WO1996011188A1 - Sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur - Google Patents

Sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur Download PDF

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Publication number
WO1996011188A1
WO1996011188A1 PCT/EP1995/003768 EP9503768W WO9611188A1 WO 1996011188 A1 WO1996011188 A1 WO 1996011188A1 EP 9503768 W EP9503768 W EP 9503768W WO 9611188 A1 WO9611188 A1 WO 9611188A1
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Prior art keywords
fluorine
chlorine
alkyl
optionally substituted
alkoxy
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PCT/EP1995/003768
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German (de)
French (fr)
Inventor
Klaus Helmut MÜLLER
Klaus König
Hans-Joachim Santel
Markus Dollinger
Klaus Stenzel
Original Assignee
Bayer Aktiengesellschaft
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Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to EP95934107A priority Critical patent/EP0784616A1/en
Priority to AU36526/95A priority patent/AU3652695A/en
Priority to CA 2201596 priority patent/CA2201596A1/en
Priority to JP8512286A priority patent/JPH10508298A/en
Publication of WO1996011188A1 publication Critical patent/WO1996011188A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C337/02—Compounds containing any of the groups, e.g. thiocarbazates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to new sulfonylaminocarbonyltriazolinones with substituents bonded via oxygen and sulfur, several ner drives and various new intermediates for their preparation and their use as herbicides and fungicides.
  • Oxygen and sulfur-bonded substituents are known (see the following "disclaimer"). However, the action of these previously known compounds is not satisfactory in all respects.
  • R 1 represents hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl,
  • R 2 represents an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl, aryl, and
  • R 3 represents an optionally substituted radical from the series alkyl, aralkyl, aryl, heteroaryl, and salts of compounds of the formula (I), where the compounds 4-methoxy-5-methylthio-2- (2-methoxycarbonyl -phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5-ethylthio-2- [2- (N-methoxy) -methylaminosulfonyl-phenylsulfonyl-aminocarbonyl ] -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-propoxy-5-allylthio-2- (2-methylphenylsulfonylaminocarbonyl) -2,4-dihydro-3H- 1,2,4-triazol-3-one, 4-methoxy-5-methylthio-2- (2-methoxycarbonylthien-3
  • n, R 1 and R 2 have the meaning given above and Z represents halogen, alkoxy, aralkoxy or aryloxy, with sulfonamides of the general formula (V)
  • R 3 has the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if
  • R 3 has the meaning given above and
  • Z represents halogen, alkoxy, aralkoxy or aryloxy, optionally in the presence of an acid acceptor and optionally in
  • R 3 has the meaning given above and
  • X represents halogen, and metal cyanates of the general formula (VIII) MOCN (VIII) in which
  • M represents an alkali metal or alkaline earth metal equivalent, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and if appropriate the compounds of the formula (I) obtained by processes (a), (b), (c) or (d) converted into salts by conventional methods.
  • R 2 is propargyl
  • the new sulfonylaminocarbonyltriazolinones with substituents of the general formula (I) bonded via oxygen and sulfur are notable for strong herbicidal and fungicidal activity.
  • the new compounds of the formula (I) have a considerably stronger herbicidal action than structurally similar compounds which are representative of the prior art, such as e.g. the well-known 4-amino-5-methylthio-2- (2-trifluoromethoxy-phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one.
  • the invention preferably relates to compounds of the formula (I) in which n represents the numbers 0, 1 or 2, R 1 is hydrogen, optionally by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 alkylcarbonyl or C 1 -C 4 alkoxycarbonyl substituted C 1 - C 6 alkyl, each for C 2 -C 6 alkenyl or C 2 - optionally substituted by fluorine, chlorine and / or bromine C 6 -alkynyl, for C 3 -C 6 -cycloalkyl or in each case optionally substituted by fluorine, chlorine, bromine and / or C 1 -C 4 -alkyl
  • C 5 -C 6 cycloalkenyl or for each optionally by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy and / or C 1 -C 4 alkoxy carbonyl-substituted phenyl or phenyl-C 1 -C 3 -alkyl
  • R 2 is optionally fluorine, chlorine, bromine cyano, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 - Alkylthio or C 1 -C 4 alkoxy-carbonyl substituted C 1 -C 6 alkyl, each for C 2 -C 6 alkenyl or C 2 -C 6 alkynyl optionally substituted by fluorine, chlorine and / or bromine, for each is optionally substituted by fluorine, chlorine, bromine and / or C 1 -C 4
  • R 4 and R 5 are identical or different and are hydrogen, fluorine, chlorine, bromine, iodine, nitro, C 1 -C 6 -alkyl (which may be replaced by fluorine,
  • R 6 for C 1 -C 4 alkyl (which may be replaced by fluorine, chlorine,
  • R 4 and / or R 5 furthermore for phenyl or phenoxy, for C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxycarbonylamino, C 1 -C 4 alkylaminocarbonylamino, di- (C 1 - C 4 alkyl) amino carbonylamino, or for the radical -CO-R 8 , where
  • R 10 is hydrogen or C 1 -C 4 alkyl
  • R 1 1 and R 12 are the same or different and are hydrogen, fluorine, chlorine,
  • R 3 represents the rest
  • R 13 and R 14 are the same or different and are hydrogen, fluorine, chlorine,
  • R 3 represents the rest.
  • R 1 5 and R 16 are the same or different and are hydrogen, fluorine,
  • Farther R 3 represents the rest,
  • R 1 7 and R 18 are the same or different and are hydrogen, fluorine,
  • R 3 represents the rest
  • R 19 and R 20 are the same or different and are hydrogen, fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 -alkyl (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 -alkoxy (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine), Di - (C 1 -C 4 -alkyl) -aminosulfonyl, C 1 -C 4 -alkoxy-carbonyl or dimethylaminocarbonyl, and
  • A stands for oxygen, sulfur or the grouping NZ, where Z stands for hydrogen, C 1 -C 4 -alkyl (which may be replaced by fluorine,
  • Chlorine, bromine or cyano is substituted), C 3 -C 6 cycloalkyl, benzyl, phenyl (which may be replaced by fluorine, chlorine, bromine or nitro is substituted), C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl or di- (C 1 -C 4 alkyl) aminocarbonyl;
  • R 3 represents the rest
  • R 21 and R 22 are identical or different and represent hydrogen, C 1 - C 4 alkyl, halogen, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 alkoxy or C 1 - C 4 haloalkoxy stand,
  • Y 1 represents sulfur or the grouping NR 23 , where
  • R 23 represents hydrogen or C 1 -C 4 alkyl
  • R 3 represents the rest
  • R 24 represents hydrogen, C 1 -C 4 alkyl, benzyl, pyndyl, quinolinyl or phenyl
  • R 25 represents hydrogen, halogen, cyano, nitro, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine is), C 1 -C 4 alkoxy
  • R 26 represents hydrogen, halogen or C 1 -C 4 alkyl, and furthermore R 3 stands for one of the groupings listed below,
  • the invention further preferably relates to sodium, potassium, magnesium, calcium, ammonium, C 1 -C 4 alkyl ammonium, di (C 1 -C 4 alkyl) ammonium,
  • the invention relates in particular to compounds of the formula (I) in which n represents the numbers 0, 1 or 2,
  • R 1 for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, for each optionally substituted by fluorine, chlorine or bromine Propenyl, butenyl, propynyl or butynyl, each optionally with fluorine, chlorine, bromine,
  • R 2 for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by fluorine, chlorine, cyano, methoxy, ethoxy, methylthio or ethylthio, for each optionally by fluorine, Chlorine or bromine-substituted propenyl, butenyl, propynyl, butynyl or allenyl, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclo- butylmethyl, cyclopentylmethyl or cyclohexylmethyl or phenyl or benzyl optionally substituted by fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy,
  • R 3 represents the rest
  • R 4 for fluorine, chlorine, bromine, methyl, ethyl, propyl, trifluoromethyl, butoxy,
  • R 3 represents the rest
  • R 10 represents hydrogen
  • R 1 1 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or dimethylaminosulfonyl and R 12 represents hydrogen;
  • R 3 represents the rest
  • R represents C 1 -C 4 alkyl
  • R 3 represents the rest
  • R 24 stands for C 1 -C 3 alkyl, phenyl or pyridyl
  • R 25 stands for hydrogen, fluorine, chlorine or bromine
  • R 26 stands for fluorine, chlorine, bromine or C 1 -C 3 alkoxycarbonyl, with the exception of the connections excluded by disclaimer above.
  • hydrocarbon radicals mentioned in the radical definitions such as alkyl, alkenyl or alkynyl, also in combinations with heteroatoms, such as in alkoxy, alkylthio or alkylamino, are straight-chain or branched, even if this is not expressly stated.
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
  • Formula (II) provides a general definition of the triazolinones to be used as starting materials in processes (a), (c) and (d) for the preparation of compounds of the formula (I).
  • n, R 1 and R 2 preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for n, R 1 and R 2 were specified.
  • R 2 has the meaning given above and
  • X represents halogen or the group -O-SO 2 -OR 2 , optionally in the presence of an acid acceptor, such as potassium hydroxide, potassium t-butoxide or potassium carbonate, and optionally in the presence of a diluent, such as methanol or ethanol, at temperatures between 0 ° C and 100 ° C and optionally subsequently oxidized in a conventional manner to corresponding sulfoxides or sulfones (see. The preparation examples).
  • R 1 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 1 .
  • the preferred metal salts of the compounds of formula (IX) are the alkali metal salts and alkaline earth metal salts, in particular the sodium, potassium, magnesium and
  • the mercapto-triazolinones of the general formula (IX) - and their meta salts - are not yet known from the literature; as new substances, they are also the subject of the present application.
  • the new mercaptotriazolinones of the formula (IX) are obtained when using semicarbazide
  • Y represents halogen, imidazolyl, alkoxy, aralkoxy or aryloxy, optionally in the presence of a reaction auxiliary, e.g. Potassium carbonate, and optionally in the presence of a diluent, e.g. Methanol or ethanol, at temperatures between 20 ° C and 150 ° C (see. The manufacturing examples).
  • a reaction auxiliary e.g. Potassium carbonate
  • a diluent e.g. Methanol or ethanol
  • R 1 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 1 ;
  • Y preferably represents fluorine, chlorine, bromine, iodine, methoxy, ethoxy,
  • the semicarbazide derivatives of the general formula (XI) are not yet known from the literature; as new substances, they are also the subject of the present application.
  • the new semicarbazide derivatives of the formula (XI) are obtained if semicarbazides of the general formula (XII)
  • X 1 -CS-Y in which Y has the meaning given above and X 1 represents halogen, if appropriate in the presence of an acid acceptor, such as, for example, triethylamine, and if appropriate in the presence of a diluent, such as, for example, methylene chloride, at temperatures between 0 ° C. and 100 ° C. (cf. the preparation examples).
  • an acid acceptor such as, for example, triethylamine
  • a diluent such as, for example, methylene chloride
  • the precursors of the formula (XIII) are known synthetic chemicals.
  • Formula (X) provides a general definition of the alkylating agents required for the preparation of the starting materials of the formula (II).
  • R 2 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 2 ;
  • X preferably represents fluorine, chlorine, bromine or iodine, in particular chlorine, bromine or iodine.
  • the compounds of formula (X) are known synthetic chemicals.
  • Formula (III) provides a general definition of the sulfonyl isocyanates to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I).
  • R 3 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 3 .
  • the starting materials of the formula (III) are known and / or can be prepared by processes known per se (cf. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687, EP-A 13480, EP- A 21641, EP-A 23141, EP-A 23422, EP ⁇
  • Formula (IV) provides a general definition of the triazolinone derivatives to be used as starting materials in process (b) according to the invention for the preparation of the compounds of the general formula (I).
  • n, R 1 and R 2 preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for n, R 1 and R 2 were specified;
  • Z preferably represents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogen or nitro-phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.
  • Z has the meaning given above and Z 1 represents halogen, alkoxy, aralkoxy or aryloxy, optionally in the presence of an acid acceptor, such as potassium t-butoxide, and optionally in the presence of a diluent, such as tetrahydrofuran or dimethoxyethane, at temperatures between 0 ° C and 100 ° C.
  • an acid acceptor such as potassium t-butoxide
  • a diluent such as tetrahydrofuran or dimethoxyethane
  • Formula (V) provides a general definition of the sulfonamides to be used as starting materials in process (b) according to the invention for the preparation of the compounds of the general formula (I).
  • R 3 preferably or in particular has the meaning which has already been given above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R 3 .
  • the starting materials of the formula (V) are known and / or can be prepared by processes known per se (cf.
  • Formula (I) sulfonic acid amide derivatives to be used as starting materials are generally defined by the formula (VI).
  • R 3 preferably or in particular has the meaning which has already been given above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R 3 ;
  • Z preferably represents fluorine, chlorine, bromine,
  • Methoxy, ethoxy, benzyloxy or phenoxy especially for methoxy or phenoxy.
  • the starting materials of the formula (VI) are known and / or can be prepared by processes known per se.
  • R 3 preferably or in particular has the meaning which has already been given above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R 3 ;
  • X preferably represents fluorine, chlorine or bromine, especially chlorine.
  • the starting materials of the formula (VII) are known and / or can be prepared by processes known per se.
  • Processes (a), (b), (c) and (d) according to the invention for the preparation of the new compounds of the formula (I) are preferably carried out using diluents. Practically all inert organic solvents can be used as diluents.
  • These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and Dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl ester, nitriles such as, for example Acetonitrile and propionitrile, amides such as e.g. Dimethylformamide, dimethyl
  • all acid binders which can customarily be used for such reactions can be used as reaction auxiliaries or as acid acceptors.
  • Alkali metal hydroxides such as e.g. Sodium and potassium hydroxide, alkaline earth metal hydroxides such as e.g. Calcium hydroxide, alkali carbonates and alcoholates such as sodium and potassium carbonate,
  • Sodium and potassium tert-butoxide also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethyl-aniline, pyridine, 2 , 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 2-ethyl, 4-ethyl and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo [4,3,0] -non-5-ene (DBN), 1,8-diazabicyclo- [5,4,0] -undec-7-ene (DBU) and 1,4-diazabicyclo [2,2, 2] octane (DABCO).
  • basic nitrogen compounds such as trimethylamine, trieth
  • reaction temperatures can be varied within a wide range in processes (a), (b), (c) and (d). In general, temperatures between -20 ° C and + 100 ° C, preferably at temperatures between
  • the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use a larger excess of one of the components used in each case.
  • the reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case. Working up takes place in the method according to the invention
  • salts can be prepared from the compounds of the general formula (I) according to the invention.
  • Such salts are obtained in a simple manner by customary salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent, e.g. Methylene chloride, acetone, tert-butyl methyl ether or toluene, and addition of a suitable base.
  • a suitable solvent e.g. Methylene chloride, acetone, tert-butyl methyl ether or toluene
  • the salts can then be isolated - if appropriate after prolonged stirring - by concentration or suction.
  • the active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers.
  • the active compounds according to the invention can e.g. can be used in the following plants:
  • the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover.
  • the compounds for weed control in permanent crops e.g. Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture land and for selective purposes Weed control can be used in annual crops.
  • the compounds of formula (I) according to the invention are particularly suitable for the selective control of dicotyledon weeds in monocotyledon crops both in the pre-emergence and in the post-emergence process.
  • the active compounds of the formula (I) according to the invention also show interesting fungicidal activity against phytopathogenic fungi, in particular against
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, natural and synthetic substances impregnated with active substances, and very fine encapsulations in polymeric substances
  • Formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents
  • organic solvents can, for example, also be used as auxiliary solvents.
  • Liquid solvents are essentially suitable.
  • Aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone,
  • Solid carrier materials that come into question are, for example, ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates, and solid carrier materials for granules are suitable "eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, come as emulsifiers and / or foam-producing agents in question: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sul
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight
  • Active ingredient preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.
  • known herbicides for example anilides, such as e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, e.g.
  • Linuron and metambazthiazuron Hydroxylamines such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; Imidazolinones such as imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as bromoxynil, dichlobenil and ioxynil; Oxyacetamides such as mefenacet; Sulfonylureas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, Met- sulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuronmethyl, triasulfuron and tribenuron-methyl; Thiol carbamates such as butylates, cycloates, dialallates, EPTC, es
  • a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying,
  • the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
  • the amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 10 g and 10 kg of active ingredient per hectare of soil, preferably between 50 g and 5 kg per ha.
  • Example 62 The compound listed in Table 1 as Example 62 can be produced, for example, as follows:
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, mix 1
  • Test plants with a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area.
  • the concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 2000 l of water / ha.
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • 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 active ingredient preparation is poured onto the floor. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
  • Emulsifier 0.3 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%.
  • Evaluation is carried out 12 days after the inoculation.
  • the compounds according to Preparation Examples 1, 4, 5 and 6 show an efficiency of 100% at an active ingredient concentration of 10 ppm.

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Abstract

New sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur have the formula (I), in which n equals 0, 1 or 2; R1 stands for hydrogen or an optionally substituted rest from the group alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl, aralkyl; R2 stands for an optionally substituted rest from the group alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl, aryl; and R3 stands for an optionally substituted rest from the group alkyl, aralkyl, aryl, heteroaryl. Certain new compounds having the formula (I) but already disclosed in EP-A 431291, are excluded. Also disclosed are salts of the new compounds having the formula (I), several processes and various new intermediate products for preparing the new compounds and their use - possibly as salts - as herbicides and fungicides.

Description

Pulfonylaminocarbonyltriazolinone mit über Sauerstoff und Schwefel  Pulfonylaminocarbonyltriazolinone with over oxygen and sulfur
gebundenen Substituenten bound substituents
Die Erfindung betrifft neue Sulfonylaminocarbonyltriazolinone mit über Sauerstoff und Schwefel gebundenen Substituenten, mehrere Nerfahren und verschiedene neue Zwischenprodukte zu ihrer Herstellung sowie ihre Verwendung als Herbizide und Fungizide. The invention relates to new sulfonylaminocarbonyltriazolinones with substituents bonded via oxygen and sulfur, several ner drives and various new intermediates for their preparation and their use as herbicides and fungicides.
Es ist bereits bekannt, daß bestimmte Sulfonylaminocarbonyltriazolinone, wie z.B. die Verbindung 4-Amino-5-methylthio-2-(2-trifluormethoxy-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, herbizide Eigenschaften aufweisen (vgl. EPA 341489; EP-A 422469; EP-A 425948; EP-A 431291). Aus dem letztgenannten Dokument sind auch bereits einige Sulfonylaminocarbonyltriazolinone mit überIt is already known that certain sulfonylaminocarbonyltriazolinones, e.g. the compound 4-amino-5-methylthio-2- (2-trifluoromethoxy-phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, have herbicidal properties (cf. EPA 341489 ; EP-A 422469; EP-A 425948; EP-A 431291). Some sulfonylaminocarbonyltriazolinones are also from the latter document with over
Sauerstoff und Schwefel gebundenen Substituenten bekannt (vgl. den nachfolgenden "Disclaimer"). Die Wirkung dieser vorbekannten Verbindungen ist jedoch nicht in allen Belangen zufriedenstellend. Oxygen and sulfur-bonded substituents are known (see the following "disclaimer"). However, the action of these previously known compounds is not satisfactory in all respects.
