WO1999057983A1

WO1999057983A1 - Crop-safened herbicidal mixtures

Info

Publication number: WO1999057983A1
Application number: PCT/US1999/005263
Authority: WO
Inventors: Daniel Carl Leep
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1998-05-14
Filing date: 1999-03-26
Publication date: 1999-11-18
Also published as: AU3183199A

Abstract

This invention relates to herbicidal mixtures of compound of Formula (I) with safeners selected from Formulae (IIa), (IIb) and (IIc) wherein R?1, R2, R3 and R4¿ are as defined in the text, herbicidal compositions of said mixtures, and a method for the use of said mixtures to control undesired vegetation.

Description

TITLE CROP-SAFENED HERBICIDAL MIXTURES

FIELD OF THE INVENTION The present invention relates to mixtures of herbicides with safeners that reduce crop injury while retaining weed control.

BACKGROUND OF THE INVENTION The control of undesired vegetation is extremely important in achieving high crop efficiency. This can be achieved by the selective control of the growth of weeds in such useful crops as alfalfa, corn (maize), peanut (groundnut), potato, rape, rice, sorghum, soybean, sugar beet, tomato, vegetables, cool-season cereals including wheat, barley and rye, perennial plantation crops including banana, citrus, cocoa, coffee, grapes, hops, plantain, pineapple, oil palm, rubber, sugarcane, tea, fruit trees, nut trees and forests, and turf, among others. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumers. The need for finding products that achieve such results continues to be commercially important.

Herbicidally active compounds are typically applied in combination with nonherbicidal formulating ingredients that facilitate application, increase wash-off resistance, improve penetration, etc. Certain rare combinations of herbicides with nonherbicidal compounds surprisingly reduce the herbicidal effect on crops while retaining useful weed control. The nonherbicidal compounds having this effect are termed "safeners" or "antidotes". By reducing crop injury while retaining control of weeds, effective weed-control selectivity is increased. Such valuable combinations have now been discovered.

SUMMARY OF THE INVENTION

This invention relates to mixtures of a particular oxotriazolecarboxamide herbicide with several compounds discovered to be useful safeners for this herbicide. The herbicidal mixtures comprise herbicidally effective amounts of the compound of Formula I

O

⁰ W .CH, N I

OCH, I ³ which is 4,5-dihydro-3-methoxy-4-methyl-5-oxo-N-[[2-(trifluoromethoxy)phenyl]sulfonyl]- lH-l,2,4-triazole-l-carboxamide (proposed common name: flucarbazone), or an agriculturally suitable salt thereof; in combination with an antidotally effective amount of a safener compound selected from the group consisting of: II

wherein

R¹ is C1-C 12 alkyl, C₃-C₇ cycloalkyl, C₂-C₈ alkenyl or C₂-C₈ alkynyl, each optionally substituted with at least one radical selected from the group consisting of halogen, hydroxy, C1-C4 alkoxy and C!-C₄ alkylthio; or an agriculturally useful salt;

O

W

COR³

II

wherein

R² is H, Cι-C₁₂ alkyl, C3-C7 cycloalkyl, C₂-C8 alkenyl or C₂-C₈ alkynyl, each optionally substituted with at least one radical selected from the group consisting of halogen, hydroxy, C!-C alkoxy and C1-C4 alkylthio; and R³ is H, Cι-C₈ alkyl, C.-C₈ haloalkyl, C₂-C₈ alkoxyalkyl or C.-C₆ hydroxyalkyl; or an agriculturally useful salt; and

O

II

wherein

R⁴ is H, Cι-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₂-C₈ alkenyl or C₂-C₈ alkynyl, each optionally substituted with at least one radical selected from the group consisting of halogen, hydroxy, C1-C4 alkoxy and C1-C4 alkylthio; or an agriculturally useful salt.

This invention also relates to herbicidal compositions comprising effective amounts of the aforesaid mixtures and at least one of the following: surfactant, solid or liquid diluent. This invention also relates to a method of controlling undesired vegetation comprising 3 applying to the locus of the undesired vegetation herbicidally effective amounts of the aforesaid mixtures.

In the above recitations, the term "alkyl", used either alone or in compound words such as "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, «-propyl, z^'-propyl and the different butyl isomers. "Alkoxy" includes, for example, methoxy, ethoxy, «-propyloxy, isopropyloxy and the different butoxy isomers. The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different: The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 12.

