DE3822448A1 - Ureidobenzoic acid derivatives - Google Patents

Abstract

The invention relates to novel ureidobenzoic acid derivatives of the general formula (I) <IMAGE> (in which Hal represents halogen and the radicals R<1>, R<2> and R<3> have the meaning given in the description), to processes for their preparation, and to their use as herbicides.

Description

The present invention relates to new ureido-benzoic acid derivatives, several processes for their manufacture and their use as herbicides and growth regulators.

It is already known that certain benzoic acids and whose derivatives have herbicidal properties (cf. R. Wegler, "Chemistry of crop protection and pesticides", Volume 2, pages 289-295; Volume 5, pages 209-217, Springer-Verlag, Berlin (1970/1977).

It is also known that numerous arylureas such as e.g. B. N '- (4-isopropylphenyl) -N, N-dimethylurea (isoproturon) exhibit herbicidal activity (see R. Wegler, "Chemistry of pesticides and pesticides, Volume 2, pages 241-253, Volume 5, pages 122-141; 434-459).  

The herbicidal activity of these previously known compounds towards harmful plants is however as well their tolerance to important crops not always satisfactory in all areas of application.

There have now been new ureido-benzoic acid derivatives of the formula (I) found

in which
Hal stands for halogen,
R¹ represents hydrogen, a saturated or unsaturated aliphatic radical with up to 5 C atoms, which can optionally be substituted by alkoxy with 1-3 C atoms, or alkoxy with 1-4 C atoms,
R² represents hydrogen, a saturated or unsaturated aliphatic radical with up to 5 C atoms optionally substituted by halogen, hydroxy or C₁-C₄alkoxy, or for alkoxy with 1-4 C atoms,
R³ represents an optionally substituted, saturated or unsaturated aliphatic radical with up to 20 C atoms, the following being selected as substituents:
Halogen, nitro, cyano, a radical -D-R⁴, alkoximino, the groups -CO-OR⁵, -CO-NR⁶R⁷, cycloalkyl, aryl or a 5- or 6-membered heterocycle, where
D represents oxygen, sulfur, sulfinyl or sulfonyl and
R⁴ stands for hydrogen, alkyl, mono- or polyunsaturated alkenyl or for optionally substituted aryl or aralkyl or for -CO-alkyl,
R⁵ represents alkyl,
R⁶ and R⁷ each independently represent hydrogen, alkyl, cycloalkyl or optionally substituted aryl or aralkyl or
R⁶ and R⁷ together with the nitrogen to which they are attached represent a 5- to 7-membered heterocycle;
in which further
R³ represents in each case optionally substituted cycloalkyl, aryl or a 5- to 7-membered heterocycle,
or in which
R² and R³ together with the nitrogen atom bonded to them form a 5- to 7-membered heterocyclic ring.

It was also found that the new ureido benzoic acid derivatives of the formula (I) are obtained when

• a) 4-amino-benzoic acid amides of the formula (II) in which Hal, R² and R³ have the meaning given above, with methyl isocyanate of the formula (III) or a carbamic acid derivative of the formula (IV)
  • a1) CH₃-N = C = O (III) in which R¹ has the meaning given above and X represents halogen or a (C₆-C₁₀) aryloxy radical,
    if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
• or if you
• b) carbonic acid derivatives of 4-amino-benzoic acid amides of the formula (V) or (VI) in which Hal, R², R³ and X have the meaning given above,
  with amines of the formula (VII) in which R¹ has the meaning given above,
  if appropriate in the presence of a diluent and a (further) acid binder;
  or if you
• c) ureido-benzoic acids of the formula (VIII) in which Hal and R1 have the meaning given above,
  with amines of the formula (IX) in which R² and R³ have the meaning given above,
  in the presence of a water-binding agent and optionally in the presence of a diluent;
  or if you
• d) ureido-benzoic acid derivatives of the formula (X) in which R¹ and Hal have the meaning given above and A for halogen, for the rest or stands for imidazolyl,
  with compounds of the formula (IX), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

Finally, it was found that the new ureido-benzoic acid derivatives of the formula (I) herbicidal, in particular also selective herbicides, properties and more also have plant growth regulatory properties.

Surprisingly, the ureido according to the invention show benzoic acid derivatives of the formula (I) significantly improved general herbicidal activity against  Harmful plants compared to those from the prior art Technology known arylureas, which chemically and connections that are obviously effective. Furthermore show the compounds of formula (I) according to the invention plant growth regulatory efficacy.

The ureido-benzoic acid derivatives according to the invention are generally defined by the formula (I). Compounds of the formula (I) in which
Hal represents fluorine, chlorine or bromine,
R¹ represents hydrogen, saturated alkyl having 1 to 4 carbon atoms, unsaturated alkyl having 2 to 5 carbon atoms, which may optionally be substituted by alkoxy having 1 to 3 carbon atoms, or represents alkoxy having 1 to 4 carbon atoms,
R² represents hydrogen, alkyl, hydroxyalkyl or alkoxyalkyl each having 1 to 4 carbon atoms in the individual alkyl parts or alkenyl having 2 to 5 carbon atoms,
R³ represents in each case optionally substituted alkyl with 1 to 12 carbon atoms or for in each case mono- or polyunsaturated alkenyl or alkynyl each with up to 12 carbon atoms, the following being selected in each case as substituents:
Fluorine, chlorine, cyano, alkoximino with 1 to 4 carbon atoms in the alkyl part, optionally with C₁-C₄-alkyl and / or fluorine or chlorine substituted cycloalkyl with 3 to 6 carbon atoms, optionally with fluorine, chlorine, bromine, nitro, trifluoromethyl, C₁- C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl-substituted phenyl, a 5- or 6-membered heterocycle which contains 1 to 3 further heteroatoms from the series oxygen and / or can contain sulfur and / or nitrogen, a radical -D-R⁴, a radical -CO-OR⁵ or a radical -CO-NR⁶R⁷, wherein
D and R⁴ have the meaning given above,
R⁵ represents alkyl having 1 to 4 carbon atoms,
R⁶ and R⁷ each independently represent hydrogen or alkyl having 1 to 6 carbon atoms or
R⁶ and R⁷ together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocycle;
with which further
R³ is optionally by fluorine, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkenyl or halogen (C₁-C₄) - alkyl (where halogen represents 1 to 5 fluorine and / or chlorine atoms) substituted cycloalkyl having 3 to 8 carbon atoms or optionally substituted phenyl, where the phenyl substituents selected are:
Fluorine, chlorine, bromine, C₁-C₄-alkyl, halogen (C₁-C₄) - alkyl (where halogen represents 1 to 5 fluorine and / or chlorine and / or bromine atoms) or a radical -D¹-R⁸, where
D¹ represents oxygen, sulfur, sulfinyl or sulfonyl
R⁸ represents hydrogen, C₁-C₄-alkyl, halogen (C₁-C₄) - alkyl (where halogen represents 1 to 5 fluorine and / or chlorine atoms), C₂-C₄-alkenyl or a radical of the formulas

-CO-O- (C₁-C₄) alkyl,

-SO₂NH₂,
-SO₂-NH- (C₁-C₄) alkyl or

stands;
in which continue
R³ represents a 5- to 7-membered heterocycle which can contain one to three identical or different heteroatoms from the series oxygen, nitrogen or sulfur and which is optionally substituted by fluorine, chlorine, bromine, iodine, C₁-C₄alkyl, Halogen-C₁-C₄-alkyl (where halogen represents 1 to 5 identical or different fluorine, chlorine, bromine or iodine atoms), by amino, alkylamino or dialkylamino, each having 1 to 4 carbon atoms in the individual alkyl parts, by nitro, Cyano, the rest -D-R⁴ (with the same meaning for D and R⁴ as above) or by a rest of the formulas

-CO-O- (C₁-C₄) alkyl,

-CO-NH- (C₁-C₄) alkyl or

-CO-N (C₁-C₄-alkyl) ₂,

which may contain carbocyclic or further heterocyclic rings in condensed form;
or with which
R² and R³ together with the nitrogen atom to which they are attached form a 5- to 6-membered ring.

