AU644291B1 - Herbicidal N-{(1,3,5-triazin-2-yl)-aminocarbonyl}- benzenesulfonamides - Google Patents

Description

P100/0il 2015101 Regulation 3.2(2)

AUSTRALIA

Patents Act 1990 644 291

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: Invention Title: HERBICIDAL N- 5-TRIAZIN-?-YL) -AMINOCARBONYL

BENZENESULFONAMIDES

S. S

S

*5 S

S

The following statement is a full description of this invention, including the best method of performing it known to us O 0.2. 0050/42042 Herbicidal N- (1,3.5-triazin-2-yl)-aminocarbonl 1benzenesulfonamides The present invention relates to triazin-2-yl)-aminocarbonyl ]-benzenesulfonamides of the general formula I

R

3 R2 0 CF 3 II

-SO

2

ORI

where R' is methyl or ethyl, R 2 is halogen, Ci-C 3 -alkylsulfonyl, trifluoromethyl or 2-methoxyethoxy and R 3 is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine or chlorine, and agriculturally useful salts thereof.

The present invention furthermore relates to a process for the preparation of the compounds I and their use as herbicides.

0: U.S. Patents 4,120,691 and 4,127,405 and EP-A 44 807 relate to sulfonylureas which have P. herbicidal action and whose general formula embraces the compounds of the general formula I which are defined at the outset.

U.S. Patent 4,120,691 describes the triazine compound A and the pyrimidine derivative B, these being .20 the most closely related structures.

0 CF 3 II A

SO

2

-NH-C-NH--/

OCH 3 II *B Cl 0 CF 3 11 N-4 C SO 2-NH-C-NH- 'N EP-A 44 807 describes two sulfonylureas C having an ortho allyloxy group.

O- 0 .CF3 25 N=-

OR

R CH 3 or CzH, 2 O.Z. 0050/42042 EP-A 48 808 describes two sulfonylureas D having a 2-chioroethoxy substituent in the aromatic moiety.

O-(CH

2 2 -Cl1 C0 F 3 D ~F~SO 2

NZ

OCH

3 Z CH or N EP-A 48 143 mentions two N-methylated sulfonylureas E without characterizing them further.

S0 2

-CH

3 0

CF

3 E 11 N-< SO H-C-N Z~

CH

3

OCH

3 Z CH or N EP-A 388 873 relates to benzoates having the 10 structure F.

C0 2 R CF3 2-NH-CNH-</

F

0 OR R CH 3 or CH U.S. Patent 4,127,405 discloses sulfcnylurea derivatives having chlorine or trifluoromethyl substitution in the ortho position of the phenyl ring and

CH

3

/OCH

3 substitution in the triazine ring C 0 CH 3

G

OCH 3 0so 2 4

'I

CF

3 0 CH 3

H

'0-SO 2

-NH-C-NH-</

OCH3 The compound G is known under the nayo ohlorosulfuron (Glean).

It is an object of the present invention to synthesize sulfonylureas which have improved properties -3compared with the known memnbers of this herbicide class and are distinguished in particular by high selectivity in sensitive crops, such as rice or corn.

We have found that this object is achieved by the N-[(1,3,5-triazin-2-yl)-aminocarbonyl)-benzenesulfonamides of the formula I which are defined at the outset.

In the formula I, Cl-C 3 -alkylsulfonyl is methyl, -ethyl-, propyl- or isopropylsulfonyl and halogen is fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine. Benzenesulfonamides in which R 2 is chlorine are particularly preferred.

The novel sulfonylureas of the formula I are obtainable by various methods which are described in the literature. Particularly advantageous methods are described in detail below by way of example.

R3 R2

CF

N-<

A: SOzNCO H 2 OR1 II III

R

3 RZ CF 3

R

3 R2 CF 3 so S HWSO 2 -NH-C-NH- N 0 ORI 0 OR IV III

IV

R3 R 2 0 CF 3 C: \IC--SO 2

NH

OR1

*VI

*R3

S

R3 R2 CF 3 0: -SO 2

NH

2 OCN-' 'N

N=<

01 v vit ORI V VII A: A sulfonyl isocyanate I is reacted in a conventional manner (EP-A-162 723) wilth about the stoichiometric amount of a 2-amino-1,3,5-triazine derivative III at from 0 to 120 0 C, preferably from 10 to 100 0 C. The 2 reaction can be carried out continuously or batchwise -4 0050/42042 under atmospheric or superatmospheric pressure (up to bar), preferably at from 1 to 5 bar.

