KR100345044B1 - N-cyanoaryl-nitrogen heterocycle - Google Patents

Abstract

The present invention relates to novel N-cyanoaryl-nitrogen heterocycles of the general formula (I), various preparations thereof, their use as herbicides and novel intermediates.

In the above formula,

R ¹ , R ² , R ³ , R ⁴ and Z are as defined in the specification.

Description

N-cyanoaryl-nitrogen heterocycle

The present invention relates to novel N-cyanoaryl-nitrogen heterocycles, various processes for their preparation, their use as herbicides and novel intermediates.

Some N-cyanoaryl-nitrogen heterocycles are already known to have herbicidal activity (see WO 91/00278, WO 92/11244, DE 4237920, EP 408382 / US 5084084, EP 438209 and EP 473551).

However, the previously known herbicidal activity or applicability to crops of N-cyanoaryl-nitrogen heteroterocycles is not entirely satisfactory.

According to the present invention a novel N-cyanoaryl-nitrogen heterocycle of the general formula (I) and salts thereof are disclosed, provided that the compound 1- (4-cyano-3-ethylsulfonyl is described in US 5084084. Amino-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine, 1- (4-cyano-3-n- Propylsulfonylamino-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine, 1- (4-cyano-3 -Isopropylsulfonylamino-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine, 1- (4-cyano -5-ethylsulfonylamino-2-fluoro-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine, 1 -(4-cyano-5-n-propylsulfonylamino-2-fluoro-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine and 1- (4-cyano-5-isopropylsulfonylamino-2-fluoro -Phenyl) -3,6-dihydro-2,6-dioxo-methyl-4-trifluoromethyl-1 (2H) -pyrimidine is excluded here.

In the above formula,

R ¹ represents hydrogen or halogen,

R ² represents halogen, cyano, amino or the group -N (A ¹ ) S0 ₂ A, wherein A is each optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, aryl Alkyl, heterocyclyl or heterocyclylalkyl, A ¹ is hydrogen or optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, arylalkylcarbonyl or aryloxy Carbonyl,

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

R ⁴ represents optionally substituted alkyl or, together with R ³ , represents alkanediyl,

Z represents one of the following groups,

In the above formula,

R ⁵ represents hydrogen, amino (bonded to N only) or optionally substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl, respectively.

Therefore, general formula (I) represents isomer compounds of the following general formulas (IA) and (IB).

The novel N-cyanoaryl-nitrogen heterocycles of formula (I) and salts thereof comprise (a) an aminoalkenoic acid ester of formula (II), optionally in the presence of a reaction aid, In the presence, reacted with cyanoaryl isocyanate of formula (III) or with cyanoarylurethane (cyanoaryl carbamate) of formula (IV), R ⁵ is hydrogen, R ¹ , R ² , R ³ and R ⁴ prepare compounds of formulas (IA) and (IB) having the abovementioned meanings, or

(b) R ⁵ is hydrogen and R ¹ , R ² , R ³ and R ⁴ represent an N-cyanoaryl-nitrogen heterocycle of the general formula (IA) or (IB), Accordingly in the presence of an acid acceptor and optionally in the presence of a diluent, reacting with an alkylating or acylating agent of the general formula (V) or (VI) in which R ⁵ is optionally substituted alkyl, alkenyl, alkynyl, alkyl Represent carbonyl or alkoxycarbonyl, and R ¹ , R ² , R ³ and R ⁴ prepare compounds of general formula (IA) and / or (IB) having the meanings mentioned above, or

(c) R ² represents halogen and R ¹ , R ³ , R ⁴ and Z represent N-cyanoaryl-nitrogen heterocycles of the general formula (I) having the abovementioned meaning, In the presence and optionally in the presence of a diluent, reacted with ammonia or an amide of formula (VII), R ² represents amino or a group -N (A ¹ ) SO ₂ A, and A, A ¹ , R ¹ , R ³ , R ⁴ and Z are obtained by preparing compounds of general formula (I) having the abovementioned meanings.

In the above formula,

R ¹ , R ² , R ³ , R ⁴ , A and, A ¹ have the above-mentioned definitions,

R ⁵ in each occurrence represents optionally substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl,

In general formula (V), X represents a halogen.

Compounds of the general formula (IA) in which R ⁵ represents amino represent a corresponding compound of the general formula (IA) in which R ⁵ represents hydrogen, for example, 1-aminooxy-2,4-dinitro-benzene according to the following formula ( It can be prepared by conventional methods by reacting with an aminoating agent such as ADNB).

(See EP 476697, Example 4).

