CZ162092A3 - Herbicides - Google Patents

Abstract

N-((1,3,5-triazin-2-yl)aminocarbonyl)benzene-sulphonamides of formula (I), and their salts are new. R1 = Me or Et; R2 = halogen, 1-3C alkylsulphonyl, CF3 or MeOCH2CH2O; R3 = H, Me, Et, MeO, EtO, Cl or F.

Description

Technical field

WMKWftew iw% n

The present invention relates to N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamides of formula (I)

o cf ₃ II n— {

SC b -NH-CN- ( ^from Y 1 IN = <

R4 ORl

(Ii) in which:

R ¹ represents a methyl or ethyl group,

R ² is halogen, C 1 -C 3 alkylsulfonyl, trifluoromethyl or 2-methoxyethoxy; and

R ³ is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine or chlorine and

R ⁴ represents a hydrogen atom or a methyl group, as well as their agriculturally useful salts.

The invention further relates to a process for the preparation of the compounds of the formula I as well as to their use as herbicides.

The present state of teevhnika

U.S. Pat. Nos. 4,120,691 and 4,127,405 and European Patent No. 44,807A relate to sulfonylureas having a herbicidal action having the general formula comprising the compounds of formula I as defined above.

U.S. Pat. No. 4,120,691 discloses triazine compounds of formula A as well as pyrimidine derivatives of formula B with the structure shown below.

(AND)

II and ₃

SO 2 -NH-C-NH 4 - ^{/ N} 5 and ₃

European Patent No. 44 807A describes two sulfonylureas of formula C

7-S0 ₂ -NH-C-NH- ^</ Ή

N = - <

OR (c) wherein it is a methyl or ethyl group, with an allyloxy group arranged in the ortho position.

European Patent No. 48,808A discloses two sulfonylureas of Formula D

IN}

O- _(CH2) 2-C1 | O / - \ II N (\ - / ~ ^SQ 2 ^"-C-NH NN- / _ ^{7 'of}

OCH 3 (D) wherein

Z is CH or N, with 2-chloroethoxy as a substituent in the aromatic moiety.

European Patent No. 48,143A discloses two N-methylated sulfonylureas of Formula E

SO ₂ -CH ₃ o CF ₃ / - <II n H // \) _ 2-NH-CN- < ^{/ x} Z | N = <

CH ₃ OCH ₃ (ε) in which

Z is CH or N, without further characterization.

European Patent No. 388 873A discloses a benzoic acid ester of formula F

CO ₂ R CF ₃

N''V-SO-NH-C-NH- ^<z 'TJ ^{11 N =} <

OR represents a methyl or ethyl group.

in which

U.S. Patent No. 4,127,405 discloses sulfonylurea derivatives having a substitution of the ortho position of the phenyl ring with a chlorine atom or a trifluoromethyl group, as well as a substitution of the triazine ring with a methyl group and a methoxy group of formula G or H

Cl 0 CH ₃ / —— (|| N - {<ζ_2 — SO ₂ -NH-C-NK- (G)

0CH ₃

CF ₃ 0 ch ₃ __ / ^J ii n_ / ^J

SO 7 —NH — C — NH — NM (h) n = - <

och ₃

Compound (Glean ^R ).

of formula G is known as chlorosulfone

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION It is an object of the present invention to synthetically produce sulfonylureas which have improved properties over known representatives of this class of herbicides and, in particular, are characterized by high selectivity in sensitive cultures such as rice or corn.

In response to this task, the N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamides of formula (I) have already been defined.

In formula (I), a (C 1 -C 3) alkylsulfonyl group represents a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and a halogen atom represents a fluorine, chlorine, bromine or iodine atom, in particular a fluorine atom or η chlorine atom. Benzenesulfonamide are particularly preferred, wherein R ⁶ is chlorine.

The sulfonylureas of formula (I) of this invention are available by various methods described in the literature. By way of example, the particularly preferred methods (A to D) described below can be explained in more detail. These methods can be used analogously for compounds substituted with an N-methyl group.

AND

R3 R2

SO ₂ NCO +

CF ₃

N— (

H ₂ N— ( ^z

N— <

ORl (III)

A: The sulfonyl isocyanate of the formula II is reacted in a manner known per se (European Patent No. 162 723A) with an approximately stoichiometric amount

2-amino-1,3,5-triazine derivative of the general formula

III at a temperature ranging from 0 to 120 ° C, preferably from 100 to 100 ° C. The reaction can be carried out under normal pressure or under pressure (up to 5 MPa), preferably under pressure

100 to 500 kPa, continuous or discontinuous.

An inert solvent or diluent is conveniently used for the reaction under such conditions. Suitable solvents are, for example, halogenated hydrocarbons, in particular chlorinated hydrocarbons, for example tetrachlorethylene, 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, chlornaphthalene, dichlornaphthalene, carbon tetrachloride , 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichlorethylene, pentachloroethane, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, 1,2-dichloroethane,

1,1-dichloroethane, 1,2-cis-dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorotoluene, m-dichlorotoluene, p-dichlorotoluene or 1,2,4-trichlorobenzene, ethers such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, di-n-butyl ether, diisobutyl ether, diisopropyl ether, diisopropyl ether, anisole, phenethol, cyclohexylmethyl ether diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole or β, β'-dichlorodiethyl ether, nitrated hydrocarbons such as nitromethane, nitroethane, nitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, or nitrobenzene nitrile, nitrobenzene, nitrobenzene , isobutyronitrile, benzonitrile or m-chlorobenzonitrile, aliphatic or cycloaliphatic hydrocarbons such as heptane, pinane, nonane, o-cymol, m-cymol, p-cymol, gasoline fractions boiling from 70 to 190 ° C, cyclohexane, methylcycloh exane, decalin, petroleum ether, hexane, ligroin, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane, 2,3,3-trimethylpentane or octane, esters such as ethyl acetate, acetoacetic acid ester or isobutyl acetate, amides such as formamide, methylformamide or dimethylformamide, ketones such as acetone or methyl ethyl ketone and the corresponding mixtures. The solvent is suitably used in an amount corresponding to 100 to 2000% by weight, preferably 200 to 700% by weight, based on the starting compound of the general formula II.

