparation Examples).
The starting materials of the general formula (IX) are partly known and/or can be prepared by known processes (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A-1900947, DE-A-2362958, DE-A-2555411, cf. also the Preparation Examples).
The starting materials of the general formula (IXa) Le A 34 486-Foreign Countries Ra N ~O
(IXa) wherein R2, R3 and R4 are each as defined above, S are novel compounds according to the invention for preparing compounds of the general formula (II). In the general formula (IXa), R2, R3 and R4 each preferably have those meanings which have already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for R2, R3 and R4.
The starting materials of the general formula (IXa) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject matter of the present application.
The novel compounds of the general formula (IXa) can be prepared by known processes (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A-1900947, DE-A-2362958, DE-A-2555411, cf. also the Preparation Examples).
The compounds of the general formula (IX) as well as the compounds of the formula (IXa) also have interesting biological properties. In particular, they show a strong herbicidal activity.
The substituted iminoazines of the general formula (Ia) are novel compounds ac-cording to the invention; they are preferably prepared by the process (b) according to the invention.
Le A 34 486-Foreign Countries The formulae (III) and (IV) provide general definitions of the compounds further to be used as starting materials in the process (a) according to the invention for prepar-ing compounds of the general formula (I). In the general formulae (III) and (IV), Rl preferably has that meaning which has already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for Rl; X' preferably represents fluorine, chlorine, bromine or the grouping -0-CO-Rl, in particular chlorine or bromine; Q' preferably represents O or S.
The starting materials of the general formulae (III) and (IV) are known organic chemicals for synthesis.
The formula (V) provides a general definition of the azinethiones to be used as start-ing materials in the process (b) according to the invention for preparing compounds 1 S of the general formula (I). In the general formula (V), R2, R3, R4, Zi, ZZ
and Z3 each preferably have those meanings which have already been mentioned above, in con-nection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for RZ, R3, R4, Z1, ZZ and Z3.
The starting materials of the general formula (V) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel azinethiones of the general formula (V) are obtained when azinones of the general formula (IX) Le A 34 486-Foreign Countries (IX), in which R2, R3, R4, Z1, ZZ and Z3 are each as defined above are reacted with a sulphurizing agent, such as, for example, phosphorus(V) sulphide (PzSs or P4S~o), if appropriate in the presence of a reaction auxiliary, such as, for ex-ample, pyridine, at temperatures between 10°C and 150°C (cf.
Preparation Ex-amples).
The starting materials of the general formula (IX) are known and/or can be prepared by processes known per se (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A-1 900 947, DE-A-2 362 958, DE-A-2 555 411, cf. also the Preparation Ex-amples).
The azinones of the general formula (IX) are obtained when azinones of the general formula (X) R~Z
I
(X)~
I
H
in which R4, Zl, ZZ and Z3 are each as defined above are reacted with halogenoarenes of the general formula (XI) Le A 34 486-Foreign Countries Rs ~ (XI), in which RZ and R3 are each as defined above and XZ represents fluorine, chlorine, bromine or iodine, if appropriate in the presence of a catalyst, such as, for example, copper(I) iodide, if appropriate in the presence of an acid acceptor, such as, for example, potassium carbonate, and if appropriate in the presence of a diluent, such as, for example, N,N-dimethyl-formamide, at temperatures between 20°C and 200°C
(cf. the Prepa-ration Examples).
The formula (VII) provides a general definition of the chloroazinium compounds to be used as starting materials in the process (c) according to the invention for prepar-ing compounds of the general formula (I). In the general formula (VII), R2, R3, R4, Zl, ZZ and Z3 each preferably have those meanings which have already been men-boned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred, particularly preferred or very particularly preferred for RZ, R3, R4, Z1, ZZ and Z3.
The starting materials of the general formula (VII) have hitherto not being disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel chloroazinium compounds of the general formula (VII) are obtained when azinones of the general formula (IX) Le A 34 486-Foreign Countries R Z~
~Z3 Z ~
~N~O
Rs ~ I (IX)~
Rz in which R2, R3, R4, Z1, ZZ and Z3 are each as defined above are reacted with chlorinating agents, such as, for example, phosgene, diphosgene, oxalyl chloride, thionyl chloride, phosphorus(III) chloride, phosphoryl chloride or phosphorus(V) chloride, if appropriate in the presence of reaction auxiliaries, such as, for example, N,N-dimethyl-formamide, and if appropriate in the presence of diluents, such as, for example, 1,2-dichloro-ethane, at temperatures between 0°C
and 150°C
(cf. the Preparation Examples).
The formula (VIII) provides a general definition of the amino compounds further to be used as starting materials in the process (c) according to the invention for prepar-ing compounds of the general formula (I). In the general formula (VIII), Rl prefer-ably has that meaning which has already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the inven-tion, as being preferred, particularly preferred or very particularly preferred for R'.
The starting materials of the general formula (VIII) are known chemicals for synthe-sis.
Suitable reaction auxiliaries for the processes (a) and (c) according to the invention are, in general, the customary inorganic or organic bases or acid acceptors.
These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium ace-Le A 34 486-Foreign Countries ' -24-tate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbon-ate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, S sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohex-ylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzyl-amine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2.2.2]-octane (DABCO), 1,5-di-azabicyclo[4.3.0)-non-5-ene (DBN), or 1,8-diazabicyclo[5.4.0)-undec-7-ene (DBU).
Further reaction auxiliaries suitable for the processes (a) and (c) according to the in-vention are phase-transfer catalysts. Examples of such catalysts which may be men-tioned are:
tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium chloride, tetrabutylammonium hydrogen sulphate, methyl-trioctylammonium chloride, hexadecyl-trimethylammonium chloride, hexadecyl-trimethylammonium bromide, benzyl-trimethylammonium chloride, benzyl-triethylammonium chloride, benzyl-trimethylammonium hydroxide, benzyl-triethylammonium hydroxide, benzyl-tributylammonium chloride, benzyl-tributylammonium bromide, tetrabutylphos-phonium bromide, tetrabutylphosphonium chloride, tributyl-hexadecylphosphonium bromide, butyl-triphenylphosphonium chloride, ethyl-trioctylphosphonium bromide, tetraphenylphosphonium bromide.
Le A 34 486-Foreign Countries _, Suitable reaction auxiliaries and/or diluents for the process (d) according to the in-vention are substances which are generally used for nitrations. These preferably in-clude sulphuric acid, acetic acid and acetic anhydride.
The processes (a), (b) and (c) for preparing the compounds of the general formula (I) are preferably carried out using one or more diluents. Suitable diluents for carrying out the processes (a), (b) and (c) according to the invention are, in addition to water, especially inert organic solvents. These include, in particular, aliphatic, alicyclic or 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 di-ethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitriles, amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene gly col monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono ethyl ether, mixtures thereof with water or pure water.
When carrying out the processes (a), (b), (c) and (d) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carned out at temperatures between -30 C and 150°C, preferably be tween -10°C and 120°C.
The processes according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the in-vention under elevated or reduced pressure - in general between 0.1 bar and 10 bar.
Le A 34 486-Foreign Countries For carrying out the processes according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possi-ble to use a relatively large excess of one of the components. The reaction is gener-ally carried out in a suitable diluent, in the presence of an appropriate reaction auxil-iary, and the reaction mixture is generally stirred at the required temperature for sev-eral hours. Work-up is carried out by customary methods (cf. the Preparation Ex-amples).
The active compounds according to the invention can be used as defoliants, desic-cants, haulm killers and, especially, as weed killers. Weeds in the broadest sense are understood to mean 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 con-nection with the following plants:
Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, An-themis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.
Le A 34 486-Foreign Countries ', Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dac-tyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Monocotyledonous crops of the genera: Album, Ananas, Asparagus, Avena, Hor-deum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
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.
The active compounds according to the invention are suitable, depending on the con-centration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and areas with and without tree plantings. Similarly, the active compounds according to the invention can be employed for controlling weeds in per-ennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns, turf and pastureland, and for the selective control of weeds in annual crops.
The compounds of the formula (I) and the compounds of the formulae (IX) and (IXa) according to the invention have strong herbicidal activity and a broad activity spec-trum when used on the soil or on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledonous and dicotyle-donous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.
Le A 34 486-Foreign Countries _28_ At certain concentrations or application rates, the active compounds according to the invention can also be employed for controlling animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.
According to the invention, it is possible to treat all plants and parts of plants. Plants are to be understood here as meaning all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurnng crop plants).
