LT3943B - Remedy for cultured plants protection, use of sulphamoyl-phenyl-carbamides for cultured plant protection, herbicidal preparation, process for preparing sulphamoyl-phenyl-carbamides - Google Patents

Abstract

The derivatives of N-acylsulfamoyl phenylcarbamate, which have the formulae given below (I), are suitable for the use as antidotes (or protective measures) of cultivated plants from the effect of phytotoxic effects of herbicides. By cultivated plants, we the mean the cultures of crops, such as soy, switch-grass, corn and rise, and by the herbicides we mean the derivatives of which are sulfonyl carbamate, chloracetanilides and the derivatives of aryloxyphenoxy propanoic acids. The derivatives of N-acylsulfamoyl phenylcarbamate have the formulae I, <IMAGE>where A is one of the following residues:<IMAGE> or <IMAGE>R<1> and R<2> one independently from another, mean hydrogen, C1-C8-alkyl, C3-C8-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, <IMAGE> or substituted C1-C4-alkoxy - or <IMAGE>-group C1-C4-alkyl, orR<1> and R<2> together mean the bridge of the C4-C6-alkylene or the bridge of C4-C6-alkylene,is divided by oxygen, sulphur, SO, SO2, NH or -N (C1-C4-alkyl),R<3> - hydrogen or C1-C4-alkyl,R<a> and R<b> one independently from another, mean hydrogen, halogen, -CN, groups of nitrotrifluorinemethyl, C1-C4-alkyl, C1-C4-alkoxy -, C1-C4- alkylthio -, C1-C4-alkylsulfinyl-, C1-C4-alkylsulfonyl, COOR<j>, -COONR<k>R<m>, -COR<n>, -SO2NR<k>R<m> or -OSO2-C1-C4-alkyl, orR<a> and R<b> together mean that the bridge of the C3-C4-alkylene, which can be substituted by halogen or C1-C4-alkyl; or the bridge of C4-alkenedienil, which can be substituted by the halogen or C1-C4-alkyl;R<g> and R<h> one independently from another, mean the hydrogen, halogen, C1-C4-alkyl, trifluormethyl, methoxy -, methylthio - or -COOR<j>, whenR<c> is hydrogen, halogen, C1-C4-alkyl or methoxy,R<d> is hydrogen, halogen, nitro-, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, -COOR<j> or -CONR<k>R<m>,R<e> is hydrogen, halogen, C1-C4-alkyl, -COOR<d>, trifluormethyl or methoxy, or R<d> and R<e> together mean that the bridge of the C3-C4-alkylene,R<f> means hydrogen, halogen or C1-C4-alkyl,R<x> and R<y> one independently from another, mean that the hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy-, C1-C4-alkylthio, -COOR<4>, trifluormethyl, nitro or CN groups,R<j>, R<k> and R<m> one independently from another mean the hydrogen or C1-C4-alkyl,R<k> and R<m> together mean the bridge of the C4-C6-alkylene, either separated by oxygen, NH or -N(C1-C4-alkyl) bridge of C4-C6-alkylene,R<n>-C1-C4-alkyl, phenyl or phenyl, is substituted by the halogen, C1-C4-alkyl, methoxy-, nitro- or trifluormethyl groups.

Description

The present invention relates to novel N-acylsulfamoylphenylurea derivatives which are useful in the protection of crop plants against phytotoxic effects of acylcyclohexanedione herbicides, sulfonylurea herbicides, chloroacetanilide herbicides and aryloxyphenoxypropionic acid herbicides.

The invention further relates to the production of new active substances and their use for the protection of crop plants. Measures containing a new active substance and herbicidal mixtures which are a combination of a herbicidal agent and an antidote, as well as methods of controlling the respective weeds are the subject of the invention. The present invention describes the treatment of crop seeds with N-acylsulfamoylphenylurea derivatives to prevent exposure to herbicides.

Herbicides from classes of substances such as sulfonylureas, haloacetanilides, and aryloxyphenoxypropionic acid derivatives are also known to cause significant damage to herbaceous plants at effective weed-free doses. The dose increase is often involuntary and accidental due to the fact that the side areas are overlapped by spraying due to the wind or by misjudging the shape of the spray solution. Climatic conditions or soil conditions may cause the recommended amount of herbicide to be too high under normal conditions. Seed quality can also affect the interaction with the herbicide. To overcome this problem, various materials have already been proposed which specifically eliminate the harmful effects of the herbicide on crop plants, i.e. protects crop plants without appreciably affecting the action of the herbicides on the weeds to be destroyed. At the same time, it has been found that the proposed antidotes are very often specific for both crop plants and herbicides and, if necessary, also for mode of action, i.e., a particular lot of antiLT 3943 B is often only applicable to a particular crop and some small classes of herbicides.

British patent no. No. 1,277,557 describes the treatment of wheat and sorghum seeds or sprouts with known oxamic acid esters and amides to protect them from damage by ALACHLOR (N-methoxymethyl-Nchloroacetyl-2,6-diethylaniline). U.S. Pat. No. 4,618,331 describes benzoxazine derivatives having a protective action against the herbicidal action of haloacetanilides and sulfonylureas. In European patent no. Benzoyloxime esters are proposed as an antidote for A-122,231 protection against sulfonylurea herbicides, and European Patent EP-A-147,365 proposes phenylglyoxylic acid oxynitrile, naphthalenedicarboxylic anhydride, thiazolecarboxylic acid ester as well as dichloroacetamides. Exhibited applications for German patent no. Publication No. 2,402,983 states that maize can be effectively protected by the addition of N-disubstituted dichloroacetamide to the soil as an antidote to chloroacetanilide. Compounds of this type are disclosed in VFR Pat. 2,828,265 and no. The data of 2,828,293 are used in the same way as antidotes for carbic acid acetanilides.

Currently, the group of N-acylsulfamoylphenylurea derivatives has been found to be unexpectedly excellent for protecting crop plants against the damaging action of sulfonylurea, chloroacetanilide herbicides or aryloxyphenoxypropanoic acid herbicides. Therefore, these N-acylsulfamoylphenylurea derivatives are hereinafter referred to as antidotes, antidotes or protective agents.

The present invention provides novel N-acylsulfamoylphenylurea derivatives according to general formula I:

where A is a radical of one of the groups:

2

R and R independently represent hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₆ alkynyl,

or substituted with C ₁ -C ₄ alkoxy or

- a group C ₁ -C ₄ alkyl, or

R ¹ and R ² - together represent a C ₄ -C ₆ alkylene bridge or a C ₄ -C ₆ alkylene bridge separated by oxygen sulfur, SO, SO ₂ , NH or - N (C ₆ -C ₆ alkyl), R ³ - hydrogen or C ₁ -C ₄ alkyl, R ^a and R ^b , independently of one another hydrogen, halogen, -CN, nitro, trifluoromethyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylsulfonyl-, COOR ^j , -COONR ^k R ^m , -COR ⁿ , -SO 2 NR ^k R ^m or -OSO ₂ -C ₁ -C ₄ alkyl, or R ^a and R ^b together represents a C ₃ -C ₄ alkylene bridge which may be substituted by halogen or C ₁ -C ₄ alkyl; or a C ₃ -C ₄ alkylene bridge which may be substituted by halogen or C ₁ -C ₄ alkyl; or a C ₄ -alkendienyl bridge which may be substituted by halogen or C ₁ -C ₄ -alkyl; R ⁹ and R ^h , independently of one another denote hydrogen, halogen, C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, methylthio or -COOR ^j, where R ^c - hydrogen, halogen, C ₁ -C ₄ alkyl or methoxy, R ^d - hydrogen, halogen, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, -COOR ^j or CONR ^k R ^m , R ^e - hydrogen, halogen, C ₁ -C ₄ alkyl, COOR ^d , trifluoromethyl or methoxy, or R ^d and R ^e together represents the C ₃ -C ₄ alkylene bridge,

R ^f is hydrogen, halogen or C ₁ -C ₄ alkyl,

R ^x and R ^y each independently represent hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, -COOR ⁴ , trifluoromethyl, nitro or CN groups ,

R ^j , R ^k and R ^m each independently represent hydrogen or C ₁ -C ₄ alkyl,

R ^k and R ^m together represent a C ₄ -C ₆ alkylene bridge, or a oxygen-substituted, NH or -N (C ₁ -C ₄ alkyl) C ₄ -C ₆ alkylene bridge,

R ⁿ is -C ₁ -C ₄ alkyl, phenyl or substituted with halogen, C ₁ -C ₄ alkyl, methoxy, nitro or trifluoromethyl phenyl.

In the explanatory notes halogen is fluorine, chlorine, bromine and iodine, most preferably fluorine, chlorine and bromine, especially chlorine. In the specification, alkyl is straight or branched chain alkyl, such as methyl, ethyl, n-propyl, isopropyl or 4-isomeric butyl. Long-chain alkyl groups are pentyl, hexyl, heptyl or octyl isomers, and long-chain alkyl are preferred, depending on the circumstances.

The alkoxy mentioned in the explanatory notes may be methoxy, ethoxy, n-propyloxy, iso-propyloxy or four isomeric butyloxy radicals, in particular methoxy, ethoxy or isopropyloxy. Alkoxyl-substituted alkyl is a radical of methoxymethyl, ethoxymethyl, methoxyethyl and ethoxyethyl, but methoxyethyl is particularly suitable.

Alkyl substituted by substituted phenyl is primarily meant phenylethyl or benzyl. C ₃ -C ₆ -alkenyl and C ₃ -C ₆ LT 3943 B

The 2 alkynyl radicals designated R and R are characterized in that they are attached to the nitrogen atom through a saturated carbon atom. Typical alkenyl and alkynyl radicals include aula, 2-butenyl, metalyl, 3-butenyl, propargyl, 2-butynyl, 3-butynyl and 2-pentenyl. Representative of cycloalkyls are cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl, preferably cyclopentyl and cyclohexyl.

The heterocycles formed from R ¹ and R ² , or R ⁵ and R ⁶ with the nitrogen atom to which they are attached are pyrrolidine, piperidine, pyrazolidine, imidazolidine, oxazolidine, thiazolidine, morpholine, thiomorpholine, piperazine or hexahydroazepine, and so on. also in the case of sulfur-containing cycles, their oxidation products. In the alkylthio, alkylsulfinyl or alkylsulfonyl radicals, alkyl has the specific meanings listed above.

When R ^a and R ^b together represent a C ₃ -C ₄ alkylene bridge, a C ₃ -C ₄ alkenylene bridge or a C ₄ -alkadienylene bridge, which may be substituted as appropriate by halogen or C ₁ -C ₄ alkyl; this, together with the phenyl ring to which the bridge is attached, forms two fused ring systems, e.g., 1,2,3,4-tetrahydronaphthalene, 1-chloro-2-methyl-3,4-dihydronaphthalene, indane, 1,2- dihydronaphthalene, Indian, naphthalene, 2-methylnaphthalene, 1-n-butylnaphthalene, 2-ethylnaphthalene, or 1-chloronaphthalene.

If the substituents R ^d and R ^e together represent a C ₃ -C ₄ alkylene bridge, then the cyclic system to which they are attached forms a multicyclic system, e.g. 2,3-tetramethylthiophene, 2,3-trimethylthiophene, 2,3- tetramethylenfuran, 3,4-tetramethylenepyridine or

In view of their good activity as herbicide antagonists, compounds in which either

(a) R ^b is hydrogen, or

b) a sulfamoyl group at the 4-position of the phenyl ring, or

(c) R ² and R ³ are hydrogen; or

d) A is a group

Of the compounds of Formula I, the basic group is those in which R ^{b is} hydrogen and the sulfamoyl group is in the 4-position of the phenyl ring. Further preferred are compounds wherein R ² , R ³ , and R ^{b are} hydrogen and the sulfamoyl group is in the 4-position of the phenyl ring.

Of the compounds of subgroup (d), those in which R,

R in ^3rd and 4th R ^{b is} hydrogen and in position. sulfamoyl the group is phenyl ring Between of the invention of compounds especially Interesting are those whose formula is la

wherein R ¹ , R ^c , R ⁹ and R ^h are the same as in formula I.

Further preferred in their operation are those compounds of formula Ia wherein R ^c is hydrogen. Another subgroup, which must be specifically mentioned, comprises compounds of formula Ia wherein R ¹ , R ⁹ and R ^h are C 1 -C 2 alkyl.

Among the compounds of the formula I according to the invention, the following are to be mentioned as the best individual compounds:

1- (4- (N-methylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (Ν-3-methylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (Ν-4-tert-Butylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (β-3-trifluoromethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (Ν-4-nitrobenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (N-2,3-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl) -3,3-dimethyl-urea, - (4- (N-3,4-dimethyl-benzoyl-sulfamoyl) -phenyl) -3-ethyl-urea,

1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-allyl-urea,

1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl (-3-phenylurea),

1- (4- (N-3,5-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (N-3,4-Dichlorobenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (N-3,4-Dimethoxybenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (N-3,4-dimethoxybenzoyl-sulfamoyl) -phenyl) -3,3-dimethyl-urea,

1- (4- (N-2,4,5-trimethoxybenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (N-1-naphthylcarbonylsulfamoyl) phenyl) -3-methylurea,

1- (4- (Ν-2-Furylcarbonylsulfamoyl) -phenyl) -3-methylurea, io

1- (4- (β-2-furylcarbonylsulfamoyl) phenyl) -3,3-dimethylurea,

1- (4- (Ν-2-Thienylcarbonylsulfamoyl) -phenyl) -3-methylurea,

1- (4- (N-piperonyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (4- (Ν-3-methylbenzoyl-sulfamoyl) -phenyl) -3,3-dimethyl-urea,

1- (3- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea,

1- (3- (Ν-2-furylcarbonylsulfamoyl) phenyl) -3,3-dimethylurea,

1- (4- (Ν-3-trifluoromethylbenzoyl-sulfamoyl) -phenyl) -3-cyclopropyl-urea,

The formula will mean the nile while (the formula is given in

Compounds I in which R ¹ has those defined for Formula I except vande2

R is hydrogen, obtained for the sulfamoylanilyl V), wherein A, R ^{1 2 3} , R ^a and R ^b are the same as for formula I,

by reaction with isocyanate (Formula VI).

R ¹ -N = C = O (VI) wherein R ¹ has the meaning given for formula I except hydrogen.

In the presence of alkylating reagents of the formula:

Lg-R ² where Lg is a leaving group such as halogen, tosyl, C ₆ H ₅ -SO ₃ - or CH ₃ OSO ₃ , and R ² is as defined for formula I except for hydrogen, the following formula I compounds may be obtained: compounds wherein R is not hydrogen.

