SK162092A3 - 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

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

SOi-NH-CN— < ^from II)

I N = - <

R4 0R1

in which

R ¹ is methyl or ethyl,

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

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

R ⁴ is H or methyl, as well as their agriculturally useful salts thereof.

The invention further relates to a process for the preparation of compounds of the formula I and to their use as herbicidal compositions.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,120,691 and 4,112,405; 44,807A relates to sulfonylureas having herbicidal activity 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.

(3) and ₃

Cl o

OCH ₃

In European patent no. No. 44,807A discloses two sulfonylureas of Formula C

II cf ₃

SO? ^- NH - C - NK - C '' NN = <

(C)

OR in which it represents a methyl or ethyl group, with an allyloxy group arranged in the ortho position.

In European patent no. No. 48,808A discloses two sulfonylureas of Formula D

CFj o- (ch ₂ ) ₂ -ci _o / 1 II N '<

— - SOo-NH — C — NH— (' ^X Z \ ^ / n = - (

OCH 3 (D) wherein

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

In European patent no. 48 143A discloses two N-methylated sulfonylureas of the formula E au

QSO2-CH3 0 CF ₃

II N- (

SO 2 -NH-CN-? ^Z from IN = - (CH ₃ OCH 3 (E) in which

Z is CH or N, without further characterization.

European Patent. 388,873A includes a benzoic acid ester of formula F

CO ₂ R _n << ^cf 3 so ₂ -nh — C-NH- < ^z || N = <

OR (F) in which

R is methyl or ethyl.

U.S. Pat. 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 <- <II N - <

\ _ / - SO2-NH-C-NH ^</ _ N ^x (G) "-" N (

OCH ₃

CF ₃ CH ₃ 0 / - <II n H cy-SO2-NH-C-NH <Yj ^of

N— (and ₃ (H)

The compound of formula G is known as chlorosulfone (Glean ^R ).

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 herbicide group and are particularly 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 the general formula (I) have already been defined.

In formula (I), a (C 1 -C 3) alkylsulfonyl group is methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, and halogen is fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine. Benzenesulfonamides are particularly preferred, wherein R ² is chlorine.

The sulfonylureas of the formula I according to the invention are available in various ways as described in the literature. By way of example, the particular 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.

R 3 r2

CF 5 -SO ₂ NCO +

ORl (ΐη m)

R 3 R ² B = SO ₂ -NH-C (IV)

II o

(III)

CF ₃ 'NN— (

ORL

R3 R2

V ^- V 5 O 2 -NH-C-NH-C, ^CF 3

yl

ORL

R 3 R ² o cf ₃

II N- <

yl

C: ^ Z ^ -SO ₂ NH ₂ + <QOC-NH- <Y 1 ^N OR 1 (V)

R3 R2

O: SO ₂ NH ₂ + (V) (VI), ^CFJ N - (

ONC-Y1-J N-X

OR1 (VII) (I)

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

Of a 2-amino-1,3,5-triazine derivative of the general formula III at a temperature ranging from 0 to 120 ° C, preferably from 10 to 100 ° C. The reaction can be carried out under normal pressure or under pressure (up to 5 MPa), preferably at a pressure of 100 to 500 kPa, in a continuous or discontinuous manner.

An inert solvent or diluent is expediently 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 -dichlorethylene, chlorobenzene fluorobenzene, bromobenzene, iodobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorotoluene, m-dichlorotoluene, 1,2-dichlorotoluene or p-dichlorotoluene; 4-trichlorobenzene, ethers, for example, ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenethol, cyclohexylmethyl ether, diethyl ether, dimethyl ether, ethylene glycol, dioxane, ethylene glycol, . n-dichlorodiethyl ether, nitrated hydrocarbons such as nitromethane, nitroethane, nitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene or o-nitrotoluene, nitriles such as acetonitrile, butyronitrile, isobutyronitrile, cyclonitrile or m-chlorobenzonitrile, such as heptane, pinane, nonane, o-cymol, m-cymol, p-cymol, gasoline fractions boiling from 70 to 190 ° C, cyclohexane, methylcyclohexane, 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 precipitates. Suitably the solvent is 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 the formula).

III). 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, it is expedient to carry out the process for preparing the novel compounds by introducing the compound of the formula II, optionally in one of the diluents mentioned above, and then adding the compound of the formula III.

After the components have been added, 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 an amount of 0.01 to 1 mol per mole 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 by direct 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-immiscible solvent and a wash as described. The desired final compound is thereby precipitated in pure form, or it can be 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. Bases such as a tertiary amine can be added to accelerate the reaction and improve product quality.

