AU3441297A

AU3441297A - Substituted aromatic carbonyl compounds and their derivatives

Info

Publication number: AU3441297A
Application number: AU34412/97A
Authority: AU
Inventors: Roland Dr. Andree; Markus Dollinger; Mark Wilhelm Drewes; Wilhelm Haas; Andreas Lender; Karl-Heinz Linker; Otto Schallner
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1996-07-11
Filing date: 1997-07-01
Publication date: 1998-02-09
Also published as: DE19627901A1; JP2000514805A; BR9710238A; WO1998002422A1; IL127802A0; EP0912527A1; CA2260201A1

Description

ONLY FOR INFORMATION Codes used to identify the PCT member States on the flyleaves of the brochures in which international applications made under the PCT are published.

Albania Liechtenstein Armenia Sri Lanka Austria Liberia Australia Lesotho Azerbaidjan Lithuania Bosnia-Herzegovina Luxembourg Barbados Latvia Belgium Monaco Burkina Fasso Republic of Moldova Bulgaria Madagascar Benin Former Yugoslav Republic Brazil of Macedonia Belarus Mali Canada Mongolia Central African Republic Mauritania Congo Malawi Switzerland Mexico Ivory Coast Niger Cameroon Netherlands China Norway Cuba New Zealand Czech Republic Poland Germany Portugal Denmark Romania Estonia Russian Federation Spain Sudan Finland Sweden France Singapore Gabon Slovenia United Kingdom Slovakia Georgia Senegal Ghana Swaziland Guinea Chad Greece Togo Hungary Tajikistan Ireland Turkmenistan Israel Turkey Iceland Trinidad and Tobago Italy Ukraine Japan Uganda Kenya United States of America Kyrghyzstan Uzbekistan Democratic People's Vietnam Republic of Korea Yugoslavia Republic of Korea Zimbabwe Kazakhstan Saint Lucia

S--

Substituted aromatic carbonvl compounds and derivatives thereof

The invention relates to novel substituted aromatic carbonyl compounds and derivatives thereof, to processes for their preparation and to their use as herbicides.

Some substituted aromatic carbonyl compounds having heterocyclyl groups attached via nitrogen are already known (cf. DE-2 102 848, DE-2 119 260, DE-2 166 456, DE- 2 342 934). However, a herbicidal activity of these compounds has not been disclosed. This invention, accordingly, provides novel substituted aromatic carbonyl compounds and their derivatives of the general formula (I)

R1 Z (I)

in which

Q represents oxygen, sulphur or imino (NH),

R' represents hydrogen or halogen,

R2 represents the grouping below

-A'-A 2-A 3

in which A' represents a single bond, represents oxygen, sulphur, -SO2-, -CO- or the grouping -N-R 4 in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, alkoxy, aryl, alkylsulphonyl and arylsulphonyl,

A' furthermore represents a radical selected from the group consisting of alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted,

A2 represents a single bond, represents oxygen, sulphur, -CO- or the grouping -N-RS- in which R represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, aryl, alkoxy, alkylsulphonyl and arylsulphonyl,

A2 furthermore represents a radical selected from the group consisting of alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted, and

A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy(thio)phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino, alkinyloxycarbonyl, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl, cycloalkylalkoxycarbonyl, aryl, aryloxy, arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl, heterocyclyl, hetero- cyclylalkyl, heterocyclylalkoxy or heterocyclylalkoxycarbonyl, each of which may optionally be substituted,

R represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio and alkylamino, each of which may optionally be substituted, and

Z represents a monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclylamino and heterocyclylimino, each of which may optionally be substituted, except for the prior-art compounds ethyl 5-chloro-4-(1,3-dihydro- ,3-dioxo-2H-isoindol- 2-yl)-2-methoxybenzoate and methyl 5-chloro-4-(1,3-dihydro-,3-dioxo-2H-isoindol- 2-yl)-2-methoxybenzoate (both known from DE-2 102 848, DE-2 119 260 and DE- 2 166 456) and methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)- 3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 34 (1993), 1889-1892).

The novel substituted aromatic carbonyl compounds and their derivatives of the general formula are obtained when substituted aromatic nitriles of the general formula (II)

R1 z (II) CN 2 R

in which

R 1 R2 and Z are each as defined above

are reacted with water, hydrogen sulphide or ammonia, if appropriate in the presence of reaction auxiliaries, and the resulting substituted aromatic carboxylic acids or their derivatives of the general formula (Ia)

R1

(la) in which

Q, R' and Z are each as defined above

are, if appropriate, converted by customary methods into substituted aromatic carbonyl compounds or their derivatives in accordance with the above definition of the compounds of the formula

The novel substituted aromatic carbonyl compounds of the general formula have strong herbicidal activity.

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkinyl, are in each case straight-chain or branched, i.e. also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably represents fluorine, chlorine or bromine, and in particular represents fluorine or chlorine.