The reaction of aniline derivatives of formula I with isocyanate VI can take place in either solvent-free or aprotic inert organic solvent. It is preferable to carry out the reaction in a solvent. Suitable solvents include hydrocarbons such as benzene, toluene, xylene or cyclohexane, carbon tetrachloride or chlorobenzene; ethers - diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles - acetonitrile or propionitrile; amides - dimethylformamide, diethylformamide or N-methylpyrrolidinone.

The most favorable reaction temperature is between -20 ° C and + 120 ° C. The copulation reaction is usually of mild exothermic nature and can occur at room temperature. In order to shorten the reaction time or even at the beginning of the reaction, it is expedient to heat the reaction mixture to boiling point for a short time. The reaction time can also be reduced by adding a few drops of alkali as a catalyst. The tertiary amines are particularly suitable for the alkali role - trimethylamine, triethylamine, quinuclidine, N, N-dimethylaminopyridine, pyridine, 1,4-diazabicyclo (2.2.2) -octane, 1,5-diazabicyclo- (4.3.0) non-5-ene. or 1,8-diazabicyclo (5.4.0) undec-7-ene.

The final products of formula I can be isolated directly as a crystalline precipitate either by concentration and / or evaporation of the solvent and purified by recrystallization or trituration of the solid precipitate in solvents where it is insoluble.

The active compounds of formula I, by the second process, sulfamoylphenylurea (formula VII),

(VII), which formula (formula

R ¹ , R ² , R ³ , R ^a and R ^b have the meanings given

I, acylates with a carboxylic acid halide

VIII)

Hal-CO-A (VIII) wherein A has the meaning given for formula I and Hal is chlorine or bromine.

The reaction of sulfamoylphenylurea derivatives of formula VII with an acylating agent of formula VIII is usually carried out in an inert organic solvent in the presence of an acid-binding substance. Suitable solvents include hydrocarbons such as benzene, toluene, xylene or cyclohexane; carbon tetrachloride or chlorobenzene, ethers - diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles - acetonitrile 3943 B or propionitrile, amides dimethylformamide, diethylformamide or N-methylpyrrolidinone. Reactions usually occur between -20 ° C and + 120 ° C. The copulation reaction is usually of mild exothermic nature and can occur at room temperature. In order to shorten the reaction time or even at the beginning of the reaction, it is expedient to heat the reaction mixture to boiling point for a short time. The reaction time can also be reduced by adding a few drops of alkali as a catalyst. Particularly suitable for the alkali role are the tertiary amines trimethylamine, triethylamine, quinuclidine, N, N-dimethylaminopyridine, pyridine, 1,4-diazabicyclo (2.2.2) octane, 1,5-diazabicyclo (4.3.0) non-5-ene or 1 , 8-diazabicyclo (5.4.0) undec-7-ene. Inorganic bases such as hydrides (e.g., sodium hydride and calcium hydride), hydroxides (e.g., sodium hydroxide and potassium hydroxide), carbonates - sodium carbonate and potassium carbonate or bicarbonates - potassium bicarbonate and sodium bicarbonate may also be used as alkali. . These bases can simultaneously be used as acid binding agents. The final products of Formula I may be isolated either directly as crystallized materials or by concentration and / or evaporation of the solvent and then purified by recrystallization or trituration of the solid residue in solvents with poor solubility.

Starting materials having formulas V, VI, VII and VIII are well known. Compounds of formulas VI and VII are partially on the market. Compounds of formulas V and VIII, for which no specific methods of preparation are described in the literature, may be prepared under conventional single step conditions according to the following reaction scheme.

base

so ₂ nh ₂ Schematic

so ₂ ~ nh ₂

Formula I compounds are stable substances under normal laboratory conditions. They do not decompose, stored at room temperature.

The antidotes or antidotes of Formula I may be used, depending on the purpose of application, for the preventive treatment of seed of crop plants (seed or sprout treatment) or before or after sowing. Alternatively, these agents may be used individually or in combination with the herbicide before or after emergence of the plants. As a rule, therefore, the plants or seeds can be treated with an antidote regardless of the moment of application of the herbicide. However, the plants may be treated simultaneously with a herbicide and an antidote (mixed in one volume). Excellent treatment is both pre-sowing (ppi) and sowing, but not yet germinating.

Antidote depletion rates for the herbicide depend on the application. Processing field or simultaneously with the herbicide and antidote (mixed in one should ^say) or separately antidote ratio of herbicide in an amount ranging between 1: 100 and 5: 1.

At a quantitative ratio of antidote to herbicide between 5: 1 and 1:50, protective action is usually assured. For seed treatment and the like, significantly lower amounts of the antidote are required, which are applied per hectare of crop compared to the amount of herbicide. In general, 0.1 to 10 g of antidote is required per kilogram of seed treatment. As a rule, full protective action is achieved by using 0.1-5 g of antidote per kg of seed.

If the antidote is to be used prior to sowing, when the seeds are swollen, it is advisable to use an antidote solution containing the active substance at a concentration

1-10000 d. The full protective effect is usually achieved at an antidote concentration of 100-1000 m. d.

There is a relatively long time between operations having a protective function, such as seed dressing and treatment of seedlings with formula I and subsequent field treatment with a herbicide. Treated seeds and seedlings can subsequently come into contact with a variety of chemicals when used in agriculture, horticulture and forestry. Therefore, the present invention relates to such crop protection agents, wherein the active ingredient is an antidote of Formula I together with Conventional carriers. These products may contain such herbicides as may be necessary to protect the crop. The subject of the invention is also propagation material of cultivated plants - seeds, seedlings treated with active substances of formula I. The active ingredients of formula I are particularly suitable for the treatment of cereal seed (soy and especially sorghum, maize and rice).

The crop plants of the present invention are, for example, cereal species - wheat, rye, barley, oats, in addition rice, millet, corn and soybean. The active compounds of formula I are best suited to protect maize, millet and rice against acylcyclohexanedione herbicides, sulfonylurea herbicides, chloroacetanilide herbicides or aryloxyphenoxy propanoic acid herbicides.

An excellent protective effect is observed in rice, sorghum and maize using an acylcyclohexanedione, sulfonylurea herbicide and aryloxyphenoxypropanoic acid based antidote having formula I. Particular mention should be made of the positive l- (4- (N10)

3,4-Dimethylbenzoylsulfamoyl) -phenyl) -3-methylurea.

Sulfonylurea herbicides, which have a deleterious effect on crop plants, can be eliminated with the help of N-acylsulfamoylphenylurea derivatives of formula I, which are widely known recently. Of the numerous publications describing sulfonylurea derivatives having herbicidal activity, it is worth mentioning, for example, U.S. Pat. European Patent Application Serial No. 4,127,405; No. EP-A-7687, EP-A-30142, EP-A-44807, EP-A-44808, EP-A-51466,

EP-A-102925,

EP-A-84020, EP-A-120814, EP-A-237292.

EP-A-87780,

EP-A-136061,

EP-A-70802,

EP-A-108708,

EP-A-184385, EP-A-206995 and

Typical herbicides based on sulfonylureas have the formula II:

/ ^{x N} \ ^E - < ^CH 2> n- ^SO 2 ^NH - ^C ° - '? / O /

G ML-J (II),

n = 0 or 1,

G is hydrogen or methyl,

X - methoxy, ethoxy, difluoromethoxy, methyl or chlorine,

Y is CH or N

Z is methoxy, methyl, difluoromethoxy, cyclopropyl or methylamine,

R ⁴ - C ₂ -C ₅ -alkoksialkoksi C ₁ -C ₄ -halogenalkoksi, C₁ Czhalogenalkiltio C ₂ -C ₄ -halogenalkenilas, chlorine or C ₁ -C ₄ alkoxycarbonyl,

R ⁵ is trifluoromethyl or di (C ₁ -C ₄ alkyl) carbamoyl,

R ⁶ is C ₁ -C ₄ alkoxycarbonyl;

R ⁷ -C ₁ -C ₄ alkoxycarbonyl;

R ⁸ is C ₁ -C ₄ alkyl.

The following compounds having the herbicidal activity are represented by formula II:

N- (3-trifluoromethylpyridin-2-ylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) urea;

N- (3-dimethylcarbamoylpyridin-2-ylsulfonyl) -N '- (4,6-dimethoxypyridin-2-yl) urea;

N - (1-Methyl-4-ethoxycarbonylpyrazol-2-ylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) urea;

N- (2-methoxycarbonylthien-3-ylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea;

N- (2-methoxycarbonylbenzylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) -urea;

N - (2-Methoxycarbonylphenylsulfonyl) -N '- (4,6-bis-difluorine such pyrimidin-2-yl) -urea;

N - (2-methoxycarbonylphenylsulfonyl) -N '- (4-ethoxy-6-methylamino-1,3,5-triazin-2-yl) urea;

N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea;

N- (2-ethoxycarbonylphenylsulfonyl) -N '- (4-chloro-6-methoxypyrimidin-2-yl) urea;

N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N'-methylurea;

N- (2-methoxycarbonylphenylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) -urea;

N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea;

N- (2- (2-chloroethoxy) -phenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea;

N- (2- (2-methoxyethoxy) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Many haloacetanilides are also known, the harmful effects of which on crop plants can be eliminated by N-acylsulfamoylfe22 nylurea derivatives of formula I. Such haloacetanilides have the general formula III:

(III) in which

L is a C ₁ -C ₄ alkylene bridge;

R ^9, R ^10, R ¹¹ independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ alkoxy, -0 0 _{4 4} haloalkyl, C ₂ -C _5, or C ₂ -alkoksialkilas -C ₅ alkylthioalkyl;

R ¹² - C ₁ -C ₄ alkoxy, -COOH, C ₁ -C ₄ alkoxycarbonyl,

-CONH ₂ , C ₁ -C ₄ alkylcarbamoyl; di-C ₁ -C ₄ alkylcarbamoyl, -CN, C ₁ -C ₄ alkylcarbonyl,

if need, changed benzene, if need, changed furil, if need, changed thienil, if need, changed pyrrolyl, if need, changed pyrazolyl, if need, changed 1,3,4-oxadiazol-2-yl, if need, changed 1,3,4-thiadiazol-2-yl,

substituted 1,2,4-triazol-3-yl if necessary

if need, changed dioxolanyl, if need, changed dioxanil, if need, changed 1,3,4-triazol-2-yl, if need, changed tetrahydrofuryl. Formula III have these specific herbicides

tannilide derivatives:

N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline,

N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline,

N-chloroacetyl-N- (2-methoxyethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (2-n-propoxyethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (2-isopropoxyethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (2-methoxyethyl) -2-ethyl-6-methylaniline,

N-chloroacetyl-N- (methoxyethyl) -2,6-diethylaniline,

N- (2-ethoxyethyl) -N-chloroacetyl) -2-ethyl-6-methylaniline,

N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2,6-diethylaniline,

N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2-ethyl-6-methylaniline,

24th N- (2-ethoxyethyl) i-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N- - (2-n-propoxyethyl) -2-ethyl-6-methylanil nas,

N-chloroacetyl-N- - (2-n-propoxyethyl) -2,6-diethylaniline,

N-chloroacetyl-N- (2-isopropoxyethyl) -2-ethyl-6-methylaniline,

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline,

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline,

N-chloroacetyl-N- -methoxycarbonylmethyl-2,6-dimethylanil- nas,

N-chloroacetyl-N- - (2,2-diethoxyethyl) -2,6-dimethylaniline, N-chloroacetyl-N- - (2-methoxy-1-methylethyl) -2,3-dimethylan linen,

N- (2-ethoxyethyl) -N-chloroacetyl-2-methylaniline, N-chloroacetyl-N- - (2-methoxyethyl) -2-methylaniline, N-chloroacetyl-N- - (2-methoxy-2-methylethyl) -2,6-dimethylan linen,

N- (2-ethoxy-2-methylethyl) -N-chloroacetyl-2-ethyl-6-methylaniline,

N-chloroacetyl-N- (1-ethyl-1-methoxyethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (2-methoxyethyl) -2-methoxy-6-methylaniline,

N-n-butoxymethyl-N-chloroacetyl-2-tert-butylaniline,

N- (2-ethoxyethyl-2-methylethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (2-methoxyethyl) -2-chloro-6-methylaniline,

N- (2-ethoxyethyl) -N-chloroacetyl-2-chloro-6-methylaniline,

N- (2-ethoxyethyl) -N-chloroacetyl-2,3,6-trimethylaniline,

N-chloroacetyl-1- (2-methoxyethyl) -2,3,6-trimethylaniline,

N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline,

N-chloroacetyl-N- (1,3-dioxolan-2-ylmethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (1,3-dioxolan-2-ylmethyl) -2-ethyl-6-methylaniline,

N-chloroacetyl-N- (1,3-dioxan-2-ylmethyl) -2-ethyl-6-methylaniline,

N-chloroacetyl-N- (2-tolylmethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (2-furylmethyl) -2-ethyl-6-methylaniline,

N-chloroacetyl-N- (2-tetrahydrofurylmethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (N, N-dimethylcarbamoylmethyl) -2,6-dimethylaniline,

N- (butoxymethyl) -N-chloroacetyl-2, β-diethylaniline,

N- (2-n-butoxyethyl) -N-chloroacetyl-2,6-diethylaniline,

N-chloroacetyl-N- (2-methoxy-1,2-dimethylethyl) -2,6-dimethylaniline,

N-chloroacetyl-N-isopropyl-2,3-dimethylaniline,

N-chloroacetyl-N-isopropyl-2-chloroaniline,

N-chloroacetyl-N- (1-H-pyrazol-1-ylmethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (1H-pyrazol-1-ylmethyl) -2-ethyl-6-methylaniline,

N-chloroacetyl-N- (1H-1,2,4-triazol-1-ylmethyl) -2,6-dimethylaniline,

N-chloroacetyl-N- (1H-1,2,4-triazol-1-ylmethyl) -2,6-diethylaniline,

N-benzoylmethyl-N-chloroacetyl-2,6-diethylaniline,

N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline,

N-chloroacetyl-N- (5-methyl-1,3,4-oxadiazol-2-yl) -2,6-diethylaniline,

N-chloroacetyl-N- (5-methyl-1,3,4-oxadiazol-2-yl) -2-ethyl6-methylaniline,

N-chloroacetyl-N- (5-methyl-1,3,4-oxadiazol-2-yl) -2-ethyl6-methylaniline,

N-chloroacetyl-N- (5-methyl-1,3,4-oxadiazol-2-yl) -2-tertbutylaniline,

N-chloroacetyl-N- (4-chlorobenzoylmethyl) -2,6-dimethylaniline,

N-Chloroacetyl-N- (1-methyl-5-methylthio-1,3,4-triazol-2-ylmethyl) -2,6-diethylaniline.