The compound of formula (II) required for the reaction is generally used in an approximately equimolar amount (with an excess or a deficiency of, for example, 0 to 20%, based on the starting compound of formula (III) in each case). The starting compound of formula III can be introduced into one of the above diluents and then added to the compound of formula II.

However, the process for the preparation of the novel compounds is expediently carried out by introducing a compound of formula II, optionally in one of the diluents mentioned above, and then adding a compound of formula III.

After the addition of the components, the reaction mixture is stirred for a further 20 minutes to 24 hours at 0 to 120 ° C, preferably at 10 to 100 ° C to complete the reaction.

Tertiary amines, such as pyridine, α-picoline, β-picoline, τ-picoline, 2,4-litidine, 2,6-lutidine, 2,4,6-collidine, p-dimethylaminopyridine, can be advantageously used as reaction accelerators. , trimethylamine, triethylamine, tri- (n-propyl) amine, 1,4-diazabicyclo [2.2.2] octane (DABCO) or 1,8-diazabicyclo [5.4.0] undec-7-ene in amounts from 0.01 to 1 mol per mol of the starting compound of formula (II).

The final compound of formula (I) is isolated from the reaction mixture in a conventional manner, for example by distilling off the solvent or directly by suction. The remaining residue may be washed with water or dilute acid to remove basic impurities. However, the residue can also be dissolved in a water-insoluble solvent and a wash as described. The desired final compound is precipitated in pure form, optionally purified by recrystallization, stirring with an organic solvent to remove impurities or chromatography.

This reaction is preferably carried out in acetonitrile, methyl tert-butyl ether, toluene or methylene chloride in the presence of 0 to 100 molar equivalents, preferably 0 to 50 molar equivalents of a tertiary amine such as 1,4-diazabicyclo [2.2.2] octane or triethylamine.

B: The corresponding sulfonylcarbamate (IV) is left in a manner known per se (European Pat.

120 814A and 101 407A) are reacted with a 2-amino-1,3,5-triazine derivative of the general formula III in an inert organic solvent at a temperature ranging from 0 to 120 ° C, preferably from 10 to 100 ° C. In this case, a base such as a tertiary amine may be added to accelerate the reaction and improve the quality of the product.

Suitable bases are, for example, tertiary amines such as those mentioned under A, in particular triethylamine or 1,4-diazabicyclo [2.2.2] octane, in an amount of from 0.01 to 1 mol per mol of the starting compound of the general formula IV.

Suitably the solvents listed under A are used as the solvent.

The solvent is used in an amount of from 100 to 2000% by weight, preferably from 200 to 700% by weight, based on the starting compound of the general formula IV.

The compound of formula (IV) required for the reaction is generally used in an approximately equimolar amount (with an excess or a deficiency of, for example, 0 to 20%, based on the starting compound of formula (III) in each case). The starting compound of the formula IV can be introduced into one of the abovementioned diluents and then added to the starting compound of the formula III.

However, it is also possible to introduce the compound of formula III into one of the diluents or solvents mentioned above and then contact it with the sulfonylcarbamate of formula IV.

In both cases, a base may be added as a catalyst before or during the reaction.

From the reaction mixture, the final compound of formula (I) may be obtained by a conventional method as described above under A.

C: The sulfonamide of the formula V is reacted in a manner known per se (European Patent Nos. 141 777A and 101 670A) in an inert organic solvent with an approximately stoichiometric amount of the phenylcarbamate of the formula VI at a temperature of 0 to 120 ° C, preferably 20 to 100 ° C. The reaction may be carried out at normal or elevated pressure (up to 5 MPa), preferably at a pressure of 100 to 500 kPa, in a continuous or discontinuous manner.

A tertiary base may be added to the reaction mixture to accelerate the reaction and improve product quality. Suitable bases for this reaction are the bases listed under A, especially triethylamine, 2,4,6-collidine, 1,4-diazabicyclo [2.2.2] octane (DABCO) or 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), in an amount of from 0.01 to 1 mole per mole of the starting compound of formula V.

Suitably the substances listed under A are used as solvents or diluents.

The solvent is used in an amount of from 100 to 2000% by weight, preferably from 200 to 700% by weight, based on the starting material of the formula IV.

The compound of formula V required for the reaction is generally used in an approximately equimolar amount (with an excess or a deficiency of, for example, 0 to 20%, based on the starting compound of formula VI in each case). The starting compound of formula (VI) may be introduced into one of the abovementioned diluents and then a compound of formula (V) may be added.

However, it is also possible to present the starting compound of formula V in one of the diluents mentioned above and then to add the carbamate of formula VI. In both cases, one or more of said bases may be added as a catalyst before or during the reaction.

