CA2246678C

CA2246678C - Substituted 2-aryl-1,2,4-triazine-3,5-di(thi)ones as herbicides

Info

Publication number: CA2246678C
Application number: CA002246678A
Authority: CA
Inventors: Karl-Heinz Linker; Kurt Findeisen; Markus Dollinger; Hans-Joachim Santel
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1996-02-22
Filing date: 1997-02-10
Publication date: 2006-10-24
Anticipated expiration: 2017-02-10
Also published as: CA2246678A1

Abstract

The invention relates to novel 2-aryl-1,2,4-triazine-3,5-di(thi)ones of the general formula (I), (see formula I) in which R1, R2, R3, R4, R5, Q1 and Q2 are each as defined in the description, to processes for their preparation and to their use as herbicides.

Description

Le A 31 606-Foreign Countries /Kri/ngb/W6/V23.03.1998 BILE, P~td-tit T~il~~~~-B
'F~#~ TRANSLATION
Substituted 2-aryl-1,2,4-triazine-3,5-di(tbi)ones The invention relates to novel substituted 2-aryl-1,2,4-triazine-3,5-di(thi)ones, to processes for their preparation and to their use as herbicides.
S
EP 11693, EP 271170, WO 86/00072, US 4755217, US 4878941, US 4956004, US
5262390, and US 5344812 disclose that certain substituted 2-aryl-1,2,4-triazine-(thi)ones have herbicidal properties. However, the compounds described therein have not attained any major importance.
This invention, accordingly, provides the novel substituted 2-aryl-1,2,4-triazine-3,5-di(thi)ones of the general formula (I), Rs Q1 R9 Ra ~ N Qz (I) 'N
Rs Rz in which Q1 represents oxygen or sulphur, Q2 represents oxygen or sulphur, R1 represents hydrogen, cyano, amino, or represents respectively option-ally substitutued alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkenyl, alkenylcarbonyl, alkenyloxycarbonyl, alkinyl, alkinylcarbonyl, alkinyloxycarbonyl, cycloalkyl or cycloalkylalkyl, R2 represents hydrogen, halogen, nitro, carboxyl, cyano, thiocarbamoyl, amino, or represents respectively optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkenyl, alkenyloxy, alkenylthio, alkinyl, alkinyloxy, alkinylthio, cycloalkyl or cycloalkylalkyl, R3 represents halogen, R4 represents cyano or thiocarbamoyl and RS represents the grouping below, -Al-A2-A3 in which A1 represents a single bond, represents oxygen, sulphur, -SO-, -S02-, -CO- or the grouping -N-A4-, where A4 represents hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylcarbonyl, arylcarbonyl, alkylsulphonyl or arylsulphonyl, A1 furthermore represents respectively optionally halogen substituted alkanediyl, alkenediyl, azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene, A2 represents a single bond, represents oxygen, sulphur, -SO-, -S02-, -CO- or the grouping -N-AS-, where AS represents hydrogen, hydroxyl, alkyl, alkoxy, aryl, alkylsulphonyl or arylsulphonyl, A2 furthermore represertt5 respectively optionally halogen-substituted alkanediyl, alkenediyl, azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene, A3 represents hydrogen with the proviso that in this case A1 and/or A2 do not represent a single bond Le A 3 I 605-Foreign Countries ~ -A3 furthermore represents hydroxyl, mercapto, amino, cyano, iso-cyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen, represents respectively optionally halogen- or alkoxy-substituted alkyl, alkoxy, alkyl-thio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl, represents re-spectively optionally halogen-substituted alkenyl, alkenyloxy, alkenylthio, alkenylamino, alkylideneamino, alkenyloxycarbon-y1; alkinyl, alkinyloxy, alkinylthio, alkinylamino or alkinyl-oxycarbonyl, represents respectively optionally halogen-, cyano-, carboxyl-, alkyl- and/or alkoxy-carbonyl-substituted cycloalkyl; cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxy-carbonyl or cycloalkyl alkoxycarbonyl, or represents respectively optionally nitro-, cyano- carboxyl-, halogen-, alkyl-, halogenalkyl-, alkyloxy-, halogenalkyloxy- and/or alkoxy-carbonyl-substituted aryl, aryl oxy; aralkyl, arylalkoxy, aryloxycarbonyl or arylalkoxycarbonyl, A3 furthermore represents respectively optionally fully or partially hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylalkyl, furylalkyl, thienylalkyl, a oxazolylalkyl, isoxazolylalkyl, thiazolylalkyl, pyridinylalkyl, pyrimidinylalkyl, pyrazolylalkoxy, furylalkoxy, represents per-hydropyranylalkoxy or pyridylalkoxy.
The novel substituted 2-aryl-I,2,4-triazine-3,5-di(thi)ones of the general formula (I), are obtained when (a) 1,2,4-triazine-3,5-di(thi)ones of the general formula (I1 j, ,. CA 02246678 1998-08-19 Le .~ 31 606-Foreign Countries k R~
Q ~
-- N
H - N Q2 (II) 'N =

in which Q1, Q2, Ri and R2 are each as defined above, are reacted with halogenobenzene derivatives of the general formula (III), R4 ~ ~ X1 (III) Rs in which R3, R4 and RS are each as defined above and Xl represents halogen, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (b) 2-aryl-1,2,4-triazine-3,5-di(thi)ones of the general formula (Ia), r CA 02246678 1998-08-19 Le A 31 606-Forei~:n Countries ' ' -5_ R3 Q~ H
i R4 ~ N Qa _ (Ia) ~N
R~ Rz in which Q1~ Q2~ R2~ R3~ R4 ~d RS are each as defined above are reacted with alkylating agents of the general formula (IV), Rl-XZ fIVI
in which Rl is as defined above and X2 represents halogen or the grouping -O-S02-O-Rl, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (c) arylhydrazones of the general formula (V), R4 ~ ~ N H N

Rs in which R3, R4 and RS are each as defined above Le A 31 606-Foreign Countries are reacted with alkali metal (thio)cyanates of the general formula (VI), M-Q 1-CN Cue) in which Q 1 is as defined above and M represents an alkali metal atom, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary and the resulting 2-aryl-1,2,4-triazolidine-3-(thi)ones of the general formula (VII), R3 0\'1 H
Ra N~N~
CHs N
Rs / CHs H (VII) in which Q 1 ~ R3, R4 and RS are each as defined above are reacted with ketocarboxylic acids of the general formula (VIII), O
2~OH
~''(R
O (VIII) in which R2 is as defined above Le A 31 606-Foreign Countries if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (d) aryl-amines of the general formula (IX), R4 ~ ~ NHz in which R3, R4 and RS are each as defined above are diazotized and subsequently reacted with a cyanoacetylcarbamic acid ester of the general formula (X), R~
NC~N~O~C H
z s O O
in which R1 is as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, and the resulting compounds of the general formula (XI), Le A 31 60G-Foreign Countries L
O~O~
R
C2Hs N-R~ _ R ~ ~ NH O
'N
RS CN
in which RI, R3, R4 and RS are each as defined above are cyclized if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (e) arylhydrazines of the general formula (XII) R'' ~ ~ NH-NHz ( Rs in which R3, R4 and RS are each as defined above are reacted with ketocarboxylic acid derivatives of the general formula (XIII), O
II O. R
R
O (XIII) in which Le A 31 606-Foreign Countries R2 is as defined above and R represents hydrogen or alkyl, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, and the resulting compounds of the general formula (XIV' O
R4 ~ ~ N H O ( 'N -Rs R2 in which R2, R3, R4 and RS are each as defined above and R represents hydrogen or alkyl, are reacted with iso(thio)cyanates of the general formula (~~, Rl-N-C-Q1 ( in which Q1 and Rl are each as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary and the resulting compounds of the general formula (XVI), i..