Some of the compounds of Formulae Ila, lib and lie can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. The compound of Formula I and some of the compounds of Formulae Ila, lib and lie can be present in the form of salts. In view of the close relationship between these compounds in their free forms and their agriculturally useful salts, including their equilibration under physiological and environmental conditions, hereinbefore and hereinafter any reference to Formula I and Formulae Ila, lib and He is to be understood as including both the free compounds and their agriculturally useful salts, where appropriate and expedient.

The salts of the compounds of Formula I and Formulae Ila, lib and lie include acid- addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of Formula I and Formulae Ila, lib and He also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or enol. Preferred salts include the lithium, sodium, potassium, triethylammonium, and quaternary ammonium salts of the compounds of Formula I.

Preferred for reasons of better weed control or improved crop safety are mixtures of the invention comprising: 4

(a) the compound of Formula I, which is 4,5-dihydro-3-methoxy-4-methyl-5-oxo-N- [[2-(trifluoromethoxy)phenyl]sulfonyl]- 1 H- 1 ,2,4-triazole- 1 -carboxamide, and the compound of Formula Ila where R¹ is CH₂CH₃, which is ethyl l-(2,4- dichlorophenyl)-5-(trichloromethyl)-lH-l,2,4-triazole-3-carboxylate (fenchlorazole- ethyl);

(b) the compound of Formula I, which is 4,5-dihydro-3-methoxy-4-methyl-5-oxo-N- [[2-(trifluoromethoxy)phenyl] sulfonyl] - 1 H- 1 ,2,4-triazole- 1 -carboxamide, and the compound of Formula lib where R² and R³ are each CH2CH3, which is diethyl l-(2,4-dichlorophenyl)-4,5-dihydro-5-methyl-lH-pyrazole-3,5-dicarboxylate (mefenpyr-diethyl); and

(c) the compound of Formula I, which is 4,5-dihydro-3-methoxy-4-methyl-5-oxo-N- [[2-(trifluoromethoxy)phenyl]sulfonyl]-lH-l,2,4-triazole-l-carboxamide, and the compound of Formula He where R⁴ is CH(CH₃)(CH₂)4CH₃, which is 1 -methylhexyl [(5-chloro-8-quinolinyl)oxy]acetate (cloquintocet-mexyl). Also preferred are herbicidal compositions comprising aforesaid preferred mixtures and at least one of the following: surfactant, solid or liquid diluent. Further preferred embodiments are methods of controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the aforesaid preferred mixtures and preferred herbicidal compositions. The preferred crops for application of the mixtures of the invention are cool-season cereals including wheat, barley and rye. Wheat and barley are particularly preferred crops.

DETAILS OF THE INVENTION The Formula I compound can be prepared as described in U.S. 5,534,486. The synthesis involves the reaction of the sulfonyl isocyanate of Formula 1 with the heterocycle of Formula 2.

O

. CH, + HN *r

N- OCH

1 2

U.S. 5,550,244 describes an alternative coupling method.

Safeners of Formula Ila and their agriculturally useful salts can be prepared as described in U.S. 4,639,266. Safeners of Formula lib and their agriculturally useful salts can be prepared by methods described in WO 91/07874. Safeners of Formula He and their agriculturally useful salts can be prepared by methods described in U.S. 4,881,966.

Combinations of the herbicidal compound of Formula I with the particular safeners of Formulae Ila, lib and He identified in Index Table A are illustrative of the scope of this invention. Index Table A

Safeners

Safener Formula R R2 R! R4

1 Ila H - -

2 Ila CH₂CH₃ - -

3 lib - H H

4 lib - CH₂CH₃ H

5 lib - H CH₂CH₃

6 lib - CH₂CH₃ CH₂CH₃

7 lie - - - H

8 He — — — CH(CH₃)(CH₂)₄CH₃

The weight ratios of the compound of Formula I to each safener of Formulae Ila, lib or He (Safeners 1-8) are in general 10:1 to 1:10, with weight ratios of 4:1 to 1:4 preferred for most uses.

