CA2189456C - Substituted aromatic thiocarboxylic acid amides and their use as herbicides - Google Patents

Substituted aromatic thiocarboxylic acid amides and their use as herbicides Download PDF

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Publication number
CA2189456C
CA2189456C CA002189456A CA2189456A CA2189456C CA 2189456 C CA2189456 C CA 2189456C CA 002189456 A CA002189456 A CA 002189456A CA 2189456 A CA2189456 A CA 2189456A CA 2189456 C CA2189456 C CA 2189456C
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group
alkyl
substituted
case
diyl
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CA002189456A
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French (fr)
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CA2189456A1 (en
Inventor
Karl-Heinz Linker
Kurt Findeisen
Roland Andree
Mark-Wilhelm Drewes
Andreas Lender
Otto Schallner
Wilhelm Haas
Hans-Joachim Santel
Markus Dollinger
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Bayer AG
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Bayer AG
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Priority claimed from DE19500439A external-priority patent/DE19500439A1/en
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Priority claimed from PCT/EP1995/001507 external-priority patent/WO1995030661A1/en
Publication of CA2189456A1 publication Critical patent/CA2189456A1/en
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Publication of CA2189456C publication Critical patent/CA2189456C/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
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    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
    • C07D211/86—Oxygen atoms
    • C07D211/88—Oxygen atoms attached in positions 2 and 6, e.g. glutarimide
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    • 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
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    • 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
    • C07D231/14—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 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
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    • 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
    • C07D231/14—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 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
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    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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    • C07D239/72—Quinazolines; Hydrogenated quinazolines
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Abstract

The invention relates to novel substituted aromatic thiocarboxylic acid amid es of general formula (I) in which R1, R2 and R3 are hydrogen or various substituents and Z is possibly substituted monocyclic or bicyclic, saturated or unsaturated heterocyclyl, heterocyclyl amino or heterocyclyl imino, and their use as herbicides.

Description

Le A 30 388-PC 1 21$9456 FILt:, t~tt~'1ia THIS A ~~~ c ffi(i"TRANSLATIOfd SUBSTITUTED AROMATIC THIOCARBOXAMIDES AND THEIR USE AS
I~~RBICIDFS
The invention relates to novel substituted aromatic thiocarboxamides, to processes for.
their preparation and to their use as herbicides.
It is ali-eady known that certain aromatic carbothioamides, for example 2,6-dichloro-benzothioamide ("chlorthiamid"), possess herbicidal properties (cf. GB-B
987253).
However, the activity of this previously known compound, especially at low application rates and concentrations, is not entirely satisfactory in all areas of application.
The novel substituted aromatic thiocarboxamides have now been found of the general formula (I) R3 Rx (4 NHz R' in which R' represents hydrogen or halogen, Rz represents the following group -A'-Az-A' in which A' represents a single bond, or represents oxygen, sulphur, -SO-, -SOz , -CO-or the group -N-A'-, in which A' represents hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylsulphonyl or arylsulphonyl, -.

-2_ 21~R456 A' additionally represents in each case optionally substituted alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or arenediyl, A2 represents a single bond, or represents oxygen, sulphur, -SO-, -SOZ , -CO
or the group -N-A"-, in which A" represents hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, aryl, alkoxy, alkylsulphonyl or arylsulphonyl, A2 additionally represents in each case optionally substituted alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or arenediyl, A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, vitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy(thio)phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alltinyloxy, alkinylamino, alkinyloxycarbonyl, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy,cycloalkylideneamino,cycloalkyloxycarbonyl,cycloalkyl-alkoxycarbonyl, aryl, aryloxy, arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl, heterocyclyl, heterocyclylalkyl, heterocyclylalkoxy or heterocyclylalkoxycarbonyl, R' represents hydrogen or halogen or together with R= represents an alkanediyl or an alkenediyl group which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an SOz group, an NH group, an N-alkyl group, a carbonyl group and/or a thiocarbonyl group, and Z represents in each case optionally substituted monocyclic or bicyclic, saturated or unsaturated heterocyclyl, heterocyclylamino or heterocyclylimino.
The novel substituted aromatic thiocarboxamides of the general formula (I) are obtained - ', ~ -3- 2189456 if substituted aromatic nitriles of the general formula (II) R3 R~
Z ~ ~ CN
R' in which R', Rz, R' and Z have the meanings given above are reacted with hydrogen sulphide (HZS) or with thioacetamide, optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent.
The novel substituted aromatic thiocarboxamides of the general formula (I) are notable for strong and selective herbicidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkinyl - alone or in conjunction with heteroatoms, such as in alkoxy, alkylthio or alkylamino - are each straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially fluorine or chlorine.
The invention preferably relates to compounds of the formula (I) in which R~ represents hydrogen, fluorine, chlorine or bromine, R= represents the following group -A~-Az-As in which A' represents a single bond, or represents oxygen, sulphur, -SO-, -SOz-, -CO-'. 1 -4- 2189456 or the group -N-A''-, in which A'' represents hydrogen, hydroxyl, C,-Ca alkyl, C; C,-alkenyl, C3 CQ alkinyl, C,-C4 alkoxy, phenyl, C,-C;
alkylsulphonyl or phenylsulphonyl, A' additionally represents in each case optionally fluorine- or chlorine-substi tuted C,-C6 alkanediyl, C.~-C6 alkenediyl, CZ C~alkinediyl, C; C6 cycloalkanediyl, C; C6 cycloalkenediyl or phenylene, A2 represents a single bond, or represents oxygen, sulphur, -SO-, -SOZ-, -CO
or the group -N-A"-, in which A' represents hydrogen, hydroxyl, C,-C4 alkyl, C3 C; alkenyl, C3-C4 alkinyl, C,-CQ alkoxy, phenyl, C; C;
alkylsulphonyl or phenylsulphonyl, A~ additionally represents in each case optionally fluorine- or chlorine-substi-tuted C,-C6 alkanediyl, Ca C6-alkenediyl, CZ C6 alkinediyl, C; C6 cycloalkanediyl, C3 C~ cycloalkenediyl or phenylene, A' represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen, or represents in each case optionally halogen- or C,-C, alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, or represents in each case optionally halogen-, cyano-, carboxyl-, C,-C4 alkyl- and/or C,-C; alkoxy-carbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or represents in each . _5_ 2189456 - .
case optionally nitro-, cyano-, carboxyl-, halogen-, C,-Ca alkyl-, C,-Cq halogenoalkyl-, C,-C4 alkyloxy-, C,-C4 halogenoalkyloxy- and/or C,-C4 alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-C,-Cg alkyl, phenyl-C,-C4 alkoxy, phenyloxycarbonyl or phenyl-C,-C4 alkoxycarbonyl, (in each case optionally totally or partially hydrogenated) pyrrolyl, pyrawlyl, imidazolyl, triawlyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiawlyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C,-C; alkyl, furyl-C,-C, alkyl, thienyl-C,-C; alkyl, oxawlyl-' C,-C4 alkyl, isoxazole-C; C4 alkyl, thiawle-C,-C4 alkyl, pyridinyl-C,-C4 alkyl, pyrimidinyl-C,-C; alkyl, pyrazolylmethoxy or furylmethoxy, or represents perhydropyrenylmethoxy or pyridylmethoxy, R' represents hydrogen, fluorine, chlorine or bromine or together with RZ
represents an allcanediyl or alkenediyl group having in each case up to 4 carbon atoms which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an SOz group, an NH group, an N-C,-C4 alkyl group, a carbonyl group and/or a thiocarbonyl group, and Z represents in each case monocyclic or bicyclic, saturated or unsaturated hetero-cyclyl, heterocyclylamino or heterocyclylimino having in each case 2 to 6 carbon atoms and 1 to 4 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen atom or sulphur atom and/or optionally up to three groups from the series -CO-, -CS-, -SO- andlor S02 , and which is optionally substituted by one or more groups from the series nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, C,-C6 alkyl (which is optionally substituted by halogen or C,-C4 alkoxy), Cz C6 alkenyl or Cz C6 alkinyl (which are in each case optionally substituted by halogen), C,-C6 allcoxy or C,-C6 alkoxy-carbonyl (which are in each case optionally substituted.by halogen or C,-C; alkoxy), Cz C6 alkenyloxy or C,-C6 alkinyloxy (which are in each case optionally substituted by halogen), C,-C6 alkylthio, Cz C6 alkenylthio or Cz C6 alkinylthio (which are in each case optionally substituted by halogen), C,-C6 alkylamino or di-(C,-C4 alkyl)-amino, _ 6 _ 2189456 C3 C6-cycloalkyl or C3 C6 cycIoalkyl-C; C~ alkyl (which are in each case optionally substituted by halogen and/or C,-C; alkyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl or phenylamino (which are in each case optionally substituted by nitro, cyano, halogen, C,-C° alkyl, C,-CQ
halogenoalkyl, C,-C4 alkyloxy, C,-C° halogenoalkyloxy and/or C,-C4 alkoxy-carbonyl).
The invention particularly relates to compounds of the formula (I) in which R' represents hydrogen, fluorine or chlorine, R' represents the following group -A~-Az-As in which A' represents a single bond, or represents oxygen, sulphur, -SO-, -SOz-, -CO-or the group -N-A°-, in which A° represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl, A' additionally represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-I,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl, Az represents a single bond, or represents oxygen, sulphur, -SO-, -SOZ , -CO-or the group -N-A°-, in which A° represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl, Az additionally represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-I,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, -7_ 2189456 propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl, A; represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n-or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethyl=
thio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethyl-sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or 10, i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s-or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, or represents in each case optionally fluorine- or chlorine-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, or represents in each case optionally fluorine-, chlorine-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl-oxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyl-methoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexyl-methoxycarbonyl, or represents in each case optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, S

