KR20000053150A - Phenyl-uracil derivatives with herbicide effect - Google Patents

Abstract

PURPOSE: Up to date, no phenyl-uracil derivatives available for extermination of weeds have been known. Novel phenyl-uracil derivatives of formula(I), multiple methods for producing the derivatives and their use as herbicides are provided. CONSTITUTION: A phenyl-uracil derivatives of formula(I) are prepared by: method(a) in which aminoalkenic esters of formula(II) are reacted with aryl isocyanate of formula(III), appropriately in the presence of acid-binding material and diluent; method(b) in which aminoalkenic esters of formula(II) are reacted with aryl urethane of formula(IV), appropriately in the presence of acid-binding material and diluent; method(c) in which phenyl-uracil derivatives of formula(Ia) are reacted with 1-amino-oxy-2,4-dinitrobenzene of formula(V), sulfate of formula(VI), or halogen compounds of formula(VII), appropriately in the presence of acid-binding material and diluent; or method(c) in which phenyl-uracil derivatives of formula(Ib) are reacted with hydrogen sulfide, appropriately in the presence of diluent. Though the phenyl-uracil derivatives of formula(I) have effective herbicidal activity on principal crops such as wheat stand well them. The derivatives are useful as defoliants, dryer, stem-killer and particularly weed-killer.

Description

Phenyl-uracil derivatives with herbicide effect

Certain cyano-phenyl-uracils with pesticidal and acaricide properties are already known (see EP-A 0 438 209, JP-A 05 025 142 and Chem. Abstr. 119, 117 269). However, the application of these materials for weed control has not been described to date.

The present invention relates to novel phenyl-uracil derivatives, many processes for their preparation and their use as pesticides.

Accordingly, the present invention provides novel phenyl-uracil derivatives of general formula (I):

Where

R ¹ represents hydrogen, amino, or optionally cyano- or halogen substituted alkyl,

R ² represents formyl, hydroxideiminomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl, or optionally cyano- or halogen-substituted alkyl,

R ³ represents hydrogen, halogen, or optionally cyano- or halogen-substituted alkyl,

R ⁴ represents cyano or thiocarbamoyl,

R ⁵ represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, halogen, or the radicals -R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -CQ ¹ -R ⁶ , -CQ ¹ -Q ² -R ⁶ , -CQ ¹ -NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ , -NH-CQ ¹ -R ⁶ , -Q ² -CQ ¹ -Q ² -R ⁶ , -NH-CQ ¹ -Q ² -R ⁶ or -Q ² -CQ ¹ -NH-R ⁶ , and

From here,

Q represents O, S, SO or SO ₂ ,

Q ¹ and Q ² independently of each other represent oxygen or sulfur,

R ⁶ optionally represents cyano-, halogen-, alkoxy-, alkylthio-, alkylcarbonyl-, alkoxycarbonyl- or alkylaminocarbonyl-substituted alkyl, or

In each case optionally represents cyano-, carboxyl-, halogen-, alkylcarbonyl-, alkoxycarbonyl- or alkylamino-carbonyl-substituted alkenyl or alkynyl,

In each case optionally represents cyano-, carboxyl-, halogen-, alkylcarbonyl- or alkoxycarbonyl-substituted cycloalkyl or cycloalkylalkyl,

In each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio- , Halogenoalkylthio-, alkylsulfinyl-, alkylsulfonyl-, alkylamino- and / or dialkylamino-substituted aryl or arylalkyl,

In each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio- , Halogenoalkylthio-, alkylsulfinyl-, alkylsulfonyl-, alkylamino- and / or dialkylamino-substituted heterocyclyl or heterocyclylalkyl,

n represents the number of 0, 1, 2 or 3.

Further, the phenyl-uracil derivatives of general formula (I)

a) reacting the aminoalkeneic ester of formula (II) with the aryl isocyanate of formula (III), if appropriate in the presence of an acid binder and, if appropriate, in the presence of a diluent,

b) reacting the aminoalkenic acid ester of formula (II) with the arylurethane of formula (IV), if appropriate in the presence of an acid binder and, if appropriate, in the presence of a diluent,

c) phenyl-uracil derivatives of general formula (la)

α) reacting with 1-amino-oxy-2,4-dinitrobenzene of general formula (V) in the presence of an acid binder and, if appropriate, in the presence of a diluent, or

β) in each case, if appropriate, in the presence of an acid binder and, if appropriate, in the presence of a diluent, with a sulfate of formula (VI) or with a halogen compound of formula (VII),

d) It was found that the phenyl-uracil derivatives of general formula (Ib) are obtained by reacting with hydrogen sulfide in the presence of a diluent:

R ⁹ -Hal (VII)

Where

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are each as defined above,

R represents alkyl, aryl or arylalkyl,

R ⁷ represents alkyl, aryl or arylalkyl,

R ⁸ represents alkyl,

R ⁹ represents alkyl, halogenoalkyl or cyanoalkyl,

Hal represents chlorine, bromine or iodine.