Formulation/Utility

The mixtures of the Formula I compound with the Formulae Ila, lib or He compounds can be formulated in a number of ways:

(a) the Formula I and Formulae Ila, lib or lie compounds can be formulated separately and applied separately, with preferably the Formulae Ila, lib or He safeners applied first; or

(b) more preferably the Formula I and Formulae Ila, lib or He compounds can be applied simultaneously in an appropriate weight ratio, e.g., as a tank mix; or

(c) most preferably the Formula I and Formulae Ila, lib or He compounds can be formulated together in the proper weight ratio.

Mixtures of the Formula I compound with the Formulae Ila, lib or He compounds will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent and/or a surfactant wherein the formulation is consistent with the 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 micro- emulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the 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 the 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 the following approximate ranges which add up to 100 percent by weight.

Weight Percent

Active

Ingredient Diluent Surfactant

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 Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd 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 growth and the like, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N-N-dialkyltaurates, lignin sulfonates, naphthalene 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, N-N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, rung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. 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 formulation, 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 the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound 1 is the compound of Formula I, which is 4,5- dihydro-3-methoxy-4-methyl-5-oxo-N-[[2-(trifluoromethoxy)phenyl]sulfonyl]- 1H- 1 ,2,4- triazole- 1 -carboxamide. Safener numbers are defined in Index Table A (page 5).

Example A High Strength Concentrate

Compound 1 9.0%

Safener 2 89.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%. Example B

Wettable Powder

Compound 1 52.0%

Safener 6 13.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. 8 Example C Granule

Compound 1 5.0%

Safener 8 5.0% attapulgite granules (low volatile matter,

0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.

Example D Aqueous Suspension

Compound 1 5.0% Safener 2 20.0% hydrated attapulgite 3.0% crude calcium ligninsulfonate 10.0% sodium dihydrogen phosphate 0.5% water 61.5%. Example E

Extruded Pellet

Compound 1 12.5%

Safener 2 12.5% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Example F

High Strength Concentrate Compound 1 89.5%

Safener 8 9.0% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.

Test results indicate that combination of the oxotriazolecarboxamide herbicide of Formula I with a safener of Formulae Ila, lib or He affords a highly active herbicidal mixture, providing unexpected safening on cool-season cereal crops such as wheat, barley and rye, while retaining good efficacy for controlling problem weeds in these crops. These combinations are valued for their ability to control gramineous weeds such as wild oats, ryegrass, blackgrass and green foxtail in cool-season cereal crops. The antidoting of the effect of the oxotriazolecarboxamide herbicide of Formula I by the safeners of Formulae Ila, lib or He on cool-season cereal crops but not on gramineous weeds is particularly surprising and valuable, because both are grasses and selective control of gramineous weeds in cereals is often difficult. Herbicidally effective amounts of the compound of Formula I and antidotally effective amounts of the safeners of Formulae Ila, lib or lie will vary depending on environmental conditions, formulation, method of application, amount and type of vegetation present, etc. The use rate ratios of Formula I to Formulae Ha, lib or He are in general 10:1 to 1 :10 by weight, with weight ratios of 4:1 to 1:4 preferred for most uses. In general, the Formula I compound is applied at a rate from 1 to 100 g ai/ha and the Formulae Ila, lib or He compounds are applied at rates from 0.1 to 1000 g ai/ha. Preferably, the Formula I compound is applied at a rate from 10 to 50 g ai/ha, and the Formulae Ila, lib or He compounds are applied at rates from 2 to 100 g ai/ha. For selective control of certain weed species in cereal crops, the mixtures of the invention are best applied when the cereal plants are at about the 1 -leaf through tillering stage and the weed plants are correspondingly young. One skilled in the art can readily determine application rates and ratios of the herbicide of Formula I to the safeners of Formulae Ha, lib or He as well as timing necessary for the desired level of weed control and crop safety.