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

From the reaction mixture, the final compound of formula (I) can be obtained in the usual manner as described above under A.

C: The sulfonamide of 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 approximate stoichiometric amount of the phenylcarbamate of formula VI at a temperature of from 0 to 120 ° C, preferably at 20 to 100 “C. The reaction may be carried out under 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 used as solvents or diluents! substances listed under A.

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 complete the reaction, stirring is continued for 20 minutes to 24 hours at 0 to 120 ° C, preferably at 10 to 100 ° C, especially at 20 to 80 ° C, after addition of the components.

The sulfonylureas of the 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 approximate stoichiometric amount of the isocyanate of formula VII at a temperature of from 0 to 150 ° C, preferably at a temperature of from 10 to 100 ° C. ° C The reactions can 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 case, 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-colllidine, in an amount of from 0.01 to 1 mol 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, and then a compound of formula (V) may be added. However, a sulfonamide may also be introduced and then the isocyanate of formula (VII) may be added.

Stirring is continued for 20 minutes to 24 hours at 0 to 120 ° C, preferably at 10 to 100 ° C, especially at 20 to 80 ° C, after addition of the components to complete the reaction.

The end product of formula (I) can be recovered 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 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.

The isocyanates of formula VII are obtained from amines of formula III by treatment with oxalyl chloride or phosgene (in an analogous manner 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 chloride with ammonia (Houben-Weyl, Metoden der organischen Chemie, vol. 9, 605 (1955)). Sulfonic acid chlorides are obtained either by the Meerwein reaction (diazotization of the appropriate amine and the copper salt catalyzed sulfochlorination) or by the chlorosulfonation of the appropriate 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 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.

Suitable solvents include, for example, 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 formula I or herbicidal compositions containing them, as well as environmentally compatible alkali and alkaline earth metal salts of these compounds, can very well control harmful plants in crops such as wheat, rice and corn without would damage the crop plants, the effect occurring especially also in the 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, oily dispersions, pastes, dusts, dusts, dusts, powders, dusts, dusts. 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 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, medium high 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 strong 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 may be homogenized by means of wetting agents, adhesives, dispersing agents or emulsifying agents in water. However, these compositions may also be prepared from a concentrate consisting of an active ingredient, a wetting agent, an adhesive, a dispersing agent or an emulsifying agent and optionally a solvent or an 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 and sulfates. as well as the sulfated hexadecanol, heptadecanol and octadecanol salts, as well as the sulfonated glycol ethers of aliphatic alcohols, the condensation products of sulfonated naphthalene and its derivatives with formaldehyde, the condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyphenol etol , tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of ethylene oxide with aliphatic alcohols, ethoxylated 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 nut 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 agents include:

I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone to form a solution suitable for use in the form of minimum drops.

II. 20 parts by weight of compound no. 1 is dissolved in a mixture consisting of 80 parts by weight of xylene, 8 parts by weight of ethylene oxide addition product and 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of dodecylbenzenesulfonic acid calcium salt and 5 parts by weight of ethylene oxide addition product 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 no. 1 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the addition product 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 no. 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of 210 DEG-280 DEG 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 no. 1 is well mixed with 3 parts by weight of sodium diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of sodium ligninsulfonic acid from sulphite waste liquors and 60 parts by weight of powdered silica gel, and the resulting mixture is ground well on a hammer mill. By finely distributing the 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 is mixed with 97 parts by weight of finely divided kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

VII. 30 parts by weight of compound no. 1 is mixed thoroughly with 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 part was thoroughly mixed with 92 parts by weight of calcium salt of 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 carried out by treatment before or after emergence. If the active ingredients are less tolerant to certain crop plants, application techniques may be used in which the herbicidal composition is sprayed by spraying so that the leaves of the susceptible crop plants are affected as little as possible, while the active ingredients ulpxvajx on the leaves of undesirable plants growing under crop plants or on the post-directed, lay-by method.

The amount of active ingredient to be applied will depend 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 ingredient per hectare, preferably from 0.01 to 0.5 kg of active ingredient per hectare.

In view of the versatility of the application methods, the compounds of the invention or compositions containing such compounds can be used in a large number of crop plants to remove undesirable plants. The following cultures are suitable, for example:

Botanical name of the Czech name

Allium cepa onions Pineapple comosus pineapple Arachis hypogaea peanuts 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 Turin Brassica rapa var. silvestris Repic Camellia sinensis tea Carthamus tinctorius safflower Citrus limon lemon Citrus sinensis orange Coffea arabica coffee (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 Hordeum vulgare barley Humulus lupulus hops

Botanical name Czech name

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

Botanical name

Czech name

Triticum durum Vicia faba Vitis vinifera Zea mays

In order to broaden the spectrum of activity and to 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 representatives of other groups of herbicidal active substances or plant growth regulators. Suitable substances for the mixture 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-dione derivatives, quinolinecarboxylic acid derivatives, phenoxyphenylpropionic acid and heteroaryloxyphenylpropionic acid, as well as their salts, esters and amides, and also other compounds.

