CA2272657A1 - Phenyl-uracil derivatives with herbicide effect - Google Patents
Phenyl-uracil derivatives with herbicide effect Download PDFInfo
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- CA2272657A1 CA2272657A1 CA002272657A CA2272657A CA2272657A1 CA 2272657 A1 CA2272657 A1 CA 2272657A1 CA 002272657 A CA002272657 A CA 002272657A CA 2272657 A CA2272657 A CA 2272657A CA 2272657 A1 CA2272657 A1 CA 2272657A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Plural Heterocyclic Compounds (AREA)
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Abstract
The invention relates to new phenyl-uracil derivatives of formula (I), in which R1, R2, R3, R4, R5 and n have the meanings cited in the description. It further relates to multiple methods for the production of said derivatives and their use as herbicides.
Description
Le A 32 055-Foreign countries WA/Dii/klu-W6 (Ib) p" ~ _ Phenyl-uracil derivatives The present invention relates to novel phenyl-uracil derivatives, to a plurality of processes for their preparation and to their use as herbicides.
Certain cyano-phenyl-uracils having insecticidal and acaricidal properties are already known (cf. EP-A 0 438 209, JP-A OS-025 142 and Chem. Abstr. 119, 117 269).
However, an application of these substances for controlling weeds has hitherto not been described.
This invention, accordingly, provides novel phenyl-uracil derivatives of the formula R' N / Ra (I), O
(RS)n in which R' represents hydrogen, amino or represents optionally cyano- or halogen-substituted alkyl, R2 represents formyl, hydroximinomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or represents optionally cyano- or halogen-substituted alkyl R3 represents hydrogen, halogen or represents optionally cyano- or halogen-substituted alkyl, R' represents cyano or thiocarbamoyl, RS represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, halogen, or represents one of the radicals -R6, -Q-R6, -NH-R6, -NH-O-R6, -NH-S02-R6, -CQ'-R6, -CQ'-QZ-R6, -CQ'-NH-R6, -Q2-CQ'-R6, -NH-CQ'-R6, -Q''-CQ'-Q2-R6, -NH-CQ'-Q'-R6 or -Q2-CQ'-NH-R6 in which Le A 32 055-Foreign countries Q represents O, S, SO or S02, Q ~ and Q2 independently of one another each represent oxygen or sulphur and R6 represents optionally cyano-, halogen-, alkoxy-, alkylthio-, alkylcarbonyl-, alkoxycarbonyl- or alkylaminocarbonyl-substituted alkyl, represents in each case optionally cyano-, carboxyl-, halogen-, alkylcarbonyl-, alkoxycarbonyl- or alkylamino-carbonyl-substituted alkenyl or alkinyl, represents in each case optionally cyano-, carboxyl-, halogen-, alkylcarbonyl- or alkoxycarbonyl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio-, halogenoalkylthio-, alkylsulphinyl-, alkylsulphonyl-, alkylamino- and/or dialkylamino substituted aryl or arylalkyl or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio-, halogenoalkylthio-, alkylsulphinyl-, alkylsulphonyl-, alkylamino- and/or dialkylamino substituted heterocyclyl or heterocyclylalkyl, and n represents the numbers 0, 1, 2 or 3.
Furthermore, it has been found that phenyl-uracil derivatives of the formula (I) are obtained when a) aminoalkenoic esters of the formula (II), R2 ~ OR
in which Le A 32 O55-Foreign countries R2 and R3 are each as defined above and R represents alkyl, aryl or arylalkyl, are reacted with aryl isocyanates of the formula O=C=N / R4 (III), (R5)n in which R4, RS and n are each as defined above, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or b) aminoalkenoic esters of the formula R2 \ OR (ii), Rs in which R, R2 and R3 are each as defined above, are reacted with arylurethanes of the formula H
i R'O ~ N / R4 (IV), O \
(RS)n Le A 32 055-Foreign countries in which R4, RS and n are each as defined above and R' represents alkyl, aryl or arylalkyl, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or c) phenyl-uracil derivatives of the formula H
i R2 N ~ O
N R4 (~a), O
(RS)n in which R2, R3, R4, RS and n are each as defined above, are either a) reacted with 1-amino-oxy-2,4-dinitrobenzene of the formula 02N / \ O-NHZ (V), if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or Le A 32 055-Foreign countries (3) are reacted with sulphates of the formula R80\
'S02 (VI) S in which R8 represents alkyl, or with halogen compounds of the formula R9-Hal (VII), in which R9 represents alkyl, halogenoalkyl or cyanoalkyl and Hal represents chlorine, bromine or iodine, in each case if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or d) phenyl-uracil derivatives of the formula R' i R2 N ~ O
N / CN (Ib)~
Ra O
(RS)n in which Le A 32 055-Foreign countries R', R2, R3, RS and n are each as defined above, are reacted with hydrogen sulphide in the presence of a diluent.
Finally, it has been found that the phenyl-uracil derivatives of the formula (I) have very good herbicidal properties.
Surprisingly, the phenyl-uracil derivatives of the formula (I) according to the invention have considerably better herbicidal activity than the constitutionally most similar prior-art substances of the same direction of action.
The formula (1) provides a general definition of the phenyl-uracil derivatives according to the invention.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched, even in combination with heteroatoms, such as in alkoxy or alkylthio.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably represents fluorine, chlorine or bromine and in particular represents fluorine or chlorine.
Preference is given to phenyl-uracil derivatives of the formula (I) in which R' represents hydrogen, amino or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R2 represents formyl, hydroximinomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R3 represents hydrogen, fluorine, chlorine, bromine or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R4 represents cyano or thiocarbamoyl, Le A 32 055-Foreign countries RS represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine or represents one of the radicals -R6, -Q-R6, -NH-R6, -NH-O-R6, -NH-S02-R6, -CQ'-R6, -CQ'-Q2-R6, -CQ'-NH-R6, -Q2-CQ'-R6, -NH-CQ'-R6, -Q2-CQ'-Q2-R6, -NH-CQI~Qz-R6 or -Q2-CQ'-NH-R6 in which Q represents O, S, SO or S02, Q' and Q2 independently of one another each represent oxygen or sulphur and R6 represents optionally cyano-, halogen-, C,-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkyl-carbonyl-, C~-C4-alkoxycarbonyl- or C,-C4-alkylaminocarbonyl-substituted alkyl having 1 to 6 carbon atoms, represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkylcarbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-alkylamino- or dimethylamino-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C 1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C 1-C4-alkylthio-, C 1 _C4-halogenoalkylthio-, C1-C4-alkylsulphinyl, C1-Cq-alkylsulphonyl-, C1-C4-alkylamino- and/or dimethylamino-substituted heterocyclyl or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and/or 1 or 2 oxygen atoms and/or one sulphur Le A 32 055-Foreign countries -g_ atom in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, and n represents the numbers 0, 1, 2 or 3.