Compounds of the formula (I) in which
Hal represents fluorine or chlorine,
R¹ represents hydrogen, saturated alkyl having 1 to 4 carbon atoms, which may optionally be substituted by methoxy or ethoxy, or represents methoxy,
R² represents hydrogen, alkyl or alkoxyalkyl each having 1 to 4 carbon atoms in the individual alkyl parts or alkenyl having 2 to 5 carbon atoms,
R³ represents optionally monosubstituted to pentasubstituted, identically or differently substituted alkyl having 1 to 10 carbon atoms or represents in each case optionally monosubstituted to pentasubstituted, identically or differently substituted, mono- or polyunsaturated alkenyl or alkynyl, each having up to 10 carbon atoms, the substituents in each case being selected are:
Fluorine, chlorine, cyano, alkoximino with 1 to 4 carbon atoms in the alkyl part, optionally monosubstituted to trisubstituted, identically or differently, by C₁-C₄alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, optionally monosubstituted to triple, identically or differently, by fluorine, chlorine, Bromine, iodine, nitro, trifluoromethyl, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-alkylthio, C₁-C₂-alkylsulfinyl or phenyl substituted by C₁-C₄-alkylsulfonyl, a 5- or 6-membered heterocycle ( which can contain 1 to 3 heteroatoms from the series oxygen and / or sulfur and / or nitrogen) and a radical -D-R⁴, a radical -CO-OR⁵ or a radical -CO-NR⁶R⁷, where
D and R⁴ have the meaning given above,
R⁵ represents alkyl having 1 to 4 carbon atoms,
R⁶ and R⁷ each independently represent hydrogen or alkyl having 1 to 6 carbon atoms or
R⁶ and R⁷ together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocycle;
with which further
R³ for optionally single to triple, identical or different by fluorine, chlorine or C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₄-alkenyl or halogen-C₁-C₂-alkyl (where halogen for 1 to 3 fluorine and / or chlorine atoms) substituted cycloalkyl having 3 to 7 ring carbon atoms or phenyl optionally monosubstituted to trisubstituted by identical or different substituents, the phenyl substituents selected being:
Fluorine, chlorine, bromine, C₁-C₄-alkyl, trifluoromethyl or a radical -D¹-R⁸, wherein
D¹ represents oxygen, sulfur, sulfinyl or sulfonyl and
R⁸ represents hydrogen or C₁-C₄ alkyl;
in which continue
R³ is a 5- to 7-membered heterocycle which can contain one to three identical or different heteroatoms from the series oxygen, nitrogen or sulfur and which is optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine or iodine , C₁-C₂-alkyl, halogen-C₁-C₂-alkyl (where halogen represents 1 to 3 identical or different fluorine or chlorine atoms), by amino, alkylamino or dialkylamino, each having 1 to 2 carbon atoms in the individual alkyl parts, by nitro , Cyano or by a C₁-C₄-alkoxy, C₁-C Alkyl-alkylthio or C₁-C₄- alkylsulfonyl radical,
or with which
R² and R³ together with the nitrogen atom to which they are attached form a 5- or 6-membered ring.

The group of compounds of the formula (I) in which
Hal stands for chlorine,
R¹ represents hydrogen, alkyl having 1 to 3 carbon atoms, which may optionally be substituted by methoxy or ethoxy, or represents methoxy,
R² represents hydrogen, alkyl having 1 to 4 carbon atoms or alkenyl having 3 to 5 carbon atoms,
R³ is in each case optionally mono- to pentasubstituted, identical or differently substituted alkyl having 1 to 10 carbon atoms, in each case mono- or polyunsaturated alkenyl or alkynyl each having up to 10 carbon atoms, the substituents selected in each case:
Fluorine, chlorine, cyano, alkoximino with 1 to 4 carbon atoms in the alkyl part, optionally monosubstituted to trisubstituted, identically or differently, by C₁-C₄alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, optionally monosubstituted to triple, identically or differently, by fluorine, chlorine, Bromine, iodine, nitro, trifluoromethyl, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-alkylthio, C₁-C₂-alkylsulfinyl or phenyl substituted by C₁-C₄-alkylsulfonyl, a 5- or 6-membered heterocycle ( which can contain 1 to 3 heteroatoms from the series oxygen and / or sulfur and / or nitrogen) and a radical -D-R⁴, where
D represents oxygen, sulfur or sulfonyl and
R⁴ stands for hydrogen, for alkyl with 1 to 4 carbon atoms, for alkenyl with 2 to 4 carbon atoms, each optionally monosubstituted to trisubstituted, identically or differently substituted, phenyl, benzyl or phenethyl, with fluorine, chlorine, bromine, C₁-C₂ as phenyl substituents -Alkyl or C₁-C₂ alkoxy are selected;
with which further
R³ represents optionally monosubstituted to trisubstituted, identically or differently, fluorine, chlorine or C₁-C₄alkyl-substituted cycloalkyl having 3 to 6 carbon atoms or optionally monosubstituted to trisubstituted, identically or differently, phenyl, the following being selected as phenyl substituents:
Fluorine, chlorine, bromine, C₁-C₄-alkyl, trifluoromethyl or a radical -D¹-R⁸, wherein
D¹ represents oxygen and
R⁸ represents hydrogen or C₁-C₄ alkyl;
in which continue
R³ is a 5- to 7-membered heterocycle which can contain one to three identical or different heteroatoms from the series oxygen, nitrogen or sulfur and which is optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine or iodine , C₁-C₂-alkyl, halogen-C₁-C₂-alkyl (where halogen represents 1 to 3 identical or different fluorine or chlorine atoms), by amino, alkylamino or dialkylamino, each having 1 to 2 carbon atoms in the individual alkyl parts, by nitro , Cyano, C₁-C₄-alkoxy, C₁-C₄-alkylthio or C₁-C₄-alkylsulfonyl,
or with which
R² and R³ together with the nitrogen atom to which they are attached form a 5- or 6-membered ring which can be substituted by one or more alkyl groups having 1 to 4 carbon atoms and / or in addition to carbon atoms, an oxygen, a sulfur atom or can contain another nitrogen atom as a ring member.

