WO1998023598A1

WO1998023598A1 - Phenyl-uracil derivatives with herbicide effect

Info

Publication number: WO1998023598A1
Application number: PCT/EP1997/006367
Authority: WO
Inventors: Roland Andree; Mark Wilhelm Drewes; Markus Dollinger
Original assignee: Bayer Aktiengesellschaft
Priority date: 1996-11-27
Filing date: 1997-11-14
Publication date: 1998-06-04
Also published as: EP0944607A1; DE19649094A1; BR9713546A; CN1253550A; KR20000053150A; JP2001504503A; CA2272657A1; AU5322298A

Abstract

The invention relates to new phenyl-uracil derivatives of formula (I), in which R<1>, R<2>, R<3>, R<4>, R<5> 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

PHENYL-URACIL DERIVATIVES WITH HERBICIDAL EFFECT

The present invention relates to new phenyl uracil derivatives, several processes for their preparation and their use as herbicides.

Certain cyano-phenyl uracils with insecticidal and acaricidal properties have already become known (cf. EP-A 0 438 209, JP-A 05-025 142 and Chem. Abstr. 1 19, 1 17 269). The use of these substances for weed control has not yet been described.

There have now been new phenyl uracil derivatives of the formula

in which

R ^{1 represents} hydrogen, amino or alkyl optionally substituted by cyano or halogen,

R ^{2 represents} formyl, hydroximinomethyl, cyano, carboxy, carbamoyl, thiocarbamoyl or alkyl optionally substituted by cyano or halogen

R ^{3 represents} hydrogen, halogen or alkyl optionally substituted by cyano or halogen,

R ^{4 represents} cyano or thiocarbamoyl,

R ⁵ for hydroxy, mercapto, amino, hydroxyamino, cyano, nitro, halogen, or for one of the radicals -R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -CQ -R ⁶ , -CQ ¹ "Q ² -R ⁶ , -CQ ^ NH-R ⁶ , -Q ² -CQ'-R ⁶ , -NH-CQ ^J -R ⁶ , -Q ² -CQ1-Q2-R6 -NH-CQ ^ Q ^Z -R ⁶ or -Q ² -CQ ¹ -NH-R ⁶ , wherein

Q represents O, S, SO or SO ₂ ,

Q and Q independently of one another represent oxygen or sulfur and

R 'represents alkyl optionally substituted by cyano, halogen, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, represents in each case alkenyl or alkynyl optionally substituted by cyano, carboxy, halogen, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl represents cycloalkyl or cycloalkylalkyl optionally substituted by cyano, carboxy, halogen, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by hydroxy, mercapto, amino, cyano,

Carboxy, carbamoyl, thiocarbamoyl, alkyl, haloalkyl, alkoxy,

Haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino and / or dialkylamino, aryl or arylalkyl which is substituted or is in each case optionally substituted by hydroxyl, mercapto, amino, cyano,

Carboxy, carbamoyl, thiocarbamoyl, alkyl, haloalkyl, alkoxy,

Halogenalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino and / or dialkylamino substituted heterocyclyl or heterocyclylalkyl, and

n represents the numbers 0, 1, 2 or 3,

found.

It has also been found that phenyl uracil derivatives of the formula (I) are obtained when Aminoalkenates of the formula

in which

R ² and R ^{1 have} the meanings given above and

R represents alkyl, aryl or arylalkyl,

with aryl isocyanates of the formula

in which

R ⁴ , R ⁵ and n have the meanings given above,

optionally in the presence of an acid binder and optionally in

In the presence of a diluent,

or

b) aminoalkenates of the formula

in which

R, R ² and R ^{3 have} the meanings given above,

with aryl urethanes of the formula

in which

R ⁴ , R ⁵ and n have the meanings given above and

R ^{7 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

R ² , R, R ⁴ , R and n have the meanings given above,

either

α) with l-amino-oxy-2,4-dinitrobenzene of the formula

or

β) with sulfates of the formula

in which R> κ ^{Λ represents} alkyl,

or

with halogen compounds of the formula

R ⁹ -Hal (VII),

in which

R ^{9 represents} alkyl, haloalkyl or cyanoalkyl and

Shark represents chlorine, bromine or iodine,

or

d) phenyl uracil derivatives of the formula

R 'ι

(lb),

FT

(R ⁵ ) n

in which

R ¹ , R ² , R ³ , R ⁵ and n have the meanings given above, reacted with hydrogen sulfide in the presence of a diluent.