The invention preferably provides compounds of the formula (I) in which

Q represents oxygen, sulphur or imino (NH),

R' represents hydrogen, fluorine, chlorine or bromine,

R2 represents the grouping below

-A'-A 2-A 3

in which

A' represents a single bond, represents oxygen, sulphur, -CO- or the grouping -N-R 4 in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of C,-C 4-alkyl, C,-C 4-alkoxy, phenyl, C,-C 4-alkoxysulphonyl and phenylsulphonyl,

A' furthermore represents a radical selected from the group consisting of C,-C 6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine,

A2 represents a single bond, represents oxygen, sulphur, -CO- or the grouping -N-R 5 in which R' represents hydrogen, hydroxyl or a radical selected from the group consisting of C,-C 4-alkyl, Ci-C 4-alkoxy, phenyl, C,-C 4-alkylsulphonyl and phenylsulphonyl,

A2 furthermore represents a radical selected from the group consisting of C,-C 6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine,

A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl and dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by halogen, C,-C 4-alkoxy or C,-C 4-alkoximino,

A3 furthermore represents a radical selected from the group consisting of alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino and alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and being in each case optionally substituted by halogen,

A3 furthermore represents a radical selected from the group consisting of cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidene- amino, cycloalkyloxycarbonyl and 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 and being in each case optionally substituted by halogen, cyano, carboxyl, C,-C 4-alkyl and/or C1-C4-alkoxy-carbonyl,

A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, phenyl-C-C 4-alkyl, phenyl-C-C 4-alkoxy, phenyloxycarbonyl and phenyl-C 1 -C 4-alkoxycarbonyl, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C, -C4-alkyL furyl-C1 -C4-alkyl, thienyl- C,-C 4-alkyl, oxazolyl-C,-C 4-alkyl, isoxazol-C -C4-alkyl, thiazol-C-C 4-alkyl, pyridinyl-q,-C 4-alkyl, pyrimidinyl-C -C4-alkyl, pyrazolylmethoxy, furylmethoxy, each of which may optionally be substituted by nitro, cyano, carboxyl, halogen,

C,-C 4-alkyl, C,-C 4-halogenoalkyl, C-C 4-alkyloxy, C-C 4-halogenoalkyloxy and/or C-C 4-alkoxy-carbonyl, represents perhydropyranylmethoxy or pyridylmethoxy,

R represents hydrogen, hydroxyl, mercapto, amino, (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio and alkylamino having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by hydroxyl, cyano, halogen, C,-C 4-alkoxy or C-C 4-alkoxy-carbonyl, and

Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclylamino and 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 or sulphur atom and/or optionally up to three groupings selected from the group consisting of -CO-,

-SO- and/or SO,- and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, C,-C 6-alkyl (which for its part may optionally be substituted by halogen or C1-C4-alkoxy), C2-C6-alkenyl and C2-C 6-alkinyl (which for their part may each optionally be substituted by halogen), C,-C 6-alkoxy and C,-C 6-alkoxy-carbonyl (which for their part may each optionally be substituted by halogen or C,-C 4-alkoxy), C,-C6-alkenyloxy or

C2-C 6-alkinyloxy (which for their part may each optionally be substituted by halogen), C,-C 6-alkylthio, C,-C 6-alkenylthio and C,-C 6-alkinylthio (which for their part may each optionally be substituted by halogen), C,-C 6-alkylamino and di-(C1 -C4-alkyl)amino, C3-C 6-cycloalkyl and C3-C6-cycloalkyl-Cq-C 4-alkyl (which for their part may each optionally be substituted by halogen and/or C,-C 4-alkyl), phenyl, phienoxy, phenylthio, phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, halogen, C,-C 4-alkyl, C-C 4-halogenoalkyl, C1 -C4-alkyloxy, C,-C 4-halogenoalkyloxy and/or C-C 4-alkoxy-carbonyl),

where the prior-art compounds ethyl 5-chloro-4-( ,3-dihydro-1,3-dioxo-2H-isoindol- 2-yl)-2-methoxy-benzoate and methyl 5-chloro-4-(1,3-dihydro-1,3-dioxo-2H-isoindol- 2-yl)-2-methoxy-benzoate (both known from DE-2 102 848, DE-2 119 260 and DE- 2 166 456) and methyl 8-chloro-3-(2-chloro-5-methoxy-4-methoxycarbonyl-phenyl)- 3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 34 (1993), 1889-1892) are excluded by disclaimer.

The invention in particular provides compounds of the formula (I) in which

Q represents oxygen, sulphur or imino (NH),

R' represents hydrogen, fluorine or chlorine,

R2 represents the grouping below

-Al-A2-A3

in which

A' represents a single bond, represents oxygen, sulphur, -CO- or the grouping -N-R 4 in which R represents hydrogen, hydroxyl or a radical selected from the group consistiig of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl and ethylsulphonyl,

A' furthermore represents a radical selected from the group consisting of 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 and propine-1,3-diyl,

A2 represents a single bond, represents oxygen, sulphur, -SO2 -CO- or the grouping -N-RS- in which R' represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl and phenylsulphonyl,

A2 furthermore represents a radical selected from the group consisting of 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 and propine-1,3-diyl,

A' represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, represents a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, s- or t-butyl, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, s- or t- butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylarnino, n- or i-propylamino, s- or t-butylarino, direthylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-prop. 'arbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl and diisopropoxyphosphoryl, each of which may optionally be substituted by fluorine, chlorine, methoxy, ethoxy, methoximino or ethoximino,

A3 furthermore represents a radical selected from the group consisting of propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl and butinyloxycarbonyl, each of which may optionally be substituted by fluorine or chlorine,

A3 furthermore represents a radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo- propylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl and cyclohexylmethoxycarbonyl, each of whch may optionally be substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl,

A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (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, isoxazolmethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy and pyridylmethoxy, each of which may optionally be substituted by 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,