Le A 31 606-Foreign Countries R' R~ Q~ ~ , R
_ ~-NHO
R4 ~ ~ N O (XVI) N-Rs Rz in which Q1, Rl, R2, R3, R4 and RS are each as defined above and R represents hydrogen or alkyl, are cyclized, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (f) 2-aryl-1,2,4-triazine-3,5-dione-6-carboxylic acids of the general formula ( N
R4 ~ O
,N -R$ COOH
in which R3, R4 and RS are each as defined above are obtained, if aryl-amines of the general formula (IX), Le A 31 606-Foreign Countries R4 ~ ~ NHZ - (IX) in which R3, R4 and R$ are each as defined above are diazotized and subsequently reacted with the malonyldiurethane of the formula (XVII), CHZ(CO-NH-COOC2H5)2 (XVII) if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary and subsequently cyclized.
It is also possible to convert the compounds of the general formula (I) according to further customary methods into other compounds of the general formula (I) according to the definition above, for example by nucleophilic substitution (for example R5: F
~ OH, SH, NH2, OCH3, OCH2CH=CH2, NHS02CH3); or by further functional group conversions (for example R2: COOH ~ H, COOH --~ COCI, COOCH3, COCI
~CONH2, CN -~ CSNH2; R4: CN ~ CSNH2; R5: N02 ~ NH2, NH2 -a F, Cl, Br, CN, NHS02CH3, S02C1) or by oxidation or sulphurization (for example Q1, Q2:
O ~ S, or S ~ O), cf. also the Preparation Examples.
The novel substituted 2-aryl-1,2,4-triazine-3,5-di(thi)ones of the general formula (I) have strong and selective herbicidal activity.
In the definition, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.

Le A 31 606-Foreign Countries _12_ Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which Q1 represents oxygen or sulphur, Q2 represents oxygen or sulphur, Rl represents hydrogen, cyano, amino, represents respectively optionally cyano- fluorine-, chlorine-, C1-Cq.-alkoxy- or Cl-Cq.-alkylthio-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents respectively optionally fluorine-, chlorine- or bromine-substituted alkenyl, alkenylcarbonyl, alkenyloxycarbonyl, alkinyl, alkinylcarbonyl or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl groups, or represents respectively optionally cyano-, fluorine-, chlorine-, bromine- or C1-Cq.-alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, R2 represents hydrogen, halogen, nitro, carboxyl, cyano, thiocarbamoyl, amino, represents respectively optionally cyano-, fluorine-, chlorine-, C1-Cq.-alkoxy- or C1-Cq-alkylthio-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents respectively optionally fluorine-, chloririe-or bromine-substituted alkenyl, alkenyloxy, alkenylthio, alkinyl, alkinyloxy or alkinylthio having in each case 2 to 6 carbon atoms in the alkenyl- or alkinyl-groups, or represents respectively optionally cyano-, fluorine-, chlorine-, bromine- or Cl-Cq.-alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 6 carbon atoms in the alkyl moiety, R3 represents fluorine, chlorine or bromine, R4 represents cyano or thiocarbamoyl and RS represents the grouping -Al-A2-A3 , in which A1 represents a single bond, represents oxygen, , sulphur, ~S0-, -S02-, -CO- or the grouping -N-A4-, where A4 represents hydrogen, hydroxyl, Cl-Cq-alkyl, Cg-Cq-alkenyl, C3-Cq-alkinyl, Cl-Cq-alkoxy, phenyl, Cl-Cq-alkylsulphonyl or phenylsulphonyl, A1 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted Cl-C6-alkanediyl, C?-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, A2 represents a single bond, represents oxygen, sulphur; -SO-, -S02-, -CO- or the grouping -N-A3-, where AS represents hydrogen, hydroxyl, Cl-Cq-alkyl; Cl-Cq-alkoxy, phenyl, Cl-Cq-alkylsulphonyl or phenylsulphonyl, A2 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted Ct-C6-alkanediyl, C~
alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, Le A 31 606-Foreign Countries A3 represents hydrogen, with the proviso that in this case A1 and/or A2 do not represent a single bond, A3 furthermore represents hydroxyl, amino, cyano, isocyano, thiocyanato, vitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, fluorine, chlorine, bromine, represents respectively optionally fluorine-, chlorine- or C 1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkyl-sulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy-(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, represents respectively optionally fluorine- or chlorine-substituted alkenyl, alkenyloxy, alkenyl-amino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyl-oxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, represents respectively optionally fluorine-, chlorine-, cyano-, carboxyl-, C1-C4-alkyl- and/or C1-C4-alkoxy-carbonyl-sub-stituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkyl-alkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cyclo-alkylalkoxycarbonyl 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 respectively optionally vitro- cyano-, carboxyl-, fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkyloxy-, C1-C4-halogenoalkyloxy-and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-C 1-C4-alkyl, phenyl-C 1-C4-alkoxy, phenyloxycarbonyl or phenyl-Cl-C4-alkoxycarbonyl, A3 furthermore represents respectively optionally fully or partially hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, _ CA 02246678 1998-08-19 Le A 31 606-Foreign Countries - 1s -pyrimidinyl, triazinyl, pyrazolyl-C1-Cq-alkyl, furyl-C1-Cq.-alkyl, thienyl-C1-Cq.-alkyl, oxazolyl-Cl-Cq.-alkyl, isoxazolyl-Cl-Cq.
alkyl, thiazolyl-C 1-Cq.-alkyl, pyridinyl-C 1-C4-alkyl, pyrimidi nyl-C1-Cq.-alkyl, pyrazolylmethoxy, furylmethoxy, represents s perhydropyranylmethoxy or pyridylmethoxy.
The invention in particular relates to compounds of the formula (~, in which Q1 represents oxygen or sulphur, Q2 represents oxygen or sulphur, Rl represents hydrogen, cyano, amino, represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, 1 s ethyl, n- or i-propyl, n-, i- s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propenylcarbonyl, butenylcarbonyl, propenyloxycarbonyl, butenyloxycarbonyl, represents propinyl, butinyl, propinylcarbonyl, butinylcarbonyl, propinyloxy-carbonyl or butinyloxycarbonyl, or represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted 2s cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexyhnethyl, R2 represents hydrogen, halogen, nitro, carboxyl, cyano, thiocarbamoyl, amino, represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- s-'or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, represents respectively optionally fluorine-, chlorine- or - bromine-substituted propenyl, propenyloxy, propenylthio, butenyl, butenyloxy or butenylthio, represents propinyl, propinyloxy, propinylthio, butinyl, butinyloxy or butinylthio, or represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclo-butyl, cyclopemyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, f0 R3 represents fluorine or chlorine, R4 represents cyano or thiocarbamoyl and RS represents the grouping -A1-A2-A3 , in which A~ represents a single bond, represents oxygen, sulphur, -SO-, -S02-, -CO- or the grouping -N-A4- , where A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl, Al furthermore represents methylene, ethane-l;l-diyl, ethane-l,2-diyl, propane-l,l-diyl, propane-1,2-diyl, propane-1;3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl or propine-1,3-diyl, A2 represents a single bond, represents oxygen, sulphur, -SO-;
-S02-, -CO- or the grouping -N-AS- , where A5 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, _ CA 02246678 1998-08-19 Le A 31 606-Foreign Countries ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl, A2 furthermore represents methylene, ethane-l, l-diyl, ethane-1,2-diyl, propane-l,l-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl or propine-1,3-diyl, A3 represents hydrogen, with the proviso that in this case A1 and/or A2 do not represent a single bond, A3 furthermore represents hydroxyl, amino, cyano, nitro, carboxy, carbamoyl, sulpho, fluorine, chlorine, bromine, represents respectively optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyi, 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, ethyl-sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethyl-sulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n-or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl or dipropoxyphosphoryl, diisopropoxyphosphoryl, represents respectively optionally fluorine- or chlorine-substituted pro-penyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyl-oxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, pro-pinyloxy, butinyloxy, propinylamino, butinylamino, propinyl-oxycarbonyl or butinyloxycarbonyl, represents respectively optionally fluorine-, chlorine-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-Le A 31606-Foreign Countries -1g -substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylinethyl, cyclopentylmethyl, cyclo-hexylmethyl, cyclo-propylmethoxy, cyclobutylmethoxy, cyclo-pentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexyl-ideneamino, cyclopentyloxycarbonyl, cyclohexyl-oxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexyl-methoxycarbonyl, or represents respectively optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, , ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n-or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxy-carbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxy-carbonyl, A3 furthermore represents (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolyl-methoxy, furylmethoxy or pyridylmethoxy.
The general or preferred radical definitions listed above apply both to the end products of the formula (I) and, in a corresponding manner, also to the starting materials or intermediates which are required in each case for the preparation. These radical definitions can be combined with each other at will, i.e. combinations between the given preferred ranges are also possible.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below.