Finally, it has been found that the phenyl-uracil derivatives of general formula (I) have very good herbicidal properties.

Surprisingly, the phenyl-uracil derivatives of general formula (I) according to the invention have significantly better herbicidal activity than the constitutively similar prior art materials having the same direction of action.

Formula (I) provides a general definition of phenyl-uracil derivatives according to the invention.

In the above definition, saturated or unsaturated hydrocarbon chains such as alkyl, alkenyl or alkynyl are in each case straight or branched even when combined with heteroatoms such as alkoxy or alkylthio.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially fluorine or chlorine.

Preferred

R ¹ represents hydrogen or amino, or optionally alkyl having 1 to 4 carbon atoms substituted with cyano-, fluorine- or chlorine-substituted,

R ² represents formyl, hydroxyliminomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or optionally alkyl having 1 to 4 carbon atoms, cyano-, fluorine- or chlor-substituted ,

R ³ represents hydrogen, fluorine, chlorine, bromine or optionally alkyl having 1 to 4 carbon atoms substituted with cyano-, fluorine- or chlorine-substituted,

R ⁴ represents cyano or thiocarbamoyl,

R ⁵ represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine or the radicals -R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -CQ ¹ -R ⁶ , -CQ ¹ -Q ² -R ⁶ , -CQ ¹ -NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ , -NH-CQ ¹ -R ⁶ , -Q ² -CQ ¹ -Q ² -R ⁶ , -NH-CQ ¹ -Q ² -R ⁶ or -Q ² -CQ ¹ -NH-R ⁶ , and

From here,

Q represents O, S, SO or SO ₂ ,

Q ¹ and Q ² independently of each other represent oxygen or sulfur,

R ⁶ is optionally cyano-, halogen-, C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -alkyl-carbonyl-, C ₁ -C ₄ -alkoxycarbon Alkyl having 1 to 6 carbon atoms, or substituted, or C ₁ -C ₄ -alkylaminocarbonyl-substituted, or

In each case optionally cyano-, carboxyl-, halogen-, C ₁ -C ₄ -alkyl-carbonyl-, C ₁ -C ₄ -alkoxy-carbonyl- or C ₁ -C ₄ -alkylamino-carbonyl- Substituted alkenyl or alkynyl having in each case 2 to 6 carbon atoms, or

In each case optionally a cyano-, carboxyl-, halogen-, C ₁ -C ₄ -alkyl-carbonyl- or C ₁ -C ₄ -alkoxy-carbonyl-substituted, in each case cycloalkyl group 3 carbon atom Or cycloalkyl or cycloalkylalkyl having from 6 to 6 and optionally having from 1 to 4 carbon atoms in the alkyl moiety,

Optionally in each case hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl -, thio carbamoyl -, C ₁ -C ₄ - alkyl -, C ₁ -C ₄ - halogenoalkyl - , C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -halogenoalkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -halogenoalkylthio-, C ₁ -C ₄ -alkyl Sulfinyl-, C ₁ -C ₄ -alkylsulfonyl-, C ₁ -C ₄ -alkylamino- or dimethylamino-substituted, in each case having 6 or 10 carbon atoms in the aryl group and optionally carbon in the alkyl moiety Aryl or arylalkyl having 1 to 4 atoms,

Optionally in each case hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl -, thio carbamoyl -, C ₁ -C ₄ - alkyl -, C ₁ -C ₄ - halogenoalkyl - , C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -halogenoalkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -halogenoalkylthio-, C ₁ -C ₄ -alkyl 2-6 carbon atoms and 1-3 nitrogen atoms in the heterocyclyl group substituted by sulfinyl, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkylamino- and / or dimethylamino-substituted, and And / or heterocyclyl or heterocyclylalkyl having one or two oxygen atoms and / or one sulfur atom and optionally having one to four carbon atoms at the alkyl site,

n is a phenyl-uracil derivative of the general formula (I) which represents the number of 0, 1, 2 or 3.

