AU658452B2 - Synergistic interaction of herbicidal aryloxypropionic acid derivatives and cyclohexanediones - Google Patents

Description

OPI DATE 05/04/93 APPLN. ID 26776/92 AOJP DATE 10/06/93 PCT NUMBER PCT/US92/07709 fhIUIIIIIIII 111111 B 22677

/(PCT)

(51) International Patent Classification 5 (11) International Publication Number: WO 93/04581 AO1N 43/40, 35/10 Al (43) International Publication Date: 18 March 1993 (18.03.93) (21) International Application Number: PCT/US92/07709 (81) Designated States: AU, BG, BR, CA, CS, HU, JP, PL, RO, RU, European patent (AT, BE, CH, DE, DK, ES, FR, (22) International Filing Date: 11 September 1992 (11.09.92) GB, GR, IE, IT, LU, MC, NL, SE).

Priority data: Published 07/758,038 12 September 1991 (12.09.91) US With international search report.

With amended claims.

='(72)-Appliant-atn=Inventors: COLBY, Robert [US/US]; 685 Belvedere Drive, Benicia, CA 94510 CASEY, John, Stephen [US/US]; 15824 Jackson Drive, Omaha, NB 68118 ANDERSON, James [GB/JO]; P.O.

Box 901, Al Jubeiha, Amman, Jordan GU30 7LU (JO).

(74) Agents: ACKERMAN, Joel, G. et al.; ICI Americas Inc., 1200 South 47th Street, Box 4023, Richmond, CA 94804-0023 (US).

Z C /47/-r Sifn47 Ga /e F I"

T

(54)Title: SYNERGISTIC INTERACTION OF HERBICIDAL ARYLOXYPROPIONIC ACID DERIVATIVES AND CYC-

LOHEXANEDIONES

x

CF

3 0 O-CH-COOR (I) -N 3

NOR

2 S(57) Abstract A synergistic herbicidal composition comprising: an aryloxypropionic acid derivative of formula and a cyclohexanedione derivative of formula (II).

WO 93/04581 PCT/ US92/07709 1 SYNERGISTIC INTERACTION OF HERBICIDAL ARYLOXYPROPIONIC ACID DERIVATIVES AND CYCLOHEXANEDIONES Background of the Invention The protection of crops from weeds and other vegetation which inhibit crop growth is a constantly recurring problem in agriculture. To help combat this problem, researchers in the field of synthetic chemistry have produced an extensive variety of chemicals and chemical formulations effective in the control of such unwanted growth. Chemical herbicides of many types have been disclosed in the literature and a large number are in commercial use.

In some cases, active herbicides have been shown to be more effective in combination than when applied individually. The result is often termed "synergism", since the combination demonstrates a potency or activity level exceeding that which it would be expected to have, based on a knowledge of the individual potencies of the components. The present invention resides in the discovery that certain aryloxypropionic acid derivatives and certain cyclohexanediones, already known individually for their herbicidal potency, display a synergistic effect when applied in combination.

Prior Art The two classes of compounds forming the combination which is the subject of the present invention are independently known in the art for their effects on plant growth. Herbicidal aryloxypropionic acid derivatives are disclosed in U.S.

Patents Nos. 4,267,336, 4,317,913 and 4,414,391; British WO 93/04581 PC/US92/07709 2 Patents Nos. 1,599,121 and 2,002,368. Also, see the Pesticide Manual, 9th ed., edited by C. R. Worthing and R. J. Hance, pp.

400, 401 and 463.

Derivatives of cyclohexanediones are disclosed as herbicides in U.S. Patent 3,950,420, EPA 80301, EP-B-85529.

Description of the Invention It has now been discovered that synergism in the control of undesirable vegetation is exhibited by compositions comprising: An aryloxypropionic acid derivative of the formula in which X is hydrogen or halogen;

R

1 is hydrogen, C1-C 6 alkyl, C 1

-C

6 alkoxyalkyl; and a cyclohexanedione derivative of the formula (R)n

OR

4 in which WO 93/04581 PCT/US92/07709 3 R is independently hydrogen; halogen; nitro; cyano; 1-C 6 alkyl; C 1 -C 6 alkyl substituted with a substituent selected from the group consisting of halogen, nitro, hydroxy,