Es wurden nun die neuen Sulfonylaminocarbonyltriazolinone mit über Sauerstoff und Schwefel gebundenen Substituenten der allgemeinen Formel (I), The new sulfonylaminocarbonyltriazolinones with substituents of the general formula (I) bonded via oxygen and sulfur
Figure imgf000003_0001
in welcher n für die Zahlen 0, 1 oder 2 steht, R 1 fur Wasserstoff oder fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Aryl, Aralkyl steht,
Figure imgf000003_0001
in which n stands for the numbers 0, 1 or 2, R 1 represents hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl,
R2 fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Cycloalkylalkyl, Aralkyl, Aryl steht, und R 2 represents an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl, aryl, and
R3 fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Ar- alkyl, Aryl, Heteroaryl steht, sowie Salze von Verbindungen der Formel (I) gefunden, wobei die Verbindungen 4-Methoxy-5-methylthio-2-(2-methoxycarbonyl-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Ethoxy-5-ethylthio-2-[2-(N-methoxy)-methylaminosulfonyl-phenylsulfonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Propoxy-5-allylthio-2-(2-methyl-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Methoxy-5-methylthio-2-(2-methoxycarbonylthien-3-yl-sulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Ethoxy-5-methylthio-2-(2-methoxy-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Ethoxy-5-ethylthio-2-[2-(2-chlor-ethoxy)-phenylsulfonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Allyloxy-5-ethylthio-2-(2-fluor-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Methoxy-5-ethylthio-2-(3- aminosulfonyl-pyridin-2-yl-sulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3- on und 4-Methoxy-5-ethylthio-2-(2,6-difluor-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on - bekannt aus EP-A 431291 - durch Disclaimer ausgeschlossen sind. R 3 represents an optionally substituted radical from the series alkyl, aralkyl, aryl, heteroaryl, and salts of compounds of the formula (I), where the compounds 4-methoxy-5-methylthio-2- (2-methoxycarbonyl -phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5-ethylthio-2- [2- (N-methoxy) -methylaminosulfonyl-phenylsulfonyl-aminocarbonyl ] -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-propoxy-5-allylthio-2- (2-methylphenylsulfonylaminocarbonyl) -2,4-dihydro-3H- 1,2,4-triazol-3-one, 4-methoxy-5-methylthio-2- (2-methoxycarbonylthien-3-yl-sulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4- triazol-3-one, 4-ethoxy-5-methylthio-2- (2-methoxy-phenylsulfonylaminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy- 5-ethylthio-2- [2- (2-chloroethoxy) phenylsulfonylaminocarbonyl] -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-allyloxy-5-ethylthio- 2- (2-fluoro-phenylsulfonylaminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-methoxy-5-ethylthio-2- (3-aminosulfonyl-pyridine-2 -yl-sulf onylaminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one and 4-methoxy-5-ethylthio-2- (2,6-difluorophenylsulfonylaminocarbonyl) -2.4 dihydro-3H-1,2,4-triazol-3-one - known from EP-A 431291 - are excluded by disclaimers.
Man erhält die neuen Sulfonylaminocarbonyltriazolinone mit über Sauerstoff und Schwefel gebundenen Substituenten der Formel (I), wenn man The new sulfonylaminocarbonyltriazolinones with substituents of the formula (I) bonded via oxygen and sulfur are obtained if
(a) Triazolinone der allgemeinen Formel (II) - j
Figure imgf000005_0001
(a) triazolinones of the general formula (II) - j
Figure imgf000005_0001
in welcher n, R1 und R2 die oben angegebene Bedeutung haben, mit Sulfonylisocyanaten der allgemeinen Formel (III) R3-SO2-N=C=O (III) in welcher R3 die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder wenn man in which n, R 1 and R 2 have the meaning given above, with sulfonyl isocyanates of the general formula (III) R 3 -SO 2 -N = C = O (III) in which R 3 has the meaning given above, optionally in the presence a reaction auxiliary and optionally in the presence of a diluent, or if one
(b) Triazolinon-Derivate der allgemeinen Formel (IV) (b) triazolinone derivatives of the general formula (IV)
Figure imgf000005_0002
Figure imgf000005_0002
in welcher n, R1 und R2 die oben angegebene Bedeutung haben und Z fur Halogen, Alkoxy, Aralkoxy oder Aryloxy steht, mit Sulfonsäureamiden der allgemeinen Formel (V) in which n, R 1 and R 2 have the meaning given above and Z represents halogen, alkoxy, aralkoxy or aryloxy, with sulfonamides of the general formula (V)
R3-SO2-NH2 (V) in welcher R 3 -SO 2 -NH 2 (V) in which
R3 die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Saureakzeptors und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder wenn man R 3 has the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if
(c) Triazolinone der allgemeinen Formel (II) (c) triazolinones of the general formula (II)
Figure imgf000006_0001
Figure imgf000006_0001
in welcher n, R1 und R2 die oben angegebene Bedeutung haben, mit Sulfonsaureamid-Derivaten der allgemeinen Formel (VI) in which n, R 1 and R 2 have the meaning given above, with sulfonic acid amide derivatives of the general formula (VI)
R3-SO2-NH-CO-Z (VI) in welcher R 3 -SO 2 -NH-CO-Z (VI) in which
R3 die oben angegebene Bedeutung hat und R 3 has the meaning given above and
Z fur Halogen, Alkoxy, Aralkoxy oder Aryloxy steht, gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls inZ represents halogen, alkoxy, aralkoxy or aryloxy, optionally in the presence of an acid acceptor and optionally in
Gegenwart eines Verdünnungsmittels umsetzt, oder wenn man In the presence of a diluent, or if one
(d) Triazolinone der allgemeinen Formel (II)
Figure imgf000007_0001
(d) triazolinones of the general formula (II)
Figure imgf000007_0001
in welcher n, R1 und R2 die oben angegebene Bedeutung haben, mit Sulfonsäurehalogeniden der allgemeinen Formel (VII) R3-SO2-X (VII) in welcher in which n, R 1 and R 2 have the meaning given above, with sulfonic acid halides of the general formula (VII) R 3 -SO 2 -X (VII) in which
R3 die oben angegebene Bedeutung hat und R 3 has the meaning given above and
X fur Halogen steht, und Metallcyanaten der allgemeinen Formel (VIII) MOCN (VIII) in welcher X represents halogen, and metal cyanates of the general formula (VIII) MOCN (VIII) in which
M fur ein Alkalimetall oder Erdalkalimetall-äquivalent steht, gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, und gegebenenfalls die nach Verfahren (a), (b), (c) oder (d) erhaltenen Verbindungen der Formel (I) nach üblichen Methoden in Salze überfuhrt. M represents an alkali metal or alkaline earth metal equivalent, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and if appropriate the compounds of the formula (I) obtained by processes (a), (b), (c) or (d) converted into salts by conventional methods.
Soweit bei den neuen Verbindungen der Formeln (I), (II) und (IV) R2 fur Propargyl steht, können sie durch Behandeln mit Basen zu entsprechenden Verbindungen, bei denen R2 fur Allenyl (= Propa-1,2-dienyl) steht, isomerisiert werden (vgl. die HerStellungsbeispiele). Die neuen Sulfonylaminocarbonyltriazolinone mit über Sauerstoff und Schwefel gebundenen Substituenten der allgemeinen Formel (I) zeichnen sich durch starke herbizide und fungizide Wirksamkeit aus. If the new compounds of the formulas (I), (II) and (IV) R 2 is propargyl, they can be treated with bases to give corresponding compounds in which R 2 is allenyl (= propa-1,2-dienyl) isomerized (see the manufacturing examples). The new sulfonylaminocarbonyltriazolinones with substituents of the general formula (I) bonded via oxygen and sulfur are notable for strong herbicidal and fungicidal activity.
Überraschenderweise zeigen die neuen Verbindungen der Formel (I) erheblich stärkere herbizide Wirkung als strukturell ähnliche, fur den Stand der Technik repräsentative Verbindungen, wie z.B. das bekannte 4-Amino-5-methylthio-2-(2-trifluormethoxy-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on. Surprisingly, the new compounds of the formula (I) have a considerably stronger herbicidal action than structurally similar compounds which are representative of the prior art, such as e.g. the well-known 4-amino-5-methylthio-2- (2-trifluoromethoxy-phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one.
Gegenstand der Erfindung sind vorzugsweise Verbindungen der Formel (I), in welcher n fur die Zahlen 0, 1 oder 2 steht, R1 fur Wasserstoff, fur gegebenenfalls durch Fluor, Chlor, Brom, Cyano, C1-C4- Alkoxy, C1-C4-Alkyl-carbonyl oder C1-C4-Alkoxy-carbonyl substituiertes C1- C6-Alkyl, fur jeweils gegebenenfalls durch Fluor, Chlor und/oder Brom substituiertes C2-C6- Alkenyl oder C2-C6-Alkinyl, fur jeweils gegebenenfalls durch Fluor, Chlor, Brom und/oder C1-C4-Alkyl substituiertes C3-C6-Cycloalkyl oderThe invention preferably relates to compounds of the formula (I) in which n represents the numbers 0, 1 or 2, R 1 is hydrogen, optionally by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 alkylcarbonyl or C 1 -C 4 alkoxycarbonyl substituted C 1 - C 6 alkyl, each for C 2 -C 6 alkenyl or C 2 - optionally substituted by fluorine, chlorine and / or bromine C 6 -alkynyl, for C 3 -C 6 -cycloalkyl or in each case optionally substituted by fluorine, chlorine, bromine and / or C 1 -C 4 -alkyl
C5-C6-Cycloalkenyl, oder fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C1-C4-Alkyl, Trifluormethyl, C1-C4- Alkoxy und/oder C1-C4- Alkoxy-carbonyl substituiertes Phenyl oder Phenyl-C1-C3-alkyl steht, R2 fur gegebenenfalls durch Fluor, Chlor, Brom Cyano, C3-C6-Cycloalkyl, C1-C4- Alkoxy, C1-C4- Alkylthio oder C1-C4-Alkoxy-carbonyl substituiertes C1-C6- Alkyl, fur jeweils gegebenenfalls durch Fluor, Chlor und/oder Brom substituiertes C2-C6-Alkenyl oder C2-C6-Alkinyl, fur jeweils gegebenenfalls durch Fluor, Chlor, Brom und/oder C1-C4-Alkyl substituiertes C3-C6-Cycloalkyl, C5- C6-Cycloalkenyl oder C3-C6-Cycloalkyl-C1-C3-alkyl, fur gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C1-C4-Alkyl, Trifluormethyl, C1-C4-Alkoxy und/oder C1-C4-Alkoxy-carbonyl substituiertes Phenyl-C1-C3-alkyl, oder fur gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C1-C4-Alkyl, Trifluormethyl, C1-C4-Alkoxy, Fluor- und/oder Chlor-substituiertes C1-C3 -Alkoxy, C1-C4-Alkylthio, Fluor- und/oder Chlor-substituiertes C1-C3-Alkylthio, C1- C4-Alkyl-sulfinyl, C1-C4-Alkylsulfonyl und/oder C1-C4-Alkoxy-carbonyl substituiertes Phenyl steht, und C 5 -C 6 cycloalkenyl, or for each optionally by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy and / or C 1 -C 4 alkoxy carbonyl-substituted phenyl or phenyl-C 1 -C 3 -alkyl, R 2 is optionally fluorine, chlorine, bromine cyano, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 - Alkylthio or C 1 -C 4 alkoxy-carbonyl substituted C 1 -C 6 alkyl, each for C 2 -C 6 alkenyl or C 2 -C 6 alkynyl optionally substituted by fluorine, chlorine and / or bromine, for each is optionally substituted by fluorine, chlorine, bromine and / or C 1 -C 4 alkyl-substituted C 3 -C 6 -cycloalkyl, C 5 - C 6 cycloalkenyl or C 3 -C 6 -cycloalkyl-C 1 -C 3 alkyl, for phenyl-C 1 -C 3 optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 -alkyl, trifluoromethyl, C 1 -C 4 -alkoxy and / or C 1 -C 4 -alkoxy-carbonyl -alkyl, or for optionally by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy, fluorine and / or chlorine substituted C 1 -C 3 alkoxy, C 1 -C 4 alkylthio, fluorine and / or chlorine substituted C 1 -C 3 alkylthio, C 1 - C 4 alkyl sulfinyl, C 1 -C 4 alkyl sulfonyl and / or C 1 -C 4 alkoxy carbonyl substituted phenyl, and
fur die Gruppierung steht,
Figure imgf000009_0001
represents the grouping,
Figure imgf000009_0001
worin wherein
R4 und R5 gleich oder verschieden sind und fur Wasserstoff, Fluor, Chlor, Brom, lod, Nitro, C1-C6-Alkyl (welches gegebenenfalls durch Fluor,R 4 and R 5 are identical or different and are hydrogen, fluorine, chlorine, bromine, iodine, nitro, C 1 -C 6 -alkyl (which may be replaced by fluorine,
Chlor, Brom, Cyano, Carboxy, C1-C4-Alkoxycarbonyl, C1-C4-Alkylamino-carbonyl, Di-(C1-C4-alkyl)amino-carbonyl, Hydroxy, C1-C4- Alkoxy, Formyloxy, C1-C4-Alkyl-carbonyloxy, C1-C4-Alkoxy-carbonyloxy, C1-C4-Alkylamino-carbonyloxy, C1-C4-Alkylthio, C1-C4- Alkylsulfinyl, C1-C4-Alkylsulfonyl, Di-(C1-C4-alkyl)-aminosulfonyl, C3-C6-Cycloalkyl oder Phenyl substituiert ist), fur C2-C6-Alkenyl (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, C1-C4- Alkoxy-carbonyl, Carboxy oder Phenyl substituiert ist), fur C2-C6- Alkinyl (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, C1- C4- Alkoxy-carbonyl, Carboxy oder Phenyl substituiert ist), fur C1-C4- Alkoxy (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Carboxy, C1-C4-Alkoxy-carbonyl, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4-Alkylsulfonyl substituiert ist), fur C1- C4-Alkylthio (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Carboxy, C1-C4-Alkoxy-carbonyl, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4- Alkylsulfonyl substituiert ist), fur C2-C6-Alkenyloxy (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano oder C1- C4-Alkoxy-carbonyl substituiert ist), fur C2-C6-Alkenylthio (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C1-C3- Alkylthio oder C1-C4-Alkoxycarbonyl substituiert ist), C3-C6- Alkinyloxy, C3-C6-Alkinylthio oder fur den Rest -S(O)p-R6 stehen, wobei p fur die Zahlen 1 oder 2 steht und Chlorine, bromine, cyano, carboxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino-carbonyl, di- (C 1 -C 4 alkyl) amino-carbonyl, hydroxy, C 1 -C 4 -alkoxy , Formyloxy, C 1 -C 4 alkylcarbonyloxy, C 1 -C 4 alkoxycarbonyloxy, C 1 -C 4 alkylamino carbonyloxy, C 1 -C 4 alkylthio, C 1 -C 4 - alkylsulfinyl, C 1 -C 4 alkylsulfonyl, di (C 1 -C 4 alkyl) aminosulfonyl, C 3 -C 6 cycloalkyl or phenyl is substituted for C 2 -C 6 alkenyl (which may be substituted by fluorine, chlorine, Bromine, cyano, C 1 -C 4 alkoxy-carbonyl, carboxy or phenyl is substituted) for C 2 -C 6 alkynyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C 1 - C 4 alkoxy carbonyl , Carboxy or phenyl), for C 1 -C 4 alkoxy (which may be substituted by fluorine, chlorine, bromine, cyano, carboxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl), for C 1 - C 4 alkylthio (which may be substituted by fluorine, chloro r, bromine, cyano, carboxy, C 1 -C 4 -alkoxy-carbonyl, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl is substituted), for C 2 -C 6- alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C 1 -C 4 -alkoxy-carbonyl) for C 2 -C 6 -alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 3 alkylthio or C 1 -C 4 alkoxycarbonyl is substituted), C 3 -C 6 alkynyloxy, C 3 -C 6 alkynylthio or for the radical -S (O) p -R 6 , where p represents the numbers 1 or 2 and
R6 fur C1-C4-Alkyl (welches gegebenenfalls durch Fluor, Chlor,R 6 for C 1 -C 4 alkyl (which may be replaced by fluorine, chlorine,
Brom, Cyano oder C1-C4-Alkoxy-carbonyl substituiert ist), C3- C6-Alkenyl, C3-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Alkoxy-C1- C4-alkylamino, C1-C4-Alkylamino, Di-(C1-C4-alkyl)-amino, Phenyl oder fur den Rest -NHOR7 steht, wobei R7 fur C1-C12- Alkyl (welches gegebenenfalls durch Fluor,Bromine, cyano or C 1 -C 4 alkoxy-carbonyl is substituted), C 3 - C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy-C 1 - C 4 alkylamino, C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, phenyl or for the radical -NHOR 7 , where R 7 is C 1 -C 12 alkyl (which may be caused by fluorine,
Chlor, Cyano, C1-C4- Alkoxy, C1-C4- Alkylthio, C1-C4-AIkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Alkyl-carbonyl, C1- C4-Alkoxy- carbonyl, C1-C4-Alkylamino-carbonyl oder Di- (C1-C4-alkyl)-amino-carbonyl substituiert ist), fur C3-C6- Alkenyl (welches gegebenenfalls durch Fluor, Chlor oder Brom substituiert ist), C3-C6-Alkinyl, C3-C6-CycloalkyI, C3 -C6-Cycloalkyl-C1-C2-alkyl, Phenyl-C1-C2-alkyl (welches gegebenenfalls durch Fluor, Chlor, Nitro, Cyano, C1-C4-Alkyl, C1-C4-Alkoxy oder C1-C4-Alkoxy-carbonyl substituiert ist), fur Benzhydryl oder fur Phenyl (welches gegebenenfalls durch Fluor, Chlor, Nitro, Cyano, C1-C4- Alkyl, Trifluormethyl, C1-C4-Alkoxy, C1-C2-Fluoralkoxy, C1-C4-Alkylthio, Trifluormethylthio oder C1-C4-Alkoxycarbonyl substituiert ist) steht, Chlorine, cyano, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkyl sulfinyl, C 1 -C 4 alkyl sulfonyl, C 1 -C 4 alkyl carbonyl, C 1 - C 4 -alkoxy-carbonyl, C 1 -C 4 -alkylamino-carbonyl or di- (C 1 -C 4 -alkyl) -amino-carbonyl), for C 3 -C 6 - alkenyl (which may be substituted by fluorine, chlorine or bromine is substituted), C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 2 alkyl, phenyl-C 1 -C 2 alkyl (which optionally by fluorine, chlorine, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 1 -C 4 alkoxy-carbonyl), for benzhydryl or for phenyl (which may be substituted by fluorine, chlorine , Nitro, cyano, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy, C 1 -C 2 fluoroalkoxy, C 1 -C 4 alkylthio, trifluoromethylthio or C 1 -C 4 alkoxycarbonyl ) stands,