_ CA 02246678 1998-08-19 Le A 31 606-Foreign Countries Cnroup 1 ~- N
Ar- N O (IA-I) ~N -H
Ar has in this case for example the meanings given below:
2-fluoro-S-chloro-4-cyano-phenyl, 2,5-dichloro-4-cyano-phenyl, 2-chloro-5-fluoro-4-cyano-phenyl, 2-chloro-4,5-dicyano-phenyl, 2,5-difluoro-4-cyano-phenyl, 2-chloro-4-cyano-5-methyl-phenyl, 2-fluoro-4-cyano-5-methyl-phenyl, 2-chloro-4-cyano-5-tri-fluoromethyl-phenyl, 2-fluoro-4-cyano-5-trifluoro-methyl-phenyl, 2,5-difluoro-4-thio-carbamoyl-phenyl, 2-fluoro-4-cyano-S-methoxy-phenyl, 2-fluoro-4-cyano-5-i-propoxy-phenyl, 2-chloro-4-cyano-5-(2-propinyloxy)-phenyl, 2-fluoro-4-cyano-5-(1-methyl-2-propinyloxy)-phenyl, 2-chloro-4-thiocarbamoyl-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-(2-propenyloxy)-phenyl, 2-chloro-4-cyano-5-methylsulphonyl-amino-phenyl, 2-fluoro-4-cyano-S-ethylsulphonylamino-phenyl, 2-fluoro-4-thio-carbamoyl-5-methylsulphonyl-phenyl, 2-chloro-4-cyano-5-ethylsulphonylamino-I S phenyl, 2-fluoro-4-cyano-5-cyclopropylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-i-propylsulphonylamino-phenyl, 2-chloro-4-thiocarbamoyl-5-ethylsulphonylamino-phenyl, 2-chloro-4-cyano-5-cyano-amino-phenyl, 2-fluoro-4-cyano-5-trifluormethyl-sulphonylamino-phenyl, 2-fluoro-4-cyano-5-(2,2-difluorethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-phenylsulphonyl-amino-phenyl, 2-fluoro-4-cyano-5-t-butyl-sulphonylamino-phenyl, 2-chloro-4-cyano-5-methoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonyl-phenyl, 2-fluoro-4-thio-carbamoyl-S-methoxycarbonyl-phenyl, 2-chloro-4-cyano-5-(N-cyclopropyl-ethyl-sulphonylamino)-phenyl, 2-fluoro-4-cyano-5-(I-methyl-2-propinylthio)-phenyl, 2-fluoro-4-cyano-5-methylamino-phenyl, 2-chloro-4-thiocarbamoyl-5-methoxycarbonylmethyl-phenyl, 2-chloro-4-cyano-5-(N-methyl-ethylsulphonylamino)-phenyl, 2-chloro-4-cyano-5-i-propoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-(bis-ethylsulphonyl-amino)-phenyl, 2-fluoro-4-cyano-5-(N-methylsulphonyl-ethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-(1-methoxy-carbonyl-ethoxy)-phenyl, 2-fluoro-4-cyano-5-cyclo-propyloxy-phenyl, 2-chloro-4-' CA 02246678 1998-08-19 Le A 31 606-Foreign Countries cyano-5-dimethylamino-phenyl, 2-fluoro-4-cyano-5-tetrahydrofurylmethoxy-phenyl, 2-fluoro-4-cyano-5-amino-phenyl, 2-fluoro-4-cyano-5-methylaminocarbonyl-phenyl, 2-fluoro-4-cyano-5-methylsulphonyloxy-phenyl, ' 2-chloro-4-cyano-5-difluoro-methoxy-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonylmethoxy-phenyl, 2-fluoro-4-cyano-5-dimethylaminocarbonyl-phenyl, 2-fluoro-4-cyano-5-cyanomethoxy-phenyl, fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl, 2-fluoro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano-S-vitro-phenyl, 2-fluoro-4-cyano-5-diethoxyphosphoryl-amino-phenyl, 2-fluoro-4-cyano-5-chlorosulphonyl-phenyl, 2-fluoro-4-cyano-5-formylamino-phenyl, 2-chloro-4-cyano-5-ethoxycarbonyloxy-phenyl, 2-fluoro-4-cyano-5-diethoxyphosphorylmethoxy-phenyl, 2-chloro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano-5-(N,N-diacetyl-amino)-phenyl, 2-fluoro-4-cyano-5-acetylamino-phenyl, 2-chloro-4-cyano-5-thiocyanato-phenyl, 2-fluoro-4-cyano-5-diethyl-amino-oxy-phenyl, 2-fluoro-4-cyano-5-tetrahydrofuryloxy-phenyl, 2-fluoro-4-cyano-5-ureido-phenyl, 2-fluoro-4-cyano-5-dimethoxymethyleneamino-phenyl, 2-chloro-4-cyano-5-ethoxymethyleneamino-phenyl, 2-fluoro-4-cyano-5-(2-chloro-ethoxy-carbonyl-oxy)-phenyl, 2-chloro-4-cyano-5-dimethylaminomethyleneamino-phenyl, 2-chloro-4-cyano-5-(perhydropyran-4-yloxy)-phenyl, 2-fluoro-4-cyano-5-(2-methoxy-carbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl, fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-s-butoxycarbonyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-carbamoyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-1-methyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(1,2-dibromo-2-methoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-chloro-2-i-propoxy-carbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-allylaminocarbonyl-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-ethoxycarbonyl-ethenyl)-phenyl, 2-fluoro-4-cyano-S-(2-chloro-2-cyclopropylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-dimethyl-aminocarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-chloro-2-ethylsulphonylamino-carbonyl-ethyl)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(2-ethylaminocarbonyl-ethenyl)-phenyl, 2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(1-ethoxycarbonylethyl)-phenyl, 2-chloro-4-cyano-S-carboxy-phenyl, 2-fluoro-4-cyano-5-1-butoxy-phenyl, 2-chloro-4-cyano-5-1-butoxy-phenyl, 2-chloro-4-cyano-5-(2-Le A 31 60C-Foreign Countries methoxy-ethoxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxycarbonylmethoxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyl-oxy)-phenyl.
Group 2 N

Ar - N O (IA-2) ~N -H
Ar has in this case the meanings listed above in Group 1.
Group 3 O nCsH7 N (IA-3 ) Ar- N O
~N -H
Ar has in this case the meanings listed above in Group 1.
Group 4 O / iC3H~
-- N
Ar- N O (IA-4) N
H
Ar has in this case the meanings listed above in Group I .

Le A 31 60G-Foreign Countries Group 5 O / C(CH3)3 -N
Ar - N O (IA-5) N-H
Ar has in this case the meanings listed above in Group 1.
Group 6 O H
-- N~
Ar - N O (IA-6) N-H
Ar has in this case the meanings listed above in Group 1.
Group 7 S CHs N
Ar- N O (Ip,_~) N-H
Ar has in this case the meanings listed above in Group 1.

i,e A 31 606-Foreign Countries Group 8 ~-- N
Ar- N S (IA-8) v N-H
Ar has in this case the meanings listed above in Group 1.
Group 9 O N
Ar - N\ S (IA-9) N-H
Ar has in this case the meanings listed above in Group 1.
Grog 10 O
~N
Ar- N O (IA-10) N-H
Ar has in this case the meanings listed above in Crroup 1.