R3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i-propylamino, each of which may optionally be substituted by hydroxyl, cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, and

Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclylamino and heterocyclylimino having in eacih c; 2 to carbon atoms and 1 to 3 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to two groupings selected from the group consisting of -CO-, -SO- and/or and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, s- or t-butyl, (which for their part may optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propinyl and butinyl (which for their part may each optionally be substituted by fluorine or chlorine); methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, methoxycarbonyl and ethoxycarbonyl (which for their part may each optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propinyloxy and butinyloxy (which for their part may optionally be substituted by fluorine or chlorine); methylthio, ethylthio, n- or i-propylthio, n-, s- or t-butylthio, propenylthio, butenylthio, propinylthio and butinylthio (which for their part may each optionally be substituted by fluorine or chlorine); methylamino, ethylamino, n- or i-propylamino, s- or t-butylamino,

*-11

dimethylamino and diethylamino; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl (which for their part may each optionally be substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, phenylthio, phenylsuiphinyl, phenylsuiphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl),

where the prior-art compounds ethyl 5-chloro-4-(1,3-dihydro- 1,3 -dioxo-2H-isoindol- 2-yl)-2-methoxy-benzoate and methyl 5-chloro-4-(1I,3-dihydro- 1,3 -dioxo-2H-isoindol- 2-yl)-2-methoxy-benzoate (both known from DE-2 102 848, DE-2 119 260 and DE- 2 166 456) and methyl 8-chloro-3-(2-chloro- 5-mTcthoxy-4-miethoxycarbonyl-phenyl)- 3,4-dihydro-5-methoxy-quinazoline-6-carboxylate (known from Tetrahedron Lett. 34 (1993), 1889-1892) are excluded by disclaimer.

In the general formula Z in particular represents the heterocyclic groupings listed below

7 6 QRN N" 'N R N NQ N ,N \Q N R8 R6 Q

(Z2

I R7 Q2 N R6 N N N

N-S N=N

(Z5 (Z)

R6 Q N

N-N I R R7 AZ)

(Z) NZZ: N -N R I R 7_ Q (Z1 (Z,

R6 0 (Z1

QI 7 RQNI N Q2 Q"N Rt- N- RiN-Q' R6 6 Qi

(Z13 (Z14)

R7

6 R N- _QI N-N

(Z16 (Z17) (Zi

Q2 N R6 N- R6 R6 R1 R6 1 (Z19) (Z20) (Z2

R6 6 R N Q2

NZ N R*6 N N-N

(Z2 (Z23) (Z24)

N-N 2

25 (Z (Z2

R6 R7 N" Q N R7 N-Q' RQ N

(Z27 (Z

where in each case

Q' represents a grouping selected from the group consisting of -CHCI-, -CHBr-, -C(=CF 2 -C(=CHCl)-, -CQ=CHBr)-, -C(=CHOCHF 2 -C(=CHOCF 3 -C(=CHOCH2CF,)-,

Q' represents oxygen, sulphur or a grouping selected from the group consisting of -CH2 CHF-, -CF21 -CHCl-, -CHBr-, -CHOCHF2 -HCF 351 -CHOCH,CF3

R' 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, chlorodifluoromethylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl, and

R7 represents hydrogen, hydroxyl, amino, cyano, methyl, ethyl, n- or i-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy,

or where, if appropriate, two adjacent groups R 6 and R 6 or R 7 and R7 or R6 and R7 together represent alkanediyl or alkenediyl having in each case up to four carbon atoms and being in each case optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and optionally interrupted by oxygen, sulphur or a grouping selected from the group consisting of SO2 -N(CH 3 or at the beginning (or at the end) or within the hydrocarbon chain.

The abovementioned general or preferred radical definitions apply both to the end products of the formula and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other at will, i.e. including combinations between the given ranges of preferred compounds.

Examples of compounds of the formula according to the invention are listed in the groups below.

Groun I

CH3

Q, R' and R3 each have the meanings given in the list below:

Q R' R2 R3 Q R1 R2 R3

O H F OH 0 F F OH O F Cl OH 0 Cl F OH Cl Cl OH 0 F Br OH O H F OCH3 0 F F OCH 3 O F Cl OCH 3 0 Cl F OCH 3

O Cl Cl OCH3 0 F Br OCH3 O H F SCH3 0 F F SCH 3 F Cl SCH3 0 Cl F SCH 3 O Cl Cl SCH3 0 F Br SCH 3 S H F OH S F F OH S F Cl OH S Cl F OH S Cl Cl OH S F Br OH S H F OCH3 S F F OCH3 S F Cl OCH 3 S Cl F OCH3 S Cl Cl OCH 3 S F Br OCH 3 S H F SCH 3 S F F SCH 3 S F Cl SCH 3 S Cl F SCH 3

Q R' R2 'R3 Q R'

S cl Cl SCH3 S F Br SCH 3 NH H F NH2 NH F F NH2 NH F Cl NH2 NH Cl F NH2 NH CI Cl NH2 NH- F Br NH, NH H F SCH 3 NH F F SCH3 NH- F Cl SCH 3 NH Cl F SCH 3 NH Cl Cl SCH 3 NH F Br SCH 3 O H COOH OH 0 F COOH OH O F COOH OH 0 Cl COOH OH Cl COOH OH 0 F COOH OH H COOCH3 OCH3 0 F COOCH3 OCH3 O F COOCH3 OCH 3 0 Cl COOCH3 OCH3 O Cl COOCH 3 OCH3 0 F COOCH3 OCH 3 O H OH OH 0 F SH OH F OH OH 0 Cl SH OH O Cl OH OH 0 F NH2 OH H OH OCH3 0 F SH OCH 3 O F OH OCH3 0 Cl SH OCH3 NH CI NH2 NH2 NH F NH 2 NH2 NH H OH SCH 3 NH F SH SCH3