Typical examples of the ureido-benzoic acid derivatives according to the invention of formula (I) - in addition to compounds described in the preparation examples - are listed in Table 1 below:  

Table 1

For example, 2-chloro-4-amino-benzoic acid-N-tert-butylamide is used and methyl isocyanate as starting materials, so can the course of the reaction of the invention Procedure a1) by the following formula represent:

If you use e.g. B. N-Methyl-N-ethyl-carbamic acid chloride and 2-chloro-4-amino-benzoic acid-N-ethyl-N-ethoxyamide as starting materials, the course of the reaction can the method a2) according to the invention by the following Formula scheme are reproduced:

For example, 3-chloro-4-dimethylaminocarbonyl phenyl isocyanate is used and dimethylamine as starting materials, so can the course of the reaction of the invention Method b1) by the following formula represent:

If, for example, N- [3-chloro-4- (tert-butylaminocarbonyl) phenyl] carbamic acid phenyl ester is used and O, N-dimethyl-hydroxylamine as starting materials, so lets the course of the reaction of the process according to the invention b2) by the following formula:

For example, 2-chloro-4- (N ', N'-dimethylureido) benzoic acid is used and piperidine as starting materials, so can the course of the reaction of the invention Process c) represented by the following formula:

For example, if you use the mixed anhydride 2-fluoro-4- (N ′, N′-dimethylureido) benzoic acid and carbonic acid ethyl ester and isopropylamine as starting materials, so can the course of the reaction of the invention Process d) by the following formula scheme:

To carry out the method according to the invention a) 4-Amino-benzoic acid amides are required by the Formula (II) generally defined.

In this formula (II), R², R³ and Hal are preferably or particularly preferred for those residues that already in connection with the description of the invention Substances of the formula (I) as preferred or were particularly preferred for these substituents. The above are very particularly preferred Substituents of formula (II) for being very special preferably listed corresponding radicals of the formula (I).

The starting compounds of formula (II) are only partial known. This is preferably obtained by using 2-halo-4-nitrobenzoic acid amides of the formula (XI)

in which Hal, R² and R³ have the meaning given above,
reduced in a conventional manner. As a reducing agent such. B. metals such as iron, zinc or tin, salts of metals in lower valence levels such as SnCl₂, salts of hydrogen sulfide, sulfites, dithionites, hydrazine, and catalytically excited hydrogen.

The still required as raw materials Compounds of the formulas (III) and (IV) are basic known or can be according to literature Establish process.

To carry out the method according to the invention b) required 4-amino-benzoic acid amides are through the formula (V) is generally defined.

In this formula (V), R², R³ and Hal are preferably or particularly preferred for those residues that already in connection with the description of the invention Substances of the formula (I) as preferred or were particularly preferred for these substituents. The above are very particularly preferred Substituents of formula (V) for that as very special preferably listed corresponding radicals of the formula (I).

The compounds of formula (V) have not yet been used known. This is preferably won by clicking on the 4-amino-benzoic acid amides already mentioned and defined above of formula (II) can act phosgene. This is preferably done in inert solvents such as Toluene or chlorobenzene or aliphatic chlorinated hydrocarbons at temperatures between 0 ° C and 150 ° C; the course of the reaction can be by the following formula are reproduced:  

To carry out the method according to the invention b) usable 4-amino-benzoic acid derivatives (VI) also generally defined by this formula. In of this formula, R², R³, Hal and X are preferably or particularly preferred for those residues that already in connection with the description of the invention Substances of formula (I) as preferred or special were preferred for these substituents. All the above-mentioned substituents are particularly preferred of the formula (VI) for being very particularly preferred enumerated corresponding radicals of the formula (I).

These compounds of formula (VI) are not yet known. In the case where X in formula (VI) is an aryloxy radical means, you get this by looking at isocyanates of the formula (V) phenols or anilines of the formula (II) chlorophenic acid phenyl act according to the following formula:  

These reactions are carried out in a generally known manner, preferably in inert solvents such as hydrocarbons, Halogenated hydrocarbons, ethers, ketones or esters, preferably in the second case in the presence of an acid-binding agent such as alkali and alkaline earth carbonates or tertiary amines.

The continue as starting materials for the invention Process b) required amines are given by the Formula (VII) generally defined.

In this formula (VII), R1 is preferably or particularly preferred for those residues that are already related with the description of the invention Substances of the formula (I) as preferred or particularly preferred for these substituents. Most notably the above-mentioned substituents are preferred of the formula (VII) for being very particularly preferred enumerated corresponding radicals of the formula (I).  

These substances are generally known.

To carry out the method according to the invention c) Ureido-benzoic acids are required by the formula (VIII) generally defined.

In this formula (VIII), R1 and Hal are preferably or particularly preferred for those residues that already in connection with the description of the invention Substances of the formula (I) as preferred or particularly preferred for these substituents were. The above are very particularly preferred Substituents of formula (VIII) for that as very special preferably enumerated corresponding residues of Formula (I).

So far, these compounds of formula (VIII) are only partially known. They are preferably made by corresponding ureido-benzoic acid ester of Formula (XII) in which R 1 and Hal have the meaning given above have and R⁹ for a lower (C₁-C₄) alkyl radical or the phenyl radical, alkaline saponification subject, according to the following reaction scheme:

This saponification takes place according to methods known from the literature, e.g. B. with aqueous sodium or potassium hydroxide solution, preferably in the presence of a water-miscible solvent, like methanol or ethanol, at temperatures between 0 ° C and 100 ° C. The free acids of the formula (VIII) are then acidified with mineral acids set free from the resulting alkali salts.

The starting materials of the formula required for this (XII) are made from the partially known benzoic acid Derivatives of the formula (XIII) prepared in an analogous manner, as it is for the manufacture of the invention Compounds of formula (I) according to process a) or b) is described above. The course of the reaction is as follows Formula scheme:  

To carry out the method according to the invention c) Amines still required are given by the formula (IX) generally defined. In this formula (IX) stand R² and R³ preferably or particularly preferred for those Leftovers already related to the description the substances of the formula (I) according to the invention as preferred or particularly preferred for these substituents were called. Stand very particularly preferably the above-mentioned substituents of formula (IX) for the as a very particularly preferred listed corresponding Residues of formula (I).

These compounds are known from the literature.

To carry out the method according to the invention d) Ureido-benzoic acid derivatives are required by the formula (X) is generally defined.

In this formula (X), R 1 and Hal preferably or particularly preferably represent those radicals which have already been mentioned as preferred or particularly preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention. The abovementioned substituents of the formula (X) very particularly preferably represent the corresponding radicals of the formula (I) listed as very particularly preferred.
A is preferably chlorine, -O-CO-OCH₃, -O-CO-OC₂H₅, -O-CO-O-CH₂-C₆H₅, -O-SO₂-C₆H₅ and -O-SO₂-C₆H₄-CH₃ (p).