C

1

-C

6 alkoxy and C 1

-C

6 alkylthio; C 2

-C

6 alkenyl; C 2 -Cg alkynyl; hydroxy; C 1

-C

6 alkoxy; C 1

-C

6 alkoxy substituted with a substituent selected from halogen and C 1

-C

6 alkoxy; C 2

-C

6 alkenyloxy; C 2

-C

6 alkynyloxy; C 2

-C

6 alkanoyloxy; (C-C 6 alkoxy)carbonyl; C 1

-C

6 alkylthio; C 1

-C

6 alkylsulfinyl; C 1

-C

6 alkylsulfonyl; sulfamoyl; N-C( 1

-C

6 alkyl)sulfamoyl; N,N-di(C 1

-C

6 alkyl)sulfamoyl; benzyloxy, substituted benzyloxy wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, C1-C alkyl, C 1 -C alkoxy and C -C haloalkyl; the group NR 0 whri R 9 and RlO arehloly;th ru R R wherein R an R10 are independently selected from the group consisting of hydrogen, C 1

-C

6 alkyl, C 2

-C

6 alkanoyl, benzoyl and benzyl; the groups formyl and C 2

-C

6 alkanoxyl and the oxime, imine and Schiff base derivatives thereof; and at least one of X is not selected from the group consisting of halogen, C 1

-C

6 alkyl and C 1

-C

6 alkoxy; Raogn isC- lyC- R2 is C1-C6 alkyl, C2-C 6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, a substitutd C 1

-C

6 alkyl, substituted with halogen, C -C 6 alkoxy, C -C 6 alkylthio, phenyl, substituted phenyl wherein the phenyl is substituted with halogen, nitro, cyano, C -C6 alkyl, C 1

-C

6 haloalkyl,

C

1

-C

6 alkoxy and C 1

-C

6 alkylthio;

R

3 is hydrogen, 1C 6 alkyl, C 1

-C

6 fluoroalkyl, C2-C6 alkenyl, C2-C6 alkynyl and phenyl; R4 is hydrogen or the keto tautomer; C1-C alkyl;

C

2

-C

6 alkenyl; C 2

-C

6 alkynyl; substituted C1-C6 alkyl wherein the alkyl group is substituted with C 1

-C

6 alkoxy, C 1

-C

6 alkylthio, C 1

-C

6 alkoxycarbonyl, phenyl, and substituted phenyl wherein the benzene ring is substituted with 1 to 3 substituents selected from the group consisting of halogen, nitro, cyano, C 1

-C

6 alkyl, C 1

-C

6 haloalkyl, C 1

-C

6 alkoxy, and

C

1

-C

6 alky1thio; C 1

-C

6 (alkyl) sulfonyl; benzene sulfonyl; substituted benzene sulfonyl wherein the benzene ring is substituted with 1 to 3 substituents selected from the group consisting of halogen, nitro, cyano, C 1

-C

6 alkyl, C1- 6 WO 93/04581 WO 9304581PCr/US92/07709 4 haloalkyl, C 1

-C

6 alkoxy and C.-C 6 alkylthio; an acyl group and an inorganic or organic cation; and n is an integer chosen from 2 to The terms "alkyl", "alkoxy"l, "alkenyl", "alkylthio", and the like are used herein to embrace both straight-chain and branched-chain radicals.

Examples of arylcoxypropionic acid derivatives useful in the present invention are: (D)-butyl 2-14-(5-trifluoromethyl-2-pyridyloxy) phenoxy 3 -prop ionate, (fluazifop'-butyl); (fluazifop); (5-trif luoromethyl-2-pyridyloxy) phenoxy3 propionic acid, (fluazifop-P and fluazifop-P-butyl); (RS) -2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy 3prop ionic acid, (haloxyfop); haloxyfop-etotyl; haloxyfop-methyl.

These and other aryloxypropionic acid derivatives within the scope of the invention can be prepared by the procedures described in U.S. Patents Nos. 4,267,336, 4,317,913, 4,414,391; EPA 23785; and British Patents Nos. 1,599,121 and 2,002,368. These references are hereby incorporated in their entirety.

Preferred cyclohexanediones included in the present invention are those in which the phenyl group is substituted with methyl groups and include: 5-(3-acetyl-2,4, 6-trimethylphenyl)-2- [l-(ethoxyimino) -propyl -hydroxycycl hex-2 -en- I -one; and 2-[1-(ethoxyimino)propyfl-3-hydroxy-5-(2,4,6-trinethyl-3-butyrylphenyl) cyclohex-2 -enone.

WO) 93/04581 PCT/US92/07709 The most preferred substituents are on the 2- and 6-position of the phenyl ring and are preferably selected from halogen, methyl and methoxy.