Crop plants can be plants which can be obtained by conventional breeding and opti-mization methods or by biotechnological and genetic engineering methods or combi-nations of these methods, including the transgenic plants and including plant culti-vars which can or cannot be protected by plant breeders' certificates. Parts of plants are to be understood as meaning all above-ground and below-ground parts and or-gans of plants, such as shoot, leaf, flower and root, examples which may be men-boned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
The treatment of the plants and parts of plants according to the invention with the active compounds is carned out directly or by action on their environment, habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one-or multi-layer coating.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric sub-stances.
Le A 34 486-Foreign Countries These formulations are produced in a known manner, for example by mixing the ac tive compounds with extenders, that is to say liquid solvents and/or solid Garners, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are:
aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated ali-phatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid Garners are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoma-ceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid Garners for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic gran-ules of inorganic and organic meals, and granules of organic material, such as saw-dust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polygly-col ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydroly-sates; suitable dispersants are: for example lignosulphite waste liquors and methyl-cellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or lattices, such as gum arabic, polyvinyl alcohol and Le A 34 486-Foreign Countries ' -30-polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
S It is possible to use colorants, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in their formulations, can also be used as mixtures with known herbicides and/or sub-stances which improve the compatibility with crop plants ("safeners"), finished for-mulations or tank mixes being possible. Also possible are mixtures with weed-killers comprising one or more known herbicides and a safener.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzfendizone, benzobicyclon, benzofenap, benzoyl-prop(-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben, chlo-ridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop Le A 34 486-Foreign Countries (-butyl), 2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (-P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxy-sulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide, flamprop(-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluri-done, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate (-ammonium), glypho-sate (-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl, -P-methyl), hexazi-none, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (al-pha-) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (-methyl), moli-nate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluor-fen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedi-pham, picolinafen, piperophos, pretilachlor, primisulfuron (-methyl), profluazol, prometryn, propachlor, propanil, propaquizafop, propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyri-date, pyridatol, pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlo-rac, quinmerac, quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron, seth-oxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sul-fosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thioben-Le A 34 486-Foreign Countries carb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, sus-pensions, emulsions, powders, pastes and granules. They are used in a customary manner, for example by watering, spraying, atomizing or broadcasting.
The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It de-pends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention is illustrated by the examples below.
Le A 34 486-Foreign Countries Preparation Examples:
Example 1 HsC \
I
N N O
/I
\ CFs (Process (a)) A mixture of 2.3 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridineimine, 2.1 g (10 mmol) of trifluoroacetic anhydride, 1.0 g (10 mmol) of tri-ethylamine and 50 ml of ethyl acetate is stirred at room temperature (about 20°C) for 60 minutes. The reaction mixture is then washed with water, dried with sodium sul-phate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diisopropyl ether and the resulting crystalline product is isolated by filtration with suction.
This gives 0.5 g (14% of theory) of 2,2,2-trifluoro-N-[S-methyl-1-(3-trifluoromethyl-phenyl)-2( 1 H)-pyridinylidene]-acetamide of melting point 11 S°C.
Example 2 HsC \ O~CsH~_i IN~~
N O
/) (Process (a)) Le A 34 486-Foreign Countries A mixture of 1.1 g (4 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyri-dineimine, 5 ml (5 mmol) of isopropyl chloroformate, 0.5 g (5 mmol) of triethyl-amine and 50 ml of ethyl acetate is stirred at room temperature (about 20°C) for 60 minutes. The reaction mixture is then washed with water, the aqueous phase is S reextracted with methylene chloride and the combined organic phases are dried with sodium sulphate and filtered. From the filtrate, the solvents are carefully distilled off under reduced pressure.
This gives 0.6 g (46% of theory) of O-methyl N-[5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-carbamate as an amorphous residue.
loge = 1.59 (determination of log P values see page 40).
Example 3 ~CN
.,F3 (Process (a)) A mixture of 1.1 g (4 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridineimine, 0.6 g (5 mmol) of cyanogen bromide, 0.5 g (5 mmol) of triethylamine and 50 ml of ethyl acetate and stirred at room temperature (about.
20°C) for minutes. The reaction mixture is then washed with water, the aqueous phase is reextracted with methylene chloride and the combined organic phases are dried with sodium sulphate and filtered. From the filtrate, the solvents are carefully distilled off 25 under reduced pressure.
Le A 34 486-Foreign Countries This gives 0.35 g (32% of theory) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidenecyanamide of melting point 165°C.
Example 4 (Process (a)) m 3 A mixture of 2.6 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridineimine, 0.6 g (10 mmol) of methyl isocyanate and 100 ml of acetonitrile is allowed to stand at room temperature (about 20°C) for two hours. The mixture is then concentrated under water pump vacuum, the residue is digested with diisopropyl ether and the resulting crystalline product is isolated by filtration with suction.
This gives 2.1 g (68% of theory) of N-methyl-N'-[5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-urea of melting point 114°C.
Example 5 H
SOZ
(Process (a)) Le A 34 486-Foreign Countries 2.9 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinimine hydrochloride, 3.1 g (30 mmol) of triethylamine and 100 ml of acetonitrile is, at room temperature (about 20°C) and with stirnng, admixed dropwise with 2.9 g (10 mmol) of trifluoromethanesulphonic anhydride. The reaction mixture is stirred at room temperature for 60 minutes and then concentrated under water pump vacuum.
The crude product obtained as residue is purified by column chromatography (silica gel, ethyl acetate/hexane, 9:1 ).
This gives 0.40 g (10% of theory) of N-[5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-trifluoromethanesulphonamide of melting point 206°C.
Example 6 ~~'wCF3 m 3 (Process (a)) A mixture of 2.9 g (10 mmol) of S-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinimine hydrochloride, 2.3 g (10 mmol) of 2-methylsulphonyl-5-trifluorometh-yl-1,3,4-thiadiazole, 4.2 g (30 mmol) of calcium carbonate and 30 ml of dimethyl sulphoxide is stirred at 100°C for 60 minutes and, after cooling, poured into about the same volume of methylene chloride. The organic phase is washed with water and saturated aqueous sodium chloride solution and then dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diethyl ether and the resulting crystalline product is isolated by filtration with suction.
Le A 34 486-Foreign Countries This gives 2.3 g (57% of theory) of N-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-S-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinimine of melting point 179°C.
Example 7 ~SOz N N
/
(Process (b)) 2.7 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinethione are initially charged in 50 ml of chloroform and, at room temperature (about 20°C) and with stirring, admixed dropwise with a solution of 2.9 g (10 mmol) of N-chloro-p-toluenesulphonamide sodium salt hydrate (chloramine T hydrate) in 50 ml of ethanol.
The reaction mixture is stirred at room temperature for 1 S hours and then concentrated under water pump vacuum, and the residue is taken up in chloroform, washed with water and then with saturated aqueous sodium bicarbonate solution, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum and the residue is kept under high vacuum at 180°C for 15 minutes.
After cooling and digestion with diisopropyl ether, the resulting crystalline product is isolated by filtration with suction.
This gives 1.8 g (49% of theory) of 4-methyl-N-[S-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-benzenesulphonamide of melting point 174°C.
Le A 34 486-Foreign Countries Example 8 ~ N~ ~
N
x HCI
(Process (c)) A mixture of 1.6 g (5 mmol) of 2-chloro-5-methyl-1-(3-trifluoromethyl-phenyl)-pyridinium chloride, 0.9 g (15 mmol) of cyclopropylamine and 50 ml of methanol is allowed to stand at room temperature (about 20°C) for 15 hours and then concentrated under water pump vacuum. The residue is taken up in methylene chloride, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is taken up in methanol and hydrochloric acid and the volatile components are carefully distilled off under reduced pressure. The crude product obtained as residue is purified by column chromatography (silica gel, ethyl acetate/hexane, 5:1 ).
This gives 1.5 g (91% of theory) of N-cyclopropyl-5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridineimine as an oily product.
loge = 1.51 (determination of log P values see page 40).
Analogously to Examples 1 to 8, and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the general formula (I) listed in Table 1 below.