Many herbicide aryloxyphenoxypropanoic acid bases are known which can be eliminated by N-acylsulfamoylphenylurea derivatives of formula I which are harmful to crops. The following aryloxyphenoxypropanoic acid derivatives have the general formula IV:

Q — O

O-CH-COT

(IV) wherein Q is one of the radicals

R

R or

R

T is -NR ¹⁵ R ¹⁶ , -N (CH) R ¹⁷ , -OR ^18, or -ON = CR ¹⁹ R ² °

R ¹³ is hydrogen or trifluoromethyl,

R ¹⁴ - hydrogen or halogen,

R ¹⁵ and R ¹⁶ independently of one another are hydrogen, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, phenyl or benzyl.

R ¹⁵ and R ¹⁶ taken together with the nitrogen atom to which they are attached form a 5-membered or 6-membered saturated heterocycle which may further contain an oxygen or sulfur atom;

R ¹⁷ is C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl, C ₃ -C ₄ alkynyl or C ₂ -C ₄ alkoxyalkyl;

R is hydrogen or the equivalent of an alkaline earth, alkaline earth metal, copper or iron;

C ₁ -C ₄ or C ₁ -alkilamonio -C ₄ -alkoksialkilamonio quaternary radical, where appropriate substituted with one or more of: amino, halogen, hydroxy, nitro group (groups), phenyl, C ₁ -C ₄ -alkoxyl; polyethoxy groups with 2-6 ethylene oxide moieties; -COOR ²¹ , -COSR ²¹ , -CONH ₂ , -CON (C ₁ -C ₄ alkoxy) -C ₁ -C ₄ alkyl, -CON-di-C ₁ -C ₄ alkyl, CONH-C ₁ - C ₄ -alkyl, -N _(Ο χ -Ο ₄ alkoxy) -C ₁ -C ₄ -alkyl or di-C ₁ -C ₄ group, C ^ -alkilammo Cgalkilas;

optionally a C ₃ -C ₉ alkenyl radical substituted by halogen or C ₁ -C ₄ alkoxyl;

optionally a C ₃ -C ₉ -alkynyl radical substituted by halogen or C ₁ -C ₄ -alkoxyl;

C ₃ -C ₉ alkynyl;

C ₃ -C ₉ -cycloalkyl;

or, optionally, phenyl substituted with nitrile, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acetyl, -COOR ²¹ , -COSR ²¹ , -CONH ₂ , -CON (C ₁ -C ₄ alkoxy) -C C ₁ -C ₄ alkyl, -CO-Ndi-C ₁ -C ₄ alkyl or -CONH-C ₁ -C ₄ alkyl;

R ¹⁹ and R ²⁰ are each C ₁ -C ₄ alkyl, together with a 3- to 6-membered alkylene chain;

R ²¹ is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₈ haloalkyl,

C ₂ -C ₆ alkoxyalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or C ₃ -C ₆ haloalkynyl,

The following herbicidal aryloxyphenoxypropanoic acid derivatives of formula IV are present: 2- (4- (5-Chloro-3-fluoro-pyridin-2-yloxy) -phenoxy) -propionic acid propargyl ester; Propargyl ester of 2- (4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -propanoic acid; Propargyl ester of 2- (4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -thiopropanoic acid; 2- (4- (5-Chloro-5-fluoro-pyridin-2-yloxy) -phenoxy) -propionic acid methyl ester; 2- (4- (5-Chloro-3-fluoro-pyridin-2-yloxy) -phenoxy) -propanoic acid butyl ester; 2- (4- (5-Trifluoromethylpyridin-2-yloxy) -phenoxy) -propanoic acid butyl ester; 2- (4- (5-Trifluoromethylpyridin-2-yloxy) -phenoxy) -propanoic acid methyl ester; 2- (4- (6-Chloroquinoxalin-2-yloxy) -phenoxy) -propanoic acid ethyl ester; 2- (4- (6-Chloro-benzoxazolin-2-yloxy) -phenoxy) -propanoic acid ethyl ester.

Acylcyclohexanedione derivatives which can be eliminated by the action of N-acylsulfamoylurea derivatives of the formula I on the harmful effects of the crop are described, for example, in European Patent Application Ser. 0 243 313. The following acylcyclohexanedione derivatives have the formula IX:

wherein A 'is a 2-7 membered alkylene bridge, a 3-7 membered alkenylene bridge which may have one or more unsaturated bonds;

n 'is zero, one or two;

R ²² is C ₁ -C ₄ alkyl or benzyl;

R ²³ - C₁-C₆ alkyl unsubstituted or substituted by halogen, Ci-C _4-alkoxy, C ₁ -C ₄ -alkylthio, C ₃ -C ₆ -cycloalkyl; phenyl, benzyl or phenylethyl wherein the phenyl rings may be substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₄ - C 1-6 haloalkoxyl, CN or nitro;

X 'is oxygen or -NOR ²⁴ ,

R ²⁴ is C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₆ haloalkenyl or C ₃ -C ₆ alkynyl.

The following herbicidal acylcyclohexanedione derivatives have the following formula:

5- (1-methylthiocyclobutan-1-yl) -2- (2,4-dichlorobenzoyl) cyclohexane-1,3-dione;

5- (1-methylthiocyclobutan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione;

5- (1-methylthiocyclobutan-1-yl) -2-cyclopropanecarbonylcyclohexane-1,3-dione;

5- (1-methylthiocyclobutan-1-yl) -2- (2,3-dichlorobenzoyl) cyclohexane-1,3-dione;

5- (1-methylsulfonylcyclobutan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione;

5- (1-methylthiocyclopropan-1-yl) -2-propionyl-cyclohexane-1,3-dione;

5- (1-ethylthiocyclopropan-1-yl) -2-propionyl-cyclohexane-1,3-dione;

5- (1-methylthiocyclopropan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione;

5- (1-methylthiocyclopropan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione;

5- (1-methylthiocyclobutan-1-yl) -2- (1-ethoxyimino-n-butyryl) -cyclohexane-1,3-dione;

5- (1-methylthiocyclopropan-1-yl) -2- (1-ethoxyimino-n-butyryl) -cyclohexane-1,3-dione;

5- (1-methylthiocyclohexan-1-yl) -2- (1-ethoxyimino-n-butyryl) -cyclohexane-1,3-dione;

5- (1-methylthiocyclobutan-1-yl) -2- (1-allyloximino-n-butyryl) -cyclohexane-1,3-dione;

5- (1-methylthiocyclopentan-1-yl) -2- (1-ethoxyimino-n-butyryl) -cyclohexane-1,3-dione;

5- (1-methylthiocyclopropan-1-yl) -2- (1- (trans-3-chloroalkyloxyimino) -n-butyryl) -cyclohexane-1,3-dione;

5- (1-methylthiocyclopropan-1-yl) -2- (1-trans-3-chloroallyloximino) -propionyl-cyclohexane-1,3-dione;

5- (1-methylthiocyclopropan-1-yl) -2- (1- (cis-3-chloroallyloximino) -propionyl) -cyclohexane-1,3-dione;

5- (1-ethylthiocyclopropan-1-yl) -2- (1-trans-3-chloralyloximino) -propionyl) -cyclohexane-1,3-dione.

Formula I antidotes are particularly well suited to protecting crop plants against the effects of Formula II, III or IV herbicides.

Agrochemicals containing a sulfonylurea, a chloroacetanilide herbicide or an aryloxyphenoxypropionic acid-based herbicide, together with an antidote of formula I, are useful as selective herbicides for useful crop crops.

In addition to the antidote of formula I, the herbicidal compositions of the present invention generally include sulfonylurea derivatives of formula II, chloroacetanilides of formula III, acylcyclohexanedione derivatives of formula IX, or aryloxyphenoxypropanoic acid derivatives of formula IV.

The amount of antidote used, if it is no longer seed treated, ranges from 0.01 to almost 5 parts by weight per part by weight of the herbicide. In practice, it determines on a case-by-case basis, i.e., depending on the type of herbicide used, the ratio corresponding to the optimal effect on a particular crop species.

The invention describes a method of selective weed control in crop plants, wherein the crop areas, parts of crops or soil of crop plants are treated with a herbicide and a compound of formula I or a mixture thereof.

Mixtures containing a herbicide / antidote combination are also part of the present invention.

In the case of weeds that need to be eradicated, we have both single and double weeds.

Various methods and techniques are used to protect crop plants from the harmful effects of chemicals used in agriculture by using compounds of formula I or mixtures containing them, such as:

I. Seed dressing

(a) Seed treatment of the active substance in the form of a wetting powder with shaking in a container until the active substance is uniformly distributed on the surface of the seeds (dry treatment). In this case, use 10 to 500 g of active ingredient of formula I (25% composition: 40 g to 2 kg of wetting powder) per 100 kg of seeds.

(b) Seed treatment of the active ingredient of formula I in an emulsion or aqueous solution of a wetting powder prepared by method (a) (wet treatment).

(c) Seed treatment by dipping the seeds in a solution of the active ingredient of the formula I for a period of 1 to 72 hours followed by desiccation if necessary (dipping, seed dipping).

Seed dressing is obviously the best way to use the active substance, since in this case the desired crop is processed directly. In these cases, usually 10 to 500 g, preferably 50 to 400 g of active substance per 100 kg of seed are used, but depending on the procedure for adding other active substances or trace elements, possible deviations to a greater or lesser half of the stated limits ( repeated staining).

II. Application from the reservoir

It is applied in a liquid mixture of antidote and herbicide (their ratio is 10: 1 to 1:30) and herbicide depletion rate in this case is from 0.001 to 10 kg per hectare. Such a mixture is usually applied from the reservoir before or after sowing, or is applied at a depth of 5 to 10 cm to the soil which has not yet been sown.

III. Contribution to seedbed

The antidote, in the form of an emulsion concentrate, wettable powder or granules, is applied to the open inoculated furrow, then, after closing the furrow, routinely uses the herbicide before the plant germinates.

IV. Isolation of the controlled active substance

The active substance solution is applied to mineral or polymeric (urea / formaldehyde) granules and allowed to dry. If necessary, a coating (pellets with a coating) may be applied, which allows for a controlled release of the active ingredient over a period of time.

The compounds of the formula I are used in their usual form or, more preferably, in the form of emulsifiable concentrates, directly sprayed or diluted pre-spray solutions, diluted emulsions, wettable powders, soluble powders, diluents. , granules, capsules. The method of application - spraying, dusting, pulverisation, spraying or irrigation, as well as the form of the active agent, is chosen according to the purpose of use and the ratio of substances to be stated.

A mixture of the active ingredient of formula I and, where appropriate, a solid or liquid additive, is prepared by conventional means, for example, by thoroughly mixing and / or grinding the active ingredient with excipients such as solvents, solid carriers and, where appropriate, surfactants.

Solvents may be aromatic hydrocarbons, preferably in the range of C ₈ to C ₁₂ , such as xylene or substituted naphthalenes, phthalic acid esters such as dibutyl phthalate or dioctyl phthalate; aliphatic hydrocarbons - cyclohexane or paraffins; alcohols and glycols as well as their ethers and esters - ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; ketones - cyclohexanone; strongly polar solvents: N-methyl-2-pyrrolidine, dimethylsulfoxide or dimethylformamide; and also if needed epoxidized vegetable oils such as epoxidized coconut or soy oil or water.

In the role of solid carriers, such as dusting and dispersing powders, natural mineral flour such as calcite, talc, kaolin, montmorillonite or atapulgite is commonly used. Highly dispersible silicic acid or highly dispersible polymers with adsorptive properties may be added to improve physical properties. Porous materials such as pumice stone, bricks, sepiolite or bentonite are used in the role of granular adsorbent carriers, while calcite or sand are used in the role of non-adsorbent carriers. In addition to these materials, a variety of granular organic and inorganic materials, including dolomite or crushed plant residues, may be used.

Nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wicking properties are used as surfactants, depending on the form of the active ingredient of formula I. A surfactant also means a mixture thereof.

Suitable surfactants are both so-called water-soluble soaps and water-soluble synthetic surfactants.

Soaps are alkaline, earth alkaline salts of higher fatty acids (C ₁₀ -C ₂₂ ), if necessary substituted with ammonium salts, such as the Na or K salts of oleic or stearic acid or of natural fatty acid mixtures, such as coconut oil or rendered animal fat. The methyl ester salts of fatty acids are still used.

However, so-called synthetic surfactants, including saturated hydrocarbon sulfonates, sulfates, benzimidazole sulfodar or alkylarylsulfonates, are more commonly used.

Saturated hydrocarbon sulfonates or sulfates are generally used in the form of alkali, earth alkaline or, where appropriate, substituted ammonium salts and have a hydrocarbon residue having from 8 to 22 carbon atoms; in addition, the alkyl moiety also includes acyl residues such as Na or Ca salt of lignin sulfonic acid, ester of doLT 3943 B decyl sulfuric acid or a mixture of saturated hydrocarbon alcohols with natural fatty acids. That list includes the salts of the esters of sulfuric acid, the sulfuric acids of saturated alcohols and those of ethylene oxide adducts. The sulfonated derivatives of benzimidazole have 2 sulfuric acid groups and one saturated acid residue with 8-22 carbon atoms. Arylalkyl sulfonates are, for example, the Na-, Ca- or triethanolamine salts of the condensation product of dodecylbenzene sulfuric acid, dibutylnaphthalenesulfonic acid or naphthalene sulfonic acid.

Corresponding phosphates, such as the salts of the phosphoric acid ester of n-nonylphenol and ethylene oxide (4-14) adduct, are also used.

For non-ionic surfactants, particular reference should be made to the polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols having from 3 to 30 etheric glycol groups and from 8 to 20 carbon atoms in the aliphatic hydrocarbon moiety and from 6 to 18 carbon atoms alkyl radical.

Still other suitable nonionic surfactants are water-soluble having from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups, polyethylene oxide adducts with propylene glycol, ethylenediamine polypropylene glycol having from 1 to 10 carbon atoms in the alkyl radical. The compounds mentioned generally have from 1 to 5 ethylene glycol moieties per propylene glycol moiety.

Examples of nonionic surfactants are nonylphenolpolyethoxyethanol, castor oil polyLT 3943 B glycol ethers, polypropylene oxide and polyethylene oxide adducts, tributylphenolpolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate are also used.

Of the cationic surfactants, quaternary ammonium salts are preferably used, wherein the N-substituent contains at least one alkyl radical of 8 to 22 carbon atoms, and the other substituents are lower alkyls, benzyls, oxyalkyls, if necessary, halogenated. Salts are usually halides, methylsulfates or ethylsulfates, such as stearyltrimethylammonium chloride or benzyl-di- (2-chloroethyl) ethylammonium bromide.

Surfactants used in molding techniques are described in the following publications: 1985 International Mc Cultcheon's Emulsifiers & Detergents, Glen Rock.NY, USA, 1985; H. Stache, Tensid-Tashenbuch, Z. Aufl., C. Hansen Verlag, Munchen, Wien 1981; M. and I. Ash, Enciclopedia of Surfactants. Vol. I-III, Chemical Publishing Co., New York, 1980-1981.