R4 und/oder R5 weiterhin fur Phenyl oder Phenoxy, fur C1-C4-Alkylcarbonylamino, C1-C4-Alkoxy-carbonylamino, C1-C4-Alkylamino-carbonyl-amino, Di-(C1-C4-alkyl)-amino-carbonylamino, oder fur den Rest -CO-R8 stehen, wobei R 4 and / or R 5 furthermore for phenyl or phenoxy, for C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxycarbonylamino, C 1 -C 4 alkylaminocarbonylamino, di- (C 1 - C 4 alkyl) amino carbonylamino, or for the radical -CO-R 8 , where
R8 fur Wasserstoff, C1-C6-Alkyl, C3-C6-Cycloalkyl, C1-C6-Alkoxy, C3-C6-Cycloalkoxy, C3-C6-Alkenyloxy, C1-C4- Alkylthio, C1-C4- Alkylamino, C1-C4-Alk0xyam.no, C1-C4-Alkoxy-C1-C4-alkylamino oder Di-(C1-C4-alkyl)-amino steht (welche gegebenenfalls durch Fluor und/oder Chlor substituiert sind), R4 und/oder R5 weiterhin fur Trimethylsilyl, Thiazolinyl, C1-C4-Alkylsulfonyloxy, Di-(C1-C4-alkyl)-aminosulfonylamino oder fur den Rest -CH=N-R9 stehen, wobei R9 fur gegebenenfalls durch Fluor, Chlor, Cyano, Carboxy, C1-C4- Alkoxy, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4- Alkylsulfonyl substituiertes C1-C6-Alkyl, fur gegebenenfalls durch Fluor oder Chlor substituiertes Benzyl, fur gegebenenfalls durch Fluor oder Chlor substituiertes C3-C6-Alkenyl oder C3-C6- Alkinyl, fur gegebenenfalls durch Fluor, Chlor, Brom, C1-C4- Alkyl, C1-C4-Alkoxy, Trifluormethyl, Trifluormethoxy oder Trifluormethylthio substituiertes Phenyl, fur gegebenenfalls durch Fluor und/oder Chlor substituiertes C1-C6-Alkoxy, C3-C6-Alkenoxy, C3-C6-Alkinoxy oder Benzyloxy fur Amino, C1-C4-Alkylamino, Di-(C1-C4-alkyl)-amino, Phenylamino, C1-C4-Alkyl-carbonylamino, C1-C4-Alkoxy-carbonylamino, C1-C4-Alkyl-sulfonylamino oder fur gegebenenfalls durch Fluor, Chlor, Brom oder Methyl substituiertes Phenylsulfonylamino steht, weiterhin R 8 for hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy, C 3 -C 6 alkenyloxy, C 1 -C 4 - Alkylthio, C 1 -C 4 alkylamino, C 1 -C 4 alkoxyam.no, C 1 -C 4 alkoxy-C 1 -C 4 alkylamino or di- (C 1 -C 4 alkyl) amino stands (which are optionally substituted by fluorine and / or chlorine), R 4 and / or R 5 furthermore represent trimethylsilyl, thiazolinyl, C 1 -C 4 -alkylsulfonyloxy, di- (C 1 -C 4 -alkyl) -aminosulfonylamino or the radical -CH = NR 9 , where R 9 represents optionally C 1 -C 6 alkyl substituted by fluorine, chlorine, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl, for benzyl optionally substituted by fluorine or chlorine, for C 3 -C 6 alkenyl or C 3 -C 6 alkynyl optionally substituted by fluorine or chlorine, for optionally substituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio substituted phenyl, for optionally substituted by fluorine and / or chlorine C 1 -C 6 alkoxy, C 3 -C 6 alkenoxy, C 3 -C 6 alkynoxy or benzyloxy for amino , C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, phenylamino, C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxycarbonylamino, C 1 -C 4 -Alkyl-sulfonylamino or if necessary Is phenylsulfonylamino substituted by fluorine, chlorine, bromine or methyl, furthermore
steht,
Figure imgf000011_0001
stands,
Figure imgf000011_0001
worin R10 für Wasserstoff oder C1-C4-Alkyl steht, where R 10 is hydrogen or C 1 -C 4 alkyl,
R1 1 und R12 gleich oder verschieden sind und fur Wasserstoff, Fluor, Chlor,R 1 1 and R 12 are the same or different and are hydrogen, fluorine, chlorine,
Brom, Nitro, Cyano, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/ oder Chlor substituiert ist), Carboxy, C1-C4-Alkoxy- carbonyl, Dimethylaminocarbonyl, C1-C4-Alkylsulfonyl oder Di-(C1- C4-alkyl)-aminosulfonyl stehen; weiterhin Bromine, nitro, cyano, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine), carboxy, C 1 -C 4 alkoxy aminosulfonyl are - carbonyl, dimethylaminocarbonyl, C 1 -C 4 -alkylsulfonyl or di- (C 4 alkyl C 1); Farther
R3 fur den Rest steht,R 3 represents the rest,
Figure imgf000012_0001
Figure imgf000012_0001
worin  wherein
R13 und R14 gleich oder verschieden sind und fur Wasserstoff, Fluor, Chlor,R 13 and R 14 are the same or different and are hydrogen, fluorine, chlorine,
Brom, Nitro, Cyano, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist) oder C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), stehen; weiterhin Bromine, nitro, cyano, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine) or C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine); Farther
R3 fur den Rest steht.
Figure imgf000012_0002
R 3 represents the rest.
Figure imgf000012_0002
worin  wherein
R1 5 und R16 gleich oder verschieden sind und fur Wasserstoff, Fluor,R 1 5 and R 16 are the same or different and are hydrogen, fluorine,
Chlor, Brom, Nitro, Cyano, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/ oder Chlor substituiert ist), fur C1-C4- Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4-Alkylsulfonyl (welche gegebenenfalls durch Fluor und/ oder Chlor substituiert sind), fur Aminosulfonyl, Mono-(C1-C4-alkyl)-aminosulfonyl, fur Di-(C1-C4-alkyl)aminosulfonyl oder C1-C4-Alkoxy-carbonyl oder Dimethylaminocarbonyl stehen; weiterhin R3 fur den Rest steht,Chlorine, bromine, nitro, cyano, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine), for C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl (which are optionally substituted by fluorine and / or chlorine), for aminosulfonyl, mono- (C 1 -C 4 alkyl) - aminosulfonyl, are di (C 1 -C 4 alkyl) aminosulfonyl or C 1 -C 4 alkoxycarbonyl or dimethylaminocarbonyl; Farther R 3 represents the rest,
Figure imgf000013_0001
Figure imgf000013_0001
worin  wherein
R1 7 und R18 gleich oder verschieden sind und fur Wasserstoff, Fluor,R 1 7 and R 18 are the same or different and are hydrogen, fluorine,
Chlor, Brom, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Brom substituiert ist), C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), fur C1-C4-Alkylthio, C1- C4-Alkylsulfinyl oder C1-C4-Alkylsulfonyl (welche gegebenenfalls durch Fluor und/oder Chlor substituiert sind), oder fur Di-(C1-C4- alkyl)-aminosulfonyl stehen; weiterhin Chlorine, bromine, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or bromine), C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine), for C 1 -C 4 -Alkyl thio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl (which are optionally substituted by fluorine and / or chlorine), or represent di- (C 1 -C 4 -alkyl) -aminosulfonyl; Farther
R3 fur den Rest steht,R 3 represents the rest,
Figure imgf000013_0002
Figure imgf000013_0002
worin  wherein
R19 und R20 gleich oder verschieden sind und fur Wasserstoff, Fluor, Chlor, Brom, Cyano, Nitro, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/ oder Chlor substituiert ist), C1-C4-Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4-Alkylsulfonyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), Di-(C1-C4-alkyl)-aminosulfonyl, C1-C4-Alkoxy-carbonyl oder Dimethylaminocarbonyl stehen, und R 19 and R 20 are the same or different and are hydrogen, fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 -alkyl (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 -alkoxy (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine), Di - (C 1 -C 4 -alkyl) -aminosulfonyl, C 1 -C 4 -alkoxy-carbonyl or dimethylaminocarbonyl, and
A fur Sauerstoff, Schwefel oder die Gruppierung N-Z steht, wobei Z fur Wasserstoff, C1-C4-Alkyl (welches gegebenenfalls durch Fluor,A stands for oxygen, sulfur or the grouping NZ, where Z stands for hydrogen, C 1 -C 4 -alkyl (which may be replaced by fluorine,
Chlor, Brom oder Cyano substituiert ist), C3-C6-Cycloalkyl, Benzyl, Phenyl (welches gegebenenfalls durch Fluor, Chlor, Brom oder Nitro substituiert ist), C1-C4-Alkylcarbonyl, C1-C4-Alkoxycarbonyl oder Di-(C1-C4-alkyl)-aminocarbonyl steht; weiterhin Chlorine, bromine or cyano is substituted), C 3 -C 6 cycloalkyl, benzyl, phenyl (which may be replaced by fluorine, chlorine, bromine or nitro is substituted), C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl or di- (C 1 -C 4 alkyl) aminocarbonyl; Farther
R3 fur den Rest steht,R 3 represents the rest,
Figure imgf000014_0001
Figure imgf000014_0001
worin  wherein
R21 und R22 gleich oder verschieden sind und fur Wasserstoff, C1- C4-Alkyl, Halogen, C1-C4-Alkoxycarbonyl, C1-C4-Alkoxy oder C1- C4-Halogenalkoxy stehen, R 21 and R 22 are identical or different and represent hydrogen, C 1 - C 4 alkyl, halogen, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 alkoxy or C 1 - C 4 haloalkoxy stand,
Y1 fur Schwefel oder die Gruppierung N-R23 steht, wobei Y 1 represents sulfur or the grouping NR 23 , where
R23 fur Wasserstoff oder C1-C4-Alkyl steht; weiterhin R 23 represents hydrogen or C 1 -C 4 alkyl; Farther
R3 fur den Rest steht,
Figure imgf000014_0002
R 3 represents the rest,
Figure imgf000014_0002
worin  wherein
R24 fur Wasserstoff, C1-C4-Alkyl, Benzyl, Pyndyl, Chinolinyl oder Phenyl steht, R25 fur Wasserstoff, Halogen, Cyano, Nitro, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C4-AlkoxyR 24 represents hydrogen, C 1 -C 4 alkyl, benzyl, pyndyl, quinolinyl or phenyl, R 25 represents hydrogen, halogen, cyano, nitro, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine is), C 1 -C 4 alkoxy
(welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist),(which is optionally substituted by fluorine and / or chlorine),
Dioxolanyl oder C1-C4-Alkoxy-carbonyl steht und Dioxolanyl or C 1 -C 4 alkoxy-carbonyl and
R26 fur Wasserstoff, Halogen oder C1-C4-Alkyl steht, und ferner R3 fur eine der nachstehend aufgefuhrten Gruppierungen steht, R 26 represents hydrogen, halogen or C 1 -C 4 alkyl, and furthermore R 3 stands for one of the groupings listed below,
Figure imgf000015_0001
Figure imgf000015_0001
mit Ausnahme der oben durch Disclaimer ausgeschlossenen Verbindungen. with the exception of the connections excluded by disclaimer above.
Gegenstand der Erfindung sind weiter vorzugsweise Natrium-, Kalium-, Magnesium-, Calcium-, Ammonium-, C1-C4-Alkyl-ammonium-, Di-(C1-C4-alkyl)-ammonium-,The invention further preferably relates to sodium, potassium, magnesium, calcium, ammonium, C 1 -C 4 alkyl ammonium, di (C 1 -C 4 alkyl) ammonium,
Tri-(C1-C4-alkyl)-ammonium-, Tetra-(C1-C4-alkyl)-ammonium, Tri-(C1-C4-alkyl)-sulfonium-, C5- oder C6-Cycloalkyl-ammonium- und Di-(C1-C2-alkyl)-benzyl-ammonium-Salze von Verbindungen der Formel (I), in welcher n, R1, R2 und R3 die oben vorzugsweise angegebenen Bedeutungen haben. Gegenstand der Erfindung sind insbesondere Verbindungen der Formel (I), in welcher n fur die Zahlen 0, 1 oder 2 steht, Tri- (C 1 -C 4 alkyl) ammonium, tetra (C 1 -C 4 alkyl) ammonium, tri- (C 1 -C 4 alkyl) sulfonium, C5 or C 6 - Cycloalkyl-ammonium and di- (C 1 -C 2 -alkyl) -benzyl-ammonium salts of compounds of the formula (I) in which n, R 1 , R 2 and R 3 have the meanings preferably given above. The invention relates in particular to compounds of the formula (I) in which n represents the numbers 0, 1 or 2,
R1 fur jeweils gegebenenfalls durch Fluor, Chlor, Cyano, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, fur jeweils gegebenenfalls durch Fluor, Chlor oder Brom substituiertes Propenyl, Butenyl, Propinyl oder Butinyl, fur jeweils gegebenenfalls durch Fluor, Chlor, Brom,R 1 for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, for each optionally substituted by fluorine, chlorine or bromine Propenyl, butenyl, propynyl or butynyl, each optionally with fluorine, chlorine, bromine,
Methyl oder Ethyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl, oder fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Methyl, Trifluormethyl oder Methoxy substituiertes Benzyl oder Phenyl steht, Methyl or ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or for benzyl or phenyl optionally substituted by fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy,
R2 fur jeweils gegebenenfalls durch Fluor, Chlor, Cyano, Methoxy, Ethoxy, Methylthio oder Ethylthio substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, fur jeweils gegebenenfalls durch Fluor, Chlor oder Brom substituiertes Propenyl, Butenyl, Propinyl, Butinyl oder Allenyl, fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Methyl oder Ethyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cyclopropylmethyl, Cyclo- butylmethyl, Cyclopentylmethyl oder Cyclohexylmethyl oder fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Methyl, Trifluormethyl oder Methoxy substituiertes Phenyl oder Benzyl steht, R 2 for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by fluorine, chlorine, cyano, methoxy, ethoxy, methylthio or ethylthio, for each optionally by fluorine, Chlorine or bromine-substituted propenyl, butenyl, propynyl, butynyl or allenyl, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclo- butylmethyl, cyclopentylmethyl or cyclohexylmethyl or phenyl or benzyl optionally substituted by fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy,
R3 fur den Rest steht,
Figure imgf000016_0001
R 3 represents the rest,
Figure imgf000016_0001
worin  wherein
R4 fur Fluor, Chlor, Brom, Methyl, Ethyl, Propyl, Trifluormethyl, Butoxy,R 4 for fluorine, chlorine, bromine, methyl, ethyl, propyl, trifluoromethyl, butoxy,
Allyloxy, Propargyloxy, Methoxy, Ethoxy, Propoxy, Isopropoxy, Difluormethoxy, Trifluormethoxy, 2-Chlor-ethoxy, 2-Methoxy-ethoxy, C1- C3-Alkylthio, C1-C3-Alkylsulfinyl, C1-C3-Alkylsulfonyl, Dimethylaminosulfonyl, Diethylaminosulfonyl, N-Methoxy-N-methylaminosulfonyl, Methoxyaminosulfonyl, Phenyl, Phenoxy oder C1-C3-Alkoxycarbonyl steht und R5 fur Wasserstoff, Methyl, Ethyl, Fluor, Chlor oder Brom steht; weiterhin Allyloxy, propargyloxy, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, 2-chloroethoxy, 2-methoxyethoxy, C 1 - C 3 alkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 - Alkylsulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, N-methoxy-N-methylaminosulfonyl, methoxyaminosulfonyl, phenyl, phenoxy or C 1 -C 3 alkoxycarbonyl and R 5 is hydrogen, methyl, ethyl, fluorine, chlorine or bromine; Farther
R3 fur den Rest steht,
Figure imgf000016_0002
R 3 represents the rest,
Figure imgf000016_0002
worin R10 fur Wasserstoff steht, where R 10 represents hydrogen,
R1 1 fur Fluor, Chlor, Brom, Methyl, Methoxy, Difluormethoxy, Trifluormethoxy, Ethoxy, Methoxycarbonyl, Ethoxycarbonyl, Methylsulfonyl oder Dimethylaminosulfonyl steht und R12 fur Wasserstoff steht; weiterhin R 1 1 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or dimethylaminosulfonyl and R 12 represents hydrogen; Farther
R3 fur den Rest steht,
Figure imgf000017_0001
R 3 represents the rest,
Figure imgf000017_0001
worin  wherein
R fur C1-C4-Alkyl steht, oder R represents C 1 -C 4 alkyl, or
R3 fur den Rest steht,
Figure imgf000017_0002
R 3 represents the rest,
Figure imgf000017_0002
worin  wherein
R24 fur C1-C3-Alkyl, Phenyl oder Pyridyl steht, R25 fur Wasserstoff, Fluor, Chlor oder Brom steht, R26 fur Fluor, Chlor, Brom oder C1-C3-Alkoxy-carbonyl steht, mit Ausnahme der oben durch Disclaimer ausgeschlossenen Verbindungen. R 24 stands for C 1 -C 3 alkyl, phenyl or pyridyl, R 25 stands for hydrogen, fluorine, chlorine or bromine, R 26 stands for fluorine, chlorine, bromine or C 1 -C 3 alkoxycarbonyl, with the exception of the connections excluded by disclaimer above.
Die oben aufgefuhrten allgemeinen oder in Vorzugsbereichen aufgefuhrten Restedefinitionen gelten sowohl für die Endprodukte der Formel (I) als auch entsprechend fur die jeweils zur Herstellung benötigten Ausgangs- bzw. Zwischenprodukte. Diese Restedefinitionen können untereinander, also auch zwischen den angegebenen bevorzugten Bereichen beliebig kombiniert werden. The general or preferred range definitions given above apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.
