HERBICIDAL MIXTURES

Abstract: This invention relates to herbicidal mixtures of methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridine-carboxylate and agriculturally suitable salts thereof with ethyl alpha ,2-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]-4-fluorobenzenepropanoate, herbicidal compositions of said mixtures, and a method for the use of said mixtures to control undesired vegetation.

Description: TITLE HERBICIDAL MIXTURES BACKGROUND OF THE INVENTION WO 94 09629 discloses mixtures of sulfonylureas and triazolinones, but does not disclose die mixtures of this invention. WO 92/15576 and WO 90/02120 disclose Foπnula I compounds and die Formula II compound, respectively, but do not disclose d e mixtures of this invention. SUMMARY OF THE INVENTION This invention relates to mixtures of die sulfonylurea of Foπnula I (meΛyl 2-[[[[(4, H__oeΛoxy-2-pyj±nio_nyl)an^ (trιΩuoromethyl>-3-pyridinecarboxylate) and agriculturally suitable salts diereof with die triazolinone of Formula II (ethyl a,2-dicMoro-5-[4-(dMuarane l)-4,5-dihydro-3-methyl-5-oxo- 1H-1,2,4- triazol- 1 -yl]-4-fluorobenzenepropanoate) , which have now been discovered to synergistically control weeds. This invention also relates to herbicidal compositions comprising effective amounts of die aforesaid mixtures and at least one of die following: surfactant, solid or liquid diluent. This invention also relates to a method for controlling undesired vegetation comprising applying to die locus of die vegetation herbicidally effective amounts of die aforesaid mixtures. Agriculturally suitable salts of the sulfonylurea of Formula I include, but are not limited to, quaternary amine salts, and die alkali metal salts of Formula la la wherein M is an alkali metal, such as lid ium, sodium or potassium. The Formula II compound may exist as two stereoisomers which include d e ' R- and S-enantiomers. One skilled in die art will appreciate tiiat one stereoisomer may be more active and/or may exhibit other beneficial effects when enriched relative to the other stereoisomer or when separated from the otiier stereoisomer. One skilled in die art knows how to separate said enantiomers. Accordingly, die present invention comprises mixtures of Formula I sulfonylurea in admixture witii d e racemic mixtures, individual stereoisomers, and enriched optically active mixtures of the Formula II enantiomers. The mixtures of die invention preferred for enhanced activity include: 1. A herbicidal mixture comprising die sulfonylurea salt of Foπnula la wherein M is Na and die triazolinone of Foπnula II. 2. A herbicidal mixture comprising die sulfonylurea of Formula I and die triazolinone of Formula II. For reason of weed control spectrum and/or crop selectivity, die preferred crops for application of die mixtures of this invention are wheat and barley. DETAILS OF THE INVENTION The Formula I sulfonylurea can be prepared as described in WO 92/15576. The synd esis involves d e coupling of die pyiidinesulfonamide of Formula 1 witii die heterocyclic carbamate of Formula 2. The mixtures of die present invention can include the sulfonylurea of Formula I as one or more of its agriculturally suitable salts. These can be prepared in a number of ways known in die art. For example, metal salts can be made by contacting d e sulfonylurea of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiendy basic anion (e.g., hydroxide, alkoxide, carbonate or hydride). Quaternary amine salts can be made by similar techniques. WO 92/15576 describes the preparation of die salt of Formula la wherein M is Na by use of sodium medioxide. Salts of die sulfonylurea of Formula I can also be prepared by exchange of one cation for anodier. Cationic exchange can be effected by direct contact of an aqueous solution of a salt of die sulfonylurea of Foπnula I (e.g., alkali or quaternary amine salt) with a solution containing die cation to be exchanged. This metiiod is most effective when die desired salt containing die exchanged cation is insoluble in water and can be separated by filtration. Exchange may also be effected by passing an aqueous solution of a salt of die sulfonylurea of Formula I (e.g., an alkali metal or quaternary amine salt) dirough a column packed witii a cation-exchange resin containing die cation to be exchanged for that of die original salt and die desired product is eluted from die column. This method is particularly useful when d e desired salt is water soluble (e.g., a potassium, sodium or calcium salt). The Formula II triazolinone can be prepared by methods described in WO 90/02120 which involve die reaction of die aniline of Foπnula 3 witii the acrylate of Formula 4 under Meerwein conditions. 