~ -8- 218945b benzyloxycarbonyl, (in each case optionally completely or partially hydro-genated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrawlylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxawlemethyl, thiawlmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylinethoxy or pyridylmethoxy, R' represents hydrogen, fluorine or chlorine or together with Rz represents an alkanediyl or alkenediyl group having in each case 1 to 3 carbon atoms which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an NH group, an N-methyl group, a carbonyl group and/or a thiocarbonyl group, and Z represents in each case monocyclic or bicyclic, saturated or unsaturated hetero-cyclyl, heterocyclylamino or heterocyclylimino having in each case 2 to 5 carbon atoms and 1 to 3 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen atom or sulphur atom and/or optionally up to two groups from the series -CO-, -CS-, -SO- and/or SO= , and which is optionally substituted by one or more groups from the series vitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which are optionally substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propinyl or butinyl (which are in each case optionally substituted by fluorine or chlorine); methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxy-carbonyl or ethoxycarbonyl (which are in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propinyloxy or butinyloxy (which are optionally substituted by fluorine or chlorine);
methyl-thio, ethylthio-, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenyl-thio, propinylthio or butinylthio (which are in each case optionally substituted by fluorine or chlorine); methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentyl-S
- WO 95/30661 218 9 4 5 ~ P~~5~01507 ~ _9_ methyl or cyclohexylmethyl (which are in each case optionally substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl, or phenylamino (which are in each case optionally substituted by vitro, cyano, fluorine; chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoro-methoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl).
Very particularly preferred groups of compounds of the formula (I) are the compounds of the formulae (Ia), (Ib) and (Ic) drawn below S
Z
N~ (la) R' (/b) rt pc) i Hz R' where R', Rz and Z have the meanings indicated above as particularly preferred, R" and R' are identical or different and independently of one another in each case indi-vidually represent hydrogen, fluorine, chlorine, methyl or ethyl - or in the formula (Ib) can also together represent oxygen or sulphur - and -lo- X189456 Q represents oxygen, sulphur, N-methyl or N-ethyl.
Z in the general formulae (I) and ((Ia), (Ib) and (Ic) represents in particular the heterocyclic groups listed below R' R, ~Q~ i s Qi 'N_Q, N N R N~ Rs N-N Q, Q, Rs Rs Rs (Z~) (~ (Z~
R' , ~ , Qz.Q~N~ R N N\ R~N~Q~N~
~N N-S N=N
Rs m Rs Rs , Q~.S~N\ R Q.Ni Rs / Ni N-N Q? Q' -N
R' ~R' Rs (Z') (~ (~) , R~N~Q ~ R~N~N~ Rs , Rs Rs Rs R~ Rs (Z,o) (Zn) (Zm) , ~ , R~N~Q~Ni Q2Q'N~ s Q' R~ N-N-Q, Q, Ri Rs Rs ~") (Z,s) WO 95/30661 ~ ~ ~ ~ ~ ~ ~ PCT/EP95/01507 _ 11 _ R' R' Q? Q' 'N-Q' 'N-Q' R N R°-C\ /~ R \ N
Q' N-N N-Q' ~17) Rs R~
R ~ QN- Q'_Q 'N\ R N QN-a ' -N R°~Q, R° R° R° R
Rs iz,~ (~ (z~') Re R' f z a~ N~
N/ N~ R '1 1I N1 Y
=N N-N a~-N

Q' R R Q /N
N-N N--cz~5) cue) where in each case Q' represents a group from the series -CO-, -CS-, -CH2 , -CH(OH)-, -CHCI-, -CHBr-, -C(=CHz)-, -C(=CHF)-, -C(=CFZ)-, -C(=CHCI)-, -C(=CHBr)-, -C(=CHOCHF~-, -C(=CHOCF3)-, -C(=CFIOCI-IZCF3)-, Qz represents oxygen, sulphur or a group from the series -CO-, -CS-, -CH2 , -CHF-, -CF= , -CHCI-, -CHBr-, -CHOCHFZ , -CHOCF; , -CHOCHzCF3 , _12_ 2189456 R6 represents hydrogen, amino, nitro, cyano, carboxyl, carbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, cyclopropyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chloro-difluoromethylthio, methylamino, ethylamino, n- or i-propylamino, dimethyl-amino, diethylamino, methoxycarbonyl or ethoxycarbonyl, and R' represents hydrogen, hydroxyl, amino, cyano, methyl, ethyl, n- or i-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy, or where optionally two adjacent groups - R6 and R6 or R' and R' or R6 and R' together represent in each case optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted alkanediyl or alkenediyl having in each case up to 4 carbon atoms which is optionally interrupted by oxygen, sulphur or a group from the series -SO-, SOZ-, -N(CH3)- or N(CZHS}- at the beginning (or at the end) or within the hydrocarbon chain.
The definitions of radicals listed above, indicated in general or in ranges of preference, apply both to the end products of the formula (I) and, correspondingly, to the respective starting materials and intermediates required for preparation. These radical definitions can be combined as desired with one another, which therefore includes any desired combinations between the indicated ranges of preferred compounds.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below.

