DD291685A5 - MEANS FOR THE PROTECTION OF CULTURAL PLANTS FROM THE PHYTOTOXIC EFFECT OF SULFONYL DRUGS, CHLOROACETAMILIDE HERBICIDES, ACYLXYX LOHEXANDION HERBICIDES OR ARYLOXYPHENOXYPROPION ACID HERBICIDES - Google Patents

Abstract

The invention relates to agents for protecting crops from the phytotoxic effect of sulfonylurea herbicides, Chloracetanilidherbiziden, Acylcydohexandionherbiziden or Aryloxyphenoxypropionsaeureherbiziden containing as active ingredients N-acylsulfamoylphenylurea of formula (I), wherein the substituents A, Ra, Rb, R1, R2 and R3, the in have the meaning given in the description. Cereals, soya, sorghum, corn and rice are preferably suitable crops. Formula (I) {means; Protection crop; before action herbicides; Protective agent N-acylsulfamoylphenylurea}

Description

belong.

65. Compounds according to claim 64, characterized in that R ^{c is} hydrogen.

66. Compounds according to claim 65, characterized in that R ¹ , R ^Q and R ^{b are} C 1 -C -alkyl.

67. 1- [4- (N-4-methylbenzoylsulfamoyl) -phenyl] -3-methylurea according to claim 55.

68. 1- [4- (N-3-methylbenzoyl-sulfamoyl) -phenyl] -3-methylurea according to claim 55.

69. 1- [4- (N-4-tert-butylbenzoyl-sulfamoyl) -phenyl] -3-methylurea according to claim 55.

70. 1- [4- (N-3-trifluoromethylbenzoyl) sulfamoyl) -phenyl] -3-methylurea according to claim

71. 1- [4- (N-4-nitrobenzoylsulfamoyl) -phenyl] -3-methviurea according to claim 55.

72. 1- [4- (N-2,3-dimethylbenzoyl-sulfamoyl) -phenyl) -3-methylurea according to claim 55.

73. 1- (4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methylurea according to claim 55.

74. 1- (4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl) -3,3-dimethylurea according to claim

75. 1- [4- {N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-ethylurea according to claim 55.

76. 1- [4- {N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-allylurea according to claim 55

77. 1- [4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl-3-phenylurea according to claim 55.

78. 1- [4- (N-3,5-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methylurea according to claim 55.

79. 1- [4- (N-3,4-dichlorobenzoyl-sulfamoyl) -phenyl] -3-methylurea according to claim 55.

80. 1- [4- (N-3,4-dimethoxybenzoyl-sulfamoyl) -phenyl] -3-methylurea according to claim

81. 1- [4- (N-3,4-Dimethoxybenzoyl-sulfamoyl) -phenyl] -3,3-dimethylurea according to claim

82. 1- [4- {N-2,4,5-Trimethoxybenzoyi-sulfamoyl) -phenyl] -3-methylurea according to claim

83. i ^ -iN-i-Naphthylcarbonyl-sulfamoyO-phenyll-S-methylurea according to claim 5ö.

84. 1- [4- (N-2-Furylcarbonyl-sulfamoyl) -phenyl] -3-methylurea according to claim 55.

85. 1- [4- (N-2-Furylcarbonyl-suifamoyl) -phenyl] -3,3-dimethylurea according to claim 55.

86. 1- (4- (N-2-Thienylcarbonyl-sulphamoyl) -phenyl] -3-methylurea according to claim 55.

87. 1- [4- (N-Piperonyloyl-sulfamoyl) -phenyl] -3-methylurea according to claim 55.

88. 1- [4- (N-3-Methylbenzoylsulfamoyl) -phenyl] -3,3-dimethylurea according to Claim 55. 80. 1- [4- (N-3-trifluoromethylbenzoylsulfamoyl) -phenyl-3- A cyclopropylurea according to claim 55.

90. 1- [3- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methylurea according to claim 55.

91. 10-IN ^ -Furylcarbonyl-sulfamoyl-D-phenyl-S-dimethylurea according to claim 55.

Field of application of the invention

The present invention relates to compositions for protecting crop plants against the phytotoxic effect of acylcyclohexanedione herbicides, sulfonylurea herbicides, chloroacetanilide herbicides and aryloxyphenylpropionic acid herbicides containing as active ingredients novel N-acylsulfamoylphenylureas. Furthermore, the invention relates to the use of the new active ingredients for the protection of crop plants.

Characteristic of the known state of the art

It is known that herbicides from the substance classes of sulfonylureas, haloacetanilides and aryloxyphenoxypropionic acid derivatives when used in an effective dose occasionally in addition to the weeds to be controlled also damage the crop plants to some extent. Overdoses are often applied unintentionally and accidentally, when overlap marginal zones in the strip-wise spraying, sol by wind action or by incorrect assessment of the broad effect of the sprayer. There may be climatic conditions or soil conditions such that the amount of herbicide recommended for normal conditions acts as an overdose. The quality of the seeds may also play a role in herbicide compatibility. To address this problem, various substances have already been proposed which are capable of specifically antagonizing the harmful effect of the herbicide on the crop, that is to protect the crop, without appreciably affecting the herbicidal action on the weeds to be controlled It has been shown that the proposed antidote both with respect to crops and with respect to the herbicide and possibly also depending on the mode of administration often very species specific, that is, a particular antidote is often suitable only for a particular crop and a few herbicidal classes.

Thus, British Patent 1,277,557 describes the treatment of wheat or sorghum seeds or sprouts with certain oxamic acid esters and amides for protection against attack by "ALACHLOR" {N-methoxymethyl-N-chloroacetyl} -ediathylaniline). U.S. Patent 4,618,331, Ber For protection against sulfonylurea herbicides, EP-A-122231 benzoyloxime ether and EP-A-147365 propose phenylglyoxylic acid nitrile oxime, naphthalenedicarboxylic anhydride, a thiazole carboxylic acid ester and dichloroacetamides as antidotes 2,402,983 are effectively protected against damage by chloroacotanilides by feeding to the soil an N-disubstituted dichloroacetamide as an antidote.Such compounds according to DE-OS 2,828,265 and 2,828,293 are also used as antidotes against herbicidal acetanilides.

Object of the invention

The invention provides agents which contain new N-acylsulfamoylphenyl ureas as active ingredients and are highly suitable for protecting crop plants against the damaging action of sulfonylurea herbicides, chloroacetanilide herbicides or arylloxyphenoxpropionic herbicides.

Explanation of the essence of the invention

It is an object of the present invention to find novel compounds which are active against the harmful effects of herbicides and to provide usable agents which contain these compounds as active ingredients. It has now been 9 found that, surprisingly, a group of N-Acylsulfamoylphenylharnstoffen this is ideal to protect crops against harmful effect of sulfonylurea herbicides Chloracetanilidherbiziden o ^H he Aryloxyphenoxypropionsäureherbiziden. These N-acylsulfamoylphenylureas are therefore also referred to hereinafter as "antidote", "antidote" or "safener".

The inventively proposed agents contain 1 new N-Acylsulfamoylphenylharnstoffe which correspond to the general formula I.

(I)

A for a rest from the Grup'je

l · Il 4

i I

e · - · ρ · · ·

R -H- 4t- or R -tt -M-,

V v

R 'and R ² independently of one another represent hydrogen, C 1 -C ₈ -alkyl, C 1 -C ₈ -cycloalkyl, C 1 -C 4 -alkenyl, C ² -C ₆ -alkynyl,

or by Ci-Ci, -alkoxy or

 = ·

R '

Ζ / * · substituted Ci-Ci ₄ alkyl, or

R ¹ and R ² together represent a C-Ce-alkylene bridge or by oxygen, sulfur, SO, SO _2, NH or N (C _t -C ₄ alkyl) -unterbrocheneC ₄ -C ₉ alkylene,

R ^{3 is} hydrogen or C 1 -C ₄ -alkyl,

R 'and R ^b independently represent hydrogen, halogen, cyano, nitro, trifluoromethyl, Ct-C ₄ alkyl, C ₁ -C ₄ -alkoxy, Ci-C ₄ -

Alkylthio, C, -C ₄ alkylsulfinyl, C ₁ -C ₄ -Aikylsulfonyl, -COOR ^I, -CONR ^k R ^rn, -COR ^n, -S0 ₂ NR ^k R ^rn odor-OSO ₂ -C ₁ -C ₄ - AIkVl, or R · and R ^b together represent a Cx-C ^ alkylene bridge, which may be substituted by halogen or C ₁ -C ₄ -Alk ^, or a C ₃ -C ₄ -alkenylonbrücko represented by halogen or C, - C ₄ alkyl, or a C ₄ alkadienylene bridge, which may be substituted by halogen or C ₁ -C ₄ -A ^ yI,

R ^g and R ^h independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl, trifluoromethyl, methoxy, methylthio or -COOR ¹ , where

R ^{c is} hydrogen, halogen, ^C 1 -C ₄ -alkyl or methoxy,

R ^d is hydrogen, halogen, nitro, C, -C ₄ -A1kyl, C, -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, -COOR 'or -CONR ¹ R ¹ ',

R "is hydrogen, halogen, C ₁ -C ₄ -alkyl, -COOR ¹ , trifluoromethyl or methoxy, or R ^d and R ° together represent a C ₃ -C ₄ -alkylene bridge,

R ^{1 is} hydrogen, halogen or C, ~ C ₄ -alkyl,

R "and R ^y are independently hydrogen, halogen, C _t -C ₄ alkyl, C, -C ₄ alkoxy, C ₁ -C ₄ -AIkYUhIO, -COOR ^4, trifluoromethyl, nitro or cyano,

R ¹ , R ^k and R ^m independently of one another denote hydrogen or C ₁ -C ₄ -alkyl,

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

R "C ₁ -C ₄ -AlkYl, phenyl or by halogen, Ci-C ₄ alkyl, methoxy, nitro or trifluoromethyl substituted phenyl.

By halogen in the definitions fluorine, chlorine, bromine and iodine, but preferably fluorine, chlorine and bromine, in particular chlorine to understand. In the definitions, alkyl is to be understood as meaning straight-chain or branched alkyl; for example, methyl, aethyl, n-propyl, i-propyl or the four isomeric butyl. Longer chain alkyl groups include the isomers of pentyl, hexyl, heptyl or octyl, with each of the unbranched chains being preferred. By alkoxy is meant: methoxy, ethoxy, n-propyloxy, i-propyloxy or the four isomeric butyloxy, but especially methoxy, ethoxy or i-propoxy. Alkoxy-substituted alkyl is preferably methoxymethyl, ethoxymethyl, methoxyethyl and ethoxyethyl, but especially methoxyethyl. Alkyl optionally substituted by optionally substituted phenyl preferably represents derivatives of phenylethyl or benzyl. C 3 -C _e -alkenyl and C 1 -C 6 -alkynyl radicals in the definition of R 'and R ² are characterized in that they are bonded via a saturated carbon atom to the nitrogen atom they carry. Typical alkenyl and alkynyl radicals are allyl, 2-butenyl, methallyl, 3-butenyl, propargyl, 2-butynyl, 3-butynyl or 2-pentenyl. Examples of cycloalkyl are cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl, but preferably cyclopentyl and cyclohexyl.

Heterocycles which are formed together from R ¹ and R ² or together of R ⁵ and R ⁶ with the nitrogen atom they carry are pyrrolidine, piperidine, pyrazolidine, imidazolidine, oxazolidine, thiazolidine, morpholine, thiomorpholine, piperazine or hexahydroazepine and, in the case of sulfur-containing rings, their oxidation products , In alkylthio, alkylsulfinyl or alkylsulfonyl, alkyl has the specific meanings enumerated above.

When R "and R ^b together represent a C ₃ -C -alkylene bridge, C ₁ -C ₄ -alkylene bridge or C ₄ -alkadienylene bridge, each of which is substituted by halogen or C ₁ -C ₄ -alkyl, together with the phenyl ring to which the backbone is attached form dinuclear systems such as, for example, 1,2,3,4-tetrahydronaphthalene, 1-chloro-2-methyl-3 / -dihydronaphthalene, indane, 1,2-dihydronaphthalene , Indene, naphthalene, 2-methylnaphthalene, 1-n-butylnaphthalene, 2-ethyl, \ aphtalin or 1-chloronaphtaline.

When the substituents R ^d and R * together represent a C 1 -C ₄ -alkylene bridge, together with the ring system to which they are attached, polynuclear systems are formed, such as, for example, 2,3-tetramethylenethiophene, 2,3-trimethylenethiophene, 2,3-tetramethylene furan, 3,4-tetramethylene pyridine or

• ·

I i

I Il

VV.

Because of their good action as herbicidal antagonists, those compounds should be emphasized in which either

a) R ^{b is} hydrogen, or

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

c) R ² and R ^{3 are} hydrogen, or

d) A for the group

.R

stands.

A preferred group of compounds of formula I are those wherein R ^{b is} hydrogen and the sulfamoyl group occupies the 4-position on the phenyl ring. Further preferred are the compounds in which R ² , R ³ and R ^{b are} hydrogen and the sulfamoyl group assumes the 4-position on the phenyl ring.

Among the compounds of subgroup d) are further preferred those in which R ² , R ³ and R ^{b are} hydrogen and the sulfamoyl occupies the 4-position on the phenyl ring.

Among the compounds of the invention, it is of particular interest to obtain those which correspond to sub-formula I a

f R ^h

R ^C

in which R ¹ , R °, R ^g and R ^{h have} the meanings given under formula I. A further preference with regard to their action is enjoyed by the compounds of the formula Ia in which R ^{c is} hydrogen.

Another particularly to be mentioned subgroup thereof represent the compounds of formula Ia, in which the radicals R ¹ , R ⁰ and R ^{h are} the C, -C ₄ alkyl groups.

Preferred individual compounds according to the invention from the scope of the formula I are:

1- [4- (N-4-Methylbenzoyl-sulfamoyl) -phenyl-3-methylurea, "i- [4- (N-3-methylbenzoylsulfamoyl) -phenyl] -3-methylurea, 1- [4- (4-methylbenzoyl) N-4-tert-butylbenzoylsulfamoyl) -ph3nyl) -3-methylurea, 1- [4- (N-3-trifluoromethylbenzoylsulfamoyl) -phenyl] -3-methylurea, 1- (4- (N-4-) Nitrobenzoyl-sulfamoyl) -phenyl-3-methylurea, 1- [4- (N-2,3-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methyl-urea, 1- (4- (N-3,4-dimethylbenzoyl-sulfamoyl ) -phenyl] -3-methylurea, 1- [4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3,3-dimethylurea, 1- [4- (N-3,4-dimethylbenzoyl-sulfamoyl ) -phenyl-3-ethylurea, 1-l4- (N-3,4-dimethylbenzoylsulfamoyl) -phenyl-3-allylurea, 1- [4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] 3-phenylurea, 1- [4- (N-3,5-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methylurea, 1- (4- (N-3,4-dichlorobenzoyl-sulfamoyl) -phenyl] -3 -methylurea, 1- [4- (N-3,4-dimethoxybenzyl-sulfamoyl) -phenyl!] - 3-methylurea, 1- [4- (N-3,4-dimethoxybenzoyl-sulfamoyl) -phenyl] -3, 3-dimethylurea, 1- [4- (N-2,4 , 5-trimethoxybenzoyl-sulfamoyl) -phenyl-3-methylurea, 1- [4- (N-1-naphthylcarbonylo-sulfamoyl) -phenyl] -3-methylurea, 1- [4- (N-2-furylcarbonyl-sulfamoyl ) -phenyl-3-methylurea, 1- [4- (N-2-furylcarbonylsulfamoyl) -phenyl] -3,3-dimethylurea, 1- [4- (N-2-thienylcarbonyl-sufamoyl) -phenyl] - 3-methylurea, 1- [4- (N-Piperonyloyl-sulfamoyl) -phenyl] -3-methylurea, 1- [4- (N-3-methylbenzoylsulfamoyl) -phenyl] -3,3-dimethylurea, 1- [4- (N-3-trifluoromethylbenzoyl-sulfamoyl) -phenyl-3-cyclopropyl-urea, 1- [3- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methyl-urea, and 1- | 3- ( N-2-furylcarbonyl-sulfarroyl) -phenyll-3,3-dimethylurea.