The compounds of formula (X) are not yet in the Literature described. You basically win them known methods by using ureido-benzoic acids Formula (VIII) with a carbonic acid alkyl ester chloride or a sulfonic acid chloride, preferably methane, Benzene or toluenesulfonic acid chloride, preferably in inert solvents and in the presence of an acid-binding Agents such as triethylamine, dimethylaniline or Converts pyridine at temperatures between -10 ° C and + 100 ° C, according to the following formula:

These compounds of formula (X) usually need not to be isolated, but can in the after raw, mostly loosened form directly into the subsequent reactions according to procedure d) be introduced.  

The reaction temperatures can be carried out the method (a-d) according to the invention within a larger range can be varied. You work without Solvents and acid binders, that's the way to go general in such a way that the components at first Temperatures between -20 ° C and + 20 ° C can react and then, if necessary, to temperatures between 70 ° C and 200 ° C heated. If you work in the presence of a Diluent and an acid binder, so lie the reaction temperatures generally between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C.

The process according to the invention is generally described in Normal pressure carried out.

To carry out the processes (a-d) according to the invention are used per mole of benzoic acid derivative of the formulas (II), (V), (VI), (VIII) or (X) generally 1.0 to 5.0 moles, preferably 1.0 to 2.0 moles, of compound of Formulas (III), (IV), (VII) and (IX) and, if applicable 1.0 to 3.0 moles, preferably 1.0 to 2.0 moles, of acid binder a.

When carrying out the method according to the invention c) is based on a previous manufacture of a reactive No benzoic acid derivatives, but a water-binding one Funds needed. As such are inorganic acid chlorides such as B. thionyl chloride, phosphorus (III) chloride and phosphorus oxychloride.  

As a diluent for carrying out the inventive Processes (a-d) come in inert organic solvents in question. These include in particular aliphatic or aromatic, optionally halogenated Hydrocarbons such as gasoline, benzene, Toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, Dichloromethane, chloroform carbon tetrachloride, Ethers such as diethyl ether, dioxane, tetrahydrofuran or Ethylene glycol dimethyl or diethyl ether, ketones such as Acetone or butanone, nitriles such as acetonitrile or propionitrile, Amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, Esters such as ethyl acetate, Sulfoxides or sulfones such as dimethyl sulfoxide or sulfolane.

As an acid binder to carry out some variants Processes a) and b) according to the invention all come usual inorganic or organic bases in question. Tertiary amines such as triethylamine are preferably used, Pyridine or N, N-dimethylaniline, alkaline earth metal oxides such as magnesium and calcium oxide, alkali and alkaline earth metal carbonates such as sodium, potassium or calcium carbonate, Alkali metal hydroxides, hydrides or alcoholates such as sodium hydroxide or potassium hydroxide, sodium hydride, Sodium methylate or potassium t-butoxide.

The processing takes place according to usual methods. In general one goes with the manufacturing method according to the invention so that one removes precipitated salts  and the remaining reaction mixture by stripping of the diluent is concentrated. Do you work in Presence of water or water-miscible solvents, one can also proceed in such a way that the reaction mixture diluted with water, the resulting mixture suction or with a water-immiscible organic solvent extracted, the organic Phase washes, concentrates and the remaining residue subject, if necessary, to conventional cleaning processes.

The active compounds according to the invention can be used as defoliants, Disiccants, herbicides and especially as Weed killers are used. Under weeds in the broadest sense all plants are to be understood who grow up in places where they are undesirable. Whether the substances according to the invention as total or selective Herbicides act essentially depends on the applied amount.

The active compounds according to the invention can, for. B. at the following plants can 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, Rorippernia, Rorippa Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

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

Monocot 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, Spochhenium, Ischatenumum, Ischaeaeaum 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 these genres, but extends to other plants in the same way.

The compounds are suitable depending on the Total weed control concentration e.g. B. on industrial and track systems and on paths and squares and without tree cover. Likewise, the connections to Weed control in permanent crops, e.g. B. forest, ornamental wood, Fruit, wine, citrus, nut, banana, coffee,  Tea, gum, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annuals Cultures are used.

The active compounds according to the invention can also be used particularly good success for selective control of mono- and dicotyledon weeds, preferably in monocotyledons Use crops such as wheat and barley.

The active compounds according to the invention also apply in the metabolism of plants and therefore can be used as growth regulators.

For the mode of action of plant growth regulators Experience has shown that an active ingredient also several different effects on plants can exercise. The effects of the substances depend essentially from the time of application related to the stage of development of the plant as well as from the on the plants or their surroundings applied amounts of active ingredient and the type of application. In any case growth regulators are supposed to regulate the crops in certain influence as desired.

Plant growth regulating substances can be used, for example Inhibition of vegetative growth of the plants used will. Such inhibition of growth is, among other things for grasses of economic interest, because this can reduce the frequency of grass cuts in ornamental gardens, Park and sports facilities on the side of the road  Airports or in orchards. From It is also important to inhibit the growth of herbaceous plants and woody plants on and around roadsides of pipelines or overland lines or more generally in areas where there is a strong growth of plants is undesirable.

The use of growth regulators is also important to inhibit the length growth of cereals. Hereby there is a risk of the plants bending reduced or completely eliminated before harvest. In addition, growth regulators in cereals can be a Culm reinforcement that also cause storage counteracts. The application of growth regulators for shortening and strengthening the straw, it allows spreading more fertilizer to increase the yield, without the risk of the grain being stored.

An inhibition of vegetative growth enables many crops a denser planting, so that Additional yields can be achieved based on the floor area can. An advantage of the smaller plants achieved in this way is also that the crop is more easily worked and harvested can be.

An inhibition of the vegetative growth of the plants can also lead to increased yields in that the  Nutrients and assimilates to a greater extent and fruiting benefit as the vegetative Plant parts.

With growth regulators, one can often also Achieve vegetative growth. This is of great use if the vegetative parts of the plant be harvested. Promoting vegetative growth can also promote the lead to generative growth in that more assimilates are formed so that more or larger fruits arise.

In some cases, yield increases can be achieved through a Interference in plant metabolism can be achieved without changes in vegetative growth to make noticable. Can also use growth regulators achieved a change in the composition of the plants become a quality improvement who can carry crop products. For example, it is possible the sugar content in sugar beets, To increase sugar cane, pineapple as well as in citrus or to increase the protein content in soy or cereals. It is also possible, for example, to break down more desirable Ingredients such as B. Sugar in sugar beets or sugar cane with growth regulators before or after to inhibit the harvest. In addition, the production or the drainage of phytochemicals influence positively. Take stimulation as an example of latex flow in rubber trees.  

Under the influence of growth regulators, it can become Formation of parthenocarpic fruits come. Furthermore, the gender of the flowers can be influenced. Can too sterility of the pollen is generated, which in the case of Breeding and production of hybrid seeds a big one Has meaning.

By using growth regulators, the Control branching of plants. On the one hand, by Breaking apical dominance the development of side shoots are promoted, especially in ornamental plant growing very desirable also in connection with growth inhibition can be. On the other hand, it is also possible to inhibit the growth of the side shoots. For this Effect exists. B. great interest in tobacco growing or when planting tomatoes.