_. ~

Group 1 HzN~N~ / \ S
N
CF~ N t NHz R
(IA I) In this formula, RZ and R', R' have the meanings indicated in the following list:

Synthesis Ex. No. R' R= R;
F F F

12 F -CH2CN _ H

13 ' F -N(CH3)S02C2H5 H

14 CI -N(CH3)S02C2H5 H

WO 95/30661 218 9 4 5 6 P~'~~S~olso7 Ex. No. R' Rz R3 15 CL ~ -N(CH3)S02C2H5 CI

16 F -NH-COCFg H

18 Ci -OH H

19 F -CFi(CHg~ H

25 F -CO-NH-CHg H

26 Cl -COOCH3 CI

27 C( -COOC2H5 H

28 F _0_C2H5 H

29 F -N(C2H5)S02C2H5 H

30 F -N(S02CH3)2 H

31 F -CO-N(CH3)2 H

32 . F -S-CH2-C~CH H

33 Cl -S-CH2-C=CH F

WO 95/30661 PCf/EP95/01507 -15- 2?89456 .
Ex. No. R' R= R' 34 F -S-GH2-C~CH Cl 35 F -O-CH(CH3)-C~CH H

38 F -O(CH2CH20~CHg H

39 F -O-GH2-CH~2 H

40 F -O-CH2-C~CH H

43 F -S-C2Hg H

44 F -S-CH{CH3)2 H

46 F -O-CH(CH2F)2 H

-OC~HCOOCZHS

-OCHCOOCHzC=CH

y ~ -16- 218946 Ex. No. R' Rz R' 51 F -NH-S02C2H5 Cl 52 F -NH-S02CH(CH3)2 H

53 F NH-S02C4Hg H

55 F N~(CH3)OC2H5 H

56 F -N~(OCH3~ H

57 F -N~Fi-N(CHg~, H

60 F -O-CS-N(CH3)2 H

61 F -S-CO-N(CH3)2 H

62 F -NH-P(O)(CH3)OC2H5 H

63 F -NH-P(O)(OC2Hg~ H

65 F -N(CH3)COCF3 H

66 F -NH-COCH(CH3)2 H

67 F -NH-CO-CO-C(CH3)3 H

- 1 _ " _ 218 9 4 5 6 P~'~'9siu1s07 Ex. No. R' R= R3 68 F -NH-CO-Nfi2 H

70 F NH-CO N(CH3)2 H

71 F -N(COCH3~ H

72 F -NfI COCH(CH3)Cl H

73 F -S-CH2-CH=CH2 H

74 CI -S-CH2-CEi=CH2 H

75 F -S-CH(CH3)C~CH H

76 F -S-CH(CH3)COOC2H5 H

77 F -S(O)-CH3 H

-S COOCH~

-S-CH2 ~

-S_ 'COOCH3 80 F ~ H

WO 95/30661 P(.'T/EP95/01507 _,8_ 2189456 Ex. No. R' R= R' _O-CO

/O~
-O-CHz 82 F ~ g ~O

86 F -OCH2-CH(C1~CH2 H

90 F -OCHZP(O)(OC2H5)2 H
91 Cl -O-CH(CHg~P(O)(OCZHS)2 H

. -, ~ -19- 2189456 Ex. No. R' R= R3 HP(07(~z~slz ~0 92 F g -O-N=C I
93 F ~,J g 94 F -O-N(C2H5~ H

96 F -NH-SO--a H
97 F -NH-SO--a CI
98 C~ -NH-SO~ H

WO 95/30661 ~ ~ ~ ~ ~ ~ PCT/EP95/01507 . ., Ex. No. R' RZ R' -NH-SO~

-NH-5~

100 F g -NH-S

-NH-SOz CH2 ~ /

103 F -NCH(CH3)2S02C2H5 H

104 F -N(CH3)S02CH(CH3)2 H

105 H -N(CH3)S02C2H5 CI

106 C1 -N(CH3)S02C4Hg H

107 F -N(CH3)SOZC2H5 H

108 ' F -N(CH3)S02CH3 H

109 F -N(S02C2H5)2 H

WO 95130661 2 1 8 9 4 5 6 P~~5101507 ._ _21 _ Ex. No. R' R= R' 110 F -N(S02CH3)S02C2H5 H

112 F N(CH3)2 H

115 Cl -O-CH(CH3~ H
116 F -O-CH(CH3~ H
117 F ~ H

119 F -O-CH2-COOC2Hg H
120 . F -S-CH2-COOCH3 H
t21 F -S-CH2-COOC2H5 H

., ~ _2~_ 2189456 Ex_ No. R' R= R' 122 Cl -S-CH2-COOC2H5 H

123 F -CH2-CH(CI)COOCH3 H

124 F -GH2-CH(CI)COOC2H5 H

125 F -CH2-CH(Cl)COIQHC2H5 H

126 CI -CH2-CH(CI)CONHC2H5 H

-CH=~HCONHCH(CH~2 127 C1 C~ H

-CHz~HCONHCH(CH~i 128 F C~ H
129 F -COOC3H7-i H
Group 2 O
HZN. N ~ 3 N

(~-2) In this formula, R', R= and R; have, for example, the meanings indicated above in Group 1.

-. ~ -23- 2189456 Group 3 H~N~N
N
CF~ N HZ
(IA-3) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group I.
rou 4 Hl~~ N
' N
CHF N !HZ
(1,a,-'1) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group I.
Group 5 (CH3)ZN\ O
N
N
CHFZ N IHZ
(IA-5) In this formula, R', Rr and R' have, for example, the meanings indicated above in Group I.

-24_ 2x89456 Group 6 H, N
N
CFF~ N HZ
In this formula, R', Rz and R' have, for example, the meanings indicated above iri Group I.
Group 7 (CH3)ZN\ 0 N
N

(i~._7) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group I.
Grou (CH3)ZN\ O
N
N
CI~ N IHZ
(IA-s) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group I.

~ -25- 2189456 Groun 9 (CH3)ZN\ O
N
N
, Br N
~_9) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group 1.
Groun 10 F

(IA-10) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.
Grou I
IHZ
(IA-I 1) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.

WO 95/30661 218 9 4 ~ b ~~~5/01507 ..

Group 12 ~~H3)3~
0 ~H2 (IA 12) In this formula, R', R2 and R' have, for example, the meanings indicated above in .
Group 1.
ou 13 N
N
N IHZ
(IA-I3) In this formula, R', Rz and R; have, for example, the meanings indicated above in Group 1.
Group 14 O
N
~~ N N Hz (IA-14) In this formula, R', ~Rz and R' have, for example, the meanings indicated above in Group 1.

Groun 1 S
S R' R2 (CHs)z~H ~ S
N N / \
C ~ N NH2 Rt (IA-IS) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.
Group 16 S
N
I N

~tA-I6) In this formula, R', Rr and R' have, for example, the meanings indicated above in Group I.
Group 17 O
~N~
SOZ t N
~N~ IHz O (IA-17) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.

Group 18 O R' Rz S
I N~N
NH
z _ .. (1p, 18) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.
rou I9 O
O ~N
H
CHa--~O z CHa (IA 19) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group I.
Grou 2 N
I I Hz O
O (IA-20}
In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.