The compounds of formula I, wherein R'die given under formula I,! Has meanings other than hydrogen and R ^{2 is} hydrogen are prepared by adding a sulfamoylaniil.i of formula V

iV

SO ₂ -NH-CO-A where A, R ³ , R 'and R ^{b have} the meanings given under formula I, with an isocyanate of the formula Vl

R'-N = C = O (Vl)

wherein R ^{1 has} the meanings given under formula I except hydrogen. By the reaction with alkylating reagents of the formula

Lg-R ² in which Lg is a leaving group such as halogen, tosyl, CeH ₆ -SO ₃ - or CH ₃ OSO ₃ -, and R ^{J are} those given under formula I.

Has meanings other than hydrogen, compounds of the formula I can be produced in which R ^{2 has} a meaning other than hydrogen. The reaction of the aniline derivatives of the formula V with the isocyanate of the formula VI can be carried out both solvent-free and in the presence of an aprotic inert organic solvent. The reactions are advantageously carried out in a solvent. Suitable solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, carbon tetrachloride or chlorobenzene, ethers such as diethyl ether, Aethylenglykoldimethyläther, D'iäthylenglykoldimethylather, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably between -2O ⁰ C and + 12O ⁰ C. The reactions of Kupplungsverfahron are generally slightly exothermic and can be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction is expediently heated for a short time to the boiling point of the reaction mixture. The reaction times can also be shortened by adding a few drops of base as the reaction catalyst. Particularly suitable bases are tertiary amines such as trimethylamine, triethylamine, quinuclidine, Ν, Ν-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 end products of the formula I can be isolated either directly as a crystallizate or by concentration and / or evaporation of the solvent and purified by recrystallization or trituration of the tact residue in solvents in which they do not dissolve well. According to a second method, the active compounds of the formula I are obtained by reacting a sulfamoylphenylurea of the formula VII

Si-co-N- ? * · (UN)

SO ₂ -NH ₂

in which R ¹ , R ² , R ³ , R * and R ^{b have} the meanings given under formula I, with a carboxylic acid halide of the formula VIII Hal-CO-A (VIII)

wherein A has the meanings given under formula I and Hai means chlorine or bromine, acylated. The reaction of the sulfamoylphenylurea of the formula VII with the acylating reagent of the formula VIII is advantageously carried out in the presence of an acid-binding agent in an inert organic solvent. Suitable solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, carbon tetrachloride or chlorobenzene, ethers such as diethyl ether, Aethylenglykoldimethyläther, Diäthylenglykoldimethyläther, Ί etrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably between -2O ⁰ C and + 12O ⁰ C. The reactions of the coupling process are generally slightly exothermic and can be carried out at room temperature, For the purpose of shortening the reaction time or to initiate the reaction is expedient for a short time to the boiling point of Reaction mixture warmed up. The reaction times can also be shortened by adding a few drops of base as the reaction catalyst. Particularly suitable bases are tertiary amines such as trimethylamine, triethylamine, quinuclidine, N, N-dimethylaminopyridine, pyridine, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo- (4.3.0) non-5-ene or the like. As bases, however, it is also possible to use inorganic bases such as hydrides such as sodium c of the calcium hydride, hydroxides such as sodium and potassium hydroxide, carbonates such as sodium and potassium carbonate or bicarbonates such as potassium and sodium bicarbonate The end products of the formula I can either be isolated directly as crystallin or by concentration and / or evaporation of the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they do not dissolve well Formulas V, VI, VII and VIII are well known The compounds of formulas VI and VII are partially commercially available According to the following reaction schemes, compounds of the formula V and VIII for which no concrete preparation processes have been described in the literature have been prepared under the conditions customary for the individual reaction steps:

Scheme 1

O ₂ N-

+ HaI-CO-A

SO ₂ -NH ₂

base

ι V

O ₂ N-

SO ₂ -NH-CO-A catalytic hydrogenation

H ₂ N-

SO ₂ -NH-CO-A

Scheme 2

+ Cl-CO-O-

SO ₂ NH ₂

base

SO ₂ NH ₂ , R ¹

νη:

R ²

^Rl Wr ^{y 'x}

SO ₂ NH ₂

Scheme 3

^Rl \

.N-CO-

R ³

^B R ^b

\ -C0-N-f y + S-OH-Cl

^{? /} R ^{3 N.} =. ^/ ft

SO ₂ -Cl NIi ₃

The compounds of formula I are stable substances under normal laboratory conditions, they do not decompose when stored at room temperature.

An antidote or antidote of formula I may be used for pretreatment (seed of cultivated plant (seed dressing or cuttings) or placed in the soil before or after sowing, depending on the intended use The treatment of the plant or the seed with the antidote can therefore be carried out independently of the time of application of the herbicide, but the treatment of the plant can also be carried out by simultaneous application of herbicide and antidote (tank mix). The premature treatment includes both pre-seed cultivation (ppi) and the treatment of sown, but not overgrown crops.

The application rates of the antidote in relation to the herbicide depend largely on the type of application. In a field treatment in which herbicide and antidote are administered either simultaneously (tank mix) or separately, the ratio of the amounts of antidote to herbicide is in the range of 1: 100 to 5: 1. In general, the full protective effect is achieved at a ratio of antidote to herbicide of 5: 1 to 1:50. However, seed dressing and similar targeted protection measures require much lower levels of antidote compared to the amounts of herbicide used per acre per acre. In general, seed germination requires 0.1 to 0.1 g of antidote per kg of seed. As a rule, with 0.1-5 g of antidote per kg of seed, the full protective effect is already achieved. If the antidote should be applied shortly before sowing by seed soaking, solutions of the antidote containing the active ingredient in a concentration of 1-10000 ppm are suitably used. In general, with concentrations of the antidote of 100-1000 ppm, the full protective effect is achieved. As a rule, there is a longer period of time between protective measures, such as seed dressing and treatment of cuttings with an antidote of formula I and the possible subsequent field treatment with herbicides. Pre-treated seed and plant material may later come into contact with various chemicals in agriculture, horticulture and forestry. The invention therefore also relates to protective agents for crops containing as active ingredient an antidote of formula I together with conventional carriers. If appropriate, such agents may additionally contain herbicides against whose influence the crop is to be protected. The invention likewise relates to reproductive material of crop plants, such as seeds, seedlings or cuttings, pretreated with active compounds of the formula I. Particularly suitable are the active ingredients of the formula I for the treatment of seeds of cereals, soy and preferably sorghum, corn and rice.

In the context of the present invention, crops are, for example, all types of cereals, such as wheat, rye, barley and oats, as well as, above all, rice, cultured vegetables, maize and soya. Millet (sorghum), corn and rice are preferably protected from the active ingredients of formula I by the action of acylcyclohexanedione herbicides, sulfonylurea herbicides, chloroacetanilide herbicides or aryloxyphenoxypropionic acid herbicides. Outstanding protection against acylcyclohexanedione herbicides, sulfonylurea-type herbicides, aryloxyphenoxypropionic acid herbicides and chloroacetanilide herbicides is observed when the antidotes of formula I are used in corn, sorghum and rice. In particular, the beneficial effect of the compound is 1- [4- (N-3,4-dimethylbenzoylsulfamoyl) -phenyl] -3-m (jthylurea singleton.

Sul.onylurea herbicides whose harmful effects on crop plants can be abolished with the aid of the N-acylsulfamoylphenylureas of the formula I have recently become known in large numbers. From the large number of publications which are devoted to the disclosure of herbicidally active sulfonylurea derivatives, examples are US Pat. No. 4,127,405 and published European patent applications EP-A-7687, EP-A-30142, EP-A-44807, EP-A- 44808, EP-M-51466, EP-A-70802, EP-A-84020, EP-A-87780, EP-A-102925, EP-A-108708, EP-A-120814, EP-ΑΙ36061, EP- A-184385, EP-A-206995 and EP-A-237292.

Typical representations of herbicidal sulfonylurea derivatives are under the formula II

E- (CH ₂ -SO ₂ -Nl-CO-N {^ Y (II)

-N {

in which E is a group

r Il Il

or yy IJ

η is the number zero or one,

G is hydrogen or methyl,

X is methoxy, ethoxy, difluoromethoxy, methyl or chlorine

Y is CH or N,

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

R ⁴ is C ^ Cs alkoxyalkoxy, C ₁ -C ₄ haloalkyl, Ct-C ^ Halogenalkylihio, Cr-C ₄ haloalkenyl, chloro or Ci-Ct-alkoxycarbonyl,

R ^{6 is} trifluoromethyl or di (C ₁ -C ₄ -alkyl) carbamoyl,

R ^{6 is} Ct-C 1-4 alkoxycarbonyl,

R ⁷ Ct-C ^ alkoxycarbonyl

R ^{8 is} C, -C ₄ alkyl.

The following herbicidal single active substances fall under the formula II:

N- (3-trifluoromethyl-pyridin-2-ylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) -urea, N- (3-dimethylcarbamoyl-pyridin-2-yls-L-nonyl! -N' - (4,6 -dimethoxypyrimidin-2-yl) urea, N · (1-methyl-4-ethoxycarbonylpyrazol-2-ylsulfonyl) -N '- (4,6-dimethoxypyramidine-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-dimethoxypyrimidine) 2-yl) -! Urea, N- (2-methoxycarbonylphenylsulfonyl) -N '- (4,6-bis-difluoromethoxypyrimidin-2-yl-urea, N- (2-methoxycarbonylphenylsulfo'iyl) -N' - (4- ethoxy-6-methylamino-1,3,5-lriazin-2-yl) urea, N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazine-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-meth-carbonyl-phenylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) -urea, N- ( 2-Chlorphen ylsulfonyl) -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, and N- (2- (2-methoxyethoxy) phenylsulfonyl) -N '- (4,6-dimethoxy-1,3, 5-tria7.in-2-yl) -urea.

Haloacetanilides whose harmful effects on crop plants can be reversed with the aid of the N-acylsulfamoylphenyiureas of the formula I have likewise become known in large numbers. Such haloacetanilides can be described by the following general formula III:

R ⁹ , - ( XR ¹²

// \. y "id

R ¹¹ V

^K V ⁰

CO-CH ₂ Cl

L is a C, -C ₄ -alkylene bridge, R ^9, R 'and R ⁰ "are each independently hydrogen, halogen, C | -C ₄ alkyl, C ₁ -C ₄ -alkoxy, C, -C ₄ haloalkyl, Cr C ₅ alkoxyalkyl or C ₁ -C ¹² alkylthioalkyl, and R ¹² C ₁ -C ₄ alkoxyC COOH, C ₁ -C ₄ alkoxycarbonyl, -CONH ₂ , C ₁ -C ₄ alkylcarbamoyl, di-C ₍ -C ₄ alkylcarbamoyl, cyano, C 1 -C 4 -alkylcarbonyl, optionally substituted benzoyl, optionally substituted furyl, optionally substituted thienyl, optionally substituted pyrrolyl,

optionally substituted pyrazolyl, optionally substituted 1,3,4-oxldiazol-2-yl, optionally substituted 1,3,4-thiadiazol-2-yl, optionally substituted 1,2,4-trirzol-3-yl,

optionally substituted dioxolanyl, '

optionally substituted dioxanyl, optionally substituted 1,3,4-triazol-2-yl or optionally substituted tetrahydrofuryl.

In particular, the following herbicidal chloroacetanilide derivatives fall into the category III:

N-Aethoxymethyl-N-chloroacetyl-ethyl-e-methylaniline, N-chloroacetyl-N-methoxymethyl-1,2-diethylaniline, N-chloro-acyl-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-methylenilin,

N-chloroacetyl-N-imethoxyethyld ^ .e-diethylaniline, N- (2-ethoxyethyl) -N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2 -methylaniline, N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2,6-dimethylaniline,

N-chloroacetyl-N, N -methoxy-1-methylethoxy-O, N-diethylaniline, N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2-ethyl-G-methylthylaniline, N- (2-ethoxyethyl) - N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N- (2-n-propoxyethyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (2-n-propoxyethyl) -2,6- diethylaniline, N-chloroacetyl-N- (2-isopropoxyethyl) -2-ethyl-6-methylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-1-dimethylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-1-diethylaniline, N- Chloroacetyl-N-methoxycarbonylmethyl ^ .e-dimethylaniline, N-chloroacetyl-N- (2,2-diethoxyethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2,3 dimethylaniline, N- (2-ethoxyethyl) -N-chloroacetyl-2-methylaniline, N-chloroacetyl-N- (2-methoxyethyl) -2-methylaniline, N-chloroacetyl-N- (2-methoxy-2-methylethyl) 2,6-dimethylaniline, N- (2-ethoxy-2-methylethyl) -N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-Nd-ethyl-i-methoxyethyl-W-dimethylaniline, N-chloroacetyl -N- (2-methoxyethyl) -2-methoxy-6-methylanil in, Nn-butoxymethyl-N-chloroacetyl-tert-butylaniline, N- (2-ethoxyethyl-2-methylethyl) -2,6-dimethylaniline, N-chloroacetyl-N, N-methoxyethyl-1-chloro-e-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 ^. -E-dimethylaniline, N-chloroacetyl-Nd.S-dioxolane ^ -ylmethyD ^ .e-dimethylaniline, N-chloroacetyl-Nd.S-dioxoian ^ -ylmethyD ^ -ethyl-e-methylaniline, N-chloroacetyl-Nd.S-dioxane ^ -ylmethyD ^ -ethyl-e-methylaniline, N-chloroacetyl-N- (2-furylmethyl) -2,6-dimethylaniline, N Chloroacetyl-N- (2-furylmethyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (2-tetrahydrofurylmethyl) -2,6-dimethylaniline, N-chloroacetyl-N-fN.N-dimethylcarbamoylmethyD ^. e-dimethylaniline, N-ln-butoxyniethyD-N-chloroacetyl ^ .e-cliethylaniline, N- (2-n-butoxyethyl) -N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N- (2-methoxy) 1,2-dimethylethyl) -2,6-dimethylaniline, N-chloroacetyl-N-isoprop yl ^ .S-dimethylaniline, N-chloroacetyl-N-isopropyl ^ -chloroaniline, N-chloroacetyl-NdH-pyrazol-1-ylmethyl) -2,6-dimethylaniline, N-chloroacetyl-NdH-pyrazol-1-ylmethyl ) -2-ethyl-6-meth /! Aniline, N-chloroacetyl-N-dH-I ^ atriazoM-ylmethyO ^ .e-dimethylaniline, N-chloroacetyl-Nd H-1,2,4-triazol-1-ylmethyl ) -2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-ethyl-e-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-ethyl-6-methylaniline, N Chloroacetyl-N- (5-methyl-1,3,4-oxadia-2-yl-2-yl) -2-tert-butylaniline, N-chloroacetyl-N- (4-chlorobi3nzoylmethyl) -2,6-dimethylaniline and N-chloroacetyl N- (1-methyl-5-methylthio-1,3,4-triazol-2-ylmethyl) -2,6-diethylaniline.