Especially preferred

R ¹ represents hydrogen, amino, methyl or ethyl,

R ² represents formyl, hydroxideiminomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl, or optionally represents fluorine- or chlorine-substituted methyl or ethyl,

R ³ represents hydrogen, chlorine or optionally fluorine- or chlorine-substituted methyl or ethyl,

R ⁴ represents cyano or thiocarbamoyl,

R ⁵ represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine or the radicals R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ ,- NH-SO ₂ -R ⁶ , -CQ ¹ -R ⁶ , -CQ ¹ -Q ² -R ⁶ , -CQ ¹ -NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ , -NH-CQ ^1- One of R ⁶ , -Q ² -CQ ¹ -Q ² -R ⁶ , -NH-CQ ¹ -Q ² -R ^6, or -Q ² -CQ ¹ -NH-R ⁶ ;

From here,

Q represents O, S, SO or SO ₂ ,

Q ¹ and Q ² independently of each other represent oxygen or sulfur,

R ⁶ is in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, methylthio-, ethylthio-, acetyl-, propynyl-, methoxycarbonyl-, ethoxycarbonyl -Methylaminocarbonyl- or ethylamino-carbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or

In each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylaminocarbonyl- or ethylaminocarbonyl- Substituted propenyl, butenyl, propynyl or butynyl, or

In each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine, acetyl-, propionyl-, methoxycarbonyl, or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, or cyclohexylmethyl,

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-, methylsulfinyl-, ethylsulfinyl-, methylsulfonyl-, ethylsulfonyl-, methylamino-, ethylamino- and Or dimethylamino-substituted phenyl, benzyl or phenylethyl, or

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-, trifluoromethyl Thio-, chlorodifluoromethylthio-, fluorodichloromethylthio-, methylsulfinyl, ethylsulfinyl-, methylsulfonyl-, ethylsulfonyl-, methylamino-, ethylamino-, n- or i- Propylamino- and / or dimethylamino-substituted, oxiranyl, octetanyl, furyl, tetrahydrofuryl, dioxoranyl, thienyl, tetrahydrothienyl, pyrrolyl, pyrazolyl, Midazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxdiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxa A heterocycle or heterocyclylalkyl selected from the group consisting of zolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl and also pyrimidinylmethyl,

n is a phenyl-uracil derivative of the general formula (I) which represents the number of 1 or 2.

The general or preferred radical definitions mentioned above apply to the final product of general formula (I) and correspondingly to the starting materials or intermediates required in each case of preparation. These radical definitions may be combined with one another as desired, ie including combinations between certain preferred ranges.

For example, when methyl 3-amino-crotonate and 3-cyano-5-fluoro-4-trifluoro-methyl-phenyl isocyanate are used as starting materials, the process according to the invention ( The reaction process in a) can be illustrated by the following scheme:

When using methyl 3-amino-crotoate and methyl N- (3-cyano-5-fluoro-4-trifluoromethylphenyl) -carbamate as starting materials, the process of (b) according to the invention The process can be illustrated by the following scheme.

1- (5-cyano-2,4-dichlorophenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) -pyrimidine and starting components as starting materials When 1-aminooxy-2,4-dinitro-benzene is used as the reaction process of the method (c, method α) according to the present invention can be illustrated by the following scheme.

1- (5-cyano-2,4-dichloro-phenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) -pyrimidine as starting material and reaction In the case of using dimethyl sulfate as a component, the process of the method (c, method β) according to the present invention can be illustrated by the following scheme.

1- (5-cyano-2,4-dichloro-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H)-as starting material In the case of using pyrimidine and hydrogen sulfide as the reaction component, the process of the method (d) according to the present invention can be illustrated by the following scheme.

Formula (II) provides a general definition of the aminoalkeneic esters which are required as starting materials for carrying out the processes (a) and (b) according to the invention. R ² and R ³ are each preferably or in particular the general formula (I) preferred to be or particular preferred that the already mentioned with respect to the compound R ² and R ³ in connection with the description of the according to the invention of the general formula (II) Have meanings. R preferably denotes alkyl, phenyl or benzyl having 1 to 4 carbon atoms. Especially preferably, R represents methyl, ethyl or phenyl.

Starting materials of formula (II) are known or can be prepared by known methods (see J. Heterocycl. Chem. 9 (1972), 513-522).

Formula (III) provides a general definition of aryl isocyanates which is required as a reaction component for carrying out process (a) according to the invention. In formula (III), R ⁴ , R ⁵ and n are each preferably or especially preferred for R ⁴ , R ⁵ and n with respect to the description of the compounds of formula (I) according to the invention Preferred have the meanings already mentioned above.

Starting materials of general formula (III) are known or can be prepared by known methods (see 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 formula (III) can be prepared by reacting aniline of formula (VIII) with phosgene at a temperature of -20 ° C to + 150 ° C in the presence of a diluent, for example chlorobenzene:

Where

R ⁴ , R ⁵ and n are as defined above, respectively.