Le A 31 606-Foreign Countries Group 11 O ~ CN
~- N
Ar- N O (IA-11) N-H
Ar has in this case the meanings listed above in Group 1.
Group 12 O / NHZ
~- N
Ar- N O (IA-12) v N-H
Ar has in this case the meanings listed above in Group 1.
Group 13 -- N
Ar- N O (IA-13) N-H
Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Group 14 N(cH3)2 N (IA-14) Ar-N O
v N-H
Ar has in this case the meanings listed above in Group 1.
Group 15 O
N (IA-15) Ar-N O
N-H
Ar has in this case the meanings listed above in Group 1.
Group 16 O
-- N
Ar- N O (IA-16) N-H
Ar has in this case the meanings listed above in Group 1.

i Le A 31 606-Foreign Countries Group 17 /- CN
N
Ar- N O (IA-17) N-H
Ar has in this case the meanings listed above in Group 1.
Group 18 N
Ar- N' O (IA-18) N-H
Ar has in this case the meanings listed above in Group 1.
Group 19 ~- SCH3 N
Ar- N O (IA-19) N-H
Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Group 20 F
O
N (IA-20) Ar-N O
N-H
Ar has in this case the meanings listed above in Group 1.
Group 21 O
~-- N~ F
Ar- N O (IA-21) N-H
Ar has in this case the meanings listed above in Group 1.
Group 22 O CI-IFZ
N
Ar - N O (IA-22) N-H
Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Group 23 N
Ar- N O (IA-23) N-H
Ar has in this case the meanings listed above in Group 1.
Group 24 N
Ar - N O (IA-24) N-H
Ar has in this case the meanings listed above in Group 1.
Group 25 O / COOC2H$
~N
Ar- N\ O (IA-25) N-H
Ar has in this case the meanings listed above in Group 1.

i Le A 31 606-Foreign Countries Group 26 -- N
Ar- N O (IA-26) N-H
Ar has in this case the meanings listed above in Group I .
Group 27 N (IA-27) Ar-N O
N-H
Ar has in this case the meanings listed above in Group 1.
Group 28 ~- CFs N
Ar - N O (IA-28) N-H
Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Group 29 O ~ C2F$
-N
Ar - N O (IA-29) v N-H
Ar has in this case the meanings listed above in Group 1.
Group 3 0 O CHs N
Ar- N O (IA-30) N-Ar has in this case the meanings listed above in Group 1.
Group 31 O / CzHs ~- N
Ar - N' O (IA-31 ) N-Ar has in this case the meanings listed above in Group 1.

i Le A 31 606-Foreign Countries Group 3 2 O / iC3H~
~N
Ar- N O (IA-32) N-Ar has in this case the meanings listed above in Group 1.
Group 3 3 ~ CH3 ~- N
Ar- N O (IA-33) N-Ar has in this case the meanings listed above in Group I .
Group 34 O CHs i N
Ar- N' S (IA-34) N-Ar has in this case the meanings listed above in Group 1.

_ CA 02246678 1998-08-19 Le A 31 606-Foreign Countries _32_ Group 3 5 S CHs N/
Ar- N S (IA-35) N-Ar has in this case the meanings listed above in Group 1.
Group 3 6 O
N
Ar- N~ ~ (IA-36) N-Ar has in this case the meanings listed above in Group 1.
Group 3 7 a p CN
i N
Ar- N' O (IA-37) N-Ar has in this case the meanings listed above in Group 1.

CA 02246678 1998-08-19 .
Le A 31 606-Foreign Countries Group 3 8 N/
Ar- N O (IA-38) v N-CHs Ar has in this case the meanings listed above in Group 1.
Group 3 9 O NHCHs ~N/
Ar-N O (IA-39) N-CHs Ar has in this case the meanings listed above in Group 1.
Group 40 O / N(CHs)2 ~N
Ar - N O (IA-40) N-CHs Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Group 41 O
~-- N
Ar-N O
N-CH3 (IA-41) Ar has m this case the meanings fisted above m Group 1.
Group 42 O
-- N
Ar- N O (IA-42) N-Ar has in this case the meanings listed above in Group 1.
Group 43 ~- CN
N
Ar- N O (IA-43) N-Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Crroup 44 ~-OCH3 N
Ar - N O (IA-44) v N-S Ar has in this case the meanings listed above in Group I .
Group 45 O ~ SCH3 N
Ar- N O (IA-45) N-Ar has in this case the meanings listed above in Group 1.
Group 4G
F
O
N
Ar - N O (IA-46) N-Ar has in this case the meanings listed above in Group 1.

Le A 3 ~ 606-Forei~~n Countries Group 47 O ~
~- N~ F
Ar- N O
N-CH3 (IA-47) Ar has in this case the meanings listed above in Group 1.
Group 48 O / CHFZ
~- N
Ar - N O (IA-48) N-Ar has in this case the meanings listed above in Group 1.
Group 49 -- N
Ar- N O (IA-49) N-Ar has in this case the meanings listed above in Group 1.

Le A 31 bDb-Foreign Countries Group 50 ~- N
Ar- N O
(IA-50) N -Ar has in this case the meanings listed above in Group 1.
Group 51 ~N
Ar- N O (IA-51) N-Ar has in this case the meanings listed above in Group 1.
Group 52 N
Ar- N O (IA-52) N-Ar has in this case the meanings listed above in Group 1.

i Le A 31 606-Foreign Countries Group 53 i N
Ar- N O (IA-53) N-Ar has in this case the meanings listed above in Group 1.
Group 54 O ~- CF3 -N
Ar- N O
(IA-54) N-Ar has in this case the meanings listed above in Group 1.
Group 55 O ~ ZFs ~-- N
Ar-N O (IA-55) N-Ar has in this case the meanings listed above in Group I.

i Le A 31 bOb-Foreman Countries Group 56 O H
~N '' Ar- N O (1A_56) N-Ar has in this case the meanings listed above in Group 1.
o Group 57 O CHs N~
Ar-N O
v N-CF3 (IA-57) Ar has in this case the meanings listed above in Group 1.
Group 5 8 ~ CzHs N
Ar- N O
N - (IA-58) Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Forei~:n Countries Group 59 ~- N
Ar- N O (IA-59) N-Ar has in this case the meanings listed above in Group 1.
Group 60 O
~N
Ar - N O (TA-60) N-Ar has in this case the meanings listed above in Group 1.
Group 61 S CHs i N
Ar - N O (IA-61 ) N-Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Crroup 62 ~- N
Ar- N O (IA-62) v N-Ar has in this case the meanings listed above in Group 1.
Group 63 CN
~- N
Ar- N O (IA-63) N-Ar has in this case the meanings listed above in Group 1.
Group 64 O CN
N
Ar- N O
(IA-64) N-Ar has in this case the meanings listed above in Group 1.

i Le A 31 606-Foreign Countries Group 65 O NHS
N
Ar- N O (IA-65) N-Ar has in this case the meanings listed above in Group 1.
Group 67 O ~ N(CH3)2 -- N
Ar - N O (IA-67) v N-Ar has in this case the meanings listed above in Group 1.
Group 68 O
-N
Ar- N O (IA-68) N-Ar has in this case the meanings listed above in Group 1.

i Le A 3 I bD6-Foreign Countries Group 69 O
~- N
Ar- N O (IA-69) N-Ar has in this case the meanings listed above in Group I.
Group 70 N
Ar - N~ O (IA-70) N-Ar has in this case the meanings listed above in Group 1.

L.e A 31 606-Foreign Countries Group 71 O ~ SCH3 . _ -N
Ar- N O (IA-71) N-Ar has in this case the meanings listed above in Group 1.
Group 72 O ~-- CN
~- N
Ar- N ~ (IA-72) N-Ar has in this case the meanings listed above in Group 1.
Group 73 O F
~- N~
Ar- N O (IA-73) v N-Ar has in this case the meanings listed above in Group I .