Aryloxyphenoxypropionsäureherbizide whose harmful effects on crops can be aufgegetiben with the aid of N-Acylsulfamoylphenylharnstoffe of formula I are known in large numbers. Such aryloxyphenoxypropionic acid derivatives can be described by the following general formula IV:

(IV)

Q for the rest

_R i 3_./ \ ._ R ⁱ³ - r>

• NR ¹ ** · N

I Il j; - - or I Il l

and T for

-NR ¹⁵ R ¹⁸ ^ N (CN) R ¹⁷ , -OR ", SR ¹⁸ or -O-N = CR ¹⁹ R ²⁰ , where

R ' ^{3 is} halogen or trifluoromethyl,

R ' ^{4 is} hydrogen or halogen,

R ¹⁶ and R ^le independently hydrogen, C ₁ -C ₈ -alkoxy, Ct-C ₈ alkyl, phenyl or benzyl, R ¹⁶ and R ^le together with the nitrogen atom carrying them a 5- to 6-membered saturated nitrogen by a Oxygen or sulfur atom can be interrupted,

R "C ₁ -C ₄ -AILvI, Cj -C alkenyl, CC ₄ alkynyl or C ₁ -C ₄ alkoxyalkyl

ri ^{18 is} hydrogen or equivalent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary C ₁ -C ₄ alkylammonium or C _t -C ₄ hydroxyalkylammonium radical; an optionally mono- or polysubstituted by amino, halogen, hydroxyl, cyano, nitro, phenyl, C ₁ -C ₄ -alkoxy, polyethoxy having 2 to 6A-ethylene oxide units, -COOR ²¹ , -COSR ² ', -CONHj.-CONfC-Cralkoxyl-C -C 1 -alkyl.-CO-N-di-C 1 -C ₄ alkyl.CONH-C ₂ -C ₄ alkyl.-NIC C 1 -C ₄ alkoxy-C 1 -C ₄ alkyl or di-C 1 -C ₄ -alkylamino-substituted C 1 -C ₄ -cycloalkyl _a- alkyl radical; a Cj-Cs-alkenyl radical optionally substituted by halogen or C ₁ -C ₄ -alkoxy; a C ₃ -C 9 -alkynyl radical optionally substituted by halogen or C ₁ -C ₄ -alkoxy; C ₃ -C ₉ -cycloalkyl; or optionally substituted by cyano, Ci-C ₄ alkyl, CHVAIkoxy, acetyl, COOR ^21, COSR ^21, -CONH _2, -CON (C, -C ₄ alkoxy) C, -C ₄ alkyl, -CO- N-di-C, C ₄ -alkyl or-CONH-C, C ₄ -alkyl-substituted phenyl,

R ¹⁹ and R ^! O independently of one another are C ¹ -C ₄ -alkyl or together form a 3 to 6-membered alkylene chain and

R ²¹ is hydrogen, C, -C _e alkyl, C, -C _e haloalkyl, CHVAIkoxyalkyl, Cj-Ce-alkenyl, Cj-Ce-haloalkyl, C3-C _e alkyne ", i, or Cs-Ce-haloalkynyl ,

In particular, the following herbicides aryloxyphenoxypropionic acid derivatives fall into the category IV:

2- [4- (5-chloro-3-fluoropyridin-2-yloxy) phenoxy) propionic acid propargyl ester 2- [4- (3,5-dichloropyridin-2-yloxy) -phenoxy] -propionic acid propargyl ester,

2- (4- (3,5-dichloropyridin-2-yloxy) -phenoxy] -thiopropionic acid propargyl ester, 2- [4- (5-chloro-3-fluoropyridin-2-yloxy) -phenoxy] -propionic acid methyl ester,

2- [4- (5-chloro-3-fluoropyridin-2-yloxy) -phenoxy] -propionic acid tert-butyl ester,

2- [4- (5-trifluoromethylpyridin-2-yluxy) -phenoxy-propionsäur6-butyl ester,

Methyl 2-i4- (5-trifluoromethyl-pyridin-2-yloxy) -phenoxy] -propionate, ethyl 2- [4- (6-chloro-quinoxalin-2-yloxy) -phenoxy] -propionate;

2- [4- (6-Chlofbenzoxazolin-2-yloxy) -phenoxy] -propionic acid ethyl ester.

Acylcyclohexanedione whose harmful effects on crop plants can be reversed with the aid of the N-acylsulfamoylphenylureas of the formula I are described, for example, in the published European Patent Application No.O243313. Such acylcyclohexanedione derivatives may be represented by the following general formula IX

? Ϊ

/ "\ /" Ni / IYl

wherein A 'is a 2-7 membered alkylene bridge, a 3-7 membered alkenylene bridge which may be mono- or polyunsaturated,

η 'zero, one or two

R _{22 is} C 1 -C ₄ -alkyl or benzyl

R ₂₃ d-Ce-alkyl, unsubstituted or substituted by halogen, Ci-C ₄ -alkoxy, C, -C ₄ alkylthio; C ₃ -C ₈ -cycloalkyl; Phenyl, benzyl or phenylethyl wherein the phenyl ring by halogen, C, -C ₄ alkyl, C, -C ₄ alkoxy, C, _-C4 alkylthio, C, -C ₄ haloalkyl,

Ci-C ^ haloalkoxy, cyano or nitro may be substituted, '

X 'oxygen or a residue NOR ₂₄ and

R _{24 is} Ci-Ce-alkyl, C, -C _e -haloalkyl, C ₃ -Cj-AlkunyI, Ca-Ce-haloalkenyl or CHV alkynyl.

In particular, the following herbicidal acylcyclohexanedione derivatives are included in formula IX:

5- (1-Methylthiocyclobutan-1-yl) -2- (2,4-dichlorobenzoyl) -cyclohexane-1,3-dione, 5- (1-methylthiocyclobutan-1-yl) -2-n-butyrylcyclohexane 1,3-dione,

5- (1-Methylthiocyclobutan-1-yl) -2-cyclopropylcarbonylcyclohexane-1,3-dione, 5- (1-methylthlocyclobutan-1-yl) -2- (2,3-dichlorobenzoyl) -cyclohexane-1, 3-dione, 5- (1-methylsulfonylcyclobutan-1-yl) -2-n-butyryl-cyclohexane-1,3-dione,

5- (1-methylthiocyclopropane-1-yl) -2-propionyl-1,3-dione,

5- (1-Aethylthiocyclopropan-1-yl) -2-propionyl-1,3-dione

5- (1-methylthiocyclopropane · 1 · yl) -2-n · butyryl · cyclohexane · 1.3 dione.

5- (1-Methylthiocyclobutan-1-yl) -2- (1-ethoximino-n-butyryl) -cyclohexane-1,3-dione, 5- (1-methylthiocyclopropan-1-yl) -2- (1-ethoximino -n-butyryl) -cyclohexane-1,3-dione, 5- (1-methylthiocyclohexan-1-yl) -2- (1-ethoximino-n-butyryl) -cyclohexane-1,3-dione, 5- (1 -Methylthiocyclobutan-i-yl) -2- (1-allyloxyiminonebutyryl) -cyclohexane-1,3-dione and 5- (1-methylthiocyclopentan-1-yl) -2- (1-ethoximino-n-butyryl) - cyclohexane-1,3-dione, 5- (1-methylthiocyclopropan-1-yl) -2- [1- (trans-3-chloroallyloximino) -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 and 5- (1-ethylthiocyclopropan-1-yl) -2-I1- (trans-3-chloroallyloximino) -propionyl) -cyclohexane-1,3- dion.

The antidotes of the formula I are particularly suitable for protecting crop plants from the herbicidal effects of the herbicides of the formulas II, III or IV.

Agrochemical agents containing in a common formulation in addition to the antidote of formula I a sulfonylurea herbicide, a chloroacetanilide herbicide or an aryloxyphenoxypropionic acid herbicide are suitable for use as selective herbicides in crops.

In addition to an antidote of the formula I, the herbicidal compositions of the invention preferably contain a sulfonylurea of the formula II, a chloroacetanilide of the formula III, an acylcyclohexanedione derivative of the formula IX or an aryloxyphenoxypropionic acid derivative of the formula IV.

The amount of antidote, unless seeded, varies between about 0.01 and about 5 parts by weight per part by weight herbicide. In practice, it is determined, on a case-by-case basis, that is, depending on the type of herbicide used, which proportion is the most appropriate in terms of optimum action on the particular crop.

The invention also relates to a method for the selective control of weeds in arable crops, wherein the crop stands, parts of the crops or cultivated areas for crops are treated with a herbicide and a compound of the formula I or an agent containing this combination. The herbicide / antidote combination containing agents also form part of the present invention.

The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds.

For the use of compounds of formula I or agents containing them for protecting crop plants against harmful effects of agrochemicals, various methods and techniques are contemplated, such as the following:

i) seed dressing

a) seed dressing with a formulated as a wettable powder by shaking in a vessel until evenly distributed on the seed surface (dry dressing). It uses about 16 to 500g of active ingredient of formula I (in a 25% formulation: 40g to 2kg spray powder) per 100kg of seed.

b) dressing the seeds with an emulsion concentrate of the active ingredient or with an aqueous solution of the formulated as a wettable powder active ingredient of the formula I according to method a) (wet pickling).

c) pickling by dipping the seed in a broth with 50-3200ppm active ingredient of the formula I for 1 to 72 hours and optionally subsequent drying of the seeds (immersion dressing, seed soaking).

The dressing of the seed or the treatment of the germinated seedling are naturally the preferred methods of application, because the drug treatment is completely directed to the target culture. As a rule, 10 g to 500 g, preferably 50 to 400 g of active substance per 100 kg of seed are used, it being possible to deviate upwards or downwards from the stated limiting concentrations (repeat pickling), depending on the methodology which also allows the addition of other active ingredients or micronutrients.

ii) Application from tank mix

A liquid work-up of a mixture of antidote and herbicide (reciprocal ratio of between 10: 1 and 1:30) is used, with the application rate of herbicide being from 0.001 to 10 kg per hectare. Such tank mix is preferably applied before or after sowing or incorporated 5 to 10cm deep in the not yet seeded soil.

iii) Application In the seed furrow

The antidote is introduced as emulsion concentrate, wettable powder or granules in the open seeded seed furrow and then applied after covering the seed furrow in a normal manner, the herbicide in the Voraufiaufverfahren.

iv) Controlled Drug Delivery

The active ingredient is dissolved in mineral granules or polymerized granules (urea / formaldehyde)

pulled up and allowed to dry. Optionally, a coating can werdon applied (coating granules), which allows dispensed dosed over a certain period of time.

The compounds of the formula I are used in unchanged form or preferably together with the auxiliaries customary in the art of formulation and are therefore used, for example, in into emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, also encapsulated. The application methods such as spraying, atomizing, dusting, scattering or pouring are chosen in the same way as the type of means according to the desired goals and the given conditions.

The formulations, d. H. the active substance of the formula I and optionally a solid or liquid additive containing agents, preparations or compositions are prepared in a known manner, for. By intimate mixing and / or grinding of the active ingredients with diluents, e.g. with solvents, solid carriers and optionally surface-active compounds (surfactants).

Suitable solvents may be: Aromatic hydrocarbons, preferably the fractions C ₈ to C ₁₂ , such as. B.

Xylolgemkche or substituted naphthalenes, phthalic acid esters such as dibutyl or Di-oktylphtha! At, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, Aethylenglykolmon ^ methyl or -a'thyläther, ketones such as cyclohexanone highly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, for. As for dusts and dispersible powders, are in the morning! natural minerals used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular adsorptive granule carriers are porous types such. Pumice, broken brick, sepiolite or bentonite, as non-sorptive carrier materials e.g. Calcite or sand in question. In addition, a variety of pre-granulated materials of inorganic or organic nature, in particular dolomite or crushed plant residues can be used.

Suitable surface-active compounds, depending on the nature of the active ingredient of Formol I to be formulated, are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

As soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C ₁ (T-Cj ₂ ), such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures, for example Coconut oil or tallow oil can also be obtained, and the fatty acid methyltaurine salts should also be mentioned.

More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical having 8 to 22 carbon atoms, wherein alkyl also includes the alkyl moiety of acyl radicals, for example the Na or Ca. Salic acid ligninsulfonic acid, dodecylsulphuric acid ester or a fatty alcohol sulfate mixture prepared from natural fatty acids. This subheading also covers the salts of sulfuric acid esters and sulfonic acids of fatty alcohol / ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and one. ¹ fatty acid residue with 8-22 carbon atoms. Alkylarylsulfonates are z. Example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates, e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) -ethylene oxide adduct in question.

As nonionic surfactants are primarily Polyglykolätherderivato of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and Alkylphonolen in question, which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diaminopolypropylene glycol and allene / polypropylene glycol having from 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenol polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 carbon atoms and have as further substituents lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldi (2-chloroethyldiethylammonium bromide.

The surfactants commonly used in formulation technology are i.a. described in the following publications:

"1985 International McCutcheon's Emulsifiers & Detergents", Glen Rock NJ USA, 1985, "H.Stache," "Tensid-Taschenbuch", 2nd edition, C. Hanser Verlag Munich, Vienna 1981,

M. and J. Ash. Nil, Chemical Publishing Co., New York, 1980-1981.

The agrochemical preparations generally contain 0.1 to 95%, in particular 0.1 to 80% active ingredient of the formula 1.1 to 99.9% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25% a surfactant.

In particular, preferred formulations are composed as follows: (% = weight percent)

Emulsifiable concentrates

active ingredient mixture 1 to 20%, preferably 5 to 10%

Surfactant: 5 to 30%, preferably 10 to 20%

liquid carrier: 50 to 94%, preferably 70 to 85%

dusts

active ingredient mixture: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Konzontrate

active ingredient mixture: 5 to 75%, preferably 10 to 50%

Water: 94 to 25 ~ .Ό, preferably 88 to 30%

surface-active water: 1 to 40%, preferably 2 to 30%

Wettable powders

Active ingredient mixture: 0.5 to 90%, preferably 1 to 80%

Surfactant: 0.5 to 20%, preferably 1 to 15%

solid support material: 5 to 95%, preferably 15 to 90%

granules

active agent mixture: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

While merchandise is more likely to be concentrated, the endve uses; Consumers usually use diluted remedies. The use forms can be diluted down to 0.001% of active ingredient. The effort amounts are in de. ' Usually 0.01 to 10kg AS / ha, preferably 0.25 to 5kg AS / ha.

