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  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
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  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
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  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
  • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
  • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D277/28—Radicals substituted by nitrogen atoms
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  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
  • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D317/28—Radicals substituted by nitrogen atoms
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  • C07—ORGANIC CHEMISTRY
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  • 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
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  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
  • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
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  • 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

Definitions

• the invention is in the technical field of the crop protection agents, such as herbicides and plant growth regulators, in particular of the herbicides for the selective control of harmful plants in crops of useful plants.
• the crop protection agents such as herbicides and plant growth regulators, in particular of the herbicides for the selective control of harmful plants in crops of useful plants.
• the present invention relates to compounds of the formula (I) and salts thereof
• R 1 is aryl which is unsubstituted or substituted and, inclusive of substituents, preferably has 6 to 30 carbon atoms, or is (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted and which, inclusive of substituents, preferably has 3 to 30 carbon atoms, or is heterocyclyl which is substituted or unsubstituted and which, inclusive of substituents, preferably has 2 to 30 carbon atoms, or
• each of the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, cyano, nitro, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 2 -C 4 )alkenyloxy, (C 2 -C 4 )haloalkenyloxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )alkylsulfinyl, (C 1 -C 4 )alkylsulfonyl, (C 1 -C 4 )haloalkylsulfinyl, (C 1 -C 4 )haloalkylsulfonyl and (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted, and phenyl which is unsubstituted
• R 2 is (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted, (C 4 -C 9 )cycloalkenyl which is unsubstituted or substituted, heterocyclyl which is unsubstituted or substituted, or phenyl, which is unsubstituted or substituted, R 2 , inclusive of substituents, preferably having up to 30 carbon atoms, or
• R 4 is a radical of the formula —B 3 —D 3 , B 3 and D 3 being as defined below and R 4 , inclusive of substituents, preferably having up to 20 carbon atoms,
• a 1 is straight-chain alkylene having 1 to 5 carbon atoms or straight-chain alkenylene or alkynylene, each of which has 2 to 5 carbon atoms, each of the three last-mentioned divalent radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, nitro, cyano, thiocyanato and radicals of the formula —B 4 —D 4 , B 4 and D 4 being as defined below,
• a 2 is a direct bond or straight-chain alkylene having 1 to 4 carbon atoms or straight-chain alkenylene or alkynylene, each of which has 2 to 5 carbon atoms, each of the three last-mentioned divalent radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, nitro, cyano, thiocyanato and radicals of the formula —B 5 —D 5 or a divalent radical of the formula V 1 , V 2 , V 3 , V 4 or V 5 ,
• each of the radicals R 6 to R 27 in each case independently of one another being hydrogen, halogen, nitro, cyano, thiocyanato or a radical of the formula —B 6 —D 6 ,
• W* is in each case an oxygen atom, a sulfur atom or a group of the formula N(B 7 —D 7 ) and
• B 5 , B 6 , B 7 , D 5 , D 6 and D 7 are as defined below,
• B 1 , B 2 , B 3 and B 7 in each case independently of one another are a direct bond or a divalent group of the formulae —C( ⁇ Z*)—, —C( ⁇ Z*)—Z**—, —C( ⁇ Z*)—NH— or —C( ⁇ Z*)—NR*—, Z* being an oxygen or sulfur atom, Z* an oxygen or sulfur atom and R* (C 1 -C 6 )alkyl, aryl, aryl-(C 1 -C 6 )alkyl, (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cycloalkyl-(C 1 -C 6 )alkyl, each of the 5 last-mentioned radicals being unsubstituted or substituted and, inclusive of the substituents, preferably having up to 20 carbon atoms,
• B 4 , B 5 and B 6 in each case independently of one another are a direct bond or a divalent group of the formulae —O—, —S(O) p —, —S(O) p —O—, —O—S(O) p —, —CO—, —O—CO—, —CO—O—O—, —S—CO—, —CO—S—, —S—CS—, —CS—S—, —O—CO—O—, —NR o —, —O—NR o —, —NR o —O—, —NR o —CO—, —CO—NR o —, —O—CO—NR o — or —NR o —CO—O—, p being the integer 0, 1 or 2 and R o being hydrogen, (C 1 -C 6 )alkyl, aryl, aryl-(C 1 -C 6 )alkyl,
• D 1 , D 2 , D 3 , D 4 , D 5 and D 6 in each case independently of one another are hydrogen, (C 1 -C 6 )alkyl, aryl, aryl-(C 1 -C 6 )alkyl, (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cycloalkyl-(C 1 -C 6 )alkyl, each of the 5 last-mentioned radicals being unsubstituted or substituted and, inclusive of substituents, preferably having up to 20 carbon atoms,
• n is n substituents X, where the X in each case independently of one another are halogen, hydroxyl, amino, nitro, formyl, carboxyl, cyano, thiocyanato, aminocarbonyl or (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, (C 1 -C 6 )alkylthio, mono(C 1 -C 6 )alkylamino, di(C 1 -C 4 )alkylamino, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, [(C 1 -C 6 )alkyl]carbonyl, [(C 1 -C 6 )alkoxy]carbonyl, mono(C 1 -C 6 )alkylaminocarbonyl, di(C 1 -C 4 )alkylaminocarbonyl, N—(C 1 -C 6 )al
• each of the last-mentioned 13 radicals being unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, cyano, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 4 )cycloalkyl, (C 3 -C 9 )cycloalkyl-amino, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, aminocarbonyl, mono(C 1 -C 4
• each of the last-mentioned 8 radicals being unsubstituted or having one or more substituents selected from the group consisting of halogen, nitro, cyano, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )haloalkoxy, formyl, (C 1 -C 4 )alkylcarbonyl and (C 1 -C 4 )alkoxycarbonyl,
• each of the last-mentioned 11 radicals being unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, cyano, thiocyanato, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 9 )cycloalkyl, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, amino
• radicals X together are a fused cycle which has 4 to 6 ring atoms and is carbocyclic or which contains hetero ring atoms selected from the group consisting of O, S and N and which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )alkyl and oxo,
• n is 0, 1, 3, 4 or 5, preferably 0, 1, 2, 3 or 4, in particular 1 or 2, and heterocyclyl in the abovementioned radicals independently of one another is in each case a heterocyclic radical having 3 to 7 ring atoms and 1 to 3 hetero atoms selected from the group consisting of N, O and S, where
• divalent radicals for example, B 1 —C( ⁇ Z*)—Z**—
• B 1 —C( ⁇ Z*)—Z**— are defined such that, in the composite groups, for example —B 1 —D 1 , that bond of the divalent radical is linked to the group D 1 which appears on the right-hand side in the formula for the divalent radical, i.e. —B 1 —D 1 is a group of the formula —C( ⁇ Z*)—Z**—D 1 ; a similar definition applies to analogous divalent radicals.