Die bei den Restedefinitionen genannten Kohlenwasserstoffreste, wie Alkyl, Alkenyl oder Alkinyl, auch in Kombinationen mit Heteroatomen, wie in Alkoxy, Alkylthio oder Alkylamino, sind auch dann, wenn dies nicht ausdrücklich angegeben ist, geradkettig oder verzweigt. Halogen steht im allgemeinen fur Fluor, Chlor, Brom oder lod, vorzugsweise fur Fluor, Chlor oder Brom, insbesondere fur Fluor oder Chlor. The hydrocarbon radicals mentioned in the radical definitions, such as alkyl, alkenyl or alkynyl, also in combinations with heteroatoms, such as in alkoxy, alkylthio or alkylamino, are straight-chain or branched, even if this is not expressly stated. Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
Verwendet man beispielsweise 2-Trifluormethoxy-phenylsulfonyl-isocyanat und 4-Methoxy-5-propylthio-2,4-dihydro-3H-1,2,4-triazol-3-on als Ausgangsstoffe, so kann der Reaktionsablauf beim erfindungsgemäßen Verfahren (a) durch das folgende Formelschema skizziert werden: If, for example, 2-trifluoromethoxy-phenylsulfonyl isocyanate and 4-methoxy-5-propylthio-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting materials, the course of the reaction in the process according to the invention (a ) are outlined by the following formula scheme:
Figure imgf000018_0001
Figure imgf000018_0001
Verwendet man beispielsweise 2-Ethylthio-benzolsulfonamid und 2-Chlorcarbonyl-4-ethoxy-5-methylsulfonyl-2,4-dihydro-3H-1,2,4-triazol-3-on als Ausgangsstoffe, so kann der Reaktionsablauf beim erfindungsgemäßen Verfahren (b) durch das folgende If, for example, 2-ethylthio-benzenesulfonamide and 2-chlorocarbonyl-4-ethoxy-5-methylsulfonyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting materials, the course of the reaction can be carried out in the process according to the invention (b) by the following
Formelschema skizziert werden: Formula scheme are outlined:
Figure imgf000018_0002
Figure imgf000018_0002
Verwendet man beispielsweise N-Methoxycarbonyl-2-methoxy-benzolsulfonamid und 5-Ethylsulfinyl-4-propoxy-2,4-dihydro-3H-1,2,4-triazol-3-on als Ausgangsstoffe, so kann der Reaktionsablauf beim erfindungsgemäßen Verfahren (c) durch das folgende If, for example, N-methoxycarbonyl-2-methoxy-benzenesulfonamide and 5-ethylsulfinyl-4-propoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting materials, the course of the reaction can be carried out in the process according to the invention (c) by the following
Formelschema skizziert werden: Formula scheme are outlined:
Figure imgf000018_0003
Figure imgf000018_0003
Verwendet man beispielsweise 2-Chlor-6-methyl-benzolsulfonsäurechlorid, 4-Allyloxy-5-benzylthio-2,4-dihydro-3H-1,2,4-triazol-3-on und Natriumcyanat als Aus- gangsstoffe, so kann der Reaktionsablauf beim erfindungsgemäßen Verfahren (d) durch das folgende Formelschema skizziert werden: If, for example, 2-chloro-6-methyl-benzenesulfonyl chloride, 4-allyloxy-5-benzylthio-2,4-dihydro-3H-1,2,4-triazol-3-one and sodium cyanate are used as the materials, the course of the reaction in process (d) according to the invention can be outlined using the following formula:
Figure imgf000019_0001
Figure imgf000019_0001
Die bei den erfindungsgemäßen Verfahren (a), (c) und (d) zur Herstellung von Verbindungen der Formel (I) als Ausgangsstoffe zu verwendenden Triazolinone sind durch die Formel (II) allgemein definiert.  Formula (II) provides a general definition of the triazolinones to be used as starting materials in processes (a), (c) and (d) for the preparation of compounds of the formula (I).
In der Formel (II) haben n, R1 und R2 vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt fur n, R1 und R2 angegeben wurden. In the formula (II), n, R 1 and R 2 preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for n, R 1 and R 2 were specified.
Die Triazolinone der allgemeinen Formel (II) sind noch nicht aus der Literatur bekannt; sie sind als neue Stoffe auch Gegenstand der vorliegenden Anmeldung. The triazolinones of the general formula (II) are not yet known from the literature; as new substances they are also the subject of the present application.
Man erhält die neuen Triazolinone der Formel (II), wenn man Mercapto-triazolinone der allgemeinen Formel (IX) AThe new triazolinones of the formula (II) are obtained if mercapto-triazolinones of the general formula (IX) A
Figure imgf000019_0002
Figure imgf000019_0002
in welcher R1 die oben angegebene Bedeutung hat, in which R 1 has the meaning given above,
- oder Metallsalze von Verbindungen der Formel (IX) - mit Verbindungen der allgemeinen Formel (X) X-R2 (X) in welcher - or metal salts of compounds of the formula (IX) - with compounds of the general formula (X) XR 2 (X) in which
R2 die oben angegebene Bedeutung hat und R 2 has the meaning given above and
X fur Halogen oder die Gruppierung -O-SO2-OR2 steht, gegebenenfalls in Gegenwart eines Säureakzeptors, wie z.B. Kaliumhydroxid, Kaliumt-butylat oder Kaliumcarbonat, und gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Methanol oder Ethanol, bei Temperaturen zwischen 0°C und 100°C umsetzt und gegebenenfalls anschließend auf übliche Weise zu entsprechenden Sulfoxiden oder Sulfonen oxidiert (vgl. die Herstellungsbeispiele). In der Formel (X) hat R1 vorzugsweise bzw. insbesondere diejenige Bedeutung, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt fur R1 angegeben wurde. X represents halogen or the group -O-SO 2 -OR 2 , optionally in the presence of an acid acceptor, such as potassium hydroxide, potassium t-butoxide or potassium carbonate, and optionally in the presence of a diluent, such as methanol or ethanol, at temperatures between 0 ° C and 100 ° C and optionally subsequently oxidized in a conventional manner to corresponding sulfoxides or sulfones (see. The preparation examples). In formula (X), R 1 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 1 .
Als bevorzugte Metallsalze der Verbindungen der Formel (IX) seien die Alkalimetallsalze und Erdalkalimetallsalze, insbesondere die Natrium-, Kalium-, Magnesium- undThe preferred metal salts of the compounds of formula (IX) are the alkali metal salts and alkaline earth metal salts, in particular the sodium, potassium, magnesium and
Calciumsalze hervorgehoben. Calcium salts highlighted.
Die Mercapto-triazolinone der allgemeinen Formel (IX) - sowie ihre Metaüsalze - sind noch nicht aus der Literatur bekannt; sie sind als neue Stoffe ebenfalls Gegenstand der vorliegenden Anmeldung. Man erhält die neuen Mercaptotriazolinone der Formel (IX), wenn man Semicarbazid¬The mercapto-triazolinones of the general formula (IX) - and their meta salts - are not yet known from the literature; as new substances, they are also the subject of the present application. The new mercaptotriazolinones of the formula (IX) are obtained when using semicarbazide
Derivate der allgemeinen Formel (XI) Derivatives of the general formula (XI)
Figure imgf000020_0001
Figure imgf000020_0001
in welcher R1 die oben angegebene Bedeutung hat und in which R 1 has the meaning given above and
Y fur Halogen, Imidazolyl, Alkoxy, Aralkoxy oder Aryloxy steht, gegebenenfalls in Gegenwart eines Reaktionshilfsmittels, wie z.B. Kaliumcarbonat, und gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Methanol oder Ethanol, bei Temperaturen zwischen 20°C und 150°C umsetzt (vgl. die Herstellungsbeispiele). Y represents halogen, imidazolyl, alkoxy, aralkoxy or aryloxy, optionally in the presence of a reaction auxiliary, e.g. Potassium carbonate, and optionally in the presence of a diluent, e.g. Methanol or ethanol, at temperatures between 20 ° C and 150 ° C (see. The manufacturing examples).
In der Formel (XI) hat R1 vorzugsweise bzw. insbesondere diejenige Bedeutung, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt fur R1 angegeben wurde; Y steht vorzugsweise fur Fluor, Chlor, Brom, lod, Methoxy, Ethoxy,In formula (XI), R 1 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 1 ; Y preferably represents fluorine, chlorine, bromine, iodine, methoxy, ethoxy,
Benzyloxy oder Phenoxy, insbesondere fur Methoxy oder Phenoxy. Benzyloxy or phenoxy, especially for methoxy or phenoxy.
Die Semicarbazid-Derivate der allgemeinen Formel (XI) sind noch nicht aus der Literatur bekannt; sie sind als neue Stoffe ebenfalls Gegenstand der vorliegenden Anmeldung. Man erhält die neuen Semicarbazid-Derivate der Formel (XI), wenn man Semicarbazide der allgemeinen Formel (XII) The semicarbazide derivatives of the general formula (XI) are not yet known from the literature; as new substances, they are also the subject of the present application. The new semicarbazide derivatives of the formula (XI) are obtained if semicarbazides of the general formula (XII)
Figure imgf000021_0001
Figure imgf000021_0001
in welcher R1 die oben angegebene Bedeutung hat, mit Acylierungsmitteln der allgemeinen Formel (XIII) in which R 1 has the meaning given above, with acylating agents of the general formula (XIII)
X1-CS-Y (XIII) in welcher Y die oben angegebene Bedeutung hat und X1 fur Halogen steht, gegebenenfalls in Gegenwart eines Säureakzeptors, wie z.B. Triethylamin, und gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Methylenchlorid, bei Temperaturen zwischen 0°C und 100°C umsetzt (vgl. die Herstellungsbeispiele). Die Vorprodukte der Formel (XII) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. J. Prakt. Chem. 313 (1971), 636-641; DE-A 2044834; Herstellungsbeispiele). X 1 -CS-Y (XIII) in which Y has the meaning given above and X 1 represents halogen, if appropriate in the presence of an acid acceptor, such as, for example, triethylamine, and if appropriate in the presence of a diluent, such as, for example, methylene chloride, at temperatures between 0 ° C. and 100 ° C. (cf. the preparation examples). The precursors of the formula (XII) are known and / or can be prepared by processes known per se (cf. J. Prakt. Chem. 313 (1971), 636-641; DE-A 2044834; production examples).
Die Vorprodukte der Formel (XIII) sind bekannte Synthesechemikalien. The precursors of the formula (XIII) are known synthetic chemicals.
Die fur die Herstellung der Ausgangsstoffe der Formel (II) benötigten Alkylierungsmittel sind durch die Formel (X) allgemein definiert. In der Formel (X) hat R2 vorzugsweise bzw. insbesondere diejenige Bedeutung, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt fur R2 angegeben wurde; X steht vorzugsweise fur Fluor, Chlor, Brom oder lod, insbesondere fur Chlor, Brom oder lod. Die Verbindungen der Formel (X) sind bekannte Synthesechemikalien. Formula (X) provides a general definition of the alkylating agents required for the preparation of the starting materials of the formula (II). In formula (X), R 2 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 2 ; X preferably represents fluorine, chlorine, bromine or iodine, in particular chlorine, bromine or iodine. The compounds of formula (X) are known synthetic chemicals.
Die beim erfindungsgemäßen Verfahren (a) zur Herstellung von Verbindungen der Formel (I) weiter als Ausgangsstoffe zu verwendenden Sulfonylisocyanate sind durch die Formel (III) allgemein definiert. Formula (III) provides a general definition of the sulfonyl isocyanates to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I).
In Formel (III) hat R3 vorzugsweise bzw. insbesondere diejenige Bedeutung, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt fur R3 angegeben wurde. In formula (III), R 3 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 3 .
Die Ausgangsstoffe der Formel (III) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687, EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EP¬The starting materials of the formula (III) are known and / or can be prepared by processes known per se (cf. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687, EP-A 13480, EP- A 21641, EP-A 23141, EP-A 23422, EP¬
A 30139, EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041, EP-A 173312). Die beim erfindungsgemäßen Verfahren (b) zur Herstellung der Verbindungen der allgemeinen Formel (I) als Ausgangsstoffe zu verwendenden Triazolinon-Derivate sind durch die Formel (IV) allgemein definiert. In der Formel (IV) haben n, R1 und R2 vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der Verbindungen der Formel (I) als bevorzugt bzw. als insbesondere bevorzugt fur n, R1 und R2 angegeben wurden; Z steht vorzugsweise fur Fluor, Chlor, Brom, Methoxy, Ethoxy, Benzyloxy, Phenoxy, Halogenoder Nitro-phenoxy, insbesondere fur Methoxy, Phenoxy oder 4-Nitro-phenoxy. A 30139, EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041, EP-A 173312). Formula (IV) provides a general definition of the triazolinone derivatives to be used as starting materials in process (b) according to the invention for the preparation of the compounds of the general formula (I). In formula (IV), n, R 1 and R 2 preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for n, R 1 and R 2 were specified; Z preferably represents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogen or nitro-phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.
Die Ausgangsstoffe der Formel (IV) sind noch nicht aus der Literatur bekannt; sie sind als neue Stoffe Gegenstand der vorliegenden Anmeldung. The starting materials of the formula (IV) are not yet known from the literature; as new substances, they are the subject of the present application.
Man erhält die neuen Verbindungen der Formel (IV), wenn man Triazolinone der allgemeinen Formel (II) The new compounds of the formula (IV) are obtained if triazolinones of the general formula (II)
Figure imgf000023_0001
Figure imgf000023_0001
in welcher n, R1 und R2 die oben angegebene Bedeutung haben, mit Kohlensäurederivaten der allgemeinen Formel (XIV) Z-CO-Z1 (XIV) in welcher in which n, R 1 and R 2 have the meaning given above, with carbonic acid derivatives of the general formula (XIV) Z-CO-Z 1 (XIV) in which
Z die oben angegebene Bedeutung hat und Z1 fur Halogen, Alkoxy, Aralkoxy oder Aryloxy steht, gegebenenfalls in Gegenwart eines Säureakzeptors, wie z.B. Kalium-t-butylat, und gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Tetrahydrofuran oder Dimethoxyethan, bei Temperaturen zwischen 0°C und 100°C umsetzt. Z has the meaning given above and Z 1 represents halogen, alkoxy, aralkoxy or aryloxy, optionally in the presence of an acid acceptor, such as potassium t-butoxide, and optionally in the presence of a diluent, such as tetrahydrofuran or dimethoxyethane, at temperatures between 0 ° C and 100 ° C.
Die beim erfindungsgemäßen Verfahren (b) zur Herstellung der Verbindungen der allgemeinen Formel (I) weiter als Ausgangsstoffe zu verwendenden Sulfonsäureamide sind durch die Formel (V) allgemein definiert. In der Formel (N) hat R3 vorzugsweise bzw. insbesondere diejenige Bedeutung, die bereits oben im Zusammenhang mit der Beschreibung der Verbindungen der Formel (I) als bevorzugt bzw. als insbesondere bevorzugt fur R3 angegeben wurde. Die Ausgangsstoffe der Formel (V) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687, EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EPA 30139, EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041, EP-A 173312). Die beim erfindungsgemäßen Verfahren (c) zur Herstellung der Verbindungen derFormula (V) provides a general definition of the sulfonamides to be used as starting materials in process (b) according to the invention for the preparation of the compounds of the general formula (I). In the formula (N), R 3 preferably or in particular has the meaning which has already been given above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R 3 . The starting materials of the formula (V) are known and / or can be prepared by processes known per se (cf. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687, EP-A 13480, EP- A 21641, EP-A 23141, EP-A 23422, EPA 30139, EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041 , EP-A 173312). The process (c) according to the invention for the preparation of the compounds of
Formel (I) als Ausgangsstoffe zu verwendenden Sulfonsäureamid-Derivate sind durch die Formel (VI) allgemein definiert. In der Formel (VI) hat R3 vorzugsweise bzw. insbesondere diejenige Bedeutung, die bereits oben im Zusammenhang mit der Beschreibung der Verbindungen der Formel (I) als bevorzugt bzw. als insbesondere bevorzugt fur R3 angegeben wurde; Z steht vorzugsweise fur Fluor, Chlor, Brom,Formula (I) sulfonic acid amide derivatives to be used as starting materials are generally defined by the formula (VI). In formula (VI), R 3 preferably or in particular has the meaning which has already been given above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R 3 ; Z preferably represents fluorine, chlorine, bromine,
Methoxy, Ethoxy, Benzyloxy oder Phenoxy, insbesondere fur Methoxy oder Phenoxy. Methoxy, ethoxy, benzyloxy or phenoxy, especially for methoxy or phenoxy.
Die Ausgangsstoffe der Formel (VI) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden. The starting materials of the formula (VI) are known and / or can be prepared by processes known per se.
Die beim erfindungsgemäßen Verfahren (d) zur Herstellung der Verbindungen der Formel (I) als Ausgangsstoffe zu verwendenden Sulfonsäurehalogenide sind durch dieThe sulfonic acid halides to be used as starting materials in process (d) according to the invention for the preparation of the compounds of the formula (I) are:
Formel (VII) allgemein definiert. In der Formel (VII) hat R3 vorzugsweise bzw. insbesondere diejenige Bedeutung, die bereits oben im Zusammenhang mit der Beschreibung der Verbindungen der Formel (I) als bevorzugt bzw. als insbesondere bevorzugt fur R3 angegeben wurde; X steht vorzugsweise fur Fluor, Chlor oder Brom, insbesondere fur Chlor. Die Ausgangsstoffe der Formel (VII) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden. Formula (VII) generally defined. In formula (VII), R 3 preferably or in particular has the meaning which has already been given above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R 3 ; X preferably represents fluorine, chlorine or bromine, especially chlorine. The starting materials of the formula (VII) are known and / or can be prepared by processes known per se.
Die erfindungsgemäßen Verfahren (a), (b), (c) und (d) zur Herstellung der neuen Verbindungen der Formel (I) werden vorzugsweise unter Verwendung von Verdünnungsmitteln durchgefuhrt. Als Verdünnungsmittel kommen dabei praktisch alle inerten organischen Lösungsmittel infrage. Hierzu gehören vorzugsweise aliphatische und aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe wie Pentan, Hexan, Heptan, Cyclohexan, Petrolether, Benzin, Ligroin, Benzol, Toluol, Xylol, Methylenchlorid, Ethylenchlorid, Chloroform, Tetrachlormethan, Chlorbenzol und o-Dichlorbenzol, Ether wie Diethyl- und Dibutylether, Glykoldimethylether und Diglykoldimethylether, Tetrahydrofüran und Dioxan, Ketone wie Aceton, Methyl-ethyl-, Methyl-isopropyl- und Methyl-isobutyl-keton, Ester wie Essigssäuremethylester und ethylester, Nitrile wie z.B. Acetonitril und Propionitril, Amide wie z.B. Dimethylformamid, Dimethylacetamid und N-Methylpyrrolidon sowie Dimethylsulfoxid, Tetramethylensulfon und Hexamethylphosphorsäuretriamid. Processes (a), (b), (c) and (d) according to the invention for the preparation of the new compounds of the formula (I) are preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and Dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl ester, nitriles such as, for example Acetonitrile and propionitrile, amides such as e.g. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone as well as dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric acid triamide.