The compositions may also contain other additives such as stabilizers, defoamers, preservatives, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

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

Ausführungsbelsplele

Preparation Examples:

Example H1: 1- / 4- [N-3,4-dimethoxybenzoyl-sulfamoyl) -phenyl / -3-methyl-urea.

H ₃ C-NH-CU-MH-V 1 -SO ₂ -NH-CO- / V-Ci-U ₅

a) N- (4-sulfamoylphenyl) -0-phenylcarbamate.

176g suifanilamide are suspended in 750 ml of dioxane and treated with 79 g of pyridine. 160 g of phenyl chloroformate are added dropwise at 15 ° C. to this mixture. The Reaktionsüuspension is stirred for 1 hour at 50 ⁰ C, cooled and stirred into 2 liters of water. The precipitated product is separated and dried. 277 g of N- (4-sulfamoylphenyl) -0-phenylcarbamate, mp 2200-223 ° C. are obtained.

b) 1- (4-sulfamoylphenyl) -3-methylurea.

To oiner suspension of 350g N- (4-sulfamoylphenyl) -0-phenylcarbamat in 1500ml of ethanol is allowed to drop at 80 ° C 330ml of a 33% ic / en ethanolic methylamine solution. From the initially clear solution, the product crystallizes out within 1.5 hours. After cooling the reaction mixture, the precipitate is separated and dried. This gives 256 g of 1- (4-sulfamoylphfyl) -3-methylurea. M.p. 211-213 ⁰ 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. 98.1 g of triethylamine are added dropwise to this mixture. The temperature of the mixture rises from room temperature to 45 ° C and the disperse components go into solution. After a short time, crystallization starts. After a further 2.5 hours, the mixture is stirred into 2.5 liters of ice water and 200 ml of 2 N sulfuric acid. The precipitated product is separated, washed with ether and dried. This gives 114.4 g of 1- / 4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl / -3-methyl urea, mp. 236-238 ⁰ C (with decomposition).

Example H2: i - ^ - IN ^ -Furylcarbonylo-sulphamoyl-phenyl-S ^ -dlmethylurea.

> -C0-NH- () · j ·, -, ·,

H ₃ C · = · -SO 2 -NH-CO- ·

a) N- (3-sulfamoylphenyl) -0-phenylcarbamate.

To a suspension of 125 g of 3-Aminobenzolsulfonamld and 57.9 g of pyridine in SOOmI dioxane is allowed to drop at 15 ⁰ C 113g Chlorameieensäurephenyleeter. The mixture is stirred for one hour b-.i room temperature and for one hour at 50 ⁰ C and then stirred into 2 liters of water. The precipitated product is separated and dried. This gives 201 g of N- (3-sulfamoylphenyl) -0-phenylcarbamate, mp 184-186 ⁰ C (with decomposition).

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

A mixture of 205 g of N- (3-sulfamoylphenyl) -0-phenylcarbamate and 158 g of a 40% aqueous solution of dimethylamine is refluxed for 3 hours in 500 ml of ethanol. The solvent is distilled off under reduced pressure. The residue is mixed with water and the resulting phenol is driven off with steam. The crystalline residue is separated after cooling the distillation flask, washed with cold methanol and dried. This gives 136 g of 1- (3-sulfamoylphenyl) -3,3-dimethylurea, mp 193-194X.

c) 6.1 g of 2-furancarboxylic acid chloride and 0.1 g of 4-dimethylaminopyridine are added to the suspension of 10.1 g of 1- (3-sulfamoylphenyl) -3,3-dimethylurea in 60 ml of acetonitrile. 9.5 g of triethylamine are added dropwise to this mixture at room temperature. The reaction mixture is stirred for f15 hours at room temperature and for one hour at 6O ⁰ C. After the mixture has cooled, 4.5 g of methanesulfonic acid are added dropwise and taken up in 1 liter of water. The separated oil crystallizes after a short time. The crystals are separated, washed with methanol and dried. This gives 11.3 g of 1 - [S-iN ^ -FurylcarbonylsulfamoyD-phenyl-SS-dimethylurea, mp 216-217 ⁰ C (with decomposition).

Example H3: 1- [4- (N-3,4-Dimothylbenzoyl-sulfamoyl) -phenyl] -3-allylharnsto (f.

, CH ₃

H ₂ C = CH-CH ₂ -NH-CO-NH- ^ ^ -SO ₂ -NH-CO- ^ ^ 'CH ₃

A suspension of 12.2 g of 4- (N-3,4-dimethylbenzoyl-sulphamoyl) -aniline in 20 ml of acetonitrile is treated dropwise with 4.1 g of triethylamine. First, a clear solution emerges from which a salt precipitates. After addition of 4.6 g of allyl isocyanate the mixture for 2 hours at room temperature and for 2 hours at 7O ⁰ C is stirred. After the mixture has cooled, it is taken up in a mixture of 1 liter of ice-water and 4.5 g of concentrated sulfuric acid. The resulting precipitate is separated, washed with ether and dried. This gives 15.1 g of 1 -l4-! N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-allylurea, mp 194-201 ⁰ C (with substitution).

Example H4: 1- [4- (N-2,3-dimethylbonoylsulfamoyl) -phenyl] -3-methylurea.

H ₃ C-NH-CO-NH- ^ ^ -SO ₂ -NH-CO- ^

^N CHj

3 ^N C

2.8 g of triethylamine are added to a suspension of 6.1 g of <1- (N-2,3-dimothylbenzoyl-sulfamoyl-1-aniline in 50 ml of acetonitrile.) 1.3 ml of methyl isocyanate are added dropwise to this mixture stirred for 2 hours at room temperature and for 6 hours at 5O ⁰ C. After cooling to room temperature the mixture in 200mi of ice water and 15 ml of 2 N sulfuric acid is added. the precipitated product is separated and dried to give 1- [4- (N-. 2,3-Dimethylbenzoylsulfamoyl) phenyl | -3-methylurea, mp 242-244 ⁰ C.

 The intermediates and end products listed in the following parts are obtained in an analogous manner.

Table 1:

R ¹

Ni-CO-NH- ·

Verb no. R ¹ R ² N- amino A phenyl Mp. [° C] l.'OOl methylamino phenyl 1002 dimethylamino phenyl 237-238 ° (decomp.) 1003 methylamino 2-tolyl 1004 methylamino 3-tolyl 234-236 ° (decomp.) 1005 Mathylamino 4-tolyl 216-218 ° (decomp.) 1006 methylamino 4-ethyl-phenyl 247-249 ° (decomp.) 1007 methylamino 4-n-propyl-phenyl 1008 methylamino 4-i-propyl-phenyl 1009 methylamino 4-n-butyl-phenyl 1010 methylamino 4-tert-butyl-phenyl 1011 methylamino 2-chloro-phenyl 250-252 ° (decomp.) 1012 methylamino 3-chloro-phenyl 239-241 ° (decomp.) 1013 methylamino 4-chloro-phenyl 222-224 ° (decomp.) 1014 methylamino 2-fluoro-phenyl 246-247 ° (decomp.) 1015 methylamino 3-fluoro-phenyl 227-229 ° (decomp.) 1016 methylamino 4-fluoro-phenyl 234-235 ° (decomp.) 1017 methylamino 2-bromo-phenyl 1018 methylamino 3-bromo-phenyl 244-245 ° (decomp.) 1019 methylamino 4-bromo-phenyl 1020 methylamino 2-iodo-phenyl 1021 methylamino 3-iodo-phenyl 1022

Table 1: Continuation

Verb no. R ¹ R ² N- Λ Mp. [ ⁰ C] 1023 methylamino 4-phenyl-.iod 1024 {! ethylamino 3-Chloromethyl-phenyl 1025 ! • (ethylamino 2-trifluoromethyl-phenyl 1026 methylamino 3-trifluoromethyl-phenyl 231-233 ° (decomp.) 1027 Melhylamino 4-trifluoromethyl-phenyl 1028 methylamino 2-methoxy-phenyl, 197-198 ° (decomp.) 1029 methylamino 3-methoxyphenyl 1030 methylamino 4-methoxy-phenyl 1031 methylamino 2-ethoxy-phenyl 1032 methylamino 3-ethoxy-phenyl 1033 methylamino 4-ethoxy-phenyl 1034 methylamino 2-methylmercapto-phenyl 1035 methylamino 2-phenyl-Methylsulionyl 1036 methylamino 2-methoxycarbonyl-phenyl 1037 methylamino 4-methoxycarbonyl-phenyl 1038 methylamino 2-Nitro-phenyl 1039 methylamino 3-Nitro-phenyl 1040 methylamino 4-Nitro-phenyl 237-238 ° (decomp.) 1041 methylamino 2-acetyl-phenyl 1042 methylamino 4-Acetyl-phenyl 1043 methylamino 3-cyano-phenyl 1044 methylamino 4-cyano-phenyl 1045 methylamino 2,3-dimethyl-phenyl 242-244 ° (decomp.) 1046 methylamino 2,4-dimethyl-phenyl 239-241 ° (decomp.) 1047 methylamino 2,5-dimethyl-phenyl 223-224 ° (decomp.) 1048 methylamino 2,6-dimethyl-phenyl 1049 amino 3,4-Dimethyl-phenyl 151-153 ° (decomp.)

Table 1 : Continuation

Verb no. R ¹ R ² N- A Mp. [ ⁰ C] 1050 methylamino 3,4-Dimethyl-phenyl 236-238 ° (decomp.) 1051 dimethylamino 3,4-Dimethyl-phenyl 233-235 ° (decomp.) 1052 ethylamino 3,4-Diir.dthyl-phenyl > 230 ° (decomp.) 1053 Propylamiiio 3,4-Dimethyl-phenyl 211-213 ° (decomp.) 1054 Isopropylarnino 3,4-Dimethyl-phenyl 235-236 ° (decomp.) 1055 cyclopropylamino 3,4-Dimethyl-phenyl 229-231 ° (decomp.) 1056 butylamino 3,4-Dimethyl-phenyl 200-202 ° (decomp.) 1057 isobutylamino 3,4-Dimethyl-phenyl 222-223 ° (decomp.) 1058 lake. butylamino 3,4-Dimethyl-phenyl 215-218 ° (decomp.) 1059 tert. butylamino 3,4-Dimethyl-phenyl 223-225 ° (decomp.) 1060 allylamino 3,4-Dimethyl-phenyl 194-201 ° (decomp.) 1061 -propargylamino 3,4-Dimethyl-phenyl 231-233 ° (decomp.) 1062 Cycloheylamino 3,4-Dimethyl-phenyl 1063 phenylamino 3,4-Dimethyl-phenyl 230-231 ° (decomp.) 1064 2-methoxy-äthylainino 3,4-Dimethyl-phenyl 166-169 ° (Zers.) 1065 benzylamino 3,4-Dimethyl-phenyl 234-236 ° (decomp.) 1066 pyrrolidinyl 3,4-Dimethyl-phenyl 1067 piperidinyl 3,4-Dimethyl-phenyl 1068 hexahydroazepinyl 3,4-Dimethyl-phenyl 1069 morpholinyl 3,4-Dimethyl-phenyl 1070 2-Hethyl-piperidinyl 3,4-Dimethyl-phenyl 1071 3-methyl-piperidinyl 3,4-Dimethyl-phenyl

Table 1 : Continuation

Verb no. R ¹ R ² N- , A Mp. [ ⁰ C 1072 4-methyl-piperidinyl 3,4-Dimethyl-phenyl 1.0.73 2,6-dimethyl-piperidinyl 3,4-Dimethyl-phenyl 1074 N-methyl-1-piperazinyl 3,4-Dimethyl-phenyl 1075 thiomorpholinyl 3,4-Dimethyl-phenyl 1076 methylamino 3,5-Dimethyl-phenyl 240-242 ° (decomp.) 1077 methylamino 2,3-dichloro ~ phenyl 1078 methylamino 2,4-dichloro-phenyl 1079 methylamino 2,5-dichloro-phenyl 1080 methylamino 2,6-dichloro-phenyl 1081 methylamino 3,4-dichloro-phenyl 240-241 ° (decomp.) 1082 methylamino 3,5-dichloro-phenyl 1083 methylamino 2,3-Difluoro-phenyl 1084 methylamino 2,4-Difluoro-phenyl 1085 methylamino 2,5-Difluoro-phenyl 1086 methylamino 2,6-difluoro-phenyl 1087 methylamino 3,4-Difluoro-phenyl 1088 methylamino 3,5-Difluoro-phenyl 1089 methylamino 3,5-dimethoxy-phenyl 1090 methylamino 2,4-dimethoxy-phenyl 1091 methylamino 2,5-dimethoxy-phenyl 1092 methylamino 2,6-dimethoxyphenyl 1093 methylamino 3,4-dimethoxy-phenyl 223-225 ° (decomp.) 1094 dimethylamino 3,4-dimethoxy-phenyl 203-207 ° (decomp.) 1095 methylamino 3,5-dimethoxy-phenyl 1096 methylamino 3,4-dinitro-phenyl 1097 methylamino 3,5-dinitro-phenyl 1098 methylamino 2-chloro-3-nitro-phenyl 1099 methylamino 2-chloro-4-nitro-phenyl 1100 methylamino 2-chloro-5-nitro-phenyl

Table 1 : Continuation

Verb no. R ¹ R ² N- , A Mp. [ ⁰ C] 1101 methylamino 3-chloro-2-nitro-phenyl 1102 Hethylamino 4-chloro-2-nitro-phenyl 1103 methylamino 3-chloro-3-nitro-phenyl 1104 Hethylamino 5-chloro-2-nitro-phenyl 1105 methylamino 2-methyl-3-nitro-phenyl 247-248 ° (decomp.) 1106 Methylairino 2-methyl-5-nitro-phenyl 1107 Hethylamino 2-Hethyl-6-nitro-phenyl 1108 methylamino 3-methyl-2-nitro-phenyl 1109 Hethylamino 3-methyl-4-nitro-phenyl 1110 methylamino 4-methyl-3-nitro-phenyl 1111 methylamino 5-Methyl-2-nitro-phenyl 1112 methylamino 4-fluoro-3-nitro-phenyl 1113 methylamino 5-chloro-2-methoxy-phenyl 1114 methylamino 4-chloro-2-methoxy-phenyl 1115 methylamino 4-chloro-6-fluoro-phenyl 1116 methylamino 4-chloro-2-fluoro-phenyl 1117 methylamino 2,4,6-trimethyl-phenyl 1118 methylamino 2,4,5-trimethoxy-phenyl 1119 methylamino 3,4,5-trimethoxy-phenyl 238-239 ° (decomp.) 1120 methylamino 1-naphthyl 240-242 ° (decomp.) 1121 methylamino 2-naphthyl 234-235 ° (decomp.) 1122 methylamino 2-furyl 245-246 ° (decomp.) 1123 dimethylamino 2-furyl 246-247 ° (decomp.) 1124 methylamino 3-furyl

Table 1 : Continuation

Verb no. R ¹ R ² N- A 2-thienyl Mp. [ ⁰ C] 1125 methylamino 2-chloro-pyridinyl 245-247 ° (decomp.) 1126 Methylamines) 2,6-dichloro-pyridinyl 1127 methylamino 2,6-dibromo-pyridinyl 138-139 ° (decomp.) 1128 Methylamines) piperonyl 1129 methylamino 3-tolyl 268-270 ° (decomp.) 1130 dimethylamino 3-trifluoromethyl-phenyl 204-207 ° (decomp.) 1131 cyclopropylamino 3-tolyl 246-247 ° (decomp.) 1132 i-propylamino 3-trifluoromethylphenyl 217-220 ° (decomp.) 1133 dimethylamino 4-chloro 229-230 ° (decomp.) 1134 amino 2-carboxyphenyl 226-228 ° (decomp.) 1135 methylamino 2-tolyl 181-183 ° (Zers.) 1136 i-propylamino 3-bromo-4-methylphenyl 236-238 ° (decomp.) 1137 methylamino 1-naphthyl 244-245 ° (decomp.) 1138 i-propylamino 1-naphthyl 235-237 ° (decomp.) 1139 allylamino 2-tolyl 218-219 ° (decomp.) 1140 allylamino 2-tolyl 195-198 ° (Zers.) 1141 3-tolylamino 197-199 ° (Zers.)