-, ~ -29- 2189456 Group 21 CH3 ~0 ~N~
~N
Hz OF
(I~.-z1) In this formula, R', R' and R' have, for example, the meanings indicated above in-Group 1.
Gro ~ 22 O
N ~N
MHz 0 (/A-22) In this formula, R', R~ and R' have, for example, the meanings indicated above in Group 1.
Group 23 C

~,e,_23) In this formula, R', Rr and R' have, for example, the meanings indicated above in Group 1.

WO 95/30661 PCf/EP95101507 -3~- 2189456 C ~3 Hz (IA 24}
In this formula, R', RZ and R' have, for example, the meanings indicated above in Group 1.
Crroup 25 HZ
., (IA-25) In this formula, R', R= and R3 have, for example, the meanings indicated above in Group I.
rou 26 l CH3 (IA 26) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.

Group 27 (IA-27) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.
Grou 2 CHF
N
r Ch (ta 2s) In this formula, Rt, R= and R' have, for example, the meanings indicated above in Group I.
Gr a 2 Cf (IA-29) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group I.

Group 30 f ~CN

(IA-30) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.
Group 31 O
N
O
(IA-31) In this formula, R', Rr and R' have, for example, the meanings indicated above in Group 1.
rou 32 O
N
CN N
HZ
(IA-32) In this formula, R', R= and R' have, for example, the meanings indicated above in Group 1.

' WO 95130661 PCT/EP95/01507 '' ~ -33-2~89456 Group 33 HZ
(IA-33) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.
Group 34 C
NOz -N

(IA~34) In this formula, R', R~ and R' have, for example, the meanings indicated above in Group 1.
Grou 3 \ S
CH3 ~ , N NHz CH3 R' (IA-3 5) In this formula, R', R= and R' have, for example, the meanings indicated above in Group 1.

WO 95/30661 PCl'/EP95/01507 ._ ~ -34- 2189456 Gr a S R' RZ
N~ ~ ~ S
N
C ~ N NH2 R' (IA-36) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.
Group '37 O
CF3~N
N ~ Hs H O
In this formula, R', R~ and R' have, for example, the meanings indicated above in Group I.
Group 38 CF3~N
N-~ IHz H S (IA-38) In this formula, R', Rr and R' have, for example, the meanings indicated above in Group 1.

_ -2188456 Grou CF3~N
N
CZHS S
(IA-39) In this formula, R', R= and R' have, for example, the meanings indicated above in Group 1.
Group 40 O
CHFz~N
N-(IA-4o) In this formula, R', Rr and R' have, for example, the meanings indicated above in Group I.
Group 41 O
CHFz~N
~N ~ Hz (IA-41) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group I.

-, -36-Group 42 R' R' S
iJ
// N
I1 ~S R' N
(IA-42) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.
Group 43 CHFa J~N
I N

(IA-43) In this formula, R', Rz and R; have, for example, the meanings indicated.
above in Group 1.
a 44 F-(CHZ\3 ~ Rs Rz N ~ ~ S
N
fi~ N NHZ
R, (~-~) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.

_37_ Group 45 iN~ IHz (IA-45) In this formula, R', R' and R' have, for example, the meanings indicated above in Group I.
Group 46 CFi3 ~N~
CH N~N

(IA-46) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group I.
Group 47 CHFZ S
Hz (1A-a7) In this formula, R', R= and R' have, for example, the meanings indicated above in Group 1.

Group 48 CF-, YI
N, ~H
(IA-48) In this formula, R', Rz and R3 have, for example, the meanings indicated above iri Group I.
rou 49 O
C
(IA-49) S In this formula, R', R2 and R' have, for example, the meanings indicated above in Group I.
Group 50 CH3 O R" R' H ~ ~ S
C 3~~ /
N-N NHZ
(IA-50) In this formula, R', ~RZ and R' have, for example, the meanings indicated above in Group 1.

P(.'T/EP95/01507 W0 95/30661 218 9 4 ~ 6 Group SI _ NHz (IA-51) In this formula, R', Rz and R' have, for example, the meanings indicated above iri Group I.
Group 52 _ F-(CHz'3 N
N, N H
z (IA-52) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.
Group 53 w J~ 3 N
N
O ~ N VHz (IA-53) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group I.

:~
0_ z~ s~4~6 Group 54 ~\/N
O~ N
N-~ HZ

(Ir1-54) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group I.
Group 55 CH
N

O
(IA-ss) In this formula, R', R' and R' have, for example, the meanings indicated above in Group I.
Group 56 O
T
~N~N
N 'H
z (IA-56) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group I.

-. ~ -41- 2 ~ 89456 Group 57 O

0 R' (IA-57) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group 1.
Group 58 O R° R' / N / \
0-~ NHZ
0 R' (IA-ss) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group I.
Group 59 CHF, O
\/N
O~ N
N IHZ
(IA-59) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group I.
r WO 95130661 PCf/EP95101507 ., ~ -42- 2~ 89456 Group 60 N-CH3 O ..
(IA-so) In this formula, R', R= and R' have, for example, the meanings indicated above in Group 1.
Group 61 S
N ~ ~~ _ v N ~ NH2 CH3 y (IA-61) In this formula, R', Rv and R' have, for example, the meanings indicated above in Group 1.
Grouu 62 N
N
i CFZ N IHZ
(IA-62) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.

, WO 95/30661 PCT/EP95101507 Group 63 O
CFg~N
N--~

(IA-63) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.
Group 64 O
CF3~N
N-NHz O ~~) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.
Group 65 O
CF3~N
N Hz NHCH3 O (Ip,_65) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group 1.

WO 95/30661 ' PCTIEP95/01507 21894~b Grog CF
(IA-66) In this formula, R', R~ and R' have, for example, the meanings indicated above in Group I.
Grog 67 O
CHFZ~N
~N ~ VHZ
NHZ O
(IA-67) 5 In this formula, R', Rz and R' have, for example, the meanings indicated above in Group I.
Group 68 CF3~N
N ~ Hz NHCH(CH3)z (IA-68) In this formula, R', R2 and R' have, for example, the meanings indicated above in Group 1.

WO 95/30661 PCT/F,P95/01507 Group 69 N
CF3-{~
N ~ HZ
CIi3 O
(IA-69) In this formula, R', Rz and R' have, for example, the meanings indicated above iri Group 1.
ro 7 O
N
CH30-~~
N ~ Hi CHI O
(IA-7o) In this formula, R', Rz and R; have, for example, the meanings indicated above in Group 1.
rpu 71 ,O
~~(/N
N
CZH50-~/

(IA-71) In this foimula, R', Rz and R' have, for example, the meanings indicated above in Group 1.

._ Group 72 S
N--~
H

(IA-72}
In this formula, R', R= and R' have, for example, the meanings indicated above in Group 1.
Group 73 cc K
S~N / \ S
CF N NHz (IA 73) In this formula, R', R~ and R' have, for example, the meanings indicated above in Group 1.
rou 74 CHFz-5 HOC Hz K
(IA-74) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group 1.