In addition, it may be useful that the compounds of formula I, alone or in combination with other herbicidal compositions, be used in admixture with other plant protection agents, for example with agents for controlling pests or phytopathogenic fungi and bacteria. Also of interest is 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 synthesis of compounds of formula I is described below.

Example 1

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

Cl o cf ₃ r - <II 'N - <

(T-SO3-NH-C-NH-) ( ^z 'N n = k

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 is 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 by volume 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

Sodium [2-chloro-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 introduced into contact with 0.66 g (3.6 mmol) of a 30% solution of sodium methoxide in methanol at 25 ° C. The resulting homogeneous solution is stirred at 25 ° C for one hour. Evaporation of the volatiles was carried out at 60 ° C under water pump vacuum to give the title compound in quantitative yield. This compound decomposes at 220-224 ° C.

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

Table 1 ' ³ f, _ν Λ ³

--SO2 --NH - C - NH-- (n

R 3,

6

ORL

Effective R?

R

R ³ Melting point (° C)

1 ^CH 3 Cl H 166-168 2 ^CH 3 0 (CH) ₃ 0CH H 108-110 3 ^CH 3 H 164-169 4 ch ₃ Cl H 220-224 (decomposition) Na-sal 5 ^CH 3 O (CH ₂ ) ₂ OCH ₃ H 119 (decomposition) Na-sal 6 ^CH 3 O (CH ₂ ) ₂ OCH ₃ H 139 (decomposition) Ca-sal 7 ^CH 3 ^CF 3 H 165 (decomposition) Na-sal 8 ^CH 3 Cl 6-C1 168 9 ch ₃ Cl H 160-163 (decomposition) Ca-sal 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 ^CH 3 0 H 16 ch ₃ F H > 220 (decomposition) Na-sal 17 ch ₃ F H > 220 (decomposition) K-salt 18 ^CH 3 F H > 220 (decomposition) Ca-sal 19 ch ₃ F 6-F 177-180 20 ^CH 3 F 6-F 180-220 (decomposition) Na-sal 21 ch ₃ F 6-F > 220 (decomposition) K-salt 22 ch ₃ F 6-F 155-159 (decomposition) Ca-sal

- continued

R ¹ R ² R ³ Melting point (° C) ^C 2 ^H 5 Cl 3-Cl 155-157 CH, Cl 3-Cl 175-177 ^C 2 ^H 5 Cl 3-Cl 197-200 (decomposition) Na-sal CH, Cl 3-Cl 198-201 (decomposition) Na-sal CH, Cl _5-CH3 175-178 (decomposition) Na-sal CH Cl _6-CH3 180-183 K-Sal ch ₃ Sat ₉ ch _x H 175-177 ch ₃ Sat ₉ ch _x H 186-188 Na-sal ch ₃ Cl 3-Cl > 220 (decomposition) K-salt ^C 2 ^H 5 Sat ₂ ch ₃ H 164-155 ^C 2 ^H 5 Cl H 149-151 ch ₃ CF _{3 6-CH3} 149-150 CH, ch _{3 6-CH3} 200 (decomposition) Na-sal CH * ^CF J H 211 (decomposition) Ca-sal CH ₃ ^SO 2 ^C 2 ^H 5 H 152-155 ^CH 3 S0 _? -nC ₃ H ₇ H 181-182 ch ₃ ^SO 2 iC ₃ ^H 7 H 173-177 br H CH 183 (decomposition) Na-sal s0 ₂ c ₂ h 5 ^H CH ₃ 173 (decomposition) Na-sal

SO ₂ -nC ₃ H ₇

H ch ₃ 180 (Decomposition) To SAL SO ^ i-C ^ H ch ₃ 196 (Decomposition) To SAL

Table 2

R 3 R 2 o CF 1 <II N - <

<* y — SO2-NH-C-N— <'

I N = {

R ² * OR1

Active substance no.

Melting point (° C)

2.1

2.2

CF.

CHCH.

CH.