Solvents and diluents which are inert under the particular reaction conditions are advantageously used for the reactions. Examples of suitable solvents are halohydrocarbons, in particular chiorohydrocarbons, eg.

tetrachioroethylene, 1,1,2,2- or 1,1, 1,2-tetrachioroethane, dichloropropane, methylene chloride,, dichiorobutane,. chlorofo~rm, chloronaphthalene, dichloronaphthalene, carbon tetrachloride.. 1,1,1- or 1,1,2-trichioroethane, trichioroethylene, pentachloroethane, m- and p-difluorobenzene, 1,2-dichloroethane, 1,1]-dichloroethane, 1 ,2-cis-dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, m- and pdichlorobenzene, p- and m-dibromobenzene, m- and p-chlorotoluene, and l,2,4-trichlorobenzene; ethers, eg.

ethyl propyl ether, methyl tert-butyl ether, n-butyl ethyl ether, di-n-buty3. ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetol, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole and A,p,'-dichlorodiethyl ether; nitrohydrocarbons, such as nitromethane, nitroethane, nitrobenzene, m- and pchloronitrobenzene and o-nittatoluene; nitriles, such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile and m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons, eg. heptane, pinane, nonane, o-, m- andl p-cymene, gasoline fractions boiling within a range of from 70 to 190 0 C, cyclohexane, methylcyclohexane, 30 decalin, petroleum ether, hexane, naphtha, 2,2,4trimethylpentane, 2,243-trimethylpentane, 2,3, 3-tnimethylpentane and octane; esters, eg. ethyl acetate, ethyl &cetoacetate and isobutyl acetate; amides, eq.

formamide, methylformamide and dimethylformamide; ketones, eg. acetone and methyl ethyl ketone, and corresponding mixtures. The iiolvent is advantageously used in an amount of from 100 to 2,000, preferably from 200 to 5 O.Z. 0050/42042 700, by weight, based on the starting material II.

The compound II required for the reaction is generally used in about an equimolar amount (for example in an amount of from 80 to 120%, based on the particular starting material III, of the stoichiometric amount).

The starting material III may be initially taken in one of the abovementioned diluents and the starting material II added.

Advantageously, however, the process for the preparation of the novel compounds is carried out by a method in which the starting material II, if necessary in one of the abovementioned diluents, is initially taken and the starting material III is then added.

To complete the reaction, stirring is carried out for a further 20 minutes to 24 hours at from 0 to 120 0

C,

preferably from 10 to 100°C, after the addition of the components.

A tertiary amine, eg. pyridine, a,p,--picoline, 2,4- and 2,6-lutidine, 2,4,6-collidine, p-dimethylamino- 20 pyridine, trimethylamine, triethylamine, tri-n-propylamine, 1,4-diazabicyclo [2.2.2]octane [DABCO] or 1,8diazabicyclo[5.4.0]undec-7-ene, can advantageously be used as a reaction accelerator in an amount of from 0.01 to 1 mol per mole of starting material II.

The end product I is isolated from the reaction mixture in a *conventional manner, for example after distilling off the solvent or directly by filtration under suction. The remaining residue may furthermore be washed with water or dilute acid to remove basic im- 30 purities. However, the residue can also be dissolved in a water-immiscible solvent and washed in the manner described. The desired end products are obtained here in pure form; if necessary, they can be purified by recrystallization, stirring in an organic solvent which takes up the impurities or chromatography.

This reaction is preferably carried out in acetonitrile, methyl tert-butyl ether, toluene or methylene 5 0.Z. 0050/42042 chloride in the presence of from 0 to 100, preferably from 0 to 50, mol equivalents of a tertiary amine, such as 1,4-diazabicyclo[2.2.2]octane or triethylamine.

B: A corresponding sulfonylcarbamate of the formula IV is reacted in a conventional manner (EP-A-120 814, EP-A-101 407) with a 2-amino-l,3,5-triazine derivative III in an inert organic solvent at from 0 to 120°C, preferably from 10 to 100°C. Bases, such as tertiary amines, may be added here, with the result that the reaction is accelerated and the product quality improved.

Suitable bases for this purpose are, for example, tertiary amines as stated under A, in particular triethylamine or 1,4-diazabicyclo [2.2.2]octane, in an amount from 0.01 to 1 mol per mole of starting material IV.

Advantageously used solvents are those stated under A.

0 The solvent is used in an amount of from 100 to 2,000, preferably from 200 to 700, by weight, based on the starting material IV.

20 The compound IV required for the reaction is generally used in about an equimolar amount (for example in an amount of from 80 to 120%, based on the particular starting material III, of the stoichiometric amount).

The starting material IV may be initially taken in one of the abovementioned diluents and the starting material III S"then added.