The Formula I and Formulae Ila, lib or He mixtures of this invention can additionally be used in combination with other commercial herbicides, insecticides or fungicides. A mixture of one or more of the following herbicides with the Formula I and Formulae Ila, lib or He mixtures of this invention may be particularly useful for weed control. Examples of other herbicides particularly useful as mixture partners are: 2,4-D, bentazon, benzoylpropethyl, bromoxynil, chlorsulfuron, chlortoluron, clodinafop, clopyralid, cyanazine, diallate, dicamba, diclofop, difenzoquat, diflufenican, fenchlorazole, fenoxaprop, flamprop-M-isopropyl, fluroglycophen-ethyl, fluroxypyr, glyphosate, imazamethabenz, ioxynil, isoproturon, linuron, MCPA, mecoprop, methabenzthiazuron, metosulam, metoxuron, metribuzin, metsulfuron methyl, N-[[(4,6-methoxy-2-pyrimidinyl)amino]- carbonyl]-2-(ethylsulfonyl)imidazo[ 1 ,2-a]pyridine-3-sulfonamide (ISO-proposed: sulfosulfuron), neburon, paraquat, pendimethalin, propanil, prosulfocarb, prosulfuron, quinclorac, simazine, terbutryn, thifensulfuron methyl, tralkoxydim, triallate, triasulfuron, tribenuron methyl and trifluralin. In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

The oxotriazolecarboxamide herbicidal compound of Formula I (Compound 1) is tested alone and in combination with a safener of Formula Ha (Safener 2), a safener of Formula lib (Safener 6) or a safener of Formula He (Safener 8). The Safener numbers are defined in Index Table A (page 5). The test data show Safener 2, Safener 6 and Safener 8 surprisingly reduce the injury caused by Compound 1 on cool-season cereal crops such as 10 wheat and barley while retaining good efficacy against undesired vegetation, including gramineous weeds.

The following protocol was used for the test in Table A. The data demonstrate the efficacy of the Formula I and Formula Ha mixtures, the Formula I and Formula lib mixtures, and the Formula I and Formula He mixtures of this invention in safening cereal crops while controlling specific weeds. The crop safening and the weed control afforded by the mixtures of this invention are not limited, however, to these species.

Test A Protocol

Spring wheat (Triticum aestivum cult. 'Katepwa') (TR-ZAS) and spring barley (Hordeum vulgare cult. 'Harrington') (HORVS) and the weeds: wild oats (Avena fatua) (AVEFA) and green foxtail (Setaria viridis) (SETvT) were grown in a greenhouse to approximately the two-leaf stage in 10-cm square plastic pots filled with a mixture of 60% sandy loam soil and 40% Metro-Mix 360™ growing medium. Treatments were applied to the test species by diluting the compounds in a non-phytotoxic solvent, and spraying the treatments onto the plants. All treatments were comprised of 5 replicates. Compound 1 was applied at 31 g ai/ha. Safener 2, Safener 6 and Safener 8 were each applied at 16 g ai/ha. Mixtures of Compound 1 at 31 g ai/ha and Safener 2 at 16 g ai/ha, Compound 1 at 31 g ai/ha and Safener 6 at 16 g ai/ha, and Compound 1 at 31 g ai/ha and Safener 8 at 16 g ai/ha, were also applied. After treatment, the plants were maintained in a greenhouse and were evaluated 11 days after spraying. All sprayed plants were evaluated for injury as compared to control plants that were sprayed only with non-phytotoxic solvent. Injury was evaluated visually using a 0 to 100% scale where 0 indicates no effect and 100 indicates complete kill.

Results of Test A are shown in Table A, which lists the observed response of individual species to Compound 1, Safener 2, Safener 6, and Safener 8 applied alone as single active ingredients, the observed response of individual species to the mixture of Compound 1 and Safener 2, the expected additive effect of the mixture of Compound 1 and Safener 2, the observed response of individual species to the mixture of Compound 1 and Safener 6, the expected additive effect of the mixture of Compound 1 and Safener 6, the observed response of individual species to the mixture of Compound 1 and Safener 8, and the expected additive effect of the mixture of Compound 1 and Safener 8. Crops other than those specifically listed are also safened and weeds other than those specifically listed are also controlled by mixtures of Compound 1 and Safener 2, Compound 1 and Safener 6, and Compound 1 and Safener 8. Different ratios of Compound 1 to Safener 2, Compound 1 to Safener 6, and Compound 1 to Safener 8, also provide effective crop safening and weed control. Different formulation types also provide useful crop safening and weed control from the combinations of Compound 1 and Safener 2, Compound 1 and Safener 6, and Compound 1 and Safener 8. 1 1

TABLE A*

Effect of Compound 1, Safener 2, Safener 6, and Safener 8 as Active Ingredients Alone and in Mixtures