These and other cyclohexanediones along with their tautomeric forms within the scope of the present invention, can be prepared by the procedures described in U.S. Patent 3,950,420, EP-A-0080301 and EP-B-0085529. These references are hereby incorporated in their entirety.

The terms "synergism" and "synergistic" are used herein to convey the result observed when a combination of herbicides demonstrates a potency in excess of that which the combination would be expected to produce on the basis of the potencies of each herbicide applied individually.

The term "herbicide" is used herein to denote a compound which controls or modifies the growth of plants. The term "herbicidally effective amount" is used to indicate the quantity of such a compound or combination of such compounds which is capable of producing a controlling or modifying effect. Controlling or modifying effects include all deviations from natural development, for example: kill, retardation, leaf burn, dwarfing and the like. The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits.

In the compositions of this invention, the aryloxypropionic acid derivative:cyclohexanedione weight ratio at which the herbicidal response is synergistic, lies within the range of 1:5 to about 30:1, preferably about 1:5 to about 15:1 and most preferably about 1:2 to about 8:1.

Application rates will depend upon the particular compounds chosen for use, the particular plant species and degree of control desired. In general, the compositions of the invention are most efficiently employed at a rate of 0.001 WO 93/04581 PCT/US92/07709 6 to 50 pounds per acre (0.001 to 56 kilograms per hectare), preferably 0.001 to 25 pounds per acre (0.001 to 28 kilograms per hectare).

The following examples provide further illustrations demonstrating the synergistic herbicidal response of the present compositions.

Example I This example demonstrates the synergistic response of butyl (R)-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy] propionic acid (fluazifop-P-butyl) and 2-[l-(ethoxyimino)propyl]-5-(2,4,6-trimethyl-3-butyryl phenyl)-1,3-cyclohexanedione in combined postemergence application to the plants giant foxtail and shattercane.

Plastic pots were filled with 2 parts sandy loam and 1 part peat moss mixed together containing the commercial fungicide cis-N[(trichloromethyl)thio]-4-cyclohexene-l,2dicarboximide (Captane) and 17-17-17 fertilizer (percentages of N-P 205

-K

20 on a weight basis). Each pot was seeded to a single plant species. The plant species included giant foxtail (Setaria faberi) and shattercane (Sorghum vulqare).

The pots were placed in a greenhouse for approximately two weeks where they were watered regularly. The greenhouse temperature was approximately 850 F. day and 800 F. night.

At the end of this period, the foliage on the emerged plants was sprayed with herbicidal emulsions formed by diluting emulsifiable concentrates of test compounds with adjuvants and water. The dilutions were made such that at a total spray volume of 25 gallons per acre, the amount of each test compound applied per pot corresponded to the desired application rate in ounces per acre. In control pots, the test compounds were applied individually at various application rates, whereas in the test pots, emulsions contained both compounds. Untreated pots were used as standards.

WO 93/04581 PCT/US92/07709 7 Sixteen days after treatment, the control and test pots were compared to the standards and rated visually in terms of percent control ranging from 0% to 100%, with 0% representing no injury to the plant species and 100% representing complete kill of all plants. All types of plant injury were taken into consideration.

For the plant species, the results of these tests are listed in Table I in the columns headed by the symbol "0" (indicating the "observed" results), each figure represent the average of three replications of the same test. These results are compared with the expected results, shown in the columns headed by the symbol derived from the control data using Limpel's formula (Limpel et al., 1962, "Weed Control by Dimethylchloroterephthalate Alone and in Certain Combinations", Proc. NEWCC., vol. 16, pp. 48-53): E=X Y XY 100 where X observed percent injury when one of the herbicides is used alone, and Y observed percent injury when the other herbicide is used alone.

An asterisk is used to indicate the tests where the results show synergism, where the observed result exceess the expected result by at least 10 percent. It is clear from the table that synergism was observed at many of the application rates tested.