However, it is also possible initially to take the starting material III in one of the stated solvents or diluents and to add the sulfonylcarbamate IV.

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

.The end product I can be obtained from the reaction mixture in a conventional manner, as stated under A.

C: A sulfonamide of the formula V is reacted in a conventional manner (EP-A-141 777 and EP-A-101 670) with about the stoichiometric amount ot a phenyl carbamate VI 7 O.Z. 0050/42042 in an inert organic solvent at from 0 to 120°C, preferably from 20 to 10 0 C. The reaction is carried out continuously or batchwise at atmospheric or superatmosphe:ic pressure (up to 50 bar), preferably at from 1 to 5 bar.

Bases such as tertiary amines, which accelerate the reaction and improve the product quality, may be added here. Suitable bases for this purpose are those stated under A, in particular triethylamine, 2,4,6collidine, 1,4-diazabicyclo[2.2.2]octane [DABCO] or 1,8diazabicyclo[5.4.0]undec-7-ene (DBU), in an amount of from 0.01 to 1 mol per mole of starting material V.

Advantageously used solvents or diluents are those stated under A.

The solvent is used in an amount of from 100 to 2,000, preferably from 200 to 700, by weight, based on the educt V.

The compound V required for the reaction is generally used in about an equimolar amount (for example in an amount of 80 to 120%, based on the particular starting materials VI, of the stoichiometric amount).

The starting material VI may be initially taken in one of the abovementioned diluents and the starting material V S* then added.

However, it is also possible initially to take the starting material V in one 6f the stated solvents and then to add the carbamate VI. In both cases, one of the stated bases may be added as a catalyst before or during the reaction.

30 To complete the reaction, stirring is carried out for a further 20 minutes to 24 hours at from 0 to 120°C, preferably from 10 to 100 0 C, in particular from 20 to 0 C, after the addition of the components.

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

D: A sulfonamide of the formula V is reacted in a 8 O.Z. 0050/42042 conventional manner (EP-A-234 352) with about the stolchiometric amount of an isocyanate VII in an inert organic solvent at from 0 to 150 0 C, preferably from 10 to 100°C. The reaction can be carried out continuously or batchwise at atmospheric or superatmospheric pressure (up to 50 bar), preferably at from 1 to 5 bar.

Bases such is tertiary amines, which accelerate the reaction and improve the product quality, may be added before or during the reaction. Suitable bases for this purpose are those stated under A, in particular triethylamine or 2,4,6-collidine, in an amount of from 0.01 to 1 mol per mole of starting material V.

Advantageously used solvents are those stated under A. The solvent is used in an amount of from 100 to 2,000, preferably from 200 to 700, by weight, based on S. the educt V.

The compound V required for the reaction is generally used in about the equimolar amount (for example in an amount of from 80 to 120%, based on the educts VII, 20 of the stoichiometric amount). The starting material VII.

can be initially taken in one of the stated diluents and the starting material V then added. However, it is also possible initially to take the sulfonamide and then to add the isocyanate VII.

To complete the reaction, stirring is carried out for a further 2Z minutes to 24 hours at from 0 to 120°C, preferably from 10 to 100°C, in particular from 20 to after the addition of the components. The end pro- .duct I can be obtained frm the reaction mixture in a 30 conventional manner, as described under A.

The sulfonyl isocyanates of the formula II which are required as starting materials can be obtained in a conventional manner from the corresponding sulfonamides by phosgenation (Houben-Weyl, 11/2 (1985) 1106 and U.S.

Patent 4,379,769) or by reaction of the sulfonamides with chlorosulfonyl isocyanate (German Laid-Open Application DOS 3,132,944).

-9 O.Z. 0050/42042 The sulfonylcarbamates of the formula IV were prepared by, or similarly to, conventional reactions (eg.

EP-A 120 814). However, tzhe sulfonyl isocyanates of the formula 11 can also be converted into the carbamates of the formula IV in a smooth reaction in an inert solvent, such as ether or dichioromethane.

Carbamates of the formula VI are obtainable by, or similarly to, known reactions (eg. EP-A 101 670), but they can also be prepared from the corresponding isocyanates VII by reaction with phenol.

The isocyanates of the formula VII are obtained from the amines of the formula III by treatment with oxalyl chloride or phosgene (by a method similar to that described in Angew. Chem. j.(1971), 407 or EP-A 388 873).

