AU8158987A - Herbicidal o-carbomethoxysulfonylureas - Google Patents

Description

HERBICIDAL O-CARBOMETHOXYSULFONYLUREAS Background of the Invention A designated o-carbomethoxysulfonylurea is an extremely attractive agricultural chemical. It has high herbicidal activity and low residual activity and is thus ideally suited to be a fallow herbicide.

The compound of the instant invention is generically disclosed in U.S. Patent 4.383.113. There is a continual need for herbicides which have high activity and low residual activity since land which has been used for production of crops is often allowed to lay fallow to regenerate itself. During the fallow period, weeds tend to grow on the land and drain it of nutrients. Thus, a herbicide is necessary which will destroy the weeds but not interfere with subsequent plantings on the land (have low residual activity).

Summary of the Invention According to the instant invention, such a herbicide has been discovered.

This invention pertains to the compound of Formula I. its agriculturally suitable compositions and its method-of-use as a herbicide for fallow.

The compound is 2-[[N-(4-methoxy-6-methyl-1,3,5- triazin-2-yl)-N-methylaminocarbonyl]aminosulfonyl]- benzoic acid, methyl ester, m.p. 146-148ºC. The compound also undergoes rapid soil dissipation and would ordinarily possess no recrop limitations.

In more detail, a compound useful for the purpose of fallow weed control would be broadspectrum in nature or be compatible with other herbicides to provide the broadspectrum control of both broadleaf and grass weeds. Additionally, the herbicide should provide nonselective control of crop species on a short-term basis such that crop plants germinating during the fallow period may be controlled while crops planted into the fallow area will not be injured. The compound useful for this purpose is highly active exhibiting control of volunteer cereals, mustards. kochia. thistles, and wild buckwheat preemergence and post-emergence. DETAILED DESCRIPTION OF THE INVENTION As part of the present invention, it has been found that unexpectedly high herbicidal activity with low residual activity, is exhibited by 2-[[N-(4- methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylaminocar- bonyl]arainosulfonyl]benzoic acid, methyl ester. The compound of the present invention has the Formula I.

Synthesis

The title compound of Formula I can be prepared by the reaction of 2-carbomethoxybenzenesulfonyl isocyanate (II) with 2-methoxy-4-methyl-6-methylaraino- 1,3,5-triazine (III). The reaction is best carried out in an inert aprotic organic solvent such as dichloromethane. 1,2-dichloroethane. tetrahydrofuran or acetonitrile at a temperature between 20° and 85°C.

The preparation of the intermediate sulfonyl isocyanate II is disclosed in U.S. Patent 4,394.506. The preparation of the aminotriazine III is taught by T. Tsujikawa et al. in Yakugaku Zasshi. 95, 512 (1975) or in Japanese Patent Application 2177('66) (Chem. Abs., 64. 14200 g, 1966). The following example further illustrates the present invention.

Example 1 2-[[-N-[4-methoxy-6-methyl-1,3,5-triazin-2-yl]- N-methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester.

To a solution of 2-carbomethoxybenzenesulfonyl isocyanate (22.4 g 93.0 mmol) in dichloromethane (100 mL) was added 2-methoxy-4-methyl-6-raethylamino-1,3,5- triazine (10.7 g. 69.6 mmol), followed by a catalytic amount of 1,4-diaza[2.2.2]bicyclooctane. After stirring overnight at ambient temperature under a nitrogen atmosphere, the reaction mixture was concentrated in vacuo. The residue was triturated with diethyl ether and then washed with 1-chlorobutane to yield the title compound as a white powder (27.8 g, m.p. 126-131°C). IR(KBr): 1735 (C=O) 1720 (C=O) 1570. 1470. 1430. 1350 (SO₂), 1285, 1270, 1170 (SO₂) and 1160 cm^-1. NMR (CDCl₃/DMSO) δ 2.7 (S. HET-CH₃)

3.4 (s. N-CH₃) 3.9 (s. CO₂CH₃)

4.05 (S. HET-OCH₃) 7.35-7.75 (m. ArH) 8.15-8.4 (m, ArH)

14.0 (broad, NH).