To stop the reaction after addition of the components is carried out with stirring for a further 20 minutes to 24 hours at a temperature of 0-120 ° C, preferably at from 10 to 100 ^e C, especially 20-80 ° C

The sulfonylureas of formula (I) are isolated from the reaction mixture by conventional methods as described under A.

D: The sulfonamide of formula V is reacted in a manner known per se (European Patent No. 234 352A) in an inert organic solvent with an approximately stoichiometric amount of the isocyanate of formula VII at a temperature of from 0 to 150 ° C, preferably from 10 to 100 ° C. 'C. The reaction may be carried out at normal or elevated pressure (up to 5 MPa), preferably at a pressure of 100 to 500 kPa, in a continuous or discontinuous manner.

In this connection, a tertiary amine may be added to the reaction mixture before or during the reaction to accelerate the reaction and improve product quality. Suitable bases for this reaction are the bases listed under A, in particular triethylamine or 2,4,6-collidine, in an amount of from 0.01 to 1 mole per mole of the starting compound of formula (V).

The solvents mentioned under A are suitably used. The solvent is used in an amount of from 100 to 2000% by weight, preferably from 200 to 700% by weight, based on the starting material of the general formula V.

The compound of formula V required for the reaction is generally used in an approximately equimolar amount (with an excess or a deficiency of, for example, 0-20% based on the starting material of formula VII). The starting compound of formula (VII) may be introduced into one of the abovementioned diluents, followed by the addition of a compound of formula (V).

Stirring is continued for 20 minutes to 24 hours at a temperature of from 0 to 24 hours after addition of the components to complete the reaction

120 ° C, preferably at a temperature of from 10 to 100 ° C, especially at 20 to 80 ° C.

The end product of formula (I) may be obtained from the reaction mixture in a conventional manner as described under A.

The sulfonyl isocyanates of the formula II required as starting compounds can be obtained in a manner known per se from the corresponding sulfonamides by phosgenation (Houben-Weyl, Metoden der organischen Chemie, Vol. 11/2, 1106 (1985)) and U.S. Pat.

379 769) or by reaction of a sulfonamide with chlorosulfonyl isocyanate (DE-OS 3 132 944).

The sulfonylcarbamates of the formula IV are prepared according to reactions which are known per se or are analogous reactions (for example, European Patent No. 120 814A).

However, the sulfonyl isocyanates of the formula II can also be converted into carbamates of the formula IV by smooth reaction with phenol in an inert solvent such as ether or dichloromethane.

The carbamates of general formula VI are available by reactions known per se (for example, European patent no.

101 670A) or are analogous reactions, but can also be prepared from the corresponding isocyanates of formula VII by reaction with phenol.

Isocyanates of formula VII are obtained from amines of formula III by treatment with oxalyl chloride or phosgene (analogous to that described in Angew. Chem. 83, 407 (1971) or in European Patent No. 388 873A).

Sulfonamides can be obtained by reacting the corresponding sulfonic acid chlorides with ammonia (Houben-Weyl, Metoden der organischen Chemie, vol. 9, 605 (1955)). Sulfonic acid chlorides are obtained either by Meerwein reaction (diazotization of the appropriate amine and copper salt catalyzed sulfochlorination) or by chlorosulfonation of a suitable aromatic compound, for example 2,5-dichlorobenzenesulfonic acid chloride, from p-dichlorobenzene (Houben-Weyl, Metoden der organischen Chemie, Vol. 9, pp. 557 et seq. (1955)).

2-Amino-4-methoxy-6-trifluoromethyl-1,3,5-triazine and 2-amino-4-ethoxy-6-trifluoromethyl-1,3,5-triazine are compounds known in the literature (Yakugaku Zasshi, 95. 499 (1975)).

Salts of the compounds of formula (I) are available in a manner known per se (European Patent No. 304,282A;

599,412A). The salts are obtained by deprotonating the corresponding sulfonylureas of the formula I in water or an inert organic solvent at temperatures from -80 to 120 ° C, preferably from 0 to 60 ° C, in the presence of a base.

Suitable bases are, for example, alkali or alkaline earth metal hydroxides, hydrides, oxides or alkoxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, sodium methoxide, sodium ethoxide and sodium tert-butoxide, sodium hydride and calcium hydride and calcium oxide.

Examples of suitable solvents are, in addition to water, alcohols such as methanol, ethanol and tert-butanol, ethers such as tetrahydrofuran and dioxane, acetonitrile, dimethylformamide, ketones such as acetone and methyl ethyl ketone, and also halogenated hydrocarbons.

The deprotonation can be carried out at normal pressure or at a pressure increased up to 5 MPa, preferably from normal pressure up to a pressure of 500 kPa.

Compounds of the formula I or herbicidal compositions containing them, as well as alkali and alkaline earth metal salts of these compounds which are environmentally compatible, can very well control harmful plants in crops such as wheat, rice and maize without would damage the crop plants, the effect also occurring also in low amounts used. The herbicidal compositions may be used by spraying, fogging, dusting, sprinkling or pickling, for example in the form of sprayable solutions, powders, suspensions, as well as high-percentage aqueous, oily or special suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, dusts or granules. The dosage forms depend on the intended use; in any case, it is intended to ensure the finest possible distribution of the active ingredient according to the invention.