The sulfonamides can be obtained by reacting the corresponding sulfonyl chlorides with Ammonia (Houben- Weyl, IMethoden der organischen Chemie, Volume 9 (1955), 605). The sulfonyl chlorides are obtained either by a Meerwein reaction (diazotization of suitable amines and sulfochiorination under catalysis with a copper salt) or by chlorosulfonation of suitable aromatics, for example 2, 15-dichlotobenzenesu f onyl chloride from p 66dichlorobenzene (Houben-Weyl, Methoden der orga.Ac hen Chemle, Volume 9 (1955), 557 et seq.).

2-Am.~rro-4-methoxy-6-trif luoromethyJ.-11 3,15triaziriLe .d 2-amino-4-ethoxy-6-trifluoromethyl-l,3,5triazine are known from the literature (Yakugaku Zasshi 0 j~(1975), 499).

The Balts of the compounds X are obtainable in a conventional manner (EP-A 30)4 282, US-A 4,599,412). They are obtained by deprotonation of the corresponding sulfonylureas I in water or in an inert organic solvent at from -80 to 120*Ct preferably from 0 to 60'Ct in the presence of a base.- Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, hydridest oxides or 0050/42042 alcoholates, such as sodium, potassium and lithium hydroxide, sodium methylate, ethylate or tert-butylate, sodium and calcium hydride and calcium oxide.

Examples of suitable solvents in addition to water are also alcohols, such as methanol, ethanol and tert-butanoll, ethers, such as tetrahydrofuran and dioxane, acetonitrilef dimethylfoztmamider ketones, surh as acetone and methyl ethyl ketone, and halgenated hydrocarbons.

The deprotonation can be carried out under atmospheric pressure or at up to 50 bar, preferably at from atmospheric pressure to a atperatnospheric pressure of 5 bar.

11 O.Z. 0050/42042 The compounds I, or herbicidal agents containing them, and environmentally friendly alkali metal and alkaline earth metal salts, provide excellent control of injurious plants in crops such as wheat, rice and Indian corn without damaging the crop plants, an effect which occurs particularly at low application rates. The compounds may be applied for instance in the form of directly sprayablJ solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

The compounds I are suitable for the preparation of solutions, orulsions, pastes and oil dispersions to be sprayed direct. Examples of inert additives are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xy:ene, paraffin, tetrahydronaphthalene, alkylated naphthalenes 20 and their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar S solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methyl- S* pyrrolidone, water, etc.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions, wottable powders or water-dispersible granules by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, ligninsulfonic acid, phenolsulfonic acid, napAthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonites, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanots, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene dervavtives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyli;a octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octy[phenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, 4fatty alcohol ethylene oxide condensates, ethoxylated O.Z, 0050/42042 castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

9 Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, by 0 neight of active ingredient.

S Examples of formulations are as follows: 9 I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for 25 application in the form of very fine drops.

99 II. 20 parts by weight of compound no. 1 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles if ethylene oxide and 1 mole of oleic acid-N- 30 monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis- ~persion is obtained 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 'sobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

O.Z. 0050/42042 IV. 20 parts by weight of compound no. 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280 0 C, and parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained 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 the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.

VI. 3 parts by weight of compound no. 1 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by S 0 neight of the active ingredient.

VII. 30 parts by weight of compound no. 1 is intimately mixed with a mixture consisting 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 this silica gel. A formulation of the (ctive ingredient is obtained 25 having good adherence.

*e VIII. 20 parts by weight of compound no. 1 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol-ether, 2 parts of the sodium salt of a phenol- 30 sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

The active ingredients or the herbicidal agents containing them may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed froi suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not. touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

4J The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.001 to 1.0, preferably 0.001 to 0.5, kg of active ingredient per hectare.

0.Z. 0050/42042 In view of the numerous application methods possible, the compounds according to the Invention may be used In a large number of crops. Those which follow are given by way of example: 0..

*bb:* be 0 me#* 0 b ,be** 0000 Botanical name Allium cepa Ananas. comosus Arachis hypogaea Asparagus officinalis Beta vulgaris spp. altissima Beta vulgaris spp. rapa Brassica napus var. napus, Brassica napus var. napobrassica Brassica rapa var. silvestris Camellia sinensls Carthamus tinctorlus, Citrus limon Citrus sinensis Coffee arabica (Coffea caniephora, Coffea liberica) Cucumis sativus Cyriodon dactylon Daucus carota Elais guineensis 25 Fragarla vesca Glycine max Gossypium hirsutum (Gossypium arboreum, Gossyplum herbaceum, Gossyplum vitifollum) HelianthU'$ annuus Hevea brasillensis Hordeum vulgare Humulus lupulus Ipomoea batatas Juglans regia Lens culinaris Linum usitatissimum LycoperSicon lycopersicum Malus spp.