Le A 34 486-Foreign Countries R' Table: Examples of compounds of the formula (I) Ex. (Position) Physical No. R' RZ R3 R4 ZI ZZ Z3 data 9 F F CF3 CH3 CH CH CH m.p.: 121 °C
'F
O
I ~ CF3 CH3 CH CH CH m.p.:175°C
~O
11 S~CzHs CF3 CH3 CH CH CH m.p.:124°C
O
12 HN~C(CH3)3 CF3 CH3 CH CH CH m.p.: 156°C
O
13 HN~CaHi ~ CF3 CH3 CH CH CH m.p.: 139°C
~S
14 SiC3H7 ~ CF3 CH3 CH CH CH m.p.: 140°C
-CO-CF3 CF3 CH3 N CH CH m.p.:128°C
Le A 34 486-Foreign Countries 16 -CHZ-C6H5 CF3 CH3 CH CH CH m.p.:253°C
17 -CO-C3H~-i CF3 CH3 CH CH CH m.p.:93°C
18 CF3 CH3 CH CH CH m.p.:98°C
O
19 -CO-CHF2 CF3 CH3 CH CH CH m.p.:137°C
20 ~"3 CF3 CH3 CH CH CH m.p.:165°C
NI \~
~ i ' _N OCH3 21 I ~ CF3 CH3 CH CH CH m.p.:148°C
22 ~Hz CF3 CH3 CH CH CH loge = 1,58 ,CH a) /O
23 O~C3H~ i CF3 CH3 CH CH CH m.p.: 188°C
/NH
24 -CO-CF3 CF3 H CH CH CH m.p.:150°C
25 -CO-CF3 CF3 (4) F CH3 CH CH CH m.p.: 180°C
26 -CO-CF3 CF3 (5) F CH3 CH CH CH m.p.: 158°C
Le A 34 486-Foreign Countries 27 N-N ~H3 CF3 CH3 CH CH CH m.p.: 179°C
H3C / ~ F
~O
28 ~e"3 CF3 CH3 CH CH CH m.p.: 201 °C
N-F~C \ S
~O
29 -CN CF3 CH3 N CH CH m.p.:148°C
30 -CO-CH3 CF3 CH3 CH CH CH m.p.: 101 °C
31 -CO-CZHS CF3 CH3 CH CH CH m.p.:113°C
32 -CO-C3H~-n CF3 CH3 CH CH CH m.p.:103°C
33 ~~H3 CF3 CH3 CH CH CH m.p.:133°C
O
34 O.CZHs CF3 CH3 CH CH CH m.p.:150°C
O
35 O~C3H~ n CF3 CH3 CH CH CH m.p.: 85°C
O
36 CHs CF3 CH3 CH CH CH m.p.:103°C
O
37 CI CF3 CH3 CH CH CH m.p.: 181 °C
CI
~O
Le A 34 486-Foreign Countries 38 -CO-C4H9-t CF3 CH3 CH CH CH m.p.:77°C
39 O~C4H9 t CF3 CH3 CH CH CH m.p.: 108°C
O
40 ~CH3 CF3 CH3 N CH CH m.p.:148°C
O
41 O~CZHs CF3 CH3 N CH CH m.p.:146°C
O
42 ~CsHi ~ CF3 CH3 N CH CH m.p.: 98°C
O
43 OiC3H7 ~ CF3 CH3 N CH CH m.p.: 123°C
O
44 .C3H; I CF3 CH3 N CH CH m.p.: 83°C
O
45 CF3 CH3 N CH CH m.p.:108°C
O
46 I CF3 CH3 N CH CH m.p.:164°C
CI
O
47 FZ CF3 CH3 N CH CH m.p.:85°C
'F
O
48 F ~ ~ F CF3 CH3 N CH CH m.p.: 157°C
HNI
' 'O
Le A 34 486-Foreign Countries Loge values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.AB by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18). Temperature: 43°C.
S
(a) Mobile phases for the determination in the acidic range: 0.1 % aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile -the corresponding data in Table 1 are labelled a).
(b) Mobile phases for the determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90%
acetonitrile - the corresponding data in Table 1 are labelled b).
The calibration was carried out using unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known loge values (determination of the loge values by the retention times using linear interpolation between two successive alkanones).
The lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.
Le A 34 48fi-Foreign Countries .2 Starting materials of the formula (II):
Example (II-1) I ~ .H
N N
/
(Process (a)) Step 1 CI_ N CI
A mixture of 2.5 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridone, 3.9 g (30 mmol) of oxalyl chloride, 40 ml of 1,2-dichloro-ethane and 2 drops of N,N-dimethyl-formamide is heated at the boil under reflux until the evolution of gas has ceased. After cooling to room temperature, the resulting crystalline product is isolated by filtration with suction.
This gives 2.1 g (65% of theory) of 2-chloro-5-methyl-1(3-trifluoromethyl-phenyl)-pyridinium chloride of melting point 194°C.
Le A 34 486-Foreign Countries Step 2 H
J
3.1 g (10 mmol) of 2-chloro-5-methyl-1-(3-trifluoromethyl-phenyl)-pyridinium chloride are taken up in 40 ml of methanol and, at temperatures between 20°C and 30°C, ammonia is introduced into this mixture until the solution is saturated. 3.6 g of (20 mmol) of sodium methoxide are then added in the form of a 30% strength solution in methanol, and the mixture is then concentrated under water pump vacuum.
The resulting product (5-methyl-1-(3-trifluorornethyl-phenyl)-2(1H)-pyridineimine) can be reacted according to the process (a) according to the invention without any further purification.
Example (II-1) N~ ~H
N
(Process ((3)) A mixture of 10 g (24 mmol) of 4-methyl-N-[5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-benzenesulphonamide and SO g of 80% strength sulphuric acid is stirred at 50°C for 15 hours and then added dropwise to a 1 molar aqueous sodium carbonate solution. The mixture is then extracted with ethyl acetate and the Le A 34 486-Foreign Countries _46_ organic phase is dried with sodium sulphate and filtered. From the filtrate, the solvent is carefully distilled off under reduced pressure.
This gives 2.3 g (38% of theory) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H) pyridineimine which can be reacted according to the process (a) according to the invention without any further purification.
Analogously to Example (II-1), it is also possible to prepare, for example, the compounds of the general formula (II) listed in Table 2 below.
Ra II ' Z~N~N~H
6 /' Z (II) 5 ~ /3\.,2 Table 2: Examples of the compounds of the formula (II) the compounds in each case being the hydrochlorides Ex. (Position) Physical No. R2 R3 R4 Z1 Z2 Z3 data II-2 CF3 H CH CH CH m.p.:269C
II-4 Cl CH3 CH CH CH
II-5 CF3 Cl CH CH CH
II-6 Br CH3 CH CH CH
II-10 CF3 C3H~-nCH CH CH
Le A 34 486-Foreign Countries Ex. (Position) Physical data No. R2 R3 R4 Z1 Z2 Z3 II-11 CF3 C3H~-i CH CH CH
II-13 CF3 (2) F CH3 CH CH CH
II-14 CF3 (4) F CH3 CH CH CH m.p.: 250C
II-15 CF3 (5) F CH3 CH CH CH m.p.: 250C
II-16 CF3 (6) F CH3 CH CH CH
II-18 sOzCH3 CH3 CH CH CH
II-19 S~2C2H5 CH3 CH CH CH
1H_~
II-25 CF3 CH3 N CH CH (DMSO-D6ls):
2.43 ppm.
Example (II-26): 5-methyl-1-(2,3-difluoromethylenedioxy-phenyl)-2(1H)-pyridine-imme, Example (II-27): 5-methyl-1-(3,4-difluoromethylenedioxy-phenyl)-2(1H)-pyridine-imine, Example (II-28): 5-methyl-1-(2,3-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridine-imine, Example (II-29): 5-methyl-1-(3,4-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridine-imine, Example (II-30): 5-methyl-1-(2,3-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridine-mane, Le A 34 486-Foreign Countries Example (II-31): S-methyl-1-(3,4-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridine-imme.
Starting materials of the formula (V):
Example (V-1) N S
A mixture of 18.7 g (74 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinone, 16.4 g (74 mmol) of phosphorus(V) sulphide and 75 ml of pyridine is heated under reflux for two hours and, after cooling, poured into 300 ml of water.
The mixture is stirred overnight and the resulting crystalline product is then isolated by filtration with suction.
This gives 12.8 g (64% of theory) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinethione of melting point 96°C.
Analogously to Example (V-1), it is also possible to prepare, for example, the compounds of the general formula (V) listed in Table 3 below.