Finally, it was found that the phenyluracil derivatives of the formula (I) have very good herbicidal properties.

Surprisingly, the phenyluracil derivatives of the formula (I) according to the invention have a substantially better herbicidal activity than the constitutionally most similar, previously known substances of the same action.

The phenyl uracil derivatives according to the invention are generally defined by the formula (I).

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkynyl - also in connection with heteroatoms, such as in alkoxy or alkylthio - are each straight-chain or branched.

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

Preferred are phenyl uracil derivatives of the formula (I) in which

R ^{1 represents} hydrogen, amino or alkyl having 1 to 4 carbon atoms which is optionally substituted by cyano, fluorine or chlorine,

R ^{2 represents} formyl, hydroximinomethyl, cyano, carboxy, carbamoyl, thiocarbamoyl or alkyl having 1 to 4 carbon atoms which is optionally substituted by cyano, fluorine or chlorine,

R ^{3 represents} hydrogen, fluorine, chlorine, bromine or, if appropriate, by cyano,

Fluorine or chlorine substituted alkyl having 1 to 4 carbon atoms,

R ^{4 represents} cyano or thiocarbamoyl, for hydroxy, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine or for one of the radicals -R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -CQi-R ⁶ , -CQ ^ Q ^ R ⁶ , -CQ ⁱ -NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ , -NH-CQ ^ R ⁶ , -Q ² -CQ! - Q ² -R ⁶ , -NH-CQ ^J -Q ² ^ ⁶ or -Q ² -CQ ¹ -NH-R ⁶ , wherein

Q represents O, S, SO or SO ₂ ,

Q ¹ and Q ² independently of one another represent oxygen or sulfur and

R ⁶ for optionally by cyano, halogen, C1-C4- alkoxy, Cι-C -

Alkylthio, -CC ₄ -alkyl carbonyl, CC ₄ - alkoxycarbonyl or CC - alkylaminocarbonyl substituted alkyl having 1 to 6 carbon atoms, for each optionally by cyano, carboxy, halogen, C1-C4-

Alkylcarbonyl, Cj-C ^ alkoxy-carbonyl or C 1 -C4-alkylamino-carbonyl-substituted alkenyl or alkynyl each having 2 to 6 carbon atoms, optionally for cyano, carboxy, halogen, Cj-C4-alkylcarbonyl or Cι -C4 -Alkoxy-carbonyl substituted cycloalkyl or

Cycloalkylalkyl, each with 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C1-C4-alkyl, C 1 -C4 -Halogen- alkyl, C1-C4-alkoxy, C 1 -C4-haloalkoxy, C 1 -C4-alkylthio, C \ - C4-haloalkylthio, Cj-C4-alkylsulfinyl, Cj-C4-alkylsulfonyl, C \ - C4-alkylamino and / or dimethylamino substituted aryl or arylalkyl each having 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part or for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, Cj-C4-alkyl , Cj-C4-haloalkyl, C] -C4-alkoxy, C \ -C4-haloalkoxy, C \ -C4-alkylthio, C] _C4-haloalkylthio, C] -C4 alkylsulfionyl, C -C4 alkylsulfonyl, C i -C4 alkylamino and / or dimethylamino substituted heterocyclic or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and / or 1 or 2 oxygen atoms and / or a sulfur atom in the heterocyclyl group and optionally 1 to 4

Carbon atoms in the alkyl part, and

n stands for the numbers 0, 1, 2 or 3.