Particular preference is given to phenyl-uracil derivatives of the formula (I) in which R1 represents hydrogen, amino, methyl or ethyl, R2 represents formyl, hydroximinomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or represents optionally fluorine- or chlorine-substituted methyl or ethyl, R3 represents hydrogen, chlorine or optionally fluorine- or chlorine-substituted methyl or ethyl, R4 represents cyano or thiocarbamoyl, RS represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine, or represents one of the radicals R6, -Q-R6, -NH-R6, -NH-O-R6, -NH-S OZ-R6, -CQ ~ -R6, -C Q ~ -Q2-R6, -CQ ~ -NH-R6, -Q2-CQ ~ -R6, -NH-CQ~-R6, -Q2-CQ~-Qz-R6, -NH-CQ~-Q2-R6 or -Q2-CQ~-NH-R6, in which Q represents O, S, SO or S02, Q1 and Q2 independently of one another represent oxygen or sulphur and R6 represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, methylthio-, ethylthio-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylaminocarbonyl- or ethylamino-carbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, or represents in each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylaminocarbonyl- or ethylaminocarbonyl-substituted propenyl, butenyl, propinyl or butinyl, Le A 32 055-Forei~~n countries or represents in each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, difluoromethyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, methylamino-, ethylamino-and/or dimethylamino-substituted phenyl, benzyl or phenylethyl, or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, trichloromethyl-, difluoromethyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, chlorodifluoromethylthio-, fluorodichloromethylthio-, methyl-sulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, methylamino-, ethylamino-, n- or i-propylamino- and/or dimethyl-amino-substituted heterocyclyl or heterocyclylalkyl from the series consisting of oxiranyl, oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl and also pyrimidinylmethyl, and n represents the numbers 1 or 2.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other as desired, i.e. including combinations between the given preferred ranges.
Le A 32 055-Foreign countries Using, for example, methyl 3-amino-crotonate and 3-cyano-5-fluoro-4-trifluoro-methyl-phenyl isocyanate as starting materials, the course of the reaction in process (a) according to the invention can be illustrated by the following equation:
H
i NH2 O / CN HaC N ~O
+ O=C=N
H3C ~ OCH3 \ ~ ~ H ~ N / CN
O \
F CFs F
Using methyl 3-amino-crotonate and methyl N-(3-cyano-S-fluoro-4-trifluoromethyl-phenyl)-carbamate as starting materials, the course of the process (b) according to the invention can be illustrated by the following equation.
H
H
NHz O + H3C0\ /N / CN HsC N ' / O
H3C ~ OCH3 O \ ~ -2CH30H H ~ N / CN
F O \
F
Using 1-(5-cyano-2,4-dichlorophenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1(2H)-pyrimidine as starting material and 1-aminooxy-2,4-dinitro-benzene as reac-tion component, the course of the reaction of the process (c, variant a) according to the invention can be illustrated by the following equation.
02N ~ ~ ONH2 NH2 F3C N ~ O
N02 F3C N ' / O
H N / CN
H N / CN
O
CI \ CI p CI CI
Using 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H)-pyrimidine as starting material and dimethyl sulphate as reaction component, Le A 32 055-Foreign countries the course of the process (c, variant B) according to the invention can be illustrated by the following equation.
H
i CH30 CH
F3C N ' / O X502 I
I CH O/ FaC N \ / O
H N / CN --t '~( I H N / CN
O I
CI \ CI O
CI \ CI
Using 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H)-pyrimidine as starting material and hydrogen sulphide as reaction component, the course of the process (d) according to the invention can be illustrated by the following equation.
FaC N O I
F3C N ~ O
I ~ CN H2S I II
H / -t H N / C-NH2 I
O CI \ CI O CI \ I CI
The formula (In provides a general definition of the aminoalkenoic esters required as starting materials for carrying out the process (a) and (b) according to the invention.
In the formula (In, RZ and R3 each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (1) according to the invention, as being preferred or as being particularly preferred for RZ and R3. R preferably represents alkyl having 1 to 4 carbon atoms, phenyl or benzyl. Particularly preferably, R represents methyl, ethyl or phenyl.
The starting materials of the formula (II) are known or can be prepared by known processes (cf. J. Heterocycl. Chem. 9 ( 1972), 513-522).
The formula (III) provides a general definition of the aryl isocyanates required as reaction components for carrying out the process (a) according to the invention. In the formula (III), R4, RS and n each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the Le A 32 055-Foreign countries compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R4, RS and n.
The starting materials of the formula (III) are known or can be prepared by known processes (cf. Tetrahedron Lett. 1967, 961-962; EP-A 0 063 905, EP-A 0 093 610, EP-A 0 093 620, EP-A 0 397 052 and EP-A 0 572 782).
Thus, aryl isocyanates of the formula (111) can be prepared by reacting anilines of the formula in which (VIII).
(RS)n R4, RS and n are each as defined above, with phosgene in the presence of a diluent, such as, for example, chlorobenzene, at temperatures between -20°C and +150°C.
The formula (IV) provides a general definition of the arylurethanes required as reaction components for carrying out the process (b) according to the invention. In the formula (IV), R4, RS and n each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (n according to the invention, as being preferred or as being particularly preferred for R4, RS and n; R' preferably represents CI-C4-alkyl, phenyl or benzyl, and in particular represents methyl, ethyl or phenyl.
The arylurethanes of the formula (IV) are known or can be prepared by known processes (cf. EP-A 0 063 905).
Thus, arylurethanes of the formula (IV) are obtained by reacting anilines of the formula Le A 32 OSS-Foreign countries H2N / R4 (VIII).
(R5)n in which R4, RS and n are each as defined above with chlorocarbonyl compounds of the formula R70-CO-Cl (IX), in which R' is as defined above, if appropriate in the presence of an acid acceptor, such as, for example, pyridine, and if appropriate in the presence of a diluent, such as, for example, methylene chloride, at temperatures between -20°C and +100°C.