The agrochemical mixtures contain, as a rule, from 0.1 to 95%, usually from 0.1 to 80% of the active ingredient of formula I, from 1 to 99.9% of a solid or liquid additive and from 0 to 25%, in particular from 0.1 to 25% surfactant.

The composition of the mixtures is particularly good as follows:

(% by weight)

Emulsifying concentrates

Active substances active 1 to 20%, preferably blend 5 to 10% Surfactants 5 to 30%, best 10 to 20% Liquid carriers 50 to 94%, best 70 to 85%

Dust preparations

Active substances active blend 0.1 to 10%, preferably 0.1 to 1% Solid carrier 99.9 to 90%, best 99.9 to 99% Suspension concentrates Active substances active blend 5 to 75%, best 10 to 50% Water 94 to 25%, best 88 to 30% Surfactant 1 to 40%, best 2 to 30% Moisturizing powder Active substances active blend 0.5 to 90%, preferably 1 to 80% Surfactant 0.5 to 20%, preferably 1 to 15%

Solid carrier up to 95%, preferably 15 to 90%

L Γ 3943 B

Granulate

Active mixture of active substances

0.5 to 30%, preferably 3 to 15%

Solid carrier

99.5 to 70%, preferably 97 to 85%

Although concentrated on the market is most convenient, dilution is usually used by the end user. The formulations used may be diluted to 0.001% active ingredient. The application rates are, as a rule, 0.01 to 10 kg of active ingredient / ha, preferably 0.25 to 5 kg of active ingredient / ha.

The formulation may also include other additives such as stabilizers, foam extinguishers, preservatives, viscosity regulators, adhesives, as well as fertilizers and other active substances for special effects.

The following examples serve to illustrate the invention. They do not limit the scope of the invention.

Examples of receipt

Example H1: 1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea

CH

CH

a) N- (4-sulfamoylphenyl) -O-phenylcarbamate

176 g of sulfanylamide are suspended in 750 ml of dioxane and mixed with 79 g of pyridine. To this mixture was added a temperature of 15 ° C. Drops 160 g of the phenyl ester of chloroformic acid. The reaction mixture is stirred for 1 hour. 50 ° C, then cooled and mixed with 2 L of water. The precipitate is separated off and dried. 277 g of N- (4-sulfamoylphenyl) -O-phenylcarbamate, m.p. temp. 220-223 ° C.

b) 1- (4-Sulfamoyl-phenyl) -3-methyl-urea Add 330 ml of 33% methylamine in ethanol to 350 g of a suspension of N- (4-sulfamoyl-phenyl) -O-phenylcarbamate in 1500 ml of ethanol at 80 ° C. From the initial clear solution within 1.5 hours. the product crystallizes. After cooling the reaction mixture, the precipitate is separated off and dried. 256 g of 1- (4-sulfamoylphenyl) -3-methylurea, m.p. temp. 211-213 ° C.

c) To a suspension of 73.3 g of 1- (4-sulfamoylphenyl) -3-methylurea in 600 ml of acetonitrile are added 56.7 g of 3,4-dimethylbenzoyl chloride and 3.9 g of 4-dimethylaminopyridine. To this mixture was added 98.1 g of triethylamine. At this point, the reaction mixture warms to 45 ° C and the dispersed particles dissolve. After that, crystallization soon begins. The next 2.5 hours the reaction mixture is mixed with 2.5 L of ice water and 200 mL of 2 N sulfuric acid. After precipitation, the product is separated off, washed with ether and dried. 114.4 g of 1- (4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea, m.p. temp. 236-238 ° C (dec.).

Example H2: 1- (3- (Ν-2-Furylcarbonyl-sulfamoyl) -phenyl) -3,3-dimethyl-urea

a) N- (3-sulfamoylphenyl) -O-phenylcarbamate

To a suspension of 125 g of 3-aminobenzenesulfonamide and 57.9 g of pyridine in 500 ml of dioxane are added dropwise 113 g of chloroformate phenyl ester at 15 ° C. The reaction mixture was stirred at room temperature for 1 h, then for 1 h. 50 ° C, and mixed with 2 l of water. The precipitate is separated off and dried. 201 g of N- (3-sulfamoylphenyl) -O-phenylcarbamate, m.p. temp. 184186 ° C (dec.).

b) 1- (3-sulfamoylphenyl) -3,3-dimethylurea

A mixture of 205 g of N- (3-sulfamoylphenyl) -O-phenylcarbamate and 158 g of 40% aqueous dimethylamine in 500 ml of ethanol is refluxed for 3 hours. The solvent is evaporated off under vacuum. The residue is mixed with water and the phenol formed is distilled off with water vapor. After cooling the distillation flask separates the crystalline residue, rinsing with cold methanol and drying. 136 g of 1- (3-sulfamoylphenyl) -3,3-dimethylurea, m.p. temp. 193-194 ^c C.

c) To a suspension of 10.1 g of 1- (3-sulfamoylphenyl) -3,3-dimethylurea in 60 ml of acetonitrile is added 6.1 g of 2-furang 4-dimethyl-temperature in a mixture of carboxylic acid anhydride and 0.1 aminopyridine. 9.5 g of triethylamine are added dropwise to this mixture. Reaction videos. at room temperature and then for 1 hour. At 60 ° C. After cooling, 4.5 g of methanesulfonic acid is added dropwise and the mixture is poured into 1 liter of water. The oil that separates soon crystallizes out. The crystalline precipitate is separated off, washed with methanol and dried. 11.3 g of 1- (3- (Ν-2-furylcarbonylsulfamoyl) -phenyl) -3,3-dimethylurea, m.p. temp. 216-217 ° C (dec.).

Example H3: 1- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-alkyl-urea

CH

H ₂ C = CH-CH ₂ -nh-co-nh

CH

To a suspension of 12.2 g of 4- (N-3,4-dimethylbenzoyl-sulfamoyl) -aniline is added 4.1 g of triethylamine in 20 ml of acetonitrile. The solution becomes clear at first and then the salt is removed. 4.6 g of allyl isocyanate are added and stirred for 2 hours. at room temperature and then for another 2 hours. At 70 ° C. After cooling, the mixture is poured into a mixture of 1 liter of ice water and 4.5 g of concentrated sulfuric acid. The precipitate is separated off, washed with ether and dried. 15.1 g of 1- (4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl) -3-allyl-urea, m.p. temp. 194-201 ° C (dec.).

Example H4: 1- (4- (N-2,3-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea

CH

To a suspension of 6.1 g of 4- (N-2,3-dimethylbenzoyl-sulfamoyl) -aniline is added 2.8 g of triethylamine in 50 ml of acetonitrile. To this mixture is added dropwise 1.3 ml of methyl isocyanate. The reaction mixture was stirred for 2 hours. at room temperature, followed by a baby. At 50 ° C. After cooling to room temperature, the reaction mixture was poured into a mixture of 200 mL of ice water and 15 mL of 2N sulfuric acid. The precipitate is separated off and dried. 1- (4- (N-2,3-Dimethylbenzoyl-sulfamoyl) -phenyl-3-methyl-urea, m.p. 242-244 ° C is obtained.

In an analogous way, it obtains the final products listed in the tables below.

table

Jungian N R ^r R ² N- A Lyd. temp. (° C) 1 2 3 4 1.001 Amino Phenyl 1.002 Methylamine Phenyl 237-238 (splits) 1.003 Dimethylamine Phenyl 1.004 Methylamine 2-tolyl 234-236 (splits) 1.005 Methylamine 3-tolyl 216-218 (splits) 1.006 Methylamine 4-tolyl 247-249 (splits) 1.007 Methylamine 4-ethylphenyl 1.008 Methylamine 4-n-propylphenyl 1.009 Methylamine 4-n-propylphenyl 1.010 Methylamine 4-n-butylphenyl 1.011 Methylamine 4-tert-butylphenyl 250-252 (splits) 1.012 Methylamine 2-chloro-phenyl 239-241 (splits) 1.013 Methylamine 3-chloro-phenyl 222-224 (splits) 1.014 Methylamine 4-chloro-phenyl 246-247 (splits)

table (continued)

1 2 3 4 1.015 Methylamine 2-fluorophenyl 227-229 (splits) 1.016 Methylamine 3-fluorophenyl 234-235 (splits) 1.017 Methylamine 4-fluorophenyl 1.018 Methylamine 2-Bromo-phenyl 244-245 (splits) 1.019 Methylamine 3-Bromo-phenyl 1.020 Methylamine 4-Bromo-phenyl 1.021 Methylamine 2-iodophenyl 1.022 Methylamine 3-iodophenyl 1.023 Methylamine 4-iodophenyl 1.024 Methylamine 3-chloromethyl-phenyl 1.025 Methylamine 2-trifluoromethylphenyl 1.026 Methylamine 3-trifluoromethyl-phenyl 231-233 (splits) 1.027 Methylamine 4-trifluoromethyl-phenyl 1.028 Methylamine 2-methoxy-phenyl 197-198 (splits) 1.029 Methylamine 3-methoxy-phenyl 1.030 Methylamine 4-methoxy-phenyl 1.031 Methylamine 2-ethoxy-phenyl 1.032 Methylamine 3-ethoxy-phenyl 1.033 Methylamine 4-ethoxy-phenyl 1.034 Methylamine 2-methylmercapto-phenyl 1.035 Methylamine 2-methylsulfonyl-phenyl 1.036 Methylamine 2-methoxycarbonyl-phenyl 1.037 Methylamine 4-methoxycarbonyl-phenyl 1.038 Methylamine 2-nitrophenyl 1.039 Methylamine 3-nitrophenyl 1.040 Methylamine 4-nitrophenyl 237-238 (splits)

table (continued)

1 2 3 4 1.041 Methylamine 2-acetylphenyl 1.042 Methylamine 4-acetylphenyl 1.043 Methylamine 3-cyanophenyl 1.044 Methylamine 4-cyanophenyl 1.045 Methylamine 2,3-dimethylphenyl 242-244 (splits) 1.046 Methylamine 2,4-dimethylphenyl 239-241 (splits) 1.047 Methylamine 2,5-dimethylphenyl 223-224 (splits) 1.048 Methylamine 2,6-dimethylphenyl 1.049 Amino 3,4-dimethylphenyl 151-153 (splits) 1.050 Methylamine 3,4-dimethylphenyl 236-238 (splits) 1.051 Dimethylamine 3,4-dimethylphenyl 233-235 (splits) 1.052 Ethylamine 3,4-dimethylphenyl 230 (splits) 1.053 Propylamine 3,4-dimethylphenyl 211-213 (splits) 1.054 Isopropylamino 3,4-dimethylphenyl 235-236 (splits) 1.055 Cyclopropylamino 3,4-dimethylphenyl 229-231 (splits) 1.056 Butylamine 3,4-dimethylphenyl 200-202 (splits) 1.057 Isobutylamine 3,4-dimethylphenyl 222-223 (splits) 1.058 secondary-butylamine 3,4-dimethylphenyl 215-218 (splits) 1.059 tert.-butylamine 3,4-dimethylphenyl 223-225 (splits) 1.060 Allylamine 3,4-dimethylphenyl 194-201 (splits) 1.061 Propargylamine 3,4-dimethylphenyl 231-233 (splits) 1.062 Cyclohexylamine 3,4-dimethylphenyl 1.063 Phenylamino 3,4-dimethylphenyl 230-231 (splits) 1.064 Of 2-methoxyethylamine 3,4-dimethylphenyl 166-169 (splits) 1.065 Benzylamino 3,4-dimethylphenyl 234-236 (splits)

table (continued)

1 2 3 4 1.066 Pyrrolidinone 3,4-dimethylphenyl 1.067 Piperidinyl 3,4-dimethylphenyl 1.068 Hexahydroacepinil 3,4-dimethylphenyl 1.069 Morpholin 3,4-dimethylphenyl 1.070 2-methylpiperidinyl 3,4-dimethylphenyl 1.071 3-methylpiperidinyl 3,4-dimethylphenyl 1.072 4-methylpiperidinyl 3,4-dimethylphenyl 1.073 2,6-dimethylpiperidine dinyl 3,4-dimethylphenyl 1,074 N-met i1-pipera z in i1 3,4-dimethylphenyl 1.075 Thiamorpholinyl 3,4-dimethylphenyl 1.076 Methylamine 3,5-Dimethylphenyl 240-242 (decomposed) 1.077 Methylamine 2,3-dichlorophenyl 1.078 Methylamine 2,4-dichlorophenyl 1.079 Methylamine 2,5-dichlorophenyl 1.080 Methylamine 2,6-dichlorophenyl 1.081 Methylamine 3,4-Dichlorophenyl 240-241 (decomposed) 1.082 Methylamine 3,5-dichlorophenyl 1.083 Methylamine 2,3-difluorophenyl 1.084 Methylamine 2,4-difluorophenyl 1.085 Methylamine 2,5-Difluorophenyl 1.086 Methylamine 2,6-difluorophenyl 1.087 Methylamine 3,4-Difluorophenyl 1.088 Methylamine 3,5-difluorophenyl 1.089 Methylamine 3,5-dimethoxy-phenyl

table (continued)

1 2 3 4 1.090 Methylamine 2,4-Dimethoxy-phenyl 1.091 Methylamine 2,5-Dimethoxy-phenyl 1.092 Methylamine 2,6-Dimethoxy-phenyl 1.093 Methylamine 3,4-Dimethoxy-phenyl 223-225 (splits) 1.094 Dimethylamine 3,4-Dimethoxy-phenyl 203-207 (splits) 1.095 Methylamine 3,5-dimethoxy-phenyl 1.096 Methylamine 3,4-Dinitrophenyl 1.097 Methylamine 3,5-Dinitrophenyl 1.098 Methylamine 2-chloro-3-nitro-phenyl 1.099 Methylamine 2-chloro-4-nitro-phenyl 1.100 Methylamine 2-chloro-5-nitro-phenyl 1.101 Methylamine 3-chloro-2-nitro-phenyl 1.102 Methylamine 4-chloro-2-nitro-phenyl 1.103 Methylamine 3-chloro-3-nitro-phenyl 1.104 Methylamine 5-chloro-2-nitro-phenyl 1.105 Methylamine 2-methyl-3-nitrophenyl 247-248 (splits) 1.106 Methylamine 2-methyl-5-nitrophenyl 1.107 Methylamine 2-methyl-6-nitrophenyl 1. 108 Methylamine 3-methyl-2-nitrophenyl 1.109 Methylamine 3-methyl-4-nitrophenyl 1.110 Methylamine 4-methyl-3-nitrophenyl 1.111 Methylamine 5-methyl-2-nitrophenyl 1.112 Methylamine 4-fluoro-3-nitrophenyl 1.113 Methylamine 5-chloro-2-methoxy-phenyl 1. 114 Methylamine 4-chloro-2-methoxy-phenyl

table (continued)