Phenyluracil derivatives of the formula (I) in which

R ^{1 represents} hydrogen, amino, methyl or ethyl,

R ^{2 stands} for formyl, hydroximinomethyl, cyano, carboxy, carbamoyl, thiocarbamoyl or for methyl or ethyl which is optionally substituted by fluorine or chlorine,

R ^{3 represents} hydrogen, chlorine or methyl or ethyl which is optionally substituted by fluorine or chlorine,

R ^{4 represents} cyano or thiocarbamoyl,

R ⁵ for hydroxy, mercapto, amino, hydroxyamino, cyano, nitro, fluorine, chlorine, bromine, or for one of the radicals R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -CO R ⁶ , -CQ QR ⁶ , -CQ NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ , -NH-CQ ^! -R ⁶ , -Q ² -CQ

Q ² -R ⁶ , -NH-CQ OR ⁶ or -Q ² -CQ ¹ -NH-R ⁶ ,

wherein

Q represents O, S, SO or SO ₂ ,

Q ¹ and Q ² independently of one another represent oxygen or sulfur and

R ⁶ for each optionally by 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 propenyl, butenyl, propynyl or butynyl which is optionally substituted by cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl, or represents in each case optionally by cyano, carboxy, fluorine, chlorine ,

Bromine, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or for each optionally by hydroxy, mercapto, amino,

Cyano, carboxy, 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 for each optionally by hydroxy, mercapto, amino, cyano , 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, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl,

Methylamino, ethylamino, n- or i-propylamino and / or dimethylamino substituted heterocyclyl or heterocyclylalkyl from the series oxiranyl, oxetanyl, furyl, tetrahydrofüryl, dioxolanyl, thienyl, tetra-hydrothienyl, pyrrolyl, pyrazolyl, azidylylolol, imidazyloxolol, imidazyloxolol, imidazyloxolyl, imidazyloxolyl, imidazyloxolol, imidazyloxolyl, imidazyloxolyl, imidazyloxolol, imidazyloxolyl, imidazyloxol , Thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl,

Pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl and pyrimidinylmethyl, and

n stands for the numbers 1 or 2.

The general or preferred radical definitions listed above apply both to the end products of the formula (I) and correspondingly for the starting or intermediate products required for the production. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.

If, for example, 3-amino-crotonic acid methyl ester and 3-cyano-5-fluoro-4-trifluoromethyl-phenyl isocyanate are used as starting materials, the course of the reaction in process (a) according to the invention can be outlined using the following formula:

If methyl 3-amino-crotonic acid and N- (3-cyano-5-fluoro-4-trifluoromethyl-phenyl) -carbamic acid methyl ester are used as starting materials, the course of process (b) according to the invention can be illustrated by the following formula .

If 1 - (5-cyano-2,4-dichlorophenyl) -3, 6-dihydro-2, 6-dioxo-4-trifluoromethyl-l (2H) -pyrimidine is used as the starting material and l-aminooxy-2,4 -dinitro-benzene as

Reaction component, the course of the process (c, variant α) can be illustrated by the following formula.

If l- (5-cyano-2,4-dichlorophenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-l (2H) -pyrimidine is used as the starting material and dimethyl sulfate as the reaction component, then the course of the process according to the invention (c, variant β) can be illustrated by the following formula.

If l- (5-cyano-2,4-dichlorophenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-l (2H) -pyrimidine is used as the starting substance and hydrogen sulfide as the reaction component , the course of process (d) according to the invention can be illustrated by the following formula.

Formula (II) provides a general definition of the aminoalkenic esters required as starting materials when carrying out process (a) and (b) according to the invention. In formula (II), R ² and R ³ preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention, preferably or as particularly preferred for R ² and R ³ preferably represents alkyl with 1 to 4 carbon atoms, phenyl or benzyl. R particularly preferably 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).

Formula (III) provides a general definition of the aryl isocyanates required as reaction components when carrying out process (a) according to the invention. In the formula (III), R ⁴ , R ⁵ and n preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R ⁴ , R ⁵ and n were specified.

The starting materials of the formula (III) are known or can be prepared by known processes (cf. Tetrahedron Lett. 1967, 961-962; EPA 0 063 905, EP-

A 0 093 610, EPA 0 093 620, EPA 0 397 052 and EPA 0 572 782).

Aryl isocyanates of the formula (III) can be prepared by using anilines of the formula

in which

R ⁴ , R ⁵ and n have the meanings given above,

with phosgene in the presence of a diluent, e.g. Chlorobenzene, at temperatures between -20 ° C and + 150 ° C.

Formula (IV) provides a general definition of the aryl urethanes required as reaction components when carrying out process (b) according to the invention. In the formula (IV), R ⁴ , R ⁵ and n preferably or particularly preferably have those meanings which have already been mentioned above in connection with the description of the Compounds of the formula (I) according to the invention have been indicated preferably or as particularly preferred for R ⁴ , R ⁵ and n; R ⁷ preferably represents CC ₄ -alkyl, phenyl or benzyl, in particular methyl, ethyl or phenyl.