Als Reaktionshilfsmittel bzw. als Säureakzeptoren können bei den erfindungsgemäßen Verfahren (a), (b), (c) und (d) alle üblicherweise fur derartige Umsetzungen verwendbaren Säurebindemittel eingesetzt werden. Vorzugsweise in Frage kommen Alkalimetallhydroxide wie z.B. Natrium- und Kaliumhydroxid, Erdalkalihydroxide wie z.B. Calciumhydroxid, Alkalicarbonate und -alkoholate wie Natrium- und Kaliumcarbonat,In the processes (a), (b), (c) and (d) according to the invention, all acid binders which can customarily be used for such reactions can be used as reaction auxiliaries or as acid acceptors. Alkali metal hydroxides such as e.g. Sodium and potassium hydroxide, alkaline earth metal hydroxides such as e.g. Calcium hydroxide, alkali carbonates and alcoholates such as sodium and potassium carbonate,
Natrium- und Kalium-tert-butylat, ferner basische Stickstoffverbindungen, wie Trimethylamin, Triethylamin, Tripropylamin, Tributylamin, Diisobutylamin, Dicyclohexylamin, Ethyldiisopropylamin, Ethyldicyclohexylamin, N,N-Dimethylbenzylamin, N,N-Dimethyl-anilin, Pyridin, 2-Methyl-, 3 -Methyl-, 4-Methyl-, 2,4-Dimethyl-, 2,6-Dimethyl-, 2-Ethyl-, 4-Ethyl- und 5-Ethyl-2-methyl-pyridin, 1,5-Diazabicyclo[4,3,0]-non-5-en (DBN), 1,8-Diazabicyclo-[5,4,0]-undec-7-en (DBU) und 1,4-Diazabicyclo[2,2,2]-octan (DABCO). Sodium and potassium tert-butoxide, also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethyl-aniline, pyridine, 2 , 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 2-ethyl, 4-ethyl and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo [4,3,0] -non-5-ene (DBN), 1,8-diazabicyclo- [5,4,0] -undec-7-ene (DBU) and 1,4-diazabicyclo [2,2, 2] octane (DABCO).
Die Reaktionstemperaturen können bei den erfindungsgemäßen Verfahren (a), (b), (c) und (d) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -20°C und +100°C, vorzugsweise bei Temperaturen zwischenThe reaction temperatures can be varied within a wide range in processes (a), (b), (c) and (d). In general, temperatures between -20 ° C and + 100 ° C, preferably at temperatures between
0°C und +80°C. Die erfindungsgemäßen Verfahren (a), (b), (c) und (d) werden im allgemeinen unter Normaldruck durchgefuhrt. Es ist jedoch auch möglich, unter erhöhtem oder vermindertem Druck zu arbeiten. 0 ° C and + 80 ° C. The processes (a), (b), (c) and (d) according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
Zur Durchfuhrung der erfindungsgemäßen Verfahren (a), (b), (c) und (d) werden die jeweils benötigten Ausgangsstoffe im allgemeinen in angenähert äquimolaren Mengen eingesetzt. Es ist jedoch auch möglich, eine der jeweils eingesetzten Komponenten in einem größeren Überschuß zu verwenden. Die Reaktionen werden im allgemeinen in einem geeigneten Verdünnungsmittel in Gegenwart eines Säureakzeptors durchgefuhrt, und das Reaktionsgemisch wird mehrere Stunden bei der jeweils erforderlichen Temperatur gerührt. Die Aufarbeitung erfolgt bei den erfindungsgemäßen VerfahrenTo carry out processes (a), (b), (c) and (d) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use a larger excess of one of the components used in each case. The reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case. Working up takes place in the method according to the invention
(a), (b), (c) und (d) jeweils nach üblichen Methoden (vgl. die Herstellungsbeispiele). (a), (b), (c) and (d) in each case by customary methods (cf. the preparation examples).
Aus den erfindungsgemäßen Verbindungen der allgemeinen Formel (I) können gegebenenfalls Salze hergestellt werden. Man erhält solche Salze in einfacher Weise nach üblichen Salzbildungsmethoden, beispielsweise durch Lösen oder Dispergieren einer Verbindung der Formel (I) in einem geeigneten Lösungsmittel, wie z.B. Methylenchlorid, Aceton, tert-Butyl-methylether oder Toluol, und Zugabe einer geeigneten Base. Die Salze können dann - gegebenenfalls nach längerem Rühren - durch Einengen oder Absaugen isoliert werden. If appropriate, salts can be prepared from the compounds of the general formula (I) according to the invention. Such salts are obtained in a simple manner by customary salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent, e.g. Methylene chloride, acetone, tert-butyl methyl ether or toluene, and addition of a suitable base. The salts can then be isolated - if appropriate after prolonged stirring - by concentration or suction.
Die erfindungsgemäßen Wirkstoffe können als Defoliants, Desiccants, Krautabtötungsmittel und insbesondere als Unkrautvernichtungsmittel verwendet werden. UnterThe active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Under
Unkraut im weitesten Sinne sind alle Pflanzen zu verstehen, die an Orten aufwachsen, wo sie unerwünscht sind. Ob die erfindungsgemäßen Stoffe als totale oder selektive Herbizide wirken, hängt im wesentlichen von der angewendeten Menge ab. Weeds in the broadest sense are to be understood as all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
Die erfindungsgemäßen Wirkstoffe können z.B. bei den folgenden Pflanzen verwendet werden: The active compounds according to the invention can e.g. can be used in the following plants:
Dikotyle Unkräuter der Gattungen: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum. Dikotyle Kulturen der Gattungen: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita. Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum. Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monokotyle Unkräuter der Gattungen: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera. Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasumirumum, Scalumumum, Scalumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monokotyle Kulturen der Gattungen: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium. Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.
Die Verwendung der erfindungsgemäßen Wirkstoffe ist jedoch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflanzen. However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.
Die Verbindungen eignen sich in Abhängigkeit von der Konzentration zur TotalUnkrautbekämpfung z.B. auf Industrie- und Gleisanlagen und auf Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die Verbindungen zur Unkrautbekämpfung in Dauerkulturen, z.B. Forst, Ziergehölz-, Obst-, Wein-, Citrus-, Nuß-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beerenfrucht- und Hopfenanlagen, auf Zier- und Sportrasen und Weideflächen und zur selektiven Unkrautbekämpfung in einjährigen Kulturen eingesetzt werden. Depending on the concentration, the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, e.g. Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture land and for selective purposes Weed control can be used in annual crops.
Die erfindungsgemäßen Verbindungen der Formel (I) eignen sich insbesondere zur selektiven Bekämpfung von dikotylen Unkräutern in monokotylen Kulturen sowohl im Vorauflauf- als auch im Nachauflauf- Verfahren. The compounds of formula (I) according to the invention are particularly suitable for the selective control of dicotyledon weeds in monocotyledon crops both in the pre-emergence and in the post-emergence process.
Darüberhinaus zeigen die erfindungsgemäßen Wirkstoffe der Formel (I) auch interessante fungizide Wirkung gegen phytopathogene Pilze, insbesondere gegenIn addition, the active compounds of the formula (I) according to the invention also show interesting fungicidal activity against phytopathogenic fungi, in particular against
Venturia inaequalis, in gewissem Umfang auch gegen Pyricularia oryzae, z.B. am Reis. Die Wirkstoffe können in die üblichen Formulierungen überfuhrt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprägnierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren Stoffen Diese Formulierungen werden in bekannter Weise hergestellt, z B durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Tragerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln Venturia inaequalis, to a certain extent also against Pyricularia oryzae, e.g. on rice. The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, natural and synthetic substances impregnated with active substances, and very fine encapsulations in polymeric substances Formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents
Im Falle der Benutzung von Wasser als Streckmittel können z.B auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden Als flüssige Lösungsmittel kommen im wesentlichen in Frage. Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten und chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Ole, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton,If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents are essentially suitable. Aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone,
Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Losungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water
Als feste Trägerstoffe kommen in Frage z B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsaure, Aluminiumoxid und Silikate, als feste Tragerstoffe fur Granulate kommen in Frage" z B. gebrochene und fraktionierte naturliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sagemehl, Kokosnußschalen, Maiskolben und Tabakstengeln, als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsaure-Ester, Polyoxyethylen-Fettalkohol-Ether, z B Alkylaryl-polyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate, als Dispergiermittel kommen in Frage z B Lignin-Sulfitablaugen und Methylcellulose Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein. Solid carrier materials that come into question are, for example, ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates, and solid carrier materials for granules are suitable "eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, come as emulsifiers and / or foam-producing agents in question: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates, and dispersants include, for example, lignin sulfite liquors and methyl cellulose Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden. Die Formulierungen enthalten im allgemeinen zwischen 0, 1 und 95 GewichtsprozentDyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used. The formulations generally contain between 0.1 and 95 percent by weight
Wirkstoff, vorzugsweise zwischen 0,5 und 90 %. Active ingredient, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Herbiziden zur Unkrautbekämpfung Verwendung finden, wobei Fertigformulierungen oder Tankmischungen möglich sind. Für die Mischungen kommen bekannte Herbizide infrage, beispielsweise Anilide, wie z.B. Diflufenican und Propanil; Arylcarbonsäuren, wie z.B. Dichlorpicolinsäure, Dicamba und Picloram; Aryloxyalkansäuren, wie z.B. 2,4-D, 2,4-DB, 2,4-DP, Fluroxypyr, MCPA, MCPP und Triclopyr; Aryloxy-phenoxy-alkansäureester, wie z.B. Diclofop-methyl, Fenoxaprop-ethyl, Fluazifop-butyl, Haloxyfop-methyl und Quizalofopethyl; Azinone, wie z.B. Chloridazon und Norflurazon; Carbamate, wie z.B. Chlorpropham, Desmedipham, Phenmedipham und Propham; Chloracetanilide, wie z.B. Alachlor, Acetochlor, Butachlor, Metazachlor, Metolachlor, Pretilachlor und Propachlor; Dinitroaniline, wie z.B. Oryzalin, Pendimethalin und Trifluralin; Diphenylether, wie z.B. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen und Oxyfluorfen; Harnstoffe, wie z.B. Chlortoluron, Diuron, Fluometuron, Isoproturon,The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible. Known herbicides, for example anilides, such as e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofopethyl; Azinones, e.g. Chloridazon and norflurazon; Carbamates, e.g. Chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides, e.g. Alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines, e.g. Oryzalin, pendimethalin and trifluralin; Diphenyl ethers, e.g. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and Oxyfluorfen; Ureas, e.g. Chlorotoluron, diuron, fluometuron, isoproturon,
Linuron und Methabenzthiazuron; Hydroxylamine, wie z.B. Alloxydim, Clethodim, Cycloxydim, Sethoxydim und Tralkoxydim; Imidazolinone, wie z.B. Imazethapyr, Imazamethabenz, Imazapyr und Imazaquin; Nitrile, wie z.B. Bromoxynil, Dichlobenil und Ioxynil; Oxyacetamide, wie z.B. Mefenacet; Sulfonylharnstoffe, wie z.B. Amidosulfuron, Bensulfuron-methyl, Chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Met- sulfuron-methyl, Nicosulfuron, Primisulfuron, Pyrazosulfuron-ethyl, Thifensulfuronmethyl, Triasulfuron und Tribenuron-methyl; Thiolcarbamate, wie z.B. Butylate, Cycloate, Diallate, EPTC, Esprocarb, Molinate, Prosulfocarb, Thiobencarb und Triallate; Triazine, wie z.B. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne und Terbutylazin; Triazinone, wie z.B. Hexazinon, Metamitron und Metribuzin; Sonstige, wie z.B. Aminotriazol, Benfuresate, Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate und Tridiphane. Linuron and methabenzthiazuron; Hydroxylamines such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; Imidazolinones such as imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as bromoxynil, dichlobenil and ioxynil; Oxyacetamides such as mefenacet; Sulfonylureas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, Met- sulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuronmethyl, triasulfuron and tribenuron-methyl; Thiol carbamates such as butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines such as atrazine, cyanazine, simazin, simetryne, terbutryne and terbutylazine; Triazinones such as hexazinone, metamitron and metribuzin; Others such as aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Schutzstoffen gegen Vogelfraß, Pflanzennährstoffen und Bodenstrukturverbesserungsmitteln ist möglich. A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus durch weiteres Verdünnen bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Emulsionen, Pulver, Pasten und Granulate angewandt werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Spritzen, Sprühen,The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying,
Streuen. Scatter.
Die erfindungsgemäßen Wirkstoffe können sowohl vor als auch nach dem Auflaufen der Pflanzen appliziert werden. Sie können auch vor der Saat in den Boden eingearbeitet werden. Die angewandte Wirkstoffmenge kann in einem größeren Bereich schwanken. Sie hängt im wesentlichen von der Art des gewünschten Effektes ab. Im allgemeinen liegen die Aufwandmengen zwischen 10 g und 10 kg Wirkstoff pro Hektar Bodenfläche, vorzugsweise zwischen 50 g und 5 kg pro ha. The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing. The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 10 g and 10 kg of active ingredient per hectare of soil, preferably between 50 g and 5 kg per ha.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den nachfolgenden Beispielen hervor. Herstellunesbeispiele: Beispiel 1 The preparation and use of the active compounds according to the invention can be seen from the examples below. Manufacturing examples: Example 1
Figure imgf000031_0002
Figure imgf000031_0002
(Verfahren (a))  (Method (a))
Eine Mischung aus 1,9 g (10 mMol) 4-Ethoxy-5-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-on, 2,7 g (1 1 mMol) 2-Methoxycarbonyl-phenylsulfonyl-isocyanat und 50 ml Acetonitril wird 16 Stunden bei 20°C gerührt. Nach Einengen im Wasserstrahlvakuum wird der Rückstand mit Diethylether digeriert und das kristalline Produkt durch Absaugen isoliert. A mixture of 1.9 g (10 mmol) of 4-ethoxy-5-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 2.7 g (11 mmol) of 2- Methoxycarbonyl-phenylsulfonyl isocyanate and 50 ml of acetonitrile is stirred at 20 ° C for 16 hours. After concentration in a water jet vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by suction.
Man erhält 3,9 g (91% der Theorie) 4-Ethoxy-5-ethylthio-2-(2-methoxycarbonylphenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on vom Schmelzpunkt 162°C. 3.9 g (91% of theory) of 4-ethoxy-5-ethylthio-2- (2-methoxycarbonylphenylsulfonylaminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one from Melting point 162 ° C.
Beispiel 2 Example 2
Figure imgf000031_0001
Figure imgf000031_0001
(Isomerisierung) Eine Mischung aus 2,8 g (6 mMol) 4-Ethoxy-5-propargylthio-2-(2-methoxycarbonylphenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on (8), 50 ml Methylenchlorid, 50 ml Wasser, 0,3 g (7,5 mMol) Natriumhydoxid und 50 mg Tetrabutylammoniumbromid wird 16 Stunden bei 20°C gerührt. Dann wird mit 2N-Salzssäure angesäuert, die organische Phase abgetrennt, mit Magnesiumsulfat getrocknet undfiltriert. Das Filtrat wird eingeengt, der Rückstand mit Diethylether digeriert und das kristallin angefallene Produkt durch Absaugen isoliert. (Isomerization) A mixture of 2.8 g (6 mmol) of 4-ethoxy-5-propargylthio-2- (2-methoxycarbonylphenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one (8 ), 50 ml of methylene chloride, 50 ml of water, 0.3 g (7.5 mmol) of sodium hydroxide and 50 mg of tetrabutylammonium bromide is stirred at 20 ° C for 16 hours. It is then acidified with 2N hydrochloric acid, the organic phase is separated off, dried with magnesium sulfate and filtered. The filtrate is concentrated, the residue is digested with diethyl ether and the crystalline product is isolated by suction.
Man erhält 2,0 g (71% der Theorie) 4-Ethoxy-5-(propa-1,2-dienylthio)-2-(2-methoxycarbonyl-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on vom Schmelzpunkt 144°C. 2.0 g (71% of theory) of 4-ethoxy-5- (propa-1,2-dienylthio) -2- (2-methoxycarbonylphenylsulfonylaminocarbonyl) -2,4-dihydro-3H-1 are obtained, 2,4-triazol-3-one with a melting point of 144 ° C.
Beispiel 3 Example 3
Figure imgf000032_0001
Figure imgf000032_0001
(Verfahren (d))  (Method (d))
Eine Mischung aus 3,2 g (20 mMol) 4-Methoxy-5-methylthio-2,4-dihydro-3H-1,2,4- triazol-3-on, 7,6 g (24 mMol) 2-(N-Methoxy-N-methylaminosulfonyl)-benzolsulfochlorid (95%ig), 2,6 g (40 mMol) Natriumcyanat, 1,2 g (15 mMol) Pyridin und 50 ml Acetonitril wird 2 Tage bei 20°C gerührt. Nach Einengen im Wasserstrahlvakuum wird der Rückstand in Methylenchlorid/Wasser aufgenommen und mit 2N- Salzsäure auf pH=3 eingestellt. Die organische Phase wird dann abgetrennt, mit Natriumsulfat getrocknet und filtriert. Das Filtrat wird im Wasserstrahlvakuum eingeengt und der Rückstand durch Behandeln mit Methanol zur Kristallisation gebracht. Man erhält 5,7 g (61% der Theorie) 4-Methoxy-5-methylthio-2-[2-(N-methoxy-N-methyl-aminosulfonyl)-phenylsulfonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-on vom Schmelzpunkt 185°C. A mixture of 3.2 g (20 mmol) of 4-methoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 7.6 g (24 mmol) of 2- ( N-methoxy-N-methylaminosulfonyl) benzene sulfochloride (95%), 2.6 g (40 mmol) sodium cyanate, 1.2 g (15 mmol) pyridine and 50 ml acetonitrile are stirred at 20 ° C. for 2 days. After concentration in a water jet vacuum, the residue is taken up in methylene chloride / water and adjusted to pH = 3 with 2N hydrochloric acid. The organic phase is then separated off, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and the residue is crystallized by treatment with methanol. 5.7 g (61% of theory) of 4-methoxy-5-methylthio-2- [2- (N-methoxy-N-methylaminosulfonyl) phenylsulfonylaminocarbonyl] -2,4-dihydro-3H- 1,2,4-triazol-3-one with a melting point of 185 ° C.
Analog zu diesen Beispielen sowie entsprechend der allgemeinen Beschreibung der erfindungsgemäßen Herstellungsverfahren können beispielsweise auch die in der nachstehenden Tabelle 1 aufgefuhrten Verbindungen der Formel (I) hergestellt werden. Analogously to these examples and in accordance with the general description of the production processes according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) listed in Table 1 below.