• the compounds of the formula (I) can form salts when a basic group such as, for example, amino or alkylamino undergoes an addition reaction with a suitable inorganic or organic acid, such as, for example, HCl, HBr, H 2 SO 4 or HNO 3 , but also oxalic acid or sulfonic acids.
• a suitable inorganic or organic acid such as, for example, HCl, HBr, H 2 SO 4 or HNO 3
• Suitable substituents which are present in deprotonated form such as, for example, sulfonic acids or carboxylic acids, can form internal salts with those groups which are capable of undergoing protonation themselves, such as amino groups.
• salts can be formed by replacing, in the case of suitable substituents such as, for example, sulfonic acids or carboxylic acids, the hydrogen by an agriculturally suitable cation.
• suitable substituents such as, for example, sulfonic acids or carboxylic acids
• salts are metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium salts and potassium salts, or else ammonium salts, salts with organic amines, or quaternary ammonium salts.
• radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and/or substituted radicals may be straight-chain or branched in the carbon skeleton in each case.
• the lower carbon skeletons for example those having 1 to 6 carbon atoms, or in the case of unsaturated groups, those having 2 to 6 carbon atoms, are preferred for these radicals.
• Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl and the like, are, for example methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meanings of the unsaturated radicals which are possible and which correspond to the alkyl radicals; for example, alkenyl is allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl;
• Cycloalkyl is a carbocyclic saturated ring system having preferably 3-8 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
• Substituted cycloalkyl encompasses cyclic systems with substituents, the substituents being bonded to the cycloalkyl radical via a double bond, for example an alkylidene group such as methylidene.
• Substituted cycloalkyl also encompasses polycyclic aliphatic systems such as, for example, bicyclo[1.1.0]butan-1-yl, bicyclo[1.1.0]butan-2-yl, bicyclo[2.1.0]pentan-1-yl, bicyclo[2.1.0]pentan-2-yl, bicyclo[2.1.0]pentan-5-yl, adamantan-1-yl and adamantan-2-yl.
• Cycloalkenyl is a carbocyclic non-aromatic partially unsaturated ring system having preferably 4-8 carbon atoms, for example 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1,4-cyclohexadienyl.
• substituted cycloalkyl apply analogously to substituted cycloalkenyl.
• Halogen is, for example, fluorine, chlorine, bromine or iodine.
• Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl which are partially or fully substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example monohaloalkyl, perhaloalkyl, CF 3 , CHF 2 , CH 2 F, CF 3 CF 2 , CH 2 FCHCl, CCl 3 , CHCl 2 , CH 2 CH 2 Cl;
• haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 Cl; this applies analogously to haloalkenyl and other halogen-substituted radicals.
• Aryl is a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and similar, preferably phenyl.
• a heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic; it preferably contains one or more, in particular 1,2 or 3, hetero atoms in the heterocyclic ring, preferably selected from the group consisting of nitrogen, oxygen and sulfur; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms.
• Suitable substituents for a substituted heterocyclic radical are those mentioned further below, and in addition also oxo.
• the oxo group may also occur on those hetero ring atoms which can exist at various oxidation stages, for example in the case of nitrogen and sulfur.
• Substituted radicals such as a substituted alkyl, alkenyl, alkynyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical are, for example, a substituted radical which is derived from the unsubstituted skeleton, the substituents having, for example, one or more, preferably 1, 2 or 3, radicals selected from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and,
• substituted cyclic radicals with aliphatic moieties in the ring also encompasses cyclic systems with those substituents which are bonded to the ring by means of a double bond, for example by means of an alkylidene group such as methylidene or ethylidene.
• substituents are, as a rule, those selected from the group consisting of halogen, for example fluorine and chlorine, (C 1 -C 4 )alkyl, preferably methyl or ethyl, (C 1 -C 4 )haloalkyl, preferably trifluoromethyl, (C 1 -C 4 )alkoxy, preferably methoxy or ethoxy, (C 1 -C 4 )haloalkoxy, nitro and cyano.
• halogen for example fluorine and chlorine
• (C 1 -C 4 )alkyl preferably methyl or ethyl
• C 1 -C 4 )haloalkyl preferably trifluoromethyl
• C 1 -C 4 )alkoxy preferably methoxy or ethoxy
• C 1 -C 4 )haloalkoxy nitro and cyano.
• Mono- or disubstituted amino is a chemically stable radical selected from the group consisting of substituted amino radicals which are n-substituted, for example, by one, or two, identical or different radicals selected from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles; alkyl radicals having 1 to 4 carbon atoms are preferred; aryl is preferably phenyl or substituted phenyl; acyl is covered by the definition given further below, preferably (C 1 -C 4 )alkanoyl. This applies analogously to substituted hydroxylamino or hydrazino.
• Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals selected from the group consisting of halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
• An acyl radical is the radical of an organic acid, for example the radical of a carboxylic acid and radicals of acids derived therefrom, such as thiocarboxylic acid, optionally n-substituted iminocarboxylic acids or the radical of carbonic monoesters, optionally n-substituted carbamic acid, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
• Acyl is, for example, formyl, alkylcarbonyl such as [(C 1 -C 4 )alkyl]carbonyl, phenylcarbonyl, alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other radicals of organic acids.
• alkylcarbonyl such as [(C 1 -C 4 )alkyl]carbonyl
• phenylcarbonyl alkyloxycarbonyl
• phenyloxycarbonyl benzyloxycarbonyl
• alkylsulfonyl alkylsulfinyl
• N-alkyl-1-iminoalkyl N-alkyl-1-iminoalkyl and other radicals of organic acids.
• radicals may be further substituted in each case in the alkyl or phenyl moiety, for example in the alkyl moiety by one or more radicals selected from the group consisting of halogen, alkoxy, phenyl and phenoxy; examples of substituents in the phenyl moiety are those substituents which have already been mentioned further above in general terms for substituted phenyl.
• the invention furthermore relates to all stereoisomers encompassed by formula (I) and mixtures of these.
• Such compounds of the formula (I) contain one or more asymmetric carbon atoms or else double bonds, which are not indicated specifically in the formulae (I).
• the formula (I) encompasses all stereoisomers which are possible and which are defined by their specific spatial form, such as enantiomers, diastereomers, Z- and E-isomers, and they can be obtained from stereoisomer mixtures by customary methods or else prepared by means of stereoselective reactions in combination with the use of stereochemically pure starting materials.