Safeners Crops Weeds

CMPD 1 SFNR 2 SFNR 6 SFNR 8 TRZAS HORVS AVEFA SETVI

Alone

31 0 0 0 Obs.^a 5 49 87 100

0 16 0 0 Obs. 0 0 0 . 0

0 0 16 0 Obs. 0 0 0 0

0 0 0 16 Obs. 0 0 0 0

Mixtures

31 16 0 0 Obs. 1 39 85 100

31 16 0 0 Exp.^b 5 49 87 100

31 0 16 0 Obs. 3 30 84 100

31 0 16 0 Exp. 5 49 87 100

31 0 0 16 Obs. 0 37 87 100

31 0 0 16 Exp. 5 49 87 100

^♦Rates are expressed in g ai ha for Compound 1 (CMPD 1), Safener 2 (SFNR 2) , Safener 6 (SFNR 6), and Safener 8 (SFNR 8). Data are reported as percent control. ^a "Obs." is the observed effect. ^b "Exp." is the expected effect. As the Safener 2, Safener 6 and Safener 8 applied alone at 16 g/ha showed no herbicidal effects, the effects expected from mixtures with Compound 1 are the same as the effect from Compound 1 applied alone at 31 g/ha. As can be seen from Table A, each of the three safeners significantly decreased injury caused by Compound 1 at 31 g/ha on wheat (TRAZS) and barley (HORVS). As the injury caused by Compound 1 was slight on wheat, the reduction of injury possible through use of these safeners was also small, but the safening was still beneficial. Compound 1 was much more injurious to barley, and the safeners provided a considerable reduction in injury. In contrast to the results for wheat and barley, the three safeners caused little or no diminution of the control provided by Compound 1 on wild oats (AVEFA) and green foxtail (SETVI). Wild oats and green foxtail are grasses and are therefore difficult to selectively control in grass crops like wheat and barley. The enhanced selectivity provided by the mixtures of this invention is thus not only surprising but also commercially valuable.

Claims

12CLAIMS What is claimed is:

1. A mixture comprising a herbicidally effective amount of the compound of Formula I

O

^ N

N-

OCH,

I or an agriculturally useful salt; in combination with an antidotally effective amount of a safener compound selected from the group consisting of:

II

cr i wherein

R¹ is C╬╣-C╬╣ alkyl, C3-C₇ cycloalkyl, C₂-C₈ alkenyl or C₂-C₈ alkynyl, each optionally substituted with at least one radical selected from the group consisting of halogen, hydroxy, C1-C4 alkoxy and C1-C4 alkylthio; or an agriculturally useful salt;

O

W

COR³

II

cr ╬▒ wherein

R² is H, C,-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₂-C₈ alkenyl or C₂-C₈ alkynyl, each optionally substituted with at least one radical selected from the group consisting of halogen, hydroxy, C1-C4 alkoxy and C1-C₄ alkylthio; and R³ is H, C -C₈ alkyl, C.-C₈ haloalkyl, C₂-C₈ alkoxyalkyl or C.-C₆ hydroxyalkyl; or an agriculturally useful salt; and 13

O

II

wherein

R⁴ is H, C.-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₂-C₈ alkenyl or C₂-C₈ alkynyl, each optionally substituted with at least one radical selected from the group consisting of halogen, hydroxy, C1-C4 alkoxy and C1-C4 alkylthio; or an agriculturally useful salt.

2. The mixture of Claim 1 wherein the safener compound is ethyl l-(2,4-dichlorophenyl)-5-(trichloromethyl)-lH-l,2,4-triazole-3-carboxylate.

3. The mixture of Claim 1 wherein the safener compound is diethyl 1 -(2,4-dichlorophenyl)4,5-dihydro-5-methyl- lH-pyrazole-3 ,5-dicarboxylate.

4. The mixture of Claim 1 wherein the safener compound is 1-methylhexyl [(5-chloro-8-quinolinyl)oxy]acetate.

5. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the mixture of any of Claims 1-4 and at least one of the following: surfactant, solid or liquid diluent.

6. A method for controlling the growth of undesired vegetation by applying to the locus of the undesired vegetation a herbicidally effective amount of the mixture of any of Claims 1^ .

7. The method of Claim 6 wherein the locus of the undesired vegetation is a crop of wheat or barley.