WO 93/04581 PTU9/70 PCT/US92/07709 TABLE I Post-emergence Application Average of Three Replications Application Rates (0 z7A A -B Control Data 0.063 0.125 0.250 0.500 1.000 %Control 2 _0:Observed Giant Foxtail 0 E IE: Exected Shattercane 0 E 92 100 0.016 0.031 0.063 0.125 0.250 32 100 100 Test Data 0.063 0.016 0 0 0 0 0.063 0.031 0 0 3 0 0.063 0.063 10 0 23* 0 0.063 0.125 75* 32 90* 43 0.063 0.250 100 100 100 100 0.125 0.125 0 "125 0.125 0.125 0.016 0.031 0.063 0.125 0.250 0 0 13 75* 100 0 0 0 32 100 10 33 60* 95* 100 27 27 27 58 100 0.250 0.016 0 0 85 82 0.250 0.031 3 0 85 82 0.250 0.063 13* 0 98* 82 0.250 0.125 80* 32 98 0.250 0.250 100 100 100 100 WO 93/04581 PCT/US92/07709 9 TABLE I (continued) Application Rates Control 2 0:Observed, E:Expected (Oz/A) Giant Foxtail Shattercane A B 0 E O E 0.500 0.016 10 7 92 92 0.500 0.03 13 7 98 92 0.500 0.063 78* 7 100 92 0.500 0.125 80* 37 100 100 0.500 0.250 100 100 100 100 1.000 0.016 43 37 100 100 1.000 0.031 68* 37 100 100 1.000 0.063 93* 37 100 100 1.000 0.125 98* 57 100 100 1.000 0.250 100 100 100 100 2 Treatments contained 1% Agridex 16 days after application denotes synergistic effect shown A Fluazifop-P-butyl; butyl (R)-2-[4-(5-trifluoromethyl-2pyridyloxy)phenoxy]propionic acid B 2-[1-(ethoxyimino)-propyl]-5-(2,4,6-trimethyl-3-butyrylphenyl)-1,3-cyclohexanedione Example II In this example, the following formulations were prepared from 2-[l-ethoxyimino)propyl]-3-hydroxy-5-(2,4,6trimethyl-3-butyrylphenyl)cyclohex-2-enone (Herbicide and the D isomer of butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]-propionate (Herbicide B).

Formulation Herbicide 125 g/l; nonionic emulsifier (methyl capped derivative of Renex 650), g/l; Aerosol OT 100, 30 g/l; and Teneco 500/100 to 1 liter.

Formulation Herbicide 125 g/l; phehyl sulfonate CALX, 45 g/l; Geopon SF 365, 45 g/l; Synperionic NPE 1800, 10 g/l and Solvesso 100 to 1.0 liter.

Field plots 2m x 2m were seeded with oilseed rape (Brassica campestris) and the plant species, perennial ryegrass (Lolium perenne) and annual bluegrass (Poa annua). At the WO 93/04581 PCT/US92/07709 time of spraying, the oilseed rape was at the 2-true leaf growth stage, the annual bluegrass was at the 3-leaf, 2-tiller stage of growth, and the ryegrass was at the 2-leaf growth stage. Formulations and above were each blended separately with 0.1% by weight of Agral and the resulting solutions were applied sequentially at various rates. Injury ratings were taken by visual determination 87 days after treatment. A scale of 0 to 10 is used where 10 is equivalent to complete kill (or 100 percent control) and 0 indicates no visual injury (or 0 percent control) as compared to untreated control plants.

For the plant species, the results of these tests are listed in Table II in the columns headed by the symbol "0" (indicating the "observed" results). These results are compared with the expected results, shown in the columns headed by the symbol as determined by the Colby formula.

The Colby formula is utilized to demonstrate the presence or absence of synergism (Colby, R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", 1967 Weeds, vol. 15, pp. 20-22): Expected effect X (100 x)y 100 where X observed effect of A and Y observed effect of B The basis of demonstraticn by comparison with the Colby formula is that Herbicide tested alone will kill a proportion of the target weeds and leave a proportion as survivors. Similarly, Herbicide tested alone will leave as survivors. When combined, A B will, however, if synergy is absent, act independently on the target weed, component A again leaving a% survivors, which survivors will be controlled by component B, with an overall effect of a% x b% 100 If, in practice, the percent control (degree of kill) is greater than that predicted by the Colby formula, WO 93/04581 PCT/US92/07709 synergism is provided by the difference between the observed and expected (Colby determined) results. As can be seen from Table II, synergism is widely evident.

TABLE II 1 Deg~ree of Kill2 Application Rates 0: Observed. E: Expected (a/ha) Ryecarass Bluegzrass A B 0 E 0 E 8 16 7 4 5 2 8 31 9 8 9 6 8 62.5 10 10 10 9 16 16 7 5 5 4 16 319 8 9 7 16 62.5 10 10 10 9 31 16 8 5 8 4 31 31 10 8 10 7 31 62.5 10 10 9 9 62.5 62.5 9 6 9 62.5 62.5 10 8 10 8 62.5 62.5 10 10 10 9 1 A 2-[l-(ethoxyimino)propyl]-3-hydroxy-5-(2,4, 6-triinethyl- 3 -butyrylphenyl) cyclohey- 2 -enone.

