PT100574B - N - {(1,3,5-TRIAZIN-2-YL) -AMINOCARBONYL} -BENZENESULFONAMIDES, PROCESS FOR THEIR PREPARATION, HERBICIDAL COMPOSITIONS CONTAINING THEM AND PROCESS TO COMBAT THE PRESENCE OF WEEDS - Google Patents

Abstract

The invention relates to N-[(1,3,5-triazin-2-yl)- aminocarbonyl]benzenesulphonamides of the general formula I <IMAGE> in which R1 denotes a methyl group or an ethyl group; R2 denotes a halogen atom, an alkylsulphonyl group with 1 to 3 carbon atoms, the trifluoromethyl group or the 2- methoxyethoxy group; R3 denotes a hydrogen atom; or one of the groups methyl, ethyl, methyl or ethoxy, or a fluorine or chlorine atom; and R4 denotes a hydrogen atom or a methyl radical; as well as the salts thereof that can be used in agriculture, the processes for the preparation thereof that are described in the claims, and the use thereof in the preparation of herbicidal compositions and in the control of weeds.

Description

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

(I) which in ir means a 1 to 3 means 2-methoxyethoxy group;

methyl group or an ethyl group;

halogen atom, an alkylsulfonyl group, a carbon atom, the trifluoromethyl group or the

R ³

R ⁴ means a hydrogen atom; or a group of methyl, ethyl, methoxy or ethoxy groups; or a fluorine or chlorine atom; and means a hydrogen atom or a methyl group;

as well as their salts usable in agriculture.

In addition, the invention relates to a process for the preparation of the compounds of formula I, as well as their use as herbicidal agents.

US patents US. 4 120 691 and

127 405 and European patent EP-A 44 807 refer to sulfonyl ureas with herbicidal effect, the general formula of which includes the compounds defined initially, of general formula I

In the US patent. 4 120 691 describes, as closer structures, the triazine A compound as well as the pyrimidine derivative B;

0CF.

II

S0 _o -NH-C-NH - (N ² ^ OCHg

THE

in European patent Br-A 44 allyloxy group two sulfonylureas Q coo. ua

i <the european sulfonylurean patent D consists of a two-way replacement

2-eloroethoxy in ectru r ·

Li

European patent n-methylated B sulfonylureas if further characterization

143 uieneionea two

SO ₂ -C! H ₀

n euiOpeia patent? —388 873 refers to you will have

of benzoic acid with the structure Ei

R = CH ₃ , C ₂ H ₅ .

U.S. Patent 4,127,405 discloses sulfonylurea derivatives with methyl substitution in the ortho position of the phenyl ring in the triazine ring.

chloromethyl or trifluor and OH ^ / OOH ^ substitution

compound G is known as the sulphone chlorine name (Glean, registered trademark).

The aim of the invention, therefore, is to synthesize sulfonylureas, which have improved properties in relation to the well-known representatives of the mentioned class of herbicide and are especially distinguished by high selectivity in sensitive crops such as rice or corn.

Corresponding to the aforementioned objective, the N - [(1,2,5-triazin-2-yl) -aminocarbonyl] “initially defined benzenesulfonamides of formula I were discovered.

In formula I, alkylsulfonyl having 1 to 3 carbon atoms means one. methylsulfonyl, propylsulfonyl or isopropylsulfonyl group; halogen represents fluorine, chlorine, bromine or iodine, especially fluorine or chlorine. Benzenesulfonamides, in which R represents chlorine, are particularly preferred.

The sulfonylureas according to the invention, of formula I, are accessible by several routes, which are described in the respective technical literature. As an example, the following (A-D) routes are particularly advantageous. with more details. Said routes can be used in a manner analogous to that of N-methyl-substituted compounds.

W

There, a sulfonyl isocyanate of formula II of its known (European patent EP-A - 162 723) with approximately the stoichiometric amount of a 2-amino-1,3,5-triazine derivative of formula III is used. a temperature of between 0 and 120 ° C, preferably between 10 and 100 ° 0. The reaction can be carried out under normal pressure or under pressure (up to 50 bar), preferably between 1 and 5 bar, continuously or intermittently.

Most advantageously, the reactions are used under the respective reaction conditions, solvent and inert diluents.

As solvents, for example, halogenated hydrocarbons, especially carbide tetrachloride, for example tetrachlorethylene, 1,1,2,2-tetraeloroethane or 1,1,1,2-te. trachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, chloronaftaline, dichloronaphthaline, carbide tetra chloride, 1,1,1-trichloroethane or 1,1,2-trichloroethane, trichlorethylene, pentachloroethane, o-difluorbenzene, m-difluorbenzene -difluorbenzene, 1,2-dichloroethane; 1,1-dichloroethane; 1,2-cis-dichloro-ethylene, chlorobenzene, fluorbenzene, bromobenzene, iodobenzene, o-dichlorobenzene, m-dichloro benzene or p-dichlorobenzene; o-dibromobenzene, p-dibromobenzene or m-dibromobenzene; o-chlorotoluene, m-chlorotoluene or p-chlorotoluene; 1,2,4-thiololobenzene; ethers, for example, ethylpropyl ether, methyl tert-butyl ether, n-butyl ethyl ether; di-m-butyl ether; diisobutyl ether; diisoanulic ether; diisopropyl ether, anisol, phenethol, cyclohexylmethyl ether; diethyl ether; ethylene glycol dimethyl ether; tetrahydrofuran, dioxane, thioanisole, ^, ^ ’- dichloro-diethyl ether;

such as nitromethane, nitroethane, nitrobenzene, o-chloronitro benzene, m-chloronitrobenzene, p-chloronitrobenzene; o-nitro-toluene; nitriles, such as acetonitrile, butyronitrile,