NH F OH SCH 3 NH Cl SH SCH 3 NH Cl OH SCH3 NH F NH2 SCH 3 O H CH 3 OCH 3 0 F OCH 3 OCH3 O F CH3 OCH 3 0 Cl OCH3 OCH 3 CI CH3 OCH 3 0 F SCH3 OCH 3

H (SCH 3 OCH3 0 F NHCH 3 OCH3

Q R' Q R1 R3

o F SCH3 OCH 3 0 CI OCH 5 OCH 3 o ci NHCH3 OCH 3 0 F SCAH OCH 3 o H SOCK3 OCH3 0 F OCHF2 00K 3 O F SOCH3 OCH 3 0 CI OCH 2CF3 OCH 3

O CI OCH 2CH2 CN OCH 3 0 F SCHCN OCH3 O F IOCH 3 0 F IOCH 3 o 0, OH 3

O F IOCH 3 0 F iOCH 3 SS, OH 3

O F OCH 3 0 F I00K 3 O0 OH3

COOCH 3 COOCH 3

O F 00K 3 0 F OCH 3 0 O 3

Q R1 !R3 Q R' R2 R3

o F OCH3 0 F OCH3 sCS H3

o ci OCH 3 0 F OCH3

0000H3 COOCH 3

o H NHSO 2CH3 OCH 3 0 F NHSO 2C2 H. OCH 3 o F NHSO 2CH3 OCH3 0 Ci NHSO 2C2H5 OCH 3 o ci NHSO 2 CH3 OCH3 0 F NHSO 2C2H5 OCH 3 NH H NHSO 2CH3 SCH 3 NH F NHS0 2C2H5 SCH3 NH F NHSO 2CH3 SCH 3 NH Cl NHS0 2 C,H5 SCH 3 NH Cl NHSO 2CH3 SCH3 NH F NHSO 2C2H5 SCH 3 O H N(S0 2 CH 3 2 OCH3 0 F NHSO 2C4Hq OCH 3 O F N(SO 2 CH3 2 0CH3 0 CI NHSO 2C4Hq OCH 3 o F NHSO 2 C3H7 OCH3 0 F NHSO 2C5 OCH3 NH H N(S0 2 CH 3 2 SCH3 NH F NHSO 2C3H7 SCH 3 NH F N(SO 2CH3 2 SCH 3 NH Cl NHS0 2C3 H7 SCH 3 NH Cl NHSO 2C4Hq SCH 3 NH F NHSO 2C5 SCH 3 o F IOCH 3 0 F OCH 3

N 0 CH3 CAH OH3

Group 2

NH2

0 NQ

R2 R3

Q, R2 and R3 each have, for example, the meanings given above in Group 1.

Group 3

CH3

14 r'

Q, R2 and R3 each have, for example, the meanings given above in Group 1.

Group 4

Q, R2 and R3 each have, for example, the meanings given above in Group 1.

Group

Q, R 2 and R3 each have, for example, the meanings given above in Group 1.

Group 6

CHF, n

Q, R2 and R3 each have, for example, the meanings given above in Group 1.

Group 7

O CHa N R1 H-N N

0 0 R2 R3

Q, R2 and R3 each have, for example, the meanings given above in Group 1.

Group 8

0 CHa N R1 N FCH N 0 k YQ

R2 R

Q, R2 and R 3 each have, for example, the meanings given above in Group 1.

Group 9

Q, R 2 and R 3 each have, for example, the meanings given above in Group 1.

GrOUD

CH F2

H 3 C) N

2 3

Q, R' and R' each have, for example, the meanings given above in Group 1.

Group 11

CF3

HS -N

2 3

R R

Q, R2 and R' each have, for example, the meanings given above in Group 1.

Group 12

CH3

-NR F2 CH \jr

2 3

Q, R1 R2 and R3 each have, for example, the meanings given above in Group 1.

Group 13

Q, R' and R' each have, for example, the meanings given above in Group 1.

Group 14

OH3

Q, R2 and R' each have, for example, the meanings given above in Group 1.

Groun

CH3

H2N "N .1

R2 R3

Q, R2 and R' each have, for example, the meanings given above in Group 1.

Using, for example, 2-(2-fluoro-4-cyano-5-methoxy-phenyl)-4-methyl-5-difl uoromethyl- 2,4-dihydro-3H- 1,2,4-tri azol-3 -one and water as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following equation:

HC O-CH3 H3C 0 O-CH3 NIN CN H2 0 N CN COOH FCH N FCH N F F

The formula (II) provides a general definition of the substituted aromatic nitriles to be used as starting materials in the process according to the invention for preparing compounds of the formula

In the formula R2 and Z 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 according to the invention, as being preferred or particularly preferred for R 2 and Z.

The starting materials of the formula (II) are known and/or can be prepared by known methods (cf. EP-370 332, EP-648 749, DE-4 238 125, DE-4 303 376, US-5 084 084, WO 95/29168).