The compounds of the formula I are generally suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions. Possible inert additives include, but are not limited to, moderate or high boiling mineral oil fractions, such as kerosene or diesel, coal tar oil, as well as vegetable and animal oils, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffinic substances, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strongly polar solvents such as Ν, Ν-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water dispersible granules by the addition of water. To produce emulsions, pastes or oil dispersions, the active compounds as such or dissolved in an oil or solvent can be homogenized with wetting agents, adhesives, dispersing agents or emulsifying agents in water. However, these compositions may also be prepared from a concentrate which consists of the active ingredient, wetting agent, adhesive, dispersing or emulsifying agent and optionally solvent or oil. These concentrates are suitable for dilution with water.

Suitable surfactants are the alkali salts, alkaline earth salts and ammonium salts of aromatic sulfonic acids, for example ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkylsulfonates, alkylarylsulfates, alkylsulfates, aluryl ether sulfates and sulfates of lauryl ether ethers. as well as salts of sulfated hexadecanol, heptadecanol and octadecanol, as well as salts of sulfonated glycol ethers of aliphatic alcohols, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, octylene polyphenol, polyoxyethylenoctylphenol phenol; , tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of ethylene oxide with aliphatic alcohols, ethoxilo castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitester, sulphite lignin lignin or methylcellulose.

Powder, spreading and dusting compositions can be prepared by mixing or grinding the active ingredient with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active ingredient to a solid carrier. Solid carriers are, for example, mineral clays such as silicic acid, silica gel, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate or urea; and plant products such as cereal flour, ground tree bark, wood flour and ground walnut shells, powdered cellulose and other solid carriers.

In general, the compositions contain from 0.1 to 95% by weight of active ingredient, preferably from 0.5 to 90% by weight of active ingredient.

Examples of such means are:

I. 90 parts by weight of Compound No. 1 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone to form a solution suitable for use as minimal drops.

II. 20 parts by weight of Compound (1) are dissolved in a mixture consisting of 80 parts by weight of xylene, parts by weight of the addition product of 8 to 10 moles of ethylene oxide and 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid. 40 mol of ethylene oxide and 1 mol of castor oil. Pouring this solution into water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

III. 20 parts by weight of Compound (1) are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of adduct of 7 moles of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of adduct of 40 moles of ethylene oxide and 1 mol of castor. oil, pouring this solution into water and finely distributing it in 100,000 parts by weight of water gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

IV. 20 parts by weight of Compound (1) are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling at 210 to 280 ° C and 10 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mol of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of Compound (1) are well mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulphonic acid sodium salt from sulphite waste liquors and 60 parts by weight of powdered silica gel and grind well hammer mill. By finely distributing this mixture in water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

VI. 3 parts by weight of Compound No. 1 are mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3% by weight of active ingredient.

VII. 30 parts by weight of Compound No. 1 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an effective composition with good adhesion is obtained.

VIII. 20 parts by weight of Compound No. 1 are intimately mixed with 92 parts by weight of calcium dodecylbenzenesulfonic acid, 8 parts by weight of polyglycol ether of an aliphatic alcohol, 2 parts by weight of sodium condensation product of phenol, urea and formaldehyde and 68 parts by weight of paraffinic mineral oil. A stable oil dispersion is obtained.

Application can be by treatment before or after emergence. If the active substances are less tolerant to certain crop plants, application techniques may be used in which the herbicidal composition is sprayed with a spraying device such that the leaves of the susceptible crop plants are affected as little as possible while the active substances adhere to the leaves of undesirable plants growing under crop plants or on uncovered soil (post-directed, lay-by method).

The amount of active substance to be administered depends on the type of control desired, the time of year, the plants selected for treatment and the growth stage from 0.001 to 1.0 kg of active substance per hectare, preferably from 0.01 to 0.5 kg of active substance per hectare.

In view of the versatility of the application methods, the compounds of the invention or compositions comprising such compounds can be used in a large number of crop plants to remove undesirable plants. Suitable cultures are, for example;

Botanical name Czech name

Allium cepa onion Pineapple comosus pineapple Arachis hypogaea peanut Asparagus officinalis asparagus Beta vulgaris spp. altissima beet sugar beet Beta vulgaris spp. rapa beet peanut Brassica napus var. napus oilseed rape Brassica napus var. napobrassica turnip Brassica rapa var. silvestris rape Camellia sinensis tea Carthamus tinctorius Safflower Citrus limon lemon tree Citrus sinensis pomerančovn ik Coffea arabica coffee tree (Coffea canephora) Cucumis sativus cucumber Cynodon dactylon Troskut prstitý Daucus carota carrots Elaeis guineensis oil cake Fragaria vasca strawberry Glycine max soya dead Gossypium hirsutum cotton (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) Helianthus annus sunflower Hevea brasiliensis rubber tree Hordeum vulgare barley Humulus lupulus hop

Botanical name Czech name

Ipomea batatas povíjnice Juglans regia Lens culinaris lentil Linum usitatissium only Lycopersicon lycopersicum tomato Malus spp. apple tree Manihot esculenta dagger Medicago sativa lucerne Musa spp. banana tree Nicotina tabacum tobacco Nicotina rusticana Olea europaea olive Oryza sativa rice Phaseoleus lunatus bean monthly Phaseoleus vulgaris bean Picea abies spruce Pinus spp. pine Pisum sativum garden peas Prunus avium bird cherry Prunus persica peach Pyrus communis pear Ribes sylvestre redcurrant Ribes uva-crispa gooseberry Ricinus communis cinnamon Saccharum officinarum sugarcane Secale cereale rye Solanum tuberosum potato Sorgum bicolor sorghum Sorgum vulgare Theobroma cacao cacao tree Trifolium pratense Red clover Triticum aestivum wheat