The aryl urethanes of the formula (IV) are known or can be prepared by known processes (cf. EPA 0 063 905).

Aryl urethanes of the formula (IV) are thus obtained by using anilines of the formula

in which

R ⁴ , R ⁵ and n have the meaning given above,

with chlorocarbonyl compounds of the formula

R ⁷ O-CO-Cl (IX),

in which

R ^{7 has} the meaning given above,

optionally in the presence of an acid acceptor, such as pyridine, and optionally in the presence of a diluent, such as methylene chloride, at temperatures between -20 ° C and + 100 ° C. The phenyluracil derivatives of the formula (Ia) required as starting materials when carrying out process (c) according to the invention are compounds according to the invention which can be prepared by processes (a) or (b) according to the invention.

That when performing the method according to the invention (c, variant α) as

Reaction component required 1-aminooxy-2,4-dinitro-benzene of the formula (V) is known (cf. J. Heterocycl. Chem. 4 (1967), 413-414).

Formula (VI) provides a general definition of the sulfates required as reaction components when carrying out the process (c, variant β). In this formula, R ⁸ preferably represents alkyl having 1 to 4 carbon atoms, particularly preferably methyl or ethyl.

The halogen compounds which can also be used as reaction components when carrying out the process (c, variant β) are as follows:

Formula (VII) generally defined. In this formula, R ⁹ preferably represents alkyl, cyanoalkyl, fluoroalkyl or chloroalkyl each having 1 to 4 carbon atoms. Shark is preferably bromine or iodine.

R ⁹ particularly preferably represents methyl or ethyl.

Shark is also particularly preferably bromine or iodine.

The phenyluracil derivatives of the formula (Ib) required as starting materials when carrying out process (d) according to the invention are compounds according to the invention which can be prepared by processes (a), (b) or (c) according to the invention.

All conventional inorganic and organic acid acceptors are suitable as acid binders when carrying out processes (a) to (c)

Consider. Alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium, or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, sodium - or potassium methanolate, ethanolate, n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N, N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N, N-dimethylaniline, N, N- Dimethyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-M ethyl, 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).

Suitable diluents for carrying out processes (a) and (b) according to the invention are all customary inert organic solvents. Aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, 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 or diethyl ether; Ketones, such as acetone,

Butanone or methyl isobutyl ketone; Nitriles, such as acetonitrile, propionitrile or butylonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone 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, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether.

The reaction temperatures can be varied within a substantial range when carrying out processes (a) and (b) according to the invention. In general, temperatures between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C. Processes (a) to (c) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to work under increased pressure or, if no volatile components are used, under reduced pressure.

Suitable diluents for carrying out process (c) according to the invention are all inert organic solvents which are customary for such reactions. In the reaction according to variant (α) aprotic polar solvents, such as e.g. N, N-dimethylformamide and N-methylpyrrolidone.

In the reaction according to variant (ß), aprotic, polar solvents such as e.g. Acetone, acetonitrile, N, N-dimethylformamide and dimethyl sulfoxide.

When carrying out process (c) according to the invention, the reaction temperatures can also be varied within a certain range. The variant (α) is generally carried out at temperatures between 0 ° C. and 100 ° C., preferably between 10 ° C. and 50 ° C. The variant (β) is generally carried out at temperatures between 0 ° C. and 200 ° C., preferably between 10 ° C. and 120 ° C.

Suitable diluents for carrying out process (d) according to the invention are all inert organic solvents which are customary for such reactions. Hydrocarbons such as e.g. Toluene, or also organic bases, such as e.g. Pyridine, triethylamine and tributylamine.

When carrying out process (d) according to the invention, the reaction temperatures can also be varied within a certain range. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 100 ° C. When carrying out process (d) according to the invention, the process is optionally carried out under elevated pressure, preferably under a pressure between 1 and 5 bar.

To carry out 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 larger excess. 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. Working up is carried out according to customary methods (cf. the production examples).

The phenyluracil derivatives of the formula (I) according to the invention are notable for strong herbicidal activity. They also show good tolerance to important crops, such as Wheat.