Under the influence of growth regulators Leaves of the plants are controlled so that a Defoliate the plants at a desired time is achieved. Such defoliation plays at mechanical harvesting of cotton plays a major role but is also in other cultures such. B. in viticulture to facilitate the harvest of interest. A defoliation the plants can also be made to the Reduce transpiration of plants before transplanting.

The fall of fruit is also possible with growth regulators Taxes. On the one hand, premature fruit fall can be prevented  will. On the other hand, the fruit fall can also or even dropping the flowers to a desired one Measures are promoted ("thinning") to the Breaking alternance. Alternance means that Peculiarity of some types of fruit, endogenous from year to year to bring very different returns. In the end it is possible with growth regulators at the time the harvest necessary to remove the fruit Reduce forces to mechanical harvesting to enable or facilitate manual harvesting.

Acceleration can also be achieved with growth regulators or delaying the ripening of the crop Reach before or after harvest. This is special Advantage, because it allows optimal adjustment leads to the needs of the market. Farther growth regulators can in some cases Improve fruit coloring. In addition, with Growth regulators also focus on time maturity can be achieved. This creates the prerequisites created that z. B. with tobacco, tomatoes or coffee a complete mechanical or manual harvest can be done in one operation.

By using growth regulators, the Plant seed or bud rest are affected, so that the plants such. B. pineapple or ornamental plants  germinate in nurseries at one time, sprout or bloom, at which they are usually unwilling to do so demonstrate. A delay in the sprouting of Buds or the germination of seeds with the help of growth regulators may be desirable in areas at risk of frost to avoid damage from late frosts.

Finally, resistance to growth regulators the plants against frost, drought or high salinity of the soil are induced. This will make the Cultivation of plants possible in areas that are usually unsuitable for this.

The active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, wettable powders, Suspensions, powders, dusts, pastes, soluble Powders, granules, suspension emulsion concentrates, Active substance-impregnated nature and synthetic Substances, fine encapsulation in polymeric substances and in coating compositions for seeds and ULV formulations.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with Extenders, i.e. liquid solvents and / or solid carriers, optionally using of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam generators Means.  

In the case of the use of water as an extender e.g. B. also organic solvents as auxiliary solvents be used. As a liquid solvent essentially come into question: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic Hydrocarbons such as cyclohexane or paraffins, 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 finely divided silica, aluminum oxide and silicates, come as solid carriers for granules in question: e.g. B. broken and fractional natural Rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifier and / or foam generator Means are possible: B. non-ionic and anionic Emulsifiers such as polyoxyethylene fatty acid esters,  Polyoxyethylene fatty alcohol ether, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates as well as protein hydrolyzates; come in as dispersants Question: e.g. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can 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 phthalocyanine dyes and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 wt .-% active ingredient, preferably between 0.5 and 90% by weight.

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known ones Find herbicides for weed control, wherein Ready formulations or tank mixes possible are.  

Known herbicides such as z. B. 1-Amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) - dione (Amethydione) or N- (2-benzothiazolyl) -N, N'-dimethyl-urea (Metabenzthiazuron) for Weed control in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one (Metamitron) for weed control in sugar beets and 4-amino-6- (1,1-dimethylethyl) -3-methylthio-1,2,4-triazin-5 (4H) -one (Metribuzin) for weed control in soybeans, in question. Also Mixtures with 3,5,6-trichloro-2-pyridinyloxy acetic acid (Triclopyr); Dichloropicolinic acid; N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline (Pendimethalin); N- (3-chloro-4-methylphenyl) -N ', N'-dimethylurea (Chlorotoluron); 2- (1-alloxyaminobutylidene) -4-methoxycarbonyl-5,5-dimethylcyclohexane - 1,3-dione (Alloxydim); 2,4-dichlorophenoxyacetic acid (2,4-D); 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (bentazone); Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (Bifenox); 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil); 2-Chloro-N - [(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl-b-enesulfonamide (Chlorosulfuron); 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid, the Methyl or its ethyl ester (diclofop); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5 (4H) -one (Ethiozine); 2-4 - [(6-chloro-2-benzoxazolyl) -oxy] -phenoxypropanoic acid, their methyl or their ethyl ester (fenoxaprop);  [(4-Amino-3,5-dichloro-6-fluoro-2-pyridinyl) -oxy] acetic acid or their 1-methylheptyl ester (fluroxypyr); Methyl 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl] -4 (5) methylbenzoate (Imazamethabenz); 3,5-diiodo-4-hydroxybenzonitrile (ioxynil); N, N-Dimethyl-N '- (4-isopropylphenyl) urea (Isoproturon); (2-methyl-4-chlorophenoxy) acetic acid (MCPA); (4-chloro-2-methylphenoxy) propionic acid (MCPP); N-methyl-2- (1,3-benzothiazol-2-yl-oxy) acetanilide (Mefenacet); 2 - [[((4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino) carbonyl] amino] sulfonyl benzoic acid or their methyl esters (Metsulfuron); 0- (6-chloro-3-phenyl-pyridazin-4-yl) -S-octyl-thiocarbonate (Pyridates); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (Terbutryne) and 3 - [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] - sulfonyl] thiophene-2-carboxylic acid -methyl ester (Thiameturon) may be an advantage. Some Mixtures surprisingly also show synergistic effects Effect.

Also a mixture with other known active ingredients such as Fungicides, insecticides, acaricides, nematicides, Protection against bird feed, plant nutrients and Soil improvers are possible.

The active ingredients as such, in the form of their formulations or the one prepared therefrom by further dilution Application forms such as ready-to-use solutions, Suspensions, emulsions, powders, pastes and granules  be applied. The application is done in the usual way Way, e.g. B. by pouring, spraying, spraying, scattering. It is also possible to use the active ingredients according to the ultra-low-volume method apply or the drug preparation or the active ingredient itself in the soil inject. It can also treat the seeds of the plants will.

The active compounds according to the invention can be used both before and can also be applied after the plants have emerged. They can also be worked into the soil before sowing will.

The amount of active ingredient used can be greater Fluctuate range. It essentially depends on the type of the desired effect. In general, the Application rates for herbicide application between 0.01 and 15 kg of active ingredient per hectare of soil, preferably between 0.05 and 10 kg per ha.

When used as growth regulators, the Active substances according to the invention also in the formulations are present in a mixture with other known active ingredients, such as fungicides, insecticides, acaricides and herbicides as well as in mixtures with fertilizers and others Growth regulators.

The application rates can be used as a growth regulator also varied over a wide range  will. Generally used per hectare Floor area from 0.01 to 50 kg, preferably 0.05 to 10 kg Active ingredient.

For the application period, the application of the Growth regulators made in a preferred period whose exact demarcation is based on the climatic and vegetative conditions.

The production and use of the invention Active ingredients are shown in the following examples.

Manufacturing examples Example 1

22.6 g (0.1 mol) of 2-chloro-4-amino-benzoic acid tert-butylamide are dissolved in 150 ml of tetrahydrofuran. 6.5 g (0.115 mol) of methyl isocyanate are added dropwise at room temperature. The mixture is stirred for 2 hours at room temperature and for 2 hours at 50 ° C, then evaporated in vacuo. This gives 2-chloro-4- (N'-methyl-ureido) -benzoic acid tert-butylamide in practically quantitative yield.
Melting point: 120-122 ° C (from toluene / diethyl ether).