Le A 3 I 606-Foreign Countries = 45 -Group 74 O ~--~
~- N F
Ar- N O (IA-74) N-Ar has in this case the meanings listed above in Group 1.
Group 75 N/
Ar - N O (IA-75) N-Ar has in this case the meanings listed above in Group I .
Grou 76 O
-- N
Ar - N O (IA-76) N-Ar has in this case the meanings listed above in Group 1.

Le A 31 bOb-Foreign Countries Group 77 N
Ar - N ~ (IA-77) N-Ar has in this case the meanings listed above in Group 1.
Group 78 O CHs N
Ar- N O (IA-78) N-CZHS
Ar has in this case the meanings listed above in Group 1.
Group 79 ~- N/
Ar - N O (IA-79) N--Ar has in this case the meanings listed above in Group 1.

Le A 31 BOG-Foreign Countries Group 80 ~-- N~
Ar - N O (IA-80) N-iC3H~
Ar has in this case the meanings listed above in Group I .
Group 81 O ~ H3 -N
Ar- N O
v (IA-81 ) N-Ar has in this case the meanings listed above in Group 1.
Group 82 O CHs ~N
Ar- N O (IA-82) N-CI
Ar has in this case the meanings listed above in Group 1.

i...

Le A 31 606-Foreign Countries Group 83 p /

~- N
Ar- N O (IA-83) N-Br Ar has in this case the meanings listed above in Group 1.
Group 84 O CHs ~- N/
Ar- N O (IA-84) N -F
Ar has in this case the meanings listed above in Group 1.
Group 85 O CHs N
Ar- N O (IA-85) N-COOH
Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Group 86 ~- N/
Ar- N O (IA-86) N-CN
Ar has in this case the meanings listed above in Crroup 1.
Group 87 O CHs N
Ar - N O (IA-87) N-CSNHZ
Ar has in this case the meanings listed above in Group 1.
Group 88 O
~N F
Ar- N O (IA-88) N-CN
Ar has in this case the meanings listed above in Group 1.

Le A 3 i 606-Foreign Countries Group 89 O ~
~- N F
Ar- N ~ (IA-89) N-Ar has in this case the meanings listed above in Group 1.
Group 90 O CHs ~N
Ar - N O (IA-90) N-NOZ
Ar has in this case the meanings listed above in Group 1.
Group 9I
O CHs N
Ar- N O (IA-91) N-NHZ
Ar has in this case the meanings listed above in Group 1.

Le A 31 606-Foreign Countries Group 92 -- N
Ar- N O (IA-92) N-Ar has in this case the meanings listed above in Group 1.
Group 93 N
Ar- N' -O (IA-93) N-N(CH3)2 Ar has in this case the meanings listed above in Group 1.
Group 94 ~N
Ar- N! O (IA-94) v N-Ar has in this case the meanings listed above in Group I .

_ CA 02246678 1998-08-19 Le A 31 606-Foreign Countries , Group 95 ~- N/
Ar- N O (IA-95) v N- S
Ar has in this case the meanings listed above in Group 1.
Group 96 ~N/
Ar- N O (IA-96) N-O
Ar has in this case the meanings listed above in Group 1.
Group 97 O CHs -- N~
Ar- N O (IA-97) N-Ar has in this case the meanings listed above in Group 1.

i _ CA 02246678 1998-08-19 Le A 31 606-Foreign Countries Groun 98 ~-- N
Ar-N O (IA-98) N - , CN
Ar has in this case the meanings listed above in Group 1.
Using, for example, 4,6-diethyl-1,2,4-triazine-3,5(2H,4H)-dione and 2,4,5-trifluoro-benzonitrile as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following equation:
F CZHs C2Hs O
F O F N
/ N ~ _. I
N~N
z s NC \ I + ~N N~ H / ~' II \C H
H ~ CzHs \ O
F O NC
F
Using, for example, 2-(4-cyano-S-ethoxy-2-fluoro-phenyl)-6-trifluoromethyl-1,2,4 triazine-3,5(2H,4H)-dione and ethylbromide as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following equation:

O O
F N~ +C H-Br F N
/ ~N N\ ~ / N N~
H - HBr \ ~ ~ C2Hs NC NC
OC~Hs OC2Hs i Le A 31 606-Foreign Countries Using, for example, acetone N-(5-chloro-4-cyano-2-fluoro-phenyl)-hydrazone and potassium thiocyanate and, in the subsequent step, pyruvic acid as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following equation:
CH ' CH3 F N ~ CH3 F NON
NH + KSCN N ~C
/ I ~ / I S
NC
NC

O.
F N
+CH3C0-CO-OH / iN~N~H
NC
CI
Using, for example, 4-amino-3-fluoro-2-methylthio-benzonitrile and ethyl cyano acetylcarbamate as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following equation:
CN
F O
NHZ H F N
I
+ N O~ --1 / NH ~N~
NC NC ~ ~ CZHS I H
SCH3 O O NC ~ OC2H5 CN
O
F N
I N
- HOC~H$ /
H
NC ~ I O

_ CA 02246678 1998-08-19 Le A 31 60G-Foreign Countries Using, for example, 2-chloro-4-cyano-5-methyl-phenylhydrazine and methyl pyruvate and, in the subsequent step, ethyl isothiocyanate as starting materials, the course of the reaction in the process (e) according to the invention can be illustrated by the following equation:

NH CI N
/ ~ + CH3 CO-CO-OCH3 / I
NH ~CH3 NC \

O
CI N ~O CI N
+ S=C=N-CZHs ( OCH3 N N
/ N _, ~T NH - H H / ~ ~ \ CZHs NC \ S ~ 3NC ~ S
CH3 CZHs CH3 Using, for example, 4-amino-2,5-dichloro-benzonitrile and sodium nitrite/hydrochloric acid and, in the subsequent step, malonyldiethylurethane as starting materials, the course of the reaction in the process (f) according to the invention can be illustrated by the following equation:
CI CI
/ NHZ NaNOz/HCI / Nz+CI
NC ~ NC \ H
CI
CI CI N ~O
+ CH2(CO-NH-COOCZHS)2 / i N ~ N w H
\ l O
NC
CI

Le A 31 606-Foreign Countries The formula (II) provides a general definition of the 1,2,4-triazine-3,5-di(thi)ones to be employed as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (II), Q1, Q2, R1 and R2 each 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) according to the invention, as being preferred or particularly preferred for Ql, Q2, Rl and R2.
The starting materials of the formula (II) are known and/or can be prepared by known methods (cf.. J. Am. Chem. Soc. 80 (1958), 976; J. Heterocycl. Chem. 16 (1979), 1649; J. Org. Chem. 23 (1958), 1951-1953).
The formula (IIl~ provides a general definition of the halogenobenzene derivatives furthermore to be used as starting materials in the process (a) according to the invention. In the formula (III), R3, R4 and RS each 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) according to the invention, as being preferred or particularly preferred for R3, R4 and R5; X1 preferably represents fluorine, chlorine or bromine, in particular fluorine.
The starting materials of the formula (III) are known and/or can be prepared by processes known per se (cf. EP 191181, EP 370332, EP 431373, EP 441004).
The formula (Ia) provides a general definition of the 2-aryl-1,2,4-triazine-3,5-di(thi)-ones to be employed as starting materials in the process (b) according to the invention. In the formula (Ia), Q1, Q2, R2 , R3, R4 and RS each 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) according to the invention, as being preferred or particularly preferred for Q1, Q2, R2 , R3, R4 and R5.