R~Z
Z
~N S
Le A 34 486-Foreign Countries Table 3: Examples of the compounds of the formula (V) Ex. (Position) No. R2 R3 R4 Z1 ZZ Z3 V-4 Cl CH3 CH CH CH
V-5 CF3 Cl CH CH CH
V-6 Br CH3 CH CH CH
V-11 CF3 C3H~-iCH CH CH
V-13 CF3 (2) F CH3 CH CH CH
V-14 CF3 (4) F CH3 CH CH CH
V-15 CF3 (5) F CH3 CH CH CH
V-16 CF3 (6) F CH3 CH CH CH
Le A 34 486-Foreign Countries Example (V-26): 5-methyl-1-(2,3-difluoromethylenedioxy-phenyl)-2(1H)-pyridine-thione, Example (V-27): 5-methyl-1-(3,4-difluoromethylenedioxy-phenyl)-2(1H)-pyridine-thione, Example (V-28): 5-methyl-1-(2,3-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridine-thione, Example (V-29): 5-methyl-1-(3,4-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridine-thione, Example (V-30): S-methyl-1-(2,3-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridinethione, Example (V-31): 5-methyl-1-(3,4-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridinethione.
Le A 34 486-Foreign Countries Intermediates of the formula (VII):
Example (VII-1) CI
A mixture of 2.5 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridone, 3.9 g (30 mmol) of oxalyl chloride, 40 ml of 1,2-dichloro-ethane and 2 drops of N,N-dimethyl-formamide is stirred at the boil under reflux until the evolution of gas has ceased. After cooling to room temperature, the resulting crystalline product is isolated by filtration with suction.
This gives 2.1 g (65% of theory) of 2-chloro-5-methyl-1-(3-trifluoromethyl-phenyl)-pyridinium chloride of melting point 194°C.
Analogously to Example (VII-1), it is also possible to prepare, for example, the compounds of the general formula (VII) listed in Table 4 below.
R~1 Y
~N+ CI
Rs ~ I (VII) Le A 34 486-Foreign Countries Table 4: Examples of compounds of the formula (VII) Y in each case represents CI
Ex. No. (Position) Physical R2 R3 R4 Z1 Z2 Z3 data VII-2 CF3 H CH CH CH m.p.:74C
VII-4 Cl CH3 CH CH CH
VII-6 Br CH3 CH CH CH
VII-11 CF3 C3H~-iCH CH CH
VII-13 CF3 (2) F CH3 CH CH CH
VII-14 CF3 (4) F CH3 CH CH CH m.p.: 250C
VII-15 CF3 (S) F CH3 CH CH CH m.p.: 265C
VII-16 CF3 (6) F CH3 CH CH CH
VII-24 CF3 CH3 N CH CH loge 2.23 a) VII-25 CF3 H CH CH C-CH3m.p.:218C
Le A 34 486-Foreign Countries Example (VII-26): 2-chloro-5-methyl-1-(2,3-difluoromethylenedioxy-phenyl)-pyridinium chloride, Example (VII-27): 2-chloro-5-methyl-1-(3,4-difluoromethylenedioxy-phenyl)-pyridinium chloride, Example (VII-28): 2-chloro-5-methyl-1-(2,3-tetrafluoroethylenedioxy-phenyl)-pyridinium chloride, Example (VII-29): 2-chloro-5-methyl-1-(3,4-tetrafluoroethylenedioxy-phenyl)-pyridinium chloride, Example (VII-30): 2-chloro-5-methyl-1-(2,3-chlorotrifluoroethylenedioxy-phenyl)-pyridinium chloride, Example (VII-31): 2-chloro-5-methyl-1-(3,4-chlorotrifluoroethylenedioxy-phenyl)-pyridinium chloride.
Le A 34 486-Foreign Countries Starting materials of the formula (IX):
Example (IX-1) N O
A mixture of 21.8 g (0.20 mol) of 5-methyl-2-pyridone, 54 g (0.24 mol) of 3-bromo-benzotrifluoride, 27.7 g (0.20 mol) of potassium carbonate, 2 g (10 mmol) of copper (I) iodide and 300 ml of N,N-dimethyl-formamide is stirred at 100°C for 15 hours and at 140°C for a further 6 hours. After cooling to room temperature, the mixture is admixed with 300 ml of ethyl acetate and then diluted with water to about twice its original volume. The organic phase is separated off and the aqueous phase is reextracted with ethyl acetate. The combined organic phases are washed with water, dried with sodium sulphate and filtered. From the filtrate, the solvent is fully distilled off under reduced pressure.
This gives 20.7 g (41% of theory) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinone of melting point 95°C.
Analogously to Example (IX-1), it is also possible to prepare, for example, the compounds of the general formula (IX) listed in Table 5 below.
Le A 34 486-Foreign Countries Z
Rs s / ~ z (IX) Table 5: Examples of compounds of the formula (IX) Ex. (Position) Physical No. R2 R3 R4 Z1 Z2 Z3 data IX-2 CF3 H CH CH CH m.p.:63C
IX-3 CN CH3 CH CH CH m.p.:188C
IX-4 Cl CH3 CH CH CH
IX-S CF3 Cl CH CH CH
IX-6 Br CH3 CH CH CH
IX-9 CF3 CH3 N CH CH m.p.:58C
IX-10 CF3 (6) F CH3 CH CH CH
IX-11 OCF3 CH3 CH CH CH m.p.:88C
IX-13 CF3 C3H~-i CH CH CH
IX-15 CF3 (2) F CH3 CH CH CH
IX-16 CF3 (4) F CH3 CH CH CH loge = 2,19 a~
IX-17 CF3 (5) F CH3 CH CH CH m.p.: 73C
IX-18 CF3 (6) F CZHS CH CH CH
Le A 34 486-Foreign Countries Ex. (Position) Physical No. R2 R3 R4 Z1 Z2 Z3 data IX-26 F CH3 CH CH CH m.p.:132C
IX-27 CF CH3 CH CH C-CH3log P =
i i ~ ~ ~ ~ ~ I 2,56x) I
Example (IX-28): S-methyl-1-(2,3-difluoromethylenedioxy-phenyl)-2(1H)-pyridinone (loge = 3.95 a)), Example (IX-29): 5-methyl-1-(3,4-difluoromethylenedioxy-phenyl)-2(1H)-pyridinone, Example (IX-30): 5-methyl-1-(2,3-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridinone, Example (IX-31): 5-methyl-1-(3,4-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridinone, Example (IX-32): 5-methyl-1-(2,3-chlorotrifluoroethylenedioxy-phenyl~2(1H~
pyridinone, Example (IX-33): 5-methyl-1-(3,4-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridinone, Example (IX-34): 3-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinone (m.p.:
122°C), Example (IX-35): 5-trifluoromethyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinone (loge = 2.78 a)).
(Determination of loge values see page 40) Le A 34 486-Foreign Countries _57_ Use Examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After 24 hours, the soil is sprayed with the preparation of active compound such that the particular amount of active compound desired is applied per unit area. The concentration of active compound in the spray liquors is chosen so that the particular amount of active compound desired is applied in 1000 litres of water per hectare.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0% - no effect (like untreated control) 100 % = total destruction In this test, for example, the compounds of Preparation Examples 1, 2, 3, IX-1, IX-3, IX-11 and IX16 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, rice.
Le A 34 486-Foreign Countries _58_ Example B
Post-emergence test Solvent: S parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants of a height of 5-15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated controls.
The figures denote:
0% = no effect (like untreated control) 100 % = total destruction In this test, for example, the compounds of Preparation Examples 1, 3, IX-1 and IX-16 exhibit strong activity against weeds.
The resulting product (5-methyl-1-(3-trifluorornethyl-phenyl)-2(1H)-pyridineimine) can be reacted according to the process (a) according to the invention without any further purification.
Example (II-1) N~ ~H
N
(Process ((3)) A mixture of 10 g (24 mmol) of 4-methyl-N-[5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinylidene]-benzenesulphonamide and SO g of 80% strength sulphuric acid is stirred at 50°C for 15 hours and then added dropwise to a 1 molar aqueous sodium carbonate solution. The mixture is then extracted with ethyl acetate and the Le A 34 486-Foreign Countries _46_ organic phase is dried with sodium sulphate and filtered. From the filtrate, the solvent is carefully distilled off under reduced pressure.
This gives 2.3 g (38% of theory) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H) pyridineimine which can be reacted according to the process (a) according to the invention without any further purification.
Analogously to Example (II-1), it is also possible to prepare, for example, the compounds of the general formula (II) listed in Table 2 below.