Figure imgf000033_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000041_0001
Figure imgf000042_0001
Die in Tabelle 1 als Beispiel 62 aufgefuhrte Verbindung kann beispielsweise wie folgt hergestellt werden: The compound listed in Table 1 as Example 62 can be produced, for example, as follows:
Figure imgf000043_0001
Figure imgf000043_0001
(Verfahren b) Eine Mischung aus 3,8 g (13 mMol) 5-Ethylthio-4-methoxy-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-on, 2,9 g (13, 1 mMol) 2-Methoxycarbonyl-thiophen-3-sulfonamid, 2,0 g (13,2 mMol) Diazabicycloundecen (DBU) und 50 ml Acetonitril wird 3 Tage bei 20°C gerührt. Dann wird auf eine Mischung aus Methylenchlorid und wäßriger Salzsäure (ca. 10%ig) gegossen und gut verrührt. Die organische Phase wird abgetrennt, mit Wasser gewaschen, getrocknet und eingeengt. Der Rückstand wird aus Diethylether kristallisiert. (Method b) A mixture of 3.8 g (13 mmol) of 5-ethylthio-4-methoxy-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 2.9 g (13.1 mmol) of 2-methoxycarbonyl-thiophene-3-sulfonamide, 2.0 g (13.2 mmol) of diazabicycloundecene (DBU) and 50 ml of acetonitrile are stirred at 20 ° C. for 3 days. Then it is poured onto a mixture of methylene chloride and aqueous hydrochloric acid (approx. 10%) and stirred well. The organic phase is separated off, washed with water, dried and concentrated. The residue is crystallized from diethyl ether.
Man erhält 2,0 g (36,5% der Theorie) 5-Ethylthio-4-methoxy-2-(2-methoxycarbonylthiophen-3-yl-sulfonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on in Form von farblosen Kristallen vom Schmelzpunkt 153°C. 2.0 g (36.5% of theory) of 5-ethylthio-4-methoxy-2- (2-methoxycarbonylthiophen-3-yl-sulfonylaminocarbonyl) -2,4-dihydro-3H-1,2,4- triazol-3-one in the form of colorless crystals with a melting point of 153 ° C.
Aυsgangsstoffe der Formel (II): Beispiel (11-1) Starting materials of formula (II): Example (11-1)
Figure imgf000044_0001
Figure imgf000044_0001
Eine Mischung aus 4,0 g (20 mMol) 4-Ethoxy-5-mercapto-2,4-dihydro-3H-1,2,4-triazol-3-on-Kaliumsalz, 4,3 g (30 mMol) Methyliodid und 50 ml Methanol wird 16 Stunden bei 20°C gerührt und anschließend eingeengt. Der Rückstand wird mit Methylenchlorid/Wasser geschüttelt, die organische Phase abgetrennt, mit Magnesiumsulfat getrocknet und filtriert. Das Filtrat wird eingeengt, der Rückstand mit Diethylether digeriert und das kristallin angefallene Produkt durch Absaugen isoliert. A mixture of 4.0 g (20 mmol) of 4-ethoxy-5-mercapto-2,4-dihydro-3H-1,2,4-triazol-3-one potassium salt, 4.3 g (30 mmol) of methyl iodide and 50 ml of methanol is stirred at 20 ° C. for 16 hours and then concentrated. The residue is shaken with methylene chloride / water, the organic phase is separated off, dried with magnesium sulfate and filtered. The filtrate is concentrated, the residue is digested with diethyl ether and the crystalline product is isolated by suction.
Man erhält 1,8 g (51% der Theorie) 4-Ethoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-on vom Schmelzpunkt 99°C. 1.8 g (51% of theory) of 4-ethoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one with a melting point of 99 ° C. are obtained.
Analog Beispiel (II- 1) können beispielsweise auch die in der nachstehenden Tabelle 2 aufgefuhrten Verbindungen der Formel (II) hergestellt werden. Analogously to Example (II-1), the compounds of the formula (II) listed in Table 2 below can also be prepared.
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Ausgangsstoffe der Formel (IX): Beispiel (IX- 1)
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Starting materials of the formula (IX): Example (IX- 1)
Figure imgf000048_0002
Figure imgf000048_0002
Eine Mischung aus 25,5 g (100 mMol) 4-Ethoxy-1-(phenoxythiocarbonyl)-semicarbazid, 6,9 g (50 mMol) Kaliumcarbonat und 150 ml Methanol wird ca. 10 Minuten unter Rückfluß erhitzt. Dann wird eingeengt, der Rückstand mit Isopropanol digeriert und das kristalline Produkt durch Absaugen isoliert. Man erhält 21 g (100% der Theorie) 4-Ethoxy-5-mercapto-2,4-dihydro-3H-1,2,4-triazol-3-on-Kaliumsalz vom Schmelzpunkt 123°C. A mixture of 25.5 g (100 mmol) of 4-ethoxy-1- (phenoxythiocarbonyl) semicarbazide, 6.9 g (50 mmol) of potassium carbonate and 150 ml of methanol is heated under reflux for about 10 minutes. It is then concentrated, the residue is digested with isopropanol and the crystalline product is isolated by suction. 21 g (100% of theory) of 4-ethoxy-5-mercapto-2,4-dihydro-3H-1,2,4-triazol-3-one potassium salt of melting point 123 ° C. are obtained.
Analog Beispiel (IX- 1) können beispielsweise auch die in der nachstehenden Tabelle 3 aufgefuhrten Verbindungen der Formel (IX) hergestellt werden: Analogously to Example (IX-1), the compounds of the formula (IX) listed in Table 3 below can also be prepared:
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000048_0001
Figure imgf000049_0001
Ausgangsstoffe der Formel (XI): Beispiel (XI- 1) Starting materials of the formula (XI): Example (XI-1)
Figure imgf000050_0002
Figure imgf000050_0002
Eine Mischung aus 47,6 g (0,4 Mol) 4-Ethoxy-semicarbazid, 41 g (0,4 Mol) Triethylamin und 400 ml Methylenchlorid wird bei 0°C bis 15°C tropfenweise mit 70 g (0,4 Mol) Chlor-thioameisensäure-phenylester versetzt und die Mischung wird dann noch 16 Stunden bei 15°C bis 20°C gerührt. Das kristallin angefallene Produkt wird dann durch Absaugen isoliert. A mixture of 47.6 g (0.4 mol) of 4-ethoxy-semicarbazide, 41 g (0.4 mol) of triethylamine and 400 ml of methylene chloride is added dropwise at 0 ° C to 15 ° C with 70 g (0.4 mol ) Chloro-thio formic acid phenyl ester added and the mixture is then stirred for 16 hours at 15 ° C to 20 ° C. The crystalline product is then isolated by suction.
Man erhält 85,7 g (84% der Theorie) 4-Ethoxy-1-(phenoxythiocarbonyl)-semicarbazid vom Schmelzpunkt 153°C. 85.7 g (84% of theory) of 4-ethoxy-1- (phenoxythiocarbonyl) semicarbazide with a melting point of 153 ° C. are obtained.
Analog Beispiel (XI-1) können beispielsweise auch die in der nachstehenden Tabelle 4 aufgefuhrten Verbindungen der Formel (XI) hergestellt werden: Analogously to example (XI-1), the compounds of the formula (XI) listed in Table 4 below can also be prepared:
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Ausgangsstoffe der Formel (XII): Beispiel (XII- 1)
Figure imgf000052_0001
Starting materials of the formula (XII): Example (XII-1)
Figure imgf000053_0001
Figure imgf000053_0001
Eine Mischung aus 24,4 g (0,2 Mol) Ethoxyamin (50%ige wässrige Lösung), 100 ml Diethylether, 28 g (0,2 Mol) Kaliumcarbonat und 10 ml Wasser wird bei 0°C unter Rühren tropfenweise mit 31 g (0,2 Mol) Chlorameisensäure-phenylester versetzt. Nach dem Abklingen der Gasentwicklung wird die organische Phase abgetrennt, die wässrige Phase mit Essigsäureethylester nachextrahiert, die vereinigten organischenA mixture of 24.4 g (0.2 mol) of ethoxyamine (50% aqueous solution), 100 ml of diethyl ether, 28 g (0.2 mol) of potassium carbonate and 10 ml of water is added dropwise at 0 ° C. while stirring with 31 g (0.2 mol) phenyl chloroformate added. After the evolution of gas has subsided, the organic phase is separated off, the aqueous phase is subsequently extracted with ethyl acetate, and the combined organic phase
Phasen mit Magnesiumsulfat getrocknet und filtriert. Das Filtrat wird eingeengt, der Rückstand in 50 ml Ethanol aufgenommen und mit 10 g (0,2 Mol) Hydrazinhydrat versetzt. Nach einer Stunde Erhitzen unter Rückfluß wird abgekühlt und filtriert. Das Filtrat wird eingeengt, der Rückstand mit Diisopropylether digeriert und das kristallin angefallene Produkt durch Absaugen isoliert. Phases dried with magnesium sulfate and filtered. The filtrate is concentrated, the residue is taken up in 50 ml of ethanol and 10 g (0.2 mol) of hydrazine hydrate are added. After refluxing for one hour, the mixture is cooled and filtered. The filtrate is concentrated, the residue is digested with diisopropyl ether and the crystalline product is isolated by suction.
Man erhält 23,4 g (98% der Theorie) 4-Ethoxy-semicarbazid vom Schmelzpunkt 83°C. 23.4 g (98% of theory) of 4-ethoxy-semicarbazide with a melting point of 83 ° C. are obtained.
Analog Beispiel (XII- 1) können beispielsweise auch die in der nachstehenden Tabelle 5 aufgefuhrten Verbindungen der Formel (XII) hergestellt werdenAnalogously to example (XII-1), the compounds of the formula (XII) listed in Table 5 below can also be prepared
Figure imgf000054_0001
Figure imgf000054_0001
Figure imgf000054_0002
Ausgangsstoffe der Formel IV: Beispiel (IV- 1):
Figure imgf000054_0002
Starting materials of formula IV: Example (IV-1):
Figure imgf000055_0001
Figure imgf000055_0001
Zu einer gut gerührten Mischung aus 16,2 g (0,1 Mol) 4-Methoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-on, 4,4 g (0,1 1 Mol) Natriumhydroxid, 100 mg Tetrabutylammoniumbromid, 250 ml Wasser und 500 ml Methylenchlorid werden bei To a well-stirred mixture of 16.2 g (0.1 mol) of 4-methoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 4.4 g (0 , 1 1 mol) of sodium hydroxide, 100 mg of tetrabutylammonium bromide, 250 ml of water and 500 ml of methylene chloride are added
20°C 17,2 g (0,1 1 Mol) Chlorameisensäure-phenylester zugetropft und noch 16 Stunden nachgerührt. Die organische Phase wird abgetrennt, mit Wasser gewaschen, getrocknet und eingeengt. Der ölige Rückstand wird mit Ether zur Kristallisation gebracht. Man erhält 24,0 g (85% der Theorie) 4-Methoxy-5-methylthio-2-phenoxycarbonyl- 2,4-dihydro-3H-1,2,4-triazol-3-on in Form farbloser Kristalle vom Schmelzpunkt 113°C 20 ° C 17.2 g (0.1 1 mol) phenyl chloroformate was added dropwise and the mixture was stirred for a further 16 hours. The organic phase is separated off, washed with water, dried and concentrated. The oily residue is crystallized with ether. 24.0 g (85% of theory) of 4-methoxy-5-methylthio-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one are obtained in the form of colorless crystals with a melting point of 113 ° C
Analog Beispiel (IV- 1) können beispielsweise auch die in der nachstehenden Tabelle 6 aufgefuhrten Verbindungen der Formel (IV) hergestellt werden. Analogously to Example (IV-1), the compounds of the formula (IV) listed in Table 6 below can also be prepared.
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Anwendungsbeispiele : Examples of use:
In den nachfolgenden Anwendungsbeispielen wird folgende Verbindung zum Vergleich herangezogen: The following connection is used for comparison in the following application examples:
Figure imgf000064_0001
Figure imgf000064_0001
4-Amino-5-methylthio-2-(2-trifluormethoxy-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on (bekannt aus EP-A431291/LeA 27156). 4-Amino-5-methylthio-2- (2-trifluoromethoxy-phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one (known from EP-A431291 / LeA 27156).
Beispiel A Example A
Post-emergence-Test Post emergence test
Lösungsmittel: 5 Gewichtsteile Aceton Solvent: 5 parts by weight of acetone
Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, mix 1
Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration. Part by weight of active ingredient with the stated amount of solvent, adds the stated amount of emulsifier and dilutes the concentrate with water to the desired concentration.
Mit der Wirkstoffzubereitung spritzt man Testpflanzen, welche eine Höhe von 5 -15 cm haben so, daß die jeweils gewünschten Wirkstoffmengen pro Flächeneinheit ausgebracht werden. Die Konzentration der Spritzbrühe wird so gewählt, daß in 2000 1 Wasser/ha die jeweils gewünschten Wirkstoffmengen ausgebracht werden. Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle. Es bedeuten: Test plants with a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 2000 l of water / ha. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
0 % = keine Wirkung (wie unbehandelte Kontrolle) 0% = no effect (like untreated control)
100 % = totale Vernichtung  100% = total annihilation
In diesem Test zeigen beispielsweise die Verbindungen gemäß den Herstellungsbeispielen 1, 2, 4, 5, 6, 7 und 8 bei durchweg sehr guter Verträglichkeit gegenüber Kulturpflanzen, wie z.B. Weizen, erheblich stärkere Wirkung gegen Unkräuter als die bekannte Verbindung (A). Entsprechendes gilt auch fur die Verbindungen gemäß den Herstellungsbeispielen 22, 29, 31 und 48 (siehe Tabelle A).
Figure imgf000066_0001
In this test, for example, the compounds according to Preparation Examples 1, 2, 4, 5, 6, 7 and 8, with very good tolerability to crop plants, such as wheat, for example, show considerably greater activity against weeds than the known compound (A). The same also applies to the compounds according to Preparation Examples 22, 29, 31 and 48 (see Table A).
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000070_0001
Beispiel B Example B
Pre-emergence-Test Pre-emergence test
Lösungsmittel: 5 Gewichtsteile Aceton Solvent: 5 parts by weight of acetone
Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration. Samen der Testpflanzen werden in normalen Boden ausgesät. Nach 24 Stunden wird der Boden mit der Wirkstoffzubereitung begossen. Dabei hält man die Wassermenge pro Flächeneinheit zweckmäßigerweise konstant. Die Wirkstofϊkonzentration in der Zubereitung spielt keine Rolle, entscheidend ist nur die Aufwandmenge des Wirkstoffs pro Flächeneinheit. Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle.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 active ingredient preparation is poured onto the floor. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
Es bedeuten: It means:
0 % = keine Wirkung (wie unbehandelte Kontrolle) 0% = no effect (like untreated control)
100 % = totale Vernichtung  100% = total annihilation
In diesem Test zeigen beispielsweise die Verbindungen gemäß den Herstellungsbeispielen 1, 4, 5, 6, 7 und 8 erheblich stärkere Wirkung gegen Unkräuter als die bekannte Verbindung (A). Entsprechendes gilt auch fur die Verbindungen gemäß den Herstellungsbeispielen 11, 12, 22, 29, 31, 33, 34, 35 und 47 (siehe Tabelle B).
Figure imgf000072_0001
In this test, for example, the compounds according to Preparation Examples 1, 4, 5, 6, 7 and 8 show considerably greater activity against weeds than the known compound (A). The same also applies to the compounds according to Preparation Examples 11, 12, 22, 29, 31, 33, 34, 35 and 47 (see Table B).
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000076_0001
Beispiel C Example C
Venturia-Test (Apfel) / protektiv Venturia test (apple) / protective
Lösungsmittel: 4,7 Gewichtsteile Aceton Solvent: 4.7 parts by weight of acetone
Emulgator: 0,3 Gewichtsteile Alkylarylpolyglykolether  Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration. To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit bespritzt man junge Pflanzen mit der Wirkstoffzubereitung bis zur Tropfhässe. Nach Antrocknen des Spritzbelages werden die Pflanzen mit einer wäßrigen Konidiensuspension des Apfelschorferregers Venturia inaequalis inokuliert und verbleiben dann 1 Tag bei 20°C und 100% relativer Luftfeuchtigkeit in einer Inkubationskabine. To test for protective efficacy, young plants are sprayed with the preparation of active compound until they are dripping. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen Venturia inaequalis and then remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 1 day.
Die Pflanzen werden dann im Gewächshaus bei 20°C und einer relativen Luftfeuchtigkeit von ca. 70% aufgestellt. The plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%.
12 Tage nach der Inokulation erfolgt die Auswertung. Evaluation is carried out 12 days after the inoculation.
In diesem Test zeigen beispielsweise die Verbindungen gemäß den Herstellungsbeispielen 1, 4, 5 und 6 bei einer Wirkstoffkonzentration von 10 ppm einen Wirkungsgrad von 100%. In this test, for example, the compounds according to Preparation Examples 1, 4, 5 and 6 show an efficiency of 100% at an active ingredient concentration of 10 ppm.
Figure imgf000078_0001
Figure imgf000078_0001

Claims

Patentansprüche  Claims
1. Sulfonylaminocarbonyltriazolinone mit über Sauerstoff und Schwefel gebundenen Substituenten der allgemeinen Formel (I), 1. sulfonylaminocarbonyltriazolinones with substituents of the general formula (I) bonded via oxygen and sulfur,
Figure imgf000079_0001
Figure imgf000079_0001
in welcher n fur die Zahlen 0, 1 oder 2 steht, R1 fur Wasserstoff oder fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Aryl, Ar- alkyl steht, in which n represents the numbers 0, 1 or 2, R 1 represents hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl,
R2 fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Cycloalkylalkyl, Aralkyl, Aryl steht, und R2 fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Aralkyl, Aryl, Heteroaryl steht, sowie Salze von Verbindungen der Formel (I), wobei die Verbindungen 4-Methoxy-5-methylthio-2-(2-methoxycarbonyl-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Ethoxy-5- ethylthio-2-[2-(N-methoxy)-methylaminosulfonyl-phenylsulfonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Propoxy-5-allylthio-2-(2-methyl-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Methoxy-5-methylthio-2-(2-methoxycarbonyl-thien-3-yl-sulfonyl-aminocarbonyl)- 2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Ethoxy-5-methylthio-2-(2-methoxy-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Ethoxy-5╌ ethylthio-2-[2-(2-chlor-ethoxy)-phenylsulfonyl-aminocarbonyl]-2,4-dihydro-3H- 1,2,4-triazol-3-on, 4-Allyloxy-5-ethylthio-2-(2-fluor-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on, 4-Methoxy-5-ethylthio-2-(3-aminosulfonyl-pyridin-2-yl-sulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on und 4-Methoxy- 5 -ethylthio-2-(2, 6-difluor-phenylsulfonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-on ausgeschlossen sind. R 2 represents an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl, aryl, and R 2 represents an optionally substituted radical from the series alkyl, aralkyl, aryl, heteroaryl, and Salts of compounds of the formula (I), the compounds 4-methoxy-5-methylthio-2- (2-methoxycarbonyl-phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazole-3- on, 4-ethoxy-5-ethylthio-2- [2- (N-methoxy) methylaminosulfonylphenylsulfonylaminocarbonyl] -2,4-dihydro-3H-1,2,4-triazol-3-one, 4- Propoxy-5-allylthio-2- (2-methylphenylsulfonylaminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-methoxy-5-methylthio-2- (2nd -methoxycarbonyl-thien-3-yl-sulfonyl-aminocarbonyl) - 2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5-methylthio-2- (2-methoxy-phenylsulfonyl -aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5╌ ethylthio-2- [2- (2-chloroethoxy) phenylsulfonylaminocarbonyl] - 2,4-dihydro-3H- 1,2,4-triazol-3-one, 4-allyloxy-5-ethylthio-2- (2-fluorophenylsulfonylaminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3- on, 4-methoxy-5-ethylthio-2- (3-aminosulfonyl-pyridin-2-yl-sulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one and 4- Methoxy-5-ethylthio-2- (2, 6-difluoro-phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazol-3-one are excluded.