1 2 3 4 1.115 Methylamine 4-chloro-6-fluoro-phenyl 1.116 Methylamine 4-chloro-2-fluoro-phenyl 1.117 Methylamine 2,4,6-trimethylphenyl 1.118 Methylamine 2,4,5-trimethoxy-phenyl 1.119 Methylamine 3,4,5-trimethoxy-phenyl 238-239 (splits) 1.120 Methylamine 1-naphthyl 240-242 (splits) 1.121 Methylamine 2-naphthyl 234-235 (splits) 1.122 Methylamine 2-furyl 245-246 (splits) 1.123 Dimethylamine 2-furyl 246-247 (splits) 1.124 Methylamine 3-furyl 1.125 Methylamine 2-way 245-247 (splits) 1.126 Methylamine 2-chloro-pyridinyl 1.127 Methylamine 2,6-dichloropyridinyl 138-139 (splits) 1.128 Methylamine 2,6-dibromopyridinyl 1.129 Methylamine Piperonyl 268-270 (splits) 1.130 Dimethylamine 3-toil · 204-207 (splits) 1.131 Cyclopropylamino 3-trifluoromethylphenyl 246-247 (splits) 1.132 Isopropylamino 3-tolyl 217-220 (splits) 1.133 Dimethylamine 3-trifluoromethylphenyl 229-230 (splits) 1.134 Amino 4-chloro 226-228 (splits) 1.135 Methylamine 2-carboxyphenyl 181-183 (splits) 1.136 Isopropylamino 2-tolyl 236-238 (splits) 1.137 Methylamine 3-Bromo-4-methyl-phenyl 244-245 (splits) 1.138 Isopropylamino 1-naphthyl 235-237 (splits) 1.139 Allylamine 1-naphthyl 218-219 (splits)

table (continued)

1 2 3 4 1.140 Allylamine 2-tolyl 195-198 (splits) 1.141 3-tolylamino 2-tolyl 197-199 (splits) 1.142 Tert-butylamine 2-tolyl 144-145 (splits) 1.143 Tert-butylamine 2,4-dimethylphenyl 226-227 (splits) 1.144 Propargylamine 1-naphthyl 149-151 (splits) 1.145 Tue butylamine 2,4-dimethylphenyl 230-232 (splits) 1.146 Propargylamine 2,4-dimethylphenyl 191-192 (splits) 1.147 Methylamine 2-biphenyl 262-264 (splits) 1.148 Tue butylamine 2,5-dimethylphenyl 208-210 (splits) 1.149 Dimethylamine 2,4-dimethylphenyl 206-209 (splits) 1.150 Dimethylamine 1-naphthyl 250 (splits) 1.151 Dimethylamine 2-tolyl 236-240 (splits) 1.152 Propargylamine 2,5-dimethylphenyl 198-200 (splits) 1.153 Methylamine 4-chloromethyl-phenyl 228-229 (splits) 1.154 Methylamine 3- (2,3-tetramethyl- len) -enyl 250 1.155 Methylamine 3- (2,3-tetramethyl- len) -furil 1.156 Methylamine 3- (4,5-Dimethyl) - thienil 238-239 (splits)

table ^ • N-CO-NH

9 of

so ₂ -nh-co-a

Compound N R ¹ R ² N- A Lyd. temp. (° C) 1 2 3 4 2.001 Amino Phenyl 2002 Methylamine Phenyl 2003 Dimethylamine Phenyl 2,004 Methylamine 2-tolyl 2005 Methylamine 3-tolyl 2006 Methylamine 4-tolyl 2007 Methylamine 2-chloro-phenyl 2008 Methylamine 4-chloro-phenyl 2009 Methylamine 3-trifluoromethyl-phenyl 2010 Methylamine 2,3-dimethylphenyl 2, 011 Methylamine 3,4-dimethylphenyl 147-152 2.012 Methylamine 1-naphthyl 2.013 Methylamine 2-naphthyl 2.014 Dimethylamine 2-furyl 216-217 (splits)

table

Compound N A R ^a Lyd. temp. (° C) 1 2 3 4 3.001 Phenyl 2-fluoro 3.002 Phenyl 3-fluoro 3.003 4-tolyl 2-fluoro 258-260 (splits) 3.004 4-tolyl 3-fluoro 3.005 4-tolyl 2-chloro 3.006 4-tolyl 3-chloro 3.007 4-tolyl 2-methyl 3.008 4-tolyl 3-methyl 3.009 3,4-dimethylphenyl 2-fluoro 246-248 (splits) 3.010 3,4-dimethylphenyl 3-fluoro 239-240 3.011 3,4-dimethylphenyl 2-chloro 3.012 3,4-dimethylphenyl 3-chloro 223-224 (splits) 3.013 3,4-dimethylphenyl 2-methyl 3.014 3,4-dimethylphenyl 3-methyl 218-220 (splits) 3.015 2-tolyl 3-fluoro 236-238 (splits) 3.016 1-naphthyl 3-fluoro 131-133 (splits) 3.017 2,4-dimethylphenyl 2-fluoro 236-238 (splits) 3.018 2,4-dimethylphenyl 3-fluoro 233-234 (splits) 3.019 1-naphthyl 2-fluoro 240-241 (splits)

table (continued)

1 2 3 4 3.020 2,3-dimethylphenyl 3-fluoro 227-230 (splits) 3.021 2,3-dimethylphenyl 2-fluoro 244-246 (splits) 3.022 2-tolyl 2-fluoro 236-237 (splits) 3.023 3,5-dimethylphenyl 3-fluoro 198-200 (splits) 3.024 3,5-dimethylphenyl 2-fluoro 244-246 (splits) 3.025 2,5-dimethylphenyl 3-fluoro 213-215 (splits) 3.026 2,5-dimethylphenyl 2-fluoro 227-229 (splits) 3.027 2-tolyl 3-methyl 176 (splits) 3.028 2-tolyl 3-chloro 218-220 (splits) 3.029 1-naphthyl 3-chloro 150 (splits) 3.030 1-naphthyl 3-methyl 153-155 (splits)

table

H ₃ C-NH-CO-NH

SO ₂ -NH-CO-A

Compound N A R ^a R ^b Lyd. ( ^C temp. 'C) 4.001 1-naphthyl 2-methyl 6-methyl 214-216 (splits) 4.002 3,4-dimethylphenyl 2-methyl 6-methyl 206-208 (splits) 4.003 2-tolyl 2-methyl 6-methyl 217-219 (splits) 4.004 1-naphthyl 2-fluoro 6-fluoro 4.005 3,4-dimethylphenyl 2-fluoro 6-fluoro 4.006 2-tolyl 2-chloro 6-chloro 4.007 4-tolyl 2-fluoro 5-fluoro 4.008 4-tolyl 2-fluoro 6-fluoro 4.009 4-tolyl 2-methyl 5-methyl

table

Compound N

Lyd. temp. (° C)

5.001 3,4-Dimethyl-phenyl

5,002 2-tolyl

5,003 1-Naphthyl

201-203 (splits)

184-186 (splits)

Triethylamine salt

138-140 (splits)

Triethylamine salt

5,004 2-tolyl

5,005 4-tolyl

5,006 3,4-Dimethyl-phenyl

5.007 2-tolyl

Examples of formulas containing active substances of the formula I or mixtures of these active substances with herbicides

Example F1

Moisturizing powder

Active substance N 1.050

Lignin sulphonate sodium

Sodium laurilsulfate

Diisobutylnaphthalene sodium sulfonate

7-8 mol ethylene oxide octylphenol polyethylene glycol ether

Highly dispersible silica

Kaolin

Sodium chloride

a) b) c)% 60% 0.5%% 5% 5%%

% 6%% 2%% 27% 27%% 59.5%

The active ingredient mixture is well mixed with additives and thoroughly ground in a suitable mill. A moisturizing powder is obtained which can be dissolved in water to any desired concentration of suspension.

Example F2

Emulsion concentrate a) b)

Active substance N 2.011 10% 1%

Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide) 3% 3%

Calcium dodecylbenzenesulfonate 3% 3%

Castor oil polyglycol ether (36 mol ethylene oxide) 4% 4%

Cyclohexanone 30% 10%% 79%

A mixture of xylenes

From these concentrates, dilutions with water can be made into any desired concentration of emulsion.

Example F3

Dust preparation Active substance N 1.050

Talk

Kaolin

a) b)

0.1% 1%

99.9%

After mixing the active ingredient mixture with a carrier and crushing it into a suitable mill, it is ready for use for dusting.

Example F4

Extruded granulate Active substance N 1.006 Sodium lignin sulphonate

Carboxymethylcellulose

Kaolin

a)%

%%

%

b)%

%%

%

The active ingredient mixture is mixed with additives, crushed and moistened with water. This mixture is passed through an extruder and then air-dried.

Example F5

Granules in shell

Active substance N 1.005 3%

Polyethylene glycol (mol. Wt. 200) 3%

Kaolin%

The finely divided active ingredient is evenly distributed on the kaolin particles dipped in polyethylene glycol in a blender. In this way, dust-free granules are obtained.

Example F6

Suspension concentrate

Active substance N 1.050

Ethylene glycol

Nonylphenolpolyethylene glycol ether (15 mol ethylene oxide)

Lignin sulphonate sodium

Carboxymethylcellulose

37% aqueous formaldehyde solution

Silicone oil 75% aqueous emulsion

Water

a)%

%%

%%

0.2%

0.8%

b)%

%%

%%

0.2%

0.8%

Example F7

Saline solution

Active substance N 1.026 5%

Isopropylamine 1%

Octylphenol polyethylene glycol ether (78 mol ethylene oxide) 3%

Water%

Example F8

Moisturizing powder

Active substance N 1.050 in admixture with N- (2-methoxyethoxy) -phenylsulfonyl) -N'- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea

Lignin sulphonate sodium

Sodium laurilsulfate

Sodium diisobutylnaphthalenesulfonate

Octylphenol polyethylene glycol ether (7-8 mol ethylene oxide)

Highly dispersible silica

Kaolin

Sodium chloride

a) b) c)% 60% 0.5%% 5% 5%%

% 6%% 2%% 27% 27%% 59.5

Mix the active ingredients well with the additives and grind 5 thoroughly in a suitable mill. Gives a volatile powder that can be dissolved in water to any desired concentration.

Example F9

Emulsion concentrate

Active substance N 2.011 in mixture with 2- (4- (5-trifluoromethylpyridin-2-yloxy) -phenoxy) -propanoic acid n-butyl ester

Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide)

Calcium dodecylbenzenesulfonate

Polyglycol ether of castor oil

b)%

% o o

Polyglycol ethereal oil (36 mol ethylene oxide)

Cyclohexanone 30% 10%

Xylene mixture 50% 79%

These concentrates can be diluted with water to give emulsions of any desired concentration.

Example F10

Preparation for dusting a) b)

Active substance N 1.050 in mixture with N- (2- (2-methoxyethoxy) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea 0.1% 1%

Talc 99.9%

Kaolin - 99%

When the active substance is mixed with the carrier and properly crushed, it is ready for use as a dusty preparation.

Example Fll

Extruded granulate a) b)

Active substance N 1.006 in mixture with N- (2- (2-methoxyethoxy) phenylsulfonyl) -N '- (4,6-

dimethoxy-1,3,5-triazin-2-yl) urea 10th o o 1 o. o Lignin sulphonate sodium 2 o 0 2 0 o Carboxymethylcellulose 1 o O 1 o o Kaolin 87 o O 96 o. o

The active ingredient mixture is mixed with additives, crushed and moistened with water. This mixture is passed through an extruder and then air-dried.

Example F12

Granules in shell

Active substance in mixture N 1.005 with N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2-ethyl-6-methylaniline 3%

Polyethylene glycol (mol. Wt. 200) 3%

Kaolin 94%

The finely divided active ingredient is evenly distributed on the kaolin particles dipped in polyethylene glycol in a blender. In this way, dust-free granules are obtained.

Example F13

Suspension concentrate

a) b)

Active ingredient n 1.050 in mixture with 2- (4- (6-chlorobenzoxazol-2-yloxy) -phenoxy) -propionic acid ethyl ester 40%

Ethylene glycol 10%

%

Nonylphenolpolyethylene glycol ether (15 mol ethylene oxide) 6% 1%

Lignin sulphonate sodium 10% 5%

Carboxymethylcellulose 1% 1%

37% aqueous formaldehyde solution

Silicone oil 75% aqueous emulsion

Water

0.2% 0.2%

0.8% 0.8%% 77%

Example F14

Saline solution

Active substance N 1.026 in admixture with 2- (4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -propionic acid propargyl ester 5%

Isopropylamine 1%

Octyphenolpolyethylene glycol ether (78 mol ethylene oxide) 3%

Water 91%

Biological samples

The ability of compounds of Formula I to protect crop plants against the phytotoxic effects of potent herbicides can be assessed using the examples below. Compounds of formula in test descriptions are called antidotes (antidotes or protective agents).

The evaluation of the test is that the action of the herbicide is individually evaluated as a percentage: 100% action corresponds to the destruction of the plant and 0% indicates no effect as in the case of untreated control plants. On the other hand, the effect of the herbicide-antidote combination is determined analogously by the percentage of herbicidal activity. The difference between the percentages obtained in the test results is called the protective effect,%.

The efficacy of the herbicide-antidote combination can be evaluated both by direct application of the two active ingredients by spraying the mixture from the reservoir as well as by separate application, as well as the time interval between their application, e.g.

Example Bl

Test with herbicide and antidote on sorghum

It is treated with a mixture of herbicide and antidote from the reservoir before germination or after germination of plants.

Funk C-623 sorghum seeds are sown in 11 cm diameter cups filled with garden soil and placed in a greenhouse with appropriate lighting and temperature. Watering and fertilizing as needed. To assess the effect of the antidote and the herbicide before germination, the mixture is treated with the solution after sowing at 550 l / ha. After the germination of the plant germination, the mixture of active substances is treated with 3-5 leaves of plants. After 21 days, evaluate test results as protective action, -.

Test results:

(a) Pre-emergence test:

Control Plants: Sorghum Funk C-623.

Treatment: Before germination, in a tank mix

250 g / ha of compound no. 1.050 and 125 g / ha of the compound N- (2- (2-methoxyethoxy) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Operation: after 21 days. after treatment + 50% protective action.

(b) Post-emergence test:

Control Plants: Sorghum Funk C-623.

Treatment: after germination: by tank mix

250 g / ha of compound no. 1.050 and 125 g / ha of N- (2- (2-me64-ethoxyethoxy) -phenylsulfonyl-N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Action: 21 days after treatment - 45% protective action.

Example B2

Test with herbicide and antidote in maize and sorghum. Seeds treated with antidotes, herbicide applied before germination or after germination of plants.