Manihot esculenta Medlcago sativa Mentha piperita Musa spp.

Nicotlana tabacum rustica) Olea europaea Common name anions pineapples peanuts (groundnuts) asparagus sugarbeets fodder beets rapeseed swedes tea plants safflower lemons orange trees coffee plants cucumbers Bermudagrass carrots oil Palms strawberries soybeans cotton sunflowers rubber plants barley hops sweet potatoes walnut trees lentils flax tomatoes apple trees c ass av a alfalfa (lucerne) peppermint banana plants tobacco olive trees 0.Z. 0050/42042 Botanical name Oryza sativa Phaseolus lunatus Phaseolus vulgaris Common name rice limabeans snapbeans, green beans, dry beans Picea abies Pinus spp.

Pisum sativum Prunus avium Prunus dulcis Prunus persica Pyrus communis Ribes sylvestre Ribes uva-crispa Ricinus communis Saccharum officinarum Secale cereale Solanum tuberosum Sorghum bicolor vulgare) 20 Theobroma cacao Trifolium pratense Triticum aestivum Triticum durum Vicia faba Vitis vinifera Zea mays Norway spruce pine trees English peas cherry trees almond trees peach trees pear trees redcurrants gooseberries castor-oil plants sugar cane rye Irish potatoes sorghum cacao plants red clover wheat durum wheat tick beans grapes Indian corn, sweet corn, maize To increase the spectrumeof action and to achieve synergistic effects, the triazinyl-substituted sulfonylureas of the formula I may be mixed with each other, or mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-din*troanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, (hetero)-aryloxyphenoxypropionic acids and salts, esters, amides thereof, etc.

It may also be useful to apply the compounds I, either alone or in combination with other herbicides, in admixture with other crop protection agents, agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.

16 0.Z. 0050/42042 Some examples Illustrating the synthesis of the compounds I are given below.

1) 2-ChlIoro-1-N-[4-methoxy-6-trif Iuoromethy 1-1, 3, 5-triazin-2-yI) -am inocarbonylj-benzenesufonamide C1 0 CF 3

OCH

3 At 25 0 C, 4.5 g (21 mmol) of 2-chlorobenzenesulfonyl isocyanate was added to a solution of 4.0 g (21 mmol) of 2-amino-4-methoxy-6-trifluaromethyl-1,3,5-trtazine in 20 ml of acetonitrile. The solution thus obtained was stirred for 21 hours at 25 0 C. The solvent was removed under reduced presssure at 40 0 C, and the solid residue was stirred vigorously for 3 hours with 1 liter of a 1:1 by volume mixture of diethyl ether and hexane. The product was suction filtered and **:dried under reduced pressure at 40 0 C. There was obtained 6.5 g (75% of theory) of the title compound; m.p. 166 168 0

C.

2) SodiumE2-chloro-l-N-[(4-methoxy-6-trifluoromethyl-1,3,5-triazin-2-yl)aminocarbonyl J-benzenesulfonamideI At 25 0 C, 0.66 g (3.6 mmuol) of a solution of sodium methanolate (3Owto) in methanol was added to a suspension of 1.5 g (3.6 nunol) of 2-chloro- (4-nethoxy-6-trifluoromethyl-1, 3-5-triazin-2-yl)-aminocarbonyl)- *benzenesulfonamide in 10 ml of methylene chloride. The homogeneous solution which formed was stirred for 1 hour at 25 0 C. After removal of the volatile portiong at 60 0 C under a water-pump vacuum the title comnpound was obtained in quantitative yield; decomposition point: 220 224 0

C.

The active ingredients given in Table 1 below are obtained analogously: .Table I R R2 0 CF 3 4 ~-SO r*4H-C-NH-<W4N 6 <ORI V 0 S.

S

,*0S06 .6 Compound no.

1 2 3 4 6 7 8 9 11 12 13 14 16 17 18 19 21 22 23 24 25 26 27 28 29 31 32 33 34 36 37 38 39 41 42 43

RI

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH.

3 CH 3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3 C 2

HS

CH

3 C 2

HS

CH

3

CH

3

CH

3

CH~

3

CH

3

CH

3 C 2

H

5

C

2

H

5 Cl.'

CH

3

CH

3

CH

3

CH

3

CH

3 CH 3 CH 3 CH 3 CH 3 R 2 ClI

O(CH

2 2 0CH 3

CF

3 Cl 0(CH 2 2 0CH 3 0(CH 2 2 0CH 3

CF

3 Cl Cl Cl Cl Cl

F

Or

I

F

F

F

F

F

F

F

Cl Cl Cl Cl Cl Cl S0 2

CH

3

SO

2

CH

3 Cl S0 2

CH

3 Cl

CF

3

CH.