CH.

ch '

135-137

99-105

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

R3 cl

CF 2 - (II N - (γ-SO 2 -NH-C-NH 4)

Ν'ττζ

OCH · 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

R3 CI

About CF ₃

II N - (i - NH - C - NH - ( ^z 'N)

OC ₂ H ₅ or its sodium salts, wherein R 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 cf θ CF ₃

II N - (Sat ₂ -nh-c-nh - C Yl n = 4

OCH or their sodium salts, wherein R 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

SO 2 -NH-C-NH-phi

OC 2H5 or their sodium salts, wherein R 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 the general formulas

R ³ o (ch ₅ ) ₅ -och. Cf ₃

II N— (

OCH ₃

II N = - (

OC2H5 or its sodium salt, wherein R 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 the formulas

R 3 SO. ₂ -CH ₃ CF ₃

N - ( ^J < 7 &gt; -SO2-NH-C-NH- ( ^from Ti

II N— <

o och ₃

R 3 SO ₂ -CH ₃ CF ₃ ? 7-SO 2 "NH-c-NH" ( ^from Tl

II N— (

The OC2H5 or sodium salts thereof, wherein ^Rj has the following meaning:

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 the formulas

R 3 SO 2 -C 2 H 5 '- (N - (

C 7 - so 2-nh-c-nh - Ti, cf ₃ n = - <

och ₃

R3 SO2-C2H5 CF _{3 '} - <N- (77 - so 2-nh-c-nh - < ^from Ti II N = <

OC2H5, -Ϊ or their sodium salts, wherein R has the following meanings:

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

4-ethoxy, hydrogen, 3-methyl, 4-methyl, 5-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

R 3 = SO ₂ - ⁿ - ^c 3 ^H 7 nH ^{CF 3}

C y-SO 2 -NH-C-NH 3 -

O OCH 3

R 3 SO 2 - n - C 3 H 7 CF 3

X y-SO2-NH-C-NH ^<z '' N II N = <

O O2H5 or its sodium salt, 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, and compounds of formula

R 3 SO 2 - C 3 H 7 _n - ( ^{CF 3}

X> -SO 2 -NH-C-NH— ( ^z Ή || N = <

OCH 3

R3 SO2- ^C1 -C3H7 n - < ^CF3E5O , -NH-C-NH — f Ή II N = <

2H5 0 or the sodium salts thereof, wherein ^Rj has the following meaning:

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,

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 growing 300 cm ³ flowers, filled with sand mixed with clay, containing approximately 3.0% of humus as a substrate, are used as culture 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 shredded germs and planted in experimental containers one day prior to treatment.

The plants to be tested are treated, depending on the form of growth, at a height of from 3 to 15 cm with the active substances suspended or emulsified in water, which is a substance which enables the active substance to be distributed. The spraying is carried out with a nozzle for finely distributing the particles. 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 thermophilic species preferred for a warmer range (20 to 35 ° C) and for other mild climatic conditions with a temperature of 10 to 20 ° C. The trial period lasts 2 to 4 weeks. During this time, the plants are grown and their response to the individual treatments evaluated.

It is scored on a scale of 0 to 100. 100 means that there is no increase 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 Gallium aparine Stellaria media Triticum aestivum Zea mays amaranth bent goosefoot chrysantema moths chickweed grass chickweed spring corn

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

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

Cl il N - < ^{CF 3} - - SO 2 -NH-C-NH - <^ 3 /

OCH ₃ (B) known from U.S. Pat. 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 active ingredient per hectare in a greenhouse

Tested plant Damage (%)

Amount used (kg / ha a.s.)

The compound of e.g. 1 Compound B

0.06 0.03 0.06 0.03 Amaranthus retroflexus 100 100 0 0 Gallium aparine 95 90 0 0 Chenopodium album 90 90 0 0

In Tables 2 and 3, the compounds of Example 1 or 3 of the present invention are compared with the comparative compounds of formulas G and H

Cl 0 CH ₃ / - (|| N - (\ _ / - SO ₂ -nh-c-nh— < ^z _

OCH 3

CF ₃ 0 ch ₃

II N- <

( ^z y-SO 2 “NH — C — NH— ( ^z Ή ' ^v -' N— (

OCH ₃

CG) (H), which are known from U.S. Pat. 4,127,405.

The results of the experiment show a surprisingly high selectivity.

The known compounds cause unacceptable damage to 85 or% of the corn culture. In contrast, the compounds of Examples 3 and 3 have a comparable good to better herbicidal effect with only 10% damage to the 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 of active substance per hectare in a greenhouse

Tested plant Damage (%)

The compound of e.g. 1 Compound G

Zea mays 10 85 unwanted plants: Amaranthus retroflexus 90 90 Gallium aparine 80 74 Table 3 Comparison of herbicidal effect compounds from of Example 3 is

comparative compound of formula H for 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.)