~, _47_ Group 75 O R' R1 ~ S
I ~~N
NH
z O R' (IA_75) In this formula, R', Rz and R; have, for example, the meanings indicated above iri Group 1.
rou 76 O R" R' ~/ ~ ~ S
N' \N
N NH
z O R~ (IA-76) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group 1.
Grou 7 __ O R' R' JJ ~ S
N' \N
CN NH
z O R' (/A_.77) In this formula, R', R= and R' have, for example, the meanings indicated above in Group 1.

ou 78 Hz (IA-7a) In this formula, R', R~ and R' have, for example, the meanings indicated above in Group I.
Group 79 N
i V
(IA 79) In this formula, R', Rr and R' have, for example, the meanings indicated above in Group I.

_49-Table 80 Hz CH3 ~~-80) In this formula, R', R' and R' have, for example, the meanings indicated above in Group 1.
Group 81 N/ 'N / \ S
NHz " .. {1A 81) In this formula, R', Rz and R' have, for example, the meanings indicated above in Group 1.
Group 82 N
H' N
V
N

S
(IA-82) In this formula, R', R= and R' have, for example, the meanings indicated above in Group I.

WO 95/30661 PCf/EP95/01507 °- 2189456 Group 83 HsC N~ ~ ~ S
I .
N NHz CF3~~ (Ip-83) In this formula, R', RZ and R' have, for example, the meanings indicated above in Group I.
rou 84 F2Cii ~ S
N
I
N NHs CH3R' (Ia-s4) In this formula, R', R2 and R' have, for example, the meanings indicated above in Group 1.
Group 85 CI-t3~ NI

t~-I) In this formula, R', R° and R' have the meanings indicated in the following list:
< <

~18945~

Ex. No. R' R4 RS

1 F CHg CH

2 Cl CHg ~3 3 H CHg CH3 rou 86 Rs R<
O wN,C~a CH3~N
/ \
N
CF~ N _ N
In this formula, R', R' and RS have, for example, the meanings indicated above in Group 85.

-. _52_ Group 87 CH
CH3~NI

In this formula, R', R° and RS have, for example, the meanings indicated above in Group 85.
Group 88 N,CH(CH3)C=CH
CH~N~ / \ S
I \N
CF~ N _ NH2 " (IC-1) In this formula, R', R° and RS have, for example, the meanings indicated above in Group 85.
Group 89 O
CH3~N
CF~ N N
(IC-2) In this formula, R', R4 and RS have, for example, the meanings indicated above in Group 85.

.' -53-Using, for example, 2-(2-fluoro-4-cyano-5-methoxy-phenyl)-4-methy l-5-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one and hydrogen sulphide as starting materials, the course of reaction of the process according to the invention can be illustrated by the following equation:
O
HzC ~ O-CHI ~C O O-CHI
N ~ ~ ~ Hz~ ~NI~
FzC~N ~N N
F FzCH ' NHz F
A general definition of the substituted aromatic nitrites to be used as starting materials in the process according to the invention for the preparation of the compounds of the general formula (I) is given by the formula (II). In the formula (II), R', R=, R' and Z
preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I), as preferred or, respectively, as particularly preferred for R', R=, R' and Z.
The starting materials of the formula (II) are known and/or can be prepared by known processes (cf. EP-A 370332; DE-A 4238125; DE-A 4303376; US-P 5084084; Prepara-tion Examples).
Suitable diluents for carrying out the process according to the invention are the custom-ary organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, for example benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether;
ketones, such as acetone, butanone or methyl isobutyl ketone; nitrites, such as acetonitrile, propionitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethyl-phosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, azines, such as pyridine, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, -54_ diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water, or pure water.
The process according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. Suitable such auxiliaries are all customary inorganic or organic bases. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, for example sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tent-butylate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also basic organic nitrogen compounds, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diaza-bicyclononene (DBN) or diazabicycloundecene (DBU).
The reaction temperatures when carrying out the process according to the invention can be varied within a relatively large range. It is generally carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C and 80°C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure, generally between 0.1 bar and 10 bar.
To carry out the process according to the invention the starting materials of the formula (II) are introduced, generally in a suitable diluent in the presence of a reaction auxiliary, and the hydrogen sulphide or the thioacetamide is slowly metered in. The hydrogen sulphide or the thioacetamide are preferably employed in a relatively large excess. The reaction mixture is stirred for a number of hours at the particular temperature required. Working up in the process according to the invention is effected in each case in accordance with customary methods (c~ the Preparation Examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weedkillers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted.
Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connec-tion with the following plants:
D_icotvledon weeds of the een ra~ Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotvledon crops of the eenera: Gossypium, Glycine, Beta, Daucus, Phaseolus;
Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the eenera~ Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cro s of the eenera~ Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and AILium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks, and on paths and areas with or without ~ -56- 21 89456 tree stands. Equally, the compounds can be employed for controlling weeds in peren nial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pastures, and for selective weed control in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both pre- and post-emergence.
To a certain extent, the compounds of the formula (I) also show a fungicidal action, for example against Pyricularia oryzae in rice.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impreg-nated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents which are mainly suitable are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffms, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylfotrnamide and dimethyl sulphoxide, and water.

Suitable solid carriers are:
for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are:
for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colourants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, axo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, examples being anilides, for example, diflufenican and propanil; arylcarboxylic acids, for example dichloropicoIinic acid, dicamba and picloram; aryloxyalkanoic acids, for example 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, for example diclofop(-methyl), fenoxaprop(-ethyl), fluazifop(-butyl), haloxyfop(-methyl) and quizalofop(-ethyl); azinones, for example chloridawn and norflurazon;
carabamates, for example chlorpropham, desmedipham, phenmaedipham and propham;
chloroacetanilides, for example alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines, for example oryzalin, pendimethalin and trifluralin; diphenyl ethers, for example acifluorfen, bifenox, chlormethoxynil (X-52), chlornitrofen, fluoroglycofen, fomesafen, halosafen, lactofen, nitrofen and oxyfluorfen; areas, for example chlortoluron, cumyluron (JC-940), diuron, dymron (daimuron), fluormeturon, isoproturon, linuron and methabenzthiazuton;
hyroxylamines, for example alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, for example imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, for example bromoxynil, dichlobenil and ioxyrul;
oxyacetamides, for example mefenacet; sulphonylureas, for example AC-014 (AC-322140), amidosulfuron, bensulfuron(-methyl), chlorimuron(-ethyl), chlorsulfuron, cinosulfuron, DPX-47, HOE-404, imazosulfuron, metsulfuron(-methyl), nicosulfuron, primisulfuron, pyrazosulfuron(-ethyl), thifensulfuron(-methyl), triasulfuron and tribenuron(-methyl);
thiocarbamates, for example butylate, cycloate, diallate, dimepiperate, EPTC, esprocarb, molinate, prosulphocarb, thiobencarb (benthiocarb) and triallate; triazines, for example atrazine, cyanazine, dimethametryn, prometryne, simazin, simetryne, terbutryne and terbutylazin; triazinones, for example hexazinon, metamitron and metribuzin;
others, for example aminotriazole, benfuresate, bensulide, bentazone, benzofenap, bromobutide, butamifos, cafenstrole (CH-900), cinmethylin, clomazone, clomeprop, clopyralid, DEH-112, difenzoquat, dimethenamid, dithiopyr, ethofumesate, flumetsulam, fluorochloridone, glufosinate, glyphosate, amiprophos(-methyl), anilofos, etobenzanid (HW-52), isoxaben, KPP-314, KUH-833, KUH-911, KUH-920, MK-243, naproanilide, NSK-850, oxadiazon, piperophos, propanil, pyrazolate, pyrazoxyfen, pyributicarb, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, i ~i i I