3

CF

3

SO

2

C

2

HS

SO 2 -n-C 3

H

7 S0 2 -i-C 3

H

7 Br so0 2 3

H

7 R 3

H

H

H

H

H

H

H

6-Cl

H

H

G-CH

3 5-Cl

H

H

H

H

H

H

6-F 6-F 6-F 6-F 3-Cl 3-ClI 3-Cl 3-Cl 6-CH 3 6-CH 3

H

H

3-Cl

H

H

6-CH 3 6-CH 3

H

H

H

H

H

H

H

Ii MP EC1C 166-168 108-110 164-169 220-224(decomp) Na salt 119 (decomp) Na salt 139 (decomp) Ca salt 165 (decomp) Na salt 168 160-163(deconp) Ca salt 232 (decomp) K salt 140-144 151-156 162-164 >220 (decomp) Na salt >220 (decomp) K salt >220 (decomp) Ca salt 177-180 180-200(decomp) Na salt >220 (decomp) K salt 155-159(decomp) Ca salt 155-157 175-177 197-200(decomp) Na salt 198-201(decomp) Na salt 175-178(decomp) Na salt 180-183 K salt 176-177 186-188 Na salt >220 (decomp) K salt 164-1 149-151 149-150 200 (decamp) 211 (decomo) 152-155 181-182 173-177 183 (decornD) 173 (decamp) 180 (decomol 196 (dJeCnmn) Nia salt Ca salt salt salt sa lt salt is o.Z. 0050/42042 The compounds listed below may be obtained analogously:

R

3 Cl 0 CF 3

OCH

3 or their Na salts, R 3 having the following meanings% hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-ethyl, 6-ethyl, 3-fluoro, 4-flunro, 5-fluoro, 6-fluoro, 3-chioro, 4-chioro, 5-chioro, 6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy;

R

3 Cl 0 CF 3 \O -O 2

-NH-C-NIH<,=\N

0C 2

H

or their Na salts, R 3 having the following meanings: hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-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; *9R3 CF 3 0 CF 3 ,**OCH 3 or their Na salts, R 3 having 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; R3 CF 3 0 CF3

OC

2

HS

or their Na salts, R 3 having the following meanings: hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, I-ethyl, 4-ethyl, 6-ethyl, 3-fluoro, 4-f luoro, 5-fluoro, 6-fluoro, 3-chloro, 0.Z. 0050/42042 4-chloro, 5-chioro, 6-chioro, 3-methoxy, 4-methoxy, 5-methoxy, 6-ruethoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy; R 3 0O(CH 2 2OCH 3 N<CF 3 (~SO 2

-N

1

VN

0 OCH 3

R

3

O(CH

2 2

-OCH

3

N-<CF

3 0 0C 2

H

or their Na salta, R3 having the following meanings: hydogen, 3-methyl, 4-methyl, 5-metiiyl, 6-methyl, 3-ethyl, 4-ethyl, 6-ethyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 4-chioro, 5-chloro, 6-chioro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy, 4-athoxy, 5-ethoxy, 6-ethoxy; R3 S0 2

-CH

3

F

03so 2

'N

11 0 OCH 3 R 3 S0 2

-CH

3 N- F 0 0C 2

H

or their Na salts, R3 having the following meanings: hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-ethyl, 6-cthyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 4-chioro, 5-chloro, 6-chloro, 3-rnethoxy, 4-methoxy, 5-methoxy, '-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy;

R

3 S0 2 -C2H 5

CF

3 0 2 \0 -S 1 N=-4 0 OCH 3 R 3 S0 2

-C

2

H

5

N<CF

3 -S0 2 -NH-j-NH-<' 0 0C 2

H

B# B B

B.

B. B B B 20 B. *B B B

B

or their Na salts, R3 having the following imeanings: hydrogen, 3-methyl, 4-mothyl, 5-methyl, 6-mothyl, 3-ethyl. 4-ethyl, 6-ethyl, 3-fl uoro, 4-fl uoro, 5-fl uoro, 6-fl uoro, 3-chl1oro, 4-chioro, 5-chloro, 6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy;

R

3 S0 2 -n-C 3

H

7 N- CF 3 SO 2

"N

0 OCH 3

R

3

SO

2 -n-C 3 H7 N- F SO- S 2

"N

I I 0 0 2 or their Na salts, R 3 having the following meanings: hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-ethyl, 6-ethyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 4-chloro, 5-chloro, 6-chioro, 3-rnethoxy, 4-rnethoxy, 5-methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy; O.Z. 0050/42042

R

3 SO 2

C

3

H

7

CF

3

R

3 S 2 -1-C 3

H

7

CF

3 >-SOZ-NH-C-NH- /-SO-NR-C-NH-j 'js 0 1 Yr-so N=f< 0 OCH 3 0 0 2

H

or their Na salts, R 3 having the following meanings: hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-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.