Botanical name

Czech name

Triticum durum Vicia faba Vitis vinifera Zea mays

In order to broaden the spectrum of activity and achieve a synergistic effect, the sulfonylureas substituted with the triazinyl group of the formula I can be mixed and used together with a large number of other herbicidally active or plant growth regulating groups. Suitable substances for the mixtures are, for example, diazines, 4H-1,3-benzoxazine derivatives, benzothiadiazinones, 2,6-nitroanilines,

N-phenylcarbamates, thiocarbamates, halogenated carboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dionic derivatives, quinolinecarboxylic acid derivatives, phenoxyphenylpropionic acids and heteroaryloxyphenyl esters, as well as their esters, their esters, and amides as well as other compounds.

In addition, it may be useful that the compounds of the formula I, alone or in combination with other herbicidal agents, be used in combination with other plant protection agents, for example, for controlling pests or phytopathogenic fungi and bacteria. Also of interest is the mixing with mineral acid salt solutions which are used to eliminate nutrient or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be used.

DETAILED DESCRIPTION OF THE INVENTION

The following are examples of the synthesis of compounds of Formula I.

Example 1

2-Chloro-1 - N - [(4-methoxy-6-trifluoromethyl-1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamide of the formula

Cl 0 CF ₃ / -, || N - (/ J> -SO 2 -NH-C-NH- <_

OCH ₃

A solution of 4.0 g (21 mmol) of 2-amino-4-methoxy-6-trifluoromethyl-1,3,5-triazine in 20 ml of acetonitrile was contacted with 4.5 g (21 mmol) of 2-chlorobenzenesulfonylisocyanate at a temperature of 25 'C. The solution thus obtained was stirred at 25 ° C for 21 hours. Then the solvent was evaporated under reduced pressure at 40 ° C and the solid residue was vigorously stirred for 3 hours with 1 liter of a 1: 1 mixture of diethyl ether and hexane. The product is filtered off with suction and dried under reduced pressure at 40 ° C. 6.5 g of the title compound of melting point 166 DEG-168 DEG C. are obtained. Yield 75%.

Example 2

(2-Chloro-1-N - [(4-methoxy-6-trifluoromethyl-1,3,5-triazin-2-yl) aminocarbonyl / benzenesulfonamide]]

A suspension of 1.5 g (3.6 mmol) of 2-chloro-1 N - [(4-methoxy-6-trifluoromethyl-1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamide in 10 mL of methylene chloride is treated with 0 mL. 66 g (3.6 mmol) of a 30% by weight solution of sodium methoxide in methanol at 25 DEG C. The resulting homogeneous solution was stirred at 25 DEG C. for one hour, after evaporation of the volatiles at 60 DEG C. under a water / water vacuum. Vacuum pump gives the title compound in quantitative yield, which decomposes at 220-224 ° C.

The active substances listed in Tables 1 and 2 below are prepared in an analogous manner.

Table 1

^{R2 R3} H s N / ^F3 Y-SO 3 -NH-C-NH-C ^ _ N

ORl

The active ingredient no R ^1.

Melting point (° C)

1 ^CH 3 Cl H 166-168 2 ^CH 3 O (CH ₂ ) ₂ OCH ₃ H 108-110 3 ^CH 3 ^CF 3 H 164-169 4 ^CH 3 Cl H 220-224 (decomposition) Na-salt 5 ^CH 3 O (CH ₂ ) ₂ OCH ₃ H 119 (decomposition) Na-salt 6 ^CH 3 O (CH ₂ ) ₂ OCH H 139 (decomposition) Ca-salt 7 CH_ O ^CF 3 H 165 (decomposition) Na-salt 8 ^CH 3 Cl 6-C1 168 9 ch ₃ Cl H 160-163 (decomposition) Ca-salt 10 ^CH 3 Cl H 232 (decomposition) K-salt 11 ^CH 3 Cl _6-CH3 140-144 12 ch ₃ Cl 5-C1 151-156 13 ^CH 3 F H 162-164 14 ch ₃ Br H 156-160 15 Dec ch ₃ 0 H 16 ^CH 3 F H > 220 (decomposition) Na-salt 17 ^CH 3 F H > 220 (decomposition) K-salt 18 ^CH 3 F H > 220 (decomposition) Ca salt 19 Dec ch ₃ F 6-F 177-180 20 May ^CH 3 F 6-F 180-220 (decomposition) Na-salt 21 CH, O F 6-F > 220 (decomposition) K-salt 22nd ch ₃ F 6-F 155-159 (decomposition) Ca-salt

- continued

Melting point (° C)

^C 2 ^H 5 GI 3-C1 ch ₃ Cl 3-Cl ^C 2 ^H 5 Cl 3-Cl ^CH 3 Cl 3-Cl ch ₃ Cl 6-CH ch ₃ Cl 6-CH ch ₃ SO ₂ CH ₃ H ^CH 3 SO ₂ CH ₃ H ch ₃ Cl 3-Cl ^C 2 ^H 5 SO ₂ CH ₃ H ^C 2 ^H 5 Cl H ch ₃ ^CF 3 6-CH ^CH 3 ch ₃ 6-CH ^CH 3 ^CF 3 H ^CH 3 ^SO 2 ^C 2 ^H 5 H ch ₃ SO ₂ -nC ₃ H ₇ H ^CH 3 Sat ₂ -C ₃ H ₇ H 8r H ^CH 3 ^SO 2 ^C 2 ^H 5 H ch ₃