-} ¾ 4

isobutyronitrile, benzonitrile, m-chlorobenzonitrile; aliphatic or cycloalactic hydrocarbons, such as for example heptane, pinane, nonane, o-cimol, m-oimol, p-cimol; oil fractions included in the boiling point range between 70 ° and 190 ° C; cyclohexane, methylcyclohexane, decalin; petroleum ether, hexane, ligroin, 2,2,4-trimethyl-pentane; 2,2,3-trimethyl-pentane; 2,3,3-trimethyl-pentane; octane; esters, such as, for example ethyl acetate, acetic acid ester, isobutyl acetate; amides, for example formamide, methylformamide, dimethylformamide; oetones, for example aceto, na, methyl ethyl ketone and corresponding mixtures. Advantageously, the solvent is used in an amount of between 100 and 2,000% by weight, preferably between 200 and 700% by weight, with respect to the starting substance of formula II.

The compound of formula II, necessary for the reaction, is generally used in approximately equimolar amounts (with an excess or a deficiency of, for example, 0 to 20% in relation to the respective starting substance of formula III). The starting substance of formula III can be placed in one of the aforementioned diluents and then adding the starting substance of formula II.

More advantageously, however, the process for the preparation of the new compounds is carried out in such a way that the starting substance of formula II is placed, possibly in one of the diluents mentioned above, and then the starting substance of formula III is added. .

To complete the reaction, after adding the components, everything is further stirred for 20 minutes to 24 hours, at a temperature in the range 0 ^to 120 ° 0, preferably between 10 and 100 ° 0.

As a catalyst for the reaction, it can be used, with

-iio advantage., a tertiary amine, for example pyridine, ° <, β, γ-picoline; 2,4-luticin, 2,6-lutidine; 2,4,6-collidine, p-dimethylamino-pyridine; trim.ethylamine, triethylamine, tri (n-prozil) amine; 1,4- ^, diaza [2,2, ^ -cyclooctane [j) ABC0] or 1,8-day za-bicyclo ^ 5.4, o] -undec-7 “ene, in an amount between 0, 01 and 1 mole for each mole of the formula II starting substance.

The final substance of formula I is isolated from the reaction mixture in a conventional manner, for example after separation by distillation of the solvents or directly by suction. The residue that remains can still be washed with water or diluted acid, to remove basic impurities. However, the residue can also be dissolved in a solvent that is not miscible with water and washed as already described. In this case, the desired final substances precipitate in pure form; eventually, they can be purified by recrystallization, stirring in an organic solvent, which captures impurities or by chromatography.

Preferably, the reaction is carried out in acetonitrile, methyl tert-butyl ether, toluene or methylene chloride, in the presence of 0 to 100 molar equivalents, preferably between 0 and 5 molar equivalents of a tertiary amine, such as 1,4-diazabicyclo [2,2,2'-octane or triethylamine.

B: - A corresponding sulfonyl chart of formula IV is used in a manner known per se (euro patents, eg EP-A - 120 814, EP-A - 101 407) in an inert organic solvent, at a temperature between 0 ^o and 120 ° C, preferably between 10 ° and 100 ° 0, with a 2-amino derivative

-1.3 »5-triazine of formula III. In this case bases can be added, such as tertiary amines, by which the reaction is accelerated and the quality of the product is improved.

Suitable bases for this case are, for example, tertiary amines such as those indicated in group A above. especially triethylamine or 1,4-diazabicyclo [2,2,2] -octane, in an amount of between 0.01 and 1 mole for each molecule of the starting substance of formula IV.

Advantageously, the solvents indicated in group A above are used as a solvent.

The solvent is used in an amount comprised between 100 and 2,000% by weight, preferably between 200 and 700% by weight, with respect to the starting substance of formula IV.

The compound required for the reaction, formula 17, is generally used in approximately equal amounts. households with an excess or a shortage of, for example, 0 to 20 $ in relation to the respective starting substance of formula III, You can place the starting substance of formula IV in one of the aforementioned diluents and then add the starting substance of formula III.

However, it is also possible to place the starting substance of formula III in one of the mentioned solvents or diluents and to add the sulfonyl carbamate of formula IV.

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

From the reaction mixture, the final product of formula I can be obtained, co-venenoionally, as indicated above in group A.

0: - A sulfonamide of formula V is used in its own way. (European patents EP-A - 141 777 and 1P-A - 101 670) in an inert organic solvent, with an approximate stoichiometric amount of a phenyl carbamate of formula

VI, at a temperature comprised between 0 and 120 ° C, preferably between 20 and 100 ° C. The reaction can take place at normal pressure or under pressure (up to 50 bar), preferably under pressure between 1 and 5 bar, continuously or intermittently.

In this case, bases such as tertiary amines can be added, which accelerate the reaction and improve the quality of the product. Thus, for oa, only those indicated in group A above are indicated as appropriate bases, especially triethylamine, 2,4,6-collidine; 1,4-diazabicyclo [2,2,2j-octane [dABCcT] or 1,8-diazabiciolo- [5,4,6] -undeo-7 -eno [l) Bu], in an amount between 0.01 and 1 mole for each mole of the starting substance V.

Advantageously, those indicated in group A above are used as a solvent or diluent.