Use examples: The herbicidal action of N-[(1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamides of the formula I on the growth of test plants is demonstrated in the following greenhouse experiments.

The vessels employed are plastic flowerpots having a volume of 300 cm 3 and 15 filled with a sandy loam containing about 3.0% humus. The seeds of the test plants are sown separately, according to species.

For the postemergence treatment, plants are used which have been sown in the pots and grown there, or they are grown separately as seedlings and transplanted to the pots a few days before treatment. The plants are grown, depending on growth form, to a height of 3 to 15 cm before being treated with the compounds, suspended or emulsified in water. The application rates for postemergence treatment are 0.06 and 0.03 kg/ha of active ingredient.

The pots are set up in the greenhouse, heat-loving species at 20 to 35 0

C,

and species from moderate climates at 10 to 20 0 C. The experiments are run o for from 2 to 4 weeks. During this period the plants are tended and their reactions to the various treatments assess(l. The Jssessment scale is 0 to S: 30 100, 100 denoting nonemergence or complete aebi-rction of at least the bvisible plant parts, and 0 denoting no damage or normal growth.

The plants employed in the greenhouse experiments are Amaranthus retroflexus, Chenopodium album, Chrysanthemum, Galium aparine, Stellaria media, Triticum aestivum and Zea mays.

I

21 Example no. 1, applied postemergence at 0.06 and 0.03 kg/ha, provides excellent control of unwanted broadleaved plants and proves to be outstandingly selective in the crop plants wheat and Indian corn.

The following table contains results of biological experiments in which the active ingredient example no. 1 was compared with compound B disclosed in U.S. 4,169,719.

C1 O CF3 SO0 2 -NH-C-N

B

OCH

3 Table 1: Comparison of the herbicidal action of Example no. 1 with that of comparative compound B on postemergence application of 0.06 and 0.03 kg/ha in the greenhouse Test plants Damage Appl. rate [kg/ha] Example 1 B 15 0.06 0.03 0.06 0.03

O

Amaranthus retroflexus 65 65 75 SGalium aparine 98 98 90 Chenopodium album 75 70 75 20 Oryza Sativa (rice) 20 0 90 6- In Tables 2 and 3 the compounds of Examples 1 and 3 according to the invention are compared with comparative substances G and H disclosed in U.S. 4,127,405.

N

S02-NH-G-NHY N

G

22 (F 3 0 CH 3 -SO -NH-C-NH--< OCH3 O.Z. 0050/42042 The results clearly demonstrate the surprisingly high selectivity.

The prior art compounds cause unacceptable damage By contrast, Examples 1 and 3 have the same (or better) and only .ause 10% damage to the crop to Indian corn (85 and good herbicidal action plants.

Table 2: Comparison of the herbicidal action of example no. 1 with that of comparative compound G on postemergence application of 0.03 kg/ha of active ingredient in the greenhouse Test plants a Zea mays Unwanted plants: 15 Amaranthus retroflexqs Galium aparine Damage Example 1 Table 3: Comparison of the herbicidal action of Example no. 3 with that of comparative compound H on postemergence application of 0.06 and 0.03 kg/ha of active ingredient in the greenhouse a a a.

S.

S

S

Test plants 25 Zea mays Unwanted plants: Amaranthus retroflexus Galium.aparine 30 Chenopodium album Sinapis alba Damage Appl. rate [kg/ha] Example 3 H 0.06 0.03 0.06 10 10 70 0.03 0 98 Compound no. 7 according to the invention provides excellent selectivity in the sensitive crops spring wheat and Indian corn, as is shown by the results in Tables 4 and 5 below.

W I f A 0.Z. 0050/42042 Table 4: Zontrol of unwanted broadleaved plants and tolerance by spring wheat and Indian corn on postemergenc. application of 0.015 kg/ha of compound no. 7 In the greenhouse Test plants Triticum aestivum Zea mays Unwarite plants: Amatanthus retroflexus 'henopodium album Stellaria media Damage Table 5: Control of unwantcd broadleaved plants and tolerance by rice on postemergence application of 0.015 kg/hia of compound no. 7 In the greenhouse 00* 0* Test plants Oryza 'iativa Unwanted plants: Amaranthus retroflexus Sinapis alba Stellaria media Damage In a further experiment, the sodium salt of comparative compound H was compared with Example 7. The results 4re given in Table 6.