Verbindungen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß darin n fur die Zahlen 0, 1 oder 2 steht, R1 fur Wasserstoff, fur gegebenenfalls durch Fluor, Chlor, Brom, Cyano, C1- C4-Alkoxy, C1-C4-Alkyl-carbonyl oder C1-C4-Alkoxy-carbonyl substituiertes C1-C6-Alkyl, fur jeweils gegebenenfalls durch Fluor, Chlor und/oder Brom substituiertes C2-C6-Alkenyl oder C2-C6-Alkinyl, fur jeweils gegebenenfalls durch Fluor, Chlor, Brom und/oder C1-C4-Alkyl substituiertes C3-C6-Cycloalkyl oder C5-C6-Cycloalkenyl, oder fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C1-C4- Alkyl, Trifluormethyl, C1-C4-Alkoxy und/oder C1-C4-Alkoxy-carbonyl substituiertes Phenyl oder Phenyl-C1-C3-alkyl steht, Compounds of the formula (I) according to Claim 1, characterized in that n represents the numbers 0, 1 or 2, R 1 represents hydrogen, optionally fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 alkylcarbonyl or C 1 -C 4 alkoxycarbonyl substituted C 1 -C 6 alkyl, for in each case optionally substituted by fluorine, chlorine and / or bromine, C 2 -C 6 alkenyl or C 2 -C 6 -alkynyl, for in each case optionally substituted by fluorine, chlorine, bromine and / or C 1 -C 4 alkyl-substituted C 3 -C 6 cycloalkyl or C 5 -C 6 cycloalkenyl, or for each optionally substituted by fluorine, chlorine , Bromine, cyano, nitro, C 1 -C 4 -alkyl, trifluoromethyl, C 1 -C 4 -alkoxy and / or C 1 -C 4 -alkoxy-carbonyl-substituted phenyl or phenyl-C 1 -C 3 -alkyl,
R2 fur gegebenenfalls durch Fluor, Chlor, Brom Cyano, C3-C6-Cycloalkyl, C1-C4- Alkoxy, C1-C4- Alkylthio oder C1-C4-Alkoxy-carbonyl substituiertes C1-C6-Alkyl, fur jeweils gegebenenfalls durch Fluor, Chlor und/oder Brom substituiertes C2-C6-AIkenyl oder C2-C6-Alkinyl, fur jeweils gegebenenfalls durch Fluor, Chlor, Brom und/oder C1-C4-Alkyl substituiertes C3-C6-Cycloalkyl, C5-C6-Cycloalkenyl oder C3-C6- Cycloalkyl-C1-C3-alkyl, fur gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C1-C4-Alkyl, Trifluormethyl, C1-C4-Alkoxy und/oder C1- C4- Alkoxy-carbonyl substituiertes Phenyl-C1-C3 -alkyl, oder fur gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C1-C4- Alkyl, Trifluormethyl, C1-C4- Alkoxy, Fluor- und/oder Chlor-substituiertes C1- C3-Alkoxy, C1-C4-Alkylthio, Fluor- und/oder Chlor-substituiertes C1- C3-Alkylthio, C1-C4-Alkyl-sulfinyl, C1-C4-Alkylsulfonyl und/oder C1-C4-Alkoxy-carbonyl substituiertes Phenyl steht, und R 2 represents optionally substituted by fluorine, chlorine, bromine cyano, C 3 -C 6 cycloalkyl, C 1 -C 4 - alkoxy, C 1 -C 4 - alkylthio or C 1 -C 4 -alkoxy-carbonyl-substituted C 1 -C 6- alkyl, each for C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl optionally substituted by fluorine, chlorine and / or bromine, for each optionally substituted by fluorine, chlorine, bromine and / or C 1 -C 4 - Alkyl substituted C 3 -C 6 cycloalkyl, C 5 -C 6 cycloalkenyl or C 3 -C 6 cycloalkyl-C 1 -C 3 alkyl, optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 - C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy and / or C 1 - C 4 alkoxy carbonyl-substituted phenyl C 1 -C 3 alkyl, or for fluorine, chlorine, bromine, cyano, nitro, if appropriate, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy, fluorine and / or chlorine substituted C 1 - C 3 alkoxy, C 1 -C 4 alkylthio, fluorine and / or chlorine substituted C 1 - C 3 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl and / or C 1 -C 4 alkoxycarbonyl substituted phenyl, and
R3 fur die Gruppierung steht
Figure imgf000081_0001
R 3 stands for the grouping
Figure imgf000081_0001
worin wherein
R4 und R5 gleich oder verschieden sind und fur Wasserstoff, Fluor,R 4 and R 5 are the same or different and are hydrogen, fluorine,
Chlor, Brom, lod, Nitro, C1-C5-Alkyl (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Carboxy, C1-C4- Alkoxycarbonyl, C1-C4-Alkylamino-carbonyl, Di-(C1-C4-alkyl)aminocarbonyl, Hydroxy, C1-C4-Alkoxy, Formyloxy, C1-C4-Alkylcarbonyloxy, C1-C4-Alkoxy-carbonyloxy, C1-C4-Alkylaminocarbonyloxy, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4- Alkylsulfonyl, Di-(C1-C4-alkyl)-aminosulfonyl, C3-C6-Cycloalkyl oder Phenyl substituiert ist), fur C2-C6-Alkenyl (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, C1-C4-Alkoxy-carbonyl, Carboxy oder Phenyl substituiert ist), für C2-C6-Alkinyl (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, C1-C4-Alkoxycarbonyl, Carboxy oder Phenyl substituiert ist), fur C1-C4-Alkoxy (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Carboxy, C1-C4-Alkoxy-carbonyl, C1-C4-Alkoxy, C1-C4- Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4-Alkylsulfonyl substituiert ist), fur C1-C4-Alkylthio (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Carboxy, C1-C4-Alkoxy-carbonyl, C1- C4-Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4-Alkylsulfonyl substituiert ist), fur C2-C6-Alkenyloxy (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano oder C1-C4-Alkoxy-carbonyl substituiert ist), fur C2-C6-Alkenylthio (welches gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C1-C3-Alkylthio oder C1- C4-Alkoxycarbonyl substituiert ist), C3-C6-Alkinyloxy, C3-C5- Alkinylthio oder fur den Rest -S(O)p-R6 stehen, wobei p fur die Zahlen 1 oder 2 steht und Chlorine, bromine, iodine, nitro, C 1 -C 5 -alkyl (which may be replaced by fluorine, chlorine, bromine, cyano, carboxy, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylamino-carbonyl, di- ( C 1 -C 4 alkyl) aminocarbonyl, hydroxy, C 1 -C 4 alkoxy, formyloxy, C 1 -C 4 alkylcarbonyloxy, C 1 -C 4 alkoxycarbonyloxy, C 1 -C 4 alkylaminocarbonyloxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, di (C 1 -C 4 alkyl) aminosulfonyl, C 3 -C 6 cycloalkyl or phenyl is substituted), for C 2 -C 6 alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C 1 -C 4 alkoxycarbonyl, carboxy or phenyl), for C 2 -C 6 alkynyl (which is optionally substituted by fluorine, Chlorine, bromine, cyano, C 1 -C 4 alkoxycarbonyl, carboxy or phenyl is substituted) for C 1 -C 4 alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxy, C 1 -C 4 alkoxy carbonyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl substituted i st), for C 1 -C 4 alkylthio (which may be replaced by fluorine, chlorine, bromine, cyano, carboxy, C 1 -C 4 alkoxycarbonyl, C 1 - C 4 alkylthio, C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl) for C 2 -C 6 alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C 1 -C 4 alkoxycarbonyl) for C 2 -C 6 -alkenylthio (which may be replaced by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 3 -alkylthio or C 1 - C 4 -alkoxycarbonyl is substituted), C 3 -C 6 -alkynyloxy, C 3 -C 5 -alkynylthio or for the radical -S (O) p -R 6 , where p stands for the numbers 1 or 2 and
R6 fur C1-C4-Alkyl (welches gegebenenfalls durch Fluor, Chlor, Brom,R 6 for C 1 -C 4 alkyl (which may be replaced by fluorine, chlorine, bromine,
Cyano oder C1-C4-Alkoxy-carbonyl substituiert ist), C3-C6- Alkenyl, C3-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Alkoxy-C1-C4- alkylamino, C1-C4-Alkylamino, Di-(C1-C4-alkyl)-amino, Phenyl oder fur den Rest -NHOR 7 steht, wobei R7 fur C1 -C12-Alkyl (welches gegebenenfalls durch Fluor, Chlor,Cyano or C 1 -C 4 alkoxy-carbonyl is substituted), C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy-C 1 - C 4 alkylamino, C 1 -C 4 alkylamino, di- (C 1 -C 4 alkyl) amino, phenyl or the radical -NHOR 7 , where R 7 is C 1 -C 12 alkyl (which optionally by fluorine, chlorine,
Cyano, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Alkyl-carbonyl, C1-C4- Alkoxy- carbonyl, C1-C4-Alkylamino-carbonyl oder Di-(C1- C4-alkyl)-amino-carbonyl substituiert ist), fur C3-C6-Alkenyl (welches gegebenenfalls durch Fluor, Chlor oder Brom substituiert ist), C3-C6-Alkinyl, C3-C6-Cycloalkyl, C3-C6- Cycloalkyl-C1-C2-alkyl, Phenyl-C1-C2-alkyl (welches gegebenenfalls durch Fluor, Chlor, Nitro, Cyano, C1-C4- Alkyl, C1-C4-Alkoxy oder C1-C4-Alkoxy-carbonyl substituiert ist), fur Benzhydryl oder fur Phenyl (welches gegebenenfalls durch Fluor, Chlor, Nitro, Cyano, C1-C4-Alkyl, Trifluormethyl, C1-C4-Alkoxy, C1-C2-Fluoralkoxy, C1-C4- Alkylthio, Trifluormethylthio oder C1-C4-Alkoxy- carbonyl substituiert ist) steht, Cyano, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 - Alkoxy-carbonyl, C 1 -C 4 -alkylamino-carbonyl or di- (C 1 - C 4 -alkyl) -amino-carbonyl is substituted) for C 3 -C 6 -alkenyl (which may be substituted by fluorine, chlorine or bromine is substituted), C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 - cycloalkyl-C 1 -C 2 alkyl, phenyl-C 1 -C 2 alkyl (which may be substituted by fluorine , Chlorine, nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -alkoxy-carbonyl is substituted), for benzhydryl or for phenyl (which may be replaced by fluorine, chlorine, nitro , Cyano, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy, C 1 -C 2 fluoroalkoxy, C 1 -C 4 alkylthio, trifluoromethylthio or C 1 -C 4 alkoxycarbonyl ) stands,
R4 und/oder R5 weiterhin fur Phenyl oder Phenoxy, fur C1-C4-Alkylcarbonylamino, C1-C4-Alkoxy-carbonylamino, C1-C4-Alkylam.nocarbonyl-amino, Di-(C1-C4-alkyl)-amino-carbonylamino, oder fur den Rest -CO-R8 stehen, wobei R 4 and / or R 5 furthermore for phenyl or phenoxy, for C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxycarbonylamino, C 1 -C 4 alkylam.nocarbonylamino, di- (C 1 - C 4 alkyl) amino carbonylamino, or for the radical -CO-R 8 , where
R8 fur Wasserstoff, C1-C6-Alkyl, C3-C6-Cycloalkyl, C1-C6- Alkoxy, C3-C6-Cycloalkoxy, C3-C6-Alkenyloxy, C1-C4- Alkylthio, C1-C4-Alkylamino, C1-C4-Alkoxyamino, C1-C4- Alkoxy-C1-C4-alkyl-amino oder Di-(C1-C4-alkyl)-amino steht (welche gegebenenfalls durch Fluor und/oder Chlor substituiert sind), R 8 for hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy, C 3 -C 6 alkenyloxy, C 1 -C 4 - alkylthio, C 1 -C 4 alkylamino, C 1 -C 4 alkoxyamino, C 1 -C 4 - Alkoxy-C 1 -C 4 -alkylamino or di- (C 1 -C 4 -alkyl) -amino (which are optionally substituted by fluorine and / or chlorine),
R4 und/oder R5 weiterhin fur Trimethylsilyl, Thiazolinyl, C1-C4-Alkylsulfonyloxy, Di-(C1-C4-alkyl)-aminosulfonylamino oder fur denR 4 and / or R 5 furthermore for trimethylsilyl, thiazolinyl, C 1 -C 4 -alkylsulfonyloxy, di- (C 1 -C 4 -alkyl) -aminosulfonylamino or for the
Rest -CH=N-R9 stehen, wobei R9 fur gegebenenfalls durch Fluor, Chlor, Cyano, Carboxy, C1- C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl oder C1- C4-Alkylsulfonyl substituiertes C1-C6-Alkyl, fur gegebenenfalls durch Fluor oder Chlor substituiertes Benzyl, fur gegebenenfalls durch Fluor oder Chlor substituiertes C3-C6-Alkenyl oder C3-C6-Alkinyl, fur gegebenenfalls durch Fluor, Chlor, Brom, C1-C4-Alkyl, C1-C4-Alkoxy, Trifluormethyl, Trifluormethoxy oder Trifluormethylthio substituiertes Phenyl, fur gegebenenfalls durch Fluor und/oder Chlor substituiertes C1- C6-Alkoxy, C3-C6-Alkenoxy, C3-C6-Alkinoxy oder Benzyloxy fur Amino, C1-C4-Alkylamino, Di-(C1-C4-alkyl)-amino, Phenylamino, C1-C4-Alkyl-carbonyl-amino, C1-C4-Alkoxycarbonylamino, C1-C4-Alkyl-sulfonylamino oder fur gegebenenfalls durch Fluor, Chlor, Brom oder Methyl substituiertes Phenylsulfonylamino steht, weiterhin -CH = NR stand 9, wherein R 9 represents optionally substituted by fluorine, chlorine, cyano, carboxy, C 1 - C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl or C 1 - C 4- Alkylsulfonyl substituted C 1 -C 6 alkyl, for benzyl optionally substituted by fluorine or chlorine, for optionally C 3 -C 6 alkenyl or C 3 -C 6 alkynyl substituted by fluorine or chlorine, for optionally substituted by fluorine, chlorine , bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio-substituted phenyl, represents optionally fluorine- and / or chlorine-substituted C 1 - C 6 alkoxy, C 3 -C 6 - Alkenoxy, C 3 -C 6 alkynoxy or benzyloxy for amino, C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, phenylamino, C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxycarbonylamino, C 1 -C 4 alkylsulfonylamino or phenylsulfonylamino optionally substituted by fluorine, chlorine, bromine or methyl
R3 fur den Rest steht
Figure imgf000083_0001
R 3 represents the rest
Figure imgf000083_0001
worin R 10 fur Wasserstoff oder C1-C4-Alkyl steht, wherein R 10 represents hydrogen or C 1 -C 4 alkyl,
R 11 und R12 gleich oder verschieden sind und fur Wasserstoff, Fluor, Chlor, Brom, Nitro, Cyano, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/ oder Chlor substituiert ist), Carboxy, C1-C4-Alkoxy-carbonyl, Dimethylaminocarbonyl, C1-C4-Alkylsulfonyl oder Di-(C1-C4-alkyl)-aminosurfonyl stehen; weiterhin R 11 and R 12 are the same or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine), carboxy, C 1 -C 4 -alkoxy-carbonyl, dimethylaminocarbonyl, C 1 -C 4 -alkylsulfonyl or di- (C 1 -C 4 -alkyl) -aminosurfonyl; Farther
R3 fur den Rest steht,R 3 represents the rest,
Figure imgf000084_0002
Figure imgf000084_0002
worin  wherein
R13 und R14 gleich oder verschieden sind und fur Wasserstoff, Fluor, Chlor, Brom, Nitro, Cyano, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist) oder C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), stehen; weiterhin R 13 and R 14 are the same or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine) or C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine); Farther
R3 fur den Rest steht,
Figure imgf000084_0001
R 3 represents the rest,
Figure imgf000084_0001
worin  wherein
R15 und R16 gleich oder verschieden sind und fur Wasserstoff, Fluor, Chlor, Brom, Nitro, Cyano, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/ oder Chlor substituiert ist), fur C1-C4-Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4- Alkylsulfonyl (welche gegebenenfalls durch Fluor und/ oder Chlor substituiert sind), fur Aminosulfonyl, Mono-(C1-C4-alkyl)- aminosulfonyl, fur Di-(C1-C4-alkyl)-aminosulfonyl oder C1-C4- Alkoxy-carbonyl oder Dimethylaminocarbonyl stehen; weiterhin R 15 and R 16 are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine), for C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 - Alkylsulfonyl (which are optionally substituted by fluorine and / or chlorine), for aminosulfonyl, mono- (C 1 -C 4 alkyl) aminosulfonyl, for di (C 1 -C 4 alkyl) aminosulfonyl or C 1 -C 4 - alkoxycarbonyl or dimethylaminocarbonyl; Farther
R3 fur den Rest steht,R 3 represents the rest,
Figure imgf000085_0001
Figure imgf000085_0001
worin  wherein
R17 und R18 gleich oder verschieden sind und fur Wasserstoff, Fluor,R 17 and R 18 are the same or different and are hydrogen, fluorine,
Chlor, Brom, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Brom substituiert ist), C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), fur C1-C4- Alkylthio, C1-C4- Alkylsulfinyl oder C1-C4-Alkylsulforiyl (welche gegebenenfalls durch Fluor und/oder Chlor substituiert sind), oder fur Di-(C1-C4-alkyl)-aminosulfonyl stehen; weiterhin Chlorine, bromine, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or bromine), C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine), for C 1 -C 4 - Alkylthio, C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulforiyl (which are optionally substituted by fluorine and / or chlorine), or represent di- (C 1 -C 4 alkyl) aminosulfonyl; Farther
R3 fur den Rest steht,R 3 represents the rest,
Figure imgf000085_0002
Figure imgf000085_0002
wonn  wonn
R19 und R20 gleich oder verschieden sind und fur Wasserstoff, Fluor,R 19 and R 20 are the same or different and are hydrogen, fluorine,
Chlor, Brom, Cyano, Nitro, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C4-Alkoxy (welches gegebenenfalls durch Fluor und/ oder Chlor substituiert ist), C1-C4-Alkylthio, C1-C4-Alkylsulfinyl oder C1-C4-Alkylsulfonyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), Di-(C1-C4-alkyl)-amino-sulfonyl, C1-C4-Alkoxy-carbonyl oder Dimethylaminocarbonyl stehen, und fur Sauerstoff, Schwefel oder die Gruppierung N-Z steht, wobei Chlorine, bromine, cyano, nitro, C 1 -C 4 -alkyl (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 -alkoxy (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine is), di (C 1 -C 4 alkyl) amino sulfonyl, C 1 -C 4 alkoxycarbonyl or dimethylaminocarbonyl, and represents oxygen, sulfur or the grouping NZ, where
Z fur Wasserstoff, C1-C4-Alkyl (welches gegebenenfalls durch Fluor, Chlor, Brom oder Cyano substituiert ist), C3-C6- Cycloalkyl, Benzyl, Phenyl (welches gegebenenfalls durch Fluor, Chlor, Brom oder Nitro substituiert ist), C1-C4-Alkylcarbonyl, C1-C4-Alkoxy-carbonyl oder Di-(C1-C4-alkyl)- aminocarbonyl steht; weiterhin Z for hydrogen, C 1 -C 4 -alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C 3 -C 6 -cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro ), C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl or di (C 1 -C 4 alkyl) aminocarbonyl; Farther
R3 fur den Rest steht,R 3 represents the rest,
Figure imgf000086_0001
Figure imgf000086_0001
worin  wherein
R21 und R22 gleich oder verschieden sind und fur Wasserstoff, C1- C4-Alkyl, Halogen, C1-C4-Alkoxycarbonyl, C1-C4-Alkoxy oder C1-C4-Halogenalkoxy stehen, R 21 and R 22 are identical or different and represent hydrogen, C 1 - C 4 alkyl, halogen, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy,
Y1 fur Schwefel oder die Gruppierung N-R23 steht, wobei Y 1 represents sulfur or the grouping NR 23 , where
R23 für Wasserstoff oder C1-C4-Alkyl steht; weiterhin R 23 represents hydrogen or C 1 -C 4 alkyl; Farther
R3 für den Rest steht,
Figure imgf000086_0002
R 3 represents the rest,
Figure imgf000086_0002
worin R24 fur Wasserstoff, C1-C4-Alkyl, Benzyl, Pyridyl, Chinolinyl oderwherein R 24 for hydrogen, C 1 -C 4 alkyl, benzyl, pyridyl, quinolinyl or
Phenyl steht, R25 fur Wasserstoff, Halogen, Cyano, Nitro, C1-C4-Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C4- Alkoxy (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), Dioxolanyl oder C1-C4-Alkoxy-carbonyl steht und Phenyl stands for R 25 for hydrogen, halogen, cyano, nitro, C 1 -C 4 alkyl (which is optionally substituted by fluorine and / or chlorine), C 1 -C 4 alkoxy (which is optionally substituted by fluorine and / or chlorine is substituted), dioxolanyl or C 1 -C 4 alkoxy-carbonyl and
R26 fur Wasserstoff, Halogen oder C1-C4-Alkyl steht, und ferner R 26 represents hydrogen, halogen or C 1 -C 4 alkyl, and further
R3 fur eine der nachstehend aufgefuhrten Gruppierungen steht, R 3 represents one of the groupings listed below,
Figure imgf000087_0001
Figure imgf000087_0001
mit Ausnahme der in Anspruch 1 durch Disclaimer ausgeschlossenen Verbindungen. with the exception of the compounds excluded in claim 1 by disclaimer.