Formula (IV) provides a general definition of arylurethane which is required as a reaction component for carrying out process (b) according to the invention. In formula (IV), R ⁴ , R ⁵ and n are each preferably or especially preferred for R ⁴ , R ⁵ and n with respect to the description of the compounds of formula (I) according to the invention Has the meanings already mentioned above as being preferred; R ⁷ preferably denotes C ₁ -C ₄ -alkyl, phenyl or benzyl, in particular methyl, ethyl or phenyl.

Arylurethanes of general formula (IV) can be prepared or known by known methods (see EP-A 0 063 905).

Thus, arylurethanes of general formula (IV) are suitable for the aniline of general formula (VIII) in the presence of an acid acceptor, for example pyridine, and if appropriate in the presence of a diluent, for example methylene chloride, from -20 ° C to +100 Obtained by reaction with a chlorocarbonyl compound of formula (IX) at a temperature of < RTI ID = 0.0 >

R ⁷ O-CO-Cl (IX)

Where

R ⁴ , R ⁵ , n and R ⁷ are each as defined above.

Phenyl-uracil derivatives of general formula (Ia), which are required as starting materials for carrying out process (c) according to the invention, can be prepared according to the invention which can be prepared by process (a) or (b) according to the invention. Compound.

The 1-aminooxy-2,4-dinitro-benzenes of the general formula (V) which are required as reaction components for carrying out the process (c, method α) according to the invention are known (see J. Heterocycl. Chem. 4 (1967), 413-414).

Formula (VI) provides a general definition of sulphate which is required as a reactive component for carrying out process (c, method β) according to the invention. In this general formula, R ⁸ preferably represents alkyl having 1 to 4 carbon atoms, particularly preferably methyl or ethyl.

Formula (VII) provides a general definition of halogen compounds which can also be used as reactive components when carrying out process (c, method β) according to the invention. In this general formula, R ⁹ preferably denotes alkyl, cyanoalkyl, fluoroalkyl or chloroalkyl having in each case 1 to 4 carbon atoms. Hal preferably represents bromine or iodine.

R ⁹ particularly preferably represents methyl or ethyl.

Hal also particularly preferably represents bromine or iodine.

Phenyl-uracil derivatives of formula (Ib), which are required as starting materials for carrying out process (d) according to the invention, can be prepared by processes (a), (b) or (c) according to the invention. Compound according to the invention.

Suitable acid binders for carrying out the processes (a) to (c) according to the invention are all conventional inorganic and organic acid acceptors. Alkali or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrates, hydroxides or alkoxides, for example sodium acetate, potassium acetate or calcium acetate, lithium amides, sodium amides, potassium amides or calcium amides, sodium carbonate, potassium carbonate or carbonate Calcium, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, ethoxide, n- or i -Propoxide, n-, i-, s- or t-butoxide; Basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclo Hexylamine, 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), 1,5-diazabicyclo- [4,3,0] -non-5-ene (DBN), or 1,8-diazabicyclo- [ 5,4,0] -undec-7-ene (DBU) is preferred.

Suitable diluents for carrying out the processes (a) and (b) according to the invention are all customary inert organic solvents. Aliphatic, cycloaliphatic or aromatic, any halogenated hydrocarbons such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; Ketones such as acetone, butanone or methyl isobutyl ketone; 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, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, di Preference is given to using ethylene glycol monomethyl ether and also diethylene glycol monoethyl ether.

When carrying out the processes (a) and (b) according to the invention, the reaction temperature can vary in a relatively wide range. In general, the process is carried out at temperatures of 0 ° C to 200 ° C, preferably 10 ° C to 150 ° C.

Processes (a) to (c) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out under reduced pressure unless elevated pressure or highly volatile compounds are used.

Suitable diluents for carrying out process (c) according to the invention are all inert organic solvents customary for such reactions. In the reaction according to method (α), preference is given to using aprotic polar solvents, for example N, N-dimethylformamide and N-methyl-pyrrolidone.

In the reaction according to method (β), it is similarly preferred to use aprotic polar solvents such as, for example, acetone, acetonitrile, N, N-dimethylformamide and dimethylsulfoxide.

When carrying out process (c) according to the invention, it is similarly possible to change the reaction temperature in a certain range. In process (α), the reaction is generally carried out at temperatures of 0 ° C to 100 ° C, preferably 10 ° C to 50 ° C. In process (β), the reaction is generally carried out at a temperature of 0 ° C to 200 ° C, preferably 10 ° C to 120 ° C.

Suitable diluents for carrying out process (d) according to the invention are all inert organic solvents customary for such reactions. Preference is given to using hydrocarbons such as toluene or other organic bases such as pyridine, triethylamine and tributylamine.