Ra II ' Z~N~N~H
6 /' Z (II) 5 ~ /3\.,2 Table 2: Examples of the compounds of the formula (II) the compounds in each case being the hydrochlorides Ex. (Position) Physical No. R2 R3 R4 Z1 Z2 Z3 data II-2 CF3 H CH CH CH m.p.:269C
II-4 Cl CH3 CH CH CH
II-5 CF3 Cl CH CH CH
II-6 Br CH3 CH CH CH
II-10 CF3 C3H~-nCH CH CH
Le A 34 486-Foreign Countries Ex. (Position) Physical data No. R2 R3 R4 Z1 Z2 Z3 II-11 CF3 C3H~-i CH CH CH
II-13 CF3 (2) F CH3 CH CH CH
II-14 CF3 (4) F CH3 CH CH CH m.p.: 250C
II-15 CF3 (5) F CH3 CH CH CH m.p.: 250C
II-16 CF3 (6) F CH3 CH CH CH
II-18 sOzCH3 CH3 CH CH CH
II-19 S~2C2H5 CH3 CH CH CH
1H_~
II-25 CF3 CH3 N CH CH (DMSO-D6ls):
2.43 ppm.
Example (II-26): 5-methyl-1-(2,3-difluoromethylenedioxy-phenyl)-2(1H)-pyridine-imme, Example (II-27): 5-methyl-1-(3,4-difluoromethylenedioxy-phenyl)-2(1H)-pyridine-imine, Example (II-28): 5-methyl-1-(2,3-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridine-imine, Example (II-29): 5-methyl-1-(3,4-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridine-imine, Example (II-30): 5-methyl-1-(2,3-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridine-mane, Le A 34 486-Foreign Countries Example (II-31): S-methyl-1-(3,4-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridine-imme.
Starting materials of the formula (V):
Example (V-1) N S
A mixture of 18.7 g (74 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinone, 16.4 g (74 mmol) of phosphorus(V) sulphide and 75 ml of pyridine is heated under reflux for two hours and, after cooling, poured into 300 ml of water.
The mixture is stirred overnight and the resulting crystalline product is then isolated by filtration with suction.
This gives 12.8 g (64% of theory) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinethione of melting point 96°C.
Analogously to Example (V-1), it is also possible to prepare, for example, the compounds of the general formula (V) listed in Table 3 below.
R~Z
Z
~N S
Le A 34 486-Foreign Countries Table 3: Examples of the compounds of the formula (V) Ex. (Position) No. R2 R3 R4 Z1 ZZ Z3 V-4 Cl CH3 CH CH CH
V-5 CF3 Cl CH CH CH
V-6 Br CH3 CH CH CH
V-11 CF3 C3H~-iCH CH CH
V-13 CF3 (2) F CH3 CH CH CH
V-14 CF3 (4) F CH3 CH CH CH
V-15 CF3 (5) F CH3 CH CH CH
V-16 CF3 (6) F CH3 CH CH CH
Le A 34 486-Foreign Countries Example (V-26): 5-methyl-1-(2,3-difluoromethylenedioxy-phenyl)-2(1H)-pyridine-thione, Example (V-27): 5-methyl-1-(3,4-difluoromethylenedioxy-phenyl)-2(1H)-pyridine-thione, Example (V-28): 5-methyl-1-(2,3-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridine-thione, Example (V-29): 5-methyl-1-(3,4-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridine-thione, Example (V-30): S-methyl-1-(2,3-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridinethione, Example (V-31): 5-methyl-1-(3,4-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridinethione.
Le A 34 486-Foreign Countries Intermediates of the formula (VII):
Example (VII-1) CI
A mixture of 2.5 g (10 mmol) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridone, 3.9 g (30 mmol) of oxalyl chloride, 40 ml of 1,2-dichloro-ethane and 2 drops of N,N-dimethyl-formamide is stirred at the boil under reflux until the evolution of gas has ceased. After cooling to room temperature, the resulting crystalline product is isolated by filtration with suction.
This gives 2.1 g (65% of theory) of 2-chloro-5-methyl-1-(3-trifluoromethyl-phenyl)-pyridinium chloride of melting point 194°C.
Analogously to Example (VII-1), it is also possible to prepare, for example, the compounds of the general formula (VII) listed in Table 4 below.
R~1 Y
~N+ CI
Rs ~ I (VII) Le A 34 486-Foreign Countries Table 4: Examples of compounds of the formula (VII) Y in each case represents CI
Ex. No. (Position) Physical R2 R3 R4 Z1 Z2 Z3 data VII-2 CF3 H CH CH CH m.p.:74C
VII-4 Cl CH3 CH CH CH
VII-6 Br CH3 CH CH CH
VII-11 CF3 C3H~-iCH CH CH
VII-13 CF3 (2) F CH3 CH CH CH
VII-14 CF3 (4) F CH3 CH CH CH m.p.: 250C
VII-15 CF3 (S) F CH3 CH CH CH m.p.: 265C
VII-16 CF3 (6) F CH3 CH CH CH
VII-24 CF3 CH3 N CH CH loge 2.23 a) VII-25 CF3 H CH CH C-CH3m.p.:218C
Le A 34 486-Foreign Countries Example (VII-26): 2-chloro-5-methyl-1-(2,3-difluoromethylenedioxy-phenyl)-pyridinium chloride, Example (VII-27): 2-chloro-5-methyl-1-(3,4-difluoromethylenedioxy-phenyl)-pyridinium chloride, Example (VII-28): 2-chloro-5-methyl-1-(2,3-tetrafluoroethylenedioxy-phenyl)-pyridinium chloride, Example (VII-29): 2-chloro-5-methyl-1-(3,4-tetrafluoroethylenedioxy-phenyl)-pyridinium chloride, Example (VII-30): 2-chloro-5-methyl-1-(2,3-chlorotrifluoroethylenedioxy-phenyl)-pyridinium chloride, Example (VII-31): 2-chloro-5-methyl-1-(3,4-chlorotrifluoroethylenedioxy-phenyl)-pyridinium chloride.
Le A 34 486-Foreign Countries Starting materials of the formula (IX):
Example (IX-1) N O
A mixture of 21.8 g (0.20 mol) of 5-methyl-2-pyridone, 54 g (0.24 mol) of 3-bromo-benzotrifluoride, 27.7 g (0.20 mol) of potassium carbonate, 2 g (10 mmol) of copper (I) iodide and 300 ml of N,N-dimethyl-formamide is stirred at 100°C for 15 hours and at 140°C for a further 6 hours. After cooling to room temperature, the mixture is admixed with 300 ml of ethyl acetate and then diluted with water to about twice its original volume. The organic phase is separated off and the aqueous phase is reextracted with ethyl acetate. The combined organic phases are washed with water, dried with sodium sulphate and filtered. From the filtrate, the solvent is fully distilled off under reduced pressure.
This gives 20.7 g (41% of theory) of 5-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinone of melting point 95°C.
Analogously to Example (IX-1), it is also possible to prepare, for example, the compounds of the general formula (IX) listed in Table 5 below.
Le A 34 486-Foreign Countries Z
Rs s / ~ z (IX) Table 5: Examples of compounds of the formula (IX) Ex. (Position) Physical No. R2 R3 R4 Z1 Z2 Z3 data IX-2 CF3 H CH CH CH m.p.:63C
IX-3 CN CH3 CH CH CH m.p.:188C
IX-4 Cl CH3 CH CH CH
IX-S CF3 Cl CH CH CH
IX-6 Br CH3 CH CH CH
IX-9 CF3 CH3 N CH CH m.p.:58C
IX-10 CF3 (6) F CH3 CH CH CH
IX-11 OCF3 CH3 CH CH CH m.p.:88C
IX-13 CF3 C3H~-i CH CH CH
IX-15 CF3 (2) F CH3 CH CH CH
IX-16 CF3 (4) F CH3 CH CH CH loge = 2,19 a~
IX-17 CF3 (5) F CH3 CH CH CH m.p.: 73C
IX-18 CF3 (6) F CZHS CH CH CH
Le A 34 486-Foreign Countries Ex. (Position) Physical No. R2 R3 R4 Z1 Z2 Z3 data IX-26 F CH3 CH CH CH m.p.:132C
IX-27 CF CH3 CH CH C-CH3log P =
i i ~ ~ ~ ~ ~ I 2,56x) I
Example (IX-28): S-methyl-1-(2,3-difluoromethylenedioxy-phenyl)-2(1H)-pyridinone (loge = 3.95 a)), Example (IX-29): 5-methyl-1-(3,4-difluoromethylenedioxy-phenyl)-2(1H)-pyridinone, Example (IX-30): 5-methyl-1-(2,3-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridinone, Example (IX-31): 5-methyl-1-(3,4-tetrafluoroethylenedioxy-phenyl)-2(1H)-pyridinone, Example (IX-32): 5-methyl-1-(2,3-chlorotrifluoroethylenedioxy-phenyl~2(1H~
pyridinone, Example (IX-33): 5-methyl-1-(3,4-chlorotrifluoroethylenedioxy-phenyl)-2(1H)-pyridinone, Example (IX-34): 3-methyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinone (m.p.:
122°C), Example (IX-35): 5-trifluoromethyl-1-(3-trifluoromethyl-phenyl)-2(1H)-pyridinone (loge = 2.78 a)).