The phenyl-uracil derivatives of the formula (Ia) required as starting materials for carrying out the process (c) according to the invention are compounds according to the invention which can be prepared by the processes (a) or (b) according to the invention.
The 1-aminooxy-2,4-dinitro-benzene of the formula (V) required as reaction component for carrying out the process (c, variant a) according to the invention is known (cf. J. Heterocycl. Chem. 4 ( 1967), 413-414).
The formula (Vn provides a general definition of the sulphates required as reaction components for carrying out the process (c, variant (3) according to the invention. In this formula, Rg preferably represents alkyl having 1 to 4 carbon atoms, and particularly preferably represents methyl or ethyl.
The formula (VII) provides a general definition of the halogen compounds which can furthermore be employed as reaction components when carrying out the process (c, Le A 32 055-Foreign countries variant 13) according to the invention. In this formula, R9 preferably represents alkyl, cyanoalkyl, fluoroalkyl or chloroalkyl having in each case 1 to 4 carbon atoms. Hal preferably represents bromine or iodine.
R9 particularly preferably represents methyl or ethyl.
Hal also particularly preferably represents bromine or iodine.
The phenyl-uracil derivatives of the formula (Ib) required as starting materials for carrying out the process (d) according to the invention are compounds according to the invention which can be prepared by the processes (a), (b) or (c) according to the invention.
Suitable acid binders for carrying out the processes (a) to (c) according to the invention are all customary inorganic and organic acid acceptors. Preference is given to using 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, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide, or potassium methoxide, ethoxide, n- or i-propoxide, 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-dimethyl-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-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo-[2,2,2]-octane (DABCO), 1,S-diazabicyclo-[4,3,0]-non-5-ene (DBN), or 1,8 diazabicyclo-[5,4,0]-undec-7-ene (DBU).
Suitable diluents for carrying out the processes (a) and (b) according to the invention are all customary inert organic solvents preference is given to using 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 Le A 32 055-Foreign countries 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; nitriles, 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 and also diethylene glycol monoethyl ether.
When carrying out the processes (a) and (b) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out at temperatures between 0°C and 200°C, preferably between 10°C and 150°C.
The processes (a) to (c) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated pressure or, if no highly volatile components are employed, under reduced pressure.
Suitable diluents for carrying out the process (c) according to the invention are all inert organic solvents which are customary for such reactions. In the reaction according to variant (a), preference is given to using aprotic polar solvents, such as, for example, N,N-dimethylformamide and N-methyl-pyrrolidone.
In the reaction according to variant (13), preference is likewise given to using aprotic polar solvents, such as, for example, acetone, acetonitrile, N,N-dimethylformamide and dimethylsulphoxide.
When carrying out the process (c) according to the invention, it is likewise possible to vary the reaction temperatures within a certain range. In the variant (a), the reaction is generally carried out at temperatures between 0°C and 100°C, preferably between 10°C and 50°C. In the variant (13), the reaction is generally carried out at temperatures between 0°C and 200°C, preferably between 10°C and 120°C.
Suitable diluents for carrying out the process (d) according to the invention are all inert organic solvents which are customary for such reactions. Preference is given to using hydrocarbons, such as, for example, toluene, or else organic bases, such as, for example, pyridine, triethylamine and tributylamine.
Le A 32 055-Foreign countries When carrying out the process (d) according to the invention, it is likewise possible to vary the reaction temperatures within a certain range. In general, the reaction is carned out at temperatures between 0°C and 150°C, preferably between 10°C and 100°C.
When carrying out the process (d) according to the invention, the reaction is, if appropriate, carned out under elevated pressure, preferably under a pressure between 1 and 5 bar.
When carrying out the processes (a) to (d) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use a relatively large excess of one of the components.
The reaction is generally carried out in a suitable diluent in the presence of an acid binder, and the reaction mixture is generally stirred at the required temperature for several hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The phenyl-uracil derivatives of the formula (I) according to the invention have potent herbicidal activity. In addition, they are also tolerated well by important crop plants, such as, for example, wheat.
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed-killers. 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 eg nera: 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.
Le A 32 055-Foreign countries Dicotyledonous crops of the enera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the eg nera: Echinochloa, Setaria, Panicum, Digitaria, S 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 eg~ nera: 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 according to the invention 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 monocotyledonous 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.
Le A 32 055-Fore~n countries 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 methylene chloride) aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also 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 carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, 1 S 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 and also 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, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible 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 90%.
Le A 32 055-Foreign countries 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 acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam-(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop(-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, 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, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, 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.
Le A 32 055-Foreign countries Mixtures 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 S kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples below.
Ix A 32 055-Foreign countries Preparation Examules:
Example 1 H
I
F3C N ~O
CI
N
H i O
~CI
CN
A mixture of 8.1 g (27 mmol) of ethyl 3-amino-4,4,4-trifluoro-crotonate, 7.5 g of potassium carbonate and 100 ml of N-methyl-pyrrolidone is heated for one hour using a water separator. 7.0 g (27 mmol) of N-(5-cyano-2,4-dichloro-phenyl)-O-ethyl-urethane are then added, and the reaction mixture is stirred at 130°C for another 4 hours. After -cooling to room temperature, the mixture is diluted with approximately identical amounts by volume of water and ethyl acetate to about four times its original volume and acidified to approximately pH 3 using concentrated hydrochloric acid. The mixture is shaken well and the organic phase is then separated off and the aqueous phase is extracted with ethyl acetate. The combined organic phases are dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate using water pump vacuum.
This gives 5.1 g (54% of theory) of 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H)-pyrimidine.
Examine 2 FsC N ~O
CI
N
H i O
-CI
CN
2.0 g (5.7 mmol) of 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-tri-fluoromethyl-1 (2H)-pyrimidine and 0.5 g of sodium bicarbonate are initially charged in 50 ml of N,N-dimethyl-formamide. After addition of 0.6 g (3 mmol) of 1-amino-oxy-2,4-dinitro-benzene, the reaction mixture is stirred at room temperature for 5 Le A 32 055-Foreign countries hours. After addition of a further 0.6 g (3 mmol) ) of 1-aminooxy-2,4-dinitro-benzene, the mixture is stirred at room temperature for another three days.
The mixture is diluted with saturated aqueous sodium chloride solution and then extracted with ethyl acetate. The organic phase is dried using sodium sulphate and filtered with suction through silica gel. The filtrate is concentrated under water pump vacuum and the residue is purified by column chromatography (silica gel, ethyl acetate).