S0 ₂ -nC ₃ K ₇

H ch ₃ Sat ₂ -C ₃ H ₇ H ch,

155-157 175-177 197-200 (decomposition) Na-salt 198-201 (decomposition) Na-salt 175-178 (rozkldd) Na-salt 180-183 K-salt 176-177 186-188 Na-salt

> 220 (decomposition) K-salt 164-155 149-151 149-150

200 (decomposition) Na-salt 211 (decomposition) Ca-salt 152-155

181-182

173-177

183 (decomposition) Na-salt 173 (decomposition) Na-salt

180 (decomposition) Na-salt

196 (decomposition) Na-salt

CF ·

Table 2

R ³ R 2 O

II n— <

^SO 2 -NH-CN-N ' N = - (r ^ ori

Active substance no

R ’

Melting point (° C)

2.1

2.2 ^CF 3 H CH ₃ CH ₃ 135-137

CH ₃ H CH ₃ CH ₃ 99-105

The following compounds of formula (I) can also be obtained in an analogous manner

R3 Cl

In cf ₃

II N— (

SO o ^- NH - C ^- NH - ( ^z 'N

OCH ₃ or sodium salts thereof, wherein R ³ has the following meanings:

hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl, 3-fluoro, 4-fluoro,

5-fluoro, 6-fluoro, 3-chloro, 4-chloro, 5-chloro, 6-chloro, 3-methoxy, 4-methoxy, 5-methoxy,

6-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy, compounds of formula

R3 Cl

About CF ₃

II N— <

2 ~ NH — C — NH— <yy N = - (

OC ₂ H ₅ or their sodium salts, where R ³ has the following meanings:

hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl,

3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl, 3-fluoro, 4-fluoro,

5-fluoro, 6-fluoro, 3-chloro, 4-chloro, 5-chloro, 6-chloro,

3-methoxy, 4-methoxy, 5-methoxy,

6-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy, compounds of formula

CF ₃

II n— (

-NH-C-NH 2 ^-

N = - (

OCH ₃ or sodium salts thereof, wherein R ³ has the following meanings:

hydrogen, 3-methyl, 4-methyl,

3-ethyl, 4-ethyl,

5-fluoro, 6-fluoro, 3-methoxy,

6-methoxy, 5-ethoxy,

5-ethyl, 6-ethyl

3-chloro, 4-chloro

4-methoxy, 3-ethoxy, -ethoxy,

5-methyl, 6-methyl, 3-fluoro, 4-fluoro, 5-chloro, 6-chloro, 5-methoxy,

4-ethoxy, compounds of formula

R3 CF ₃ CF ₃ O \ (II N <

<* γ-SO2-NH-C-NH— <Nm N = /

OC ₂ H ₅ or its sodium salts, where R ³ has the following meanings:

hydrogen, 3-methyl, 4-methyl,

3-ethyl, 4-ethyl,

5-fluoro, 6-fluoro, 3-methoxy,

6-methoxy, 5-ethoxy,

5-ethyl, 6-ethyl

3-chloro, 4-chloro

4-methoxy, 3-ethoxy, -ethoxy,

5-methyl, 6-methyl, 3-fluoro, 4-fluoro, 5-chloro, 6-chloro, 5-methoxy

4-ethoxy, compounds of the general formulas (CH 2) r -OCH 3 CF 3 E - SO _{2 -} NH - C - NH - NH x ^/ II N = - <

OCK ₃ ^R , ° ( ^CH 2) 2 ° ^ch 3 CF ₃ y - so 2-nh-c-nh - < ^from Nm II

OC2H5 or sodium salts thereof, wherein R ³ has the following meanings:

hydrogen, 3-methyl, 4-methyl, 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl

5-fluoro, 6-fluoro, 3-chloro, 4-chloro 3-methoxy, 4-methoxy

6-methoxy, 3-ethoxy, 5-ethoxy, 6-ethoxy,

5-methyl, 6-methyl, 3-fluoro, 4-fluoro, 5-chloro, 6-chloro, 5-methoxy 4-ethoxy, compounds of the general formulas

R3 SO2-CH3

V-SO2-NH-C-NH—

N = S

R3 SO5-CH3 CF3

V— <n- <

7 — Sat ₂ -nh-c-nh— ( ^z > 1 || N = - <

O OCH3 cf ₃

II

O

OC 2 ^{H 5} or sodium salts thereof, wherein R ^J has the following meanings:

hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl, 3-fluoro, 4-fluoro,

5-fluoro, 6-fluoro, 3-chloro, 4-chloro, 5-chloro, 6-chloro, 3-methoxy, 4-methoxy, 5-methoxy,

6-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy, compounds of formulas

R3 so tl ·

SO 2 - C 2 H 5 CF 3

N- <

SO 2 -NH-C-NH- ^<z 'N II N <

OCH3

R3 SO tl ·

C2H5-SO2 _CF3

N— (

SO 2 -NH-C-NH- / Tj II N = <

oc ₂ h ₅ or their sodium salts, where R ³ has the following meanings:

5-methyl, 6-methyl, 3-fluoro, 4-fluoro, 5-chloro, 6-chloro, 5-methoxy, 4-ethoxy, hydrogen, 3-methyl, 4-methyl, 3-ethyl, 4 -ethyl, 5-ethyl, 6-ethyl