• R 1 is preferably phenyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, sulfo, cyano, thiocyanato, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 9 )cycloalkyl, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, aminocarbonyl, mono(C 1 -C
• R 1 is preferably also (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, cyano, thiocyanato, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino and di(C 1 -C 4 )alkylamino and which, inclusive of substituents, has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, in particular 3 to 15 carbon atoms.
• R 1 is preferably also heterocyclyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, sulfonyl, cyano, thiocyanato, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 9 )cycloalkyl, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, aminocarbonyl, mono
• R 1 is preferably also (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl or (C 2 -C 6 )alkynyl, each of the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, cyano, nitro, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 2 -C 4 )alkenyloxy, (C 2 -C 4 )haloalkenyloxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )alkylsulfinyl, (C 1 -C 4 )alkylsulfonyl, (C 1 -C 4 )haloalkylsulfinyl, (C 1 -C 4 )haloalkyls
• R 1 is preferably (C 1 -C 4 )alkyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )alkylsulfonyl, (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted, and phenyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )alkyl and (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, amino, mono- and di[(C 1 -C 4 )alkyl]amino, (C 1 -C 4 )
• R 1 is furthermore by way of preference (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, benzyl or [(C 3 -C 6 )cycloalkyl]-(C 1 -C 2 )alkyl, in particular (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl or [(C 3 -C 6 )cycloalkyl]methyl, preferably —CH 3 , —CH 2 F, —CHF 2 , —CF 3 , —CH 2 Cl, —CHCl 2 , —CCl 3 , —CH 2 Br, —CHBr 2 , —CH 2 CH 3 , —CH 2 CH 2 F, —CF 2 CHF 2 , —CH 2 CH 2 Cl, —CH 2 CH 2 Br —CH(CH 3 ) 2 , —CF(CH 3 ) 2 , —C(CH 3 )alky
• R 2 are of particular interest, independently of the radicals R 1 , R 3 , R 4 , A 1 , A 2 and (X) n and preferably in combination with preferred meanings of one or more of these radicals:
• R 2 is preferably (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of the radicals A), B), C) and D), where
• Group A) is composed of the radicals halogen, hydroxyl, amino, nitro, formyl, carboxyl, aminocarbonyl, sulfo, cyano, thiocyanato and oxo,
• Group B) is composed of the radicals (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, (C 1 -C 6 )alkylthio, mono(C 1 -C 6 )alkylamino, di(C 1 -C 4 )alkylamino, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 3 -C 0 )cycloalkyl, (C 4 -C 9 )cycloalkenyl, (C 1 -C 6 )alkylidene, (C 4 -C 9 )cycloalkylidene, radicals of the formulae R′—C( ⁇ Z′)—, R′—C( ⁇ Z′)—Z—, R′—Z—C( ⁇ Z′)—, R′R′′N—C( ⁇ Z′)—, R′—Z—C( ⁇ Z′)—O—, R′R′′
• Group C) is composed of radicals as shown for group B), but each radical being substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, sulfo, cyano, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 9 )cycloalkyl, (C 4 -C 9 )cycloalkylene, (C 4 -C 9 )cycloalkylidene, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, aminocarbonyl,
• each of the last-mentioned 21 radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, nitro, cyano, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkoxy, formyl, (C 1 -C 4 )alkylcarbonyl and (C 1 -C 4 )alkoxycarbonyl and, in the case of cyclic radicals, also (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl and (C 1 -C 6 )alkylidene, and in the case of cyclic radicals also (C 1 -C 6 )alkyl, (C 1 -C 6 )haloalkyl and (C 1 -C 6 )alkylidene, and
• Group D) is composed of divalent or trivalent aliphatic bridges having 1 to 6, preferably 1 to 4, carbon atoms which, in the case of divalent bridges, connect two and in the case of trivalent bridges three carbon atoms of the cyclic skeleton and the radical RW thus represents the radical of a bicycle or tricycle, each of the bridges being unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, nitro, cyano, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )haloalkoxy, formyl, (C 1 -C 4 )alkylcarbonyl, (C 1 -C 4 )alkoxycarbonyl and oxo,
• R 2 inclusive of substituents, preferably has 3 to 20 carbon atoms, in particular 3 to 15 carbon atoms.
• Preferred (C 3 -C 9 )cycloalkyl radicals are cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl, cyclobutyl or cyclopentyl.
• R 2 is preferably also (C 4 -C 9 )cycloalkenyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of the radicals A), B), C) and D) as they are defined as radicals for R 2 ⁇ (C 3 -C 9 )cycloalkyl, and, inclusive of substituents, preferably has 4 to 20 carbon atoms, in particular 4 to 15 carbon atoms.
• (C 4 -C 9 )cycloalkenyl radicals are 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl and 3-cyclopentenyl.
• R 2 is preferably also heterocyclyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of the radicals A), B), C) and D) as they are defined as radicals for R 2 ⁇ (C 3 -C 9 )cycloalkyl.
• R 2 is preferably also phenyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of the radicals A), B) and C) as they are defined as radicals for R 2 ⁇ (C 3 -C 9 )cycloalkyl.
• R 2 inclusive of substituents, preferably has up to 20 carbon atoms, in particular up to 15 carbon atoms, very especially up to 10 carbon atoms.
• R 2 is preferably (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of the radicals A), B), C) and D), where
• Group A) is composed of the radicals halogen, hydroxyl, nitro, formyl, aminocarbonyl, cyano and thiocyanato,
• Group B) is composed of the radicals (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 2 -C 4 )alkenyl, (C 2 -C 4 )alkynyl, (C 3 -C 6 )cycloalkyl, (C 4 -C 6 )cycloalkenyl, (C 1 -C 4 )alkylidene, (C 4 -C 6 )cycloalkylidene, radicals of the formulae R′—C( ⁇ Z′)—, R′—C( ⁇ Z′)—Z—, R′—Z—C( ⁇ Z′)—, R′R′′N—C( ⁇ Z′)—, R′—Z—C( ⁇ Z′)—O—, R′R′′N
• Group C) is composed of radicals as shown in Group B), but each radical is substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 6 )cycloalkyl, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, aminocarbonyl, mono(C 1 -C 4 )alkylaminocarbonyl, di(C 1 -C 4 )alkylaminocarbonyl, phenyl, phenoxy, phenylthio, phenylcarbonyl, heterocyclyl
• each of the last-mentioned 8 radicals is unsubstituted or has one or more substituents selected from the group consisting of halogen, nitro, cyano, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylcarbonyl and (C 1 -C 4 )alkoxycarbonyl, and
• Group D) is composed of divalent aliphatic bridges which connect two carbon atoms of the cyclic skeleton, the radical R 2 thus representing the radical of a bicycle, for example bicyclo[1.1.0]butan-1-yl, bicyclo[1.1.0]butan-2-yl, bicyclo[2.1.0]pentan-1-yl, bicyclo[2.1.0]pentan-2-yl or bicyclo[2.1.0]pentan-5-yl, where each of the bridges is unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkyl-carbonyl, (C 1 -C 4 )alk
• R 2 is especially preferably (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, cyano, thiocyanato, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, (C 1 -C 4 )alkylidene, mono(C 1 -C 4 )alkylamino and di(C 1 -C 4 )alkylamino or heterocyclyl or phenyl, each of the last-mentioned two radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, cyano
• R 3 are of particular interest, independently of the radicals R 1 , R 2 , R 4 , A 1 , A 2 and (X) n and preferably in combination with preferred meanings of one or more of these radicals:
• R 3 is hydrogen, (C 1 -C 4 )alkyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, cyano, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino and di(C 1 -C 4 )alkylamino, or phenyl or (C 3 -C 6 )cycloalkyl, each of the last-mentioned 2 radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, sulfonyl, cyano, thiocyanato, (
• R 4 are of particular interest, independently of the radicals R 1 to R 3 , A 1 , A 2 and (X) n and preferably in combination with preferred meanings of one or more of these radicals:
• R 4 is a radical of the formula —B 3 —D 3 where B 3 and D 3 are preferably as defined further below.