3 4 Foπnulation/Utilitv The mixtures of die Foπnula I (including Formula la) and Foπnula II compounds can be formulated in a number of ways: (a) me Formula I arid Formula π compounds can be formulated separately and applied separately or applied simultaneously in an appropriate weight ratio, e.g., as a tank mix; or (b) the Formula I and Foπnula II compounds can be formulated togedier in die proper weight ratio. Mixtures of the Foπnula I and Foπnula II compounds will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent and/or a surfactant wherein die formulation is consistent widi die physical properties of the active ingredients, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and or suspoemulsions) and d e like which optionally can be diickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and d e like which can be water- dispersible ("wettable") or water-soluble. Active ingredients can be (micro)- encapsulated and further formed into a suspension or solid formulation; alternatively d e entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredients. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredients, diluent and surfactant within die following approximate ranges which add up to 100 percent by weight. Weight Percent Active Ingredient Diluent Sffl actaηt Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates) Dusts 1-25 70-99 0-5 Granules and Pellets 0.01-99 5-99.99 0-15 High Strength Compositions 90-99 0-10 0-2 Typical solid diluents are described in Watirins, et al., Handbook of Insecticide Dust Diluents and Carriers, lad Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growtii and die like, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyedioxylated alkylphenols, polyedioxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N -dialkyltaurates, lignin sulfonates, naphdialene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillinite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, dimediyl sulfoxide, N-alkylpyrrolidone, ediylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphd alenes, oils of olive, castor, linseed, tung, sesame, com, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-med yl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tettahydrofiirfuryl alcohol. Solutions, including emulsifiable concentrates, can be prepared by simply mixing die ingredients. Chemically stabilized aqueous sulfonylurea or agriculturally suitable sulfonylurea salt dispersions are taught in U.S. 4,936,900. Solution formulations of sulfonylureas with improved chemical stability are taught in U.S.4,599,412. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet -milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566. For further information regarding foπnulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, 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; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989. In die following Examples, all percentages arc by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds identified on Page 8. Example A High Strength Concentrate Compound 1 33.0% Compound 2 65.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%. Example B Wettable Powder Compound 1 22.0% Compound 2 43.0% dodecylphenol polyethylene glycol ether 2.0% sodium Ug nsulfonate 4.0% sodium sflfcoaluminate 6.0% montmorillonite (calcined) 23.0%. Example C Granule Compound 1 3.5% Compound 2 6.5% attapulgite granules flow volatile matter, 0.71 0.30 mm; U.S.S. No. 25-50 sieves) 90.0%. Example D Aqueous Suspension Compound 1 8.5% Compound 2 16.5% hydrated attapulgite 3.0% crude calcium Ugninsulfonate 10.0% sodium dihydrogen phosphate 0.5% water 61.5%. Example E Extruded Pellet Compound 1 8.5% Compound 2 16.5% anhydrous sodium sulf ate 10.0% crude calcium Ugninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calc im magnesium bentonite 59.0%. Test results indicate that mixtures of compounds of Formula I and Foπnula II are highly active heibicides, providing 1 