A modification of this procedure involving reduction of the reaction volume, followed by the addition of xylene. led to precipitation of the title compound as a white powder, m.p. 146-148°C. Formulations

Useful formulations of the compound of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient (s) and at least one of (a) about 0.1% to 20% surfactant (s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

* Active ingredient plus at least one of a surfactant or a diluent equals 100 weight percent. Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are some- times desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins. et al., "Handbook of Insecticide Dust Diluents and Carriers". 2nd Ed., Dorland Books. Caldwell. New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience. New York. 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifiers Annual". MC Publishing Corp., Ridgewood. New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents". Chemical Publishing Co., Inc., New York, 1964. list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, micro- biological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and. usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see. for example. Littler. U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration". Chemical Engineering, December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook". 5th Ed., McGraw-Hill. New York, 1973. pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux. U.S. Patent 3.235.361. February 15. 1966. Col. 6. line 16 through Col. 7. line 19 and Examples 10 through 41;

R. W. Luckenbaugh. U.S. Patent 3.309,192, March 14. 1967. Col. 5. line 43 through Col. 7, line 62 and Examples 8. 12. 15. 39. 41. 52. 53. 58. 132. 138-140. 162-164. 166. 167 and 169-182:

H. Gysin and E. Knusli, U.S. Patent 2.891.855. June 23. 1959. Col. 3. line 66 through Col. 5. line 17 and Examples 1-4;

G. C. Klingman. "Weed Control as a Science". John Wiley and Sons. Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans. "Woed Control Handbook". 5th Ed., Blackwell Scientific Publications. Oxford. 1968. pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

Example 2 Wettable Powder

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13%

The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, re- blended, and packaged. Example 3 Wettable Powder

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46%

The ingredients are blended, coarsely hammer- milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.

Example 4 Granule Wettable Powder of Example 3 5% attapulgite granules 95%

(U.S.S. 20-40 mesh; 0.84-0.42 mm) A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules while tumbling in a double-cone blender. The granules are dried and packaged.

Example 5 Extruded Pellet

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid. methyl ester 25% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% calcium/magnesium bentonite 59%

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled. Example 6

Oil Suspension

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid. methyl ester 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70%

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

Example 7 Wettable Powder

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester 20% sodium alkylnaphthalenesulfonate 4% sodium ligninsulfonate 4% low viscosity methyl cellulose 3% attapulgite 69%

The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged. Example 8 Low Strength Granule

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester 1%

N,N-dimethylformamide 9% attapulgite granules 90%

(U.S.S. 20-40 sieve) The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

Example 9 Aqueous Suspension

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid. methyl ester 40.0% polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7% The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

Example 10 Solution 2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosuIfonyl]benzoic acid, methyl ester sodium salt 5% water 95% The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use. Example 11 Low Strength Granule

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester 0.1% attapulgite granules 99.9%

(U.S.S. 20-40 mesh) The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.

Example 12 Granule

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosuIfonyl]benzoic acid, methyl ester 80% wetting agent 1% crude ligninsulfonate salt (containing 10% 5-20% of the natural sugars) attapulgite clay 9%

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use. Example 13 High Strength Concentrate

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]arainosulfonyl]benzoic acid. methyl ester 99.0% silica aerogel 0.5% synthetic amorphous silica 0.5%

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

Example 14 Wettable Powder

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester 90.0% dioctyl sodium sulfosuccinate 0.1% synthetic fine silica 9.9%

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.

Example 15 Wettable Powder 2-[[N-(4-methoxy-6-raethyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosuIfonyl]benzoic acid, methyl ester 40% sodium ligninsulfonate 20% montraorillonite clay 40% The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged. Example 16 Oil Suspension

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester 35% blend of polyalcohol carboxylic 6% esters and oil soluble petroleum sulfonates xylene 59% The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

Example 17 Dust

2-[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N- methylaminocarbonyl]aminosulfonyl]benzoic acid, methyl ester 10% attapulgite 10% Pyrophyllite 80%

The active ingredient it blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

The compound of the instant invention may be used in combination with the following herbicides. 2,4-D flurochloridone