5-fluoro, 6-fluoro, 3-chloro, 4-chloro 3-methoxy, 4-methoxy

6-methoxy, 3-ethoxy, 5-ethoxy, 6-ethoxy, compounds of formulas

S0 ₂ R n-C3H7 $ V-SO ₂ -NH-C-NH- (II-al ^from N = <

cf ₃ and ₃

R ³ SO ₂ —n — C ³ H 7 n __ ( ^{CF 3}

Ο-SO ₂ —NH — C — NH— < ^z Ή II N = /

OO ₂ H5 or its sodium salts, where R ³ has the following meanings:

hydrogen, 3-methyl, 4-methyl, 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl

5-fluoro, 6-fluoro, 3-chloro, 4-chloro 3-methoxy, 4-methoxy

6-methoxy, 3-ethoxy, 5-ethoxy, 6-ethoxy,

5-methyl, 6-methyl, 3-fluoro, 4-fluoro, 5-chloro, 6-chloro, 5-methoxy, 4-ethoxy, and compounds of formula

R3 S0 ₂ - i - C ₃ H ₇ CF ₃ \ z - < ^Z N - ( ^J <* y - SO 2 -NH-C-NH- < ^z 'N || _N - <o och ₃

R 3 SO ₂ -Cl ₃ H _{7 n -} ; ^CF3

ΧΑ-SO 2 -NH-C-NH- < ^z ^ N II N = <

θ2 ^Η 5 or their sodium salts, where R ³ has the following meanings:

hydrogen, 3-methyl, 4-methyl, 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl

5-fluoro, 6-fluoro, 3-chloro, 4-chloro 3-methoxy, 4-methoxy

6-methoxy, 3-ethoxy, 5-ethoxy, 6-ethoxy.

5-methyl, 6-methyl, 3-fluoro, 4-fluoro, 5-chloro, 6-chloro, 5-methoxy, 4-ethoxy,

Examples of use

The herbicidal effect of the N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamides (I) on the growth of the test plants is demonstrated by the greenhouse experiment described below.

Plastic pots for cultivation of 300 cm 3 sand filled with clay admixture containing approximately 3.0% humus as substrate are used as cultivation vessels. The seeds of the test plants are sown separately per area depending on the species.

For post-emergence treatment, either directly sown or grown plants in the same containers are selected or used first as detached loops and planted in experimental containers one day prior to treatment.

Depending on the form of growth, the plants to be tested are treated with active substances suspended or emulsified in water, which is a substance capable of distributing the active substance, at a height of from 3 to 15 cm. The spraying is carried out with a nozzle for fine particle distribution. The amount used for post-emergence treatment is 0.06 or 0.03 kg of active substance (a. S.) Per hectare.

The test vessels are placed in a greenhouse, with a warmer range (20 to 35 ° C) being preferred for thermophilic species and 10 to 20 ° C for other mild climatic conditions. The trial period lasts 2 to 4 weeks. During this time, the plants are grown and their reactions to the individual treatments evaluated.

It is graded on a scale of 0 to 100. 100 means that there is no growth or complete destruction of at least the above-ground part of the plants, and 0 indicates that there is no damage or normal growth.

The plants used in the greenhouse experiments comprise the following species.

Latin name

Czech name

Amaranthus retroflexus Chenopodium album Chrysantemum Galium aparine Stellaria media Triticum aestivum Zea mays Amaranth chrysantema

With 0.06 or 0.03 kg of active ingredient per hectare, in the post-emergence treatment method, broad-leaved unwanted plants can be very well suppressed with the compound of Example 1, while at the same time having excellent selectivity in wheat and maize crop plants.

The following table shows the results of biological experiments comparing the active compound of Example 1 with the compound of formula B

Cl cf ₃ (J> -SO 2 -NH-C-NH-

OCH ₃ (B) known from U.S. Patent No. 4,169,719.

Table 1

Comparison of the herbicidal effect of the compound of Example 1 with the comparative compound of formula B in post-emergence use at a dose of 0.06 or 0.03 kg of active substance per hectare in a greenhouse

Tested plant Damage (%)

Amount used (kg / ha a.s.)

Example 1 Compound B

0.06 0.03 0.06 0.03 Amaranthus retroflexus 100 ALIGN! 100 ALIGN! 0 0 Galium aparine 95 90 0 0 Chenopodium album 90 90 0 0

Tables 2 and 3 compare the compounds of Examples 1 or 3 according to the invention with the comparative compounds of formulas G and H

Cl o ch ₃ / - (. II N - (so 2-nh-c-nh - < ^z _ Nm and ₃ (G)

₃ 0 CH

II N— <

SO2-NH-C-NH- < ^z

N = - <

(H)

OCH ₃ which are known from U.S. Patent No. 4,127,405.

The results of the experiments clearly demonstrate a surprisingly high selectivity.

The known compounds cause unacceptable damage to 85 or 70% of the corn culture. In contrast, the compounds of Examples 1 and 3 have a comparable good to better herbicidal effect with only 10% damage to crop plants.