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention as total or selective

Herbicides act essentially depends on the amount used.

The active compounds according to the invention can e.g. can be used in the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abuti- Ion, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus,

Taraxacum. Dicotyledon cultures of the genera Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita

Monocotyledonous weeds of the genera Echmochloa, Setaπa, Panicum, Digitaπa, Phleum, Poa, Festuca, Eleusine, Brachiaπa, Lo um, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoπa, Fimbπstyp, Eleusanspasum, Sagittapal, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera

Monocot cultures of the genera Oryza, Zea, Tπticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Alhum

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to others

plants

Depending on the concentration, the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, for example forest, ornamental wood, fruit, wine , Citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture fields and for selective weed control in annual crops

The compounds of formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon crops both in the pre-emergence and in the post-emergence process

The active ingredients can be converted into the usual formulations, such as

Solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances as well as very fine encapsulations in polymeric substances These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents are essentially suitable. Aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as

Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water

Solid carrier materials are possible: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silicic acid, aluminum oxide and silicates are used as solid carriers for granules

Question e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, as emulsifiers and / or foam-generating agents Question, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates, and dispersants include, for example, lignin sulfite waste liquors and methyl cellulose

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho- lipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

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

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.

Known herbicides are suitable for the mixtures, for example acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benzazoline, benfuresate, bensulfuron (-methyl) , Bentazon, Benzofenap, Benzoylprop (- ethyl), Bialaphos, Bifenox, Bromobutide, Bromofenoxim, Bromoxynil, Butachlor,

Butylates, Cafenstrole, Carbetamides, Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cinmethylin, Cinosulfuro, Clethodim, Clodinafop (-propargyl), Clomazone, Clopulfulamon, Clopyrulamone, Clopyrulamone, Clopyrulamone, Clopyrulamone, Clopyrulamone, Clopyrulamon, Pyrethanol Cumyluron, cyanazines, cycloates, cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham,

Dialallate, dicamba, diclofop (-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamide, diquat, dithiopyr, diuron, dymron, EPTC, esprocarbon, ethalfletsuron, ethalfletsuron -methyl), ethofumesate, ethoxyfen, etobenzanide, 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), Imazamethazyr, Imazamoxaza, Imazamoxaza, Imazamoxaza Imazethapyr, Imazosulfuron, Ioxynil, Isopropalin, Isoproturon, Isoxaben, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA,

MCPP, Mefenacet, Meta itron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (- methyl), Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Norbenzonon, Nicbenulonazon, Nicalinulazuron, Nicalinulazuron, Nicalinulazuron, Nicalinulazuron Oxyfluorfen, paraquat, penimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron (-methyl),

Prometryn, Propachlor, Propanil, Propaquizafop, Propyzamide, Prosulfocarb, Prosulfonon, Pyrazolate, Pyrazosulfuron (-ethyl), Pyrazoxyfen, Pyributicarb, Pyridate, Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quizalofop (-ethyl), Quizalofop (-ethyl) - 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 Triflusulfur.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is 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 usual way, e.g. by pouring, spraying, spraying, sprinkling.

The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing. The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.

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

Manufacturing examples:

example 1

A mixture of 8.1 g (27 mmol) of 3-amino-4,4,4-trifluoro-crotonic acid ethyl ester, 7.5 g of potassium carbonate and 100 ml of N-methyl-pyrrolidone is heated for one hour on a water separator. Then 7.0 g (27 mmol) of N- (5-cyano-2,4-dichlorophenyl) -O-ethyl-urethane are added, and the reaction mixture is stirred at 130 ° C. for a further 4 hours. After cooling to room temperature, the mixture is diluted to about four times the volume with approximately equal volumes of water and ethyl acetate and acidified to approximately pH 3 with concentrated hydrochloric acid. After shaking well, the organic phase is separated off and the aqueous phase is extracted with ethyl acetate. The combined organic phases are dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum.

5.1 g (54% of theory) of l- (5-cyano-2,4-dichlorophenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) - are obtained. pyrimidine.