Le A 31 b06-Foreign Countries The starting materials of the formula (Ia) are novel compounds according to the invention; they can be prepared by the processes (a) and (c) to (f) according to the invention.
The formula (IV) provides a general definition of the alkylating agents furthermore to be employed as starting materials in the process (b) according to the invention. In the formula (IV), Rl preferably or in particular has those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or particularly preferred for Ri; X2 preferably represents fluorine, chlorine, bromine, iodine, methoxysulphonyloxy or ethoxysulphonyloxy, in particular chlorine or bromine.
The starting materials of the formula (IV) are known organic chemicals for synthesis.
The formula (V) provides a general definition of the arylhydrazones to be employed ~as starting materials in the process (c) according to the invention for preparing compounds of the formula (I). In the formula (V), R3, R4 and RS each 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) according to the invention, as being preferred or particularly preferred for R3, R4 and R5.
The starting materials of the formula (V) are known and/or can be prepared by known processes (cf. WO 86/00072, US 4956004).
The formula (VI) provides a general definition of the alkali metal (thio)cyanates furthermore to be employed as starting materials in the process (c) according to the invention. In the formula (VI), Q 1 preferably or in particular has those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or particularly preferred for Q 1 ~ M preferably represents lithium, sodium, potassium, rubidium or caesium, in particular sodium or potassium.

Le A 31 606-Foreign Countries The starting materials of the formula (VI) are known chemicals for synthesis.
The formula (VIII) provides a general definition of the ketocarboxylic acids furthermore to be employed as starting materials in the process (c) according to the invention. In the formula (VIII, R2 preferably or in particular has those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or particularly preferred for R2.
The starting materials of the formula (VIII are known organic chemicals for synthesis.
The formula (IX) provides a general definition of the aryl amines to be employed as starting materials in the processes (d) and (fj according to the invention for preparing compounds of the formula (I). In the formula (IX), R3, R4 and RS each preferably or in particular have those meanings which have been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or particularly preferred for R3, R4 and R5.
The starting materials of the formula (IX) are known and/or can be prepared by known processes (cf. EP 224001, EP 303573, DE 3835168, EP 40389I).
The formula (X) provides a general definition of the cyanoacetylcarbamic acid esters furthermore to be employed as starting materials in the process (d) according to the invention. In the formula (X), Rl preferably or in particular has those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or particularly preferred for Rl.
The starting materials of the formula (X) are known organic chemicals for synthesis.

Le ~ 31 606-Foreign Countries The formula (XII) provides a general definition of the arylhydrazines to be employed as starting materials in the process (e) according to the invention for preparing compounds of the formula (I). In the formula (XII), R3, R4 and RS each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the formula (I) according to the invention, as being preferred or particularly preferred for R3, R4 and R5.
The starting materials of the formula (XII) are known and/or can be prepared by known processes (cf. EP 370332).
The formula (XIII) provides a general definition of the ketocarboxylic acid derivatives furthermore to be employed as starting materials in the process (e) according to the invention. In the formula (XIII), R2 preferably or in particular has those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or particularly preferred for R2~ R preferably represents hydrogen or Cl-Cq.-alkyl, in particular hydrogen, methyl or ethyl.
The starting materials of the formula (XIII) are known organic chemicals for synthesis.
The formula (X~ provides a general definition of the iso(thio)cyanates furthermore to be employed as starting materials in the process (e) according to the invention. In the formula (X~, Q1 and R1 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) according to the invention, as being preferred or particularly preferred for Q 1 and R1.
The starting materials of the formula (X~ are known chemicals for synthesis The malonyldiurethane of the formula (XVII) to be employed as starting material in the process according to the invention is a known chemical for synthesis.

_ CA 02246678 1998-08-19 Le A 31 606-Foreign Countries Suitable diluents for carrying out the processes (a) to (f) according to the invention are in particular inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitrites, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N
methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
Suitable reaction auxiliaries for the processes (a) to (f) are generally the customary inorganic or organic bases or acid accepters. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or i-propoxide or potassium n- or i-propoxide, sodium n-, or i-, s- or t-butoxide or potassium n-, i-, s- or t-butoxide;
furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-di-methyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-Le A 31 606-Foreign Countries methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo-[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), or 1,8-diaza-bicyclo[5,4,0]-undec-7-ene (DBU).
S When carrying out the processes (a) to (f) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, temperatures of between -20°C and +150°C, preferably between 0°C and +120°C, are employed.
The processes (a) to (f) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - in general beween 0,1 bar and 10 bar.
In the practice of the processes (a) to (f) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use in each case one of the components in a relatively large exess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for a number of hours at the temperature required. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially as weed killers. By weeds in the broadelst sense, there are to be understood all plants which grow in locations where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the eg nera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, _ i _ Le A 31 606-Foreign Countries , Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solarium, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the eg nera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solarium, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: 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, Agrostic, Alopecurus and Apera. , Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative 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, on lawns, turf and pasture-land, and for the selective control of weeds in annual cultures.
The compounds of the formula (I) according to the invention are suitable in particular for selectively controlling monocotyledonous and dicotyledonous weeds in Le A 31 606-Foreign Countries monocotyledonous and docotyledonous crops, both pre-emergence and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules 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 dispersing agents and/or foam-forming agents.
If the extender used is water, it is also possible to employ for example organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are:
aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methyleme chloride, aliphatic hydrocarbons, such as cyclohexane or paraffns, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl Icetone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diato-maceous earth, and ground synthetic minerals, such as finely divided silica, alumima and silicates, suitable solid carriers for granules are: for example crushed arid fractionated natural rocks such as calcite, marble, pumise, sepiolite and dolomite, ~as well as 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-forming agents are: for example nonionic and anionic Le A 31 606-Forei~:n Countries emulsifers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
i It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain 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, for example anilides, such as diflufenican and propanil; arylcarboxylic acids, such as dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones, such as chloridazon and norflurazon; carbamates, such ~as chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides, such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines, such as oryzalin, pendimethalin and trifluralin;
diphenyl Le A 31 60&-Foreign Countries . .

ethers, such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, such as imazethapyr, imazamethabenz, imazapyr and imazaquin; nitrites, such as bromoxynil, dichlobenil and ioxynil;
oxyacetamides, such as mefenacet; sulphonylureas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfitron and tribenuron-methyl; thiocarbamates, such as butylate, cycloate, diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate;
triazines, such as atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine;
triazinones, such as hexazinone, metamitron and metribuzin; and others, such as aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzo-quat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulfosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
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 ef~'ect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.

Le A 31 G06-Foreign Countries The preparation and use of the active compounds according to the invention can be seen from the Examples below.
Preparation Examples:
Example 1:
F O ~ NHz -- N
NC ~ ~ N O
N-F CHs At 70°C, 7.1 g (50 mMol) of 4-amino-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 6.9 g (50 mMol) of potassium carbonate and 7.9 g (50 mMol) of 2,4,5-Trifluoro-benzonitrile in 100 ml of dimethyl sulphoxide axe stirred for 4 hours, the mixture is subsequently cooled to room temperature and stirred into ice-water and precipitated product is filtered oil with suction, dried and recrystallized from ethanol.
2.9 g (20 % of theory) of 2-(2,4-difluoro-4-cyano-phenyl)-4-amino-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione of melting point 125°C are obtained.
Example 2:
F O H
N
NC ~ ~ N O
N-F
CHs At 120°C, 2.54 g (20 mMol) of 6-methyl-1,2,4-triazine-3,5(2H,4H)-dione in 50 ml of dimethyl sulphoxide are stirred with 2.8 g (20 mMol) of potassium carbonate and 3.14 g (20 mol) of 2,4,5-trifluoro-benzonitrile for 12 hours, the mixture is _ Le A 31 606-Foreign Countries subsequently cooled to room temperature and stirred with water, the pH is adjusted to using hydrochloric acid and precipitated product is filtered off with suction, stirred with water and dried.
5 4.6 g (87% of theory) of 2-(2,4-difluoro-4-cyano-phenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione of melting point 214°C are obtained.
Example 3:
H
F O
-- N
NC ~ ~ N O
N-O