The compound of e.g. 3 Compound H 0.06 0.03 0.06 0.03 Zea mays 10 10 70 70 unwanted plants: Amaranthus retroflexus 90 90 90 90 Gallium aparine 95 60 10 0 Chenopodium album 98 98 98 98 Sinapsis alba 95 90 90 90

Excellent selectivities in sensitive cultures, exemplified by rice, spring wheat and maize, are achieved with compound no. 7 according to the present invention, as shown by the results summarized in Tables 4 and 5 below.

Table 4

Suppression of undesirable broadleaf plants, while being compatible with, for example, the crop plants of common spring wheat and maize for postemergence application of compound no. 7 at a dose of 0.015 kg of active ingredient per hectare in the greenhouse

Tested plant Damage (%)

Triticum aestivum 10 Zea mays 15 unwanted plants:

Amaranthus retroflexus 90 Chenopodium album 75 Stellaria Media 100

Table 5

Suppression of undesirable broadleaf plants, while being tolerated for rice as an exemplary crop plant by post-emergence application of compound no. 7 at a dose of 0.015 kg of active ingredient per hectare in the greenhouse

Tested plant

Damage (%)

Oryza sativa 10 undesirable plants:

Amaranthus retroflexus 95 Sinapsis alba 70 Stellaria media 100

In a further 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 1. 7 with the sodium salt of the comparative compound of formula H when applied post-emergence 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.)

The compound of e.g. 7 Sodium salt

0.06 0.03 of compound H 0.06 about, Zea mays 10 0 100 100 unwanted plants: Amaranthus retroflexus 100 100 90 90 Gallium aparine 98 98 70 60 Chenopodium album 100 100 100 100

The selectivity results of the compounds according to the experiment clearly demonstrate the surprisingly high present excellent herbicidal effect of the invention.

? ν 16ίϋ -w

Claims (8)

PATENT CLAIMS 1. N - / (1,3,5-Triazin-2-yl) aminocarbonyl / benzenesulfonamides of formula I tl · 0 CF II N— < SO2-NH-CN- < ^from Y1 IN = < Fwd) R4 OR1 in which R ¹ is methyl or ethyl, R is halogen, C 1 -C 3 alkylsulfonyl, trifluoromethyl or 2-methoxyethoxy; and R ³ is H, methyl, ethyl, methoxy, ethoxy, fluorine or chlorine and R ⁴ represents a hydrogen atom or a methyl group, the same as their agriculturally useful salts. 2. N - / (1,3,5-triazin-2-yl) aminocarbonyl / benzenesulfonamide of the formula I according to claim 1, wherein R ² is chlorine or trifluoromethyl. 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 sulfonyl isocyanate of the formula II is present. R 3 R 2 SO ₂ NCO (II) wherein R ² and R ^{3 have the} meanings set forth in claim 1, ¹⁶ in a known manner in an inert solvent with an approximate stoichiometric amount of a 2-amino-1,3,5-triazine derivative of the general formula III cf ₃ N- ( R * HN— ( ^from Ή (III) N = < ORl in which R ¹ and R ^{4 have the} meanings given in claim 1. 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 carbamate of formula IV is ^{R 3} / ^{R 2} wherein n 3 R and R have the meanings given in claim 1, reacted in an inert organic solvent in a known manner at a temperature of from 0 to 120 ° C with an approximate stoichiometric amount of 2-amino-1,3,5-triazine of the general formula III. 5. A process for the preparation of the N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamides of the formula I as claimed in claim 1, wherein the corresponding sulfonamide of the formula V is: R3 R2 SO ₂ NH ₂ (V) in which R ² and R ³ are as defined in claim 1, is in known manner reacted in an inert organic solvent with a phenyl carbamate of formula VI CF O-oXn-Ta '- | N < R * OR1 (VI) wherein R ¹ and R ^{4 have the} meanings given in claim 1. 6. A process for the preparation of the N - [(1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamide of formula I wherein R &lt; ⁴ &gt; is hydrogen according to claim 1, wherein the corresponding sulfonamide of formula V R 3 R ₂ with ₂ nh ₂ (V) wherein R ² and R ^{3 have the} meanings specified in claim 1 are reacted in an inert organic solvent with an isocyanate of the general formula VII in a known manner C ^p 3 N- ( OCN <Ή ^of ivilla) N = - ( ORl in which R ¹ is as defined in claim 1. A herbicidal composition comprising N - [(1,3,5-triazin-1-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, characterized in that a herbicidal effective amount of N - [(1,3,5-triazin-2-yl) aminocarbonyl / benzenesulfonamide of the formula I] is applied to the plants and / or their habitat. of claim 1 or a salt thereof.