unexpected synergistic control of selected grass and broadleaf weeds. The mixtures are valued, because tiiey retain acceptable levels of crop selectivity in certain major agronomic crops such as barley, cotton, wheat, corn, soybeans and rice. The mixtures are particularly valued because of die acceptable levels of crop selectivity they retain in barley and wheat. The Formula I and Formula II mixtures of this invention can additionally be used in combination witii other commercial heibicides, insecticides or fungicides. A mixture of one or more additional herbicides witii the Formula I and Formula II mixtures of this invention may be particularly useful for weed control. Examples ' of other herbicides as mixture partners are: anilofos, teι_n_furon methyl, chlorsulfuron, cinosulfuron, imazamed abenz, mefluidide, metsulfuron methyl, rimsulfuron, d ifensulfuron methyl, triasulfuron and tribenuron methyl, and herbicides with a similar spectrum of control but a different mode of action such as, but not limited to: barban, bentazon, bifenox, bromoxynil, bromoxynil heptanoate, bromoxynil octanoate, chloridazon, chlortoluron, clodinafσp, clopyralid, cyanazine, dicamba, diclofop, dichloiprop, diclofop, difenzoquat, fenoxaprop, flamprop, flupoxam, fluridone, flurtamone, glufosinate, glyphosate, ioxynil, isoproturon, isσxaben, MCPA, MCPA-diioediyl, MCPB, mecoprop, mecoprop-P, methabenzthiazuron, metribuzin, pendimethalin, tri-allate, tralkoxydim, ϋifltαralin, (2,4-dichlorophenoxy)acetic acid, and 4-(2,4-dichloro- phenoxy)butanoic acid. In certain instances, combinations with herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management. An heibicidally effective amount of both die compounds of Formula I and Formula II will vary depending on die specific compounds selected, environmental conditions, formulation, method of application, amount and type of vegetation present, etc. The use rate ratios of Formula I to Foπnula II are in general 1:15 to 1:1, with ratios of 1:4 to 1:1 preferred for most uses. A use rate ratio of 1:2 is particularly preferred. In general, the Formula I compounds should be applied at a rate from 0.0005 to 1 kg ai ha and Foπnula II compounds should be applied at a rate from 0.001 to 2 kg ai/ha. Preferably, Foπnula I compounds should be applied at a rate from 0.002 to 0.03 kg aiha, and d e Foπnula II compound should be applied at a rate from 0.004 to 0.03 kg ai/ha. One skilled in die art can readily determine application rates and ratios of herbicides of Formula I to the herbicide of Formula II as well as timing necessary for the desired level of weed control and crop safety. The following Foπnula I sulfonylurea (Compound 1) was tested in combination with die Foπnula II triazolinone (Compound 2). Compound 1 Compound 2 The following Test protocol was used for the Tests in Tables 1-3. The data demonstrate the efficacy of d e Formula I and Foπnula II mixtures of this invention against specific weeds. The weed control afforded by die mixtures of this invention are not limited, however, to these species. Test Protocol Cereal crops were planted during fall into areas of high natural infestations of weed species such as; Galium aparine (GALAP), Viola arvensis (VIOAR), and various Veronica sp. (V. persica (VERPE), and V. hederaefolia (VERHE)). Test plots were typically 20 sq meters (2 meters wide by 10 meters in length), with die entire test plot area treated postemergence to the crops and weeds. Compound 1 and Compound 2 were both formulated as single active ingredients in 50% strength dry flowable granules. Compound 1 and Compound 2 were formulated as a mixture in a ratio of 1:2 respectively, in 50% total active ingredient strength paste extruded granules. Herbicides were applied to die test area by diluting d e formulated herbicides in an aqueous solution to d e appropriate concentration to deliver the desired use rate, spray volumes between 150 to 300 I ιa were typically used. The prepared test solutions were tiien sprayed onto die test plot using approximately 2 bars pressure through standard T-Jet flat-fan nozzles. Unless specifically indicated, no additional adjuvants such as surfactants were added to die spray solution. Individual treatments were typically replicated three times at any given field trial location. Assessments of weed control were made by