When carrying out process (d) according to the invention, it is similarly possible to change the reaction temperature in a certain range. In general, the reaction is carried out at 0 ° C to 150 ° C, preferably at 10 ° C to 100 ° C.

When carrying out process (d) according to the invention, the reaction is carried out under elevated pressure, preferably 1 to 5 bar, if appropriate.

When carrying out the processes (a) to (d) according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a relatively excess amount. The reaction is generally carried out in a suitable solvent in the presence of an acid binder and the reaction mixture is generally stirred for several hours at the required temperature (see, Preparation Examples).

The phenyl-uracil derivatives of formula (I) according to the invention have effective herbicidal activity. In addition, important crop plants, such as wheat, are well tolerated against them.

The active compounds according to the invention can be used as defoliants, desiccants, stem-killers and in particular weed-killers. In the broadest sense, weeds should be understood as all plants that grow in undesirable positions. Whether the material according to the invention acts collectively or as a selective herbicide 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 following genus: Sinapis, Lepidium, Gallium, Stellaria, Matricaria, Anthemis, Galinsoga, Ke Nopodium, Urtica, Senesio, 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 following genus: Gossypium, Glycine, Beta, Doucus, Phaseolus, Pisum, Solanum, Linum ), Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis ) And Cucurbita.

Monocot weeds in the genus: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festusca, Festuca, Eleusin, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Sino Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Iscamum ), Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocot crops of the following genus: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum Panicum), Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is not limited at all in the above, but also extends to other plants in the same way.

The compounds of the invention are suitable for the overall control of weeds, depending on concentration, for example on industrial areas and railways, and on sidewalks and plazas with or without trees. Similarly, the compounds of the present invention include, for example, plantation, ornamental water, orchard, vineyard, citrus field, nut orchard, banana plantation, coffee plantation, tea plantation, rubber plantation, palm plantation, cocoa plantation, soft fruit plantation and hop field, grass And to control weeds in perennial crops growing on racetrack grass and pasture, and to selectively control weeds in annual crops.

The active compounds of formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous crops by both pre- and post-germination methods.

The active compounds are usually used as solutions, emulsions, hydrating powders, suspensions, powders, powders, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active compounds, and microcapsules in polymeric materials. It can be converted into the formulation of.

These formulations are prepared by known methods, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. .

When water is used as the extender, for example an organic solvent can also be used as an auxiliary solvent. Liquid solvents are mainly aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins, for example mineral oil fractions, mineral oils and vegetable oils. Alcohols such as aliphatic hydrocarbons, butanol or glycol and ethers and esters thereof, as well as strong polar solvents such as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, dimethylformamide and dimethyl sulfoxide, are suitable Do.

Solid carriers are suitable, for example, ammonium salts and ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly dispersed silica, alumina and silicates. . Solid carriers for granulation include, for example, pulverized and classified natural rocks such as calcite, marble, pumice, calcite and dolomite, and synthetic granules of inorganic and organic powders, and organic such as sawdust, coconut husk, corncobs and tobacco stems. Granules of material are suitable. Emulsifiers and / or foam-forming agents include, for example, nonionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers such as polyoxyethylene fatty acid esters, alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, aryls Sulfonates and proteolytic products are suitable. Suitable dispersants are, for example, lignin-sulfite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose, gum arabic, polyvinyl alcohol and polyvinyl acetate, powders, natural and synthetic polymers in granular or latex form, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids Can be used for As other additives, mineral oil and vegetable oil may be used.

Inorganic pigments such as iron oxide, titanium oxide and prussian blue, and colorants such as alizarin dyes, azo dyes and organic dyes such as metal phthalocyanine dyes and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc Can be used.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of active compound.

In the case of weed control, the active compounds according to the invention on their own or in the form of preparations can be used as mixtures with known herbicides, as a finished preparation or as a possible tank mixture.