The 11 cm diameter cups, filled with garden soil, are sown with antidote-treated Blizzard maize seeds and Funk C-623 sorghum seeds, and placed in a greenhouse with appropriate lighting and temperature. Water and fertilize if necessary. To assess the effect before emergence, the herbicide (550 l / ha) is applied immediately after sowing. To assess the effect on the germination of plants, 3-5 leaves are applied to the herbicide. Accordingly, after 12-26 days, the assay is evaluated for percent protective performance.

Test results:

(a) Test in maize:

Control plants: Blizzard corn.

Treatment: Seed treatment with N 1.050 using 0,5 g, 1 or 2 g per kilogram of maize seed.

Herbicide before germination:

400 g / ha of N-chloroacetyl-N- (2-methoxy-1-methoxyethyl) -ethyl-6-methylaniline, or

240 g / ha N- (2- (3,3,3-trifluoropropen-1-yl) phenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -ourea, or

120, 60 or 30 g / ha of N- (2- (2-methoxyethoxy) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Herbicide after germination:

120 g / ha of N- (2-methoxycarbonylthien-3-ylsulfonyl) -N'- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea, or

480 g / ha N- (2- (3,3,3-trifluoropropen-1-yl) phenylsulfonyl-N '- (4-methoxy-6-methyl-6-methyl-1,3,5-triazine-2) -il) urea, or

120 g / ha of N- (2-methoxycarbonylphenylsulfonyl) -N- (4-difluoromethoxy-6-methoxypyrimidin-2-yl) urea, or

120 g / ha of N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl) urea, or

120 g / ha N- (2-methoxycarbonylphenylsulfonyl) -N '- (4,6bis-difluoromethoxy-pyrimidin-2-yl) -urea, or g / ha N- (2- (2-chloroethoxy) -phenylsulfonyl) -N'- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea, or g / ha of N- (2- (2-chloroethoxy) -phenylsulfonyl) -N '- (4-methoxy- 6-methyl-1,3,5-triazin-2-yl) urea, or g / ha 2- (4- (6-chloroquinoxalin-2-yloxy) -phenoxy) -propanoic acid ethyl ester, or g / ha 2- (4- (6-chlorobenzoxazol-2-yloxy) -phenoxy) -propanoic acid ethyl ester, or g / ha of 2- (4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -propanoic acid propargyl ester, or g / ha of N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-ethoxy-6-methylamino-1,3,5-triazin-2-yl) -urea, or

240, 120, 60 or 30 g / ha of N- (2- (2-methoxy) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Performance (DAT - days after use)

Antidote: beico amount in g / kg of seeds Herbicidal cido dose Method of application of the herbicide (pre-emergence; post-emergence) Protective ginis act- mas, 0, o 1 2 3 4 5 2 4000 N-chloroacetyl-N- (2-methoxy-1- ethyl) -2-ethyl-6-methylaniline pre / 14DAT 40 1 240 N- (2- (3,3,3-trifluoropropen-1-yl) phenylsulfonyl) -N ¹ - (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea pre / 20DAT 25th 1 480 _ H _ post / 20DAT 30th 2 120 N- (2- (2-methoxyethoxy) -phenylsulfonyl) -N '- (4,6-dimethyl- toxic-1,3,5-triazin-2-yl) - urea pre / 12DAT 70 1 120 _ u _ pre / 12DAT 65 0, 5 120 _ H _ pre / 12DAT 65 2 60 _ 11 _ pre / 12DAT 65 1 60 _ n _ pre / 12DAT 65 0, 5 60 _ H _ pre / 12DAT 70

1 2 3 4 5 2 30th _ n _ pre / 12DAT 55 1 30th _ II _ pre / 12DAT 50 0, 5 30th _ lf _ pre / 12DAT 55 2 240 _ II _ post / 20DAT 65 1 240 _ IT _ post / 20DAT 65 0, 5 240 _ II _ post / 20DAT 50 2 120 _ II _ post / 20DAT 60 1 120 _ II _ post / 20DAT 55 0.5 120 _idj II _ post / 20DAT 25th 2 60 _ II _ post / 20DAT 40 1 60 _ II _ post / 20DAT 40 0.5 60 _ II _ post / 20DAT 35 2 30th _ II _ post / 20DAT 25th 1 30th _ II _ post / 20DAT 30th 0.5 30th _ II _ post / 20DAT 15th 1 120 N- (2-methoxycarbonylthiene-3- ylsulfonyl) -N '- (4-methoxy-6- methyl-1,3,5-triazin-2-yl) - urea post / 16DAT 20th 1 120 N- (2-methoxycarbonylphenyl) sulfonyl) -N '- (4-difluoromethoxy- si-6-methoxy-pyrimidin-2-yl) - urea post / 16DAT 15th 1 120 N- (2-methoxycarbonylphenyl) sulfonyl) -N '- (4-cyclopropyl) 6-methoxy-1,3,5-triazine-2- il) -urea post / 16DAT 20th

1 2 3 4 5 1 120 N- (2-Methylcarbonylphenyl) sulfonyl-N '- (4,6-bis-difluoro- methoxy-pyrimidin-2-yl) -urea post / 16DAT 20th 1 10th N- (2- (2-chloroethoxy) phenylsulfonyl) -N '- (4-methoxy-6- methyl-1,3,5-triazin-2-yl) - urea post / 16DAT 35 1 30th 2- (4- (6-chloroquinoxaline-2-) yloxy) -phenoxy) -propane acid ethyl ester post / 16DAT 30th 1 30th 2- (4- (3,5-Dichloropyridine-2-) yloxy) -phenoxy) -propane propargyl ester of acid post / 16DAT 45 1 10th N- (2-methoxycarbonylphenyl) sulfonyl) -N '- (4-ethoxy-6-methyl- tilamino-1,3,5-triazin-2-yl) - urea post / 16DAT 30th 1 60 2- (4- (6-chlorobenzoxazole-2-) yloxy) -phenoxy) -propane acid ethyl ester post / 16DAT 30th

(b) Test for sorghum:

Plants: Sorghum, Variety Funk C-623

Treatment: Seed treatment 0.5 g, 1 g or 2 g compound per kilogram of sorghum seed.

Herbicide before germination:

1000 g / ha of N-chloroacetyl-N '- (2-methoxy-1-methoxyethyl) ethyl-6-methylaniline, or

250 g / ha N- (2- (3,3,3-trifluoropropen-1-yl) phenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -ourea, or

120, 60 or 30 g / ha of N- (2- (2-methoxyethoxy) -phenylsulfonyl) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Herbicide after germination:

480 g / ha N- (2- (3,3,3-trifluoropropen-1-yl) phenylsulfonyl-N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) - urea, or g / ha 2- (4- (6-chloroquinoxalin-2-yloxy) -phenoxy) -propanoic acid ethyl ester, or g / ha 2- (4- (6-chlorobenzoxazol-2-yloxy) -phenoxy) proparic acid ethyl ester, or g / ha 2- (4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -propionic acid propargyl ester, or g / ha 2- (4- (5-trifluoromethylpyridin-2) butyl ester of -yloxy) -phenoxy) -propanoic acid, or

240, 120, 60 or 30 g / ha of N- (2- (2-methoxy) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Performance (DAT - days after use)

On the i- Herbicidal Herbicide Protective given: c ido using the imo ginis beico dose way (pre- act- quantity before sudy- mas, g / kg a mill; postal g. 0 seeds after germination) 1 2 3 4 5 1 1000 N-chloroacetyl-N- (2-methoxy-1- ethyl) -2-ethyl-6-methylaniline pre / 26DAT 35 1 250 N- (2- (3,3,3-trifluoropropene-1-) il) -phenylsulfonyl) -N'- (4-me- toxic-1,3,5-triazin-2-yl) - urea pre / 20DAT 45 1 480 _ n _ post / 20DAT 40 2 120 N- (2- (2-methoxyethoxy) phenylsulfonyl) -N '- (4,6-dimethoxy) 1,3,5-triazin-2-yl) - urea pre / 12DAT 55 1 120 _ II _ pre / 12DAT 55 0.5 120 _ II _ pre / 12DAT 60 2 60 _ »1 _ pre / 12DAT 55 1 60 _ II _ pre / 12DAT 50 0, 5 60 _ II _ pre / 12DAT 60 2 30th _ II _ pre / 12DAT 70 1 30th _ II _ pre / 12DAT 65 0, 5 30th _ II _ pre / 12DAT 70 2 240 _ II _ post / 20DAT 50 1 240 _ II _ post / 20DAT 60 0.5 240 _ II _ post / 20DAT 60 2 120 _ II _ post / 20DAT 50 1 120 _ II _ post / 20DAT 65

1 2 3 4 5 0.5 120 _ n _ post / 20DAT 60 2 60 _ n _ post / 20DAT 45 1 60 _ n _ post / 20DAT 65 0.5 60 _ n _ post / 20DAT 60 2 30th _ »1 _ post / 20DAT 30th 1 30th _ II _ post / 20DAT 45 0.5 30th _ IT _ post / 20DAT 50 1 60 2- (4- (6-chlorobenzoxazol-2-yl) oxy) -phenoxy) -propanoic acid ethyl ester post / 16DAT 33 1 15th 2- (4- (6-chloroquinoxaline-2-) yloxy) -phenoxy) -propane acid ethyl ester post / 16DAT 40 1 15th 2- (4- (3,5-Dichloropyridine-2-) yloxy) -phenoxy) -propane propargyl ester of acid post / 16DAT 50 1 30th Butyl ester of 2- (4- (5-trifluoromethylpyridin-2-yloxy) -phenoxy) -propanoic acid post / 16DAT 20th

Test results:

Example B3

Test with herbicide and antidote in rice.

The seed pre-swells in the dispersion of the antidote, treated with the herbicide before emergence.

Seeds of rice S-201 48 h. swelling in an aqueous dispersion of the antidote, followed by drying for 24 hours.

and shallowly sown in 9x9 cm cups filled with well-moistened garden soil. Spray an aqueous solution of herbicide 550 l / ha - sprayed on the soil surface after sowing. Plants are placed in a greenhouse with an appropriate temperature / light ratio. Watering and fertilizing as needed. After

The 26-day test is evaluated by the protective performance%.

Results:

Plants: S-201 variety rice.

Treatment: Seed swelling 48 hours. 300 ppt of compound N 1.050; pre-emergence treatment with 30 g / ha of N- (2- (2-methoxyethoxy) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Performance: 55 days after treatment - 55% protective action.

Claims (62)