The process according to the invention for preparing the novel compounds of the formula is preferably carried out in the presence of a reaction auxiliary. These include water and the customary organic diluents, oxidizing agents, such as, for example, hydrogen peroxide or sodium chlorite, and also amidosulphonic acid.

When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between 0°C and 150°C, preferably between 20 0 C and 120 0 C.

The process according to the invent'on is generally carried out under atmospheric pressure. However, it is also po. sbeS to carry out the process according to the invention under elevated or reduced pressure generally between 0.1 bar and 10 bar.

For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to employ one of the components in a relatively large excess. 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 several hours at the required temperature. 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 ki'lers and, especially, as weedkillers. By weeds in the broadest 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 genera: 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.

Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

M iocotyledonous 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, Agrostis, 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 hop fields, on lawns, sports fields and pasture-land. Furthermore, the compounds can also be used for the selective control of weeds in annual cultures.

The compounds of the formula according to the invention are suitable in particular for selectively controlling monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous 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 use 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 methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, 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 ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also 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 finely divided silica, alumina and silicates, suitable solid ca.-rirs for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also 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 emulsifiers, 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 and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Possible further additives are mineral and vegetable oils.

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

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 acetochior, acifluorfen (-sodiumn), aclonifen, alachior, alloxydim(-sodium), ametryne, amidochior, amnidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron (-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, Carbetamide, chiomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumnyluron, cvanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachior, di methametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfiuralin, ethametsulfuron(-methyl), ethofumnesate, ethoxyfen, etobenzanid, fenoxaprop-ethyl, flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flunAzXazin, flumipropyn, fluometuron, fluorochlori done, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomnesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachior, methabenzthiazuron, metobelizuron, metobromuron, metolachior, metosulam, metoxuron, metsulfuron(-methyl), metribuzin, molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norfiurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachior, propanil, propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.

Mirtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, 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 effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

Pren~aration Examples:

Example 1

COOH

At approximately 45'C, a mixture of 1.0 g (2.93 mmol) of l-(4-cyano-2-fluoro- 5-formyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-l (2H)-pyrimidine, 150 ml of water, 0.58 g (6 mmol) of amidosuiphonic acid and 0.54 g(6 mmol) of sodium chlorite is stirred for approximately 24 hours. The mixture is then shaken with ethyl acetate and the organic phase is separated off, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump vacuum.

This gives 0.90 g (82% of theory) of 1-(4,5-bis-carboxy-2-fluoro-phenyl)-3,6-dihydro- 2,6-dioxo-3-methy]-4-trifluoromethyl- 1(2H)-pyrimidine as an amorphous residue.

Example 2

T 'COOCH 3 COOCH 3

A mixture of 0.80 g (2.24 mmol) of 1-(4,5-bis-carboxy-2-fluoro-phenyl)-3,6-dihydro- 2,6-dioxo-3-methyl-4-trifluoromethyl- 1(2H)-pyrimidine, 0.70 g (5 mmol) of potassium carbonate, 0.64 g (5 mmol) of dimethyl sulphate and 20 ml of acetone is heated at the boil under reflux for approximately 20 hours. The mixture is then concentrated under water pump vacuum and the residue is taken up in 50 ml of water, acidified with 2N hydrochloric acid, then covered with a layer of 4 ml of diethyl ether and slowly diluted with petroleum ether with stirring. The resulting crystalline product is isolated by filtration with suction.

This gives 0.38 g (42% of theory) of 1-(4,5-bis-methoxycarbonyl-2-fluoro-phenyl)- 3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine of melting point 141 0 C.

Example 3

CH3 FaC N O F

O NH

NH SCH 3 SO 2

C2H

4.5 g (1.0 mmol) of l-(3-ethylsulphonylamino-2-fluoro-4-thiocarbamoyl-phenyl)- 3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-l(2H)-pyrimidine are initially charged in 50 ml of methylene chloride and admixed dropwise with 1.5 g (1.2 mmol) of dimethyl sulphate. The reaction mixture is heated under reflux for approximately 3 hours and stirred at room temperature (approximately 20 0 C) for a further 15 hours. After addition of a further 0.5 ml of dimethyl sulphate, the mixture is heated under reflux for a further 5 hours and subsequently concentrated under water pump vacuum. The residue is stirred with diethyl ether and the resulting crystalline product is isolated by filtration with suction.

This gives 4.4 g (94% of theory) of 1-(3-ethylsulphonylamino-2-fluoro-4-(S-methyl- thiocarbonimidoyl-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- (2H)- pyrimidine of melting point 212 0 C.

Similarly to Preparation Examples 1 to 3, and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the formula listed in Table I below.