This gives 0.4 g (20% of theory) of 3-amino-1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H)-pyrimidine of melting point 198°C.
Example 3 FsC N ~O
CI
N
H
O
-CI
CN
A mixture of 2.4 g (6.9 mmol) of 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1(2H)-pyrimidine, 0.9 g (6.9 mmol) of dimethyl sulphate, 0.6 g of sodium bicarbonate and 100 ml of acetone is heated under reflux for hours. After addition of a further 0.2 g of dimethyl sulphate, the mixture is heated under reflux for a further 3 hours and, after addition of a further 0.5 ml of dimethyl sulphate, for another 18 hours. The mixture is then concentrated under water pump vacuum. The residue is shaken with water/ethyl acetate. The organic phase is dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is crystallized by digestion with diisopropyl ether and the product is isolated by filtration with suction.
This gives 0:6 g (24% of theory) of 1-(S-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6 dioxo-3-methyl-4-trifluoromethyl-1 (2H)-pyrimidine of melting point 161 °C.
Using the abovementioned methods, the substances listed with their formula in the table below are also prepared.
Le A 32 O55-Foreign countries Table 1 R' I
Rz N\ /O
''N~ R°
O
~RS)n Ex. R' R2 R3 (position)(position) n Physical No. R4 RS data 4 H CF3 H (5-) (2-) F, (4-)2 m.p.: 236C
CN
CH3 CF3 H (5-) (2-) F, (4-)2 m.p.: 199C
CN
6 CH3 CF3 H (5-) (2-) F, (4-)2 m.p.: 148C
CN CN
Certain cyano-phenyl-uracils having insecticidal and acaricidal properties are already known (cf. EP-A 0 438 209, JP-A OS-025 142 and Chem. Abstr. 119, 117 269).
However, an application of these substances for controlling weeds has hitherto not been described.
This invention, accordingly, provides novel phenyl-uracil derivatives of the formula R' N / Ra (I), O
(RS)n in which R' represents hydrogen, amino or represents optionally cyano- or halogen-substituted alkyl, R2 represents formyl, hydroximinomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or represents optionally cyano- or halogen-substituted alkyl R3 represents hydrogen, halogen or represents optionally cyano- or halogen-substituted alkyl, R' represents cyano or thiocarbamoyl, RS represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, halogen, or represents one of the radicals -R6, -Q-R6, -NH-R6, -NH-O-R6, -NH-S02-R6, -CQ'-R6, -CQ'-QZ-R6, -CQ'-NH-R6, -Q2-CQ'-R6, -NH-CQ'-R6, -Q''-CQ'-Q2-R6, -NH-CQ'-Q'-R6 or -Q2-CQ'-NH-R6 in which Le A 32 055-Foreign countries Q represents O, S, SO or S02, Q ~ and Q2 independently of one another each represent oxygen or sulphur and R6 represents optionally cyano-, halogen-, alkoxy-, alkylthio-, alkylcarbonyl-, alkoxycarbonyl- or alkylaminocarbonyl-substituted alkyl, represents in each case optionally cyano-, carboxyl-, halogen-, alkylcarbonyl-, alkoxycarbonyl- or alkylamino-carbonyl-substituted alkenyl or alkinyl, represents in each case optionally cyano-, carboxyl-, halogen-, alkylcarbonyl- or alkoxycarbonyl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio-, halogenoalkylthio-, alkylsulphinyl-, alkylsulphonyl-, alkylamino- and/or dialkylamino substituted aryl or arylalkyl or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio-, halogenoalkylthio-, alkylsulphinyl-, alkylsulphonyl-, alkylamino- and/or dialkylamino substituted heterocyclyl or heterocyclylalkyl, and n represents the numbers 0, 1, 2 or 3.
Furthermore, it has been found that phenyl-uracil derivatives of the formula (I) are obtained when a) aminoalkenoic esters of the formula (II), R2 ~ OR
in which Le A 32 O55-Foreign countries R2 and R3 are each as defined above and R represents alkyl, aryl or arylalkyl, are reacted with aryl isocyanates of the formula O=C=N / R4 (III), (R5)n in which R4, RS and n are each as defined above, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or b) aminoalkenoic esters of the formula R2 \ OR (ii), Rs in which R, R2 and R3 are each as defined above, are reacted with arylurethanes of the formula H
i R'O ~ N / R4 (IV), O \
(RS)n Le A 32 055-Foreign countries in which R4, RS and n are each as defined above and R' represents alkyl, aryl or arylalkyl, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or c) phenyl-uracil derivatives of the formula H
i R2 N ~ O
N R4 (~a), O
(RS)n in which R2, R3, R4, RS and n are each as defined above, are either a) reacted with 1-amino-oxy-2,4-dinitrobenzene of the formula 02N / \ O-NHZ (V), if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or Le A 32 055-Foreign countries (3) are reacted with sulphates of the formula R80\
'S02 (VI) S in which R8 represents alkyl, or with halogen compounds of the formula R9-Hal (VII), in which R9 represents alkyl, halogenoalkyl or cyanoalkyl and Hal represents chlorine, bromine or iodine, in each case if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or d) phenyl-uracil derivatives of the formula R' i R2 N ~ O
N / CN (Ib)~
Ra O
(RS)n in which Le A 32 055-Foreign countries R', R2, R3, RS and n are each as defined above, are reacted with hydrogen sulphide in the presence of a diluent.
Finally, it has been found that the phenyl-uracil derivatives of the formula (I) have very good herbicidal properties.
Surprisingly, the phenyl-uracil derivatives of the formula (I) according to the invention have considerably better herbicidal activity than the constitutionally most similar prior-art substances of the same direction of action.
The formula (1) provides a general definition of the phenyl-uracil derivatives according to the invention.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched, even in combination with heteroatoms, such as in alkoxy or alkylthio.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably represents fluorine, chlorine or bromine and in particular represents fluorine or chlorine.