The solvent is used in an amount between 100 and 2,000% in. weight, preferably between 200 and 700% by weight, in relation to educto V.

compound of formula V required for the reaction, is generally employed in equimolar amounts, approximately mind (with an excess or a deficiency, for example ^a 0 to 20% relative àsrespeotivas starting materials of formula VI). You can place the starting substance of formula VI in one of the aforementioned diluents and then add the starting substance of formula V.

However, the starting substance of formula V can also be placed in one of the aforementioned solvents and then added the formula VI oarbaraate. In both cases, one of the mentioned bases can be added as a catalyst before or during the reaction.

For completion of the reaction after the addition the mixture is stirred further components for 20 minutes to 24 hours at a temperature between 0 ^o and 120 ° 0, preferably between 10 ° and 100 ° C, in particular between 20 ° and 8 ° C .

The sulfonylureas of formula I are isolated from the reaction mixture by conventional procedures, as described in group A above.

Employs A sulfonamide in a manner known per se formula V (European patent application EP-A - 234 352) in an inert organic solvent with an approximately estequiométrioa amount of an isocyanate VII at a temperature between 0 and ^the 0 ° 150- , preferably between 10 ° and 100 ° 0. The reaction can be carried out at normal pressure or under a sub-pressure (up to 50 bar), preferably at a pressure between 1 and 5 bar, continuously or intermittently.

In this case, before or add bases, such as reaction amines and improve the quality of these, these are those already during the reaction that can be added, which accelerate the product. The appropriate bases mentioned in group A above, especially triethylamine or 2,4,6-collidine, in a quantity between 0.01 and 1 mole for each mole of the starting substance of formula V.

Advantageously, those already indicated in group A above are used as solvents.

The solvent is used in an amount of between 100 and 2,000 $ by weight, preferably between 200 and 700 $ by weight relative to the educto V.

compound of formula V, necessary for the reaction, is generally used in almost equimolar amounts (with an excess or a deficiency of, for example, 0 to 20% in

311 relation to the formula VII scholar). You can introduce subs. starting value of formula VII num. of the aforementioned diluents and then add the starting substance of formula V. However, you can also add the sulfonamide and then add the isocyanate of formula VII.

For completion of the reaction, after addition of nents made up stir further for 20 minutes to 24 hours at a temperature between 0 ^o and 120 ° 0, preferably from 10 ° to 100 ° 0, especially between 20 ° and 80 ° C. From the reaction mixture, the final product I can be obtained in a conventional manner, as already described in group A. above.

The sulfonyl isocyanates, required as starting substances, of formula II, can be obtained in a conventional way, from the respective sulfonamides, by means of phosgenization (Houben-Weye 11/2 (1985), page 1106 and US patent US · 4,379,769) or by reaction of the sulfone mids with chlorosulfonyl isocyanate (German patent DE-OS 3 132 944).

The sulfonyl carbonates of formula IV were pre. stopped according to or in analogy to the reactions themselves known, (European patent EP-A 120 814). However, the sulfonyl isocyanates of formula II in a smooth reaction can also be converted into an inert solvent, such as ether or dichloromethane with phenol, into the carbamates of formula IV.

The carbamates of formula VI are obtained according to or in analogy to conventional reactions (for example, European patent EP-A 101 670); however, they can also be prepared from the corresponding isocyanates of formula VII, by reaction in. phenol.

Formula VII isocyanates are obtained from formula III amines by treatment with oxalyl chloride or phosgene (in analogy to studies in Angew. Chem. 83 (1971), page 407, and European patent EP-A 388 873 ).

Sulfonamides can be obtained by reacting the corresponding sulphonic acid chlorides with ammonia ^ consul the work of Houben-Weye, Methoden der Organisohen Chemie ” ₍ volume 9 (1955), page 557 and following).

The compounds: 2-amino-4-methoxy-6-trifluormethyl-1,3,5-triazine and 2-amino-4-ethoxy-6-trifluormethyl-1,3,5-triazine are known from the respective technical literature (see Yakgaku Zasshi 95 (1975), page 499).

The two compounds of formula I are obtained in a manner known per se (European patent EP-A - 304 282, US patent US-A - 4,599,412). Said salts are obtained by deprotonization of the corresponding sulfonylureas of formula I, in water or in an inert organic solvent and at temperatures between -80 ° 0 and 120 ° C, preferably between 0 ° C and 60 ° C, in the presence of a base.

Suitable bases are, for example, alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal hydrides or alkaline earth metal hydrides, alkali metal oxides or alkaline earth metal oxides or alkali metal alkoxides or alkaline earth metal alcoholates, such as sodium hydroxide, potassium hydroxide and lithium hydroxide; sodium methanolate, sodium ethanolate and sodium tert-butanolate, sodium hydrogen and calcium hydrogen, and calcium oxide.

As solvents, for example, in addition to water, alcohols such as methanol, ethanol and tert-butanol ethers, such as tetrahydrourane and dioxane, are also of interest; acetonitrile; tilformamide dime; ketones, such as acetone and methyl ethylethone, and also halogenated hydrooarbonides.

Deprotonization can be carried out under normal pressure or at pressures up to 50 bar, preferably at normal pressure up to an overpressure of 5 bar.

The compounds of formula I or the herbicidal agents that contain them, as well as their salts, tolerated by the environment, alkali metals or alkaline earth metals can fight weeds in other areas such as wheat, rice and corn; this annihilation effect of weeds occurs, mainly also with reduced amounts of adjustment. Said bold compounds can be used, for example in the form of directly sprayable solutions, powders, suspensions, also high percentage suspensions, aqueous, oily and other, or dispersions in oil, pastes, dusting agent, spreading agents or granules, by spraying, nebulizing, dusting, spreading or watering. The application forms depend on the purpose of use; in any case, they must ensure, as far as possible, the finest distribution of the active substances according to the invention.