acaricides, nematicides, bird repellants, plant nutrients and soil conditioners, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsion's, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or spreading.
The invention also provides a method of combatting unwanted plants, wherein a compound or composition of the invention is caused to act on the unwanted plants, their habitat or both.
The active compounds according to the invention can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 10 g and 10 kg of active compound per hectare of soil surface, preferably between 50 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples which follow.
Preparation examples:
Example 1 O NH-S02-C2Hs N- 'N C j-I
N NHz F

l I

- 59a -Hydrogen sulphide is passed at from 50°C to 60°C
to saturation point into a mixture of 5.5 g (15 mmol) of 2-(4-cyano-2-fluoro-5-ethylsulphcnylamino-phenyl)-5,6,7,8-tetrahydro-1,2,4-triazolo[4,3-a]pyridin-3(2H)-one, 5 ml of triethylamine and 50 ml of pyridine and the mixture is stirred at 60°C for 30 minutes more. It is then concentrated in vacuo, the residue is stirred with 2 N
hydrochloric acid and the solids are filtered -6~- 2189456 off. The solid product is recrystallized from isopropanol.
4.8 g (80% of theory) of 2-(2-fluoro-5-ethylsulphonylamino-4-thiocarbamoyl-phenyl)-5,6,7,8-tetrahydro-1,2,4-triazolo[4,3-a]pyridin-3(2H)-one are obtained of melting point 220°C.
Example 2 p NHZ
Hsr.2\N~N ~S
\ / CAN
FCC ~-= p 4.04 g (0.04 mol) of triethylamine are added to 6.3 g (0.02 mol) of 2-(2-fluoro-4-cyano-5-amino-phenyl)-4-ethyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one in 100 ml of acetone. Hydrogen sulphide is passed in rapidly at 23°C, and the internal temperature rises to 33°C. The reaction is complete after 1 hour. The solution is concentrated on a rotary evaporator and the residue is recrystallized from isopropanol.
2.9 g (42% of theory) of 2-(2-fluoro-4-thiocarbamoyl-5-amino-phenyl)-4-ethyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one are obtained of melting point 161°C.
Example 3 S Nf+SOz-CzHs S
\ / ~N
N
FzCH~ F
11 g (0.0276 mol) of 2-(2-fluoro-4-cyano-5-ethylsulphonylaminophenyl)-4-methyl-difluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-thione are stirred at 70°C for 4.5 hours in 100 ml of pyridine while passing in hydrogen sulphide. The solution is concentrated on a rotary evaporator, the residue is stirred in water, the mixture is acidified with concentrated hydrochloric acid, and precipitated product is filtered off, washed with water and recrystallized from isopropanol.
9 g (77% of theory) of 2-(2-fluoro-4-thiocarbamoyl-5-ethylsulphonylaminophenyl)-4-methyl-5-difluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-thione are obtained of melting point 183°C.
In analogy to Preparation Examples 1, 2 and 3 and in accordance with the general description of the preparation process according to the invention it is also possible, fow example, to prepare the compounds of the formula (I) listed in Table 1 below.
R' Rz S
z ~ ~ cn NHz R' Table 1: Examples of the compounds of the formula (I) Ex. No. R' Rz R' Z Melting point (°C) 4 F F H ~ 110 HsCW N ~ N~
_ I
N
FJC
S F -NH-S02-C2H5 H ~ 143 HsCW N ~ N~
_ I
N

CHI HOC ~N~ N~
_ I
N
F=CH

! 62 2189456 Ex. No. R' R' R' Z Melting point (°C) 7 F -NH-S02-C2H5 H ~ 237 HOC-NHS ~~ (.lriethyl-N
ammoaium salt) 8 F F H ~ \N S N/ 220 J~C
_ t N
F=CH
9 F -NH-S02-C2H5 H ~'' 218 H~CwN~N~
_ I
N
FZCH
F NH-S02-C2H5 H N~N~ 185 N

I1 F F H ~ z18 ~N~
N
~N~
N

Ex. No. R' R= R' Z Melting point (°C) 13 F I~IH-S02-C2H5 H 2I0 14 F NH-S02-C2Hg H ~'I 203 HaCi~N~N/
_ I
~''~ N
F2CH' 15 F F H o I~ 185 ~CwN~N/
_ I
N
F=CH
16 F i -soz-C=Hs H

CHz HsCz ~ N
_ f N
FCC
17 F -OCH(CH3)2 H o 206 N~N~
I
N
18 F OH H o 250 N~N~
I
N

. ..
-64- 21894( Ex. No. R' R= R' Z Melting point (°C) 19 F -N-SOz-C=H5 H O 98 Cl'~a FaC ~N-N
20 F -Nfi-S02-C2Hg H O 208 FaC~N-N--H3C~ \'O
FaC~N-N-.
HOC \\S
22 F -IQH-S02-C2H5 H H3C [ O (amorphous) N~

O
[ I
N~
O
24 F -N-SOz CH3 H O 167 CHI F C N-N-H~C~ O

. -, -65-Ex. No. R' R- R' Z Melting point (°C) FzC~N
N
H,C~ O
27 F F H ~ I99 O
H~C~N~N/
_ I
N
FCC
29 F -NH-S02-CH3 H O'I 200 H~C~N~N/
_ I
N
FCC
30 F -NH-S02-CH(CH3)2 H OII 204 HaCwN~N~
_ I
N
FCC

-, ~ -66- 2~ g945b Ex. No. R' R= R' Z Melting point (C) H~C~N~N~

_ 1 ~'~'N

FzC
32 F -~'CH-C-CH H 122 C ~C~

Hs N

_ I
N

F$C
33 F -~Hi C-CH H C'I 190 H~C~N~N/

_ 1 N

F'C
34 F NH-S02-CH3 H sI' 178 H3C~N~N/

_ I
N
35 F NH-S02-C3H7 H ~II 203 HjC~N~N/

_ I
N
36 F -Nfi-S02-C2H5 H ~ 199 (CH~zCH w ~ N/

N
_ I
N
HrC~

., ~' -67- 2189456 Ex. No. R' R= R' Z Melting point (C) 37 F. -NH-S02-C2H5 H ~ 153 HsCz~N N/

I
N
38 F -NH-S02-C2H5 H ~ 206 ~~zCH w N ~ N/

_ I
~''~N
(CH~zCH~
39 F -NH-S02-C2H5 H ~I( 167 ~CswN~N/

N
40 F F H ~ 130 HaCwN~N/

_ I
N
~

FsC
.
HsC~N N/

_ I
N

FsC
42 F -OC2H40CH3 H ~I! 148 HaCwN~N/

_ I
N

FsC

.., ~ -6g- z~s94~6 Ex. No. R' R= R' Z Melting point (°C) 43 F -OC2H5 H ~I 155 i N/
I
-N
i N/
I
- N
i N/
i -N
g ~ 202 46 F -OCH(CH3)2 ~
N- _N/
~~O
47 F -OC2H5 H ~ 185 N~N/
~~O
48 F -NH-S02-C2H5 H ~I 111 i N/
-N
49 H -NH-S02-C2H5 H ~I 118 N/
I
- N