• R 4 is preferably hydrogen, (C 1 -C 4 )alkyl, phenyl or (C 3 -C 6 )cycloalkyl, each of the 3 last-mentioned radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, sulfonyl, cyano, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 9 )cycloalkyl, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkyl]
• formyl [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, aminocarbonyl, mono(C 1 -C 4 )alkylaminocarbonyl or di(C 1 -C 4 )alkylaminocarbonyl; in particular hydrogen, methyl, ethyl, n-propyl or isopropyl; especially preferably hydrogen.
• a 1 is of particular interest, independently of the radicals R 1 to R 4 , A 2 and (X) n and preferably in combination with preferred meanings of one or more of these radicals:
• a 1 is straight-chain alkylene having 1 to 5 carbon atoms or straight-chain alkenylene or alkynylene, each of which has 2 to 5 carbon atoms, each of the three last-mentioned divalent radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, nitro, cyano, thiocyanato and a radical of the formula —B 4 —D 4 ,
• B 4 is a direct bond or a divalent group of the formulae —O—, —SO 2 —, —CO—, —O—CO—, —NR o —, —NR o —CO—, —CO—NR o —, —O—CO—NR o — or —NR o —CO—O—,
• R o and D 4 independently of one another are in each case hydrogen, (C 1 -C 4 )alkyl, phenyl, phenyl-(C 1 -C 4 )alkyl, (C 3 -C 6 )cycloalkyl or (C 3 -C 6 )cycloalkyl-(C 1 -C 4 )alkyl, each of the last-mentioned 5 radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, sulfonyl, cyano, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4
• a 1 is preferably a radical of the formula
• a 1 is especially preferably a radical of the formula —CH 2 CH 2 — or —CH 2 CH 2 CH 2 — which is unsubstituted or substituted by one or two radicals of the formula hydroxyl, (C 1 -C 4 )alkyl or (C 1 -C 4 )alkoxy.
• a 2 is of particular interest, independently of the radicals R 1 to R 4 , A 1 and (X) n and preferably in combination with preferred meanings of one or more of these radicals:
• a 2 is preferably
• each of the radicals R 6 to R 27 in each case independently of one another is hydrogen, halogen, nitro, cyano, thiocyanato or a radical of the formula —B 6 —D 6 ,
• W* is in each case oxygen, sulfur or a group of the formula N(B 7 —D 7 ) and B 5 , B 6 , B 7 , D 5 , D 6 and D 7 are as defined below,
• a 2 is especially preferably a direct bond or a group of the formula —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 —O—CH 2 —, —CH 2 —O—CH 2 —CH 2 —, —CH 2 —CH 2 —O—CH 2 —, —CH 2 —S—CH 2 —, —CH 2 —S—CH 2 —CH 2 —, —CH 2 —CH 2 —S—CH 2 —, —CH 2 —NH—CH 2 —, —CH 2 —NH—CH 2 —CH 2 —, —CH 2 —CH 2 —NH—CH 2 —, —CH 2 —N(CH 3 )—CH 2 —, —CH 2 —N(CH 3 )—CH 2 —CH 2 — or —CH 2 —CH 2 —N(CH 2 —
• B 1 , B 2 , B 3 and B 7 are preferably in each case independently of one another a direct bond or a divalent group of the formulae
• B 1 , B 2 , B 3 and B 1 independently of one another to be a direct bond or a divalent group of the formulae —C( ⁇ Z*)—, —C( ⁇ Z*)—Z**—, —C( ⁇ Z*)—NH— or —C( ⁇ Z*)—NR*—, where Z* ⁇ O or S.
• B 4 , B 5 and B 5 are preferably in each case independently of one another a direct bond or a
• [0102] divalent group of the formulae —O—, —S(O) p —, —S(O) p —O—, —O—S(O) p —, —CO—, —O—CO—, —CO—O—, —S—CO—, —CO—S—, —S—CS—, —CS—S—, —O—CO—O—, —NR o —, —O—NR 9 —, —NR o —O—, —NR o —CO—, —CO—NR o —, —O—CO—NR o — or —NR o —CO—O—, where p is the integer 0, 1 or 2 and R o hydrogen, (C 1 -C 4 )alkyl, phenyl, phenyl-(C 1 -C 4 )alkyl, (C 3 -C 6 )cycloalkyl or (C 3 -C
• B 4 , B 5 and B 6 independently of one another are a direct bond or a
• D 1 , D 2 , D 3 , D 4 , D 5 and D 6 independently of one another preferably are hydrogen, (C 1 -C 6 )alkyl, phenyl, phenyl-(C 1 -C 4 )alkyl, (C 3 -C 6 )cycloalkyl or (C 3 -C 6 )cycloalkyl-(C 1 -C 6 )alkyl, each of the 5 last-mentioned radicals being unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, sulfo, cyano, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkyl
• D 1 , D 2 , D 3 , D 4 , D 5 and D 6 independently of one another are
• n is n substituents X, where the X preferably in each case independently of one another are halogen, hydroxyl, amino, nitro, formyl, carboxyl, cyano, thiocyanato, aminocarbonyl or (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 2 -C 4 )alkenyl, (C 2 -C 4 )alkynyl, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, mono(C 1 -C 4 )alkylaminocarbonyl, di(C 1 -C 4 )alkylaminocarbonyl, N—(C 1 -C 6
• each of the last-mentioned 13 radicals being unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, cyano, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 6 )cycloalkyl, (C 3 -C 6 )cycloalkylamino, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, aminocarbonyl, mono(C 1 -C 4 )alkylaminocarbonyl, di(C 1 -C 4 )alkylaminocarbon
• each of the last-mentioned 9 radicals being unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, amino, nitro, formyl, carboxyl, cyano, thiocyanato, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, (C 3 -C 6 )cycloalkyl, [(C 1 -C 4 )alkyl]carbonyl, [(C 1 -C 4 )alkoxy]carbonyl, amino
• radicals X together are a fused cycle which has 4 to 6 ring atoms and is carbocyclic or contains hetero ring atoms selected from the group consisting of O, S and N and which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )alkyl and oxo.