Possible components for the mixture include known herbicides such as acetochlor, acifluorfen (-sodium), acloniphene, alachlor, alkoxydim (-sodium), amethrin, amidochlor, amidosulfuron, Asulam, Atrazine, Azimsulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bentazone, Benzophene, Benzoylprop (-ethyl), Bialafoss, Biphenox, Bromobutide, Bromofe Green heart, bromoxynil, butachlor, butyrate, carfenstrol, carbamide, clomethoxyphene, chlorambene, chloridazone, chlorimuron (-ethyl), chlornitropen, chlorsulphron, chlortol Luron, cinnamiclin, cynosulfuron, cletodim, clodinapop (-propargyl), clomazone, clopyralide, clopyrasulfuron, cloransullam (-methyl), cumyluron, cyanazine , Cycloate, cyclosulfamuron, cyacryldim, sihalofop (-butyl), 2,4-D, 2,4- DB, 2,4-DP, desmedipharm, dialate, dicamba, diclofo (-butyl), dipfencuart, diflufenican, dimefuron, dimepiperate, dimethaclor, dimethamethrin , Dimethenamid, dinitramine, diphenamide, diquat, dithiopyr, diuron, dimron, EPTC, esprocarb, etafluralin, etamethsulfuron (-methyl), etofumesate, ethoxyphene , Etobenzanide, phenoxaprop (-ethyl), flamprop (-isopropyl), flamprop (-isopropyl-L), flamprop (-methyl), plazasulfuron, fluazipope ( -Butyl), flumetsulam, pullumiclolac (-pentyl), flumioxazine, flumipropine, fluoromethuron, fluorocloridone, fluoroglycopene (-ethyl), flupoxam, flupropacyl , Flurenol, flulidone, fluoxypyr, fluprimidol, flutarmone, pomesafen, glufosinate (-ammonium), glyphosate (-isopropylammonium) ), Halosafen, halophosphope (-ethoxyethyl), hexazinone, imazamethabenz (-methyl), imazamethafil, imazamox, imazaphyr, imazaquin, imazetapyr, imazasulfuron , Isoxyyl, isoprophalin, isoproturon, isoxaben, isoxaprutol, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitrone, metazachlor , Metabenzthiazuron, methopenzuron, methopromurone, metolachlor, methotsalam, metoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide, naph Ropeamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzaline, Oxadiazone, Oxyfluorophene, Paraquat, Pendimethalin, Penmedipham, Piperophos, Pretilachlor, Free Misulfuron (-methyl), promethrin, propachlor, propanyl, propaquizapov, propizamide, pro Pocarb, prosulfuron, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxifen, pyributicab, pyridate, pyrithiobac (-sodium), quinclolac, quinmerac, quizolopop ( -Ethyl), quizolopop (-p-tefuryl), rimsulfuron, cetoxydim, simazine, cymetrin, sulcotrione, sulfentrazone, sulfomethuron (-methyl), sulfosate, tebutam , Butbutyurine, tebutylrazine, terbutrin, tenylchlor, thiafluamide, thiazopyr, thiadiazimine, thifensulfuron (-methyl), thiobbencarb, thiocarbazil, traxoximem, tri Alate, triasulfuron, tribennuron (-methyl), triclopyr, tridiphane, tripleuralline and triplelusulfuron.

Mixtures with other known active compounds, for example fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and canning aids, are also possible.

The active compounds can be used on their own, in the form of preparations or by further dilution, in the form of use, for example in the form of ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The active compounds are used in conventional manner, for example by spraying, spraying, atomizing or scattering.

The active compounds according to the invention can be applied before or after germination of plants. They can be incorporated into the soil before seeding.

The amount of active compound used may vary within a substantial range. This is essentially dependent on the nature of the desired effect. Generally used amounts are from 1 g to 10 kg, preferably from 5 g to 5 kg of active compound per hectare of soil surface.

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

Manufacturing Example

Example 1

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 for 1 hour using a water separator Heated. Then 7.0 g (27 mmol) N- (5-cyano-2,4, -dichloro-phenyl) -O-ethyl urethane were added and the reaction mixture was stirred at 130 ° C. for another 4 hours. After cooling to room temperature, the mixture was diluted with approximately equal volume of water and ethyl acetate to about 4 times its original volume and acidified to approximately pH 3 with concentrated hydrochloric acid. The mixture was shaken well, then the organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, dried over sodium sulfate and filtered. The solvent was carefully distilled from the filtrate using a water pump vacuum.

Thus, 5.1 g of 1- (5-cyano-2,4-dichloro-phenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) -pyrimidine ( 54% of theory).

Example 2

2.0 g (5.7 mmol) of 1- (5-cyano-2,4-dichloro-phenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) -pyrimidine ) And 0.5 g sodium bicarbonate were 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 was stirred at room temperature for 5 hours. After addition of 0.6 g (3 mmol) of additional 1-aminooxy-2,4-dinitro-benzene, the mixture was stirred for another 3 days at room temperature. The mixture was diluted with saturated aqueous sodium chloride solution and then extracted with ethyl acetate. The organic phase was dried using sodium sulfate and suction filtered using silica gel. The filtrate was concentrated under water pump vacuum and the residue was purified by column chromatography (silica gel, ethyl acetate).

Thus, 3-amino-1- (5-cyano-2,4-dichloro-phenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 ( 0.4 g (20% of theory) of 2H) -pyrimidine were obtained.