DEFINITION OF INVENTION 1. Formula derivatives I having N-acylsulfamoylphenylurea in which A is a radical: 1. 2 R and R independently represent hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₆ alkynyl, or substituted C ₁ -C ₄ alkoxy or R ^J y is a C ₁ -C ₄ alkyl group, or R ¹ and R ² - together represent a C ₄ -C ₆ alkylene bridge or a C ₄ -C ₆ alkylene bridge separated by oxygen, sulfur, SO, SO ₂ , NH or - N (C ₁ -C ₄ alkyl), R ³ - hydrogen or C ₁ -C ₄ alkyl, R ^a and R ^b , independently of one another hydrogen, halogen, -CN, nitrotrifluoromethyl, C ₁ -C ₆ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl, C _{1 -} C 1-4 alkylsulfonyl-, COOR ^j , -COONR ^k R ^m , -COR ⁿ , -SO ₂ NR ^k R ^m or -OSO ^ C 1-6 alkyl, or R ^a and R ^b together represents a C ₃ -C ₄ alkylene bridge which may be substituted by halogen or C ₁ -C ₄ alkyl; or a C ₃ -C ₄ alkylene bridge which may be substituted by halogen or C ₁ -C ₄ alkyl; or a C ₄ -alkendienyl bridge which may be substituted by halogen or C ₁ -C ₄ -alkyl; R ⁹ and R ^h , independently of one another hydrogen, halogen, C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, methylthio or -COOR ³ when R ^c - hydrogen, halogen, C ₁ -C ₄ alkyl or methoxy, R ^d - hydrogen, halogen, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkyl- '75 sulfinyl- C ₁ -C ₄ alkylsulfonyl, -COOR ^j or CONR ^k R ^exist, R ^e is hydrogen, halogen, C 1 -C 4 alkyl, COOR ^d , trifluoromethyl or methoxy, or R ^d and R ^e together represent a C ₃ -C ₄ alkylene bridge, R ^f is hydrogen, halogen or C ₁ -C ₄ alkyl, R ^x and R ^y each independently represent hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, -COOR ⁴ , trifluoromethyl, nitro or CN groups , R ^j , R ^k and R ^m each independently represent hydrogen or C ₁ -C ₄ alkyl, R ^k and R ^m together represent a C ₄ -C ₆ alkylene bridge, or a oxygen-substituted, NH or -N (C ₁ -C ₆ alkyl) C ₄ -C ₆ alkylene bridge, R ⁿ is -C ₁ -C ₄ alkyl, phenyl or substituted with halogen, C ₁ -C ₄ alkyl, methoxy, nitro or trifluoromethyl phenyl. Compounds of formula I according to claim 1, characterized in that A is a radical of one of the groups: R ¹ and R ² each independently represent hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, R is either C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl, or R ^J 1 2 R and R together represent a C ₄ -C ₆ alkylene bridge or a C ₄ -C ₆ alkylene bridge separated by oxygen, sulfur, SO, SO ₂ , NH or -N (C ₁ -C ₄ alkyl), R ³ is hydrogen or C ₁ -C ₄ alkyl, R ^a and R ^b each independently represent hydrogen, halogen, -CN, nitrotrifluoromethyl groups, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 3 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4; C ^ alkylsulfonyl-, COOR ^j, R ^{k is not} -COONR, -COR ^n, -SO 2 NR ^k R ^m or -OSO ₂ -C ₁ -C ₄ -alkyl or R ^a and R ^b together represents a C ₃ -C ₄ alkylene bridge which may be substituted by halogen or C ₁ -C ₄ alkyl; or a C ₃ -C ₄ alkylene bridge which may be substituted by halogen or C ₁ -C ₄ alkyl; or a C ₄ -alkendienyl bridge which may be substituted by halogen or C 1 -C 4 -alkyl; R ⁹ and R ^h , independently of one another hydrogen, halogen, C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, methylthio or -COOR ' ¹ when R ^c - hydrogen, halogen, C ₁ -C ₄ alkyl or methoxy, R ^d - hydrogen, halogen, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkiltio- C _x -C ₄ -alkilsulfinil- C ₁ -C ₄ alkylsulfonyl, -COOR ^j or -CONR ^k R ^m , R ^e - hydrogen, halogen, C ₁ -C ₄ alkyl, COOR ^d , trifluoromethyl or methoxy, or R ^d and R ^e together represents the C ₃ -C ₄ alkylene bridge, R ^f - hydrogen, halogen or C ₁ -C ₄ alkyl, R ^x and R ^Y , independently of one another hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, -COOR ⁴ , trifluoromethyl, nitro or CN groups, R ^j , R ^k and R ^m , independently of one another, represents hydrogen or C ₁ -C ₄ alkyl, R ^k and R ^m together denotes a C ₄ -C ₆ alkylene bridge, or a oxygen-substituted, NH or -N (C ₁ -C ₄ alkyl) C ₄ -C ₆ alkylene bridge, R ⁿ is -C ₁ -C ₄ alkyl, phenyl or substituted with halogen, C ₁ -C ₄ alkyl, methoxy, nitro or trifluoromethyl phenyl. Compounds according to claim 1, characterized in that R ^b is hydrogen. Compounds according to claim 1, characterized in that the sulfamoyl group is in the 4-position of the phenyl ring. Compounds according to claim 1, other than Wherein R and R represent hydrogen. 6. Compounds according to claim 1, characterized in that R ^b is hydrogen and the sulfamoyl group is in the 4-position of the phenyl ring. Compounds according to claim 1, characterized in that R ² , R ³ and R ^b represent hydrogen and the sulfamoyl group is in the 4-position of the phenyl ring. 8. Compounds according to claim 1, wherein A is a group 9. Compounds according to claim 8, wherein R ² , R ³ and R ^b represent hydrogen and the sulfamoyl group is in the 4-position of the phenyl ring. Compounds according to claim 1, characterized in that they have the formula la Compounds according to claim 10, characterized in that R ^c is hydrogen. ischian Compounds according to claim 11, characterized in that R ¹ , R ^b and R ^h are C ₁ -C ₄ alkyl. 13th 1- (4- (Ν-4-Methylbenzoyl-sulfamoyl) -3-methyl-urea according to claim 1. 14th 1- (4- (Ν-3-Methylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 15th 1- (4- (Ν-4-tert-Butylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 16th 1- (4- (Ν-3-Trifluoromethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 17th 1- (4- (Ν-4-Nitrobenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 18th 1- (4- (N-2,3-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 20th 1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3,3-dimethyl-urea according to claim 1. 21st 1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-ethyl-urea according to claim 1. 22nd 1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-allyl-urea according to claim 1. 1- (4- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-phenyl-urea according to claim 1. 24th 1- (4- (N-3,5-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 25th 1- (4- (N-3,4-Dichlorobenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 1- (4- (N-3,4-Dimethoxybenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 27th 1- (4- (N-3,4-Dimethoxybenzoyl-sulfamoyl) -phenyl) -3-dimethyl-urea according to claim 1. 28th 1- (4- (N-2,4,5-Trimethoxybenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 29th 1- (4- (N-1-Naphthylcarbonyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 30th 1- (4- (β-2-Furylcarbonyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 1- (4- (Ν-2-Furylcarbonylsulfamoyl) -phenyl) -3,3-dimethylurea according to claim 1. 32. 1- (4- (β-2-Thienylcarbonyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 33. 1- (4- (N-Piperonyloyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 34. 1- (4- (Ν-3-Methylbenzoyl-sulfamoyl) -phenyl) -3,3-dimethyl-urea according to claim 1. 35. 1- (4- (Ν-3-Trifluoromethylbenzoyl-sulfamoyl) -phenyl) -3-cyclopropyl-urea according to claim 1. 1- (3- (N-3,4-Dimethylbenzoyl-sulfamoyl) -phenyl) -3-methyl-urea according to claim 1. 37. 1- (3- (Ν-2-Furylcarbonylsulfamoyl) -phenyl) -3,3-dimethylurea according to claim 1. 38. A crop protection agent against phytotoxic sulfonylurea herbicides, chloroacetanilide herbicides, acylcyclohexanedione herbicides or aryloxyphenoxypropanoic acid herbicides, characterized in that it comprises an active ingredient of the formula I according to claim 1. 39. A method of protecting crop plants against phytotoxic sulfonylurea herbicides, chloroacetanilide herbicides or aryloxyphenoxypropanoic acid herbicides comprising the active ingredient of the formula I according to claim 1. 40. The method of claim 39, wherein the crop is rice, corn, millet, cereal bread or soy. 41. The method of claim 40, wherein the crop is rice, corn or millet. 42. The method of claim 39, wherein the crop is millet and the herbicide is sulfonylurea. 43. A method as claimed in claim 39, which is used for protecting crop plants against phytotoxic sulfonylurea herbicides of formula II. E- (CH ₂ ) _n -SO ₂ -NH-CO-N (II) wherein E is a group or n is 0 or 1 G is hydrogen or methyl X - methoxy, ethoxy, difluoromethoxy, methyl or chlorine, Y = CH or N, Z is methoxy, methyl, difluoromethoxy, cyclopropyl or methylamine, R ⁴ - C ₂ -C ₅ alkoxyalkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ haloalkylthio, C ₂ -C ₄ haloalkenyl, chlorine or C ₁ -C ₄ alkoxycarbonyl, R ⁵ is trifluoromethyl or di (C ₃ -C ₄ alkyl) carbamoyl, R ⁶ - C ₁ -C ₄ alkoxycarbonyl, R - ^ - ^ - alkoxycarbonyl, R ⁸ is C ₁ -C ₄ alkyl. 44. The method of claim 43, wherein the sulfonylurea of formula II is selected from the group consisting of: N- (3-trifluoromethylpyridin-2-ylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) urea; N - (3-Dimethylcarbamoylpyridin-2-ylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) urea; N- (1-Methyl-4-ethoxycarbonylpyrazol-2-ylsulfonyl) -N '(4,6-dimethoxypyrimidin-2-yl) urea; N - (2-methoxycarbonylthien-3-ylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea; N- (2-methoxycarbonylbenzylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) -urea; N- (2-methoxycarbonylphenylsulfonyl) -N '- (4,6-bis-difluoromethoxy-pyrimidin-2-yl) -urea; N - (2-methoxycarbonylphenylsulfonyl) -N '- (4-ethoxy-6-methylamino-1,3,5-triazin-2-yl) urea; N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea; N- (2-ethoxycarbonylphenylsulfonyl) -N '- (4-chloro-6-methoxypyrimidin-2-yl) urea; N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N'-methylurea; N- (2-methoxycarbonylphenylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) urea; N- (2-chlorophenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea; N- (2- (2-chloroethoxy) -phenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea; N- (2- (2-methoxyethoxy) -phenylsulfonyl) -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea. 45. A method as claimed in claim 39, which is used for protecting crop plants against the phytotoxic action of chloroacetanilide herbicides of formula III: in which e L - C ₁ -C ₄ alkylene bridge; 9 10 11 R, R, R independently of one another are hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C _x -C ₄ haloalkyl, C ₂ -C ₅ alkoxyalkyl or C ₂ - C ₅ alkylthioalkyl; R ¹² - C ₁ -C ₄ alkoxy, -COOH, C ₁ -C ₄ alkoxycarbonyl, -CONH ₂ , C ₁ -C ₄ alkylcarbamoyl; di-C ₁ -C ₄ alkylcarbamoyl, -CN, C 1-4 alkylcarbonyl, if need, changed benzene, if need, changed furil, if need, changed thienil, if need, changed pyrrolyl, if need, changed pyrazolyl, if need, changed 1,3,4-Oxadiazol-2-yl if need, changed 1,3,4-thiadiazol-2-yl, if need, changed 1,2,4-triazol-3-yl, substituted dioxolanyl, if necessary, substituted dioxanyl, if necessary, substituted 1,3,4-triazol-2-yl, if necessary, substituted tetrahydrofuryl. 46. The method of claim 45, wherein the chloroacetanilides of formula III are selected from the group consisting of: N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline, N-chloroacetyl-N- (2-methoxyethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (2-n-propoxyethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (2-isopropoxyethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (2-methoxyethyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (methoxyethyl) -2,6-diethylaniline, N- (2-ethoxyethyl) -N- (chloroacetyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2,6-diethylaniline, N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2-ethyl-6-methylaniline, N- (2-ethoxyethyl) -N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N- (2-n-propoxyethyl) -2-ethyl-6-methylan linen, - N-chloroacetyl-N- - (2-n-propoxyethyl) -2,6-diethylaniline, N-chloroacetyl-N- - (2-isopropoxyethyl) -2-ethyl-6-methylan linen, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N- -methoxycarbonylmethyl-2,6-dimethylanil- no, N-chloroacetyl-N- - (2,2-diethoxyethyl) -2,6-dimethylaniline, N-chloroacetyl-N- - (2-methoxy-1-methylethyl) -2,3-dimethylan linen, N- (2-ethoxyethyl) -N-chloroacetyl-2-methylaniline, N-chloroacetyl-N- - (2-methoxyethyl) -2-methylaniline, N-chloroacetyl-N- - (2-methoxy-2-methylethyl) -2,6-dimethylan linen, N- (2-ethoxy-2-methylethyl) -N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N- - (1-ethyl-1-methoxyethyl) -2,6-dimethylan linen, N-chloroacetyl-N- - (2-methoxyethyl) -2-methoxy-6-methylan linen, N-n-butoxymethyl-N-chloroacetyl-2-tert-butylaniline N- (2-ethoxyethyl-2-methylethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (2-methoxyethyl) -2-chloro-6-methylaniline, N- (2-ethoxyethyl) -N-chloroacetyl-2-chloro-6-methylaniline, N- (2-ethoxyethyl) -N-chloroacetyl-2,3,6-trimethylaniline, N-chloroacetyl-1- (2-methoxyethyl) -2,3,6-trimethylaniline, N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline, N-chloroacetyl-N- (1,3-dioxolan-2-ylmethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (1,3-dioxolan-2-ylmethyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (1,3-dioxan-2-ylmethyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (2-tolylmethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (2-furylmethyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (2-tetrahydrofurylmethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (N, N-dimethylcarbamoylmethyl) -2,6-dimethylaniline, N- (butoxymethyl) -N-chloroacetyl-2,6-diethylaniline, N- (2-n-butoxyethyl) -N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N- (2-methoxy-1,2-dimethylethyl) -2,6-dimethylaniline, N-chloroacetyl-N-isopropyl-2,3-dimethylaniline, N-chloroacetyl-N-isopropyl-2-chloroaniline, N-chloroacetyl-N- (1-H-pyrazol-1-ylmethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (1-H-pyrazol-1-ylmethyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (1-H-1,2,4-triazol-1-ylmethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (1-H-1,2,4-triazol-1-ylmethyl) -2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N- (5-methyl-1,3,4-oxadiazol-2-yl) -2,6-diethylaniline, N-chloroacetyl-N- (5-methyl-1,3,4-oxadiazol-2-yl) -2-ethyl6-methylaniline, N-chloroacetyl-N- (5-methyl-1,3,4-oxadiazol-2-yl) -2-ethyl6-methylaniline, N-chloroacetyl-N- (5-methyl-1,3,4-oxadiazol-2-yl) -2-tertbutylaniline, N-chloroacetyl-N- (4-chlorobenzoylmethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (1-methyl-5-methylthio-1,3,4-triazol-2-ylmethyl) -2,6-diethylaniline. 