The compounds of formula I are generally suitable for the preparation of directly sprayable solutions,

oils, pastes or dispersions in oil. Inert additive substances are of interest, among others, fractions of mineral oils with a medium to high boiling point, such as semen or diesel oil; and tar oils, as well as oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrooarbonates, for example toluene, xylene, paraffin.

tetrahydronaphthaline; alkylated naphthalines or their derivatives;

methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strongly polar solvents, such as Ν, Ν-dimethylformamide, dimethyl sulfoxide ,. N-methylpyrrolidone or water.

Aqueous forms of application can also be prepared from emulsion concentrates, dispersions, pastes, wettable feet or water-dispersible granules, by adding water * For the preparation of emulsions, pastes or dispersions in oil, the substrates such as, or derived in an oil or solvent, by means of wetting agents, adhesive agents, dispersing agents or emulsifying agents in water. However, stable concentrates can also be prepared from an active substance and wetting agents, adhesives, dispersing agents or emulsifying agents, and, if appropriate, solvents, and possibly solvents or oil, which are suitable for a dilution with water.

As surfactants, alkali metal and alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example ligninosulfonic acid, phenolsulfonic acid, naithalinosulfonic acid and dibutylnaphthalinosulfonic acid, as well as fatty acids, alkyl sulfonates and alkylaryl sulphonates, alkyl sulphates, lauryl ether sulphates and fatty alcohol sulphates, as well as salts of sulphated hexadecanols, heptadecanois and octadecanols, and fatty alcohol glioolic ether; condensation products of sulfonated naphthalene and its derivatives with formaldehyde; condensation products of naphthalene or naphthalinosulfonic acids with phenol and maldehyde; polyoxy ether, ethyleneoctylphenol, ethoxylated isooctylphenol, ethoxylated octylphenol or ethoxylated monylphenol; alkylphenol ether, tributylphenylpolygliool ether; alcohols of

alkylaryl polyethers; isotridecyl alcohol; condensers of fatty alcohol with ethylene oxide; ethoxyl castor oil; polyoxyethylenealkyl or polyoxypropylene ether; polyglycolic ether acetate with lauryl alcohol; sorbitoj ester of ligninosulfite or methylelulose bleaches.

Spraying agents, spreading agents and powdering agents can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, for example coating granules, impregnating granules and homogeneous granules can be prepared by binding the active substances to the solid carrier agents. Solid carrier agents are mineral materials, such as silicon acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, pasty mass, sandy-clay slime, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate; magnesium oxide; ground synthetic materials; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate; ureas and vegetable products, such as cereal flours, tree bark flours, nut case flour and sawdust; cellulose powder or other solid carrier substances.

The formulations generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active substance.

Examples of formulations are as follows:

I. - 90 parts by weight of compound # 2 are mixed. 1 with 10 parts by weight of N-methyl - ^ - pyrrolidone and a solution is obtained, which is suitable for use in the form of tiny drops.

II. - 20 parts by weight of compound no. 2 are dissolved. 1 in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the assembly product of 8 to 10 moles of ethylene oxide in 1 mole of N-monoethanolamide of oleic acid, 5 parts by weight of calcium salt dodecylbenzenesulfonic acid; and 5 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. Upon pouring and fine distribution of the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained, having 0.02% by weight of the active substance.

III.

- 20 parts by weight of compound # 2 are dissolved. 1 in a mixture consisting of 40 parts by weight of cyclohexanone, parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide in 1 mole of isooctyl phenol, and 10 parts by weight of the product of the assembly of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and fine distribution of the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained, which contains 0.02% by weight of the active substance.

IV. - 20 parts by weight of active substance no. _{0 are} dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a fraction of mineral oil with a boiling point between 210 ° and 280 ° C, and 10 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring and fine distribution of the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained, which contains 0.02% by weight of active substance.

V.

- 20 parts by weight of active substance n2. 1 are well mixed with 3 parts by weight of the sodium salt of diisobutyl naphthalino sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulphite bleach and 60 parts by weight of acid gel silica in the form of powder, everything being ground in a hammer mill. Through the fine distribution of the mixture in

20,000 parts by weight of water, a spray solution is obtained, which contains 0.1% by weight of the active substance,

SAW. - 3 parts by weight of active substance n2 are mixed.

with 97 parts by weight of finely divided kaolin. In this way, a dusting agent is obtained, which contains 3% by weight of said active substance.

VII. - 30 parts by weight of active substance n2 are intimately mixed. 1, with a mixture consisting of 92 parts by weight of the silicic acid gel in the form of powder and 8 parts by weight of paraffin oil, which was sprayed on the surface of said silicic acid gel. In this way, a composition of the active substance with an adherence capacity is obtained.

VIII. - 20 parts by weight of active substance n2 were mixed very well. 1 with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of polyglycolic ether with fatty alcohol, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of an oil paraffin mineral. An oily and stable dispersion is obtained.

The application can take place in the process

the post-emergence process of the plants. In case

since they are active substances that, for certain crop plants, are less tolerated, then application techniques can be developed in which the herbicides are sprayed with the help of spray devices, such that the leaves of the plants sensitive crops are not affected as quickly as possible while the active substances reach the leaves of weeds that grow below or reach the bare surface of the soil (post-orientation, deviation).