• n is preferably 0, 1, 2 or 3, in particular 1 or 2.
• (X) n is preferably furthermore n substituents X, where the X in each case independently of one another are halogen, hydroxyl, amino, nitro, formyl, carboxyl, cyano, thiocyanato, (C 1 -C 4 )alkyl, cyano-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylamino, di-[(C 1 -C 4 )alkyl]amino, halo-(C 1 -C 4 )alkyl, hydroxy-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy-(C 1 -C 4 )alkyl, halo(C 1 -C 4 )alkoxy-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkylthio, halo-(C 1 -C 4
• two adjacent radicals X together are a fused cycle which has 4 to 6 ring atoms and is carbocyclic or contains hetero ring atoms selected from the group consisting of O, S and N and which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )alkyl and oxo.
• (X) n is especially preferably n substituents X, where X in each case independently of one another is halogen, OH, NO 2 , CN, SCN (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, (C 1 -C 4 )alkylcarbonyl or (C 1 -C 4 )alkyloxycarbonyl, the last-mentioned four radicals being unsubstituted or substituted by halogen or (C 1 -C 4 )alkoxy, and very especially preferably n substituents X, where X in each case independently of one another is halogen, hydroxyl, (C 1 -C 4 )alkyl or (C 1 -C 4 )alkoxy.
• Heterocyclyl is especially preferably a heterocyclic radical having 3 to 6 ring atoms and one (1) heteroatom selected from the group consisting of N, O and S, in particular a heteroaromatic radical having 5 or 6 ring atoms or a saturated or partially unsaturated heterocyclic (not heteroaromatic) radical having 3 to 6 ring atoms.
• heterocyclyl is preferably a heterocyclic radical having 5 or 6 ring atoms and 2 or 3 heteroatoms selected from the group consisting of N, O and S, in particular pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, triazolyl or piperazinyl, dioxolanyl, oxazolinyl, isoxazolinyl, oxazolidinyl, isoxazolidinyl or morpholinyl.
• the number of the carbon atoms of the total of the carbon atoms of the two radicals A 1 and A 2 —R 2 is
• a 1 a group of the formula —CH 2 — or —CH 2 CH 2 — and R 1 ⁇ (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 2 -C 6 )haloalkenyl or (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted, preferably, R 1 ⁇ (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl or (C 3 -C 6 )cycloalkyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of (C 1 -C 4 )alkyl and (C 1 -C 4 )alkyl.
• the total number of the carbon atoms of the radicals A 1 and A 2 —R 2 together is one of the abovementioned alternative a).
• the composite group —A 2 —R 2 is preferably cyclopropyl (hereinbelow also “c-Pr”), CH 2 -c-Pr, —(CH 2 ) 2 -c-Pr, cyclobutyl (hereinbelow also “c-Bu”), CH 2 -c-Bu; (CH 2 ) 2 -c-Bu, oxiranyl, oxiranyl methyl or 2-(oxiranyl)-eth-1-yl.
• the present invention also relates to processes for the preparation of the compounds of the formula (I) or their salts, which comprises
• Fu is a functional group selected from the group consisting of carboxylic ester, carboxylic orthoester, carboxylic acid chloride, carboxamide, carboxylic anhydride and trichloromethyl with a compound of the formula (III) or an acid addition salt thereof
• Z 1 is an exchangeable radical or leaving group, for example chlorine, trichloromethyl, (C 1 -C 4 )alkylsulfonyl and unsubstituted or substituted phenyl-(C 1 -C 4 )alkylsulfonyl or (C 1 -C 4 )alkylphenylsulfonyl with a suitable amine of the formula (V) or an acid addition salt thereof
• the compounds of the formulae (II) and (III) are preferably reacted with base catalysis in an inert organic solvent such as, for example, tetrahydrofuran (THF), dioxane, acetonitrile, dimethylformamide (DMF), methanol and ethanol, at temperatures between ⁇ 10° C. and the boiling point of the solvent, preferably at 20° C. to 60° C.; if acid addition salts of the formula (III) are used, they are, as a rule, liberated in situ with the aid of a base.
• an inert organic solvent such as, for example, tetrahydrofuran (THF), dioxane, acetonitrile, dimethylformamide (DMF), methanol and ethanol
• Suitable bases or basic catalysts are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal alkoxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal carbonates or organic bases such as triethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
• the base in question is employed, for example, in the range of 0.1 to 3 mol equivalents based on the compound of the formula (III).
• the compound of the formula (II) may be employed, for example, in equimolar amounts or in an excess of up to 2 mol equivalents relative to the compound of the formula (III).
• the compounds of the formulae (IV) and (V) are preferably reacted with base catalysis in an inert organic solvent such as, for example, THF, dioxane, acetonitrile, DMF, methanol and ethanol, at temperatures between ⁇ 10° C. and the boiling point of the solvent or solvent mixture in question, preferably at 20° C. to 60° C.; if the compound (V) is used as an acid addition salt, it is, if appropriate, liberated in situ using a base.
• an inert organic solvent such as, for example, THF, dioxane, acetonitrile, DMF, methanol and ethanol
• Suitable bases or basic catalysts are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal alkoxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal carbonates or organic bases such as triethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
• the base in question is employed, as a rule, in the range of 1 to 3 mol equivalents based on the compound of the formula (IV).
• the compound of the formula (IV) can be employed, for example, in equimolar amounts relative to the compound of the formula (V) or in an excess of up to 2 mol equivalents.
• the starting materials of the formulae (II), (III), (IV) and (V) are either commercially available or can be prepared by, or analogously to, processes known from the literature. Some of the compounds of the formulae (III) and (V) are novel and also subject of the invention. Also, the compounds can be prepared, for example, by one of the processes described hereinbelow.