(Determination of loge values see page 40) Le A 34 486-Foreign Countries _57_ Use Examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After 24 hours, the soil is sprayed with the preparation of active compound such that the particular amount of active compound desired is applied per unit area. The concentration of active compound in the spray liquors is chosen so that the particular amount of active compound desired is applied in 1000 litres of water per hectare.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0% - no effect (like untreated control) 100 % = total destruction In this test, for example, the compounds of Preparation Examples 1, 2, 3, IX-1, IX-3, IX-11 and IX16 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, rice.
Le A 34 486-Foreign Countries _58_ Example B
Post-emergence test Solvent: S parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants of a height of 5-15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated controls.
The figures denote:
0% = no effect (like untreated control) 100 % = total destruction In this test, for example, the compounds of Preparation Examples 1, 3, IX-1 and IX-16 exhibit strong activity against weeds.
Claims (17)
1. Substituted iminoazines of the general formula (I) in which R1 represents nitro, cyano or one of the groupings -R5, -CQ1-Q2-R5, -NH-CQ1-Q2-R5 or -SO2-R6, R2 represents nitro, cyano, SF5, halogen or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl or alkylsulphonyloxy, R3 represents hydrogen or halogen, or together with R2 represents optionally substituted alkylenedioxy, R4 represents hydrogen, cyano, carboxyl, carbamoyl, halogen or optionally substituted alkyl, Q1 represents O (oxygen), S (sulphur) or N-R5, Q2 represents a single bond or represents O (oxygen), S (sulphur) or N-R5, R5 represents hydrogen, amino or in each case optionally substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylideneamino, alkenyl, alkenyloxy, alkinyl, cycloalkyl, cycloalkylamino, cycloalkylalkyl, aryl, arylamino, arylalkyl, heterocyclyl or heterocyclylalkyl, R6 represents in each case optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl, Z1 represents N (nitrogen) or C-R4, Z2 represents N (nitrogen) or C-R4, and Z3 represents N (nitrogen) or C-R4.
2. Compounds according to Claim 1, characterized in that R1 represents cyano or one of the groupings -R5, -CQ1-Q2-R5, -NH-CQ1-Q2-R5 or -SO2-R6, R2 represents nitro, cyano, SF5, halogen or in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl or alkylsulphonyloxy having in each case 1 to 5 carbon atoms, R3 represents hydrogen or halogen, or together with R2 represents optionally halogen-substituted alkylenedioxy having 1 to 3 carbon atoms, R4 represents hydrogen, cyano, carboxyl, carbamoyl, halogen or optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 5 carbon atoms, Q1 represents O (oxygen) or S (sulphur), R5 represents hydrogen or amino, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, represents alkylamino having 1 to 6 carbon atoms, represents dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents alkylideneamino having up to 6 carbon atoms, represents in each case optionally cyano- or halogen-substituted alkenyl, alkenyloxy or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl, cycloalkylamino or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, represents in each case optionally nitro-, cyano-, phenyl-, phenoxy-, phenylthio-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halo-genoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-halogenoalkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-halogenoalkylsulphonyl- or di-(C1-C4-alkyl)-aminosulphonyl-substituted aryl, arylamino or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, phenyl-, phenoxy-, phenylthio-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogeno-alkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkyl-sulphinyl-, C1-C4-halogenoalkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-halogenoalkylsulphonyl- or di-(C1-C4-alkyl)-amino-sulphonyl-substituted monocyclic or bicyclic heterocyclyl or heterocyclylalkyl having in each case up to 10 carbon atoms and up to 4 nitrogen atoms and/or 1 or 2 oxygen or sulphur atoms in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, R6 represents optionally halogen-substituted alkyl having 1 to 6 carbon atoms, represents optionally halogen-substituted alkenyl having 2 to 6 carbon atoms, represents optionally halogen- or C1-C4-alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, represents in each case optionally nitro-, cyano-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-halogenoalkylsulphinyl-, C1-C4-alkyl-sulphonyl-, C1-C4-halogenoalkylsulphonyl- or di-(C1-C4-alkyl)-amino-sulphonyl-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-halogenoalkylsulphinyl-, C1-C4-alkyl-sulphonyl-, C1-C4-halogenoalkylsulphonyl- or di-(C1-C4-alkyl)-amino-sulphonyl-substituted monocyclic or bicyclic heterocyclyl or heterocyclylalkyl having in each case up to 10 carbon atoms and up to 4 nitrogen atoms and/or 1 or 2 oxygen or sulphur atoms in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, Z1 represents C-R4, Z2 represents C-R4, Z3 represents C-R4.
3. Compounds according to Claim 1 or 2, characterized in that R2 represents vitro, cyano,SF5, fluorine, chlorine or bromine, or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methyl-sulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylsulphonyl-oxy, ethylsulphonyloxy, n- or i-propylsulphonyloxy, R3 represents hydrogen, fluorine, chlorine or bromine, or together with R2 represents in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy, R4 represents hydrogen, cyano, carboxyl, carbamoyl, fluorine, chlorine, bromine or represents optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, Q1 represents O (oxygen), R5 represents hydrogen or amino, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents dimethyl-amino or diethylamino, represents propylideneamino or butylidene-amino, represents in each case optionally cyano-, fluorine-, chlorine-and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutyl-amino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, represents in each case optionally vitro-, cyano-, phenyl-, phenoxy-, phenylthio-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-or t-butyl-, dichloromethyl-, difluoromethyl-, trichloromethyl-, tri-fluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-, meth-oxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, rnethylsulphinyl-, ethylsulphinyl-, trifluorometh-ylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethyl-sulphonyl- or dimethylaminosulphonyl-substituted phenyl, naphthyl, phenylamino, benzyl or phenylethyl, or represents in each case optionally cyano-, phenyl-, phenoxy-, phenylthio-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, difluoromethyl-, trichloromethyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n-or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluorometh-ylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted heterocyclyl or heterocyclylalkyl from the group consisting of furyl, tetrahydrofuryl, benzofuryl, thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzo-pyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzo-thiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, quinolinyl, pyrimidinyl, furylmethyl, thienylmethyl, pyrrolylmethyl, pyrazolylmethyl, oxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl, R6 represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine- and/or bromine-substituted propenyl or butenyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclo-propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, difluoromethyl- trichloromethyl-, trifluoromethyl-, chlorodifluoro-methyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methyl-sulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-, methyl-sulphonyl-, ethylsulphonyl-, trifluoromethylsulphonyl- or dimethyl-aminosulphonyl-substituted phenyl or naphthyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, difluoromethyl-, trichloromethyl-, trifluoromethyl-, chlorodifluoromethyl-, fluoro-dichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluorometh-oxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethyl-sulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphon-yl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted heterocyclyl or heterocyclylalkyl from the group consisting of furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzopyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzo-thiazolyl, pyridinyl, quinolinyl, pyrimidinyl, furylmethyl, thienyl-methyl, pyrrolylmethyl, pyrazolylinethyl, oxazolylmethyl, thiazolyl-methyl, pyridinylmethyl, pyrimidinylmethyl, Z1 represents CH, Z2 represents CH, Z3 represents CH.
4. Compounds according to any of Claims 1 to 3, characterized in that R2 represents cyano, fluorine, chlorine or bromine, or represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, methyl-sulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methyl-sulphonyloxy or ethylsulphonyloxy, R4 represents hydrogen, cyano, fluorine, chlorine, bromine, or represents optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl or ethyl, R5 represents hydrogen or amino, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methylamino, ethylamino, n- or i-propylamino, represents dimethylamino, represents in each case optionally fluorine-, chlorine- and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, or repre-sents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluorometh-oxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethyl-sulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-, ethyl-sulphonyl-, trifluoromethylsulphonyl- or dimethylaminosulphonyl-substituted phenyl, phenylamino, benzyl or phenylethyl, R6 represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclopentyl or cyclohexyl, or represents optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, meth-ylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoro-methylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethyl-sulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethyl-sulphonyl- or dimethylaminosulphonyl-substituted phenyl.