R Z. (I

Table 1: Examples of compounds of the formula (I)

Ex. Q R' R2 R3 Z Melting No. Ipoint (oC)

SCH 3 NH2 1H-NMR 4 NH F NHSO 2C2H5 F3 C N, O (DMSO-D,,

N 6.45 ppm

0

0 H OH OH CH3 157 N N

6 O H OH OCH3 CH3 183 H3C-N N O

O N

Ex. Q R R2 R3 Melting No. point

7 0 H 011 0C 2 H5 CH3 165

8 0 H H C2H5 CH3 98 ~N H3C-N sI 0

F3 C NO

0

NH F NHSO 2C2H5 SCH 3 OH3 12 F3C N 0

0

11 NH4 F NHSO 2 C 2 H 5 SCH3 CF3 178 H3 CN N

NI-S 0 2CH 3 NH2 FOC Ny0

Starting materials of the fomula (II):

Example (1-1)

Step 1

With stirring, 0.17 g (1.2 mmol) of pivaloyl chloride are added to a mixture of 0.50 g (1.2 mmol) of 1-(4-cyano-2-fluoro-5-trifluoroacetylamino-phenyl)-3,6-dihydro- 2,6-dioxo-3-methyl-4-trifluoromethyl-l(2H)-pyrimidine, 1 ml of triethylamine and ml of acetonitrile, and the reaction mixture is stirred at 20 0 C for 18 hours and at 60 0 C for a further 15 hours. The mixture is then concentrated under water pump vacuum, the residue is shaken with IN hydrochloric acid/ethyl acetate and the organic phase is separated off, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum and the residue is worked-up by column chromatography (silica gel, chloroform/ethyl acetate, Vol.: 1:1).

In addition to unreacted 1-(4-cyano-2-fluoro-5-trifluoroacetylamino-phenyl)- 3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- (2H)-pyrimidine (first fraction: 0.30 0.2 g (50% of theory) of 1-(4-cyano-2-fluoro-5-amino-phenyl)-3,6-dihydro-2,6- dioxo-3-methyl-4-trifluoromethyl-l(2H)-pyrimidine are obtained as second fraction.

Melting point: 195°C.

Step 2

CH3 F C N

H

0r CN

COOCH 3

A mixture of 1.8 g (21 mmol) of methyl acrylate, 1.6 g (15.5 mmol) of t-butyl nitrite, 1.6 g (12 mmol) of copper(II) chloride and 50 ml of acetonitrile is cooled to approximately 0°C, and a solution of 3.3 g (10 mmol) of 1-(5-amino-4-cyano-2-fluoro- phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H)-pyrimidine in 20 ml of acetonitrile is added dropwise at this temperature. The reaction mixture is allowed to warm to room temperature and stirred at this temperature for 18 hours. The mixture is subsequently, after addition of 20 ml of IN hydrochloric acid, extracted with ethyl acetate and the organic phase is dried with sodium sulphate and filtered. The filtrate is concentrated and the residue is worked-up by column chromatography. This gives 2.8 g (65% of theory) of l-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)- phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H)-pyrimidine of melting point 46 0 C.

0.22 g of sodium hydride (60% strength) are added with stirring to a mixture of 2.0 g (4.6 mmol) of 1-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl]- 3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine and 30 ml of N,N-dimethylformamide which had been cooled to 0°C, and the reaction mixture is stirred initially at 0°C for 15 minutes, then at 20°C for approximately 60 minutes and finally at 60 0 C for 6 hours. The mixture is then concentrated under water pump vacuum, the residue is stirred with diisopropyl ether and the resulting crystalline product is isolated by filtration with suction.

This gives 1.1 g (60% of theory) of 1-[4-cyano-2-fluoro-5-(2-methoxycarbonyl- ethenyl)-phenyfl-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethylk I(2H)-pyrimidine of melting point 154'C.

Step 3

OH3 F3 0 NYO F

H1 N~

CN

H 0

Ozone is introduced for 45 minutes into a mixture of 8.7 g (22 mmol) of 1-[4-cyano- 2-fluoro-5-(2-methoxycarbonyl-ethenyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methy- 4-trifluoromethiyl-1(211)-pyrimidine and 600 ml of methylene chloride which had been cooled to -70'C. The cooling bath is then removed, and the mixture is admixed with 10 ml of dimethyl suiphide. After the mixture has warmed to room temperature (about the phases are separated and the organic phase is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diethyl ether and the crystalline product is isolated ny filtration with suction.

This gives 7.4 g (99% of theory) of l-(4-cyano-2-fluoro-5-formyl-phenyl)-3,6-dihydro- 2,6-dioxo-3-methyl-4-trifluoromethyl-1I(2H)-pyrimidine of melting point 177C.

Use Examples:

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone Emulsifier: I 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 preparation of active compound is sprayed onto the soil 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 amounts of active compound desired in each case are applied in 1000 1 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, at an application rate of 60 g/ha, for example the compound of Preparation Example 2 exhibits very potent activity against weeds such as Avena fatua Setaria Abutilon Amaranthus Galium (95% and Sinapis (100%).

Example B

Post-emergence test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Test plants which have a height of 5-15 cm 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 amounts of active compound desired in each case are applied in 1000 1 of water/ha.

The figures denote:

0% no effect (like untreated control) 100% total destruction

In this test, at an application rate of 60 g/ha, for example the compound of Preparation Example 2 exhibits very potent activity against weeds such as Abutilon (100%), Amaranthus Galium and Sinapis (100%).