5.2 g {20 mMol) of 2-(2,4-difluoro-4-cyano-phenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione are initially charged in 50 ml of acetonitrile with 2.8 g (40 mMol) of 3-butin-2-ol, and at room tempeature (about 20°C), the mixture is mixed a little at a time with 1.15 g (40 mMol) of sodium hydride (80% strength in paraffin) and the mixture is stirred at room temperature for 12 hours. The mixture is concentrated under reduced pressure, the residue is stirred with water, the pH is adjusted to 5 using concentrated hydrochloric acid and the precipitated product is isolated by filtration.
5.8 g (92 % of theory) of 2-(2-fluoro-4-cyano-5-but-1-in-3-yl-oxy-phenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione of melting point 153°C (decomp.) are obtained.
Example 4:
F O ~ C'2H5 ~- N
NC ~ ~ N O
N-O

Le A 31 606-Foreign Countries At room temperature (about 20°C), 1.6 g (5 mMol) of 2-(2-fluoro-4-cyano-5-but-1-in-3-yl-oxy-phenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione in 50 ml of dimetliyl sulphoxide are stirred with 1.38 g (10 mMol) of potassium carbonate and 1.56 g (10 mMol) of ethyl iodide for 12 hours. The mixture is concentrated under reduced pressure, the residue is stirred with water, the pH is adjusted to 5 using concentrated hydrochloric acid and the precipitated product is isolated by filtration.
1.6 g (93.5% of theory) of 2-(2-fluoro-4-cyano-5-but-1-in-3-yl-oxy-phenyl)-4-ethyl-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione of melting point 139°C are obtained.
Similar to Preparation Examples 1 to 4 and in accordance with the general description of the preparation processes according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) listed in Table 1 below.
R3 Q~ R~
N/
R4 ~ Qz v N-Rs Rz (I) Le A 31 X06-Foreign Countries 'Fable 1: Examples of compounds of the general formula (I) Ex.R1 R~ Q1 Q R' R'* R' Physical No. 2 Data NH2 C(CH3)3O O F CN F Mp.:120C

6 H H O O F CN F Mp.: >250C
a 7 H CH3 O O F CN F Mp.:130C

8 CH3 CH3 O O F CN OCH(CH3)C---CHMp.:102C

9 H H O O F CN OCH(CH3)C=CH Mp.:202C

CH3 H O O F CN OCH(CH3)C---CHMp.:129C

11 H H O O F CN NHS02C2H5 Mp.:121C
(Decomp.) i 12 H H O O F CN OCH2-C---CH Mp.:175C

13 CH3 H O O F CN OCH2-C=CH Mp.: 137C

14 CH3 H O O F CN NHS02C2H5 Mp.:187C
[contains about 30%-N(CH3)-]

CH3 H O O F CN OCH2CH=CH2 Mp.:139C

16 CH(CH3)2 CH3 O O F CN OCH(CH3)C=CH Mp.:112C

17 C2H5 H O O F CN OC2H5 Mp.:142C

18 C2H5 H O O F CN OCH2-C=CH 1H NMR:

19 C2H5 H O O F CN OCH(CH3)C---CHMp.:132C

CH(CH3)2 H O O F CN OCH(CH3)C---CHMp.:70C

21 H H O O F CN OC2H5 Mp.:150C

22 H H O O F CN OH Mp.:220C

23 CH2CH2F H O O F CN OCH(CH3)C=CH

24 (CH2)3F H O O F CN OCH(CH3)C---CH

CH2-C---CHH O O F CN OCH(CH3)C---CHMp.:132C

26 CH2CH2F CH3 O O F CN OCH(CH3)C---CHMp.:119C

27 (Cl-I2)3F CH3 O O F CN OCH(CH3)C---CHMp.:115C

28 Cl-I3 CH3 O O F CN NHS02C2H5 Mp.:129C

29 CH2CH=CH2 H O O F CN OCH(CH3)C---CHMp.:84C

Le A 31 606-Foreign Countries Ex.R 1 R~ Q Q R~ Ry' R~ Physical No. 1 2 Data.

30 CH3 CH3 O O F CN NHS02CH3 Mp.:115C
I

31 (CH2)3F H O O F CN F Mp.:85C

32 H CH3 O O F CN NHS02CH3 Mp.:140 33 (CH2)3F CH3 O O F CN NHS02CH3 Mp.: 108C

34 CH3 H O S F CN OCH(CH3)C---CH(amorphous) 35 CH2CH2F H O O F CN OCH2C=CH Mp.:135C

36 (cH2)2cF=cF2H O O F CN OCH2C=CH (amorphous) 37 (CH2)3F H O O F CN OCH2C~CH Mp.:126C

38 (cH2)zcF-cF2H O O F CN NHS02C2H5 Mp.:88C

39 (CH2)3F CH3 O O F CSNH2 NHS02CH3 Mp.: >210C

40 C2H5 H O O F CN N(C2H5)S02C2H5Mp.: 154C

41 CH3 H O O F CN N(CH3)S02C2H5Mp.:91C

42 H H O O F CN N(S02C2H5)2 Mp.: >250C

43 CH3 H O O F CN N(S02C2H5)2 Mp.:164C

44 CH3 H O O F CN NHS02C2H5 Mp.:233C
, 45 CH2CH2F H O O F CN NHS02C2H5 Mp.:190C

46 (CH2)3F H O O F CN NHS02C2H5 Mp.:98C

47 (CH2)3F H O O F CN NHS02CH3 Mp.:186C

48 CH2CH2F H O O F CN NHS02CH3 Mp.:178C

Le A 31 606-Foreign Countries Use examples:
Examnte A
Pre-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is watered with the preparation of the active compound. Advantageously, the amount of water per unit area is kept constant. The active compound concentration in the preparation is not important, only the active compound application rate per unit area matters.
After three weeks, the degree of damage to the plants is rated in % damage in comparison with the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, for example, the compounds of Preparation Example 7, 8, 10, 17, 18 and 19 exhibit, at an application rate between 60 and 125 g/ha, very strong activity against weeds such as Alopecurus (70 to 100 %), Digitaria (70 to 100 %), Sorghum (70 to 100 %), Amaranthus (100 %), Chenopodium (100 %) and Solanum (100 %), and they are tolerated well by crops, such as, for example, wheat (up to 20 %), barley (0 to 10 %), Maize (0 %), Soya (10 to 20 %) and cotton (0 to 30 %).

i Le A 31 606-Foreign Countries _~2_ 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-l5cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage ~in comparison with the development of the untreated control.
The figures denote:
0 % = no effect (like untreated control) 100 % = total destruction In this test, for example, the compounds of Preparation Example 7, 8 and 10 exhibit, at outwall rates between 60 and 125 g/ha, very strong activity against weeds such 'as Digitaria (70 to 95 %), Echinochloa (80 to 100 %), Setaria (70 to 100 %), Datura (100 %), Solanum (100 %) and Viola (100 %), and they are well tolerated by crops, such as, for example, wheat (0 to 10%) and barley (0%).