Table 1: Continuation

Verb no. R ¹ R ² N- , A Mp. [ ⁰ C] 1142 tert-butylamino 2-tolyl 144-145 ° (decomp.) 1143 tert-butylamino 2,4-dimethylphenyl 226-227 ° (decomp.) 1144 -propargylamino 1-naphthyl 149-151 ° (decomp.) 1145 tea. butylamino 2,4-dimethylphenyl 230-232 ° (decomp.) 1146 -propargylamino 2,4-dimethylphenyl 191-192 ° (Zers.) 1147 methylamino 2-biphenyl 262-264 ° (decomp.) 1148 lake. butylamino 2,5-dimethylphenyl 208-210 ° (decomp.) 1149 Dimethylamine 2,4-dimethylphenyl 206-209 ° (decomp.) 1150 Dimethylamine 1-naphthyl > 25O ° (Zers.) 1151 dimethylamino 2-tolyl 236-240 ° (decomp.) 1152 -propargylamino 2,5-dimethyl-phenyl 198-200 ° (decomp.) 1153 methylamino 4-chloromethyl-phenyl 228-229 ° (decomp.) 1154 methylamino 3- (2,3-tetramethylene) thienyl > 250 ° 1155 methylamino 3- (2,3-tetramethylene) furyl 1156 methylamino 3- (4,5-dimethyl) thienyl 238-239 ° (decomp.)

"2:

R ¹ R ²

N-CO-NH- ·

'- SO ₂ -NH-CO-A

Verb no. R ¹ R ² N- amino A phenyl Mp. [ ⁰ C] 2001 Methylamines) phenyl 2002 dimethylamino phenyl 2003 methylamino 2-tolyl 2004 Me thylamino 3-tolyl 2005 methylamino 4-tolyl 2006 methylamino 2-chloro-phenyl 2007 methylamino 4-chloro-phenyl 2008 methylamines 3-trifluoromethyl-phenyl 2009 methylamino 2,3-dimethyl-phenyl 2010 methylamino 3,4-Dimethyl-phenyl 2011 methylamino 1-naphthyl 147-152 ° 2012 methylamino 2-naphthyl 2013 dimethylamino 2-furyl 2014 216-217 ° (decomp.)

Table 3:

H ₃ C-NH-CO-NH- '

SOz-NH-CO-A

Verb no. A phenyl R ^a 2-fluoro Mp. [ ⁰ C] 3001 phenyl 3-fluoro 3002 4-tolyl 2-fluoro 3003 4-tolyl 3-fluoro 258-260 ° (decomp.) 3004 4-tolyl 2-chloro about 270 ° (decomp.) 3005 4-tolyl 3-chloro 3006 4-tolyl 2-methyl 3007 4-tolyl 3-methyl 3008 3,4-Dimethyl-phenyl 2-fluoro 3009 3,4-Dimethyl-phenyl 3-fluoro 246-248 ° (decomp.) 3010 3,4-Dimethyl-phenyl 2-chloro 239-240 ° 3011 3,4-Dimethyl-phenyl 3-chloro 3012 3,4-Dimethyl-phenyl 2-methyl 223-224 ° (decomp.) 3013 3,4-Dimethyl-phenyl 3-methyl 3014 2-tolyl 3-fluoro 218-220 ° (decomp.) 3015 1-naphthyl 3-fluoro 236-238 ° (decomp.) 3016 2,4-dimethyl-phenyl 2-fluoro 131-133 ° (decomp.) 3017 2,4-dimethyl-phenyl 3-fluoro 236-238 ° (decomp.) 3018 1-naphthyl 2-fluoro 233-234 ° (decomp.) 3019 2,3-dimethyl-phenyl 3-fluoro 240-241 ° (decomp.) 3020 2,3-dimethyl-phenyl 2-fluoro 227-230 ° (decomp.) 3021 244-246 ° (decomp.)

Table 3: Continuation

Verb no. A 2-tolyl 2-fluoro Mp. [° C] 3022 3,5-Dimethyl-phenyl 3-fluoro 236-237 ° (decomp.) 3023 3,5-Dimethyl-phenyl 2-fluoro 198-200 ° (decomp.) 3024 2,5-dimethyl-phenyl 3-fluoro 244-246 ° (decomp.) 3025 2,5-dimethyl-phenyl 2-fluoro 213-215 ° (decomp.) 3026 2-Tclyl 3-methyl 227-229 ° (decomp.) 3027 2-tolyl 3-chloro 176 ° (decomp.) 3028 1-naphthyl 3-chloro 218-220 ° (decomp.) 3029 1-Nr.phtyl 3-methyl 150 ° (decomp.) 3030 153-155 ° (decomp.)

Table 4:

H ₃ C-NH-CO-NH-

Verb no. A 1-naphthyl R ^a R ^b Mp. [° C] 4001 3,4-Dimethyl-phenyl 2-methyl 6-Methyl 214-216 ° (decomp.) 4002 2-Toiyl 1-naphthyl 2-methyl 6-Methyl 206-208 ° (decomp.) 4,003 4,004 3,4-Dimethyl-phenyl 2-methyl 2-fluoro 6-methyl 6-fluoro 217-219 ° (decomp.) 4005 2-tolyl 2-fluoro 6-fluoro 4006 4-tolyl 2-chloro 6-chloro 4007 4-tolyl 2-fluoro 5-fluoro 4008 4-tolyl 2-fluoro 5-fluoro 4009 2-methyl 5-Methyl

Table 5:

^ _R ^b

H ₃ C-NH-CO-NH- ^ - SO ₂ -NH-CO-A

Verb no. A i? ^a n ^b Mp. [ ⁰ Cl 5001 3,4-Dimethyl-phenyl X / ' 201-203 ° (decomp.) 5002 2-tolyl 184-186 ° (dec.) As Triäthyl- amine salt 5003 1-naphthyl \ _ / * 138-140 ° (dec.) As Triäthyl- amine salt * \ / 5004 2-tolyl t- · / \ _# \ _ / * 5005 4-tolyl , ^{/ = x} . 5006 3,4-Dimethyl-phenyl / \ 5007 2-tolyl \ κ '

a) 5% b) _ 6% O _ 20% 67% 60% 2% 0.5 ° /. 6% 5% 5% 27% 5% 2% 3% 27% - _

a) 10% b) 1% 3% 3% 3% 3% 4% 30% 50% 4% 10% 79%

Formullerungsbelsplele for compounds of the formula I or mixtures of these compounds with herbicides

Example FI

Injection powder Active ingredient No. 1,050 Na lignosulfonate Na lauryl sulfate Na diisobutylnaphthalenesulfonate Octylphenol polyethylene glycol ether 7-8 moles of AeO) Highly dispersed silicic acid Kaolin

Sodium chloride - - 59.5%

The active substance mixture is mixed well with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F2

Emulsion Concentrate Active Ingredient No. 2,011 octylphenol polyethylene glycol ether M-5 moles of AeO) Ca-dodecylbenzenesulfonate castor oil polyglycol ether (36MoIAeO) cyclohexanone xylene mixture

From these concentrates emulsions of any desired concentration can be prepared by dilution with water.

Example F3

Dust substance no. 1,050 Talcum

Kaolin - 99%

Ready-to-use dusts are obtained by mixing the active ingredient mixture with the carrier and grinding on a suitable mill.

Example F4

Extruder Granules Active ingredient No. 1.006 N'3-Ligninsulfonate Carboxymethylcellulose Kaolin

The active ingredient mixture is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

Example F5

Umhültungs granules

Active ingredient No. 1.005 3%

Polyethylene glycol (MG 200) 3%

Kaolin 94%

The finely ground active substance mixture is uniformly applied in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

Example F6

Suspension concentrate Active substance No. 1.OEC ethylene glycol Nonylphenolpolyethylene glycol ether (15MoIAeO) Na lignin sulphonate Carboxymethylcellulose 37% aqueous formaldehyde solution Silicone oil in the form of a 75% aqueous emulsion Water

a) b) - 0.1% 1% 99.9%

a) b) 10% 1% 2% 2% 1% 1% 87% 96%

a) b) 40% 5% 10% 10% 6% 1% 10% 5% 1% 1% 0.2% 0.2% 0.8% 0.8% 32% 77%

Example F7

Saline solution »

Drug # 1,026 Isopropylamine Octylphenol Polyethylene Glycol Ether (78MoIAeC) Water

5% 1%

3% 91%

Example F8

Spray powder a) b) c)

Drug # 1,050 in 20% 60% 0.5%

Mixture with N- [2- (2-methoxyethoxy) phenylsulfonyl-N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea] Na lignosulfonate Na lauryl sulfate Na diisobutylnaphthalenesulfonate Octylphenolpolyethylene glycol ether 7 -8 moles of AeO) fumed silica kaolin

sodium chloride

The active substance mixture is mixed well with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

5% - 5% 5% - · 6% 5 / o - 6% 3% _ 67% 2% 2% _ 27% 27% - - _ 59.5%

Example F9

a) 10%

b)

1%

Emulsion Concentrate Active ingredient No. 2,011 in admixture with 2- [4- (5-trifluoro, -tethylpyndin-2-yloxy) -phenoxy] -propionic acid n-butyl ester Octylphenolpolyethylene glycol ether (4-5 moles of AeO) Ca-dodecylbenzenesulfonate Ricinusölpolyglykoläther (36MoIAeO ) Cyclohexanone xylolemic

From these concentrates emulsions of any desired concentration can be prepared by dilution with water.

3% 3% 3% 3% 4% 4% 30% 10% 50% 79%

Example F10

Stsubemlttel drug no. 1,050 in admixture with N- [2- (2-methoxyethoxy) -phenylsulfonyl] -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea talc

kaolin

a) 0.1%

99.9%

b)

1%

99%

Ready-to-use dusts are obtained by mixing the active ingredient mixture with the carrier and grinding on a suitable mill.

a) 10%

b) 1%

Example F11 Extruder granules

Active ingredient No. 1.006 in mixture with N- [2- (2-methoxyethoxy) phenylsulfonyl] -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea Na lignin sulfonate carboxymethyl cellulose kaolin

The active ingredient mixture is mixed with the additives, milling and moistened with water. This mixture is extruded and then dried in a stream of air.

2% 2% 1% 1% 87% 96%

Example F12

Casing Granules _v

Drug # 1,005 in 3%

Mix with

N-chloroacetyl-N- (2-methoxy-1-

methylethyl) -2-ethyl-6-methyl-

aniline

Polyethylene glycol (MG200) 3%

Kaolin 94%

The finely ground active substance mixture is uniformly applied in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

Example F13

Suspension concentrate a) b)

Drug # 1,050 in 40% 5%

Mix with

2- [4- (6-chlorobenzoxazol-2-yloxy) -

phenoxyj-propionic acid ethyl

ester

Ethylene glycol 10% 10%

Nonylphenoipolyäthylenglykoläther

(15MoIAeO) 6% 1% Na ligninsulfonate 10% 5% carboxymethylcellulose 1% 1% 37% aqueous formaldehyde solution 0.2% 0.2% Silicone oil in the form of a 75% aqueous emulsion 0.8% 0.8% water 32% 77% Example F14 saline solution Active ingredient No. 1,026 in 5% Mix with 2- (4- (3,5-Dichloro-2- yloxy) phenoxy] propionate propargyl isopropylamine 1% Oktylphenolpolyäthylenglykoläther (78MoIAeO) 3% water 91%.

Biological examples

The ability of the compounds of formula I to protect crops from the phytotoxic effects of strong herbicides can be seen from the following examples. In the description of the fungicide, the compounds of the formula I are called antidotes (antidotes or safeners).

The evaluation of the tests is carried out in such a way that on the one hand the effect of the herbicide alone is made in%, wherein 100% effect corresponds to the killing of the plants and 0% effect means no effect as in the untreated control plants. On the other hand, the effect of the herbicide-antidote combination is also determined in% herbicidal action in the same way. The difference between the two percentages obtained is reported as "% protection" in the test results.

The effect of the herbicide-antidote combination can be assessed both in direct simultaneous administration of the two active ingredients in a single injection process in tank mix, as well as in separate and also with time-shifted application, such as seedbed antidote and postemergic herbicidal treatment.

Example B1: Experiment with herbicide and antidote in millet (sorghum). Herbicide and antidotes are applied together as tank mix pre-emergence or post-emergence.

In 11 cm diameter pots filled with garden soil seeds of sorghum "Funk G-623" are sown and grown in the greenhouse under adapted temperature and light conditions, irrigated and fertilized as needed A mixture of antidote and herbicide in an amount of water of 550 l / ha applied directly after sowing.For the determination of the post-active effect of the drug mixture is applied after emergence of the plants in the 3- to 5-leaf stage.After 21 days after treatment, the test evaluation the "effectiveness in%".

Test results:

a) preemergent test:

 Test plant: Sorghum "Funk G-623"

Treatment: preemergentmitTankmischungvon250g / haVerbindungNr.1.050und125g / Han | 2- (2-Mt _l tl \ oxyäthoxy) -

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

 Effect: 21 days after application:

50% protective effect.

b) Postemergent test: Test plant: Sorghum "Funk G-623"

Treatment: postemergent with tank mix of 250g / ha compound no. 1,050 and 125g / haN- (2- (2-methoxyethoxy) -

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

Effect 21 days after Appli ^{1 nt} ion:

45% protective effect.

Example B2: Experiment with herbicide and antidotes in corn and sorghum.

The antidote is stained on the seed, the herbicide is applied pre-emergence or postemergence. In pots of 11 cm diameter, filled with garden soil, seeds of maize stained with the antidote are sown with "Blizzard" soybeans and "Funk G-623" sorghum and grown in the greenhouse under adapted temperature and light conditions. Irrigation and fertilization is done as needed. To determine the pre-emetic effect, the herbicide is applied in a quantity of water of 550 l / ha directly after sowing. For the determination of the postemergent effect, the herbicide is applied after emergence of the plants in the 3- to 5-leaf stage. Each 12 to 26 days after the treatment, the test evaluation of the "protective effect in%".

Test results: a) Maize tests:

Test plant: Corn "Blizzard"

Treatment: Seed dressing with 0.5 g, 1 or 2 g of Compound No. 1,050 per kg of corn seed.