The amounts of application of active substance, depending on the herbicidal agent, and the time of year, the target plants and their growth phase, are between 7 0.001 and 1.0 Kg / ha, preferably between 0.01 and 0, 5KG / ha.

Considering the multiple facets of the application processes, the compounds according to the invention or the agents that contain them can still be used in a certain additional number of crop plants to combat weeds or unwanted ones. For example,

these cultures;

Botanical name

Allium cepa

Ànanas comosus

Arachis hypogaea

Asparagus officinalis

Beta vulgaris spp. very high

Beta vulgaris spp. rapa

Brassica napus var. napus

Brassica napus var. napobrassica Brassica rapa var. silvestris Camellia sinensis

German Name

Onion

Ananas

Peanut

Asparagus

Common beet

Turnip

White turnip

Red turnip

Turnips

Tea bush

Botanical name

Carthamus tinctorius

Citrus limon

Citrus sinensis

Ooffea arabica (Ooffea canephora,

Coffea liberica)

Cucumis sativus

Cynodon dactylon

Dauous oarota

Elaeis guineensis

Fragaria vesoa

Glyoine max

Gossypium hirsutum (gossypium arboreum, Gossypium herbaceum,

Gossypium vitifolium)

Helianthus annuus

Hevea brasiliensis

Hordeum vulgare

Humulus lupulus

Ipomoea potatoes

Juglans regia

Lens culinaris

Linum usitatissimum

Lycopersicon lycopersicum.

Malus spp.

Manihot esculenta

Medicago sativa

Musa spp.

Nicotiana tabacum (N. rusticia)

Olea europaea

Oryza sativa

Phaseolus lunatus

German Name

Bastard saffron

Lemon

Oranges

Coffee

Cucumber

Grass

Carrot

Palm tree

Strawberry

Soy beans

Cotton

Sunflower

Rubber tree

Barley

Hop

Sweet potato

Walnut

Lenti

Winter linen

Tomato

Apple

Manioc

Lucerne

Banana

Tobacco

Oliveira

Rice

Moon beans

Botanical name

Phaseolus vulgaris

Picea abies

Pinus spp.

Pisum sativum

Prunus avim

Persian Prunus

Pyrus com.ru.unis

Ribes sylvestre

Ribes grape-crispa

Ricinus communis

Saccharum officinarum

Secale cereale

Solanum tuberosum

Sorghum bicolor (S. vulgare)

Theobroma cacao

Trifolium praten.se

Triticum aestivum.

Triticum durum.

Vicia faba

Vitis vinifera

Zea mays

German Name

Pepper

Abetonordico

Pine

Sweet pea

Cherry tree

Peach

Wait

Gooseberry

Grape

Ricino

Sugar cane

Rye

Potato

Bicolor sorghum

Cacaneiro

Clover

Wheat

Durum wheat

Pava

Vine

Corn

To widen the range of activities and to obtain synergistic effects, the triazinyl-substituted sulfonylureas of formula I can be mixed and applied together with numerous representatives of other representatives of other groups of active herbicidal or growth-regulating substances. As an example, mention is made, as components of the mixture, diazines, 4H-3> 1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitro - an.ilin.as, N-phenyl carbamates, thiolcarbamates, acids halogenated carboxylics, triazines, amides, ureas, diphenyl ether, triazines, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinoline carboxylic acid derivatives, phenyloxy-phenyl-propionic acids or heteroaryloxy acids fe · nil-propionones, as well as their salts, esters and amides, and others.

In addition, it may be useful to use the compounds of formula I alone or in combination with other herbicides, and also mixed with other plant protection agents, for example with agents to combat pests or phytopathogenic fungi, or bacteria. There is also interest in the possibility of forming a mixture with solutions of mineral salts, which are used to fill deficiencies in food and trace elements. Non-phytotoxic oils and oily concentrates can also be added.

The following are Synthesis Examples of the compounds of formula I.

1) 2-chloro-1-N'-4-methoxy-6-trifluoromethyl-1,3,5-triazin-2-yl) -aminocarbonyl-benzenesulfonamide;

A solution of 4.0 g (21 mmoles) of 2-amino-4-methoxy-6-trifluormethyl-1,5,5-triazine in 20 ml of acetonitrile was mixed at 25 ° C with 4, 5 g (21 mmoles) of 2-chloro-benzenesulfonyl isoeyanate. The solution like that. obtained was stirred for 21 hours at 25 ° C. The solvent was then removed under reduced pressure at 40 ° C and the solid residue was stirred with 1 liter of a ml.

Λ

- 25 4 ture of diethyl ether / hexane (v: v 1/1), for 3 hours, vigorously. The product was sucked off and dried in vacuo at 40 ° C. 6.5 g (75% of theory) of the title compound were obtained with. a melting point between 166 ° -168 ° C.

2)

Sodium 2-chloro-1-N- (4-methoxy-6-trifluormethyl-1,5,5-triazin-2-yl) -aminocarbonyl-benzenesulfonamide;

A suspension of 1.5 g (3.6 mmol) of 2-chloro-1- (4-methoxy-6-trifluormethyl-1,5,5-triazin-2-yl) -aminocarbonyl-benzenesulfonamide was mixed in of 10 ml of methylene chloride, at a temperature of 25Â ° C, with 0.66 g (3.6 mmol) of a solution of sodium methanolate (at 30% by weight) in methanol. The homogeneous solution, which was formed, was stirred for 1 hour at 25 ° C. After removing the volatile components at a temperature of 60 ° C, in a water stream vacuum, the title compound was obtained in quantitative yield, with a decomposition point

The 0 is between 220 and 224 0.