47. A method as claimed in claim 39, which is used for protecting crop plants against the phytotoxic aryloxyphenoxypropanoic acid herbicide of formula IV: QO ciu i ^J O-CH-COT (IV) in which Q is one of the radicals T is -NR ¹⁵ R ¹⁶ , R ¹³ is hydrogen R ¹⁴ is hydrogen N (CN) R ¹⁷ , OR ¹⁸ , SR ¹⁸ or either trifluoromethyl or halogen, i Q -O-N = CR R when R ¹⁵ and R ¹⁶ independently of one another are hydrogen, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkyl, phenyl or benzyl, R ¹⁵ and R ¹⁶ taken together with the nitrogen atom to which they are attached form a 5-membered or 6-membered saturated heterocycle which may optionally contain an oxygen or sulfur atom; R is C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl, C ₃ -C ₄ alkynyl or C ₂ -C ₄ alkoxyalkyl; R is hydrogen or a quaternary C ₁ -C ₆ -alkylammonium or C ₁ -C ₄ -alkoxyalkylammonium equivalent of an alkali, earth alkaline metal, copper or iron, optionally substituted with one or more amino groups, halogens, hydroxyls, nitro group (s), phenyl, C ₁ -C ₄ alkoxy; polyethoxy groups with 2-6 ethylenedioxy moieties; -COOR ²¹ , -COSR ²¹ , -CONH ₂ , -CON (C ₁ -C ₄ alkoxy) -C ₁ -C ₄ alkyl, -CON-di-C ₁ -C ₄ alkyl, CONH-C ₁ - C ₄ alkyl, -N (C ₁ -C ₄ alkoxy) -C ₁ -C ₄ alkyl, or di-C ₁ -C ₄ alkylamino C ₁ -C ₈ alkyl; optionally a C ₃ -C ₉ alkenyl radical substituted with halogen or C ₁ -C ₂ alkoxy; optionally a C ₃ -C ₉ -alkynyl radical substituted by halogen or C ₁ -C ₄ -alkoxyl; C ₃ -C ₉ -azinyl; C ₃ -C ₉ -cycloalkyl; or phenyl optionally substituted with nitrile, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl, acetyl, -COOR ²¹ , -COSR ²¹ , -CONH ₂ , -CON (C ₁ -C ₄ -alkoxy) ) -C ₁ -C ₈ -alkyl, -CO-Ndi-C ₁ -C ₄ -alkyl or -CONH-C ₁ -C ₄ -alkyl; 19 20 R and R separately are C 1 -C 4 alkyl and together are alkylene; 3-6 naLT 3943 B R ²¹ is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₅ haloalkyl, C ₂ -C ₆ -alkoxyalkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkyl or C ₃ -C ₆ -haloalkynyl. 48. The method of claim 47, wherein the aryloxyphenoxy-propanoic acid derivatives of formula IV are selected from the group consisting of: Propargyl ester of 2- (4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -propanoic acid; Propargyl ester of 2- (4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -thiopropanoic acid; 2- (4- (5-Chloro-3-fluoro-pyridin-2-yloxy) -phenoxy) -propanoic acid methyl ester; 2- (4- (5-Chloro-3-fluoro-pyridin-2-yloxy) -phenoxy) -propanoic acid butyl ester; 2- (4- (5-Trifluoromethylpyridin-2-yloxy) -phenoxy) -propanoic acid butyl ester; 2- (4- (5-Trifluoromethylpyridin-2-yloxy) -phenoxy) -propanoic acid methyl ester; 2- (4- (6-Chloroquinoxalin-2-yloxy) -phenoxy) -propanoic acid ethyl ester; 2- (4- (6-Chlorobenzoxazolin-2-yloxy) -phenoxy) -propanoic acid ethyl ester. 49. A method as claimed in claim 38, which is used for protecting crop plants against phytotoxic acylcyclohexanedione herbicides of formula IX: (IX) wherein A 'is a 2-7 membered alkylene bridge, a 3-7 membered alkenylene bridge which may have one or more unsaturated bonds; n 'is zero, one or two; R is C ₁ -C ₄ alkyl or benzyl; R ²³ - C ₁ -C ₈ alkyl, unsubstituted or substituted by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₃ -C ₆ cycloalkyl; phenyl, benzyl or phenylethyl where the phenyl rings may be substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ - C ₄ -haloalkoxyl, CN or nitro; X 'is oxygen or -NOR, R ^{24 is} -C ₁ -C ₈ alkyl, C ₁ -C ₈ haloalkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₈ haloalkenyl, or C ₃ -C ₆ alkynyl. ⁵⁰ 50. The method of claim 49, wherein the acylcyclohexanedione herbicides are selected from the group consisting of: 5- (1-methylthiocyclobutan-1-yl) -2- (2,4-dichlorobenzoyl) cyclohexane-1,3-dione; 5- (1-methylthiocyclobutan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione; 5- (1-methylthiocyclobutan-1-yl) -2-cyclopropanecarbonylcyclohexane-1,3-dione; 5- (1-methylthiocyclobutan-1-yl) -2- (2,3-dichlorobenzoyl) cyclohexane-1,3-dione; 5- (1-methylsulfonylcyclobutan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione; 5- (1-methylthiocyclopropan-1-yl) -2-propionyl-cyclohexane-1,3-dione; 5- (1-ethylthiocyclopropan-1-yl) -2-propionyl-cyclohexane-1,3-dione; 5- (1-methylthiocyclopropan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione; 5- (1-methylthiocyclopropan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione; 5- (1-methylthiocyclobutan-1-yl) -2- (1-ethoxyimino-n-butyryl) -cyclohexane-1,3-dione; 5- (1-methylthiocyclopropan-1-yl) -2- (1-ethoxyimino-n-butyryl) -cyclohexane-1,3-dione; 5- (1-methylthiocyclobutan-1-yl) -2- (1-allyloximino-n-butyl) -cyclohexane-1,3-dione; 5- (1-methylthiocyclopentan-1-yl) -2- (1-ethoxyimino-n-butyryl) -cyclohexane-1,3-dione; 5- (1-methylthiocyclopropan-1-yl) -2- (1- (trans-3-chloroalkyloxyimino) -n-butyryl) -cyclohexane-1,3-dione; 5- (1-methylthiocyclopropan-1-yl) -2- (1-trans-3-chloroallyloximino) -propionyl-cyclohexane-1,3-dione; 5- (1-methylthiocyclopropan-1-yl) -2- (1- (cis-3-chloroallyloximino) -propionyl) -cyclohexane-1,3-dione; 5- (1-Ethylthiocyclopropan-1-yl) -2- (1-trans-3-chloralyloximino) -propionyl) -cyclohexane-1,3-dione. Use of sulfamoylphenylurea derivatives of the formula I according to claim 1 for the protection of crop plants against the harmful sulfonylurea herbicides, chloroacetanilide herbicides, acylcyclohexanedione herbicides and herbicides aryloxyphenoxypropanoic acid. Use of sulfamoylphenyl urea derivatives of the formula I according to claim 1 for the protection of crop plants against the harmful effects of sulfonylurea herbicides, chloroacetanilide herbicides or aryloxyphenoxypropanoic acid based herbicides. 53. The use according to claim 52, wherein the sulfonylurea herbicides are compounds of formula II E- (CH ₂ ) _n -SO ₂ -NH-CO-N - (G) _N (II) wherein E is a group n - 0 or 1, G - hydrogen a: X is methoxy, etho a methyl, i, difluoromethoxy methyl or chlorine, Y = CH or N, Z is methoxy, methyl, difluoromethoxy, cyclopropyl or methylamine, R ⁴ - C ₂ -C ₅ -alkoksialkoksi C ₁ -C ₄ -halogenalkoksi C ₁ -C ₄ haloalkylthio, C ₂ -C ₄ -halogenalkenilas, chlorine or C ₁ -C ₄ alkoxycarbonyl, R ⁵ is trifluoromethyl or di (C ₁ -C ₄ alkyl) carbamoyl, R ⁶ - C ₁ -C ₄ alkoxycarbonyl, R ⁷ - C ₁ -C ₄ alkoxycarbonyl, R ⁸ is C ₁ -C ₄ alkyl. 54. The use according to claim 52, wherein the chloroacetanilide herbicides are Formula III compounds wherein L is a Cγ-ρ-acyclic bridge; R ⁹ , R ¹⁰ , R ¹¹ independently of one another are hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl, C ₂ -C ₅ alkoxyalkyl or C ₂ -C ₅ alkylthioalkyl; R ¹² - C ₁ -C ₄ alkoxy, -COOH, C ₁ -C ₄ alkoxycarbonyl, -CONH ₂ , C 1 -C 4 -alkylcarbamoyl; di-C ₁ -C ₄ alkylcarbamoyl, -CN, C ₁ -C ₄ alkylcarbonyl, if need, changed benzene, if need, changed furil, if need, changed thienil, if need, changed pyrrolyl, if need, changed pyrazolyl, if need, changed 1,3,4-Oxadiazol-2-yl 1, 3, 4-thiadiazol-2-yl substituted if necessary if need if need if need if need if need modified replaced modified replaced modified 1.2.4-triazol-3-yl, dioxolanyl, dioxanyl, 1.3.4-Triazol-2-yl, tetrahydrofuryl. 55. The use according to claim 52, wherein the aryloxyphenoxypropanoic acid based herbicides are compounds of formula IV Q — O CIL I ^J O-CH-COT (IV) in which Q is one of the radicals T is -NR ¹⁵ R ¹⁶ , -N (CN) R, OR SR, z ~ .1 92 C or -O-N = CR R when, 18 R ¹³ is hydrogen or trifluoromethyl, R ¹⁴ - hydrogen or halogen, R ¹⁵ and R ¹⁶ independently of one another are hydrogen, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkyl, phenyl or benzyl; R ¹⁵ and R ¹⁶ taken together with the nitrogen atom to which they are attached form a 5-membered or 6-membered saturated heterocycle which may further contain an oxygen or sulfur atom; 1 7 R is C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl, C ₃ -C ₄ alkynyl or C ₂ -C ₄ alkoxyalkyl; R is hydrogen or the equivalent of an alkaline earth, alkaline earth metal, copper or iron; C ₁ -C ₄ or C ₁ -alkilamonio -C ₄ -alkoksialkilamonio quaternary radical, where appropriate substituted with one or more amino, halogen, hydroxy, nitro group (groups), phenyl, C ₁ -C ₄ -alkoxyl; polyethoxy groups with 2-6 ethylene oxide moieties; -COOR ²¹ , -COSR ²¹ , -CONH ₂ , -CON (C ₁ -C ₄ alkoxy) -C ₁ -C ₄ alkyl, -CON-di-C ₁ -C ₄ alkyl, CONH-C ₁ -C ₄ - alkyl, -N (C ₁ -C ₄ alkoxy) -C ₁ -C ₂ alkyl or a di-C ₁ -C ₄ alkylamino group of _{4 to 9} alkyl; optionally a C ₃ -C ₉ alkenyl radical substituted by halogen or C ₁ -C ₄ alkoxyl; optionally a C ₃ -C ₉ -alkynyl radical substituted by halogen or C ₁ -C ₄ -alkoxyl; C ₃ -C ₉ alkynyl; C ₃ -C ₉ -cycloalkyl; 100 or optionally phenyl substituted with nitrile, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl, acetyl, -COOR ²¹ , -COSR ²¹ , -CONH ₂ groups, -CON (C ₁ -C ₄₎ -alkoxy) -C ₁ -C ₄ alkyl, -CO-Ndi-C ₁ -C ₄ alkyl or -CONH-C ₁ -C ₄ alkyl; R ¹⁹ and R ^{20 are} independently C ₁ -C ₄ alkyl and together are a 3- to 6-membered alkylene chain; R ²¹ is hydrogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C ₂ -C ₆ alkoxyalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or C ₃ -C ₆ haloalkynyl. 56. The use according to claim 52, wherein the acylcyclohexanedione herbicides are compounds of formula IX wherein A 'is a 2-7 membered alkylene bridge, a 3-7 membered alkenyl bridge which may have one or more unsaturated bonds; n 'is zero, one or two; R ^{22 is} -C ₁ -C ₄ alkyl or benzyl; 2 3 R ₁ -C ₁ -C ₈ alkyl unsubstituted or substituted by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₃ -C ₆ cycloalkyl; phenyl, benzyl or phenylethyl wherein the phenyl rings may be substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl, C ₁ -C ₄ alkoxyl, C ₁ -C ₄ alkylthio, C ₃ - C ₄ haloalkyl, C ₁ -C ₄ -halogenalkoksilu, CN or nitro; 101 X 'is oxygen or -NOR ²⁴ , R ^{24 is} -C ₁ -C ₈ alkyl, C ₁ -C ₈ haloalkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₈ haloalkenyl, or C ₃ -C ₆ alkynyl. 57. A herbicidal preparation for use in a crop of plants useful for selective weed control, characterized in that it contains as active substances both a sulfonylurea herbicide, an acylcyclohexanedione herbicide, a chloroacetanilide herbicide or an aryloxyphenoxypropanoic acid-based herbicide according to claim 1 and ir. 58. A herbicidal preparation for use in a crop of plants useful for selective weed control, wherein the active ingredient comprises both a sulfonylurea herbicide, a chloroacetanilide herbicide or an aryloxyphenoxypropanoic acid based herbicide and an antidote according to claim 1 having the formula I. 59. The preparation of claim 57, wherein the acylcyclohexanedione herbicide is a compound of formula IX wherein A 'is a 2-7 membered alkylene bridge, a 3-7 membered alkenylene bridge which may have one or more unsaturated bonds; n 'is zero, one or two; 102 R ^{22 is} -C ₁ -C ₄ alkyl or benzyl; R ^{23 is} -C ₁ -C ₈ alkyl, unsubstituted or substituted by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₃ -C ₆ cycloalkyl; phenyl, benzyl or phenylethyl wherein the phenyl rings may be substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -haloalkoxy, CN or nitro groups; 2 4 X 'is oxygen or -NOR, R ^{24 is} -C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₆ haloalkenyl, or C ₃ -C ₆ alkynyl. 60. The preparation of claim 58, wherein the sulfonylurea herbicide is a compound of formula II wherein E is R. 0 or 1, and N 103 G is hydrogen or methyl, X - methoxy, ethoxy, difluoromethoxy, methyl or chlorine, D Y is CH or N Z is methoxy, methyl, difluoromethoxy, cyclopropyl or methylamine, R ⁴ - C ₂ -C ₅ alkoxyalkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ haloalkylthio, C ₂ -C ₄ haloalkenyl, chlorine or C ₁ -C ₄ alkoxycarbonyl, R ⁵ is trifluoromethyl or di (C ₁ -C ₄ alkyl) carbamoyl, R ⁶ is C ₁ -C ₄ alkoxycarbonyl; R ₁ -C ₁ -C ₄ alkoxycarbonyl; R ⁸ is C ₁ -C ₄ alkyl. 61. The preparation of claim 58, wherein the chloroacetanilide herbicide is A compound of Formula III 35 in which L is a C 1 -C 6 alkylene bridge; 104 R ⁹ , R ¹⁰ , R ¹¹ independently of one another are hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy _/ C ₁ -C ₄ haloalkyl, C ₂ -C ₅ alkoxyacyl or C ₂ - C ₅ alkylthioalkyl; R ¹² - C ₁ -C ₄ alkoxy, -COOH, C ₁ -C ₂ alkoxycarbonyl, -CONH ₂ , C ₁ -C ₄ alkylcarbamoyl; di-C ₁ -C ₄ alkylcarbamoyl, -CN, C 1 -C 1 -alkylcarbonyl, if need, changed benzene, if need, changed furil, if need, changed thienil, if need, changed pyrrolyl, if need, changed pyrazolyl, if need, changed 1,3,4-oxadiazol-2-yl, if need, changed 1,3,4-thiadiazol-2-yl, if need, changed 1,2,4-triazol-3-yl, if need, changed dioxolanyl, if need, changed dioxanil, if need, changed 1,3,4-triazol-2-yl, if need, changed tetrahydrofuryl. 62. The preparation of claim 58, wherein the aryloxyphenoxypropanoic acid-based herbicide is a compound of formula IV wherein Q is one of the radicals wherein T is -NR ¹⁵ R ¹⁵ , -N (CN) R ¹⁷ , OR ^18, or -ON = CR ¹⁹ R ²⁰ when R ¹³ is hydrogen or trifluoromethyl, R ¹⁴ - hydrogen or halogen, R ¹⁵ and R ¹⁶ independently of one another are denyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, phenyl benzyl, vanarban 106 R ¹⁵ and R ¹⁶ taken together with the nitrogen atom to which they are attached form a 5-membered or 6-membered saturated heterocycle which may further contain an oxygen or sulfur atom; R ¹⁷ is C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl, C ₃ -C ₄ alkynyl or C ₂ -C ₄ alkoxyalkyl; 1 δ R is hydrogen or the equivalent of an alkaline earth, alkaline earth metal, copper or iron; C ₁ -C ₄ or C ₁ -alkilamonio -C ₄ -alkokialkilamonio quaternary radical, where appropriate substituted with one or more amine groups' nalogenais, hydroxyl, nitro group (groups), phenyl, C ₁ -C ₄ -aikoksilais; polyethoxy groups with 2-6 ethylene oxide moieties; -COOR ^21, -COSR ^21, -CONH _2, -CON (Cj - ^ - alkoxy) ₃ -Ο -Ο ₄ alkyl, -CON-di-C ₁ -C ₄ -alkyl, -alkoxy) -C ₁ -C ₄ -alkyl or C 1 -C 8 alkyl; CONH-Ci-C ^ alkyl, -N _(χ -0 0 ₄ di-C ₁ -C ₄ alkylamino group, where appropriate, C ₃ -C _s alkenyl radical substituted by halogen or C ₁ -C ₄ -alkoxyl; optionally a C ₃ -C ₉ -alkynyl radical substituted by halogen or C ₁ -C ₄ -alkoxyl; C ₃ -C ₉ alkynyl; C ₃ -C ₉ -cycloalkyl; or phenyl optionally substituted with nitrile, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl, acetyl, -COOR ²¹ , -COSR ²¹ , -CONH ₂ , -CON (C ₁ -C ₄ -alkoxy) -C ₁ -C ₄ alkyl, -CO-Ndi-C ₁ -C ₄ alkyl or -CONH-C ₁ -C ₄ alkyl; R ¹⁵ and R ^{20 are} independently C _; -C ₄ alkyl, together with an alkylene chain; 3-6 naLT 3943 B 107 R ²¹ - hydrogen C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C ₂ -C ₆ alkoxyalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or C ₃ -C ₆ haloalkynyl.