" , WO 95/30661 PCT/EP95/01507 ~ 69 2189456 Ex. No. R' R= R' Z Melting point (C) 50 F -NH-SOZ-C3H~_n H Ct 143 i N~
t -N
51 F -OCZHqOCZHqOCHg H 168 FiCH ~
N

_ I
N
52 F -NH-S02-C3H7-n H CHa (amorphous) FaC N ~S

~N~
~

O
53 F -NH-S02-C3H~_a H CHa 232 FaC~! N ~O

~N~

ff ~IO~I
54 F -NH-SOZ-C3H7_i H CHa 226 FaC N O

O
55 F -NH-S02-C3H7_i H O 187 ~C~.N~N~

I I
J= N

FaC

y -70-Ex. No. R' R- R' Z Melting point (°C) 56 F -NH-S02-CgH7-i H 236 ~N/
~~~//'''~~ I
N
i7 F -NH-S02-C3H7_i H 252 ~N/
[~ N
58 F -NH-S02-C3H7-i H C 109 HsC tJ~N/
I
N
FzCH
59 F -NH-S02-C3H7-i H C ~ 207 Hs =~N N/
I
N
F=CH

60 F -NH-S02-C3H7-i H ht3C
/
N
-N
61 F -N(CH3}-S02C2H5 H ~'I 102 HaC N~N/
I I
J=N

Ex. No. R' R= R' Z Melting point (°C) 62 F -NH-S02-C2H5 H ~II 185 ~C N~N/
I
N
lisC
63 Cl -NH-S02-C2H5 H OII 121 ~'~aC N~~N/
F ~N
a FiCH
~N N/
I I
.'~N
Fi~C
65 F -lYH-S02-C2H5 H O 195 N/
O

~C N~N~ 193 (decomp) DBU salt N
FiCH

WO 95/30661 PCT/F,P95/01507 ~ -72- 2189456 Preparation of the st~rtine comnounds~
Example II-1:
F3C~ CFi3 / N
N ~
~ N"O
F
i F
CN
5.8 g (0.042 mol) of potassium carbonate are added at room temperature to 6.3 g (0.034 mol) of 4-methyl-3-trifluoromethyl-1,2,4-triazolin-5-one (cf. e.g. US
3,780,052) and 5.4 g (0.034 mol) of 2,4,5-trifluorobenzonitrile (cf. e.g. EP 191181) in 150 ml of dimethyl sulphoxide and the mixture is subsequently heated at 100°C for 14 hours. For working up, the cooled reaction mixture is placed in water, adjusted to a pH
of 2 with dilute hydrochloric acid and subjected several times to extraction with dichloromethane.
The combined organic phases are dried over sodium sulphate and concentrated in vacuo. The residue is chromatographed over silica gel (eluent:
dichloromethane).
6.2 g (60% of theory) of 1-(4-cyano-2,5-difluorophenyl)-4-methyl-3-trifluoromethyl-1,2,4-triawlin-5-one are obtained of melting point 74°C.

-73- 21894.56 Example II-2 F
0.83 g (0.006 mol) of potassium carbonate is added at room temperature to 1.52 g (0.005 mol) of I-(4-cyano-2,5-difluorophenyl)-4-methyl-3-trifluoromethyl-1,2,4-triazolin-5-one and 0.48 g (0.005 mol) of methanesulphonamide in SO ml of dimethyl sulphoxide and the mixture is subsequently heated at 120°C for 12 hours. For working up, the cooled reaction mixture is placed in water, adjusted to a pH of 2 with dilute hydrochloric acid and subjected several times to extraction with dichloromethane. The combined organic phases are dried over sodium sulphate and concentrated in vacuo.
The residue is chromatographed over silica gel (eluent:
dichloromethane/methanol 20:1).
0.55 g (28% of theory) of 1-(4-cyano-2-fluoro-5-methylsulphonylaminophenyl)-4-methyl-3-trifluoromethyl-1,2,4-triazolin-5-one is obtained of melting point 67°C.
Examule II-3 FCC
H
CN
0.3 g (10 mmol) of sodium hydride (80%) is added at from 0°C to 5°C to an initial charge of 1.8 g (10 mmol) of ethyl 3-amino-4,4,4-trifluoro-crotonate in 30 ml of F~C~ CHI

dimethylformamide and 2 ml of toluene. The mixture is stirred at from 0°C to 5°C for 30 minutes. After the mixture has been cooled to -70°C, 0.9 g (5 mmol) of 4-cyano-2,5-difluoro-phenyl isocyanate - dissolved in 10 ml of toluene - is added and the mixture is stirred at from -60°C to -70°C for I50 minutes. After the cooling bath has been removed, 2 ml of acetic acid are added. The mixture is then diluted with water to about twice the volume and subjected to extraction with ethyl acetate. The organic phase is concentrated and the residue is crystallized with diisopropyl ether.
1.1 g (69% of theory) of I-(4-cyano-2,5-difluoro-phenyl)-3,6-dihydro-2,6-dioxo-trifluoromethyl-1-(2H)-pyrimidine are obtained of melting point 194°C.
Example II-4 CFiz A mixture of 0.83 g (3 mmol) of 1-(4-cyano-2,5-difluorophenyl)-3,6-dihydro-2,6-dioxo-3,4-dimethyl-1(2H)-pyrimidine, 0.32 g (3 mmol) of methane sulphonamide, 0.6 g of potassium carbonate and 10 m of dimethyl sulphoxide is heated at 120°C
for 10 hours.
After cooling, the mixture is poured into ice-water and acidified with 2 N
hydrochloric IS acid. It is then subjected to extraction with ethyl acetate and the organic phase is washed with water, dried with sodium sulphate and filtered. The solvent is carefully removed from the filtrate by distillation under a water-pump vacuum.
0.8 g (76% of theory) of 1-(4-cyano-2-fluoro-5-methylsulphonylaminophenyl)-3,6-dihydro-2,6-dioxo-3,4-dimethyl-I(2H)-pyrimidine is obtained as crystalline residue (melting point >250°C).
NHS02Cti~

2?89456 -,5 -, ~
Use Examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive.
After three weeks, the degree of damage to the plants is rated in % damage in compari-son to the development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% = total destruction WO 95/30661 PCT/F,P95101507 .. ~
-7 6- 2?9456 Tablc Pre-emergence test/greenhouse Active Applica-BarleyMaize Amaran-Cheno- Matri-Portu-Sola-compound lion thus podium curialaca num (Synthesis rate Example (glha) Number) (3) 125 0 0 100 100 100 100 100 (5) 125 0 0 100 100 90 90 100 (6) 125 0 30 100 I00 93 100 100 (7) I25 30 0 100 100 95 100 95 Table B
Pre-emergence test/greenhouse Active Applica-Wheat Abu- Amatan-Cheno-Matri-Portu-Sola-Maize compound lion thilonthus podiumcaria laca num (Synthesisrate Example (g/ha) Number) .

22 250 0 20 lOD 100 100 100 95 100 13 60 0 0 100 t00 100 70 90 100 16 b0 10 0 95 20 100 90 80 80 --.
-7g- 2189456 Table B (continued) Pre-emergence testJgreenhouse Active Applica- Wheat Abu- Amaran-Cheno-Matri-Portu-Sola-Maize compound lion thilonthus podiumcarialaca num (Synthesis rate Example (glha) Number) 46 60 0 70 100 100 100 100 '100 100 47 30 0 0 lOD 95 100 IOD 100 100 WO 95/30661 P(.'f/EP95/01507 '~ 79 2189456 Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of active compound in such a way as to apply the particular amounts of active compound desired per unit area. After three weeks, the degree of damage to the plants is rated in damage in comparison to the development of the untreated control.
The figures denote:
0% = no action (like untreated control) 100% = total destruction °- 2189456 Table C

Post-emergence test/greenhouse Active Applica-Wheat Maiu Abu- Amaran-Cheno- Sola-Vero-compound tion thilonthus podium num nica (Synthesisrate Example (g/ha) Number) 3 30 10 30 100 100 100 lOD 100 ~

.

17 8 10 10 100 100 95 !00 100 -$' - 2189456 Table (continued) Post-emergence test/greenhouse Active Applica-Wheat Maize Abu- Amaran- Cheno-Sola-Vero-compound tion thilonthus podiumnum nica (Synthesisrate Example (g/ha) Number) 34 15 0 30 100 100 100 100 100' 50 15 5. 70 100 95 80 100 95 S1 ~ 1S 1S 60 100 100 70 100 100

Claims (8)

CLAIMS:
1. A substituted aromatic thiocarboxamide of the general formula (I):