Preference is given to phenyl-uracil derivatives of the formula (I) in which R' represents hydrogen, amino or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R2 represents formyl, hydroximinomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R3 represents hydrogen, fluorine, chlorine, bromine or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R4 represents cyano or thiocarbamoyl, Le A 32 055-Foreign countries RS represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine or represents one of the radicals -R6, -Q-R6, -NH-R6, -NH-O-R6, -NH-S02-R6, -CQ'-R6, -CQ'-Q2-R6, -CQ'-NH-R6, -Q2-CQ'-R6, -NH-CQ'-R6, -Q2-CQ'-Q2-R6, -NH-CQI~Qz-R6 or -Q2-CQ'-NH-R6 in which Q represents O, S, SO or S02, Q' and Q2 independently of one another each represent oxygen or sulphur and R6 represents optionally cyano-, halogen-, C,-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkyl-carbonyl-, C~-C4-alkoxycarbonyl- or C,-C4-alkylaminocarbonyl-substituted alkyl having 1 to 6 carbon atoms, represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkylcarbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-alkylamino- or dimethylamino-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C 1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C 1-C4-alkylthio-, C 1 _C4-halogenoalkylthio-, C1-C4-alkylsulphinyl, C1-Cq-alkylsulphonyl-, C1-C4-alkylamino- and/or dimethylamino-substituted heterocyclyl or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and/or 1 or 2 oxygen atoms and/or one sulphur Le A 32 055-Foreign countries -g_ atom in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, and n represents the numbers 0, 1, 2 or 3.
Particular preference is given to phenyl-uracil derivatives of the formula (I) in which R1 represents hydrogen, amino, methyl or ethyl, R2 represents formyl, hydroximinomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or represents optionally fluorine- or chlorine-substituted methyl or ethyl, R3 represents hydrogen, chlorine or optionally fluorine- or chlorine-substituted methyl or ethyl, R4 represents cyano or thiocarbamoyl, RS represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine, or represents one of the radicals R6, -Q-R6, -NH-R6, -NH-O-R6, -NH-S OZ-R6, -CQ ~ -R6, -C Q ~ -Q2-R6, -CQ ~ -NH-R6, -Q2-CQ ~ -R6, -NH-CQ~-R6, -Q2-CQ~-Qz-R6, -NH-CQ~-Q2-R6 or -Q2-CQ~-NH-R6, in which Q represents O, S, SO or S02, Q1 and Q2 independently of one another represent oxygen or sulphur and R6 represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, methylthio-, ethylthio-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylaminocarbonyl- or ethylamino-carbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, or represents in each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylaminocarbonyl- or ethylaminocarbonyl-substituted propenyl, butenyl, propinyl or butinyl, Le A 32 055-Forei~~n countries or represents in each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, difluoromethyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, methylamino-, ethylamino-and/or dimethylamino-substituted phenyl, benzyl or phenylethyl, or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, trichloromethyl-, difluoromethyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoromethylthio-, chlorodifluoromethylthio-, fluorodichloromethylthio-, methyl-sulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, methylamino-, ethylamino-, n- or i-propylamino- and/or dimethyl-amino-substituted heterocyclyl or heterocyclylalkyl from the series consisting of oxiranyl, oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl and also pyrimidinylmethyl, and n represents the numbers 1 or 2.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other as desired, i.e. including combinations between the given preferred ranges.
Le A 32 055-Foreign countries Using, for example, methyl 3-amino-crotonate and 3-cyano-5-fluoro-4-trifluoro-methyl-phenyl isocyanate as starting materials, the course of the reaction in process (a) according to the invention can be illustrated by the following equation:
H
i NH2 O / CN HaC N ~O
+ O=C=N
H3C ~ OCH3 \ ~ ~ H ~ N / CN
O \
F CFs F
Using methyl 3-amino-crotonate and methyl N-(3-cyano-S-fluoro-4-trifluoromethyl-phenyl)-carbamate as starting materials, the course of the process (b) according to the invention can be illustrated by the following equation.
H
H
NHz O + H3C0\ /N / CN HsC N ' / O
H3C ~ OCH3 O \ ~ -2CH30H H ~ N / CN
F O \
F
Using 1-(5-cyano-2,4-dichlorophenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1(2H)-pyrimidine as starting material and 1-aminooxy-2,4-dinitro-benzene as reac-tion component, the course of the reaction of the process (c, variant a) according to the invention can be illustrated by the following equation.
02N ~ ~ ONH2 NH2 F3C N ~ O
N02 F3C N ' / O
H N / CN
H N / CN
O
CI \ CI p CI CI
Using 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H)-pyrimidine as starting material and dimethyl sulphate as reaction component, Le A 32 055-Foreign countries the course of the process (c, variant B) according to the invention can be illustrated by the following equation.
H
i CH30 CH
F3C N ' / O X502 I
I CH O/ FaC N \ / O
H N / CN --t '~( I H N / CN
O I
CI \ CI O
CI \ CI
Using 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H)-pyrimidine as starting material and hydrogen sulphide as reaction component, the course of the process (d) according to the invention can be illustrated by the following equation.
FaC N O I
F3C N ~ O
I ~ CN H2S I II
H / -t H N / C-NH2 I
O CI \ CI O CI \ I CI
The formula (In provides a general definition of the aminoalkenoic esters required as starting materials for carrying out the process (a) and (b) according to the invention.
In the formula (In, RZ and R3 each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (1) according to the invention, as being preferred or as being particularly preferred for RZ and R3. R preferably represents alkyl having 1 to 4 carbon atoms, phenyl or benzyl. Particularly preferably, R represents methyl, ethyl or phenyl.
The starting materials of the formula (II) are known or can be prepared by known processes (cf. J. Heterocycl. Chem. 9 ( 1972), 513-522).
The formula (III) provides a general definition of the aryl isocyanates required as reaction components for carrying out the process (a) according to the invention. In the formula (III), R4, RS and n each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the Le A 32 055-Foreign countries compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R4, RS and n.
The starting materials of the formula (III) are known or can be prepared by known processes (cf. Tetrahedron Lett. 1967, 961-962; EP-A 0 063 905, EP-A 0 093 610, EP-A 0 093 620, EP-A 0 397 052 and EP-A 0 572 782).
Thus, aryl isocyanates of the formula (111) can be prepared by reacting anilines of the formula in which (VIII).
(RS)n R4, RS and n are each as defined above, with phosgene in the presence of a diluent, such as, for example, chlorobenzene, at temperatures between -20°C and +150°C.
The formula (IV) provides a general definition of the arylurethanes required as reaction components for carrying out the process (b) according to the invention. In the formula (IV), R4, RS and n each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (n according to the invention, as being preferred or as being particularly preferred for R4, RS and n; R' preferably represents CI-C4-alkyl, phenyl or benzyl, and in particular represents methyl, ethyl or phenyl.