• the compound of the formula (IV) or a direct precursor thereof can be prepared, for example, as follows:
• Z 2 is (C 1 -C 4 )alkyl or phenyl-(C 1 -C 4 )alkyl and R 3 is as defined in formula (I) affords compounds of the formula (IV) in which Z 1 —SZ 2 .
• Z 3 is (C 1 -C 4 )alkyl or phenyl-(C 1 -C 4 )alkyl affords compounds of the formula (IV) where Z 1 —S—Z 3 .
• the carboxylic acid derivatives of the formula (II) are reacted with the amidinothiourea derivatives of the formula (VI) in an organic solvent such as, for example, acetone, THF, dioxane, acetonitrile, DMF, methanol, ethanol, at temperatures of ⁇ 10° C to the boiling point of the solvent, preferably at 0° C. to 20° C., preferably with base catalysis.
• the reaction may also be carried out in water or aqueous solvent mixtures with one or more of the abovementioned organic solvents. If (VI) is employed as an acid addition salt, it may be liberated, if appropriate, in situ using a base.
• Suitable bases or basic catalysts are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal alkoxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal carbonates or organic bases such as triethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
• the base in question is employed, for example, in the range of 1 to 3 mol equivalents based on the compound of the formula (VI).
• Compounds of the formulae (II) and (VI) can be employed, for example, in equimolar amounts or in an excess of up to 2 mol equivalents of the compound of the formula (II).
• the principles of the processes in question are known from the literature (cf. H. Eilingsfeld, H. Scheuermann, Chem. Ber.; 1967, 100, 1874), the corresponding intermediates of the formula (IV) are novel.
• amidines of the formula (VII) are reacted with the N-cyanodithioiminocarbonates of the formula (VII) in an inert organic solvent such as, for example, acetonitrile, DMF, dimethylacetamide(DMA), N-methylpyrrolidone (NMP), methanol and ethanol, at temperatures from ⁇ 10° C. to the boiling point of the solvent, preferably at 20° C. to 80° C., preferably with base catalysis. If (VII) is employed as an acid addition salt, it may be liberated, if appropriate, in situ using a base.
• an inert organic solvent such as, for example, acetonitrile, DMF, dimethylacetamide(DMA), N-methylpyrrolidone (NMP), methanol and ethanol
• Suitable bases or basic catalysts are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal alkoxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal carbonates or organic bases such as triethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
• the base in question is employed, for example, in the range of 1 to 3 mol equivalents based on the compound of the formula (VIII), compounds of the formulae (VII) and (VIII) can be employed, as a rule, in equimolar amounts or with an excess of 2 mol equivalents of the compound of the formula (VII).
• the reactants are reacted for example with acid catalysis in an inert organic solvent such as, for example, toluene, chlorobenzene, chlorinated hydrocarbons at temperatures between ⁇ 10° C. and the boiling point of the solvent, preferably at 20° C. to 80° C., it being possible for the intermediates which form to be chlorinated in situ using a suitable chlorinating reagent such as, for example, phosphorus oxychloride.
• Suitable acids are, for example, hydrohalic acids such as HCl or else Lewis acids such as, for example AlCl 3 or BF 3 (cf. U.S. Pat. No. 5,095,113, Du Pont).
• the reactants are reacted, for example, with acid catalysis in an inert organic solvent such as, for example, toluene, chlorobenzene, chlorinated hydrocarbons at temperatures between 40° C. and the boiling point of the solvent, preferably at ⁇ 10° C. to 30° C.
• suitable acids are hydrohalic acids such as HCl or else Lewis acids such as, for example, AlCl 3 or BF 3 (cf. EP-A-130939, Ciba Geigy).
• Acids which are suitable for preparing the acid addition salts of the compounds of the formula (I) are the following: hydrohalic acids such as hydrochloric acid or hydrobromic acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids and hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid or lactic acid, and also sulfonic acids such as p-toluenesulfonic acid or 1,5-naphthalenedisulfonic acid.
• hydrohalic acids such as hydrochloric acid or hydrobromic acid
• phosphoric acid phosphoric acid
• nitric acid sulfuric acid
• sulfuric acid mono- or bifunctional carboxylic acids and hydroxycarboxylic acids
• hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric
• the acid addition compounds of the formula (I) can be obtained in a simple manner by the customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable organic solvent such as, for example, methanol, acetone, methylene chloride or benzine, and adding the acid at temperatures from 0 to 100° C., and they can be isolated in the known manner, for example by filtration, and, if appropriate, purified by washing with an inert organic solvent.
• a suitable organic solvent such as, for example, methanol, acetone, methylene chloride or benzine
• the base addition salts of the compounds of the formula (I) are preferably prepared in inert polar solvents such as, for example, water, methanol or acetone at temperatures from 0 to 100° C.
• bases which are suitable for the preparation of the salts according to the invention are alkali metal carbonates such as potassium carbonate, alkali metal hydroxides and alkaline earth metal hydroxides, for example NaOH or KOH, alkali metal hydrides and alkaline earth metal hydrides, for example NaH, alkali metal alkoxides and alkaline earth metal alkoxides, for example sodium methoxide, potassium tert-butoxide, or ammonia or ethanolamine.
• alkali metal carbonates such as potassium carbonate
• alkali metal hydroxides and alkaline earth metal hydroxides for example NaOH or KOH
• alkali metal hydrides and alkaline earth metal hydrides for example NaH
• Quarternary ammonium salts can be prepared, for example, by double decomposition or condensation with quarternary ammonium salts of the formula [NRR′R′′R′′′] + X ⁇ where R, R′, R′′ and R′′′ independently of one another are (C 1 -C 4 )alkyl, phenyl or benzyl and X ⁇ is an anion, for example Cl ⁇ or OH ⁇ .
• solvents termed “inert solvents” in the above process variants are to be understood as meaning in each case solvents which are inert under the reaction conditions in question, but which need not be inert under any reaction conditions.
• the compounds of the formula (I) according to the invention and their salts, all termed hereinbelow as compounds of the formula (I) (according to the invention), have an excellent herbicidal activity against a broad range of economically important monocotyledonous and dicotyledonous harmful plants.
• the active substances also act efficiently on perennial weeds which produce shoots from rhizomes, root stocks or other perennial organs and which are difficult to control. In this context, it does not matter whether the substances are applied pre-planting, pre-emergence or post-emergence.
• Examples of weed species on which the active substance acts efficiently are, from amongst the monocotyledons, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and also Cyperus species from the annual sector and from amongst the perennial species Agropyron, Cynodon, Imperata and Sorghum, and also perennial Cyperus species.
• the range of action extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, lpomoea, Matricaria, Abutilon and Sida from amongst the annuals, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds.