The novel N-cyanoaryl-nitrogen heterocycles of formula (I) and salts thereof are characterized by strong herbicidal activity.

In the definition, saturated or unsaturated hydrocarbon chains such as alkyl, alkanediyl, alkenyl or alkynyl are in each case straight or branched. Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

The present invention preferably

R ¹ represents hydrogen, fluorine, chlorine or bromine,

R ² represents fluorine, chlorine, bromine, cyano, amino or group -N (A ¹ ) SO ₂ A,

From here,

A represents a radical selected from the series each having up to 10 carbon atoms and each comprising alkyl, alkenyl or alkynyl optionally substituted by fluorine, chlorine, bromine, cyano or C _1-4 -alkoxy, or

A also has 3 to 8 carbon atoms each at the cycloalkyl moiety and optionally 1 to 4 carbon atoms at the alkyl moiety, each optionally substituted by fluorine, chlorine, bromine, cyano or C _1-4 -alkyl Cycloalkyl or cycloalkylalkyl, or

A also has 6 or 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, respectively, by fluorine, chlorine, bromine, cyano, nitro, carboxyl, carbamoyl, or fluorine and / or respectively Or C _1-4 -alkyl, C _1-4 -alkoxy, C _1-4 -alkylthio, C _1-4 -alkylsulfinyl or C _1-4 -alkylsulfonyl, optionally substituted by chlorine, or By dimethyl aminosulfonyl or diethylaminosulfonyl or by C _{1-4 -alkoxycarbonyl} optionally substituted by fluorine, chlorine, bromine, methoxy or ethoxy, or fluorine, chlorine, bromine, cya, respectively Aryl or arylalkyl optionally substituted by phenyl, phenyloxy or phenylthio optionally substituted by furnace, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy, or

A also has 2 to 6 carbon atoms and 1 to 4 nitrogen atoms and / or 1 or 2 oxygen or sulfur atoms at each saturated or unsaturated heterocyclyl moiety and optionally 1 to 4 carbon atoms at the alkyl moiety C _1-4 -alkyl, C _1-4 -alkoxy, C _1- optionally substituted with fluorine, chlorine, bromine, cyano, nitro, carboxyl, carbamoyl, or each with fluorine and / or chlorine ₄ -alkylthio, C _1-4 -alkylsulfinyl, C _1-4 -alkylsulfonyl or C _1-4 -alkoxycarbonyl or fluorine, chlorine, bromine, cyano, methyl, methoxy, Heterocyclyl or heterocyclylalkyl optionally substituted by phenyl, phenoxy or phenylthio optionally substituted by trifluoromethyl and / or trifluoromethoxy,

A ¹ represents hydrogen or alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl or alkoxycarbonyl, each having up to 6 carbon atoms and each optionally substituted by halogen or C _1-4 -alkoxy, or Phenylcarbonyl, naphthylcarbonyl, phenylmethylcarbonyl, naphthylmethylcarbonyl, optionally substituted with fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy, respectively, Phenoxycarbonyl or naphthyloxycarbonyl,

R ³ represents hydrogen, fluorine, chlorine, bromine, cyano, or alkyl optionally substituted by fluorine and / or chlorine and having 1 to 6 carbon atoms,

R ⁴ represents alkyl optionally substituted by fluorine, chlorine, bromine, methoxy or ethoxy and having 1 to 6 carbon atoms, or represents alkanediyl having 2 to 8 carbon atoms together with R ³ ,

Z represents one of the following groups,

From here,

R ⁵ represents hydrogen or amino, or each has up to 6 carbon atoms and each represents fluorine, chlorine, bromine, cyano, C _1-4 -alkoxy, C _1-4 -alkyl-carbonyl or C _1-4 A compound of formula (I) representing alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl, optionally substituted by alkoxy-carbonyl, and hydroxides, hydrides, amides of sodium, potassium or calcium thereof; Carbonate, sodium or potassium C _1-4 -alkanolate, ammonia, C _1-4 -alkylamine, di- (C _1-4 -alkyl) -amine, tri- (C _1-4 -alkyl) -amine or It relates to salts with bases such as tris- (2-hydroxyethyl) amine, except the known compounds mentioned above in general formula (I).

In particular,

R ¹ represents hydrogen, fluorine or chlorine,

R ² represents fluorine, chlorine, bromine, cyano, amino or group -N (A ¹ ) SO ₂ A,

From here,

A represents methyl, ethyl, n- or i-propyl, n-i-, s- or t-butyl or n-, i-, s- or t-pentyl, each optionally substituted by fluorine or chlorine, or

A also represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by fluorine, chlorine, bromine, methyl and / or ethyl ,

A is also fluorine, chlorine, bromine, cyano, nitro, carboxy, methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, Phenyl, naphthyl, phenylmethyl or phenylethyl optionally substituted by ethylsulfityl, methylsulfonyl, ethylsulfonyl, dimethylaminosulfonyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or phenyl Or

A is also fluorine, chlorine, bromine, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, Thienyl, pyrazolyl or pyridyl optionally substituted by methoxycarbonyl or ethoxycarbonyl,

A ¹ is hydrogen or methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl optionally substituted by fluorine, chlorine, methoxy or ethoxy, respectively , Butynyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, or Phenylcarbonyl or phenoxycarbonyl,

R ³ represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, ethyl or n- or i-propyl,

R ⁴ represents methyl, ethyl, n- or i-propyl, each optionally substituted with fluorine or chlorine, or represents trimethylene or tetramethylene together with R ³ ,

Z represents one of the following groups,

From here,

R ⁵ is hydrogen, amino, or methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl, optionally substituted by fluorine, chlorine or cyano, respectively, A compound of formula (I) representing butynyl, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, and hydroxides, hydrides, amides or carbonates of sodium, potassium or calcium, sodium or potassium C _{1- 4} -alkanolate, ammonia, C _1-4 -alkylamine, di- (C _1-4 -alkyl) -amine, tri- (C _1-4 -alkyl) -amine or tris- (2-hydroxyethyl ) Salts with bases such as amines, with the exception of the known compounds mentioned above in general formula (I).

A very particularly preferred group of compounds of formula (1) are those of formula (14), wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meaning given as particularly preferred above.

The general radical definitions mentioned above, or the definitions given in the preferred ranges, all apply to the final product of general formula (I), and similarly also apply to the starting materials or intermediates necessary in each case in the preparation.

These radical definitions may optionally be combined with one another, ie combinations between the given ranges of preferred compounds are possible.

Examples of compounds of the general formula (I) according to the invention are shown in Table 1 below.

For example, when methyl 3-aminocrotonate and 4-cyano-2,5-difluorophenyl isocyanate are used as starting materials, the reaction process of the method (a) according to the present invention can be summarized as follows. Can:

For example, 1- (3-chloro-4-cyano-phenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) -pyrimidine and methyl bromide When using as starting material, the reaction process of the method (b) according to the present invention can be summarized by the following formula:

For example, 1- (4-cyano-2,5-difluoro-phenyl) -3,6-dihydro-3,4-dimethyl-2,6-dioxo-1 (2H) -pyrimidine And when ethanesulfonamide is used as starting material, the reaction process of process (c) according to the invention can be summarized by the following formula:

Formula (II) provides a general definition of aminoalkenoic acid esters which are used as starting materials in the process (a) according to the invention for the preparation of compounds of formula (I).

In the general formula (II), R ³ and R ⁴ are preferably or especially meaning mentioned as preferred or particularly preferred for R ³ and R ⁴ in the above definitions of the compounds of general formula (I) according to the invention Has

R is preferably C _1-4 -alkyl, phenyl or modified, in particular methyl or phenyl.

Starting materials of formula (II) are known and / or known methods [Heterocycl. Chem. 9 (1972), 513-522).

Formula (III) provides a general definition of cyanoaryl isocyanate which is used as another starting material in process (a) according to the invention.

In the general formula (III), R ¹ and R ⁴ are preferably or particularly referred to as preferred or particularly preferred for R ¹ and R ² in the above definition of the compound of general formula (I) according to the invention. Has Cyanoaryl isocyanates of the general formula (III) are many new materials which are not known in the literature so far and are the subject of the present application.

The novel cyanoaryl isocyanates of the general formula (III) are cyanoarylamines of the general formula (VIII) in which R ¹ and R ² have the above-mentioned meanings in the presence of a diluent such as, for example, chlorobenzene. Obtained by reaction with phosgene at from + 150 ° C. (see Preparation Example).

Wherein R ¹ and R ² have the meanings mentioned above.

The cyanoarylurethanes used as starting materials for process (a) according to the invention are generally defined by the general formula (IV). In formula (IV), R ¹ and R ² preferably or in particular define definitions which are mentioned as preferred or particularly preferred for R ¹ and R ² in the definition of the compounds of formula (I) according to the invention. And R preferably represents C _1-4 -alkyl, phenyl or benzyl, in particular methyl or phenyl.

Cyanoarylurethanes of general formula (IV) are novel materials which are not yet known in the literature and they are the subject of the present application.

The novel cyanoarylurethanes of the general formula (IV) are prepared by the cyanoarylamines of the general formula (VIII) in the presence of an acid acceptor such as for example pyridine and optionally in the presence of a diluent such as for example methylene chloride. It is obtained by reaction with a chlorocarbonyl compound of general formula (IX) at 0 ° C to 100 under.

In the above formula,

R has the meanings mentioned above.

The process (a) according to the invention for producing a novel N-cyanoaryl-nitrogen heterocycle of general formula (I) is preferably carried out using a diluent. Suitable diluents are virtually all organic solvents. These are preferably aliphatic and aromatic hydrocarbons, optionally halogenated hydrocarbons, for example phantan, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride Chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether, dibutyl ether, glycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and Methyl isobutyl ketones, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also Dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphate triamide may be included.

Process (a) according to the invention is preferably carried out in the presence of a reaction aid. Suitable reaction aids are mainly acid acceptors. Preferably, alkali metal hydrides and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal hydroxides and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and hydroxide Calcium, alkali metal carbonate, alkali metal hydrogen carbonate and alkaline earth metal carbonate, such as sodium carbonate, sodium bicarbonate, potassium carbonate or potassium carbonate, and calcium carbonate, alkali metal acetate, such as sodium acetate and potassium acetate, alkali Metal alcoholates such as sodium methylate, sodium ethylate, sodium propylate, sodium isopropylate, sodium butylate, sodium isobutylate, sodium t-butylate, potassium methylate, potassium ethylate, potassium propylate Potassium isopro Latex, potassium butyrate, potassium isobutylate and potassium t-butylate, also basic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, Ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl -, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 3,5-diazabicyclo [4.3.0] -non-5-ene (DBN) , 1,8-diazabicyclo [5.4.0] -undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2] -octane (DABCO) are suitable as reaction aids .

In the case of carrying out process (a) according to the invention, the reaction temperature can be varied over a relatively wide range. In general, the reaction is carried out at a temperature of -120 ° C to + 100 ° C, preferably at a temperature of -70 ° C to + 80 ° C.

In general, process (a) according to the invention is carried out at atmospheric pressure, but can also be carried out at elevated or reduced pressure.

In order to carry out process (a) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, one of the two components used in each case can be used in relatively excess. The reaction is generally carried out in the presence of a suitable diluent in the presence of a reaction aid and the reaction mixture is stirred for several hours at the required temperature in each case. The post-treatment in process (a) according to the invention is carried out by conventional methods in each case (see Production Examples).

Formulas (IA) and (IB) wherein R ⁵ represents hydrogen are N-cyanoaryl-nitrogen heterocycles used as starting materials in the process (b) according to the invention for the preparation of compounds of general formula (I). Provide a general definition of.

In the general formulas (IA) and (IB), R ¹ , R ² , R ³ and R ⁴ are preferably or in particular in the above definition of compounds of general formula (I) according to the invention R ¹ , R ² , It has the definition mentioned as preferred or particularly preferred for R ³ and R ⁴ .

Starting materials of formulas (IA) and (IB) for process (b) are novel compounds according to the invention, which can be prepared by process (a) according to the invention.

Formulas (V) and (VI) provide a general definition of alkylating agents used as another starting material in process (b) according to the invention.

In the general formulas (V) and (VI), R ⁵ preferably or in particular has the definition mentioned as preferred or particularly preferred for R ⁵ in the above definitions of the compounds of the general formula (I) according to the invention. .

Starting materials of formulas (V) and (VI) are known chemicals for organic synthesis.

Process (b) according to the invention is preferably carried out using a diluent. Suitable diluents are those already mentioned mainly in the description of process (a) according to the invention.

Acid acceptors that can be used in process (b) according to the invention are all acid-binding agents which can be customarily used for such reactions. Alkali metal hydrides and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal hydroxides and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal Carbonates, alkali metal hydrogencarbonates, alkaline earth metal carbonates and alkaline earth metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, and calcium carbonate, alkali metal acetates such as sodium acetate and acetic acid Potassium, alkali metal alcoholates such as sodium methylate, sodium ethylate, sodium propylate, sodium isopropylate, sodium butylate, sodium isobutylate, sodium t-butylate, potassium methylate, potassium ethylate, Potassium Propylate, Knife Isopropylate, potassium butyrate, potassium isobutylate and potassium t-butylate, also basic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexyl Amine, ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4 -Dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo [4,3,0] -non-5- En [DBN], 1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2] -octane (DABCO) This is suitable.

In the case of carrying out process (b) according to the invention, the reaction temperature can be varied over a relatively wide range. In general, the reaction is carried out at a temperature of 0 ° C to 120 ° C, preferably at a temperature of 10 ° C to 100 ° C.

In general, process (b) according to the invention is carried out at atmospheric pressure, but can also be carried out under elevated or reduced pressure.

In order to carry out process (b) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, one of the two components used in each case can be used in relatively excess. The reaction is generally carried out in the presence of a suitable diluent in the presence of an acid acceptor and the reaction mixture is stirred for several hours at the required temperature in each case. Post-treatment in the process (b) according to the invention is carried out by conventional methods in each case (see Production Examples).

When R ² represents halogen, general formula (I) is general of the N-cyanoaryl-nitrogen heterocycle used as starting material in the process (c) according to the invention for preparing the compound of general formula (I). Provide a ral justice.

In general formula (I), R ¹ , R ³ , R ⁴ and Z are preferably or in particular defined in R ¹ , R ³ , R ⁴ and Z in the above definition of compounds of general formula (I) according to the invention. With definitions mentioned as preferred or particularly preferred for the invention.

Starting materials of formula (I) for process (c) are novel compounds according to the invention, which can be prepared by processes (a) and (b) according to the invention.

Formula (VII) provides a general definition of the amide used as another starting material in process (c) according to the invention.

In the general formula (VII), A preferably or in particular has the definitions mentioned as preferred or particularly preferred for A in the above definitions of the compounds of the general formula (I) according to the invention.

Starting materials of formula (VII) are known chemicals for organic synthesis.

Process (c) according to the invention is preferably carried out using a diluent. Suitable diluents are mainly those already mentioned in the description of the process (a) according to the invention.

If appropriate, the method (c) according to the invention is carried out in the presence of an acid acceptor. Suitable acid acceptors are those already mentioned in the description of process (b) according to the invention.

In the case of carrying out process (c) according to the invention, the temperature can be varied over a relatively wide range. In general, the reaction is carried out at a temperature of 0 ° C to 200 ° C, preferably 20 ° C to 180 ° C.

In general, the process (c) according to the invention is carried out at atmospheric pressure, but can also be carried out under elevated or reduced pressure.

In order to carry out process (c) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, one of the two components used in each case can be used in relatively excess. In general, the reaction is carried out in the presence of a suitable diluent in the presence of an acid acceptor and the reaction mixture is stirred for several hours at the required temperature in each case. The post-treatment in process (c) according to the invention is carried out by conventional methods in each case (see: Production practice).

The active compounds according to the invention can be used as deciduous, drying, hardwood killing agents and, in particular, herbicides, where weeds are understood in the broad sense to all plants which grow in unwanted places. Whether the substance according to the invention acts as a total herbicide 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 in 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, Festus, Eleusin, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Sino Cynodon, Monochoria, Fimbistylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischamum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocots of the 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 at all limited in them and 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 zones and railroads, and on many sidewalks and plazas with or without trees. Similarly, the compounds of the present invention are for example plantation, ornamental water, plantation, orchard, vineyard, citrus field, nut orchard, banana plantation, coffee plantation, tea plantation, rubber plantation, palm plantation, cocoa plantation, soft fruit plantation and It can be used to control weeds in perennial crops growing on lawns, turf and pastures that fit in hop fields and for selective control of weeds in annual crops.

Compounds of formula (I) according to the invention, including those given up by abandoners, are dicotyledonous in dicotyledonous and dicotyledonous crops, such as wheat, corn and soybeans, in particular by both pre- and post-emergence methods. Although particularly suitable for selectively controlling weeds, each compound also has selective activity in all of the above crops.

The active compounds are 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 may be converted to a conventional formulation such as.

These formulations are prepared by known methods, for example by admixing the active compound with a weighting agent, ie a liquid solvent and / or a solid carrier, optionally using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. .

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

Solid carriers include, 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. Suitable solid granules include: granules of crushed and crushed natural ore, inorganic and organic powders, such as calcite, marble, pumice, calcite and dolomite, as well as sawdust, coconut husks, corncobs and tobacco Granules of organic material such as stems are suitable; Emulsifiers and / or foam-forming agents include nonionic and anionic emulsifiers such as polyoxyethylene fatty alcohol ethers such as polyoxyethylene fatty acid esters, alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, aryl sulfonates and Albumin hydrolysis products are suitable and dispersants are, for example, lignin-sulfite waste and methylcellulose.

Adhesives such as carboxymethylcellulose and powders such as Arabian high, polyvinyl alcohol and polyvinyl acetate, natural and synthetic polymers in granular or latex form, phospholipids and synthetic phospholipids such as cephalin and lecithin can be used in the formulation. Mineral oil and vegetable oil may be used as other additives.

Trace amounts such as inorganic pigments such as iron oxide, tyran oxide and prussian blue and colorants such as organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and traces such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc You can also use nutrients.

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

In order to control weeds, the active compounds according to the invention can also be used as mixtures with known herbicides, as such or in the form of their preparations, in the form of finished product preparations or tank mixtures.

Suitable herbicides for the mixture include, for example, anilides such as diflufenican and propanyl; Arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram: for example 2,4-D, 2,4-DB, 2,4-DP, fluoxypyr, MCPA, MCPP and trichloro Aryl oxyalkanoic acids such as pyrroles: for example aryloxy-phenoxy-alkanes such as diclopop-methyl, phenoxaprop-ethyl, fluazip-butyl, haloxy-methyl and quinaclo-ethyl Acid esters: for example azinones such as chloridazone and norflurazone; Carbamates such as, for example, chlorprofam, desmedipham, penmedipham and profam; Chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor: for example dinitro, such as oryzaline, pendimethalin and trituralin Aniline: diphenyl ethers such as, for example, acifluorfen, biphenox, fluoroglycopene, pomessafen, halosafen, lactofen and oxyfluorophene: for example chlortoluron, diuron, fluoromethuron, iso Ureas such as proturon, linuron and metabenzthiazuron: for example hydroxylamines such as alkoxydim, cletodim, cycloxydim, cetoxydim and trakoxydim: for example imazetapyr, forehead Imidazolinones such as jametabenz, imazafir and imazaquin: nitriles such as bromocinyl, diclobenyl and ioxynyl: oxiases such as mefenacet Amides: for example amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cynosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensul Sulfonylureas such as furon-methyl, triasulfuron and tribenuron-methyl; Thiocarbamates such as, for example, butyrate, cycloate, di-acrylate, EPTC, esprocarb, molinate, prosulfocarb, theobencarb and trialate: e.g. atrazine, cyanazine, sima Triazines such as gin, simethrin, terbutrin and terbutylazine: triazinones such as hexazinone, metamitron and metrizine: for example aminotriazole, benfuresate, betazone, shin Methylene, clomazone, clopyralide, dipfencuart, dithiopyr, etofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinclolac, quinmerac, sulfo Known herbicides such as states and others such as tridiphane.

Mixtures with other known active compounds such as fungicides, insecticides, acaricides, acaricides, algal repellents, plant nutrients and soil structure improvers are also possible.

The active compounds can be used as such, in the form of their preparations or in ready-to-use forms prepared from their preparations by further dilution such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in conventional manner, for example by watering, spraying, spraying or spreading.

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

The amount of active compound used can vary within a significant range. This is essentially dependent on the nature of the desired effect. Generally, the amount used is 10 g to 10 kg, preferably 50 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 following examples.

Manufacturing Example

Example 1

(Method (a))

1.8 g (10 mMol) of ethyl 3-amino-4,4,4-trifluorocrotonate were introduced into 30 ml of dimethylformamide and 2 ml of toluene and 0.3 g (10 mMol) of sodium hydride (80%) Is added at 0 ° C to 5 ° C. The mixture is stirred at 0 ° C. to 5 ° C. for 30 minutes.

After the mixture was cooled to -70 ° C, 0.9 g (5 mMol) of 4-cyano-2,5-difluoro-phenyl isocyanate dissolved in 10 ml of toluene was added, and the mixture was -60 ° C to -70 ° C. Stir for 150 minutes. After the cooling bath is removed, 2 ml of acetic acid are added. The mixture is then diluted with water up to approximately twice its volume and extracted with ethyl acetate. The organic phase is concentrated and the residue is crystallized using diisopropyl ether.

1- (4-cyano-2,5-difluoro-phenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) -pyridine at melting point of 194 ° C 1.1 g (69% of theory) of midine are obtained.

Example 2

(Method (b))

3.2 g (10 mMol) of 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1 (2H) -A mixture of pyrimidine, 3.1 g (20 mMol) diethyl sulfate, 2.8 g potassium carbonate and 100 ml acetonitrile is refluxed for 3 hours. Then it is concentrated in vacuo and shaken with water / chloroform to extract, the organic phase is again concentrated in vacuo and the residue is separated by column chromatography (silica gel, petroleum ether / ethyl acetate 1: 1).

The first aliquot obtained was 0.30 g of 1- (4-cyano-2,5-difluoro-phenyl) -1,6-dihydro-2-ethoxy-6-oxo-4-trifluoromethyl -Pyrimidine (amorphous), the second aliquot is 0.38 g of 1- (4-cyano-2,5-difluoro-phenyl) -3,6-dihydro-2,6-dioxo-3- Ethyl-4-trifluoromethyl-1 (2H) -pyrimidine (amorphous, ¹ H-NMR: d = 6.36 ppm). Total yield: 0.68 g (20% of theory).

Example 3

(Method (c))

0.83 g (3 mMol) of 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro-2,6-dioxo-3,4-dimethyl-1 (2H)- A mixture of pyrimidine, 0.32 g (3 mMol) methanesulfonamide, 0.6 g potassium carbonate and 10 ml dimethyl sulfoxide is refluxed at 120 ° C. for 10 hours. After the mixture is cooled, it is poured into ice-water and acidified with 2N hydrochloric acid. Then, extracted with ethyl acetate, the organic phase is washed with water, dried using sodium sulfate and filtered. The solvent is carefully removed from the filtrate by distillation under a water pump vacuum.

0.8 g (76% of theory) of 1- (4-cyano-2-fluoro-5-methylsulfonylaminophenyl) -3,6-dihydro-2,6-dioxo-3,4-dimethyl -1 (2H) -pyrimidine is obtained as colonic residue. (Melting point:> 250 ° C).

Examples of compounds of (IA) and (IB) or compounds of formula (I) which can be prepared analogously to Examples 1 to 3 according to the general description of the preparation process according to the invention are shown in Table 2 below.

Starting material of general formula (III):

Example (III-1)

660 g of phosgene is condensed with 1.6 liters of chlorobenzene at -5 ° C to 0 ° C. At the same temperature, a solution of 400 g of 4-cyano-2,5-difluoro-aniline in 800 ml of chlorobenzene is added dropwise in 60 minutes. Subsequently, the reaction mixture is gradually heated to 120 ° C. (HCl is generated) and after reaching a temperature of 80 ° C., phosgene is continuously passed through. After heating at 120 ° C. for 1 hour, excess phosgene is purged with nitrogen and the reaction mixture is worked up by distillation.

248 g (53% of theory) of 4-cyano-2,5-difluoro-phenyl isocyanate having a melting point of 53 ° C. at a boiling point of 108 ° C. to 110 ° C. and a pressure of 14 millibar are obtained.

Starting material of general formula (IV):

Example (IV-1)

13.0 g (0.05 mol) of ethyl chloroformate at 20 ° C. in a mixture of 11.5 g (0.05 mo1) of 4-cyano-fluoro-5-methylsulfonylaminoaniline, 18 g of pyridine and 400 ml of methylene fluoride It is added dropwise with stirring, and the reaction mixture is further stirred at 20 ° C to 30 ° C for 30 minutes. The mixture is then washed with water and then with 5% hydrochloric acid, again with water, dried over sodium sulfate, filtered and the filtrate is evaporated. The residue is immersed in a small amount of ethyl acetate and separated by suction filtration of the product obtained in crystalline form.

Obtain 15.8 g (85% of theory) of N-ethoxycarbonyl-N- (2-cyano-4-fluoro-5-ethoxycarbonylamino-phenyl) -methanesulfonamide at a melting point of 129 ° C. .

For example, compounds of formula (IV) shown in Table 3 below may also be prepared similarly to examples (IV-I).

Use Example

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 then diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Seeds of the test plants are sown in standard soil and after 24 hours, the active compound preparations are irrigated. It is advantageous to maintain a constant amount of water per unit area.

The concentration of active compound in the formulation is not critical, only the amount of active compound applied per unit area is an important factor. After 3 weeks, the degree of damage of the plants is compared to the development of the untreated control and the damage is graded in%.

The figures represent the following:

0% = no effect (same as untreated control)

100% = Complete Exam

In this test, for example, the compounds according to Preparation Examples 2 (second aliquot) and 12 show potent activity against weeds, while for example have good resistance to crops such as corn.

Example B

Post Germination Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

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

Test plants of 5 to 15 cm in height are sprayed with a formulation of the active compound by applying a desired amount of the desired active compound per unit area. After 3 weeks, the degree of damage of the plants is compared to the development of the untreated control and the damage is graded in%.

The figures represent the following:

0% = no effect (same as untreated control)

100% = Complete Exam

In this test, for example, the compounds according to Preparation Examples 2 (second aliquot) and 12 exhibit potent activity against weeds, while for example have good resistance to crops such as wheat.

Claims (9)

N-cyanoaryl-nitrogen heterocycle of formula (I) and hydroxides, hydrides, amides or carbonates of sodium, potassium or calcium, sodium or potassium C _1-4 -alkanolate, ammonia, C _1-4 Salts with an -alkylamine, di- (C _1-4 -alkyl) -amine, tri- (C _1-4 -alkyl) -amine or tris- (2-hydroxyethyl) amine base: In the above formula R ¹ represents hydrogen, fluorine or chlorine, R ² represents a group —N (A ¹ ) SO ₂ A, From here A represents methyl, ethyl, n- or i-propyl, or n-, i-, s- or r-butyl, each substituted or unsubstituted by chlorine, or A is also cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentyl, unsubstituted or substituted by one or more substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and ethyl, respectively Methyl or cyclohexylmethyl, A ¹ is hydrogen or methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl, buty substituted or unsubstituted by methoxy or ethoxy, respectively Nil, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, R ³ represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, ethyl or n- or i-propyl, R ⁴ represents methyl, ethyl, n- or i-propyl, unsubstituted or substituted by fluorine or chlorine, respectively, or represents trimethylene or tetramethylene together with R ³ , Z represents one of the following groups; From here, R ⁵ is hydrogen, amino, or methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propy, unsubstituted or substituted by fluorine, chlorine or cyano, respectively; Nil, butynyl, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, Provided that Compound 1- (4-cyano-3-ethylsulfonylamino-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -Pyrimidine, 1- (4-cyano-3-n-propylsulfonylamino-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H) -pyrimidine, 1- (4-cyano-3-isopropylsulfonylamino-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoro Methyl-1 (2H) -pyrimidine, 1- (4-cyano-3-ethylsulfonylamino-2-fluoro-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl -4-trifluoromethyl-1 (2H) -pyrimidine, 1- (4-cyano-5-n-propylsulfonylamino-2-fluoro-phenyl) -3,6-dihydro-2, 6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine and 1- (4-cyano-5-isopropylsulfonylamino-2-fluoro-phenyl) -3, 6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine is excluded. The aminoalkenoic acid ester of formula (II) is reacted with cyanoaryl isocyanate of formula (III) in the presence or absence of a reaction aid and in the presence or absence of a diluent, or Reaction with noarylurethane (cyanoarylcarbamate) to prepare a compound of formula (I) wherein R ⁵ represents hydrogen and R ¹ , R ² , R ³ and R ⁴ have the meanings mentioned in claim 1 A process for preparing an N-cyanoaryl-nitrogen heterocycle of formula (I) according to claim 1. In the above formula, R ¹ , R ² , R ³ and R ⁴ have the meanings referred to in claim 1, R represents alkyl, aryl or arylalkyl. A herbicide composition characterized by containing at least one N-cyanoaryl-nitrogen heterocycle of formula (I) according to claim 1. A process for controlling unwanted plants, characterized in that the N-cyanoaryl-nitrogen heterocycle of formula (I) acts on plants or their environment. A process for preparing a herbicide composition, characterized in that the N-cyanoaryl-nitrogen heterocycle of formula (I) is mixed with at least one substance selected from the group consisting of a weighting agent and a surfactant. Cyanoaryl Isocyanates of Formula (III): In the above formula, R ¹ and R ² have the meanings mentioned in claim 1. Cyanoarylurethane of Formula (IV): In the above formula, R ¹ and R ² have the meanings mentioned in claim 1, R represents alkyl, aryl or allylalkyl. R ⁵ represents hydrogen and R ¹ , R ² , R ³ and R ⁴ represent N-cyanoaryl-nitrogen heterocycles of formula (I) according to claim 1 having the meanings mentioned in claim 1, In the presence or absence of an acid acceptor and in the presence or absence of a diluent, R ⁵ is methyl unsubstituted or substituted by fluorine, chlorine or cyano, respectively, by reaction with an alkylating or acylating agent of general formula (V) or (VI). , Ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl, butynyl, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl is selected from R ¹ , R ² , R ³ and R ⁴ make N-cyanoaryl- of general formula (I) according to claim 1, characterized in that they produce compounds of general formula (I) having the meanings mentioned in claim 1. How to prepare a nitrogen heterocycle: In the above formula, R ⁵ is methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl, butynyl, unsubstituted or substituted by fluorine, chlorine or cyano, respectively, Acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, X represents a halogen. R ² represents halogen, R ¹ , R ³ , R ⁴ and Z represent N-cyanoaryl-nitrogen heterocycles of the general formula (I) according to claim 1 having the meaning mentioned in claim 1, In the presence or absence of a receptor and in the presence or absence of a diluent, reacted with ammonia or an amide of formula (VII), R ² represents a group —N (A ¹ ) SO ₂ A, and A, A ¹ , R ¹ , N-cyanoaryl-nitrogen of formula (I) according to claim 1, characterized in that R ³ , R ⁴ and Z prepare compounds of formula (I) having the meanings mentioned in claim 1 How to prepare a heterocycle: Wherein A and A ¹ have the meanings referred to in claim 1.