Example 2

2.0 g (5.7 mmol) of 1- (5-cyano-2,4-dichlorophenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) pyrimidine and 0.5 g of sodium hydrogen carbonate are placed in 50 ml of N, N-dimethylformamide. After addition of 0.6 g (3 mmol) of l-aminooxy-2,4-dinitro-benzene, the reaction mixture is stirred for 5 hours at room temperature. After adding a further 0.6 g (3 mmol) of 1-aminooxy-2,4-dinitro-benzene, the mixture is stirred for a further three days at room temperature. After dilution with saturated, aqueous sodium chloride solution, the mixture is shaken out with ethyl acetate. The organic phase is dried with sodium sulfate and suction filtered through silica gel. The filtrate is concentrated in a water jet vacuum and the residue is purified by column chromatography (silica gel, ethyl acetate).

0.4 g (20% of theory) of 3-amino-1- (5-cyano-2,4-dichlorophenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-l is obtained (2H) pyrimidine, melting point 198 ° C.

Example 3

A mixture of 2.4 g (6.9 mmol) l- (5-cyano-2,4-dichlorophenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-l (2H) - pyrimidine, 0.9 g (6.9 mmol) of dimethyl sulfate, 0.6 g of sodium hydrogen carbonate and 100 ml of acetone are heated under reflux for 18 hours. After adding a further 0.2 g of dimethyl sulfate, the mixture is heated under reflux for a further 3 hours and after adding a further 0.5 ml of dimethyl sulfate. Then it is concentrated in a water jet vacuum. The residue is shaken with water / ethyl acetate. The organic phase is dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum, the residue is crystallized by digestion with diisopropyl ether and the product is isolated by suction. 0.6 g (24% of theory) of l- (5-cyano-2,4-dichlorophenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-l is obtained (2H) -pyrimidine, melting point 161 ° C.

The substances listed in the following table are also manufactured according to the methods given above.

Table 1

Examples of use:

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 about 24 hours, the active ingredient preparation is poured onto the floor. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:

0% = no effect (like untreated control)

100% = total annihilation

In this test, the substances according to the invention listed in Examples 2, 3 and 6, at application rates of 60 to 250 g / ha and with good tolerance to wheat, show an efficiency of 80% or more against various weeds. Example B

Post emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the specified amount is given

Amount of emulsifier and dilute the concentrate with water to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 1000 l of water / ha. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:

0% = no effect (like untreated control)

100% = total annihilation

In this test, the substances according to the invention listed in Examples 2, 3 and 6 show an efficiency of 80% or more compared to various weeds at application rates between 60 and 2000 g / ha.

Claims

claims

Phenyl uracil derivatives of the formula

in which

R ^{4 represents} cyano or thiocarbamoyl,

R ⁵ for hydroxy, mercapto, amino, hydroxyamino, cyano, nitro, halogen, or for one of the radicals -R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH- SO ₂ -R ⁶ , -CQ ⁶ , -CQ -QR ⁶ , -CQϊ-NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ _; _NH-CQ! -R ⁶ ₃ -Q ² -CQ ¹ -Q2.R6 ₎ -NH-CQ ⁱ -Q ^ R ⁶ or -Q ² -CQ NΗ-R ⁶ , in which

Q represents O, S, SO or SO ₂ , Q ¹ and Q ² independently of one another represent oxygen or sulfur and

R ^{6 represents} alkyl optionally substituted by cyano, halogen, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, represents in each case optionally substituted by cyano, carboxy, halogen, alkylcarbonyl, alkoxycarbonyl or alkylamino-carbonyl or alkynyl, in each case optionally by cyano , Carboxy, halogen,

Alkylcarbonyl or alkoxycarbonyl-substituted cycloalkyl or cycloalkylalkyl represents, in each case optionally by hydroxyl, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,

Alkylsulfinyl, alkylsulfonyl, alkylamino and / or dialkylamino substituted aryl or arylalkyl or each in each case optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,

Alkylsulfinyl, alkylsulfonyl, alkylamino and / or dialkylamino substituted heterocyclyl or heterocyclylalkyl, and

n stands for the numbers 0, 1, 2 or 3.