Herblzld-pre-emergence:

4000 g / haN-chloroacetyl-N- (2-methoxy-1-methoxyethyl) -ethyl-6-methylaniline, or 240 g / ha of N-I2- (3,3,3-trifluoropropen-1-yl) -phenylsulfonyl) - N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea, or

120,60oder30g / Han [2- (2-methoxyethoxy) -pr-enylsulfonyl] -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) -urea.

Herbizld-postemergence:

120 g / haN- (2-methoxycarbonylthien-3-ylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl! Urea, or

480g / Han L2 (3,3,3-trifluoropropene-1-yl) phenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea, or

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

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

120 g / haN- (2-methoxycarbonylphenylsulfonyl) -N '- (4,6-bis-difluoromethoxypyrimidin-2-yl) urea, or 10 g / haN-12- (2-chloroethoxy) -phenylsulfonyl] -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea, or 30g / ha 2 - [4- (6-chloro-quinoxalin-2-yloxy) -phenoxy] -propionic acid ethyl ester, or 60g / ha 2 - [4- (6-chlorobenzoxazol-2-yloxy) -phenoxy] -propionic acid ethyl ester, or 30g / ha 2 -l4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -propionic acid-propargyl ester, or 10g / haN- (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-methoxyethoxy) -phenylsulfonyl] -N '- (4,6-dimexy) -1,3,5-triazin-2-yl) urea.

Effect: (DAT: days after application)

Safener pickling amount in g / kg seeds Herbicide dose in g / ha N-chloroacetyl-N- (2-methoxy-1-ethyl) -2-ethyl-6-methylaniline Type of application of the herbicide / evaluation Protection effect in% 2 4000 N- [2- (3,3,3-trifluoropropen-1-yl) -phenylsulfonyl] -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea pre / 14 DAT 40 1 2A0 pre / 20 DAT 25 1 480 N- [2- (2-methoxyethoxy) phenylsulfonyl] -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) urea post / 20 DAT 30 2 120 pre / 12 DAT 70 1 120 pre / 12 DAT 65 0.5 120 pre / 12 DAT 65 2 60 pre / 12 DAT 65 1 60 pre / 12 DAT 65 0.5 60 pre / 12 DAT 70 2 30 pre / 12 DAT 55 1 30 pre / 12 DAT 50 0.5 30 pre / 12 DAT 55 2 240 post / 20 DAT 65 1 240 post / 20 DAT 65 0.5 240 post / 20 DAT 50 2 120 post / 20 DAT 60 1 120 post / 20 DAT 55 0.5 120 post / 20 DAT 25 2 60 post / 20 DAT 40 1 60 post / 20 DAT 40 0.5 60 post / 20 DAT 35 2 30 post / 20 DAT 25 1 30 post / 20 DAT 30 0.5 30 post / 20 DAT 15

continuation

Safener pickling amount in g / kg seeds Herbicide dose in g / ha N- (2-methoxycarbonylthien-3-yl-sulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea Type of application of the herbicide / evaluation Protection effect in% 1 120 N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-difluoromethoxy-6-methoxy-pyrimidin-2-yl) -urea post / 16 DAT 20 1 120 N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl) urea post / 16 DAT 15 1 120 N- (2-methoxycarbonylphenylsulfonyl) -N '- (4,6-bis-difluoromethoxypyrimidin-2-yl) urea post / 16 DAT 20 1 120 N- [2- (2-chloroethoxy) -phenyl-sulfonyl] -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea post / 16 DAT 20 1 10 2- [4- (6-chloroquinoxalin-2-yloxy) -phenoxy] -propionic acid ethyl ester post / 16 DAT 35 1 30 2- [4- (3,5-dichloropyridin-2-yloxy) -phenoxy] -propionic acid propargyl ester post / 16 DAT 30 1 30 N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-ethoxy-6-methylamino-1,3,5-triazin-2-yl) urea post / 16 DAT 45 1 10 2- [4- (6-chlorobenzoxazol-2-yloxy) -phenoxy] -propionic acid ethyl ester post / 16 DAT 30 1 60 post / 16 DAT 30

b) Sorghum tests:

Test plant: Sorghum "FunkG-623"

Treatment: Seed dressing with 0,5g, 1 or 2g of Compound No. 1,050 per kg of sorghum seed. Herbizld-pre-emergence:

1000 g / ha of N-chloroacetyl-N- (2-methoxy-1-metioxyethyl) ethyl-6-methylaniline, or 250 g / haN- [2- (3,3,3-trifluoropropen-1-yl) -phenylsulfonyl] - N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea, or 120, 60 or 30 g / haN- [2- (2-methoxy-ethoxy) -phenylsulfonyl] -N' - ( 4,6-dimethoxy-1,3,5-triazin-2-yl) -urea. Postemergence herbicide:

480g / Han [2- (3,3,3-trifluoropropene-1 yl) phenylsulfonyl] -N '- 4-methoxy-6-methyl-1,3,5-triazin-2-yD-urea; or 15g / ha 2 ~ (4- (6-chloroquinolalin-2-yloxy) -phenoxy) -propionic acid ethyl ester, or ethyl 60g / ha 2 - [4- (6-chlorobenzoxazol-2-yloxy) -phenoxy] -propionate , or 15g / ha 2 - [4- (3,5-dichloropyridin-2-yloxy) -phenoxy) -propionic acid-propargyl ester, or 30g / ha 2 - [4- (5-trifluoromethyl-pyridin-2-yloxy) -phenoxy] -propionic acid butyl, or 240, 20, 60 or 30 g / ha of N- (2- (2-methoxyethoxy) phenylsulfonyl] -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) urea.

Effect: (DAT: days after application)

Safener pickling amount in g / kg seeds Herbicide dose in g / ha N-chloroacetyl-N- (2-methoxy-1-ethyl) -2-ethyl-6-methylaniline Type of application of the herbicide / evaluation Protection effect in% 1 1000 N- [2- (3,3,3-trifluoropropen-1-yl) -phenylsulfonyl] -N'- (4-methoxy-6-methyl-1,3,5-triaζin-2-yl) -urea pre / 26 DAT 35 1 250 pre / 20 DAT 45 1 480 N- [2- (2-methoxyethoxy) phenylsulfonyl] -N '- (4,6-dimethoxy-1,3,5-triazin-2-yl) urea post / 20 DAT 40 2 120 pre / 12 DAT 55 1 120 pre / 12 DAT 55 0.5 120 pre / 12 DAT 60 2 60 pre / 12 DAT 55 1 60 pre / 12 DAT 50 0.5 60 pre / 12 DAT , 60 2 30 pre / 12 DAT 70 1 30 pre / 12 DAT 65 0.5 30 pre / 12 DAT 70 2 240 post / 20 DAT 50 1 240 post / 20 DAT 60 0.5 240 post / 20 DAT 60 2 120 post / 20 DAT 50 1 120 post / 20 DAT 65 0.5 120 post / 20 DAT 60 2 60 post / 20 DAT 45 1 60 post / 20 DAT 65 0.5 60 post / 20 DAT 60 2 30 post / 20 DAT 30 1 30 post / 20 DAT 45 0.5 30 post / 20 DAT 50

continuation

Safener pickling amount in g / kg seeds Herbicide dose in g / ha 2- [4- (6-chlorobenzoxazol-2-yloxy) -phenoxy] -propionic acid ethyl ester Type of application of the herbicide / evaluation Protection effect in % 1 60 2- [4 ~ (6-chloroquinoxaline-2-yloxy) -phenoxy] -propionic acid ethyl ester post / 16 DAT 33 1 15 2- [A- (3,5-dichloropyridin-2-yloxy) -phenoxy] -propionic acid propargyl ester post / 16 DAT AO 1 15 2- [4- (5-trifluoromethylpyridin-2-yloxy) -phenoxy] -propionic acid-butyl ester post / 16 DAT 50 1 30 post / 16 DAT 20

Test results:

Example B3: Experiment with herbicide and antidote in rice.

The seeds are pre-swollen in antidote dispersion, the herbicide applied in pre-emergence.

Rice seeds of the variety "S-201" are pre-swollen for 48 hours in an aqueous dispersion of the antidote (seed soaking), then kept dry for 24 hours and finally seeded in pots {9cm χ 9cm), filled with swampy-moist garden soil, superficially. The herbicide is sprayed onto the soil surface at a rate of 5501 / ha immediately after sowing, and the plants are grown in the greenhouse under adapted temperature and light conditions.

Irrigation and fertilization is done as needed. 26 days after the treatment, the test evaluation of the "protective effect in%" takes place.

Test results: Test plant: Treatment:

Effect:

Rice "S-201"

Seed swelling for 48 hours in a 300 ppm solution of Compound No. 1,050, followed by pre-engraftment with 30 g / haN- (2- (2-methoxyethoxy) phenylsulfonyl] -N '(4,6-dimethoxy-1,3, 5-triazin-2-yl) -hamstoff.

26 days after application:

55% protective effect.

Claims (63)