• the active substances according to the invention likewise effect outstanding control of weeds which occur under the specific conditions of rice growing, such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus.
• the compounds according to the invention are applied to the soil surface before germination, then the weed seedlings are either prevented completely from emerging, or the weeds grow until they have reached the cotyledon stage but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.
• the compounds according to the invention have an excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, maize, sugar beet, cotton and soya, are damaged not at all, or only to a negligible extent.
• the present compounds are highly suitable for selectively controlling undesired plant growth in plantings for agricultural use, inclusive of ornamental plantings.
• the substances according to the invention have excellent growth-regulating properties in crop plants. They engage in the plant metabolism in a regulating manner and can thus be employed for the targeted control of plant constituents and for facilitating harvesting, such as, for example, by provoking desiccation and stunted growth. Furthermore, they are also suitable for generally regulating and inhibiting undesired vegetative growth, without simultaneously destroying the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops because lodging can be reduced hereby, or prevented completely.
• the active substances can also be employed for controlling harmful plants in crops of known genetically modified plants, or genetically modified plants yet to be developed.
• the transgenic plants are distinguished by particular advantageous properties, for example by resistances to certain pesticides, mainly certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses.
• Other particular properties relate, for example, to the harvested material with regard to quantity, quality, storage properties, composition and specific constituents.
• transgenic plants are known where the starch content is increased or the starch quality is altered or those where the harvested material has a different fatty acid spectrum.
• the compounds of the formula (I) according to the invention or their salts are preferably employed in economically important transgenic crops of useful plants and ornamentals, for example cereals such as wheat, barley, rye, oats, sorghum and millet, rice, cassava and maize, or else crops of sugar beet, cotton, soya, oil seed rape, potatoes, tomatoes, peas and other vegetables.
• cereals such as wheat, barley, rye, oats, sorghum and millet
• rice, cassava and maize or else crops of sugar beet, cotton, soya, oil seed rape, potatoes, tomatoes, peas and other vegetables.
• the compounds of the formula (I) can preferably be employed as herbicides in crops of useful plants which are resistant to the phytotoxic effects of the herbicides or have been rendered thus by means of genetic engineering.
• transgenic crop plants which are resistant to certain herbicides of the glufosinate type (cf., for example, EP-A0242236, EP-A-242246) or the glyphosate type (WO 92/00377) or the sulfonylurea type (EP-A-0257993, U.S. Pat. No. 5,013,659),
• transgenic crop plants for example cotton, which are capable of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to specific pests (EP-A-01 42924, EP-A01 93259),
• transgenic crop plants whose fatty acid spectrum is modified (WO 91113972).
• nucleic acid molecules may be introduced into plasmids which allow mutagenesis or a sequence change by means of recombination of DNA sequences. It is possible, for example, with the aid of the abovementioned standard methods to perform base exchanges, to remove subsequences or to add natural or synthetic sequences.
• adaptors or linkers may be attached to the fragments.
• plant cells with a reduced activity of a gene product can be generated by expressing at least one corresponding antisense RNA, a sense RNA to achieve a cosuppressory effect or by expressing at least one ribozyme of suitable construction which specifically cleaves transcripts of the abovementioned gene product.
• DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present on the other hand DNA molecules which only encompass parts of the coding sequence, but these parts must be long enough in order to effect, in the cells, an antisense effect.
• Use may also be made of DNA sequences which show a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
• the protein which has been synthesized may be located in any desired compartment of the plant cell.
• sequences are known to the skilled worker (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).
• the transgenic plant cells may be regenerated by known techniques to give complete plants.
• the transgenic plants can be plants of any desired plant species, that is to say monocotyledonous and also dicotyledonous plants.
• the compounds (I) according to the invention can preferably be employed in transgenic crops which are resistant to herbicides from the group of the sulfonylureas, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances.
• the invention therefore also relates to the use of the compounds (1) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
• the use according to the invention for controlling harmful plants or for regulating the growth of plants also includes the case where the active substance of the formula (I) or a salt thereof is only formed in the plant or the soil from a precursor (“prodrug”) after its application to the plant.
• the compounds according to the invention can be employed in the conventional preparations as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules.
• the invention therefore also relates to herbicidal and plant-growth-regulating compositions which comprise compounds of the formula (I).
• the compounds of the formula (I) can be formulated in various ways, depending on the prevailing biological and/or chemico-physical parameters.
• examples of possible formulations which are suitable are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions on an oil or water basis, solutions which are miscible with oil, capsule suspensions (CS), dusts (DP), seed-dressing products, granules for broadcasting and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
• WP wettable powder
• Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also comprise ionic and/or nonionic surfactants (wetters, dispersants), for example, polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates or alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2′-dinaphthylmethane-6,6'disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurinate, in addition to a diluent or inert substance.
• ionic and/or nonionic surfactants for example, polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated
• the herbicidal active substances are, for example, ground finely in conventional apparatuses such as hammer mills, blower mills and air-jet mills and mixed with the formulation auxiliaries, either concomitantly or thereafter.
• Emulsifiable concentrates are prepared, for example, by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of these, with addition of one or more ionic and/or nonionic surfactants (emulsifiers).
• organic solvent for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of these, with addition of one or more ionic and/or nonionic surfactants (emulsifiers).
• Emulsifiers which can be used are, for example: calcium salts of alkylarylsulfonic acids, such as calcium dodecylbenzenesulfonate or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty acid esters.
• alkylarylsulfonic acids such as calcium dodecylbenzenesulfonate or nonionic emulsifiers
• fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates
• alkyl polyethers sorbitan esters such as sorbitan
• Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc or natural clays, such as kaolin, bentonite or pyrophyllite, or diatomaceous earth.
• finely divided solid substances for example talc or natural clays, such as kaolin, bentonite or pyrophyllite, or diatomaceous earth.
• Suspension concentrates may be water- or oil-based. They can be prepared, for example, by wet grinding by means of commercially available bead mills, if appropriate with addition of surfactants, as they have already been mentioned above for example in the case of the other formulation types.
• Emulsions for example oil-in-water emulsions (EW)
• EW oil-in-water emulsions
• Granules can be prepared either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carriers such as sand, kaolinites or of granulated inert material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or alternatively mineral oils. Suitable active substances can also be granulated in the manner which is conventional for the production of fertilizer granules, if desired in a mixture with fertilizers.
• Water-dispersible granules are prepared, as a rule, by the customary processes such as spray-drying, fluidized-bed granulation, disk granulation, mixing in high-speed mixers and extrusion without solid inert material.