5. Compounds according to any of Claims 1 to 4, characterized in that R2 represents trifluoromethyl and/or R4 represents methyl.
6. Compounds according to any of Claims 1 to 5, characterized in that R1 represents cyano or one of the groupings -CQ1-Q2-R5 or -SO2-R6, R2 represents trifluoromethyl, difluoromethoxy or trifluoromethoxy, R3 represents hydrogen, fluorine or chlorine, or together with R2 - in the ortho position - represents difluoromethylenedioxy or tetrafluoro-ethylenedioxy, R4 represents hydrogen, fluorine, chlorine, bromine or methyl, Q1 represents O (oxygen) or S (sulphur), Q2 represents a single bond or represents O (oxygen), S (sulphur) or N-R5, R5 represents hydrogen, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n-or i-propyl, represents in each case optionally fluorine-, chlorine-and/or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine- or methyl-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, tri-fluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, trifluorometh-ylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethyl-sulphonyl- or dimethylaminosulphonyl-substituted phenyl or benzyl, R6 represents in each case optionally fluorine-, and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine- or methyl-substituted cyclopropyl, cyclopentyl or cyclohexyl, or represents optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, meth-ylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoro-methylthio-, methylsulphinyl-, ethylsulphinyl-, trifluoromethyl-sulphinyl-, methylsulphonyl-, ethylsulphonyl-, trifluoromethyl-sulphonyl- or dimethylaminosulphonyl-substituted phenyl, Z1 represents CH, Z2 represents CH, and Z3 represents CH.
7. Process for preparing substituted iminoazines of the formula (I) according to any of Claims 1 to 6, characterized in that (a) iminoazines of the general formula (II) in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of Claims 1 to 6 - or acid adducts of iminoazines of the general formula (II), -are reacted with compounds of the general formula (III) X1-R1 (III) in which R1 is as defined in any of Claims 1 to 6, X1 represents halogen, -SO2CH3, -O-CO-R5 or -O-SO2-R6 and R5 and R6 are each as defined in any of Claims 1 to 6, or with iso(thio)cyanates of the general formula (IV) Q1=C=N-R5~ (IV) in which Q1 and R5 are each as defined in any of Claims 1 to 6, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or that (b) azinethiones of the general formula (V) in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of Claims 1 to 6 are reacted with compounds of the general formula (VI) M+ C~N-SO2-R6~~~(VI) in which R6 is as defined in any of Claims 1 to 6 and M represents a metal equivalent, if appropriate in the presence of one or more diluents, or that (c) chloroazinium compounds of the general formula (VII) in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of Claims 1 to 6, and Y represents Cl, PCl4, POCl4 or PCl6 are reacted with amino compounds of the general formula (VIII) H2N-R1~ (VIII) in which R1 is as defined in any of Claims 1 to 6, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or that (d) iminoazines of the general formula (II) in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of Claims 1 to 6 - or acid adducts of iminoazines of the general formula (II) -are reacted with nitric acid, if appropriate in the presence of a reaction auxiliary and/or diluent.
8. Iminoazines of the general formula (II) in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of Claims 1 to 6, or their acid adducts.
9. Azinethiones of the general formula (V) in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of Claims 1 to 6.
10. Chloroazinium compounds of the general formula (VII) in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of Claims 1 to 6, and Y represents Cl, PCl4, POCl4 or PCl6.
11. Compounds of the general formula (IXa) in which R2, R3 and R4 are each as defined in any of Claims 1 to 6.
12. Method for controlling undesirable vegetation, characterized in that at least one compound according to any of Claims 1 to 6 and 11 is allowed to act on undesirable plants and/or their habitat.
13. Use of a compound according to any of Claims 1 to 6 and 11 for controlling undesirable plants.
14. Use of a compound of formula (IX) ~
in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of claims 1 to 6 for controlling undesirable plants.
in which R2, R3, R4, Z1, Z2 and Z3 are each as defined in any of claims 1 to 6 for controlling undesirable plants.
15. Herbicidal composition, characterized in that it comprises a compound according to any of Claims 1 to 6 and 11 and customary extenders and/or surfactants.
16. Herbicidal composition characterized in that it comprises a compound of formula (IX) according to claim 14 and customary extenders and/or surfactants.
17. Process for preparing a herbicidal composition, characterized in that at least one compound according to any of Claims 1 to 6 and 11 is mixed with extenders and/or surfactants.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10024938.8 | 2000-05-19 | ||
| DE10024938A DE10024938A1 (en) | 2000-05-19 | 2000-05-19 | New substituted iminoazine derivatives useful as herbicides, especially for weed control in crops |
| PCT/EP2001/005203 WO2001090071A2 (en) | 2000-05-19 | 2001-05-08 | Substituted iminoazines used as herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2409142A1 true CA2409142A1 (en) | 2002-11-15 |
Family
ID=7642873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002409142A Abandoned CA2409142A1 (en) | 2000-05-19 | 2001-05-08 | Substituted iminoazines |
Country Status (15)
| Country | Link |
|---|---|
| US (2) | US7186834B2 (en) |
| EP (1) | EP1286968A2 (en) |
| JP (1) | JP2004525067A (en) |
| KR (1) | KR20030016252A (en) |
| CN (1) | CN1227234C (en) |
| AR (1) | AR028393A1 (en) |
| AU (2) | AU6227101A (en) |
| BR (1) | BR0110824A (en) |
| CA (1) | CA2409142A1 (en) |
| DE (1) | DE10024938A1 (en) |
| MX (1) | MXPA02011370A (en) |
| PL (1) | PL363841A1 (en) |
| RU (1) | RU2265596C9 (en) |
| UA (1) | UA73173C2 (en) |
| WO (1) | WO2001090071A2 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003014087A1 (en) * | 2001-08-06 | 2003-02-20 | Asahi Glass Company, Limited | Process for preparation of 5-methyl-1-phenyl-2(1h) -pyridinone |
| CN100358872C (en) * | 2003-11-14 | 2008-01-02 | 上海睿星基因技术有限公司 | The derivatives of pyridone and use thereof |
| EP2591784B1 (en) | 2005-05-10 | 2016-09-14 | Intermune, Inc. | Pyridine-2-one-derivatives as modulators of stress-activated protein kinase system |
| US8039632B2 (en) * | 2006-11-13 | 2011-10-18 | Neurosearch A/S | 2-aminio-pyridine derivatives and their use as potassium channel modulators |
| WO2008058536A1 (en) * | 2006-11-13 | 2008-05-22 | Neurosearch A/S | Novel 4-amino-pyridine derivatives and their use as potassium channel modulators |
| CA2677949C (en) * | 2007-02-22 | 2016-02-09 | Paul Anthony Worthington | Iminipyridine derivatives and their uses as microbiocides |
| CA2726588C (en) | 2008-06-03 | 2019-04-16 | Karl Kossen | Compounds and methods for treating inflammatory and fibrotic disorders |
| EP2484655A1 (en) * | 2011-02-04 | 2012-08-08 | Vironova AB | A thionation process and a thionating agent |
| MX348495B (en) | 2011-09-13 | 2017-06-14 | Monsanto Technology Llc | Methods and compositions for weed control. |
| UA116088C2 (en) | 2011-09-13 | 2018-02-12 | Монсанто Текнолоджи Ллс | Method and compositions for weed control |