1. A means for protecting crops from the phytotoxic effect of sulfonylurea herbicides, ChloracetanilidherbUidon, Acylcyclohexandionherbiziden or Aryloxyphenoxypropionsäureherbiziden, characterized in that it is in addition to carrier and / or other additives an active ingredient dor formula I. ^R2 cO-N - (J- (D ³ N A for a rest of the group R ^e -tt -H- or R - * f ~ . R ¹ and R ² are independently hydrogen, C _r C ₈ alkyl, Cs-Ca-cycloalkyl, C ₃ -C ₆ -AlkenyI, Cr-Ce-alkynyl, \ ^ Or by Ci-Ci ₁ -alkoxy or substituted Ci-Ci, -alkyl, or R ¹ and R ² together for a C-Ca-alkylene bridge or an interrupted by oxygen, sulfur, SO, SO ₂ , NH or -N (Cr-C ₁₄ alkyl) - interrupted C ₄ -C ₆ alkylene, R ^{3 is} Hydrogen or C ₁ -C ₄ -alkyl, R ^a and R ^b independently represent hydrogen, halogen, cyano, nitro, trifluoromethyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ -alkoxy, Cr-C ₄ alkylthio, C ^ C ^ alkylsulfinyl. C ₁ -C ₄ alkylsulfonyl, -COOR ¹ , -CONR ¹ , -COR ₂ , -SO ₂ NR ^k R ^m, OdOR-OSO ₂ C ₁ -C ₄ -alkyl, or R ^a or R ^b together represent 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 -alkenylene bridge which may be substituted by halogen or C ₃ -C ₄ -alkyl, or a C ₁ - Alkadienylene bridge, which may be substituted by halogen or C ₁ -C ₄ -AlkYl, and R ^g and R ^{h are} independently hydrogen, halogen, C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, methylthio or -COCr. ' oiehen, where R ^{c is} hydrogen, halogen, C ₁ -C ₄ -alkyl or methoxy, R ^d is hydrogen, halogen, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, Cr-C ₄ alkylthio, Cr-C ₄ alkylsulfinyl, C ₁ -C ₄ -AIkYlSuIfOnYl ^ COOR'oder- CONR ^k R ^m , R ^{e is} hydrogen, halogen, C ₁ -C ₄ -alkyl- _1- COOR ", trifluoromethyl or methoxy, or R ^d and R ^c together represent a C ₃ -C ₄ -alkylene bridge, R ^{f is} hydrogen, halogen or C ₁ -C ₄ -alkyl, R ^x and R ^v independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, -COOR ⁴ , trifluoromethyl, nitro or cyano, R ', R ^k and R ^m independently of one another denote hydrogen or C ₁ -C ₄ -alkyl, R ^k and R ^m together represent a Cj-Ce-alkylene bridge or an interrupted by oxygen, NH or -N (Ci-C ₄ - alkylJ- interrupted C ^ -Ce-alkylene bridge, and R ^{n is} C ₁ -C ₄ alkyl, phenyl or by halogen, C ₁ -C ₄ alkyl, methoxy, nitro or trifluoromethyl substituted phenyl. 2. Composition according to claim 1, characterized in that in the formula IAfür a group from the group _R ^e _jp-i_ or R ^e -H 4i-, R ¹ and R ² are each independently hydrogen, Ci-C ₈ alkyl, C ₃ -C ₈ -CyClOaIkyI, C ₃ -C ₆ -AlkenyI, Qj-Ce-alkynyl, ^ · Or by Ci-Ci _1- Alkoxy or substituted Ci-Ci, -alkyl, or • = - \ y R ¹ and R ² together represent a C ₁ -C ₆ -alkylene bridge or a C ₄ -C ₆ -alkylene bridge interrupted 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 "and R ^b independently of one another represent hydrogen, halogen, cyano, nitro, trifluoromethyl, C ₁ -C ₄ - Alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ alkylthio-Al, Cr-C ₄ alkylsulfinyl, C ^ Q-Alkybulfonyl, -COOR ', -CONR ^k R ^m, -COR ^n, -SO ₂ NR ^k R ^m or-OSO ₂ -C, -C ₄ alkyl, and R ^g and R ^h independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl, trifluoromethyl, methoxy, methylthio or -COOR ', where R ^{c is} hydrogen, halogen, C ₁ -C ₄ -alkyl or methoxy, R ^{d is} 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 -alkylsulfonylC COC R ¹ or -CONR ^k R ^m , R ^{e is} hydrogen, halogen, C ₁ -C ₄ alkyl, -COOR ¹ , trifluoromethyl or methoxy, or R ^d and R ^e together represent a Cs-Q-alkylene bridge R ^{f is} hydrogen, halogen OdBrC ₁ -C ₄ -alkyl, R ^x and R ^v independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, -COOR ⁴ , trifluoromethyl, nitre or cyano, R ¹ , R ^k and R ^m independently of one another. / Hydrogen or C ₁ -C ₄ -alkyl, R ^k and R ^m together denote a Cr-Ce-alkylene bridge or an interrupted by oxygen, NH OdOr-N (C ₁ -C ₄ alkyl) Cf-Ce-alkylene bridge, and R ^{n is} C ₁ -C ₄ -alkyl, phenyl or by halogen, C ₁ -C ₄ -alkyl, methoxy, nitro or trifluoromethyl-substituted phenyl. 3. Mittnl according to claim 1, characterized in that in the formula IR ^{b is} hydrogen. 4. Mittol according to claim 1, characterized in that occupied in the formula I, the Sulfainoylgruppe the 4-Stuillung on the phenyl ring. 5. Composition according to claim 1, characterized in that in the formula IR ² and R ^{3 is} hydrogen. 6. A composition according to claim 1, characterized in that in formula IR ^{b is} hydrogen and the sulfamoyl group assumes the 4-position on the phenyl ring. 7. Composition according to claim 1, characterized in that in the formula IR ² , R ³ and R ^{b are} hydrogen and the sulfambyl group occupies the 4-position on the phenyl ring. 8. Composition according to claim 1, characterized in that in the formula IA for the group stands. 9. Composition according to claim 8, characterized in that R ² , R ³ and R ^{b are} hydrogen and the sulfamoyl group occupies the 4-position on the phenyl ring. 10. Compounds according to claim characterized in that the active ingredient of sub-formula la JV R ¹ -NH-CO-NH- ( ^ -SO ₂ -NH-CO- * * (la) • ⁼ 'V belongs. 11. A composition according to claim 10, characterized in that in the formula La R ^{c is} hydrogen. 12. A composition according to claim 11, characterized in that in the sub-formula la R ¹ , R ⁹ and R ^h CT-C4-alkyl. 13. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-4-methylbenzoylsulfamoyl) -phenyl] -3-methylurea. 14. Composition according to claim 1, characterized in that it contains as active ingredient 1 - [4- (N-3-Methylbenzoylsulfamoyl) -phenyl-3-methylurea. 15. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-4-tert-butylbenzoyl-sulfamoyl) -phenyl] -3-methylurea. 16. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3-trifluoromethylbenzoyl-sulfamoyl) -phenyl] -3-methylharns off. 17. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-4-nitrobenzoylsulfamoyl) -phenyl) -3-methylurea. 18. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-2,3-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methylurea. 19. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl) -3-methylurea. 20. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3,3-dimethylurea. 21. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-ethylurea. 22. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-allyl urea. 23. A composition according to claim 1, characterized in that it contains as active ingredient 1- (4- (N-3,4-dimethylbenzo / l-sulfamoyl) -phenyl] -3-phenylurea. 24. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3,5-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methylurea. 25. A composition according to claim 1, characterized in that .ils active ingredient 1- [4- (N-3,4-dichlorobenzoyl-sulfamoyl) -phenyl] -3-methylurea entf / t. 26. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3,4-dimethoxybenzoyl-sulfamoyl) -phenyl] -3-methylurea. 27. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3,4-dimethoxybenzoyl-sulfamoyl) -phenyl] -3,3-dimethylurea. 28. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-2,4,5-trimethoxybenzoyl-sulfamoyl) -phenyl] -3-methylurea. 29. A composition according to claim 1, characterized in that it contains as active ingredient 1 - [4- (N-I-Naphthylcarbonyl-sulfamoyl) -phenylj-3-methylurea. -A- 291 68Ü 30. A composition according to claim 1, characterized in that it contains as active ingredient 1 - [4- (N-2-furylcarbonylsulfamoyl) -phenyl-3-methylurea. 31. A composition according to claim 1, characterized in that it as Wirksto. r 1 - [4- {N-2-furylcarbonylsulfamoyl} -phenyl] -3,3-dimethylurea. 32. Composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-2-thienylcarbonyl-sulphamoyl) -phenyl] -3-methylurea. 33. Composition according to claim 1, characterized in that os contains as active ingredient 1- [4- (N-Piperonyloylsulfamoyl) -phenyl] -3-methylurea. 34. Composition according to claim 1, characterized in that it contains as active ingredient 1- (4- (N-3-methylbenzoylsulfamoyl) -phenyl] -3,3-dimethylurea. 35. A composition according to claim 1, characterized in that it contains as active ingredient 1- [4- (N-3-trifluoromethylbenzoyl-sulfamoyD-phenyll-S-cyclopropylurea. 36. A composition according to claim 1, characterized in that it contains as active ingredient 1- [3- (N-3,4-dimethylbenzoyl-sulfamoyl) -phenyl] -3-methylurea. 37. Composition according to claim 1, characterized in that it contains as active ingredient 1- [3- (N-2-Furylcarbonylsulfamoyl) -phenyl] -3,3-dimethylurea. 38. Composition according to claim 1, characterized in that it is in the crops rice, maize, sorghum, cereals or soybeans. 39. Composition according to claim 38, characterized in that it is the crops rice, maize or sorghum. 40. Composition according to claim 1, characterized in that it boi the crops to sorghum and the herbicides are sulfonylureas. 41. Composition according to claim 1, c'ää characterized in that it is for protecting crops from the phytotoxic effect of sulfonylurea herbicides of the formula II E- (CH ₂ ) -SO ₂ -NH-CO-N- - { Y (II) ι v / wherein E a group \ _ / \ _ ¹ J ¹ J / ' W 'VV or ft? Ϊ ⁸ η is the number zero, G is hydrogen or methyl, X is methoxy, ethoxy, difluoromethoxy, methyl or chlorine Y is CH or N, Z is methoxy, methyl, difluoromethoxy, cyclopropyl or methylamino, R ^{4 is} Cz-Cs-alkoxyalkoxy, Cr-d-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 -alkylcarbamoyl, R ^{6 is} C 1 -C 4 alkoxycarbonyl, R ⁷ CC ^ alkoxycarbonyl, and R ^{8 is} C ₁ -C ₄ -alkyl, is used. 42. Composition according to claim 41, characterized in that the sulfonylureas of the formula II from the group N- (3-trifluoromethylpyridin-2-ylsulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) urea, N- (3-dimethylcarbamoylpyridin-2-ylsulfonyl) -N' - (4,6-dimethoxypyrimidine -2-yl) urea, N-ii-methyl ^ -ethoxycarbonylpyrazole ^ -sylsulfonyD-N'-l ^ e-dimethoxypyrir'dine ^ -yD-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-difluoromethoxypyrimidin-2-yl) urea, N- (2-methoxycarbonylphenylsulforiyl) -N' - (4-ethoxy-S-methylamino-1,3 , 5-tria2in-2-yl) -urea, N- (2-mef oxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea, N- (2-Aethoxycarbonylphenylsulfonyl) -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-ylj-urea, and N- [2- (2-methoxyethoxy) -phenylsulfonyl] -N '- (4,6-dimethoxy-1,3,5-triazine 2-yl) urea. 43. Composition according to claim 1, characterized in that it is for protecting crops from the phytotoxic effect of Chloracetanilidherbiziden of formula III .- ( LR ¹² 'χ> - <(HD _oll A = · 'CO-CH ₂ Cl ^R V ° L is a C 1 -C 4 -alkylene bridge, R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl, C ₂ -C ₆ alkoxyalkyl or C ₂ -C ₅ alkylthioalkyl, and R ^{12 is} C ₁ -C ₄ -alkoxy ^ COOH, C ₁ -C ₄ -alkoxycarbonyl, -CONH ₂ , C ₁ -C ₄ -alkylcarbamoyl, di-C ₁ -C -alkylcarbamoyl, cyano, C ₁ -C ₄ -alkylcarbonyl, optionally substituted benzoyl, optionally substituted furyl, optionally substituted thienyl, optionally substituted pyrrolyl, optionally substituted pyrazolyl, optionally substituted 1,3,4-oxadiazol-2-yl, optionally substituted l, 3,4-thiadiazol-2-yl, optionally substituted 1,2,4-triazol-3-yl, optionally substituted dioxolanyl, optionally substituted dioxanyl, optionally substituted 1,3,4-triazol-2-yl or optionally substituted tetrahydrofuryl. 44. Composition according to claim 43, characterized in that the chloroacetanilides of the formula III from the group N-ethoxymethyl-N-chloroacetyl ^ ethyl-e-methylaniline, N-chloroacetyl-N-methoxymethyl ^ ö-diethylaniline, N-chloroacetyl-N- (2-methoxyethyl) -2,6-dimethylaniline, N-chloroacetyl-N- (2-n-propoxyäthyl) -2,6-dimethyl? Nilin, N-chloroacetyl-N- (2-isopropoxyäthyl) -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-methylaniline, N-chloroacetyl-N- (2-methoxy-1-methylethyl) -2,6-dimethylaniline, N-chloroacetyl-N - ^ - methoxy-i-methyläthyO ^^ diethylaniline, N-chloroacetyl-N- (2-methoxy-1-m8thyläthyl) -2-äthy! -6-methylaniline, N- (2-ethoxyethyl) -N-chloroacetyl-2 _/ 6-diethylaniline, N-chloroacetyl-N- (2-n-propoxyethyl) -2-ethyl-6-methylaniline, N-chloroacetyl-N- (2-n -propoxyethyl) -2,6-diethylaniline, N-chloroacetyl-N- (2-isopropoxyethyl) -2-ethyl-6-methylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-G-dimethylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl je-diethylaniline, N-chloroacetyl-N-methoxycarbonylmethyl ^^ - dimethylaniline, N-chloroacetyl-N- (2,2-diethoxyethyl) -2,6-dimethylaniline, N-chloroacetyl-N, N -methoxy-1-methylethyl J -dimethylaniline, N- (2-ethoxyethyl) -N-chloroacetyl-2-methylaniline, N-chloroacetyl-N- (2-methoxyethyl) -2-methylaniline, N- Chloroacetyl-N- (2-methoxy-2-methylethyl) -2 _/ 6-dimethylaniline, N- (2-ethoxy-2-methylethyl) -N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl N, N-ethyl-i-methoxyethyl, N-chloroacetyl-N- (2-methoxyethyl) -2-methoxy-6-methylaniline, Nn-butoxymethyl-N-chloroacetyl-tert-butylaniline, N- 2-ethoxyethyl-2-methylethyl) -2,6-dimethylaniline, M-chloroacetyl-N-1-methoxyethyl-1-chloro-B-methylaniline, N- (2-ethoxyethyl) -N-chloroacetyl-2-chloro-6-methylaniline . N, 1-Aethoxyethyl-N-chloroacetyl, ω-e-trtimethylaniline, N-chloroacetyl-1- (2-methoxyethyl) -2,3,6-trimethylaniline, N-chloroacetyl-N-cyanomethyl, ↑ B-dimethylaniline, N Chloroacetyl-N- (1,3-dioxolan-2-ylmethyl) -2,6-d ^! Tiethylanilin, N-chloroacetyl-N-ii.a-dioxolane ^ ^ -ylmethyD ethyl-e-methylaniline, N-chloroacetyl-N-ii.S-dioxane ^ ^ -ylmethylj ethyl-e-methylaniline, N-chloroacetyl-N ^ ^ -furylmethylj .e-dimethyl aniline, N-chloroacetyl-N 1 -furylmethyD 1 -ethyl-e-methylaniline, N-chloroacetyl-N- (2-tetrahydrofurylmethyl) -2,6-dimethylaniline, N-chloroacetyl-N-N, N-dimethylcarbamoylmethyl, 1-dimethylaniline, N-in-ButoxymethyD-N-chloroacetyl ^^ - diethylaniline, N, - n -butoxyethyl-N-chloroacetyl-.e-diethylaniline, N-chloroacetyl-N- {2-methoxy-1,2-dimethylethyl) -2,6-dimethylaniline, N-chloroacetyl-N-isopropyl; -dimethylaniline, N-chloroacetyl-N-isopropyl-1-chloroaniline, N-chloroacetyl-N-dH-pyrazol-1-yl-methoxy-N-dimethylaniline, N-chloroacetyl-N-d-pyrazol-1-ylmethyl-ethyl-B -methylanilin, N-chloroacetyl-N-ilH-I ^ atriazoi-i-ylmethyD ^ e-dimethylaniline, N-chloroacetyl-N-dH-i ^^ -triazol-i-ylmethyD ^ e-diethylaniline, N-benzoylmethyl-N-chloroacetyl ^ .e-diethylaniline, N-benzoylmethyl-N-chloroacetyl-ethyl-S-methylaniline, N-chloroacetyl-N-iB-methyl-1-SA-oxadiazole ^ -yD-ethyl-e-methylaniline, N-chloroacetyl-N-is-methyl-1-aoxadiazol-cy-D-tert-butylaniline, N-chloroacetyl -N1-chlorobenzoylmethyl-1-.-Dimethylaniline and N-chloroacetyl-Nd-methyl-B-methylthio-1-SA-triazole-1-methyl-methyl-1-diethylaniline. 