Phenyluracil derivatives of the formula (I) according to Claim 1, in which

R 2 stands for formyl, hydroximinomethyl, cyano, carboxy, carbamoyl, thiocarbamoyl or for alkyl with 1 to 4 carbon atoms optionally substituted by cyano, fluorine or chlorine, R ^"represents hydrogen, fluorine, chlorine, bromine or alkyl having 1 to 4 carbon atoms which is optionally substituted by cyano, fluorine or chlorine,

R represents cyano or thiocarbamoyl,

R ⁵ for hydroxy, mercapto, amino, hydroxyamino, cyano, nitro, fluorine,

Chlorine, bromine or for one of the radicals -R ⁶ , -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -CQ R ⁶ , -CQ ⁱ 'OR ⁶ , - CQ NH-R ⁶ , - CQ R ^Ö ,

-NH-CQ! -R6 _; -Q2_CQ1-Q ² -R6, -NH-CQi-Q ^ R ⁶ or -Q ² -CQ ^[ -NH- R ⁶ , wherein

Q represents O, S, SO or SO ₂ ,

Q and Q ² independently of one another represent oxygen or sulfur and

R ^{6 is} optionally substituted by cyano, halogen, -C-alkoxy, d- C ₄ -alkylthio, -C-C-alkylcarbonyl, Cj-C -alkoxy-carbonyl or C -C -alkylamino-carbonyl substituted alkyl with 1 to 6 carbon atoms, each optionally by cyano, carboxy, halogen, C \ -

C4-alkyl-carbonyl, C] -C4-alkoxy-carbonyl or -CC4-alkyl-amino-carbonyl-substituted alkenyl or alkynyl each having 2 to 6 carbon atoms, optionally for cyano, carboxy, halogen, C1 -C4-

Alkyl carbonyl or -C -C4 alkoxy carbonyl substituted

Cycloalkyl or cycloalkylalkyl each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4

Carbon atoms in the alkyl part, in each case optionally by hydroxyl, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C 1 -C 4 -alkyl, C i -C4 haloalkyl, C \ -C4 alkoxy, C 1 -C4 haloalkoxy, C1-C4 alkylthio, C 1 -C haloalkylthio, C1-C4 alkylsulfinyl, C1-C4 alkyl sulfonyl, C \ -C4 -Alkylamino and / or dimethylamino substituted aryl or arylalkyl each having 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part or for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, Cj-C4 -Alkyl, Cι -C4-haloalkyl, C1-C4- alkoxy, Cj-C4-haloalkoxy, C! -C -alkylthio, Cι_C4-haloalkylthio, C1-C4-alkylsu.fi- nyl, C1 -C4- alkylsulfonyl, 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 a sulfur atom in the heterocyclyl group and optionally 1 to 4

Carbon atoms in the alkyl part, and

n stands for the numbers 0, 1, 2 or 3.

Process for the preparation of phenyluracil derivatives of the formula (I) according to

Claim 1, characterized in that one

a) Aminoalkenic acid esters of the formula

in which

R ² and R ^{3 have} the meanings given above and

R represents alkyl, aryl or arylalkyl, with aryl isocyanates of the formula

in which

R ⁴ , R ⁵ and n have the meanings given above,

or

b) aminoalkenic acid esters of the formula

in which

R, R ² and R ^{3 have} the meanings given above,

with aryl urethanes of the formula

in which

R ⁴ , R ⁵ and n have the meanings given above and

R ^{7 represents} alkyl, aryl or arylalkyl,

or

c) phenyl uracil derivatives of the formula

in which

R, R, R, R and n have the meanings given above,

either

α) with l-amino-oxy-2,4-dinitrobenzene of the formula

or

β) with sulfates of the formula

in which

R ^{x represents} alkyl,

or

with halogen compounds of the formula

R ⁹ -Hal (VII),

in which

R ^{9 represents} alkyl, haloalkyl or cyanoalkyl and

Shark represents chlorine, bromine or iodine,

or d) phenyl uracil derivatives of the formula

in which

R, R, R °, R and n have the meanings given above,

reacted with hydrogen sulfide in the presence of a diluent.

4. Herbicidal agents, characterized in that they contain at least one phenyluracil derivative of the formula (I) according to Claim 1.

5. Use of phenyl uracil derivatives of the formula (I) according to Claim 1 for combating weeds.

6. A method of combating weeds, characterized in that phenyl uracil derivatives of the formula (I) according to claim 1 are applied to the weeds and / or their habitat.

Process for the preparation of herbicidal compositions, characterized in that phenyluracil derivatives of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active substances.