Verbindungen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß darin n fur die Zahlen 0, 1 oder 2 steht, Compounds of formula (I) according to claim 1, characterized in that n stands for the numbers 0, 1 or 2,
R1 für jeweils gegebenenfalls durch Fluor, Chlor, Cyano, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t- Butyl, fur jeweils gegebenenfalls durch Fluor, Chlor oder Brom substituiertes Propenyl, Butenyl, Propinyl oder Butinyl, fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Methyl oder Ethyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl, oder fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Methyl, Trifluormethyl oder Methoxy substituiertes Benzyl oder Phenyl steht, R2 fur jeweils gegebenenfalls durch Fluor, Chlor, Cyano, Methoxy, Ethoxy, Methylthio oder Ethylthio substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, fur jeweils gegebenenfalls durch Fluor, Chlor oder Brom substituiertes Propenyl, Butenyl, Propinyl, Butinyl oder Allenyl, fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Methyl oder Ethyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cyclopropylmethyl, Cyclobutylmethyl, Cyclopentylmethyl oder Cyclohexylmethyl oder fur jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Methyl, Trifluormethyl oder Methoxy substituiertes Phenyl oder Benzyl steht, R 1 for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, for each optionally substituted by fluorine, chlorine or bromine Propenyl, butenyl, propynyl or butynyl, for each cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or for benzyl each optionally substituted by fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy or phenyl, R 2 for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by fluorine, chlorine, cyano, methoxy, ethoxy, methylthio or ethylthio, for each optionally by fluorine, Chlorine or bromine-substituted propenyl, butenyl, propynyl, butynyl or allenyl, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or for each optionally by fluorine, Chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy-substituted phenyl or benzyl,
R3 fur den Rest steht,
Figure imgf000088_0001
R 3 represents the rest,
Figure imgf000088_0001
worin R4 fur Fluor, Chlor, Brom, Methyl, Ethyl, Propyl, Trifluormethyl,where R 4 for fluorine, chlorine, bromine, methyl, ethyl, propyl, trifluoromethyl,
Butoxy, Allyloxy, Propargyloxy, Methoxy, Ethoxy, Propoxy,Butoxy, allyloxy, propargyloxy, methoxy, ethoxy, propoxy,
Isopropoxy, Difluormethoxy, Trifluormethoxy, 2-Chlor-ethoxy, 2- Methoxy-ethoxy, C1-C3 -Alkylthio, C1-C3-Alkylsulfinyl, C1-C3- Alkylsulfonyl, Dimethylaminosulfonyl, Diethylaminosulfonyl, N- Methoxy-N-methylaminosulfonyl, Methoxyaminosulfonyl, Phenyl,Isopropoxy, difluoromethoxy, trifluoromethoxy, 2-chloroethoxy, 2-methoxy-ethoxy, C 1 -C 3 alkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 alkylsulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, N-methoxy- N-methylaminosulfonyl, methoxyaminosulfonyl, phenyl,
Phenoxy oder C1-C3- Alkoxy-carbonyl steht und Phenoxy or C 1 -C 3 - alkoxy-carbonyl and
R5 fur Wasserstoff, Methyl, Ethyl, Fluor, Chlor oder Brom steht; weiterhin R 5 represents hydrogen, methyl, ethyl, fluorine, chlorine or bromine; Farther
R3 fur den Rest
Figure imgf000088_0002
R 3 for the rest
Figure imgf000088_0002
worin R10 fur Wasserstoff steht, wherein R 10 represents hydrogen,
R1 1 fur Fluor, Chlor, Brom, Methyl, Methoxy, Difluormethoxy, Trifluormethoxy, Ethoxy, Methoxycarbonyl, Ethoxycarbonyl, Methylsulfonyl oder Dimethylaminosulfonyl steht und R12 fur Wasserstoff steht; weiterhin R 1 1 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or dimethylaminosulfonyl and R 12 represents hydrogen; Farther
R3 fur den Rest steht.
Figure imgf000089_0001
R 3 represents the rest.
Figure imgf000089_0001
worin  wherein
R fur C1 -C4-Alkyl steht, oder R represents C 1 -C 4 alkyl, or
R3 fur den Rest steht,
Figure imgf000089_0002
R 3 represents the rest,
Figure imgf000089_0002
worin  wherein
R24 fur C1-C3-Alkyl, Phenyl oder Pyridyl steht, R 24 represents C 1 -C 3 alkyl, phenyl or pyridyl,
R25 fur Wasserstoff, Fluor, Chlor oder Brom steht, R26 fur Fluor, Chlor, Brom oder C1-C3-Alkoxy-carbonyl steht, mit Ausnahme der in Anspruch 1 durch Disclaimer ausgeschlossenen Verbindungen. R 25 stands for hydrogen, fluorine, chlorine or bromine, R 26 stands for fluorine, chlorine, bromine or C 1 -C 3 alkoxy-carbonyl, with the exception of the compounds excluded in claim 1 by disclaimer.
4. Verfahren zur Herstellung der Verbindungen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß man (a) Triazolinone der allgemeinen Formel (II) 4. A process for the preparation of the compounds of formula (I) according to claim 1, characterized in that (a) triazolinones of the general formula (II)
Figure imgf000090_0002
Figure imgf000090_0002
in welcher n, R1 und R2 die in Anspruch 1 angegebene Bedeutung haben, mit Sulfonylisocyanaten der allgemeinen Formel (III) in which n, R 1 and R 2 have the meaning given in claim 1, with sulfonyl isocyanates of the general formula (III)
R3-SO2-N=C=O (III) in welcher R 3 -SO 2 -N = C = O (III) in which
R3 die in Anspruch 1 angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder daß man R 3 has the meaning given in claim 1, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or that
(b) Triazolinon-Derivate der allgemeinen Formel (IV) (b) triazolinone derivatives of the general formula (IV)
Figure imgf000090_0001
Figure imgf000090_0001
in welcher n, R1 und R2 die oben angegebene Bedeutung haben und Z fur Halogen, Alkoxy, Aralkoxy oder Aryloxy steht, mit Sulfonsäureamiden der allgemeinen Formel (V) R3-SO2-NH2 (V) in welcher in which n, R 1 and R 2 have the meaning given above and Z represents halogen, alkoxy, aralkoxy or aryloxy, with sulfonamides of the general formula (V) R 3 -SO 2 -NH 2 (V) in which
R3 die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder daß man R 3 has the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or that
(c) Triazolinone der allgemeinen Formel (II) (c) triazolinones of the general formula (II)
Figure imgf000091_0001
Figure imgf000091_0001
in welcher n, R1 und R2 die oben angegebene Bedeutung haben, mit Sulfonsäureamid-Derivaten der allgemeinen Formel (VI) in which n, R 1 and R 2 have the meaning given above, with sulfonamide derivatives of the general formula (VI)
R3-SO2-NH-CO-Z (VI) in welcher R 3 -SO 2 -NH-CO-Z (VI) in which
R3 die oben angegebene Bedeutung hat und R 3 has the meaning given above and
Z fur Halogen, Alkoxy, Aralkoxy oder Aryloxy steht, gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder daß man Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or that
(d) Triazolinone der allgemeinen Formel (II)
Figure imgf000092_0001
(d) triazolinones of the general formula (II)
Figure imgf000092_0001
in welcher n, R1 und R2 die oben angegebene Bedeutung haben, mit Sulfonsäurehalogeniden der allgemeinen Formel (VII) in which n, R 1 and R 2 have the meaning given above, with sulfonic acid halides of the general formula (VII)
R3-SO2-X (VII) in welcher R 3 -SO 2 -X (VII) in which
R3 die oben angegebene Bedeutung hat und X fur Halogen steht, und Metallcyanaten der allgemeinen Formel (VIII) R 3 has the meaning given above and X represents halogen, and metal cyanates of the general formula (VIII)
MOCN (VIII) in welcher MOCN (VIII) in which
M fur ein Alkalimetall oder Erdalkalimetall-äquivalent steht, gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, und gegebenenfalls die nach Verfahren (a), (b), (c) oder (d) erhaltenen Verbindungen der Formel (I) nach üblichen Methoden in Salze überfuhrt. M represents an alkali metal or alkaline earth metal equivalent, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and if appropriate the compounds of the formula (I) obtained by processes (a), (b), (c) or (d) converted into salts by conventional methods.
5. Herbizide und fungizide Mittel, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung der Formel (I) gemäß Anspruch 1. 5. Herbicidal and fungicidal compositions, characterized in that they contain at least one compound of the formula (I) according to Claim 1.
6. Verwendung von Verbindungen der allgemeinen Formel (I) zur Bekämpfung von unerwünschtem Pflanzenwachstum und/oder von phytopathogenen Pilzen. 6. Use of compounds of general formula (I) for combating undesirable plant growth and / or phytopathogenic fungi.
7. Triazolinone der allgemeinen Formel (II) 7. Triazolinones of the general formula (II)
Figure imgf000093_0002
Figure imgf000093_0002
in welcher n fur die Zahlen 0, 1 oder 2 steht, R1 fur Wasserstoff oder fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Aryl, Aralkyl steht, und in which n represents the numbers 0, 1 or 2, R 1 represents hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, and
R2 fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Cycloalkylalkyl, Aralkyl, Aryl steht. R 2 represents an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl, aryl.
8. Triazolinon-Derivate der allgemeinen Formel (IV) 8. Triazolinone derivatives of the general formula (IV)
Figure imgf000093_0001
Figure imgf000093_0001
in welcher n fur die Zahlen 0, 1 oder 2 steht, R1 fur Wasserstoff oder fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Aryl, Aralkyl steht, R2 fur einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Cycloalkylalkyl, Aralkyl, Aryl steht, und in which n represents the numbers 0, 1 or 2, R 1 represents hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, R 2 represents an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl, aryl, and
Z fur Halogen, Alkoxy, Aralkoxy oder Aryloxy steht. Z represents halogen, alkoxy, aralkoxy or aryloxy.
9. Mercapto-triazolinone der allgemeinen Formel (IX) 9. Mercapto-triazolinones of the general formula (IX)
Figure imgf000094_0002
Figure imgf000094_0002
in welcher R1 fur Wasserstoff oder fur einen gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Aryl, Aralkyl steht, und Metallsalze von Verbindungen der Formel (IX) in which R 1 represents hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, and metal salts of compounds of the formula (IX)
10. Semicarbazid-Derivate der allgemeinen Formel (XI) 10. Semicarbazide derivatives of the general formula (XI)
Figure imgf000094_0001
in welcher R1 fur Wasserstoff oder für einen gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Aryl, Aralkyl steht, und
Figure imgf000094_0001
in which R 1 represents hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, and
Y fur Halogen, Imidazolyl, Alkoxy, Aralkoxy oder Aryloxy steht. Y represents halogen, imidazolyl, alkoxy, aralkoxy or aryloxy.
PCT/EP1995/003768 1994-10-05 1995-09-22 Sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur WO1996011188A1 (en)

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CA 2201596 CA2201596A1 (en) 1994-10-05 1995-09-22 Sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur
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WO1997003056A1 (en) * 1995-07-11 1997-01-30 Bayer Aktiengesellschaft Herbicidal sulphonylamino(thio)carbonyl compounds
WO1997046540A1 (en) * 1996-05-30 1997-12-11 Bayer Aktiengesellschaft Substituted sulphonyl amino(thio)carbonyl compounds and their use as herbicides
US6297192B1 (en) 1998-01-24 2001-10-02 Bayer Aktiengesellschaft Selective herbicides based on N-aryl-triazoline(thi)ons and N-arlysulfonylamino(thio)carbonyl-triazoline(thi)ons
US6316386B1 (en) 1996-09-23 2001-11-13 Bayer Aktiengesellschaft Selective herbicides based on arylsulphonylaminocarbonyltriazolinones
US6869968B1 (en) 1996-03-21 2005-03-22 Allmirall Prodesfarma S.A. 2-(3H)-oxazolone derivatives and their use as COX-2 inhibitors
US7115543B2 (en) 2000-06-30 2006-10-03 Bayer Cropscience Ag Aryl sulfonyl amino carbonyl triazole based selective herbicides
USRE39607E1 (en) 1995-07-11 2007-05-01 Bayer Aktiengesellschaft Herbicidal sulphonylamino(thio) carbonyl compounds
EP2371823A1 (en) 2010-04-01 2011-10-05 Bayer CropScience AG Cyclopropyl-substituted phenylsulfonylamino(thio)carbonyltriazolinones, their production and use as herbicides and plant growth regulators

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CN110734433B (en) * 2018-07-19 2020-09-11 东莞市东阳光农药研发有限公司 Triazole compound and application thereof in agriculture

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Cited By (14)

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US6525211B1 (en) 1995-07-11 2003-02-25 Bayer Aktiengesellschaft Herbicidal sulphonylamino(thio)carbonyl compounds
WO1997003056A1 (en) * 1995-07-11 1997-01-30 Bayer Aktiengesellschaft Herbicidal sulphonylamino(thio)carbonyl compounds
USRE39607E1 (en) 1995-07-11 2007-05-01 Bayer Aktiengesellschaft Herbicidal sulphonylamino(thio) carbonyl compounds
US6251831B1 (en) 1995-07-11 2001-06-26 Bayer Aktiengesellschaft Herbicidal sulphonylamino(thio)carbonyl compounds
EP1344771A1 (en) * 1995-07-11 2003-09-17 Bayer CropScience AG 2-alkoxy-phenylsulphonic acid derivatives as intermediates for herbicidal sulphonylamino(thio)carbonyl compounds
US6869968B1 (en) 1996-03-21 2005-03-22 Allmirall Prodesfarma S.A. 2-(3H)-oxazolone derivatives and their use as COX-2 inhibitors
US6677277B1 (en) 1996-05-30 2004-01-13 Bayer Aktiengesellschaft Substituted sulphonyl amino(thio)carbonyl compounds and their use as herbicides
WO1997046540A1 (en) * 1996-05-30 1997-12-11 Bayer Aktiengesellschaft Substituted sulphonyl amino(thio)carbonyl compounds and their use as herbicides
JP2000514408A (en) * 1996-05-30 2000-10-31 バイエル・アクチエンゲゼルシヤフト Substituted sulfonylamino (thio) carbonyl compounds and their use as herbicides
US6316386B1 (en) 1996-09-23 2001-11-13 Bayer Aktiengesellschaft Selective herbicides based on arylsulphonylaminocarbonyltriazolinones
US6297192B1 (en) 1998-01-24 2001-10-02 Bayer Aktiengesellschaft Selective herbicides based on N-aryl-triazoline(thi)ons and N-arlysulfonylamino(thio)carbonyl-triazoline(thi)ons
US7115543B2 (en) 2000-06-30 2006-10-03 Bayer Cropscience Ag Aryl sulfonyl amino carbonyl triazole based selective herbicides
EP2371823A1 (en) 2010-04-01 2011-10-05 Bayer CropScience AG Cyclopropyl-substituted phenylsulfonylamino(thio)carbonyltriazolinones, their production and use as herbicides and plant growth regulators
WO2011120926A1 (en) 2010-04-01 2011-10-06 Bayer Cropscience Ag 4-cyclopropyl-2-[(5-oxo-4,5-dihydro-1,2,4-triazol-1-yl)(thio)carbonyl­aminosulfonyl]benzoic acid derivatives, processes for preparing them and use as herbicides and plant growth regulators

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