The arylurethanes of the formula (IV) are known or can be prepared by known processes (cf. EP-A 0 063 905).
Thus, arylurethanes of the formula (IV) are obtained by reacting anilines of the formula Le A 32 OSS-Foreign countries H2N / R4 (VIII).
(R5)n in which R4, RS and n are each as defined above with chlorocarbonyl compounds of the formula R70-CO-Cl (IX), in which R' is as defined above, if appropriate in the presence of an acid acceptor, such as, for example, pyridine, and if appropriate in the presence of a diluent, such as, for example, methylene chloride, at temperatures between -20°C and +100°C.
The phenyl-uracil derivatives of the formula (Ia) required as starting materials for carrying out the process (c) according to the invention are compounds according to the invention which can be prepared by the processes (a) or (b) according to the invention.
The 1-aminooxy-2,4-dinitro-benzene of the formula (V) required as reaction component for carrying out the process (c, variant a) according to the invention is known (cf. J. Heterocycl. Chem. 4 ( 1967), 413-414).
The formula (Vn provides a general definition of the sulphates required as reaction components for carrying out the process (c, variant (3) according to the invention. In this formula, Rg preferably represents alkyl having 1 to 4 carbon atoms, and particularly preferably represents methyl or ethyl.
The formula (VII) provides a general definition of the halogen compounds which can furthermore be employed as reaction components when carrying out the process (c, Le A 32 055-Foreign countries variant 13) according to the invention. In this formula, R9 preferably represents alkyl, cyanoalkyl, fluoroalkyl or chloroalkyl having in each case 1 to 4 carbon atoms. Hal preferably represents bromine or iodine.
R9 particularly preferably represents methyl or ethyl.
Hal also particularly preferably represents bromine or iodine.
The phenyl-uracil derivatives of the formula (Ib) required as starting materials for carrying out the process (d) according to the invention are compounds according to the invention which can be prepared by the processes (a), (b) or (c) according to the invention.
Suitable acid binders for carrying out the processes (a) to (c) according to the invention are all customary inorganic and organic acid acceptors. Preference is given to using 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, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide, or potassium methoxide, ethoxide, n- or i-propoxide, 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-dimethyl-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-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo-[2,2,2]-octane (DABCO), 1,S-diazabicyclo-[4,3,0]-non-5-ene (DBN), or 1,8 diazabicyclo-[5,4,0]-undec-7-ene (DBU).
Suitable diluents for carrying out the processes (a) and (b) according to the invention are all customary inert organic solvents preference is given to using 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 Le A 32 055-Foreign countries 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; nitriles, 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 and also diethylene glycol monoethyl ether.
When carrying out the processes (a) and (b) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out at temperatures between 0°C and 200°C, preferably between 10°C and 150°C.
The processes (a) to (c) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated pressure or, if no highly volatile components are employed, under reduced pressure.
Suitable diluents for carrying out the process (c) according to the invention are all inert organic solvents which are customary for such reactions. In the reaction according to variant (a), preference is given to using aprotic polar solvents, such as, for example, N,N-dimethylformamide and N-methyl-pyrrolidone.
In the reaction according to variant (13), preference is likewise given to using aprotic polar solvents, such as, for example, acetone, acetonitrile, N,N-dimethylformamide and dimethylsulphoxide.
When carrying out the process (c) according to the invention, it is likewise possible to vary the reaction temperatures within a certain range. In the variant (a), the reaction is generally carried out at temperatures between 0°C and 100°C, preferably between 10°C and 50°C. In the variant (13), the reaction is generally carried out at temperatures between 0°C and 200°C, preferably between 10°C and 120°C.
Suitable diluents for carrying out the process (d) according to the invention are all inert organic solvents which are customary for such reactions. Preference is given to using hydrocarbons, such as, for example, toluene, or else organic bases, such as, for example, pyridine, triethylamine and tributylamine.
Le A 32 055-Foreign countries When carrying out the process (d) according to the invention, it is likewise possible to vary the reaction temperatures within a certain range. In general, the reaction is carned out at temperatures between 0°C and 150°C, preferably between 10°C and 100°C.
When carrying out the process (d) according to the invention, the reaction is, if appropriate, carned out under elevated pressure, preferably under a pressure between 1 and 5 bar.
When carrying out the processes (a) to (d) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use a relatively large excess of one of the components.
The reaction is generally carried out in a suitable diluent in the presence of an acid binder, and the reaction mixture is generally stirred at the required temperature for several hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The phenyl-uracil derivatives of the formula (I) according to the invention have potent herbicidal activity. In addition, they are also tolerated well by important crop plants, such as, for example, wheat.
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed-killers. 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 eg nera: 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.
Le A 32 055-Foreign countries Dicotyledonous crops of the enera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the eg nera: Echinochloa, Setaria, Panicum, Digitaria, S 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 eg~ nera: 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 according to the invention 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 monocotyledonous 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.
Le A 32 055-Fore~n countries 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 methylene chloride) aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also 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 carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, 1 S 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 and also 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, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible 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 90%.
Le A 32 055-Foreign countries 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 acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam-(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop(-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, 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, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, 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.
Le A 32 055-Foreign countries Mixtures 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 S kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples below.
Ix A 32 055-Foreign countries Preparation Examules:
Example 1 H
I
F3C N ~O
CI
N
H i O
~CI
CN
A mixture of 8.1 g (27 mmol) of ethyl 3-amino-4,4,4-trifluoro-crotonate, 7.5 g of potassium carbonate and 100 ml of N-methyl-pyrrolidone is heated for one hour using a water separator. 7.0 g (27 mmol) of N-(5-cyano-2,4-dichloro-phenyl)-O-ethyl-urethane are then added, and the reaction mixture is stirred at 130°C for another 4 hours. After -cooling to room temperature, the mixture is diluted with approximately identical amounts by volume of water and ethyl acetate to about four times its original volume and acidified to approximately pH 3 using concentrated hydrochloric acid. The mixture is shaken well and the organic phase is then separated off and the aqueous phase is extracted with ethyl acetate. The combined organic phases are dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate using water pump vacuum.
This gives 5.1 g (54% of theory) of 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H)-pyrimidine.