45. A composition according to claim 1, characterized in that it is for protecting crops from the phytotoxic effect of Aryloxyphenoxypropionsäureherbiziden of formula IV ^ CO-T _{(| V)} Q for the rest K ^{11 R} "\ AA undTfür -NR ¹⁸ R ¹⁶ , -N (CN) R ¹⁷ , -OR ¹⁸ , SR ¹⁸ or -O-N = CR ¹⁹ R ²⁰ , where R ^{13 is} halogen or trifluoromethyl, R ^{14 is} hydrogen or halogen, R ¹⁵ and R ¹⁶ independently of one another hydrogen, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkyl, phenyl or benzyl, R ¹⁵ and R ¹⁶ together with the nitrogen atom carrying them, form a 5- to 6-membered saturated nitrogen heterocycle which an oxygen or sulfur atom may be interrupted, R ^{17 is} C ₁ -C -alkyl, C ₁ -C ₄ -alkenyl, C ₁ -C ₄ -alkynyl or C ₂ -C ₄ -alkoxyalkyl I, R ^{18 is} hydrogen or equivalent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary Cv-CvAlkylammonium or Cr-GrHydroxyalkylamtmonium residue; an optionally mono- or polysubstituted by amino, halogen, hydroxyl, cyano, nitro, phenyl, C 1 -C ₄ -alkoxy, polyethoxy having 2 to 6 GÄthylenoxideinheiten ^ COOR ²¹ , -COSR ²¹ , -CONH ₂ , CONtC ^ C ^ alkoxyj-C -Ci-alkyl.-CO-N-di-d-CralkyLCONH-dC ^ alkyl, -NICv-Ct-alkoxyH ^ C-alkyl or di-Cv-Gj-alkylamino substituted C ^ Cg-alkyl radical; an optionally substituted by halogen OdOrCi-C ₄ -Akoxyy Cy-Cg-alkenyl radical; a C 1 to C 4 alkynyl radical optionally substituted by halogen or CH, alkoxy; Cr-Cg-cycloalkyl; or optionally by cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, acetyl, -COOR ²¹ , COSR ²¹ -CONH ₂ , -CON (C ₁ -C ₄ -alkoxy) C ₁ -C ₄ -alkyl , -CO-N-di-C ₁ -C ₄ -alkyl or -CONH-C ₁ -C -alkyl-substituted phenyl, R ¹⁹ and R ²⁰ independently of one another are C 1 -C ₄ -alkyl or together form a 3 to 6-membered alkylene chain R ^{21 is} hydrogen, C 1 -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, C ₃ -C ₆ alkylOlYl, C ₁ -C ₆ haloalkylCyCe-alkynyl, orCgCe -haloalkynyl. 46. Composition according to claim 45, characterized in that the Aryloxyphenoxypropionsäurederivate of formula IV from the group 2- [4- (3,5-dichloropyridin-2-yloxy) phenoxy] propionate propargyl, 2- [4- (3,5-dichloropyridin-2-yloxy) -phenoxy] -thiopropionic acid propargyl ester, methyl 2- [4- (5-chloro-3-fluoropyridin-2-yloxy) -phenoxyl-propionate, 2 - butyl [4- (5-chloro-3-fluoropyridin-2-yloxy) -phenoxy] -propionate, 2- [4- (5-trifluoromethylpyridin-2-yloxy) -phenoxy] -propionic acid-butyl ester, 2- Methyl 4- (5-trifluoromethyl-pyridin-2-yloxy) -phenoxy] -propionate, ethyl 2- [4- (6-chloro-quinoxalin-2-yloxy) -phenoxy] -propionate and 2- [4- (6-chlorobenzoxazoline) 2-yloxy) -phenoxy] -propionic acid ethyl ester. 47. A composition according to claim 1, characterized in that it is for protecting crops from the phytotoxic effect of Acylcyclohexandionherbiziden of formula IX ? Ϊ wherein A is a 2-7 membered alkylene bridge, a 3-7 membered alkenylene bridge which may be mono- or polyunsaturated, η 'zero, one or two R _{22 is} C ₁ -C ₄ -alkyl or beYicyl R _{23 is} C ₁ -C ₆ -alkyl, unsubstituted or substituted by halogen, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkyl radical; Ca-Ce-cycloalkyl; Phenyl, benzyl or phenylethyl, where the phenyl ring is represented by halogen C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -haloalkoxy, Cyan or nitro may be substituted,
X 'oxygen or a residual NOR ₂₄ and
R ₂₄ C ₁ -C ₄ -alkyl, Cv-Ce-Hrlogenalkyl, C ₃ -Ce-Al keny I ₁ C ₃ -C ₆ haloalkenyl or C ₃ -C ₆ -alkynyl. 48. Composition according to claim 47, characterized in that the Acylcyclohexandionherbizide from the group 5- (1-Methylthiocyclobutan-1-yl) -2- (2,4-dichlorobenzoyl) -cyclohexane-1,3-dione, 5- (1-methylthiocyclobutan-1-yl) -2-n-butyrylcyclohexane 1,3-dione, 5- (1-methylthiocyclobutan-1-yl) -2-cyclopropylcarbonylcyclohexane-1,3-dione, 5- (1-methylthiocyclobutan-1-yl) -2- (2,3-dichlorobenzoyl ) -cyclohexane-1,3-dione, 5- (1-methylsulfonycycarbanutan-1-yl) -2-n-butyrylcyclohexane-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 and 5- (1-methylthiocyclopropan-1-yl) - 2-n-butyryl-cyclohexane-1,3-dione, 5- (1-methylthiocyclobutan-1-yl) -2- (1-ethoximino-n-butyryl) -cyclohexane-1,3-dione, 5- (1 -Methylthiocyclopropan-1-yl) -2- (1-ethoximino-n-butyryl) -cyclohexane-1,3-dione, 5- (1-methylthiocyclohexan-1-yl) -2- (1-ethoximino-n-butyryl ) -cyclohexane-1,3-dione, 5- (1-methylthiocyclobutan-1-yl) -2- (1-glyoxymino-n-butyryl) -cyclohexane-1,3-dione and 5- (1-methylthiocyclopentane-1 -yl) -2- (1-ethoximino-n-butyryl) -cyclohexane-1,3-dione, 5- (1-methylthiocyclopropa n-J-yl) -2- / 1- (trans-3-chlorallyloximino) -n-butyryl / -cyclohexane-1,3-dione, 5- (1-methylthiocyclopropane-1-yl) -2- / 1- (trans-3-chlorallyloximino) -propionyl / -r.yclohexan-1,3-dione, 5- {1-Methylthiocyclopropan-1-yl) -2- / 1- (cis-3-chloroallyloximino) -propionyl / -cyclohexane-1,3-dione and 5- (1-ethylthiocyclopropan-1-yl) -2- / 1- (trans-3-chloroallyloximino) -propionyl-cyclohexane-1,3-dione was selected. 49. Use l Sulfamoylphenylureas of the formula I according to claim 1, characterized in that they are used to protect crops against the damaging effect of sulfonylurea herbicides, Chloracetanilidenherbiziden, Acylcyclohexandionherbiziden or Aryloxyphenoxypropionsäureherbiziden. 50. Use according to claim 49, characterized in that it is in the sulfonylurea herbicides compounds of the formula II E a group 1 J ' ο- * - η G X Y R ⁴ R ⁶ R ⁸ R ⁷ R ⁸ ir the number zero or one, hydrogen or methyl, Methoxy, ethoxy, difluoromethoxy, methyl or chlorine CH or N, Methoxy, methyl, difluoromethoxy, cyclopropyl or methylamino, C ₂ -C ₆ -alkoxy, alkoxy, C 1-6 -haloalkoxy, C ₁ -C ₆ -haloalkylthio, C ₂ -C ₄ -haloalkenyl, Chlorine or Cr-Q-alkoxycarbonyl, trifluoromethyl or DilCr-Cj-alkyOcarbamoyl, Ci-C ^ alkoxycarbonyl, C ^ C ^ alkoxycarbonyl, and C ₁ -C ₄ alkyl mean, is. 51. Use according to claim 49, characterized in that the chloroacetanilide herbicides are compounds of the formula III LR ¹ (IH) R ¹¹ CO-CH ₂ Cl JLO wherein L is a C, -C ₄ -alkylene bridge, R ⁹ , R ¹⁰ and R ¹¹ independently of one another are hydrogen, halogen, Cy-Gt-alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ - Hnlogenalkyl, C2-CB-Aikoxyalkyl or Cr-Cs-alkylthioalkyl, _un d R ^{12 is} C ₁ -C ₄ -alkoxy, -COOH, CT-C-alkoxycarbonyl, -CONH ₂ , C ₁ -C ₁ -alkylcarbamoyl, di-C ₁ -C ₄ -alkylcarbamoyl, cyano, C ₁ -d-alkylcarbonyl, optionally substituted benzoyl, optionally substituted furyl, optionally substituted thienyl, optionally substituted pyrrolyl, optionally substituted pyrazolyl, optionally substituted 1,3,4-oxadiazol-2-yl, optionally substituted 1,3,4-thiadiazol-2-yl, optionally substituted 1,2,4-triazol-3-yl, optionally substituted dioxolanyl, optionally substituted dioxanyl, optionally substituted 1,3,4-triazol-2-yl or optionally substituted tetrahydrofuryl, is. Use according to Claim 49, characterized in that the aryloxyphenoxypropionic acid herbicides are compounds of the formula IV (IV) wherein .AA ^R "\ AA I IJ - or I Il | _ undTfür -NR ¹⁸ R ¹⁶ , -N (CN) R ¹⁷ , -OR ¹⁸ , SR ¹⁸ or -O-N = CR ¹⁹ R ²⁰ , wherein R ^{13 is} halogen or trifluoromethyl, R ^{14 is} hydrogen or halogen, R ¹⁶ and R ¹⁶ independently of one another are hydrogen, C ₁ -C ₃ -alkoxy, C ₁ -C ₆ -alkyl, phenyl or benzyl, R ¹⁵ and R ¹⁶ together with the nitrogen atom carrying them, a 5- to 6-membered saturated nitrogen heterocycle which may be interrupted by an oxygen or sulfur atom, R ¹⁷ is C, -C ₄ -alkyl, Qr-C-alkenyl, C ^ Cy-AIkinyl or C ₂ -C ₄ alkoxyalkyl, R ^{18 is} hydrogen or equivalent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary CT-Cy-alkylammonium or C ^ d-hydroxyalkylammonium radical; an optionally mono- or polysubstituted by amino, halogen, hydroxyl, cyano, nitro, phenyl, C ₁ -C ₄ -alkoxy, polyethoxy with 2 to 6-alkylene oxide units, -COOR ²¹ , -COSR ²¹ , -CONH ₂ , -N (C ₁ -C ₄ alkoxy) -C ₁ -C 4 alkyl or di-Cv-C ₄ alkylamino-substituted C ₁ -C ₉ -AHCyITeSt; a Cy-Cg-alkenyl radical optionally substituted by halogen or C ₁ -C ₄ -alkoxy; a is optionally substituted by halogen OdBrC ₁ -C ₄ -alkoxy C3-C9 alkynyl, C ₃ -C ₉ -Cycloaikyl; or optionally by cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, acetyl, -COOR ²¹ , COSR ²¹ , -CONH ₂ , -CON (C ₁ -C ₄ -alkoxy) -C ₁ -C ₄ alkyl, -CO-N-di-C ₁ -C ₄ alkyl or -CONH - ^ - Cj-alkyl substituted phenyl, R ¹⁹ and R ^{20 are} independently C 1 -C 4 alkyl or together form a 3 to 6 membered alkylene chain and R ^{21 is} hydrogen, C ₁ -C ₆ -alkyl, d-Ce-haloalkyl, C ₁ -C ₆ -alkoxyalkyl, C ₃ -C ₆ -alkylene I, Cs-Ce-haloalkyl-Cs-Ce-alkynyl or Cj-Ce-haloalkynyl. 53. Use according to claim 48, characterized in that it is in the Aceycyclohexandionherbiziden compounds of formula IX fl if ¹ • · i ^{/ s} : ^{/ N} R2 3 (ix) where A is a 2-7g! lower alkylene bridge, a 3 ~ 7-membered alkenylene bridge which may be mono- or polyunsaturated, n 'zero, one or two R ₂₂ C ₁ -C ₄ -AlkYlOdOrBOnZyI R _{23 is} C ₁ -C ₆ -alkyl, unsubstituted or substituted by halogen, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkyl radical; C ₃ -C ₆ -cycloalkyl; Phenyl, benzyl or phenylethyl, where the phenyl ring is substituted by halogen C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylamino, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, cyano or nitro be! X 'oxygen or a residue NOR ₂₄ and Mean C ₆ alkenyl, C ₃ -C ₆ haloalkenyl or C ₃ -C ₆ -AIkJnYl - R ₂₄ C ₁ -C ₆ -alkyl, Cv-Ce-haloalkyl, C3. 54. A method for the selective control of weeds in crops, characterized in that the crops or their acreage with both a Sulfonyiharnstoffherbizid, a Acylcyclohexandionherbizid, a Chloracetanilidh6rbizid or Aryloxyphenoxypropionsäureherbizid and an effective amount of an N-Aoylsulfamoylphenylharnstoffes of formula I according to claim 1 as Treated antidote. 55. N-Acylsulfamoylphenylureas of the formula I SO ₂ -NlI-CO-A wherein Afor a rest of the group s. If W R -If W-odor • · R ¹ and R ² independently of one another represent hydrogen, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkyl, ) Or by Ci-Ci, -alkoxy or substituted Ci-Cc, -alkyl, odor R ¹ and R ² together represent a C ₄ -C ₆ alkylene or by oxygen, sulfur, SO, SO2, NH odor-N (C ₁ -C ₄ -alkyl) -unterbrochene C ₄ -C ₆ alkylene, R ^{3 is} hydrogen or C ₁ -C ₄ -alkyl, R ^a and R ^b independently of one another are hydrogen, halogen, cyano, nitro, trifluoromethyl, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C -alkylsulfinyl, C ₂ -C ₄ -alkylsulfonyl, -COOR ', -CONR ^k R ^m , -COR ", -SO ₂ NR ^k R ^m OdOr-OSO ₂ -C ₁ -C ₄ -AlkYl, or R ^a and R ^b together represent a C ₃ -C ₄ -Alkyienbrücke represented by halogen or C ₁ -C ₄ Alkyl, or a C ₃ -C ₄ alkenylene bridge which may be substituted by halogen or C ₃ -C ₄ alkyl, or a C ₄ alkadienylene bridge substituted by halogen or C ₁ -C ₄ alkyl and R ⁹ and R ^{h are} independently hydrogen, halogen, C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, methylthio or -COOR ', wherein R ° is hydrogen, halogen, C ₁ -C ₄ -alkyl or methoxy, R ^{d is} hydrogen, halogen, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylmethylene, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, -COOR ¹ or -CRR ¹ " ¹ , R ^{e is} hydrogen, halogen, C ₁ -C ₄ alkyl, -COOR ¹ , trifluoromethyl or methoxy, or R ^d and R ° together for a Cr-Gj-alkylene bridge, R ^{f is} hydrogen, halogen is OdBrC ₁ -C ₄ -alkyl, R ^x and R ^y independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, -COOR ⁴ , trifluoromethyl, nitro or cyano, R ', R ^k and R ^m independently of one another denote hydrogen or C ₁ -C ₄ -alkyl, R ^k and R ^m together denote θϊηβ C ₄ -C ₆ -alkylene bridge or an interrupted by oxygen, NH or -N (C ₁ -C ₄ alkyl) Cs-Ce-alkylene bridge, and R "Ci-C ₄ alkyl, phenyl or by halogen, C ₁ -C ₄ alkyl, methoxy, nitro or trifluoromethyl substituted phenyl. 56. Compounds of the formula I according to claim 55, characterized in that A is a radical from the group .1. ,f. R ^e -U HI-odor R- ^e -II · W- , V v R ¹ and R ² independently of one another are hydrogen, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₃ -C ₆ -alkenyl, cy-Ce-alkynyl, R ^X * - · p ~ · ^ W 'or by C ₁ -Ci ₁ -alkoxy or - • ^ · substituted Ci-Cu-alkyl, or R ¹ and R ² together represent a Gj-Ce-alkylene bridge or an interrupted by oxygen, sulfur, SO, SO 2, NH OdOr-N (C ₁ -C ₄ -AIkYl) - interrupted Gj-Ce-alkylene bridge, R ^{3 is} hydrogen or C 1 -C ₄ -alkyl, R ^a and R ^b independently of one another represent hydrogen, halogen, cyano, nitro, trifluoromethyl, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -alkyl Alkylsulfonyl, -COOR ', -CONR ¹¹ R " ¹ , -COR ⁿ , -SO ₂ NR ^k R ^m or -OSOz-C ^^ alkyl, and R ⁰ and R ^h independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl, trifluoromethyl, methoxy, methylthio or -COOR ¹ , where R ^{c is} hydrogen, halogen, C ₁ -C ₄ -alkyl or methoxy, R ^{d is} hydrogen, halogen, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C -alkylsulfinyl, C 1 -C 4 -alkylsulfonyl, -COOR 'or -CONR ^k R ^m , R ^{e is} hydrogen, halogen, C ₁ -C ₄ -alkyl- _1- COOR ', trifluoromethyl or methoxy, or R ^d and R ° together represent a Cs-d-alkylene bridge R ^{f is} hydrogen, halogen or C ₁ -C ₄ -alkyl, R * and R ^v independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, -COOR ⁴ , trifluoromethyl, nitro or cyano, R ', R ^k and R ^{m are,} independently of one another, hydrogen or C ₁ -C ₄ -alkyl, R ^k and R ^m together denote a d-Ce-alkylene bridge or one represented by oxygen, NH 2 -O-N-N (C ₁ -C ₄ -alkyl ₎ . Alkyl) - interrupted Cj-Cß-alkylene bridge, and R "C ₁ -C ₄ alkyl, phenyl or by halogen, C ₁ -C ₄ alkyl, methoxy, nitro or trifluoromethyl-substituted phenyl. 57. Compounds according to claim 55, characterized in that R ^{b is} hydrogen. 58. Compounds according to claim 55, characterized in that the sulfamoyl occupies the A position on the phenyl ring. 59. Compounds according to claim 55, characterized in that R ² and R ^{3 are} hydrogen. 60. Compounds according to claim 55, characterized in that R ^{b is} hydrogen and the sulfamoyl group assumes the 4-position on the phenyl ring. 61. Compounds according to claim 55, characterized in that R ² , R ³ and R ^{b are} hydrogen and the sulfamoyl group assumes the 4-position on the phenyl ring. 62. Compounds according to claim 55, characterized in that A represents the group stands. 63. Compounds according to claim 55, characterized in that R ² , R ³ and R ^{b are} hydrogen and the sulfamoyl group occupies the 4-position on the phenyl ring. 64. Compounds according to claim 55, characterized in that they are the sub-formula I a f / NIO / *