Example 3

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 ), A mixture of 0.9 g (6.9 mmol) of dimethylsulfate, 0.6 g of sodium bicarbonate and 100 ml of acetone were heated under reflux for 18 hours. After addition of 0.2 g of dimethyl sulphate, the mixture was heated under reflux for an additional 3 hours, and additional 0.5 ml dimethyl sulphate was added followed by another 18 h. The mixture was then concentrated under water pump vacuum. The residue was shaken with water / ethyl acetate. The organic phase was dried over sodium sulfate and filtered. The filtrate was concentrated under water pump vacuum, the residue was crystallized by decomposition with diisopropyl ether and the product was separated by suction filtration.

Thus, 1- (5-cyano-2,4-dichloro-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 ( 0.6 g (24% of theory) of 2H) -pyrimidine were obtained.

Using the above-mentioned method, the materials listed together with their structural formulas in the following table were also prepared.

Table 1

Example of use

Example A

Germination test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent, the specified amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Seeds of the test plants were planted in ordinary soil. After approximately 24 hours, the active compound preparations were watered in the soil. The amount of water sprayed per unit area is advantageously constant The concentration of the active compound in the formulation is not critical, only the rate of application of the active compound per unit area is important.

After 3 weeks, the degree of damage to the plants is graded as% damage compared to the development of untreated controls.

The figures represent the following:

0% = no effect (like untreated control)

100% = complete relief

In this test, the compounds according to the invention listed in Examples 2, 3 and 6 exhibit 80% or more potency against various weeds at application rates of 60 to 250 g / ha and wheat is well tolerated against them.

Example B

Post Germination Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent, the specified amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Formulations of active compounds are sprayed by applying a specific amount of the desired active compound per unit area to test plants 5-15 cm tall. The concentration of the spray solution was chosen such that a particular concentration of the desired active compound was applied with 1000 liters of water per ha.

After 3 weeks, the extent of damage to the plants was graded as% damage compared to the development of untreated controls.

The figures represent the following:

0% = no effect (like untreated control)

100% = complete relief

In this test, the materials according to the invention listed in Examples 2, 3 and 6 showed 80% or more potency against various weeds at application rates of 60 to 2000 g / ha.

Claims (7)