Example 2

To the solution of 19.8 g (0.1 mol) of 2-chloro-4-amino-benzoic acid dimethylamide in 150 ml of toluene Room temperature until saturation phosgene. The solution gradually becomes weak with further introduction of phosgene heated to boiling and finally for so long  boiled under reflux until the temporarily occurred Almost completely solved the precipitation. Subsequently one drives residual quantities by blowing in nitrogen Phosgene and hydrogen chloride, the solution is filtered and then conducts gaseous dimethylamine at 15-25 ° C to a slight excess. Small amounts insoluble Shares are filtered off. The one after distilling off of the solvent remaining residue stirred with a little diethyl ether and with ice cooling left for a few hours. The educated Crystals are suctioned off and air dried. 23.4 g (87% of theory) of 2-chloro-4- (N ′, N′-dimethyl-ureido) -benzoic acid-dimethylamide are obtained from the melting point 116-118 ° C.

Example 3

In the solution of 34.6 g (0.1 mol) of 2-chloro (4-phenoxycarbonylamino) benzoic acid tert-butylamide in 250 ml About 10 g (approx 0.2 mol) of dimethylamine. With weak initiation the solution is gradually heated to further dimethylamine to boil and cook for 2 hours under reflux. The remaining after distilling off the solvent  The residue is dissolved in 200 ml of dichloromethane, the solution twice briefly with very dilute aqueous sodium hydroxide solution shaken and then washed neutral. The solution is dried over sodium sulfate evaporated, the residue with a little diisopropyl ether stirred. The deposited crystals are suctioned off and air dried. 20.2 g (68% d. Th.) 2-Chloro-4- (N ', N'-dimethyl-ureido) -benzoic acid tert-butylamide melting point 162-164 ° C.

Example 4

27 g (0.1 mol) of 2-chloro-4- (N'-methyl-N'-isopropyl-ureido) -benzoic acid are dissolved in 200 ml of tetrahydrofuran. 10.1 g (0.1 mol) of triethylamine are added and the mixture is added dropwise with ice cooling at 10-15 ° C 10.85 g (0.1 mol) of carbonic acid ethyl ester chloride a. The mixture is 2 hours stirred at room temperature. Then you give 7.3 g (0.1 mol) tert-butylamine, stirred for 1 hour at room temperature and heated under reflux for a further 2 hours. The mixture is evaporated in vacuo, the residue taken up in dichloromethane. This solution will with water, dilute sodium hydroxide solution and again with water washed, dried and evaporated. 24.4 g are obtained  (75% of theory) 2-chloro-4- (N'-methyl-N'-isopropyl-ureido) -benzoic acid tert.-butylamido from the melting point 164 ° C (from White spirit).

Analogous to Examples 1-4 or according to the general Description of the manufacturing method according to the invention can also be used in Table 2 below Compounds of formula (I) listed will:

Table 2

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

In a stirred autoclave, a solution of 25.7 g (0.1 mol) 2-chloro-4-nitro-benzoic acid tert-butylamide (Mp: 138-140 ° C) in 200 ml of dioxane with 5 g of Raney nickel transferred. Press into the closed container 20-30 ° C and 40 bar overpressure hydrogen until the Pressure remains constant. The vessel is relaxed, the catalyst suction filtered and the solution evaporated in vacuo. 22.3 g (practically quantitative yield) 2-chloro-4-amino-benzoic acid tert-butylamide. Melting point: 106-108 ° C.

Example (II-2)

2-Chloro-4-amino-benzoic acid (S) -1-phenyl-ethylamide is obtained in an analogous manner from the melting point 106 ° C (from Toluene).

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

22.6 g (0.1 mol) of 2-chloro-4-amino-benzoic acid tert-butylamide are dissolved in 250 ml of tetrahydrofuran. For this 10.1 g (0.1 mol) of triethylamine are added and then added dropwise with cooling at 10-15 ° C 15.7 g (0.1 mol) carbonic acid phenyl ester chloride a. The mixture becomes 2 Stirred for hours at room temperature and then in vacuo evaporated. The residue is dissolved in 200 ml dichloromethane dissolved, with water, dilute hydrochloric acid and again washed with water. The one dried over sodium sulfate Solution is evaporated, the remaining one The residue is stirred with a little ether, suction filtered and dried. 26 g (75% of theory) of 2-chloro-4-phenoxycarbonylamino-benzoic acid tert-butylamide are obtained from Melting point 158-160 ° C.

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

27 g (0.1 mol) of 2-chloro-4- (N ′, N′-dimethyl-ureido) -benzoic acid ethyl ester are dissolved in 250 ml of ethanol. 9 ml (0.15 mol) of conc. Caustic soda and the mixture is refluxed for 2 hours. The ethanol is distilled off in vacuo, the residue in water  dissolved, the solution acidified, the precipitate suctioned off and dried. 17 g (70% of theory) are obtained 2-chloro-4- (N ′, N′-dimethyl-ureido) -benzoic acid from Melting point 168-170 ° C (from ethyl acetate).

Analogue are available:

Example (VIII-2)

2-chloro-4- (N′-methyl-ureido) benzoic acid, melting point: 225-226 ° C.

Example (VIII-3)

2-chloro-4- (N'-methyl-N'-isopropyl-ureido) benzoic acid, Melting point: 171-172 ° C.

Starting materials of the formula (XII) Example (XII-1)

In the solution of 100 g (0.5 mol) of 2-chloro-4-amino-benzoic acid ethyl ester in 1 l of toluene is passed at room temperature until saturation phosgene. Among others weak introduction of phosgene, the mixture is heated gradually to the boil and then boil down Reflux until a clear solution is obtained. in the  Nitrogen stream is then distilled about 0.5 l of toluene from. The remaining solution is passed under cooling at 10-15 ° C dimethylamine until weakly basic reaction a. The precipitated salt is filtered off, the Evaporated solution in vacuo. Remain as a residue 116 g (86% of theory) of ethyl 2-chloro-4- (N ′, N′-dimethylureido) benzoate from melting point 104-106 ° C (from Toluene).

Example (XII-2)

In an analogous manner, ethyl 2-chloro-4- (N'-methyl-N'-isopropyl-ureido) benzoate is obtained from the melting point 77-78 ° C.

Example (XII-3)

In the solution of 20 g (0.1 mol) of 2-chloro-4-amino-benzoic acid ethyl ester dropwise in 150 ml of tetrahydrofuran at room temperature 6 g (0.105 mol) of methyl isocyanate. The Mixture is 2 hours at room temperature and 2 hours stirred at 35-40 ° C and then in weakly with hydrochloric acid acidified water stirred. The secluded Crystals are suctioned off and dried. You win 25 g (practically quantitative) of 2-chloro-4- (N'-methyl-ureido) -benzoic acid ethyl ester melting point 150-151 ° C (from ethanol).  