Examine 2 FsC N ~O
CI
N
H i O
-CI
CN
2.0 g (5.7 mmol) of 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-tri-fluoromethyl-1 (2H)-pyrimidine and 0.5 g of sodium bicarbonate are initially charged in 50 ml of N,N-dimethyl-formamide. After addition of 0.6 g (3 mmol) of 1-amino-oxy-2,4-dinitro-benzene, the reaction mixture is stirred at room temperature for 5 Le A 32 055-Foreign countries hours. After addition of a further 0.6 g (3 mmol) ) of 1-aminooxy-2,4-dinitro-benzene, the mixture is stirred at room temperature for another three days.
The mixture is diluted with saturated aqueous sodium chloride solution and then extracted with ethyl acetate. The organic phase is dried using sodium sulphate and filtered with suction through silica gel. The filtrate is concentrated under water pump vacuum and the residue is purified by column chromatography (silica gel, ethyl acetate).
This gives 0.4 g (20% of theory) of 3-amino-1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H)-pyrimidine of melting point 198°C.
Example 3 FsC N ~O
CI
N
H
O
-CI
CN
A mixture of 2.4 g (6.9 mmol) of 1-(5-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1(2H)-pyrimidine, 0.9 g (6.9 mmol) of dimethyl sulphate, 0.6 g of sodium bicarbonate and 100 ml of acetone is heated under reflux for hours. After addition of a further 0.2 g of dimethyl sulphate, the mixture is heated under reflux for a further 3 hours and, after addition of a further 0.5 ml of dimethyl sulphate, for another 18 hours. The mixture is then concentrated under water pump vacuum. The residue is shaken with water/ethyl acetate. The organic phase is dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is crystallized by digestion with diisopropyl ether and the product is isolated by filtration with suction.
This gives 0:6 g (24% of theory) of 1-(S-cyano-2,4-dichloro-phenyl)-3,6-dihydro-2,6 dioxo-3-methyl-4-trifluoromethyl-1 (2H)-pyrimidine of melting point 161 °C.
Using the abovementioned methods, the substances listed with their formula in the table below are also prepared.
Le A 32 O55-Foreign countries Table 1 R' I
Rz N\ /O
''N~ R°
O
~RS)n Ex. R' R2 R3 (position)(position) n Physical No. R4 RS data 4 H CF3 H (5-) (2-) F, (4-)2 m.p.: 236C
CN
CH3 CF3 H (5-) (2-) F, (4-)2 m.p.: 199C
CN
6 CH3 CF3 H (5-) (2-) F, (4-)2 m.p.: 148C
CN CN
7 H CF3 H (5-) (2)OH, (4)-Cl2 m.p.: 279C
CN
Le A 32 OSS-Foreign countries Use Examples: ' Example A
Pre-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After approximately 24 hours, the soil is watered with the preparation of active compound. The amount of water per unit area is advantageously kept constant. The concentration of active compound in the preparation is immaterial, only the application rate of the active compound per unit area matters.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, the compounds according to the invention listed in Examples 2, 3 and 6 exhibit, at application rates of 60 to 250 g/ha, an efficacy of 80% or more against various weeds, and they are well tolerated by wheat.
Le A 32 055-Foreign countries Example B
Post-emergence Test S Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of the active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of 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 such 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, the substances according to the invention listed in Examples 2, 3 and 6 exhibit, at application rates between 60 and 2000 g/ha, an efficacy of 80% or more against various weeds.
CN
Le A 32 OSS-Foreign countries Use Examples: ' Example A
Pre-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After approximately 24 hours, the soil is watered with the preparation of active compound. The amount of water per unit area is advantageously kept constant. The concentration of active compound in the preparation is immaterial, only the application rate of the active compound per unit area matters.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, the compounds according to the invention listed in Examples 2, 3 and 6 exhibit, at application rates of 60 to 250 g/ha, an efficacy of 80% or more against various weeds, and they are well tolerated by wheat.
Le A 32 055-Foreign countries Example B
Post-emergence Test S Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of the active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of 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 such 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, the substances according to the invention listed in Examples 2, 3 and 6 exhibit, at application rates between 60 and 2000 g/ha, an efficacy of 80% or more against various weeds.
Claims (7)
1. Phenyl-uracil derivatives of the formula , in which R1 represents hydrogen, amino or represents optionally cyano- or halogen-substituted alkyl, R2 represents formyl, hydroximinomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or represents optionally cyano- or halogen-substituted alkyl R3 represents hydrogen, halogen or represents optionally cyano- or halogen-substituted alkyl, R4 represents cyano or thiocarbamoyl, R5 represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, halogen, or represents one of the radicals -R6, -Q-R6, -NH-R6, -NH-O-R6, -NH-SO2-R6, -CQ1-R6, -CQ1-Q2-R6, -CQ1-NH-R6, -Q2-CQ1-R6, -NH-CQ1-R6, -Q2-CQ1-Q2-R6, -NH-CQ1-Q2-R6 or -Q2-CQ1-NH-R6 in which Q represents O, S, SO or SO2, Q1 and Q2 independently of one another each represent oxygen or sulphur and R6 represents optionally cyano-, halogen-, alkoxy-, alkylthio-, alkylcarbonyl-, alkoxycarbonyl- or alkylaminocarbonyl-substituted alkyl, represents in each case optionally cyano-, carboxyl-, halogen-, alkylcarbonyl-, alkoxycarbonyl- or alkylamino-carbonyl-substituted alkenyl or alkinyl, represents in each case optionally cyano-, carboxyl-, halogen-, alkylcarbonyl- or alkoxycarbonyl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio-, halogenoalkylthio-, alkylsulphinyl-, alkylsulphonyl-, alkylamino- and/or dialkylamino-substituted aryl or arylalkyl or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio-, halogenoalkylthio-, alkylsulphinyl-, alkylsulphonyl-, alkylamino- and/or dialkylamino-substituted heterocyclyl or heterocyclylalkyl, and n represents the numbers 0, 1, 2 or 3.