The active substances mentioned below, in Tables 1 and 2, are obtained according to a similar preparation method.

Table 1

Active substance .............. R ¹ R ² R ³ Pf ° C

Cl

166-168

Table 1 (Oont.)

Substance

active R ¹ ? R R ³ Federal Police. ° 0 2 ch ₃ 0 (CH ₂ ) ₂ 00H ₃ H 108-110 3 ch ₃ CP ₃ H 164-169 4 ch ₃ Cl H 220-224 (Dec.) Salt sodium 5 0H ₃ 0 (CH ₂ ) ₂ 00H ₃ H 119 (Dec.) Salt of sodium 6 ch ₃ O (CH ' ₂ ) ₂ OOH ₃ H 139 (Dec.) Salt of sodium 7 CH. 3 ^CT 3 faith 165 (Dec.) Salt of sodium 8 CH ₃ 01 6-01 168 9 ch ₃ 01 H 160-163 (Dec.) Calcium Oal 10 ch ₃ 01 H 232 (Dec.) Potassium salt 11 0H ₃ 01 6-CH ₃ 140-144 12 oh ₃ 01 5-01 151-156 13 ch ₃ B H 162-164 14 ch ₃ Br H 156-160 15 ch ₃ J H 16 CH ₃ B H > 220 (Dec.) Sodium salt 17 OH. B H > 220 (Dec.) salt of

potassium

Table 1 (Cont.) Substance 2 l R ³ Federal Police. ° C active R ¹ 18 CH ₃ F H > 220 (Dec.) Salt of calcium 19 ch ₃ F 6-F 177-180 20 ch ₃ F 6-F 180-200 (Dec.) Salt sodium 21 CH ₃ F 6-F > 220 (Dec.) Potassium salt 22 ch ₃ F 6-F 155-159 (Dec.) Calcium salt 23 π xt ^σ 2 ^κ 5 Cl 3-01 155-157 24 oh ₃ Cl 3-01 175-177 25 ° 2 ^H 5 Cl 3-01 197-200 (Dec.) Salt sodium 26 ch ₃ Cl 3-C1 198-201 (Dec.) Salt sodium 27 oh ₃ Cl 6-CH ₃ 175-178 (Dec.) Salt sodium 28 oh ₃ Cl 6-CH ₃ 180-183 Salt of bread tassium 29 ch ₃ SO ₂ CH ₃ H 176-177 30 ch ₃ SO ₂ CH ₃ H 186—188 Salt sodium 31 OH 3 Cl 3-01 > 220 (Dec.) Potassium salt

I

Table 1 (Oont.) Substance active D-L there 2 l 32 CgH ^ SO ₂ CH ₃ 33 ° 2 ^H 5 01 34 ch ₃ ^ct 3 35 oh ₃ CH ₃ 36 oh ₃ CF. 3 37 0Ii ₃ so ₂ c ₂ h ₅ 38 CH ₃ SOg-n-C ^ H? 39 ch ₃ SO g — i — C 40 Br H 41 SOgOgH ^ H 42 SO ₂ -nC ₃ H ₇ H 43 SOg-i-C ^ H? H

R ^{2 3} P.ff, ° 0

H 164-165

H 149-151

6-CH ^ 149-150

6-CH ₃ 200 (Dec.) Sodium salt

H 211 (Dec.) Salt of kelium

H 152-155

H 181-182

H 173-177

CH ₃ 183 (Dec.) Sodium salt

0H ₃ 173 (Dec.) Sodium salt

0H ₃ 180 (Deo.) Sodium salt

0H ₃ 196 (Deo.) Sodium salt • Table 2 p3 R θ

SOg-NH-C-N

R '

Active substance N2. R ² R ^ R ¹ R ⁴ PF ° C

2.1 0F ₃ Ξ CH ₃ 0H ₃ 135-137

2.2 C? ₃ H CH ₃ CH ₃ 99-105

Similarly, the following compounds can be obtained:

□ or its sodium salts, in which R has the following meaning: hydrogen, 3-ethyl, 4-methyl, 5-methyl, 6-methyl; 3-ethyl, 4-ethyl, 5-ethyl, β-ethyl; 3-fluorine, 4-fluorine, 5-fluorine β-fluorine; 3-oloro, 4-chloro, 5-chloro, 6-chloro; 4-methoxy, 4-methoxy, 5-methoxy, β-methoxy; 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy

OC ₂ H ₅ following meaning hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl; 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl; 3-fluorine, 4-fluorine, 5-fluorine 6-fluorine; 3-chlorine, 4-chlorine, 5-chlorine, 6-chlorine; 3-methoxy, 4-methoxy, 5-methoxy, β-methoxy; 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy

r

or its sodium salts, i.e., hydrogen, 3-ethyl, 4-ethyl, 5-methyl, 6-methyl; 3- © ethyl, 4-ethyl, 5-ethyl, β-ethyl; 3-fluorine, 4-fluorine, 5-fluorine, 6-fluorine; 3-chlorine, 4-chlorine, 5-chlorine, 6-chlorine; 3-methoxy, 4-iaetoxy _and 5-methoxy, Î ± -methoxy; 3-ethoxy, 4-ethoxy, 5-ethoxy, b-ethoxy;

-tM.