• To prepare disk, fluidized-bed, extruder and spray granules see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 et seq.; “Perry's Chemical Engineer's Handbook”, 5th Ed., McGraw-Hill, New York 1973, p. 8-57.
• the agrochemical preparations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active substance of the formula (I).
• the active substance concentration in wettable powders is, for example, approximately 10 to 90% by weight, the remainder to 100% by weight being composed of customary formulation components.
• the active substance concentration can amount to approximately 1 to 90, preferably 5 to 80,% by weight.
• Formulations in the form of dusts usually comprise 1 to 30% by weight of active substance, preferably in most cases 5 to 20% by weight of active substance, while sprayable solutions comprise approximately 0.05 to 80, preferably 2 to 50,% by weight of active substance.
• the active substance content depends partly on whether the active compound is in liquid or solid form and on which granulation auxiliaries, fillers and the like are being used.
• the water-dispersible granules for example, comprise between 1 and 95% by weight of active substance, preferably between 10 and 80% by weight.
• the active substance formulations mentioned comprise, if appropriate, the adhesives, wetters, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors, pH regulators and viscosity regulators which are conventional in each case.
• Active substances which can be employed as components in mixed formulations or in a tank mix, together with the active substances according to the invention are, for example, known active substances as they are described in, for example, Weed Research 26, 441445 (1986), or “The Pesticide Manual”, 10th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1994 and the literature cited therein.
• Herbicides which are known from the literature and which may be combined with the compounds of the formula (I) are, for example, the following active substances (note: the compounds are either designated by the “common name” of the International Organization for Standardization (ISO) or by the chemical name, if appropriate together with a customary code number): acetochlor; acifluorfen; aclonifen; AKH 7088, i.e.
• the formulations which are present in commercially available form are, if appropriate, diluted in the customary manner, for example using water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules.
• Preparations in the form of dusts, soil granules, granules for broadcasting and sprayable solutions are conventionally not diluted further with other inert substances prior to use.
• the application rate required of the compounds of the formula (I) varies with the external conditions such as, inter alia, temperature, humidity and the nature of the herbicide used. It may vary within wide limits, for example between 0.001 and 10.0 kg/ha or more of active substance, but it is preferably between 0.005 and 5 kg/ha.
• a solution prepared from 0.32 g (0.014 mol) of sodium and 10 ml of methanol is added to 1.90 g (0.00613 mol) of 3-phenyl-1-cyclobutyl-1-(biguanidino)propane hydrochloride in 30 ml of methanol and 2 g of molecular sieve 3 ⁇ (Angstrom). Then, 1.10 g (0.0092 mol) of methyl 1-fluoro-1-methylpropionate are added dropwise and the mixture is stirred first for 2 hours at 25° C. and then for 4 hours at 65° C. The reaction mixture is filtered, the filtrate is concentrated and the residue is taken up in ethyl acetate.
• a methoxide solution prepared from 1.2 g (0.05 mol) of sodium and 100 ml of methanol is added to 8.1 g (0.025 mol) of 3-(3,5-dimethylphenyl)-1-cyclopropyl-1-(1-biguanidino)propane hydrochloride in 50 ml of methanol and 7 g of ground molecular sieve 3 ⁇ .
• 5.4 g (0.045 mol) of methyl 1-fluoro-1-methylpropionate are added and the mixture is stirred for 2 hours at 25° C. and then for 4 hours at 65° C.
• the reaction mixture is filtered, the filtrate is concentrated and the residue is taken up in ethyl acetate.
• a methoxide solution prepared from 1.2 g (0.05 mol) of sodium and 100 ml of methanol is added to 8.4 g (0.025 mol) of 4-(3,5-dimethylphenyl)-i-cyclopropyl-1-(1-biguanidino)butane hydrochloride in 50 ml of methanol and 7 g of ground molecular sieve 3 ⁇ .
• 5.4 g (0.045 mol) of methyl 1-fluoro-1-methyl-propionate are then added and the mixture is stirred for 2 hours at 25° C. and then for 4 hours at 65° C.
• the reaction mixture is filtered, the filtrate is concentrated and the residue is taken up in ethyl acetate.
• a dust is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as inert material and grinding the mixture in a hammer mill.
• a wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetter and dispersant and grinding the mixture in a pinned-disk mill.
• a dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example approx. 255 to above 277° C.) and grinding the mixture in a ball mill to a fineness of below 5 microns.
• alkylphenol polyglycol ether ®Triton X 207
• isotridecanol polyglycol ether 8 EO
• paraffinic mineral oil oil
• An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol as emulsifier.
• water-dispersible granules are obtained by homogenizing and precomminuting, on a colloid mill,
• Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds plants are placed in sandy loam soil in plastic pots and covered with soil.
• the compounds according to the invention which are formulated in the form of wettable powders or emulsion concentrates are then applied to the surface of the soil cover in the form of an aqueous suspension or emulsion at an application rate of 600 to 800 l of water/ha (converted), in various dosages.
• the pots are placed in the greenhouse and kept under good growth conditions for the weeds. After the test plants have emerged, the damage to the plants or the negative effect on the emergence is scored visually after a test period of 3 to 4 weeks by comparison with untreated controls. As shown by the test results, the compounds according to the invention have a good herbicidal pre-emergence action against a broad range of grass weeds and dicotyledonous weeds. For example, Example Nos.
• the agents according to the invention also have a good herbicidal post-emergence action against a broad range of economically important grass weeds and dicotyledonous weeds.
• Transplanted and seeded rice and typical broad-leaved and monocotyledonous rice weeds are grown in the greenhouse to the three-leaf stage ( Echinochloa crus - galli 1.5 leaf) under paddy rice conditions (depth of the water 2-3 cm) in sealed plastic pots. They are then treated with the compounds according to the invention.
• the formulated active substances are suspended, dissolved or emulsified in water and applied in various dosages by pouring into the water with which the test plants are flooded. After this treatment, the test plants are placed in the greenhouse under ideal growth conditions and kept thus over the entire experimental period.
• the test is evalued by means of visually scoring the damage to the plants by comparison with untreated controls.
• the compounds according to the invention have a very good herbicidal action against harmful plants.
• the compounds of Example Nos. 4-1, 4-2, 4-14, 4-15, 4-23, 4-24, 94, 9-5, 9-9, 9-7 and 9-10 show, in the test, a very good herbicidal action against harmful plants which are typical for rice cultivation, such as, for example, Cyperus monti, Echinochloa crusgalli and Sagittaria pygmaea.
• some substances also leave Gramineae crops such as, for example, barley, wheat, rye, sorghum, maize or rice unharmed.
• Gramineae crops such as, for example, barley, wheat, rye, sorghum, maize or rice unharmed.

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