Claims

CLAIMS:

1. A substituted 2-aryl-1,2,4-triazine-3,5-di(thi)one of the general formula (I):

wherein:
Q1 represents O or S;
Q2 represents O or S;
R1 represents: (i) H, cyano or amino, (ii) optionally cyano-, F-, Cl-, C1-C4-alkoxy- or C1-C4-alkylthio-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, (iii) optionally F-, Cl- or Br-substituted alkenyl, alkenylcarbonyl, alkenyloxycarbonyl, alkinyl, alkinylcarbonyl or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl groups, or (iv) optionally cyano-, F-, Cl-, Br- or C1-C4-alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and for the cycloalkylalkyl 1 to 4 carbon atoms in the alkyl moiety;
R2 represents: (i) H, a halogen atom, nitro, carboxyl, cyano, thiocarbamoyl or amino, (ii) optionally cyano-, F-, Cl-, C1-C4-alkoxy- or C1-C4-alkylthio-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, (iii) optionally F-, Cl- or Br-substituted alkenyl, alkenyloxy, alkenylthio, alkinyl, alkinyloxy or alkinylthio having in each case 2 to 6 carbon atoms in the alkenyl- or alkinyl-groups, or (iv) optionally cyano-, F-, Cl-, Br- or C1-C4-alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and for the cycloalkylalkyl 1 to 6 carbon atoms in the alkyl moiety;
R3 represents F, Cl or Br;
R4 represents cyano or thiocarbamoyl; and R5 represents the grouping -A1-A2-A3, wherein:
A1 represents:
(a) a single bond, -O-, -S-, -SO-, -SO2-, -CO- or the grouping -N-A4-, wherein A4 represents H, hydroxyl, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl, or (b) optionally F-, Cl- or Br-substituted C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene;
A2 represents:
(a) a single bond, -O-, -S-, -SO-, -SO2-, -CO- or the grouping -N-A5-, wherein A5 represents H, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl, or (b) as defined for A1; and A3 represents:
(a) H, with the proviso that in this case A1, A2 or both A1 and A2 do not represent a single bond, (b) (i) hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, F, Cl or Br, (ii) optionally F-, Cl- 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) optionally F- or Cl-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) optionally F-, Cl-, 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 when present 1 to 4 carbon atoms in the alkyl groups, or (v) optionally nitro-, cyano-, carboxyl-, F-, Cl-, Br-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkyloxy-, Cl-C4-halogenoalkyloxy-, C1-C4-alkoxy-carbonyl- or a combination thereof-substituted phenyl, phenyloxy, phenyl-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenyloxycarbonyl or phenyl-C1-C4-alkoxycarbonyl, or (c) optionally fully or partially hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C1-C4-alkyl, furyl-C1-C4-alkyl, thienyl-C1-C4-alkyl, oxazolyl-C1-C4-alkyl, isoxazolyl-C1-C4-alkyl, thiazolyl-Cl-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-Cl-C4-alkyl, pyrazolylmethoxy, furylmethoxy, perhydropyranylmethoxy or pyridylmethoxy.

2. A substituted 2-aryl-1,2,4-triazine-3,5-di(thi)one of the general formula (I) according to claim 1, wherein:
Q1, Q2 and R4 are as defined in claim 1;
R1 represents: (i) H, cyano or amino, (ii) optionally cyano-, F-, Cl-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, or n- or i-propoxycarbonyl, (iii) optionally F-, Cl- or Br-substituted propenyl, butenyl, propenylcarbonyl, butenylcarbonyl, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinylcarbonyl, butinylcarbonyl, propinyloxycarbonyl or butinyloxycarbonyl, or (iv) optionally cyano-, F-, Cl-, Br-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl;
R2 represents: (i) H, a halogen atom, nitro, carboxyl, cyano, thiocarbamoyl or amino, (ii) optionally cyano-, F-, Cl-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n-or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, (iii) optionally F-, Cl- or Br-substituted propenyl, propenyloxy, propenylthio, butenyl, butenyloxy or butenylthio, propinyl, propinyloxy, propinylthio, butinyl, butinyloxy or butinylthio, or (iv) optionally cyano-, F-, Cl-, Br-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl;
R3 represents F or Cl; and R5 represents the grouping -A1-A2-A3, wherein:
A1 represents:
(a) a single bond, -O-, -S-, -SO-, -SO2-, -CO- or the grouping -N-A4-, wherein A4 represents H, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl, or (b) 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 or propine-1,3-diyl;
A2 represents:
(a) a single bond, -O-, -S-, -SO-, -SO2-, -CO- or the grouping -N-A5-, wherein A5 represents H, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl, or (b) as defined for A1; and A3 represents:
(a) as defined in claim 1, (b) (i) hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, F, Cl or Br, (ii) 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) 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) 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, or (v) 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 or benzyloxycarbonyl, or (c) optionally fully or partially hydrodgenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy.

3. A process for preparing a substituted 2-aryl-1,2,4-triazine-3,5-di(thi)one of the general formula (I) according to claim 1 or 2, comprising:
(a) reacting, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, a 1,2,4-triazine-3,5-di(thi)one of the general formula (II):

wherein Q1, Q2, R1 and R2 are as defined in claim 1 or 2, with a halogenobenzene derivative of the general formula (III):

wherein R3, R4 and R5 are as defined in claim 1 or 2, and X1 represents a halogen atom; or (b) reacting, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, a 2-aryl-1,2,4-triazine-3,5-di(thi)one of the general formula (Ia):

wherein Q1, Q2, R2, R3, R4 and R5 are as defined in claim 1 or 2, with an alkylating agent of the general formula (IV):

R1-X2 (IV) wherein R1 is as defined in claim 1 or 2, and X2 represents a halogen atom or the grouping -O-SO2-O-R1, wherein R1 is as defined in claim 1 or 2; or (c) reacting, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, an arylhydrazone of the general formula (V):

wherein R3, R4 and R5 are as defined in claim 1 or 2, with an alkali metal (thio)cyanate of the general formula (VI):

M-Q1-CN (VI) wherein Q1 is as defined in claim 1 or 2, and M represents an alkali metal atom and reacting, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, the resulting 2-aryl-1,2,4-triazolidine-3-(thi)one of the general formula (VII):

wherein Q1, R3, R4 and R5 are as defined in claim 1 or 2, with a ketocarboxylic acid of the general formula (VIII):

wherein R2 is as defined in claim 1 or 2; or (d) diazotizing an aryl-amine of the general formula (IX):

wherein R3, R4 and R5 are as defined in claim 1 or 2, and subsequently reacting, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, with a cyanoacetlcarbamic acid ester of the genral formula (X) wherein R1 is as defined in claim 1 or 2, and the resulting compound of the general formula (XI):

wherein R1, R3, R4 and R5 are as defined in claim 1 or 2, is cyclized, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary; or (e) reacting, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, an arylhydrazine of the general formula (XII):

wherein R3, R4 and R5 are each as defined in claim 1 or 2, with a ketocarboxylic acid derivative of the general formula (XIII):

wherein R2 is as defined in claim 1 or 2, and R represents H
or alkyl, and the resulting compound of the general formula (XIV):

wherein R2, R3, R4 and R5 are as defined in claim 1 or 2, and R is as defined above, is reacted, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, with an iso(thio)cyanate of the general formula (XV):

R1-N=C=Q1 (xv) wherein Q1 and R1 are as defined in claim 1 or 2, and the resulting compound of the general formula (XVI):

wherein Q1, R1, R2, R3, R4 and R5 are as defined in claim 1 or 2, and R is as defined above, is cyclized, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary; or (f) a 2-aryl-1,2,4-triazine-3,5-dione-6-carboxylic acid of the general formula (XIX) wherein R3, R4 and R5 are as defined in claim 1 or 2 is obtained, by diazotizing an aryl-amine of the general formula (IX):

wherein R3, R4 and R5 are as defined in claim 1 or 2, and subsequently reacted, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, with the malonyldiurethane of the formula (XVII):

CH2(CO-NH-COOC2H5)2 (XVII) and subsequently cyclized.

4. A herbicidal composition comprising at least one substituted 2-aryl-1,2,4-triazine-3,5-di(thi)one of the general formula (I) according to claim 1 or 2, and an extender, a surfactant or a mixture thereof.

5. A method for controlling unwanted plants, wherein a substituted 2-aryl-1,2,4-triazine-3,5-di(thi)one of the general formula (I) according to claim 1 or 2, or a composition according to claim 4, is allowed to act on the unwanted plants or their habitats.

6. Use of a substituted 2-aryl-1,2,4-triazine-3,5-di(thi)one of the general formula (I) according to claim 1 or 2, or a composition according to claim 4, for controlling unwanted plants.

7. A process for preparing herbicidal composition, wherein a substituted 2-aryl-1,2,4-triazine-3,5-di(thi)one of the general formula (I) according to claim 1 or 2, is mixed with an extender, a surfactant or a mixture thereof.