Table 6: Comparison between the herbicidal action of Example no. 7 and that of the sodium salt of comparative compound H on postemergence application of 0.06 and (1.03 kg/ha in the greenhouse 0 0 *000 0090 Test plants see* .6 0 Damage Appl. rate (kg/ha] Example 7 Na salt of H 0.06 0.03 0.06 0.03 10 0 100 100 Zea mays Unwanted plants: Amaranthus retrofle~us Galium aparine Chenopodium album 100 98 100 These results clearly demonstokta the surprisingly high selectivity of the compound acc-rding to the invarition and Its excellent herbicidal action.

Claims (6)

1. N-E(1l, 3 ,-Triazin-2-yl)aminocarbonylj-benzenesulfonamides of the formula I R3 R2 0 I, Oso Z-H-C OR1 where R 1 is me~thyl or ethyl, RZ is halogen, Cl-C 3 -alkylsulfonyl, trifluoromethyl or 2-methoxyethoxy and R3 Is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine or chlorine, and agriculturally useful salts thereof.

2. N-(1,3,5-Triazin-2-yl)aminocarbonylJ-benzenesulfonamjdes of the formula 1, R2 denoting chlorine.

3.1 A process for tlte manufacture of N-((1,3,5-triazin-2-yl)amino- carbonyljbenzenesulfon~imidc of the formula I as set forth in claim 1, wherein a sulfonyl isocyanato II R3 R2 (AY S0 2 NCO X1 is reacted in conventional manner In an inert organic solvent with approximately the stoichiometric amount of a 2-amino-1,3,5-triazine 20 derivative II CF 3 1 Hz-< 'N III. OR1

4. A process for the manufacture of N-[(1,3,5-triazin-2-yl)amIno- .4.4 carbonyl]-benzenesulfonamides of' the formula I as set forth iz claim 1, wherein a carbainate of the formula IV R3 RZ SOZ-N(H-C-0-0 IV is reacted In conventional manwnr In an inert organic solvent at from 0 to 120 0 C with approximately the stoichiometric amount of a 2-amino-1,3,5-trtazine III. 1 4 O.Z. 0050/42042 A process for the maniufacture of N-Ul(,3,5-triazin-2-y ()amiino- carbonyl]-benzenesulft~namides of the formula I as set forth in claim 1, wherein a corresponding sulfonamide of the fortrula V R 3 RZ Y O-SO ZNH 2 V is reacted in conventional manner in an inert organic solvent with a phenylcarbanate VI 0 CF 3 OR 1 6, A process for the manufacture of N-[(l,3,5-triazin-2-yl)amino- carbonylj-benzenesulfonamides of the formula as set forth in e latim 1, wherein a corresponding sulfonamide of the foiwmula V R3 R2 "A A V is rea~cted in conventional manner in an inert organic .5,lvent with an Isocyanate of the formula V11 CF 3 OCN_<_V VI

7. A process for the matuufacture of salts of compo unds I as set forth in *claim 1, wherein a compcund of the formula I as set forth in claim I is deprotonated in conventional manner in water or an inert organic solvent with a base. oo* 8. Herbicidal agent containing an N-[(1,3,5-trtazin-2-yl)anino- Soso carbonylJ-benzenesulfonamide of the formula I as set forth in claim 1, or a salt thereof, and conventional carriers.

9. A process for combating the growth of unwanted plants, wherein a herbicidally effective amount of an N-[(l,3,5-trtazln-2-yl)amno- carbonyll-benzenc-sulfonamide of the formula I as set forth in claim 1, or a salt thereof, is allowed to act on the plants and/or their habitat. 4~j~ LATED this 2nd day of June 1992. S' ASF AKTIENGESELLSCHAFT -F WATERMARK PATENT TRADEM'ARK ATTORNEYS "THE ATRIUM", 290 BURWOOD ROAD xl~l HAWTHORN. VIC. J122. 26 O.Z. 0050/4.2042 ABSTRACT OF THE DISCLOSURE: 3,5-Triazin-2-yl)aminocarbonyllbenzene- sulfonamides of the general formula I R 3 R 2 0 CF 3 0 2 -N H--C-NH- t I, ORI where RI is methyl or ethyl, R2 Is halogen, C 1 -C 3 -alkylsulfonyl, trifluoramethyl or 2-methoxyethoxy and R 3 is hydrogen, methyl,. ethyl, methoxy, ethoxy, fluorine or chlorine, and their agriculturally useful salts, methods of manufacturing them, and their use.