Example A Post emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation you mix 1 part by weight of active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with Water to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with the active substance preparation, so that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 2000 l of water / ha. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
It means:

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

In this test, for example, the connections show of the production examples (3), (10), (13), (20), (21)  and (22) - compared to the comparative agent isoproturon with approximately the same tolerability Cultivated plants such as B. wheat and barley considerably stronger action against weeds such as B. Amaranthus, Ipomoea, Mentha, Sinapis and Veronica, at an application rate from Z. B. 500 g / ha.  

Example B Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, gives the specified amount of emulsifier and dilute the concentrate with water on the desired concentration.

Seeds of the test plants are sown in normal soil and watered with the active ingredient preparation after 24 hours. The amount of water per unit area is kept expediently constant. The drug concentration in the preparation does not matter, it is crucial only 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 development the untreated control. It means:

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

In this test, the compounds according to the invention show the formula (I) very good effect.

Claims (9)

1. Ureido-benzoic acid derivatives of the general formula (I) in which
Hal stands for halogen,
R¹ represents hydrogen, a saturated or unsaturated aliphatic radical with up to 5 C atoms, which can optionally be substituted by alkoxy with 1-3 C atoms, or alkoxy with 1-4 C atoms,
R² represents hydrogen, a saturated or unsaturated aliphatic radical with up to 5 C atoms optionally substituted by halogen, hydroxy or C₁-C₄alkoxy, or for alkoxy with 1-4 C atoms,
R³ represents an optionally substituted, saturated or unsaturated aliphatic radical with up to 20 C atoms, the following being selected as substituents:
Halogen, nitro, cyano, a radical -D-R⁴, alkoximino, the groups -CO-OR⁵, -CO-NR⁶R⁷, cycloalkyl, aryl or a 5- or 6-membered heterocycle, where
D represents oxygen, sulfur, sulfinyl or sulfonyl and
R⁴ stands for hydrogen, alkyl, mono- or polyunsaturated alkenyl or for optionally substituted aryl or aralkyl or for -CO-alkyl,
R⁵ represents alkyl,
R⁶ and R⁷ each independently represent hydrogen, alkyl, cycloalkyl or optionally substituted aryl or aralkyl or
R⁶ and R⁷ together with the nitrogen to which they are attached represent a 5- to 7-membered heterocycle;
in which further
R³ represents in each case optionally substituted cycloalkyl, aryl or a 5- to 7-membered heterocycle,
or in which
R² and R³ together with the nitrogen atom bonded to them form a 5- to 7-membered heterocyclic ring. 2. ureido-benzoic acid derivatives of the general formula (I) according to claim 1, characterized in that therein
Hal represents fluorine, chlorine or bromine,
R¹ represents hydrogen, saturated alkyl having 1 to 4 carbon atoms, unsaturated alkyl having 2 to 5 carbon atoms, which may optionally be substituted by alkoxy having 1 to 3 carbon atoms, or represents alkoxy having 1 to 4 carbon atoms,
R² represents hydrogen, alkyl, hydroxyalkyl or alkoxyalkyl each having 1 to 4 carbon atoms in the individual alkyl parts or alkenyl having 2 to 5 carbon atoms,
R³ represents in each case optionally substituted alkyl having 1 to 12 carbon atoms or represents in each case mono- or polyunsaturated alkenyl or alkynyl each having up to 12 carbon atoms, the selected substituents in each case:
Fluorine, chlorine, cyano, alkoximino with 1 to 4 carbon atoms in the alkyl part, optionally substituted by C₁-C₄-alkyl and / or fluorine or chlorine-substituted cycloalkyl with 3 to 6 carbon atoms, optionally by fluorine, chlorine, bromine, nitro, trifluoromethyl, C₁- C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl-substituted phenyl, a 5- or 6-membered heterocycle which contains 1 to 3 further heteroatoms from the series oxygen and / or can contain sulfur and / or nitrogen, a radical -D-R⁴, a radical -CO-OR⁵ or a radical -CO-NR⁶R⁷, wherein
D and R⁴ have the meaning given above,
R⁵ represents alkyl having 1 to 4 carbon atoms,
R⁶ and R⁷ each independently represent hydrogen or alkyl having 1 to 6 carbon atoms or
R⁶ and R⁷ together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocycle;
that continue in it
R³ for optionally by fluorine, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkenyl or halogen (C₁-C₄) alkyl (where halogen represents 1 to 5 fluorine and / or chlorine atoms) substituted cycloalkyl having 3 to 8 carbon atoms or optionally substituted phenyl, where the phenyl substituents selected are:
Fluorine, chlorine, bromine, C₁-C₄-alkyl, halogen (C₁-C₄) alkyl (where halogen represents 1 to 5 fluorine and / or chlorine and / or bromine atoms) or a radical -D¹-R⁸, where
D¹ represents oxygen, sulfur, sulfinyl or sulfonyl
R⁸ represents hydrogen, C₁-C₄ alkyl, halogen (C₁-C₄) alkyl (where halogen represents 1 to 5 fluorine and / or chlorine atoms), C₂-C₄ alkenyl or a radical of the formulas -CO- O- (C₁-C₄) alkyl, -SO₂NH₂, -SO₂-NH- (C₁-C₄) alkyl or stands;
that continues in it
R³ represents a 5- to 7-membered heterocycle which can contain one to three identical or different heteroatoms from the series oxygen, nitrogen or sulfur and which is optionally substituted by fluorine, chlorine, bromine, iodine, C₁-C₄alkyl, Halogen-C₁-C₄-alkyl (where halogen represents 1 to 5 identical or different fluorine, chlorine, bromine or iodine atoms), by amino, alkylamino or dialkylamino, each having 1 to 4 carbon atoms in the individual alkyl parts, by nitro, Cyano, the radical -D-R⁴ (with the same meaning for D and R⁴ as above) or by a radical of the formulas-CO-O- (C₁-C₄) alkyl, -CO-NH- (C₁-C₄) alkyl or -CO-N (C₁-C₄-alkyl) ₂, and which may contain fused carbocyclic or other heterocyclic rings;
or that in it
R² and R³ together with the nitrogen atom to which they are attached form a 5- to 6-membered ring. 3. ureido-benzoic derivatives of the general formula (I) according to claim 1, characterized in that therein
Hal represents fluorine or chlorine,
R¹ represents hydrogen, saturated alkyl having 1 to 4 carbon atoms, which may optionally be substituted by methoxy or ethoxy, or represents methoxy,
R² represents hydrogen, alkyl or alkoxyalkyl each having 1 to 4 carbon atoms in the individual alkyl parts or alkenyl having 2 to 5 carbon atoms,
R³ represents optionally monosubstituted to pentasubstituted, identically or differently substituted alkyl having 1 to 10 carbon atoms or represents in each case optionally monosubstituted to pentasubstituted, identically or differently substituted, mono- or polyunsaturated alkenyl or alkynyl, each having up to 10 carbon atoms, the substituents in each case being selected are:
Fluorine, chlorine, cyano, alkoximino with 1 to 4 carbon atoms in the alkyl part, optionally monosubstituted to trisubstituted, identically or differently, by C₁-C₄-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, optionally monosubstituted to triple, identically or differently, by fluorine, chlorine, Bromine, iodine, nitro, trifluoromethyl, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-alkylthio, C₁-C₂-alkylsulfinyl or phenyl substituted by C₁-C₄-alkylsulfonyl, a 5- or 6-membered heterocycle ( which can contain 1 to 3 heteroatoms from the series oxygen and / or sulfur and / or nitrogen) and a radical -D-R⁴, a radical -CO-OR⁵ or a radical -CO-NR⁶R⁷, where
D and R⁴ have the meaning given above,
R⁵ represents alkyl having 1 to 4 carbon atoms,
R⁶ and R⁷ each independently represent hydrogen or alkyl having 1 to 6 carbon atoms or
R⁶ and R⁷ together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocycle;
that continue in it
R³ for optionally single to triple, identical or different by fluorine, chlorine or C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₄-alkenyl or halogen-C₁-C₂-alkyl (where halogen for 1 to 3 fluorine and / or chlorine atoms) substituted cycloalkyl having 3 to 7 ring carbon atoms or phenyl optionally monosubstituted to trisubstituted by identical or different substituents, the phenyl substituents selected being:
Fluorine, chlorine, bromine, C₁-C₄-alkyl, trifluoromethyl or a radical -D¹-R⁸, wherein
D¹ represents oxygen, sulfur, sulfinyl or sulfonyl and
R⁸ represents hydrogen or C₁-C₄ alkyl;
that continues in it
R³ is a 5- to 7-membered heterocycle which can contain one to three identical or different heteroatoms from the series oxygen, nitrogen or sulfur and which is optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine or iodine , C₁-C₂-alkyl, halogen-C₁-C₂-alkyl (where halogen represents 1 to 3 identical or different fluorine or chlorine atoms), by amino, alkylamino or dialkylamino, each having 1 to 2 carbon atoms in the individual alkyl parts, by nitro , Cyano or by a C₁-C₄-alkoxy, C₁-C Alkyl-alkylthio or C₁-C₄-alkylsulfonyl radical,
or that in it
R² and R³ together with the nitrogen atom to which they are attached form a 5- or 6-membered ring. 4. ureido-benzoic acid derivatives of the general formula (I) according to claim 1, characterized in that therein
Hal stands for chlorine,
R¹ represents hydrogen, alkyl having 1 to 3 carbon atoms, which may optionally be substituted by methoxy or ethoxy, or represents methoxy,
R² represents hydrogen, alkyl having 1 to 4 carbon atoms or alkenyl having 3 to 5 carbon atoms,
R³ is in each case optionally mono- to pentasubstituted, identical or differently substituted alkyl having 1 to 10 carbon atoms, in each case mono- or polyunsaturated alkenyl or alkynyl each having up to 10 carbon atoms, the substituents selected in each case:
Fluorine, chlorine, cyano, alkoximino with 1 to 4 carbon atoms in the alkyl part, optionally monosubstituted to trisubstituted, identically or differently, by C₁-C₄-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, optionally monosubstituted to triple, identically or differently, by fluorine, chlorine, Bromine, iodine, nitro, trifluoromethyl, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-alkylthio, C₁-C₂-alkylsulfinyl or phenyl substituted by C₁-C₄-alkylsulfonyl, a 5- or 6-membered heterocycle ( which can contain 1 to 3 heteroatoms from the series oxygen and / or sulfur and / or nitrogen) and a radical -D-R⁴, where
D represents oxygen, sulfur or sulfonyl and
R⁴ stands for hydrogen, for alkyl with 1 to 4 carbon atoms, for alkenyl with 2 to 4 carbon atoms, each optionally monosubstituted to trisubstituted, identically or differently substituted, phenyl, benzyl or phenethyl, with fluorine, chlorine, bromine, C₁-C₂ as phenyl substituents -Alkyl or C₁-C₂ alkoxy are selected;
that continue in it
R³ represents optionally monosubstituted to trisubstituted, identically or differently, fluorine, chlorine or C₁-C₄alkyl-substituted cycloalkyl having 3 to 6 carbon atoms or optionally monosubstituted to trisubstituted, identically or differently, phenyl, the phenyl substituents selected being:
Fluorine, chlorine, bromine, C₁-C₄-alkyl, trifluoromethyl or a radical -D¹-R⁸, wherein
D¹ represents oxygen and
R⁸ represents hydrogen or C₁-C₄ alkyl;
that continues in it
R³ is a 5- to 7-membered heterocycle which can contain one to three identical or different heteroatoms from the series oxygen, nitrogen or sulfur and which is optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine or iodine , C₁-C₂-alkyl, halogen-C₁-C₂-alkyl (where halogen represents 1 to 3 identical or different fluorine or chlorine atoms), by amino, alkylamino or dialkylamino, each having 1 to 2 carbon atoms in the individual alkyl parts, by nitro , Cyano, C₁-C₄-alkoxy-, C₁-C₄-alkylthio- or C₁-C₄-alkylsulfonyl,
or that in it
R² and R³ together with the nitrogen atom to which they are attached form a 5- or 6-membered ring which can be substituted by one or more alkyl groups having 1 to 4 carbon atoms and / or in addition to carbon atoms, an oxygen, a sulfur atom or can contain another nitrogen atom as a ring member. 5. A process for the preparation of ureido-benzoic acid derivatives of the general formula (I) according to claim 1, characterized in that