wherein:
R1 represents H, F, Cl or Br;
R2 represents the group: -A1-A2-A3, wherein:
A1 represents: (i) a single bond, O, S, -SO-, -SO2- or -CO-, (ii) the group: -N-A4-, wherein A4 represents H, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl, or (iii) in each case optionally F- or Cl-substituted C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkenediyl or phenylene, A2 represents: (i) or (ii) as defined for A1, or in each case optionally F- or Cl-substituted C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, and A3 represents: (i) H, hydroxyl, amino, cyano, isocyano, thiocyano, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl or a halogen atom, (ii) in each case optionally halo- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, (iii) in each case optionally halo-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, (iv) in each case optionally halo-, cyano-, carboxyl-, C1-C4-alkyl-, C1-C4-alkoxy-carbonyl- or a combination thereof-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and 1 to 4 carbon atoms in the alkyl groups, (v) in each case optionally nitro-, cyano-, carboxyl-, halo-, C1-C9-alkyl, C1-C4-haloalkyl-, C1-C4-alkyloxy-, C1-C4-haloalkyloxy-, C1-C4-alkoxycarbonyl- or a combination thereof- substituted phenyl, phenyloxy, phenyl-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenyloxycarbonyl or phenyl-C1-C4-alkoxycarbonyl, wherein in each case the phenyl is optionally totally or partially hydrogenated, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C1-C4-alkyl, furyl-C1-C4-alkyl, thienyl-C1-C4-alkyl, oxazolyl-C1-C4-alkyl, isoxazole-C1-C4-alkyl, thiazole-C1-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy or furylmethoxy, or (vi) perhydropyranylmethoxy or pyridylmethoxy;

R3 represents: (i) H, F, Cl or Br, or (ii) together with R2 represents an alkanediyl or an alkenediyl group having in each case up to 4 carbon atoms which optionally contains at the beginning or end thereof or within the hydrocarbon chain an oxygen atom, a sulphur atom, an NH group, an N-C1-C4-alkyl group, a carbonyl group, a thiocarbonyl group or a combination thereof; and Z represents a heterocyclic group selected from:

wherein in each case:
Q1 represents -CO-, -CS-, -CH2-, -CH(OH)-, -CHCI-, -CHBr-, -C(=CH2)-, -C(=CHF)-, -C(=CF2)-, -(=CHCl)-, -C(=CHBr)-, -C(=CHOCHF2)-, -C(=CHOCF3)- or -C(=CHOCH2CF3)-, Q2 represents O, S, -CO-, -CS-, -CH2-, -CHF-, -CF2-, -CHCI-, -CHBr-, -CHOCHF2-, -COCF3- or -CHOCH2CF3-, R6 represents H, amino, nitro, cyano, carboxyl, carbamoyl, F, Cl, Br, methyl, ethyl, n- or i-propyl, cyclopropyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethyl, chlorodifluoromethylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl, and R7 represents H, hydroxyl, amino, cyano, methyl, ethyl, n- or i-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy, or optionally two adjacent groups R6 and R6, R7 and R7 or R6 and R7 together represent in each case optionally F, Cl-, Br-, methyl-, ethyl-, n- or i-propyl-substituted alkanediyl or alkenediyl having in each case up to 4 carbon atoms which are optionally interrupted by O, S, -SO-, SO2-, -N(CH3)- or N(C2H5)- at the beginning or end thereof or within the hydrocarbon chain.
2. ~A substituted aromatic thiocarboxamide of the general formula (I) according to claim 1, wherein:
R1 represents H, F or Cl;
A1 represents: (i) as defined for A1 in claim 1, (ii) the group -N-A4-, wherein A4 represent: H, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl, or (iii) methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl;

A2 represents: (i) as defined for A1 in claim 1, (ii) the group -N-A4-, wherein A4 represents H, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl, or (iii) as defined above for A1;

A3 represents: (i) H, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, F, Cl or Br, (ii) in each case optionally F-, Cl-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, (iii) in each case optionally F-or Cl-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, (iv) in each case optionally F-, Cl-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, (v) in each case optionally nitro-, cyano-, carboxyl-, F-, Cl-, Br, methyl-, ethyl-, n-or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl-, ethoxycarbonyl- or a combination thereof-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, wherein in each case the phenyl or benzyl is optionally completely or partially hydrogenated, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolemethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy, or (vi) pyridylmethoxy;

R3 represents: (i) H, F or Cl, or (ii) together with R2 represents an alkanediyl or alkenediyl group having in each case up to 3 carbon atoms which optionally contains at the beginning or end thereof or within the hydrocarbon chain an oxygen atom, a sulphur atom, an NH group, an N-methyl group, a carbonyl group, a thiocarbonyl croup or a combination thereof.
3. A substituted aromatic thiocarboxamide of the general formula (I) according to claim 1, wherein:
R1 represents F;
R2 represents -NH-SO2-C2H5;
R3 represents H; and Z represents
4. ~A process for the preparation of a substituted aromatic thiocarboxamide of the general formula (I) according to any one of claims 1 to 3, comprising reacting a substituted aromatic nitrile of the general formula (II):
wherein R1, R2, R3 and Z are as defined in any one of claims 1 to 3, with hydrogen sulphide (H2S) or with thioacetamide, optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent.
5. ~A herbicidal composition, comprising at least one substituted aromatic thiocarboxamide of the general formula (I) according to any one of claims 1 to 3, and an extender, a surfactant or a mixture thereof.
6. ~A method of combatting unwanted plants, wherein a substituted aromatic thiocarboxamide of the general formula (I) according to any one of claims 1 to 3, or a composition according to claim 5, is caused to act on the unwanted plants, their habitat or both.
7. ~Use of a substituted aromatic thiocarboxamide of the general formula (I) according to any one of claims 1 to 3, or a composition according to claim 5, for combatting unwanted plants.
8. ~A process for the production of a herbicidal composition, comprising mixing a substituted aromatic thiocarboxamide of the general formula (I) according to any one of claims 1 to 3, with an extender, a surfactant or a mixture thereof.
CA002189456A 1994-05-04 1995-04-21 Substituted aromatic thiocarboxylic acid amides and their use as herbicides Expired - Fee Related CA2189456C (en)

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