Claims

Patent claims

1. Aromatic carbonyl compounds and their derivatives of the general formula (I)

R1

Z. i (I)

in which

Q represents oxygen, sulphur or imino (NH),

R' represents hydrogen or halogen,

R 2 repres.nts the grouping below

-A'-A2-A 3

in which A' represents a single bond, represents oxygen, sulphur, -SO-, -SO2 -CO- or the grouping -N-R 4 in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, alkoxy, aryl, alkylsulphonyl and arylsulphonyl,

A' furthermore represents a radical selected from the group consisting of alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted,

A2 represents a single bond, represents oxygen, sulphur, -SO-,

-SO 2 -CO- or the grouping -N-R 5 in which RS represents hydrogen, hydroxyl or a radical selected from the group consisting of alkyl, aryl, alkoxy, alkylsulphonyl and arylsulphonyl,

A2 furthermore represents a radical selected from the group consisting of alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl and arenediyl, each of which may optionally be substituted, and

A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy(thio)phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino, alkinyloxycarbonyl, cyclalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl, cycloalkylalkoxycarbonyl, aryl, aryloxy, arylalkyl, arylalkoxy, ary!voxycarbonyl, arylalkoxycarbonyl, heterocyclyl, heterocyclylalkyl, heterocyclylalkoxy or heterocyclylalkoxycarbonyl, each of which may optionally be substituted,

R3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio and alkylamino, each of which may optionally be substituted, and

Z represents a monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclyl amino and heterocyclylimino, each of which may optionally be substituted, except for ethyl 5-chloro-4-(1 ,3-dihydro- I,3-dioxo-2H-isoindol-2-y l)-2-methuxy- benzoate, methyl 5-chloro-4-(1I,3-dihydro- 1,3-dioxo-2H-isoindol-2-yl)-2- methoxybenzoate, methyl 8-chloro-3-(2-ch loro-5-methoxy-4-methoxycarbonyl- phenyl)-3,4-di hydro-5-methoxy-qu inazoli ne-6-carboxyl ate.

2. Aromatic carbonyl compounds of the general formula according to Claim 1, characterized in that

Q represents oxygen, sulphur or imino (NH),

R' represents hydrogen, fluorine, chlorine or bromine,

R2 represents the grouping below

3 -A '-A7-A

in which

A' represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-R4 in which R' represents hydrogen, hydroxyl or a radical selected from the group consisting of C,-C 4-alkyl, C,-C 4-alkoxy, phenyl, C,-C 4 -alkoxysulphonyl and phenyl sul phony],

A' furthermore represents a radical selected from the group consisting of C,-C 6 -alkanediyl, C2 -C6 -alkenediy], C2 -C6 -alkinediyl, C3-C 6-CYCloalkanediyl, C3-C6 -CYCloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine,

A2 represents a single bond, represents oxygen, sulphur, -SO 2 -CO- or the grouping -N-R 5 in which R5 represents hydrogen, hi droxyl or a radical selected from the group consisting of C,-C 4-alkyl, C,-C 4-alkoxy, phenyl, Ci-C 4-alkylsulphonyl and phenylsulphonyl,

A2 furthermore represents a radical selected from the group consisting of Cl-C 6-alkanediyl, C2-C6-alkenediyl, Cz-C 6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl and phenylene, each of which may optionally be substituted by fluorine or chlorine,

A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl, ilkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl and dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by halogen, C,-C 4-alkoxy or C,-C 4-alkoximino,

A3 furthermore represents a radical selected from the group consisting of alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino and alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and being in each case optionally substituted by halogen,

A3 furthermore represents a radical selected from the group consisting of cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl and 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 and being in each case optionally substituted by halogen, cyano, carboxyl, C,-C 4-alkyl and/or Ci-C 4-alkoxycarbonyl,

A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, phenyl-Cl-C 4 -alkyl, phenyl-C1 -C 4-alkoxy, phenyloxycarbonyl and phenyl-C-C 4-alkoxycarbonyl, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl- Cl-C 4-alkyl, furyl-C1 -C 4-alkyl, thienyl-C1 -C4-alkyl, oxazolyl-C,-C 4-alkyl, isoxazol-C1 -C 4-alkyl, thiazol-C1 -C 4-alkyl, pyridinyl-C,-C 4-alky), pyrimidinyl-C-C 4-alkyl, pyrazolylmethoxy, furylmethoxy, each of which may optionally be substituted by nitro, cyano, carboxyl, halogen, CI-C 4-alkyl, C-C 4-halogenoalkyl, C-C 4-alkyloxy, C,-C 4-halogenoalkyloxy and/or C -C4-alkoxy-carbonyl, represents perhydropyranylmethoxy or pyridylmethoxy,

R3 represents hydrogen, hydroxyl, mercapto, amino, (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of alkyl, alkoxy, alkylthio and alkylamino having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by hydroxyl, cyano, halogen, C1-C4-alkoxy or C1-C4-alkoxy- carbonyl, and

Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclylamino and heterocyclylimino having in each case 2 to 6 carbon atoms and I to 4 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulphur atom and/or optionally up to three groupings selected from the group consisting of -SO- and/or SO2- and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, C1-C6-alkyl (which for its part may optionally be substituted by halogen or C,-C 4 alkoxy), C2-C,6-alkenyl and C2-C6-alkinyl (which for their part may each optionally be substituted by halogen), C-C 6-alkoxy and C,-C 6-alkoxy- carbony] (which for their part may each optionally be substituted by halogen or C1-C4-alkoxy), C2 C6 -alkenyloxy or C2 -C6 -alkinyloxy (which for their part may each optionally be substituted by halogren), Cl-C 6 -alkylthio, C2 -C6-alkenylthio and C2 -C6-alkinylthio (which for their part may each optionally be substituted by halogen), C1 -C6-alkylamino and di-(CI-C 4 alkyl)amino, C 3 -C6 -cycloalkyl and C3-C6 -cycloalkyl-C1 -C4-alkyl (which for their part may each optionally be substituted by halogen and/or CI-C 4 alkyl), phenyl, phenoxy, phenylthio, phenylsuiphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, halogen, C1 -C4-alkyl, C1 -C4-halogenoalkyl, Cl-C 4-alkyloxy, C1 -C4 -halogenoalkyloxy and/or C1-C4 -alkoxy-carbonyl), except for ethyl 5-chloro-4-(1I,3-dihydro- 1,3-di oxo-2H-isoi ndol-2-yl)-2-methoxy- benzoate, methyl 5-chloro-4-(1I,3-dihydro-1I,3-dioxo-2H-isoindol-2-yi)-2- methoxy-benzoate, methyl 8-chloro-3--(2-chloro-5-methoxy-4-methoxycarbony 1- phenyl)-3,4-dihydro-5-methoxy-quinazoli ne-6-carboxyl ate.