2. Phenyl-uracil derivatives of the formula (I) according to Claim 1 in which R1 represents hydrogen, amino or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R2 represents formyl, hydroximinomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R3 represents hydrogen, fluorine, chlorine, bromine or represents optionally cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R4 represents cyano or thiocarbamoyl, R5 represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine or represents one of the radicals -R6, -Q-R6, -NH-R6, -NH-O-R6, -NH-SO2-R6, -CQ1-R6, -CQ1-Q2-R6, -CQ1-NH-R6, -Q2-CQ1-R6, -NH-CQ1-R6, -Q2-CQ1-Q2-R6, -NH-CQ1-Q2-R6 or -Q2-CQ1-NH-R6 in which Q represents O, S, SO or SO2, Q1 and Q2 independently of one another each represent oxygen or sulphur and R6 represents optionally cyano-, halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-substituted alkyl having 1 to 6 carbon atoms, represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-alkylamino- or dimethylamino-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety or represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl-, C1-C4-alkylamino- and/or dimethylamino-substituted heterocyclyl or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and/or 1 or 2 oxygen atoms and/or one sulphur atom in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, and n represents the numbers 0, 1, 2 or 3.
3. Process for preparing phenyl-uracil derivatives of the formula (I) according to Claim 1, characterized in that a) aminoalkenoic esters of the formula , in which R2 and R3 are each as defined above and R represents alkyl, aryl or arylalkyl, are reacted with aryl isocyanates of the formula , in which R4, R5 and n are each as defined above, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or b) aminoalkenoic esters of the formula , in which R, R2 and R3 are each as defined above, are reacted with arylurethanes of the formula, , in which R4, R5 and n are each as defined above and R' represents alkyl, aryl or arylalkyl, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or c) phenyl-uracil derivatives of the formula , in which R2, R3, R4, R5 and n are each as defined above, are either a) reacted with 1-amino-oxy-2,4-dinitrobenzene of the formula , if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or are reacted with sulphates of the formula in which R8 represents alkyl, or with halogen compounds of the formula R9-Hal (VII), in which R9 represents alkyl, halogenoalkyl or cyanoalkyl and Hal represents chlorine, bromine or iodine, in each case if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or d) phenyl-uracil derivatives of the formula , in which R1, R2, R3, R5 and n are each as defined above, are reacted with hydrogen sulphide in the presence of a diluent.
4. Herbicidal compositions, characterized in that they contain at least one phenyl-uracil derivative of the formula (I) according to Claim 1.
5. Use of phenyl-uracil derivatives of the formula (I) according to Claim 1 for controlling weed.
6. Method for controlling weeds, characterized in that phenyl-uracil derivatives of the formula (I) according to Claim 1 are applied to the weeds and/or their habitat.
7. Process for preparing herbicidal compositions, characterized in that phenyl-uracil derivatives of the formula (I) according to Claim 1 are mixed with extenders and/or surfactants.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19649094A DE19649094A1 (en) | 1996-11-27 | 1996-11-27 | Phenyl uracil derivatives |
| DE19649094.4 | 1996-11-27 | ||
| PCT/EP1997/006367 WO1998023598A1 (en) | 1996-11-27 | 1997-11-14 | Phenyl-uracil derivatives with herbicide effect |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2272657A1 true CA2272657A1 (en) | 1998-06-04 |
Family
ID=7812900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002272657A Abandoned CA2272657A1 (en) | 1996-11-27 | 1997-11-14 | Phenyl-uracil derivatives with herbicide effect |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0944607A1 (en) |
| JP (1) | JP2001504503A (en) |
| KR (1) | KR20000053150A (en) |
| CN (1) | CN1253550A (en) |
| AU (1) | AU5322298A (en) |
| BR (1) | BR9713546A (en) |
| CA (1) | CA2272657A1 (en) |
| DE (1) | DE19649094A1 (en) |
| WO (1) | WO1998023598A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4639459B2 (en) * | 1999-11-01 | 2011-02-23 | 住友化学株式会社 | 6-hydroxy-5,6-dihydrouracil compound |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK366887A (en) * | 1986-07-31 | 1988-05-13 | Hoffmann La Roche | pyrimidine |
| US4941909A (en) * | 1987-06-19 | 1990-07-17 | Hoffmann-La Roche Inc. | Heterocyclic compounds |
| AU2328188A (en) * | 1987-09-23 | 1989-04-18 | Ciba-Geigy Ag | Heterocyclic compounds |
| US5041156A (en) * | 1987-10-22 | 1991-08-20 | Ciba-Geigy Corporation | 3-aryluracils for the control of weeds |
| DE59007059D1 (en) * | 1989-06-29 | 1994-10-13 | Ciba Geigy Ag | HETEROCYCLIC COMPOUNDS. |
| AU627906B2 (en) * | 1989-07-14 | 1992-09-03 | Nissan Chemical Industries Ltd. | Uracil derivatives and herbicides containing the same as active ingredient |
| EP0438209B1 (en) * | 1990-01-18 | 1994-09-21 | Nissan Chemical Industries, Limited | Uracil derivatives and pesticides containing the same as active ingredient |
| JPH0525142A (en) * | 1991-07-12 | 1993-02-02 | Nissan Chem Ind Ltd | Uracil derivative and noxious organism controlling agent |
| DE4131038A1 (en) * | 1991-09-20 | 1993-04-01 | Basf Ag | SUBSTITUTED 3-PHENYLURAZILES |
| EP0542685A1 (en) * | 1991-11-13 | 1993-05-19 | Ciba-Geigy Ag | 3-Aryluracile derivatives and their use against weeds |
-
1996
- 1996-11-27 DE DE19649094A patent/DE19649094A1/en not_active Withdrawn
-
1997
- 1997-11-14 WO PCT/EP1997/006367 patent/WO1998023598A1/en not_active Application Discontinuation
- 1997-11-14 CA CA002272657A patent/CA2272657A1/en not_active Abandoned
- 1997-11-14 BR BR9713546-1A patent/BR9713546A/en not_active Application Discontinuation
- 1997-11-14 JP JP52421998A patent/JP2001504503A/en active Pending
- 1997-11-14 AU AU53222/98A patent/AU5322298A/en not_active Abandoned
- 1997-11-14 EP EP97950192A patent/EP0944607A1/en not_active Withdrawn
- 1997-11-14 CN CN97180093A patent/CN1253550A/en active Pending
- 1997-11-14 KR KR1019990704085A patent/KR20000053150A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| BR9713546A (en) | 2000-01-25 |
| JP2001504503A (en) | 2001-04-03 |
| WO1998023598A1 (en) | 1998-06-04 |
| AU5322298A (en) | 1998-06-22 |
| EP0944607A1 (en) | 1999-09-29 |
| CN1253550A (en) | 2000-05-17 |
| DE19649094A1 (en) | 1998-05-28 |
| KR20000053150A (en) | 2000-08-25 |
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