or its sodium salts, which have the following meanings: hydrogen, S-uotyl, 4-uethyl, 5-aethyl, 6-methyl; 3-ethyl, 4-ethyl,> -ethyl, 6-ethyl; 3-fluoro, 4-fluoro, 5-fluoro, ó-fluoro 3-chloro, 4-oloro, 5-eloro, 6-chloro; 3-ethoxy, 4-methoxy, 5-ethoxy, 6-netoxy; 3-ethoxy, 4-otoxy, 5-ethoxy, 6-ethoxy;

0 (CH _o ) o-0GH

O (OH _n ) n “OCH

t the following means hydrogen, 3-aethyl, 4-uethyl, 5-aethyl, 6-methyl; 3- 31

-ethyl, 4-ethyl, ‘5-ethyl, β-ethyl; 3 "fluorine, 4-fluorine, 5-fluorine

6-fluorine; 3, chlorine, 4-chlorine, 5-chlorine, β-chlorine; 3-methoxy, 4-methoxy, 5-methoxy, β-methoxy; 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy

or its sodium salts, in. which has the following meaning:

hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl; 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl; 3-fluorine, 4-fluor, 5-fluorine, β-fluorine; 3-chlorine, 4-chlorine, 5-chlorine, β-chlorine; 3-methoxy, 4-ra.ethoxy, 5-methoxy, β-niethoxy; 3-ethoxy, 4-ethoxy, 5-ethoxy, β-ethoxy

λ ~ or its sodium salts, in. that R ^w has the following meaning:

hydrogen, 3-methyl, 4-methyl, 5-methyl, β-methyl; 3-ethyl, 4-ethyl, 5-ethyl-6-ethyl; 3-fluorine, 4-fluorine, 5-fluorine, 6-fluorine; 3-chlorine, 4-chlorine, 5-chlorine, β-chlorine; 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy; 3-stoxi, 4-ethoxy, 5-ethoxy, 6-ethoxy;

or its sodium salts, in which R ³ has the following meaning hydrogen, 3-detyl, 4-methyl, 5-methyl, 6-methyl; 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl; 3-fluorine, 4-fluorine, 5-fluorine 6-fluorine; 3-chlorine, 4-chlorine, 5-chlorine, toxi,

3-chlorine, 4-chlorine, 5-chlorine, 6-chlorine; 3-methoxy, 4-me5-methoxy, 6-methoxy; 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy

OF or its sodium salts, in which R ³ has the following meaning hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl; 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl; 3-fluorine, 4-fluorine, 5-fluorine β-fluorine; 3-oloro, 4-oloro, 5-chloro, β-chloro; 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy; 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy

Application Examples:

herbicidal effect £ N- (l, _3? 5-triazin-2-yl) -benzenesulfonamide -aminocarbonilj of formula I on the growth of test plants is presented by the fol lowing in growth chamber assays.

serve the 300 cm ⁰ pots and sand as substrate. If, as containers of flower crops, plastic, with a clay capacity having about 3> 0% humus, the seeds of the test plants are sown according to the species, separately, at a shallow depth.

For post-emergence treatment purposes, seeds are placed directly, or plants already developed are chosen in the same pots, or they are

leased separately as nursery plants and transplanted, a few days before treatment, to the test containers.

Depending on the form of growth, the plants leave with one. growth height between 3 and 15 cm, are then treated with the active substances suspended in water as a distribution agent, or are emulsified, if: i nd the said active substances sprayed by nozzle for fine distribution. The amount of application for post-emergence treatment was 0.06 or 0.03 kg / ha of active substance (s.a.).

The test vessels are placed in a greenhouse, where, for species that like heat, hotter temperature ranges (20 to 35 ° C) are preferred, and for temperate climates, temperatures comprised between between 10 and 20 ° 0. The test time lasts for 2 to 4 weeks. During the said period, the plants are taken care of and their reaction to the separate treatments is evaluated.

An assessment is made on a scale of 0 to 100. In this case, 100 means that there was no attack on the planks or a complete annihilation of at least the parts above the earth, and 0 means that there was no damage. , that is, there was a period of normal growth.

The plants tested in the tests carried out on plaster are made up of the following species:

Latin name

Amaranthus retroflexus

Chenopodium album

Ohrysanthemum

G-alium aparine

German name

Fox Tail

White goose foot

Chrysanthemum

Rooster's foot

- 34 ^

Latin name

Stellaria media

Triticum aestivum

Zea mays

German name

Star

Wheat

Corn

With the use of 0.06 or 0.03 kg / ha of active substance, in an application process after the emergence of the plants, it is possible to combat the undesirable plants, with broad leaves, as in Example 1, with an excellent simultaneous selectivity in corn and wheat crop plants.

In the following table, the results of biological research are gathered, in which the active substance according to the invention, Example 1, was compared with the known compound B described in the US patent. 4,169,719.

ç? ₃ och ₃

Table 1: - Comparison of the herbicidal activity of compound 1 Gone

Example with comparative compound B, number, application after emergence of plants, using 0.06 or 0.03 kg / ha of active substance, in greenhouses

Test plans

Damage Amount of Application Example 1 B [kg / ha w.a. 0.06 0.03 0.06 0.03

Amaranthus retroflexus

Galium aparine

Chenopodium album

100 100 0 0 95 90 0 0 90 90 0 0

J.

In Tables 2 and 3, the compounds according to the invention, from comparative Examples G or H, known in US are compared. 4 127 405 í or 3, with substances from the United States patent

G ·

The test results clearly showed surprisingly high selectivities.

Conventional compounds cause unacceptable damage, between 85 and 70% in the corn crop. In contrast, the compounds of Examples 1 or 3, with equally good or even better herbicidal activity, caused only 10% damage to the crop plants.