visual inspection at intervals following herbicide application. The specific tests for Tables 1-3 were final evaluations which ranged from 34 to 200 days after application. A visual rating system was used based on a percentage scale from 0 to 100%, relative to an adjacent untreated control plot or test area. On this scale 0% represents no visual differences relative to an untreated control, 100% represents complete kill of the given crop or weed species. Colby's equation was used to calculate the expected additive herbicidal effect of d e mixtures of Compound 1 and Compound 2. Colby's equation (Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967)) calculates die expected additive effect of herbicidal mixtures, and for two active ingredients is of die form: P a+b = P a + P b - (P a P b / 100) wherein P^ j , is the percentage effect of the mixture expected from additive contribution of the individual components, P a is die observed percentage effect of the first active ingredient at die same use rate as in the mixture, and P D is the observed percentage effect of the second active ingredient at die same use rate as in the mixture. Tables 1 through 3 represent final visual assessments of control of specific weeds with Compound 1 and Compound 2 applied alone as single active ingredients, applied as a mixture of the two active ingredients of Compound 1 and Compound 2, and d e expected additive effect of die herbicidal mixture of Compound 1 and Compound 2 (Colby's equation). Different ratios of Compound 1 to Compound 2, and different formulation types, should also provide useful weed control from die combination of die two herbicides. TABLE 1* Control of Viola arvensis Using Compound 1 and Compound 2 as Single Active Ingredients and in Admixture Rate Compound (K ai ha) Test 1 Test 2 Test 3 Test 4 Test 5 1 10 72 38 0 35 75 2 20 83 63 0 10 50 1 + 2 10 + 20 97 (95)t 97 (77) 65 (0) 70 (42) 100 (88) Tests 1-5 were conducted at different locations. Data are reported as percent control Expected effects in parentiieses are calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967) IΔB EJ* Control of Two Veronica sp. Using Compound 1 and Compound 2 as Single Active Ingredients and in Admixture VERPEt VERHEt Rate Compound (g ai ha) Test l Test 2 Test 3 Test 4 Test 5 Test 6 1 10 37 47 0 0 20 23 2 20 100 92 50 70 70 89 1 + 2 10 + 20 100 (100)* 98 (96) 70 (50) 80 (70) 85 (76) 97 (92) * Tests 1-6 were conducted at different sites. Data are reported as percent control t Weed species: VERPE = Veronica persica; VERHE = Veronica hederaefolia % Expected effects in parentheses are calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967) IΔBJJ S* Control of Galium aparine Using Compound 1 and Compound 2 as Single Active Ingredients and in Admixture Rate Compound (« ai/ha) Test 1 Test 2 Test 3 Test 4 1 10 70 85 55 75 2 . 20 89 90 75 85 1 + 2 10 + 20 94 (97)t 100 (98) 90 (89) 99 (96) * Tests 1-4 were conducted at different sites. Data are reported as percent control t Expected effeαs in parentheses are calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967)

Claims: CLAIMS 1. A herbicidal mixture comprising an herbicidally effective amount of the compound of Formula I which is mediyl 2-[[[[(4,6-djmedιoxy-2-py)imid yl)amino]carbonyl]amino]- sulfonyl]-6-(trι_luoromethyl)-3-pyridinecarboxylate and agriculturally suitable salts thereof and an herbicidally effective amount of die compound of Foπnula II which is ethyl α,2-dicWoro-5-[4^difluoromethyl)-4 t 5-dihydro-3-methyl-5-oxo-l f ' - 1 ,2,4-triazol-l -yl]-4-fluorobenzenepropanoate. 2. An agriculturally suitable composition for controlling die growth of undesired vegetation comprising an effective amount of the heibicidal mixture of Claim 1 and at least one of die following: surfactant, solid or liquid diluent 3. A method for controlling die growth of undesired vegetation comprising contacting the locus to be protected with a herbicidally effective amount of die composition of Claim 2. 4. A heibicidal mixture of Claim 1 comprising the sodium salt of die compound of Foπnula I and die compound of Foπnula II.

Inventors: TEANEY SHAWN RANDOLPH, TEANEY, SHAWN, RANDOLPH
Applicants: DU PONT, TEANEY SHAWN RANDOLPH, E.I. DU PONT DE NEMOURS AND COMPANY, TEANEY, SHAWN, RANDOLPH
Application year: 1995
Main classification: A01N47
IPC codes: A01N47