• a) 4-amino-benzoic acid amides of the formula (II) in which Hal, R² and R³ have the meaning given above,
  with methyl isocyanate of the formula (III) or a carbamic acid derivative of the formula (IV) in which R¹ has the meaning given above and X represents halogen or a (C₆-C₁₀) aryloxy radical,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
  or that one
• b) carbonic acid derivatives of 4-amino-benzoic acid amides of the formula (V) or (VI) in which Hal, R², R³ and X have the meaning given above,
  with amines of the formula (VII) in which R¹ has the meaning given above,
  if appropriate in the presence of a diluent and a (further) acid binder;
  or that one
• c) ureido-benzoic acids of the formula (VIII) in which Hal and R1 have the meaning given above,
  with amines of the formula (IX) in which R² and R³ have the meaning given above,
  in the presence of a water-binding agent and optionally in the presence of a diluent;
  or that one
• d) ureido-benzoic acid derivatives of the formula (X) in which R¹ and Hal have the meaning given above and A for halogen, for the rest or stands for imidazolyl,
  with compounds of the formula (IX), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

6. Herbicides and plant growth regulators, characterized by containing at least one Ureido-benzoic acid derivative of the general formula (I) according to claim 1. 7. Weed control procedures and / or for regulating plant growth, characterized in that that you get ureido-benzoic acid derivatives of the formula (I) according to claim 1 on the weeds and / or their living space.   8. Use of ureido-benzoic acid derivatives of Formula (I) according to claim 1 for combating weeds and / or as plant growth regulators. 9. Process for the preparation of herbicidal or plant growth regulating agents, characterized in that you get ureido-benzoic acid derivatives of formula (I) according to claim 1 with extenders and / or surfactants mixed.