3. Aromatic carbonyl compounds of the general formula according to Claim 1, characterized in that

Q represents oxygen, sulphur or imino (NH),

R' represents hydrogen, fluorine or chlorine,

R2 represents the grouping below

-Al-A 2 -A3

in which

A' represents a single bond, represents oxygen, sulphur, -SO-, -SO2-, -CO- or the grouping -N-R 4 in which R4 represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl and ethylsulphonyl,

A' furthermore represents a radical selected from the group consisting of 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 and propine-1,3-diyl,

A2 represents a single bond, represents oxygen, sulphur, -SO-, -CO- or the grouping -N-R5 in which R5 represents hydrogen, hydroxyl or a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or 1-propylsulphonyl and phenylsulphonyl,

A2 furthermore represents a radical selected from the group consisting of 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 and propine-1,3-diyl,

A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, represents a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, s- or t-butyl, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, s- or t- pentyloxy, methylthio, ethylthio, n- or i-propylthio, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl and diisopropoxyphosphoryl, each of which may optionally be substituted by fluorine, chlorine, methoxy, ethoxy, methoximino or ethoximino,

A3 furthermore represents a radical selected from the group consisting of propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl and butinyloxycarbonyl, each of which may optionally be substituted by fluorine or chlorine,

A3 furthermore represents a radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cycIobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo-propylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopenty lideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl and cyclohexylmethoxycarbonyl, each of which may optionally be substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl,

A3 furthermore represents a radical selected from the group consisting of phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (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, isoxazolmethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy and pyridylmethoxy, each of which may optionally be substituted by 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,

R 3 represents hydrogen, hydroxyl, mercapto, amino (in which case Q does not represent sulphur) or represents a radical selected from the group consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i- propylamino, each of which may optionally be substituted by hydroxyl, cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxy- carbonyl, and

Z represents an in each case monocyclic or bicyclic, saturated or unsaturated radical selected from the group consisting of heterocyclyl (exception: piperazinyl), heterocyclylamino and 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 or sulphur atom and/or optionally up to two groupings selected from the group consisting of -SO- and/or SO 2 and which is optionally substituted by one or more groupings selected from the group consisting of nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, s- or t-butyl, (which for their part may optionally be substituted hy fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propinyl and butinyl (which for their part may each optionally be substituted by fluorine or chlorine); methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, methoxycarbonyl and ethoxycarbonyl

(which for their part may each optionally be substituted by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propinyloxy and butinyloxy (which for their part may optionally be substituted by fluorine or chlorine); methylthio, ethylthio, n- or i-propylthio, s- or t- butylthio, propenylthio, butenylthio, propinylthio and butinylthio (which for their part may each optionally be substituted by fluorine or chlorine); methylamino, ethylamino, n- or i-propylamino, s- or t-butylamino, dimethylamino and diethylamino; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl (which for their part may each optionally be substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, pheny]thio, phenylsulphinyl, phenylsulphonyl and phenylamino (which for their part may each optionally be substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy. difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl),

except forethyl 5-chloro-4-(1 ,3-dihydro- 1,3-dioxo-2H-isoindol-2-yl)-2-methoxy- benzoate, methyl 5-chloro-4-(1,3-dihydro- 1,3-dioxo-2H-isoindol-2-yl)-2- methoxy-benzoate, methyl 8-chloro-3 .(2-chloro-5-methoxy-4-methoxycarbonyl- phenyl)-3,4-dihydro-5-methoxy-quinazoline-6-carboxylate.

4. Process for preparing aromatic carbonyl compounds of the general formula (I)

R z (I)

R3 RR2 R

in which

R2 R Q and Z are each as defined in Claim 1, characterized in that aromatic nitriles of the formula (II)

R1

I (II) NCN 2 R

in which

R 2 and Z are each as defined above

are reacted with water, hydrogen sulphide or ammonia and the resulting substituted aromatic carboxylic acids or their derivatives of the general formula (Ia)

in which

Q, R 2 and Z are each as defined above

are converted by customary methods into substituted aromatic carbonyl compounds or their derivatives in accordance with the above definition of the compounds of the formula

Herbicidal compositions, characterized in that they contain at least one aromatic carbonyl compound of the formula according to Claim 1.

6. Method for controlling undesirable plants, characterized in that aromatic carbonyl compounds of the formula according to Claim I are allowed to act on undesirable plants and/or their habitat.

7. Use of aromatic carbonyl compounds of the formula according to Claim I for controlling undesirable plants.

8. Process for preparing herbicidal compositions, characterized in that aromatic carbonyl compounds of the formula according to Claim 1 are mixed with extenders and/or surfactants.