Phenyl-uracil derivatives of general formula (I): Where R ¹ represents hydrogen, amino, or optionally cyano- or halogen substituted alkyl, R ² represents formyl, hydroxideiminomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl, or optionally cyano- or halogen-substituted alkyl, R ³ represents hydrogen, halogen, or optionally cyano- or halogen-substituted alkyl, R ⁴ represents cyano or thiocarbamoyl, R ⁵ represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, halogen, or the radicals -R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -CQ ¹ -R ⁶ , -CQ ¹ -Q ² -R ⁶ , -CQ ¹ -NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ , -NH-CQ ¹ -R ⁶ , -Q ² -CQ ¹ -Q ² -R ⁶ , -NH-CQ ¹ -Q ² -R ⁶ or -Q ² -CQ ¹ -NH-R ⁶ , and From here, Q represents O, S, SO or SO ₂ , Q ¹ and Q ² independently of each other represent oxygen or sulfur, R ⁶ optionally represents cyano-, halogen-, alkoxy-, alkylthio-, alkylcarbonyl-, alkoxycarbonyl- or alkylaminocarbonyl-substituted alkyl, or In each case optionally represents cyano-, carboxyl-, halogen-, alkylcarbonyl-, alkoxycarbonyl- or alkylamino-carbonyl-substituted alkenyl or alkynyl, In each case optionally represents cyano-, carboxyl-, halogen-, alkylcarbonyl- or alkoxycarbonyl-substituted cycloalkyl or cycloalkylalkyl, In each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio- , Halogenoalkylthio-, alkylsulfinyl-, alkylsulfonyl-, alkylamino- and / or dialkylamino-substituted aryl or arylalkyl, In each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, alkylthio- , Halogenoalkylthio-, alkylsulfinyl-, alkylsulfonyl-, alkylamino- and / or dialkylamino-substituted heterocyclyl or heterocyclylalkyl, n represents the number of 0, 1, 2 or 3. The method of claim 1, R ¹ represents hydrogen or amino, or optionally represents cyano-, fluorine- or chlorine-substituted alkyl having 1 to 4 carbon atoms, R ² represents formyl, hydroxyliminomethyl, cyano, carboxyl, carbamoyl, thiocarbamoyl or optionally alkyl having 1 to 4 carbon atoms, cyano-, fluorine- or chlor-substituted , R ³ represents hydrogen, fluorine, chlorine, bromine or optionally alkyl having 1 to 4 carbon atoms substituted with cyano-, fluorine- or chlorine-substituted, R ⁴ represents cyano or thiocarbamoyl, R ⁵ represents hydroxyl, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine or the radicals -R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -CQ ¹ -R ⁶ , -CQ ¹ -Q ² -R ⁶ , -CQ ¹ -NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ , -NH-CQ ¹ -R ⁶ , -Q ² -CQ ¹ -Q ² -R ⁶ , -NH-CQ ¹ -Q ² -R ⁶ or -Q ² -CQ ¹ -NH-R ⁶ , and From here, Q represents O, S, SO or SO ₂ , Q ¹ and Q ² independently of each other represent oxygen or sulfur, R ⁶ is optionally cyano-, halogen-, C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -alkyl-carbonyl-, C ₁ -C ₄ -alkoxycarbon Alkyl having 1 to 6 carbon atoms, or substituted, or C ₁ -C ₄ -alkylaminocarbonyl-substituted, or In each case optionally cyano-, carboxyl-, halogen-, C ₁ -C ₄ -alkyl-carbonyl-, C ₁ -C ₄ -alkoxy-carbonyl- or C ₁ -C ₄ -alkylamino-carbonyl- Substituted alkenyl or alkynyl having in each case 2 to 6 carbon atoms, or In each case optionally a cyano-, carboxyl-, halogen-, C ₁ -C ₄ -alkyl-carbonyl- or C ₁ -C ₄ -alkoxy-carbonyl-substituted, in each case cycloalkyl group 3 carbon atom Or cycloalkyl or cycloalkylalkyl having from 6 to 6 and optionally having from 1 to 4 carbon atoms in the alkyl moiety, Optionally in each case hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl -, thio carbamoyl -, C ₁ -C ₄ - alkyl -, C ₁ -C ₄ - halogenoalkyl - , C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -halogenoalkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -halogenoalkylthio-, C ₁ -C ₄ -alkyl Sulfinyl-, C ₁ -C ₄ -alkylsulfonyl-, C ₁ -C ₄ -alkylamino- or dimethylamino-substituted, in each case having 6 or 10 carbon atoms in the aryl group and optionally carbon in the alkyl moiety Aryl or arylalkyl having 1 to 4 atoms, Optionally in each case hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl -, thio carbamoyl -, C ₁ -C ₄ - alkyl -, C ₁ -C ₄ - halogenoalkyl - , C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -halogenoalkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -halogenoalkylthio-, C ₁ -C ₄ -alkyl 2-6 carbon atoms and 1-3 nitrogen atoms in the heterocyclyl group substituted by sulfinyl, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkylamino- and / or dimethylamino-substituted, and And / or heterocyclyl or heterocyclylalkyl having one or two oxygen atoms and / or one sulfur atom and optionally having one to four carbon atoms at the alkyl site, n is a phenyl-uracil derivative of formula (I) representing a number of 0, 1, 2 or 3. a) reacting the aminoalkeneic ester of formula (II) with the aryl isocyanate of formula (III), if appropriate in the presence of an acid binder and, if appropriate, in the presence of a diluent, b) reacting the aminoalkenic acid ester of formula (II) with the arylurethane of formula (IV), if appropriate in the presence of an acid binder and, if appropriate, in the presence of a diluent, c) phenyl-uracil derivatives of general formula (la) α) reacting with 1-amino-oxy-2,4-dinitrobenzene of general formula (V) in the presence of an acid binder and, if appropriate, in the presence of a diluent, or β) in each case, if appropriate, in the presence of an acid binder and, if appropriate, in the presence of a diluent, with a sulfate of formula (VI), with a halogen compound of formula (VII), d) A process for the preparation of phenyl-uracil derivatives of formula (I) according to claim 1, characterized in that the phenyl-uracil derivatives of formula (Ib) are reacted with hydrogen sulfide in the presence of a diluent: R ⁹ -Hal (VII) Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are each as defined above, R represents alkyl, aryl or arylalkyl, R ⁷ represents alkyl, aryl or arylalkyl, R ⁸ represents alkyl, R ⁹ represents alkyl, halogenoalkyl or cyanoalkyl, Hal represents chlorine, bromine or iodine. A herbicidal composition comprising at least one phenyl-uracil derivative of formula (I) according to claim 1. Use for weed control of phenyl-uracil derivatives of general formula (I) according to claim 1. A method of controlling weeds, characterized by applying the phenyl-uracil derivative of formula (I) according to claim 1 to weeds and / or their habitats. A process for preparing the herbicide composition, characterized in that the phenyl-uracil derivative of formula (I) according to claim 1 is mixed with an extender and / or a surfactant.