| EP2755467B1 (en) | 2011-09-13 | 2017-07-19 | Monsanto Technology LLC | Methods and compositions for weed control |
| MX343072B (en) | 2011-09-13 | 2016-10-21 | Monsanto Technology Llc | Methods and compositions for weed control. |
| MX343071B (en) | 2011-09-13 | 2016-10-21 | Monsanto Technology Llc | Methods and compositions for weed control. |
| AR092742A1 (en) | 2012-10-02 | 2015-04-29 | Intermune Inc | ANTIFIBROTIC PYRIDINONES |
| US10568328B2 (en) | 2013-03-15 | 2020-02-25 | Monsanto Technology Llc | Methods and compositions for weed control |
| MX2016012808A (en) | 2014-04-02 | 2017-01-05 | Intermune Inc | Anti-fibrotic pyridinones. |
| RU2701370C2 (en) * | 2014-04-11 | 2019-09-26 | Зингента Партисипейшнс Аг | Fungicidal derivatives of n'-[2-methyl-6 [2-alkoxyethoxy]-3-pyridyl]-n-alkylformamidine for use in agriculture |
| AU2016289413B2 (en) * | 2015-07-06 | 2020-03-26 | Bayer Cropscience Aktiengesellschaft | Nitrogenous heterocycles as a pesticide |
| AR112682A1 (en) * | 2017-08-17 | 2019-11-27 | Syngenta Participations Ag | HERBICIDE COMPOUNDS |
| WO2019105871A1 (en) | 2017-11-29 | 2019-06-06 | Bayer Aktiengesellschaft | Nitrogenous heterocycles as a pesticide |
| AR114422A1 (en) * | 2018-03-30 | 2020-09-02 | Syngenta Participations Ag | HERBICIDE COMPOUNDS |
| WO2019215076A1 (en) * | 2018-05-08 | 2019-11-14 | Bayer Aktiengesellschaft | Process for preparing nitrogen-containing heterocycles |
| CN108715584B (en) * | 2018-06-22 | 2021-06-25 | 四川大学华西医院 | Fluorescent molecule with N-pyridine-2- (1H) -nitrile imine as mother nucleus, and preparation and application thereof |
| CN113423273A (en) * | 2019-02-15 | 2021-09-21 | 先正达农作物保护股份公司 | Herbicidal composition |
| BR112021015914A2 (en) * | 2019-02-15 | 2021-10-05 | Syngenta Crop Protection Ag | HERBICIDAL COMPOSITIONS |
| BR112021016003A2 (en) * | 2019-02-15 | 2021-11-09 | Syngenta Crop Prot Ag | Herbicidal compositions |
| AU2020223404A1 (en) * | 2019-02-15 | 2021-08-19 | Syngenta Crop Protection Ag | Herbicidal compositions |
| JP2022520969A (en) * | 2019-02-15 | 2022-04-04 | シンジェンタ クロップ プロテクション アクチェンゲゼルシャフト | Weeding composition |
| EP3771714A1 (en) * | 2019-07-30 | 2021-02-03 | Bayer AG | Nitrogen-containing heterocycles as pesticides |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2947755A (en) * | 1959-02-05 | 1960-08-02 | Wallace & Tiernan Inc | Substituted 1-m-aminophenyl-2-pyridones |
| US3761240A (en) | 1968-01-16 | 1973-09-25 | Rohm & Haas | Plant growth inhibition with n aryl pyrid 2 ones |
| US3503986A (en) | 1968-01-16 | 1970-03-31 | Rohm & Haas | N-aryl-3-cyano-4,6-dimethylpyrid-2-ones |
| DE1670315B1 (en) * | 1968-02-10 | 1972-05-31 | Basf Ag | 1- (m-Trifluoromethylphenyl) -4-methoxy-5-halo-pyridazone- (6) derivatives |
| DE2016691A1 (en) * | 1970-04-08 | 1971-10-21 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Process for the preparation of 6-chloropyridazinium compounds |
| DE2031571A1 (en) * | 1970-06-26 | 1971-12-30 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Halopyridazinium halides prepn - useful as intermediates for plant-protection agents and dyes |
| AT308760B (en) * | 1971-08-27 | 1973-07-25 | Chemie Linz Ag | Process for the preparation of new pyridazon-6-imines and their salts |
| US4052509A (en) | 1972-12-18 | 1977-10-04 | Affiliated Medical Research, Inc. | Method for reducing serum uric acid levels |
| CA1049411A (en) | 1972-12-18 | 1979-02-27 | Affiliated Medical Research | N-substituted pyridone and general method for preparing pyridones |
| US4042699A (en) | 1972-12-18 | 1977-08-16 | Affiliated Medical Research, Inc. | Method for reducing serum glucose levels |
| US3839346A (en) | 1972-12-18 | 1974-10-01 | Affiliated Med Res | N-substituted pyridone and general method for preparing pyridones |
| DE4021439A1 (en) | 1989-12-14 | 1991-06-20 | Bayer Ag | 2-iminopyridine DERIVATIVES |
| AU3440597A (en) * | 1996-07-02 | 1998-01-21 | Novartis Ag | N-phenylimino heterocyclic derivatives and their use as herbicides |
-
2000
- 2000-05-19 DE DE10024938A patent/DE10024938A1/en not_active Withdrawn
-
2001
- 2001-04-30 AR ARP010102042A patent/AR028393A1/en unknown
- 2001-05-08 AU AU6227101A patent/AU6227101A/en active Pending
- 2001-05-08 BR BR0110824-7A patent/BR0110824A/en not_active Application Discontinuation
- 2001-05-08 PL PL01363841A patent/PL363841A1/en not_active Application Discontinuation
- 2001-05-08 KR KR1020027014545A patent/KR20030016252A/en not_active Application Discontinuation
- 2001-05-08 CA CA002409142A patent/CA2409142A1/en not_active Abandoned
- 2001-05-08 AU AU2001262271A patent/AU2001262271B2/en not_active Ceased
- 2001-05-08 US US10/276,867 patent/US7186834B2/en not_active Expired - Fee Related
- 2001-05-08 JP JP2001586260A patent/JP2004525067A/en not_active Withdrawn
- 2001-05-08 CN CNB018097898A patent/CN1227234C/en not_active Expired - Fee Related
- 2001-05-08 RU RU2002134455/04A patent/RU2265596C9/en not_active IP Right Cessation
- 2001-05-08 WO PCT/EP2001/005203 patent/WO2001090071A2/en active Application Filing
- 2001-05-08 MX MXPA02011370A patent/MXPA02011370A/en active IP Right Grant
- 2001-05-08 EP EP01936338A patent/EP1286968A2/en not_active Withdrawn
- 2001-08-05 UA UA20021210277A patent/UA73173C2/en unknown
-
2006
- 2006-01-18 US US11/333,976 patent/US7329757B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| RU2265596C2 (en) | 2005-12-10 |
| CN1430608A (en) | 2003-07-16 |
| US20060122062A1 (en) | 2006-06-08 |
| EP1286968A2 (en) | 2003-03-05 |
| AU2001262271B2 (en) | 2007-01-04 |
| AR028393A1 (en) | 2003-05-07 |
| MXPA02011370A (en) | 2003-06-06 |
| US7329757B2 (en) | 2008-02-12 |
| CN1227234C (en) | 2005-11-16 |
| UA73173C2 (en) | 2005-06-15 |
| WO2001090071A3 (en) | 2002-09-06 |
| KR20030016252A (en) | 2003-02-26 |
| US7186834B2 (en) | 2007-03-06 |
| RU2265596C9 (en) | 2006-05-27 |
| US20040029881A1 (en) | 2004-02-12 |
| JP2004525067A (en) | 2004-08-19 |
| AU6227101A (en) | 2001-12-03 |
| WO2001090071A2 (en) | 2001-11-29 |
| PL363841A1 (en) | 2004-11-29 |
| BR0110824A (en) | 2004-01-06 |
| DE10024938A1 (en) | 2001-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7329757B2 (en) | Substituted iminoazines | |
| US20050209251A1 (en) | Substituted pyrazolo-pyrimidine-4-ones | |
| DE10000600A1 (en) | New N-substituted oxazolyl-uracil and thiazolyl-uracil derivatives useful as herbicides, especially for weed control in crops | |
| US6649760B2 (en) | Substituted phenyluracils | |
| JP2004525129A (en) | Substituted fluoroalkoxyphenylsulfonylurea | |
| WO2001091558A1 (en) | Herbicidal agents based on substituted carboxamides | |
| AU2001258255B2 (en) | Substituted benzoylcyclohexenones | |
| EP1244634B1 (en) | Substituted benzoylcyclohexane diones for use as herbicides | |
| US6573219B1 (en) | Substituted heterocyclyl-2H-chromenes | |
| AU2002223604B2 (en) | Substituted phenyluracils | |
| US20040110640A1 (en) | Herbicidal substituted benzoylpyrazoles | |
| DE10037618A1 (en) | Substituted heterocyclylakylamino-1,3,5-triazines | |
| US20040186021A1 (en) | Substituted benzo-nitro-heterocycles | |
| DE10043790A1 (en) | Substituted 1-aryl-pyridin-2- (thi) one | |
| US6602827B1 (en) | Herbicidal 5-chlorodifluoromethyl-1,3,4-thiadiazol-2-yl-oxyacetanilides | |
| CA2443385A1 (en) | Substituted fluoralkoxyphenylsulfonylamino(thio)carbonyltriazolino(thi)ones | |
| CA2417385A1 (en) | Substituted aryl ketones and their use as herbicides | |
| CA2476501A1 (en) | Substituted aryl ketones | |
| DE10055499A1 (en) | 6-heterocyclyl-3-oxo-3,4-dihydro-quinoxaline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |