DE4412079A1 - N-Cyanoaryl-nitrogen-heterocycles - Google Patents

Abstract

The invention relates to novel N-cyanoaryl-nitrogen-heterocycles of the general formula (I) <IMAGE> in which R<1>, R<2>, R<3>, R<4> and Z have the meanings given in the description, to a plurality of processes for their preparation, to their use as herbicides, and to novel intermediates.

Description

The invention relates to new N-cyanoaryl nitrogen heterocytes, several ver drive to their manufacture, their use as herbicides and new intermediates Products.

It is already known that certain N-cyanoaryl nitrogen heterocycles have herbicidal properties (cf. WO 91/00278, WO 92/11244, DE 42 37 920 EP 408382 / US 5084084, EP 438209, EP 473551).

The herbicidal activity or the tolerance of the previously known N-cyanoaryl However, nitrogen heterocycles versus crops are not entirely satisfied posed.

There have now been the new N-cyanoaryl nitrogen heterocycles of the general Formula (I) found

in which
R¹ represents hydrogen or halogen,
R² represents halogen, cyano, amino or the grouping -N (A¹) SO₂A,
where A stands for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,
and A 1 represents hydrogen or represents optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, arylalkylcarbonyl or aryloxycarbonyl,
R³ represents hydrogen, halogen, cyano or optionally substituted alkyl,
R⁴ represents optionally substituted alkyl or together with R³ represents alkanediyl,
Z represents one of the groupings below

wherein
R⁵ represents hydrogen, amino (only bonded to N) or optionally substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl,
and their salts, the compounds 1- (4-cyano-3-ethylsulfonylamino phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrim-idin, 1 - (4-Cyano-3-n-propylsulfonylamino-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-tri fluoromethyl-1 (2H) -pyrimidine, 1- (4-cyano -3-i-propylsulfonylamino-phenyl) -3,6-di hydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine, 1- (4-cyano-5-ethyl sulfonylamino- 2-fluorophenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifl-uoromethyl-1 (2H) -pyrimidine, 1- (4-cyano-5-n-propylsulfonylamino-2 -fluorophenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) pyrimidine and 1- (4-cyano-5-i-propyl sulfonylamino-2-fluorine -phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifl-uoromethyl-1 (2H) -pyrimidine - all known from US 5084084 - are excluded by disclaimer.

The general formula (I) stands for the isomeric compounds according to general formulas (IA) and (IB)

The new N-cyanoaryl nitrogen heterocycles of the general formula are obtained (I) and their salts when one

• (a) for the preparation of compounds of the formula (IA) and (IB) in which R⁵ represents hydrogen and R¹, R², R³ and R⁴ have the meanings given above,
  Aminoalkenic acid esters of the general formula (II) in which
  R³ and R⁴ have the meanings given above and
  R represents alkyl, aryl or arylalkyl,
  with cyanoaryl isocyanates of the general formula (III) in which
  R¹ and R² have the meanings given above,
  or with cyanoaryl urethanes (cyanoaryl carbamates) of the general formula (IV) in which
  R¹ and R² have the meanings given above and
  R represents alkyl, aryl or arylalkyl,
  if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
  or if you
• (b) for the preparation of compounds of the formulas (IA) and / or (IB) in which R⁵ represents optionally substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl and R¹, R², R³ and R⁴ have the meanings given above,
  N-cyanoaryl nitrogen heterocytes of the general formulas (IA) or (IB)
  in which R⁵ represents hydrogen and R¹, R², R³ and R⁴ have the meanings given above,
  with alkylating agents or acylating agents of the general formulas (V) or (VI) X-R⁵ (V) R⁵-O-SO₂-O-R⁵ (VI) in which R⁵ represents optionally substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl and X in the formula (V) represents halogen,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,
  or if you
• (c) for the preparation of compounds of the formula (1) in which R² is amino or the grouping -N (A¹) SO₂A and A, A¹, R¹, R³ R⁴ and Z have the meanings given above,
  N-cyanoaryl nitrogen heterocycles of the general formula (I) in which R² is halogen and R¹, R³, R⁴ and Z have the meanings given above,
  with ammonia or with amides of the general formula (VII) HN (A¹) SO₂A (VII) in which
  A and A¹ have the meanings given above,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.

The compounds of the formulas (IA) in which R⁵ stands for amino can known manner by reacting corresponding compounds of the formula (IA), in which R⁵ is hydrogen, with aminating agents, such as. B. 1- Aminooxy-2,4-dinitro-benzene (ADNB), according to the formula scheme below are produced (cf. EP 476697, Example 4):

The new N-cyanoaryl nitrogen heterocycles of the general formula (I) and the salts of which are notable for their strong herbicidal activity.

In the definitions are the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl, in each case straight-chain or ver branches.

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

The invention preferably relates to compounds of the formula (I) in which
R¹ represents hydrogen, fluorine, chlorine or bromine,
R² is fluorine, chlorine, bromine, cyano, amino or the grouping -N (A¹) SO₂A, wherein
A represents a radical of the series alkyl, alkenyl or alkynyl, each optionally substituted by fluorine, chlorine, bromine, cyano or C₁-C₄alkoxy, each having up to 10 carbon atoms,
A furthermore represents cycloalkyl or cycloalkylalkyl which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁-C₄alkyl and has 3 to 8 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the alkyl part,
A further for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl (which are each optionally substituted by fluorine and / or chlorine), by dimethylaminosulfonyl or diethylaminosulfonyl, by C₁-C₄alkoxy carbonyl (which is optionally substituted by fluorine, chlorine, bromine, methoxy or ethoxy), by phenyl, phenyloxy or phenylthio (which are each optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy) substituted aryl or arylalkyl having 6 or 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part,
A further for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxy carbonyl (which are each optionally substituted by fluorine and / or chlorine), by phenyl, phenoxy or phenylthio (which are each optionally by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy) are substituted heterocyclic or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 4 nitrogen atoms and / or 1 to 2 oxygen or sulfur atoms in the saturated or unsaturated heterocyclyl part and optionally 1 to 4 carbon atoms in the alkyl part, and
A¹ for hydrogen or for alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by halogen or C₁-C₄alkoxy, each having up to 6 carbon atoms, or for phenylcarbonyl, naphthylcarbonyl, phenylmethylcarbonyl, naphthylmethylcarbonyl, phenoxycarbonyl or naphthyloxycarbonyl ( which are each optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy),
R³ represents hydrogen, fluorine, chlorine, bromine, cyano or alkyl which has 1 to 6 carbon atoms and is optionally substituted by fluorine and / or chlorine,
R⁴ represents alkyl which has 1 to 6 carbon atoms and is optionally substituted by fluorine, chlorine, bromine, methoxy or ethoxy,
or together with R³ represents alkanediyl having 2 to 8 carbon atoms, and
Z represents one of the groupings below

wherein
R⁵ for hydrogen, amino or in each case optionally substituted by fluorine, chlorine, bromine, cyano, C₁-C₄-alkoxy, C₁-C₄-alkyl-carbonyl or C₁-C₄-alkoxy-carbonyl-substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl each has up to 6 carbon atoms and their salts with bases, such as. B. sodium, potassium or calcium hydroxide, hydride, amide or carbonate, sodium or potassium C₁-C₄ alkanolates, ammonia, C₁-C₄-alkyl amino, di- (C₁-C₄-alkyl) -amines, tri- (C₁-C₄-alkyl) amines or also with tris (2-hydroxyethyl) amine, the above compounds being excluded.

The invention relates in particular to compounds of the formula (I) in which
R¹ represents hydrogen, fluorine or chlorine,
R² is fluorine, chlorine, bromine, cyano, amino or the grouping -N (A ') SO₂A, in which
A represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, which is optionally substituted by fluorine or chlorine,
A furthermore represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by fluorine, chlorine, bromine, methyl and / or ethyl,
A further for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, dimethyl aminosulfonyl, methoxycarbonyl, ethoxycarbonate Propoxycarbonyl or phenyl substituted phenyl, naphthyl, phenylmethyl or phenylethyl,
A further represents thienyl, pyrazolyl or pyridyl, which is optionally substituted by fluorine, chlorine, bromine, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methyl thio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethyl sulfonyl, methoxycarbonyl or ethoxycarbonyl, and
A¹ for hydrogen, for each optionally substituted by fluorine, chlorine, methoxy or ethoxy, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl, butynyl, methoxy, ethoxy, n - or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, represents phenyl carbonyl or phenoxycarbonyl,
R³ represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, ethyl, n- or i-propyl,
R⁴ represents methyl, ethyl, n- or i-propyl, each optionally substituted by fluorine or chlorine,
or together with R³ is trimethylene or tetramethylene, and
Z represents one of the groupings below

wherein
R⁵ for hydrogen, amino or for each optionally substituted by fluorine, chlorine or cyano substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl, butynyl, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl and their salts with bases, such as. B. sodium, potassium or calcium hydroxide, hydride, amide or carbonate, sodium or potassium C₁-C₄ alkanolates, ammonia, C₁-C₄-alkylamines, di- (C₁-C₄-alkyl) - amines, tri- (C₁-C₄-alkyl) amines or also with tris (2-hydroxyethyl) amine, the above compounds being excluded.

A very particularly preferred group of compounds of formula (I) are Compounds of formula (IA) in which R¹, R², R³, R⁴ and R⁵ the above as have particularly preferably given meaning.  

The radicals listed above or specified in preferred ranges definitions apply to both the end products of formula (I) and correspondingly for the respective starting materials or Intermediates.

These residual definitions can be among themselves, that is, between the specified ranges of preferred connections, can be combined as desired.

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

Table I

Examples of the compounds of the formula (I)

If, for example, 3-aminocrotonic acid methyl ester and 4-cyano-2,5- difluoro-phenyl isocyanate as starting materials, so the course of the reaction can Process (a) according to the invention is outlined by the following formula become:

For example, if 1- (3-chloro-4-cyano-phenyl) -3,6-dihydro-2,6-dioxo- 4-trifluoromethyl-1 (2H) pyrimidine and methyl bromide as starting materials, so can the course of the reaction in process (b) according to the invention by the following Formula scheme are outlined:

For example, if 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro-3,4- dimethyl-2,6-dioxo-1 (2H) pyrimidine and ethanesulfonamide as starting materials, see above can the course of the reaction in process (c) according to the invention by the the following formula scheme is outlined:

The process (a) according to the invention for the preparation of compounds of Formula (I) aminoalkenates to be used as starting materials are by the formula (II) is generally defined.

In formula (II) R³ and R⁴ preferably or in particular that Be interpretation already above in connection with the description of the Invention compounds of formula (I) preferably or as in particular before were given for R³ and R⁴.

R is preferably C₁-C₄ alkyl, phenyl or benzyl, in particular for Methyl or phenyl.

The starting materials of formula (II) are known and / or can be known Processes are prepared (cf. J. Heterocycl. Chem. 9 (1972), 513-522).

The ver in the process (a) according to the invention as starting materials Turning cyanoaryl isocyanates are generally defined by the formula (III).

In formula (III), R¹ and R² preferably or in particular have those interpretations already above in connection with the description of the he Compounds of formula (I) according to the invention preferably or as in particular were particularly preferred for R 'and R².  

The cyanoaryl isocyanates of the general formula (III) are not yet out of the Literature known and are the subject of the present An as new substances report.

The new cyanoaryl isocyanates of the formula (III) are obtained if cyanoaryl amines of the general formula (VIII)

in which
R¹ and R² have the meanings given above,
with phosgene in the presence of a diluent, such as. B. chlorobenzene, at temperatures between -20 ° C and + 150 ° C (see. The manufacturing examples).

In process (a) according to the invention, optionally as starting materials Cyanoaryl urethanes using are generally defined by the formula (IV). In formula (IV), R¹ and R² preferably have those in particular Meanings already above in connection with the description of Ver compounds of the formula (I) as preferred or as particularly preferred for R ′ and R² have been given; R is preferably C₁-C₄ alkyl, phenyl or Benzyl, especially for methyl or phenyl.

The cyanoaryl urethanes of the general formula (IV) are not yet out of the Literature known; as new substances they are the subject of the present An report.  

The new cyanoaryl urethanes of the formula (IV) are obtained if cyanoaryl amines of the general formula (VIII) - above - with chlorocarbonyl compounds general formula (IX)

RO-CO-Cl (IX)

in which
R has the meaning given above,
optionally in the presence of an acid acceptor, such as. As pyridine, and optionally in the presence of a diluent, such as. B. methylene chloride, at temperatures between 0 ° C and 100 ° C (see. The preparation examples).

Process (a) according to the invention for the preparation of the new N-cyanoaryl Nitrogen heterocycles of formula (I) are preferably used using Diluents performed. These come in handy as diluents all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as Pentane, hexane, heptane, cyclohexane, petroleum ether, petrol, ligroin, benzene, toluene, Xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorine benzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such. B. acetonitrile and propio nitrile, amides such as B. dimethylformamide, dimethylacetamide and N-methyl pyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexamethylphos phosphoric triamide.

Process (a) according to the invention is preferably carried out in the presence of a Re action aid carried out. The most important reaction aids here are Suitable acid acceptors. Alkali metal and earth are preferred alkali metal hydrides, such as lithium, sodium, potassium and calcium hydride, alkali metal and alkaline earth metal hydroxides, such as lithium, sodium, potassium and Calcium hydroxide, alkali metal and alkaline earth metal carbonates and hydrogen  carbonates, such as sodium and potassium carbonate or bicarbonate, and Calcium carbonate, alkali metal acetates such as sodium and potassium acetate, alkali metal alcoholates, such as sodium and potassium methylate, ethylate, propylate, iso propylate, butylate, isobutylate and tert-butylate, further basic nitrogen ver bonds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diiso butylamine, 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, 1,5-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).

The reaction temperatures in process (a) according to the invention can be in can be varied over a wide range. Generally one works at Tem temperatures between -120 ° C and + 100 ° C, preferably at temperatures between -70 ° C and + 80 ° C.

Process (a) according to the invention is generally carried out under atmospheric pressure carried out. However, it is also possible to increase or decrease it Pressure to work.

To carry out process (a) according to the invention, the respective be necessary starting materials are generally used in approximately equimolar amounts puts. However, it is also possible to use either of the two To use components in a larger excess. The reactions are generally in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture becomes several Stirred for hours at the required temperature. The workup takes place in the process (a) according to the invention in each case by customary methods (see the manufacturing examples).

The process (b) according to the invention for the preparation of compounds of Formula (I) to be used as starting materials N-cyanoaryl nitrogen hetero cyclen are by the formulas (IA) and (IB) - with the proviso that R⁵ for Hydrogen is - generally defined.  

In the formulas (IA) and (IB), R¹, R², R³ and R⁴ preferably or in particular special meanings already mentioned above in connection with the Be preferably the compounds of the formula (I) according to the invention or as particularly preferred for R¹, R², R³ and R⁴ have been specified.

The starting materials of the formulas (IA) and (IB) for process (b) are inventive measured new connections; they can by the method according to the invention (a) are produced.

The ver in the process (b) according to the invention as starting materials turning alkylating agents are generally de through the formulas (V) and (VI) finishes.

In the formulas (V) and (VI), R⁵ preferably or in particular has that Be interpretation already above in connection with the description of the Invention compounds of formula (I) preferably or as in particular before was given for R⁵.

The starting materials of the formulas (V) and (VI) are known organic synthesis chemicals.

Method (b) according to the invention is preferably carried out using a Diluent carried out. Above all those Ver fertilizers into consideration, which were already in the description of the inventive according to method (a).

All of them can be used as acid acceptors in process (b) according to the invention Acid binder which can usually be used for such reactions be set. Alkali metal and alkaline earth metal are preferred hydrides, such as lithium, sodium, potassium and calcium hydride, alkali metal and Alkaline earth metal hydroxides such as lithium, sodium, potassium and calcium hydroxide, alkali metal and alkaline earth metal carbonates and bicarbonates, such as sodium and potassium carbonate or bicarbonate and calcium carbonate, alkali metal acetates such as sodium and potassium acetate, alkali metal alcoholates, such as sodium and potassium methylate, ethylate, propylate, isopropylate,  -butylate, -isobutylate and tert-butoxide, also basic nitrogen compounds, such as Trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, di cyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethyl benzylamine, 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-ene (DBN), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2] octane (DABCO).

The reaction temperatures in process (b) according to the invention can be in can be varied over a wide range. Generally one works at Tem temperatures between 0 ° C and 120 ° C, preferably at temperatures between 10 ° C and 100 ° C.

Process (b) according to the invention is generally carried out under normal pressure carried out. However, it is also possible to increase or decrease it Pressure to work.

To carry out process (b) according to the invention, the respective be necessary starting materials are generally used in approximately equimolar amounts puts. However, it is also possible to use either of the two To use components in a larger excess. The reactions are generally in a suitable diluent in the presence an acid acceptor, and the reaction mixture becomes several Stirred for hours at the required temperature. The workup takes place in the method (b) according to the invention in each case by customary methods (see the manufacturing examples).

The process (c) according to the invention for the preparation of compounds of Formula (I) to be used as starting materials N-cyanoaryl nitrogen hetero Cycles are by the formula (I) - with the proviso that R² for halogen stands - generally defined.

In formula (I) then R¹, R³, R⁴ and Z preferably or in particular have those meanings that are already above in connection with the description  the compounds of formula (I) according to the invention preferably or as in particular were particularly preferably given for R¹, R³, R⁴ and Z.

The starting materials of the formula (I) for process (c) are new according to the invention Links; they can be prepared by processes (a) and (b) according to the invention be put.

To continue to be used as starting materials in process (c) according to the invention The amides are generally defined by the formula (VII).

In formula (VII), A preferably or in particular has the meaning that already above in connection with the description of the Ver Compounds of formula (I) preferably or as particularly preferred for A. was given.

The starting materials of formula (VII) are known organic synthesis chemicals.

Process (c) according to the invention is preferably carried out using a Diluent carried out. Above all those Ver fertilizers into consideration that have already been described in the invention according to method (a).

Process (c) according to the invention is optionally carried out in the presence of a Acid acceptor performed. Here, those acid acceptors come in Consideration already given in the description of the method (b) according to the invention were called.

The reaction temperatures in process (c) according to the invention can be in can be varied over a wide range. Generally one works at Tem temperatures between 0 ° C and 200 ° C, preferably at temperatures between 20 ° C and 180 ° C.  

Process (c) according to the invention is generally carried out under normal pressure carried out. However, it is also possible to increase or decrease it Pressure to work.

To carry out process (c) according to the invention, the respective be necessary starting materials are generally used in approximately equimolar amounts puts. However, it is also possible to use one of the two coms used in each case components in a larger excess. The reactions are in the generally in a suitable diluent in the presence of an acid Acceptors performed, and the reaction mixture is several hours at each required temperature stirred. The processing takes place at the he Process (c) according to the invention in each case by customary methods (cf. Her position examples).

The active compounds according to the invention can be used as defoliants, desiccants, herbs killers and especially used as weed killers. Weeds in the broadest sense are understood to mean all plants that are in places grow up where they are undesirable. Whether the substances according to the invention as total or selective herbicides act essentially depends on the applied Amount off.

The active compounds according to the invention can, for. B. in the following plants be used:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicot 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: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, sorghum, panicum, saccharum, pineapple, asparagus, allium.

However, the use of the active compounds according to the invention is by no means limited to. limited to these genera, but also extends in the same way other plants.

Depending on the concentration, the compounds are suitable for the total weed control z. B. on industrial and track systems and on paths and Places with and without tree cover. Likewise, the connections to Weed control in permanent crops, e.g. B. forest, ornamental trees, fruit, wine, Citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hops, on ornamental and sports turf and pastures and for selective Weed control can be used in annual crops.

The compounds of formula (I) according to the invention are particularly suitable for selective control of dicotyledon weeds in monocotyledons and dicotyledons Cultures such as B. in wheat, corn and soybeans, both in pre-emergence and in Post-emergence procedure, but the individual connections also in all mentioned cultures act selectively.

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient impregnated natural and synthetic materials as well as very fine encapsulation in polymeric fabrics.

These formulations are prepared in a known manner, e.g. B. by Vermi the active ingredients with extenders, i.e. liquid solvents and / or fe Most carriers, optionally using surface-active agents  agents, i.e. emulsifiers and / or dispersants and / or foam-producing agents Means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkylnaph thalines, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons substances such as cyclohexane or parartins, e.g. B. petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and esters, Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and Water.

The following are suitable as solid carriers: e.g. B. ammonium salts and natural rock powders such as kaolins, clays, Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic stone powder, such as highly disperse silica, aluminum oxide and Silicates, as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours and Granules made of organic material such as sawdust, coconut shells, corn cobs and tobacco stems; come in as emulsifying and / or foaming agents Question: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; when Dispersants come into question: z. B. lignin sulfite and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine 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 Weight percent active ingredient - preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their Formulations also in a mixture with known herbicides Weed control are used, with ready formulations or Tank mixes are possible.

Known herbicides are suitable for the mixtures, for example anilides, such as B. Diflufenican and Propanil; Arylcarboxylic acids, such as. B. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy alkanoic acid esters, such as. B. diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, Haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and Norflurazon; Carbamates, e.g. B. chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as e.g. B. alachlor, acetochlor, butachlor, Metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines such as e.g. B. Oryzalin, pendimethalin and trifluralin; Diphenyl ether, such as. B. Acifluorfen, Bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as B. chlorotoluron, diuron, fluometuron, isoproturon, linuron and Methabenzthiazuron; Hydroxylamines, such as. B. Alloxydim, Clethodim, Cyclo xydim, sethoxydim and tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, Imazamethabenz, imazapyr and imazaquin; Nitriles such as B. bromoxynil, Dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonylureas, such as B. amidosulfuron, bensulfüron-methyl, chlorimuron-ethyl, chlorosulfuron, Cinosulfuron, Metsulfuron-methyl, Nicosulfuron, Primisulfuron, Pyrazosulfuron ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, such as B. butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, Thiobencarb and triallates; Triazines, e.g. B. atrazine, cyanazine, simazine, Simetryne, Terbutryne and Terbutylazin; Triazinones such as e.g. B. hexazinone,  Metamitron and metribuzin; Others, such as B. aminotriazole, benfuresate, Bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, Ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plants nutrients and soil structure improvers are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used become. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.

The active compounds according to the invention can be used both before and after Emergence of the plants can be applied. You can also sow before sowing Be incorporated into the floor.

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 10 g and 10 kg of active ingredient per hectare of soil area, preferably between 50 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention start out the following examples.  

Manufacturing examples example 1 (Method (a))

1.8 g (10 mmol) of 3-amino-4,4,4-trifluoro-crotonic acid ethyl ester are dissolved in 30 ml Dimethylformamide and 2 ml of toluene and at 0 ° C to 5 ° C with 0.3 g (10th mmol) sodium hydride (80%) added. The mixture is at 30 ° C for 30 minutes stirred up to 5 ° C. After the mixture has cooled to -70 ° C., 0.9 g (5 mmol) 4-Cyano-2,5-difluorophenyl isocyanate - dissolved in 10 ml of toluene - added and the mixture is stirred at -60 ° C to -70 ° C for 150 minutes. After removing the Cooling bath 2 ml of acetic acid are added. Then add water to about diluted twice the volume and extracted with ethyl acetate. The organic phase is concentrated and the residue with diisopropyl ether Brought crystallization.

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

Example 2 (Method (b))

A mixture of 3.2 g (10 mmol) of 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro- 2,6-dioxo-4-trifluoromethyl-1 (2H) pyrimidine, 3.1 g (20 mmol) diethyl sulfate, 2.8 g Potassium carbonate and 100 ml of acetonitrile is heated under reflux for 3 hours. Then it is concentrated in vacuo, shaken with water / chloroform, the organic phase again concentrated in vacuo and the residue through Column chromatography (silica gel, petroleum ether / ethyl acetate 1: 1) separates.

The first fraction obtained is 0.30 g of 1- (4-cyano-2,5-difluorophenyl) -1,6-dihydro-2 ethoxy-6-oxo-4-trifluoromethyl-pyrimidine (amorphous) and as a second fraction 0.38 g 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro-2,6-dioxo-3-ethyl-4-trifl-uormethyl- 1 (2H) pyrimidine (amorphous, 1 H NMR: d = 6.36 ppm). Overall yield: 0.68 g (20% of theory).  

Example 3 (Method (c))

A mixture of 0.83 g (3 mmol) of 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro- 2,6-dioxo-3,4-dimethyl-1 (2H) pyrimidine, 0.32 g (3 mmol) methanesulfonamide, 0.6 g of potassium carbonate and 10 ml of dimethyl sulfoxide is heated to 120 ° C. for 10 hours. After cooling, the mixture is poured onto ice water and with 2N hydrochloric acid acidified. The organic phase is then extracted with ethyl acetate washed with water, dried with sodium sulfate and filtered. From the filtrate the solvent is carefully distilled off in a water jet vacuum.

0.8 g (76% of theory) of 1- (4-cyano-2-fluoro-5-methylsulfonylamino) are obtained phenyl) -3,6-dihydro-2,6-dioxo-3,4-dimethyl-1 (2H) -pyrimidine as a crystalline back stood (melting point <250 ° C).  

Analogous to Examples 1 to 3 and in accordance with the general Description of the manufacturing method according to the invention can for example the compounds of formula (I) listed in Table 2 below - or of the formulas (IA) and (IB) - are produced:

Table 2

Examples of the compounds of the formula (I)

Starting materials of formula (III) Example (III-1)

660 g of phosgene are condensed in 1.6 liters of chlorobenzene at -5 ° C to 0 ° C. Then a solution of 400 g of 4-cyano-2,5- difluoro-aniline in 800 ml of chlorobenzene was added dropwise within 60 minutes. The reaction mixture is then slowly (HCl evolution!) To 120 ° C heated, after reaching a temperature of 80 ° C continuously phosgene is initiated. After heating for one hour at 120 ° C, excess becomes Blown out phosgene with nitrogen and then worked up by distillation.

248 g (53% of theory) of 4-cyano-2,5-difluoro-phenyl isocyanate are obtained Boiling point 108-110 ° C / 14 mbar (melting point: 53 ° C).  

Starting materials of formula (IV) Example (IV-1)

A mixture of 11.5 g (0.05 mol) of 4-cyano-2-fluoro-5-methylsulfonylamino aniline, 18 g pyridine and 400 ml methylene chloride is stirred at 20 ° C with 13.0 g (0.05 mol) of ethyl chloroformate were added dropwise and that The reaction mixture is stirred for a further 30 minutes at 20 ° C. to 30 ° C. Then with water, then with 5% hydrochloric acid and again with water washed, dried with sodium sulfate, filtered and the filtrate concentrated. Of the the remaining residue is digested with a little ethyl acetate and the crystalline product is isolated by suction.

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

Analogously to example (IV-1), those in the following can also be used, for example Compounds of formula (IV) listed in Table 3 can be prepared.

Table 3

Examples of the compounds of the formula (IV)

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, mix 1 Part by weight of active ingredient with the specified amount of solvent, specifies the added amount of emulsifier and dilute the concentrate with water to the desired concentration.

Seeds of the test plants are sown in normal soil and after 24 hours doused with the active ingredient preparation. You keep the amount of water per Area unit expediently constant. The drug concentration in the Preparation does not matter, the only decisive factor is the application rate of the Active ingredient per unit area. After three weeks, the degree of damage to the Plants 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, for example, show the connections according to the manufacturing process Example 2 (2nd fraction) and 12 with good tolerance to crops such as B. corn, very strong action against 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, mix 1 Part by weight of active ingredient with the specified amount of solvent indicates that given amount of emulsifier and dilute the concentrate with water to the desired concentration. With the preparation of the active ingredient, you spray test plants, which have a height of 5-15 cm so that the respectively desired Active ingredient quantities are applied per unit area. After three weeks the degree of damage to the plants is rated in% damage in comparison to Development of the untreated control. It means:

0% = no effect (like untreated control)
100% = total annihilation

In this test, for example, show the connections according to the manufacturing process Example 2 (2nd fraction) and 12 with good tolerance to crops such as B. wheat, strong action against weeds.

Claims (10)

1. N-cyanoaryl nitrogen heterocycles of the general formula (I) in which
R¹ represents hydrogen or halogen,
R² represents halogen, cyano, amino or the grouping -N (A¹) SO₂A,
where A stands for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,
and A¹ represents hydrogen or represents optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, arylalkylcarbonyl or aryloxycarbonyl,
R³ represents hydrogen-halogen, cyano or optionally substituted alkyl,
R⁴ represents optionally substituted alkyl or together with R³ represents alkanediyl,
Z represents one of the groupings below wherein
R⁵ represents hydrogen, amino (only bonded to N) or in each case optionally substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl,
and their salts, the compounds 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 -i-propyl sulfonylamino-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluorometh-yl-1 (2H) -pyrimidine, 1- (4-cyano-5-ethylsulfonylamino-2 -fluorophenyl) -3,6-di hydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine, 1- (4-cyano-5- n-propylsulfonylamino-2-fluorine -phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-tri fluoromethyl-1 (2H) -pyrimidine and 1- (4-cyano-5-i-propylsulfonylamino-2-fluoro- phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) - pyrimidine are excluded. 2. N-cyanoaryl nitrogen heterocycles of the general formula (I) according to claim 1, characterized in that
R¹ represents hydrogen, fluorine, chlorine or bromine,
R² is fluorine, chlorine, bromine, cyano, amino or the grouping - N (A¹) SO₂A, in which
A represents a radical of the series alkyl, alkenyl or alkynyl, each optionally substituted by fluorine, chlorine, bromine, cyano or C₁-C₁alkoxy, each having up to 10 carbon atoms,
A is furthermore cycloalkyl or cycloalkyl alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁-Cteilalkyl and has 3 to 8 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the alkyl part,
A further for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkyl sulfonyl (which are each optionally substituted by fluorine and / or chlorine), by dimethylaminosulfonyl or diethylamino sulfonyl, by C₁-C₄alkoxycarbonyl (which is optionally substituted by fluorine, chlorine, bromine, methoxy or ethoxy), by phenyl, phenyloxy or phenylthio (which are each optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy) substituted aryl or arylalkyl having 6 or 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part,
A further for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄ alkoxycarbonyl (which are each optionally substituted by fluorine and / or chlorine), by phenyl, phenoxy or phenylthio (which are each optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy are) substituted heterocyclyl or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 4 nitrogen atoms and / or 1 to 2 oxygen or sulfur atoms in the saturated or unsaturated heterocyclyl part and optionally 1 to 4 carbon atoms in the alkyl part, and
A¹ for hydrogen or for alkyl, alkenyl, alkynyl, alkoxy, alkyl carbonyl or alkoxycarbonyl, each optionally substituted by halogen or C₁-C₄-alkoxy, each having up to 6 carbon atoms, or for phenylcarbonyl, naphthylcarbonyl, phenylmethyl carbonyl, naphthylmethylcarbonyl, phenoxycarbonyl or naphthyl oxycarbonyl (which are each optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy),
R³ represents hydrogen, fluorine, chlorine, bromine, cyano or alkyl which has 1 to 6 carbon atoms and is optionally substituted by fluorine and / or chlorine,
R⁴ represents alkyl which has 1 to 6 carbon atoms and is optionally substituted by fluorine, chlorine, bromine, methoxy or ethoxy,
or together with R³ represents alkanediyl having 2 to 8 carbon atoms, and
Z represents one of the groupings below wherein
R⁵ for hydrogen, amino or optionally substituted by fluorine, chlorine, bromine, cyano, C₁-C₄-alkoxy, C₁-C₄-alkyl carbonyl or C₁-C₄-alkoxy-carbonyl-substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl, each with up is 6 carbon atoms and their salts with bases, such as. B. sodium, potassium or calcium hydroxide, hydride, amide or carbonate, sodium or potassium C₁-C₄ alkanolates, ammonia, C₁-C₄-alkyl amino, di- (C₁-C₄-alkyl) -amines, tri- (C₁-C₄-alkyl) amines or also with tris (2-hydroxyethyl) amine, the compounds mentioned in claim 1 being excluded by disclaimer. 3. N-cyanoaryl nitrogen heterocycles of the general formula (I) according to claim 1, characterized in that
R¹ represents hydrogen, fluorine or chlorine,
R² is fluorine, chlorine, bromine, cyano, amino or the grouping - N (A¹) SO₂A, in which
A represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl which is optionally substituted by fluorine or chlorine,
A furthermore represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexyl methyl which is optionally substituted by fluorine, chlorine, bromine, methyl and / or ethyl,
A further for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methyl thio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, dimethylaminosulfonyl, methoxycarbonyloxyoxycarbonyl, ethoxycarbonyl or phenyl substituted phenyl, naphthyl, phenylmethyl or phenylethyl,
A further represents thienyl, pyrazolyl or pyridyl, which is optionally substituted by fluorine, chlorine, bromine, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methoxycarbonyl or ethoxycarbonyl, and
A¹ for hydrogen, for each optionally substituted by fluorine, chlorine, methoxy or ethoxy, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl, butynyl, methoxy, ethoxy, n - or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, represents phenylcarbonyl or phenoxycarbonyl,
R³ represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, ethyl, n- or i-propyl,
R⁴ represents in each case optionally substituted by fluorine or chlorine - methyl, ethyl, n- or i-propyl,
or together with R³ is trimethylene or tetramethylene, and
Z represents one of the groupings below wherein
R⁵ for hydrogen, amino or for each optionally substituted by fluorine, chlorine or cyano substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl, butynyl, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl and their salts with bases, such as. B. sodium, potassium or calcium hydroxide, hydride, amide or carbonate, sodium or potassium C₁-C₄ alkanolates, ammonia, C₁-C₄-alkylamines, di- (C₁-C₄-alkyl) - amines, tri- (C ₁-C₄-alkyl) amines or also with tris (2-hydroxyethyl) amine, the compounds mentioned in claim 1 being excluded by disclaimer. 4. Process for the preparation of N-cyanoaryl nitrogen heterocycles of the general formula (I) in which
R¹, R², R³, R⁴ and Z have the meanings given in claim 1
and their salts, characterized in that one

• (a) for the preparation of compounds of the formula (IA) and (IB) in which R⁵ represents hydrogen and R¹, R², R³ and R⁴ have the meanings given above,
  Aminoalkenic acid esters of the general formula (II) in which
  R³ and R⁴ have the meanings given above and
  R represents alkyl, aryl or arylalkyl,
  with cyanoaryl isocyanates of the general formula (III) in which
  R¹ and R² have the meanings given above,
  or with cyanoaryl urethanes (cyanoaryl carbamates) of the general formula (IV) in which
  R¹ and R² have the meanings given above and
  R represents alkyl, aryl or arylalkyl,
  if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
  or that one
• (b) for the preparation of compounds of the formulas (IA) and / or (IB) in which R⁵ represents optionally substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl and R¹, R², R³ and R⁴ have the meanings given above, N-cyanoaryl nitrogen heterocycles of the general formulas (IA) or (IB)
  in which R⁵ represents hydrogen and R¹, R², R³ and R⁴ have the meanings given above,
  with alkylating agents or acylating agents of the general formulas (V) or (VI) X-R⁵ (V) R⁵-O-SO₂-O-R⁵ (VI) in which R⁵ represents optionally substituted alkyl, alkenyl, alkynyl, alkylcarbonyl or alkoxycarbonyl and X in the formula (V) represents halogen,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,
  or that one
• (c) for the preparation of compounds of the formula (I) in which R² is amino or the grouping -N (A¹) SO₂A and A, A¹, R¹, R³ R⁴ and Z have the meanings given above,
  N-cyanoaryl nitrogen heterocycles of the general formula (I) in which R² represents halogen and R¹, R³, R⁴ and Z have the meanings given above,
  with ammonia or with amides of the general formula (VII) HN (A¹) SO₂A (VII) in which
  A and A¹ have the meanings given above,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.

5. Herbicidal agents characterized by a content of at least one N-cyanoaryl nitrogen heterocycle of the formula (I) according to the claims 1 to 4. 6. Process for combating undesirable plants, characterized records that N-cyanoaryl nitrogen heterocycles of the general Formula (I) according to claims 1 to 4 on the plants and / or their Living space. 7. Use of N-cyanoaryl nitrogen heterocytes of the general formula (I) according to claims 1 to 4 for combating undesirable Plants. 8. A process for the preparation of herbicidal compositions, characterized in that that N-cyanoaryl nitrogen heterocycles of the general formula (I) according to claims 1 to 4 with extenders and / or surfaces mixed active substances. 9. Cyanoaryl isocyanates of the general formula (III) in which
R¹ represents hydrogen or halogen,
R² represents halogen, cyano, amino or the grouping -N (A¹) SO₂A,
where A stands for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,
and A¹ stands for hydrogen or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, arylalkylcarbonyl or aryloxycarbonyl. 10. Cyanoaryl urethanes of the general formula (IV) in which
R¹ represents hydrogen or halogen,
R² represents halogen, cyano, amino or the grouping -N (A¹) SO₂A,
where A stands for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,
and A¹ represents hydrogen or represents optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, arylalkylcarbonyl or aryloxycarbonyl and
R represents alkyl, aryl or arylalkyl.