Table 2: - Comparison of the herbicidal activity of the compound of Example 1, with the comparative compound G, in an application after the plant allergy, of 0.03 kg / ha of active substance, in the greenhouse.

Test plans

Zea mays

Damage ($)

Example 1 G

Damage Plants (/) test Example 1G

Undesirable plants:

-Amaranthus retroflexus 9090

-Galium aparine 8074 gabela 3: - Comparison of the herbicidal activity of compound n2> 3 of the Example, with the similar compound H, in an application after the emergence of plants, of 0.06 or 0.03 kg / ha of active substance, in greenhouse.

Damage Plants (/) test Quantity applied [Kg / ha s.a.]

Example 3 H

0.06 0.03 0.06 0.03 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 -Sinapis alba 95 90 90 90 Obtained excellent selectivities in cultures sensitive examples: rice, wheat summer and corn , with 0

compound n2. 7 according to the present invention, as shown in the results shown in Tables 4 and 5 below.

gabela 4: - Combat undesirable broadleaf plants with simultaneous compatibility in relation to exemplified crops: summer wheat and corn, in an application after the emergence of plants, of 0.015 kg of active substance per hectare, of

Compound jf n.2. 7, in a greenhouse.

Test plans

Triticum aestivum

Zea mays

Undesirable plants:

-Amaranthus retroflexus

-Chenopodium album

-Stellaria media

Damage (%)

100

Table 5; - Oombate to broadleaf plants, undesirable with simultaneous tolerance in the case of the exemplified crop: - rice, in application, process application after the emergence of the plants, of 0.015 kg of active substance per hectare, of the comp. to 7 »in an oven.

Test plans

Damage (%)

Oryza sativa10

Undesirable plants:

-Amaranthus retroflexus95

-Sinapis alba70

-Stellaria media100

In another trial, the sodium salt of Example 7 was compared. The results are shown in Table 6.

Table 6: - Comparison of the herbicidal activity of exemplary compound no. 7, with 0 sodium salt of comparative compound H, applied after the emergence of plants, of 0.06 or 0.03 kg / ha of active substance, in an oven.

Test plans

Damage (0)

How much applied [Kg / ha s.aj [

Example 7 Na H salt

0.06 0.03 0.06 0.03 Zea mays 10 0 100 100 Undesirable plantsí -Amaranthus retroflexus 100 100 90 90 -Galium aparine 98 98 70 60 -Ohenopodium album 100 100 100 100

The results of the tests clearly demonstrate the excellent and high selectivity, with simultaneous extraordinary herbicidal activity of the compound according to the present invention.

Claims (2)

CLAIMS: there. N - [(1,3,5-triazin-2-yl) -aminocarbonyl] -benzenesulfonamides characterized by the fact that they have the general formula (I) in which R4 means a methyl group or an ethyl group; R means a halogen atom, an alkylsulfonyl group having 1 to 3 carbon atoms, the trifluoromethyl group or the 2-methoxyethoxy group; R means a hydrogen atom; or one of the methyl, ethyl, methoxy or ethoxy groups, or a fluorine or chlorine atom; and R4 means a hydrogen atom or a methyl group; as well as their salts usable in agriculture. 2a. N - [(1,3,5-triazin-2-yl) -aminocarbonyl] -benzenesulfonamides of general formula (I), according to Claim 1, characterized in that R stands for chlorine or trifluoromethyl. 3a. Process for the preparation of N- [(.1,3,5-triazin-2-yl) aminocarbonyl] -benzenesulfonamides of the general formula (I) according to claim 1, characterized in that an isocyanate of sulfonyl of general formula (II) R3 R ² GO-SO2NCO II in an inert organic solvent, with an approximately stoichiometric amount of a 2-amino-1,3,5-triazine derivative of the general formula (III) CF 3 R * HN— ( ^z Ή N— < 0R1 III 4th. Process for the preparation of N - [(1,2,5-triazin-2-yl) aminocarbonyl] -benzenesulfonamides of general formula (I) according to claim 1, characterized in that a carbamate of formula general (IV) IV in an inert organic solvent at a temperature between 0 ^o and 120 ° C with an approximately stoichiometric amount of a 2-amino1,3,5-triazine of formula (III). 5th. Process for the preparation of N - [(1,3,5-triazin-2-yl) aminocarbonyl] -benzenesulfonamides of the general formula (I) according to claim 1, characterized in that a corresponding sulfonamide of general formula (V) in an inert organic solvent, with a phenylcarbamate of general formula (VI) SAW 6th. Process for the preparation of N - [(1, 3,5-triazin-2-yl) aminocarbonyl] -benzenesulfonamides of general formula (I), wherein R ⁴ means a hydrogen atom according to claim 1 , characterized in that a corresponding sulfonamide of general formula (V) is reacted in an inert organic solvent with an isocyanate of general formula (VII) N — K OCN— <ί Ni VII la. Herbicidal composition containing an N - [(1,2,5-triazin-2yl) -aminocarbonyl] -benzenesulfonamides of the general formula (I) according to claim 1, or a salt thereof, as well as the usual carrier substances. 8th. Process to combat the growth of undesirable plants, characterized by the fact that an herbicidally effective amount of an N - [(1,3,5triazin-2-yl) -aminocarbonyl] -benzenesulfonamides of the general formula (I) is acted, according to with claim 1, or a salt thereof, on plants and / or their habitat, preferably comprised between 0.01 and 0.5 kg / ha.