2.4-DB fluroxypyr barban glyphosate basagran imazaquin bentazone ioxynil benzoylpropethyl i soproturon bifenox L-flarαpropisopropyl bromofenoxium linuron bromoxynil Lontrel butraline MCP chlometexynil MCPA chlorfenprop-methyl MCPB clepyralid (3.6-DCP) mecoprop (MCPP) chlorsulfuron methabenzthiazuron chlortoluron metoxuron cyanazine metribuzin diallate metsulfuron dicamba metsulfuron methyl dichlorprop (2,4-DP) neburon diclofop-methyl nitrofene difenzoquat paraquat dinoseb (DNBP) pendimethaline dinoterbe picloram diquat propanil diuron TBA DNOC terbutryn flamprop isopropyl triallate flamprop methyl trifluraline

3-methyl-6-[4,5-dihγdro-5-methyl-5-(1-methylethyl)- 4-oxo-1H-imidazol-2-yl]benzoic acid, methyl ester 3-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino- carbonyl]aminosulfonyl]-2-thiophenecar boxy lie acid. methyl ester

4-chloro-2-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)- aminocarbonyl]aminosulfonyl]benzoic acid, (1-methyl ethyl)ester

Most preferably in combination with: • 3-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino- carbonyl]aminosulfonyl]-2-thiophenecarboxylic acid, methyl ester:

• 3-methyl-6-[4,5-dihydro-5-methyl-5-(1-methylethyl)- 4-oxo-1H-imidazol-2-yl]benzoic acid, methyl ester: • difenzoquat; or

• diclofop-methyl. Ut i l ity

The compound of this invention is useful for the control of weeds in land which is laying fallow. It controls a broad spectrum of broadleaf weeds with low residual activity. Since it is rapidly dissipated in soil, it may be used in situations or where crops sensitive to herbicides now in use will subsequently be planted.

A compound useful for the purpose of fallow weed control is broadspectrum in nature or compatible with other herbicides to provide the broadspectrum control of both broadleaf and grass weeds. Additionally, it should provide nonselective control of crop species on a short-term basis such that crop plants germinating during the fallow period may be controlled while crops planted into the fallow area will not be injured. A compound useful for this purpose is highly active exhibiting control of volunteer cereals, mustards, kochia. thistles, and wild buckwheat preemergence and postemergence.

The rates of application are from 8 to 125 g/ha. The exact rate used will depend on the weeds to be controlled, and their stage of growth, the climate, other herbicides used in combination with it. formulas tion. etc. The exact rate to be used may be selected by one with ordinary skill in the art.

This compound may be used with other compounds including other sulfonylureas, the diarylethers. the ureas. the triazines and the carbamates. The herbicidal properties of this chemical are shown in the greenhouse test that follows.

Procedure

Plastic trays were lined with polyethylene liners and filled with pasteurized Sassafras sandy loam soil (pH 6.5. 1% O.M.). One tray was planted with wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), Italian ryegrass (Lolium multiflorum), and rapeseed (Brassica napus). A second tray was planted with Matricaria inodora. cleavers bedstraw (Galium aparine), Russian thistle (Salsola kali), shepherdspurse (Capsella bursa-pastoris), kochia (Kochia scoparia), black nightshade (Solanum nigrum), speedwell (Veronica persica), wild buckwheat (Polygonum convolvulus), and sugarbeet (Beta vulgaris). For postemergence treatments, the first tray was planted 14 days before spraying, and the second tray was planted 24 days before treatment. Plants in the postemergence treatments ranged in height from 1 to 15 cm depending on specie. Wheat, barley, and wild oats were in the 2-leaf stage of development (Zadoks Stage 11). A second set of trays were prepared in an identical manner before spraying to service as preemergence treatments. Herbicides were diluted in a non-phytotoxic solvent and applied to the trays using a belt sprayer. Additionally, three other species were evaluated: Veronica hederaefolia. chickweed (Stellaria media) and Viola arvensis. These plantings were grown in five inch pots containing the same soil as described previously. The plants were grown for 22 days before treatment. Herbicide application was made in a similar manner as the screening trays.

Plants were grown in the greenhouse for 21 days at which time Visual ratings were made by comparing to an untreated control treatment. Ratings were based on a scale of 0 = no effect to 100 = complete kill.

Claims (2)

WHAT IS CLAIMED IS:

1. A method for controlling the growth of undesired vegetation in land which is laying fallow which comprises applying to the locus to be protected an effective amount of a compound of Formula I.

2. The metood of claim 1 wherein an effective amount of 3-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)- aminocarbonyl]-aminosulfonyl]-2-thiophenecarboxylie acid, methyl ester is used in conjuction with the other compound.