Table 2

Comparison of the herbicidal effect of the compound of Example 1 with the comparative compound of formula G in post-emergence use at a dose of 0.03 kg active ingredient per hectare in a greenhouse

Tested plant Damage (%)

Example 1 Compound G

Zea mays 10 85 undesirable plants: Amaranthus retroflexus 90 90 Galium aparine 80 74

Table 3

Comparison of the herbicidal effect of the compound of Example 3 with the comparative compound of formula H in post-emergence use at a dose of 0.06 or 0.03 kg active ingredient per hectare in a greenhouse

Tested plant Damage (%)

Amount used (kg / ha a.s.)

Example 3 Compound H

0.06 0.03 0.06 O, Zea mays 10 10 70 70 undesirable plants: Amaranthus retroflexus 90 90 90 90 Galium aparine 95 60 10 0 Chenopodium album 98 98 98 98 Sinapsis alba 95 90 90 90

Excellent selectivities in sensitive cultures, exemplified, rice, common wheat and maize, are achieved with Compound No. 7 of the present invention, as shown in the results summarized in Tables 4 and 5 below.

Table 4

Suppression of undesirable broadleaf plants with simultaneous tolerability for example cultivated plants of common spring and maize by post-emergence application of compound 7 at a rate of 0.015 kg of active substance per hectare in a greenhouse

Tested plant Damage (%)

Triticum aestivum 10 Zea mays 15 Dec undesirable plants: Amaranthus retroflexus 90 Chenopodium album 75 Stellaria media 100 ALIGN!

Table 5

Suppression of undesirable broadleaf plants at the same time tolerability for rice culture as exemplified by postemergence application of compound 7 at 0.015 kg of active ingredient per hectare in a greenhouse

Tested plant

Damage (%)

Oryza sativa 10 undesirable plants: Amaranthus retroflexus 95 Sinapsis alba 70 Stellaria media 100 ALIGN!

In another experiment, the sodium salt of the comparative compound of formula H is compared with the active compound of Example 7. The results are summarized in Table 6.

Table 6

Comparison of the herbicidal effect of the compound of Example 7 with the sodium salt of the comparative compound of formula H in post-emergence application at a dose of 0.06 or 0.03 kg of active substance per hectare in a greenhouse

Tested plant Damage (%)

Amount used (kg / ha a.s.)

Example 7 Sodium salt

0.06 0.03 of compound H 0.06 O, Zea mays 10 0 100 ALIGN! 100 ALIGN! undesirable plants: Amaranthus retroflexus 100 ALIGN! 100 ALIGN! 90 90 Galium aparine 98 98 70 60 Chenopodium album 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN!

The results of the experiments clearly show a surprisingly high selectivity with simultaneous excellent herbicidal activity of the compounds according to the invention.

- 37 _Λ. ,, ívátWREČEX

40α? £ ί · ³ office ¹ θ ° θ Jurigníannova ιθ

Claims (8)

PATENT CLAIMS 1. N - / (1,3,5-Triazin-2-yl) aminocarbonyl / benzenesulfonamides of the general formula I 0 CF ₃ ¹¹ SO3-NH-CN— < ^z 'n IN— ( R 4 OR 1 (I) wherein R ¹ represents a methyl or ethyl group, R ² is halogen, C 1 -C 3 alkylsulfonyl, trifluoromethyl or 2-methoxyethoxy; and O R represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a fluorine atom or a chlorine atom and R ⁴ represents a hydrogen atom or a methyl group, as well as their agriculturally useful salts. N - [(1,3,5-Triazin-2-yl) aminocarbonyl] benzenesulfonamides of the formula I according to claim 1, wherein R ² represents a chlorine atom or a trifluoromethyl group. A process for the preparation of the N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamides of the formula I according to claim 1, characterized in that the sulfonyl isocyanate of the formula II R3 R2 so ₂ nco (Π) in which R ² and R ³ have the meanings given in claim 1, is in known manner reacted in inert solvent with approximately the stoichiometric amount of 2-amino-l, 3,5-triazine derivative of the formula III CF ₃ N— ( R «HN— < ^from 'WN = < ORI (III) in which R ¹ and R ⁴ have the meanings given in claim 1. A process for the preparation of N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamides of the formula I according to claim 1, characterized in that the carbamate of the formula IV in.? SO ₂ -NH-co- (IV) wherein R ² and R ³ have the meanings given in claim 1, reacted in an inert organic solvent in a manner known per se at a temperature of from 0 to 120 ° C with an approximately stoichiometric amount of 2-amino-1,3,5-triazine of the general formula III. A process for the preparation of N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamides of formula (I) according to claim 1, characterized in that the corresponding sulfonamide of formula (V): O o R 'and ^RJ have the meanings given in claim 1, reacted in a manner known per se in an inert organic solvent with a phenylcarbamate of the general formula VI (VI) in which: R ¹ and R ⁴ have the meanings given in claim 1. in 6. A process for the preparation of the N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamides of formula (I) wherein R &lt; ⁴ &gt; is hydrogen according to claim 1, wherein the corresponding sulfonamide of formula IN R3 R2 SO 2 NH 2 (V) wherein r ² and R ³ are as defined in claim 1, is reacted in an inert organic solvent with an isocyanate of formula VII in a manner known per se CF ₃ OCN— < ^z 'N ( ^V1 0 N ³¹ / ORI in which R ¹ has the meaning indicated in claim 1. 7. A herbicidal composition comprising the N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamide of the formula I as claimed in claim 1 or a salt thereof, and a customary carrier therefor. 8. A method for controlling the growth of undesirable plants, comprising treating the plants and / or their habitat with a herbicidally effective amount of N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamide of the formula I according to claim 1. of claim 1 or a salt thereof.