B D isomer of butyl-2-[4-(5-trifluoromethyl-2-pyridyloxy) 2 phenoxy) prop ionate where 0 no injury complete kill WO 93/04581 PC/US92/07709 12 Example III This example demonstrates the synergistic response of Herbicide used in Example I and 5-(3-acetyl-2,4,6trimethylphenyl)-2-[l-(ethoxyimino)-propyl]-3-hydroxycyclohex- 2-en-1-one (Herbicide C).

The following formulations were prepared: Formulation included Herbicide 125 g/l; emulsifier 50 g/l; made up to 1.0 liter with Solvesso 100; and formulation (c) included Herbicide 125 g/l; non-ionic emulsifier, 110 g/l; anisole, 400 g/l made up to 1.0 liter with Solvesso 150.

Pots in the greenhouse were seeded with large crabgrass (Digitaria sanquinalis), barnyardgrass (Echinochloa crusgalli), goosegrass (Eleusine indica), guineagrass (Panicum maximum), and johnsongrass (Sorghum halepense).

At the time of spraying, each plant species had 4 leaves per plant. The above formulations were blended and the final solution blended with 0.1% by weight of AGRAL 90 and by weight of ACTIPON. The final solution was applied through a greenhouse track sprayer at a volume of 200 liters per hectare.

Nineteen days after treatment, the degree of injury was rated visually in terms of percent control ranging from 0 to 100%, with 0% representing no control and 100% representing complete kill of all plants in the pot. The degree of kill was then assessed and compared with the expected kill as determined by the Colby formula presented in Example II. It is clear from Table III that synergism was observed at many of the application rates tested.

WO 93/04581 PCT/US92/07709 13 TABLE III Postemerqence Application Application Control 2 0:Observed; E:Expected Rates Crab- Goose- Guinea- Johnson- (q/ha) grass Millet grass grass grass B C O E O E O E 0 E O E 1 7 0 32* 7 45* 5 55* 8 10 1 52* 17 97 92 48* 24 63 59 1 52* 7 100* 75 95* 78 95* 79 100 97 2 50* 3 98* 47 93* 15 85* 57 85* 37 2 60* 8 35* 53 97 93 97* 65 100 2 92* 10 100* 66 98* 80 100* 90 100 98 1 B Fluazifop-P-butyl; butyl 2-[4(5-trifluoromethyl-2pyridyloxy) phenoxy] -propionate C 5-(3-acetyl-2,4,6-trimethylphenyl)-2-[-ethoxyimino) 2 propyl] -3-hydroxycyclohex-2-en-l-one 19 days after treatment Synergistic effect shown, the observed result exceeded the expected result by at least 10 percent The compositions of this invention are useful r..

herbicides demonstrating synergistic activity for the control of undesirable vegetation. The compositions can be formulated in the same manner in which herbicides are generally formulated. The compounds may be applied either separately or combined as part of a two-part herbicidal system.

The object of the formulation is to apply the compositions to the locus where control is desired by a convenient method. The "locus" is intended to include soil, seeds, and seedlings, as well as established vegetation.

Formulations will generally contain several additives. Among these are some inert ingredients and diluent carriers such as organic solvents, water, oil and water, water in oil emulsions, carriers of dust and granules, and surface active, wetting, dispersing, and emulsifying agents.

WO 93/04581 PCT/US92/07709 14 Fertilizers, such as ammonium nitrate, urea, potash and superphosphates may also be added.

Aids to rooting and growth, such as compost, manure, humus, sand, etc. may likewise be added.

The formulations are commonly dusts, wettable powders, granules, solutions or emulsifiable concentrates.

Dusts are free-flowing powder compositions containing the herbicidal compound impregnated on a particulate carrier. The particle size of the carrier is usually in the approximate range of 30 to 50 microns. Examples of suitable carriers are talc, bentonite, diatomaceous earth, and pyrophyllite. Anticaking and antistatic agents can be added, if desired. The composition generally contains up to 50% of active ingredient. Dusts, like liquid compositions, can be applied by spraying from boom sprayers, hand sprayers or airplanes.

Wettable powders are finely divided compositions comprising a particulate carrier impregnated with the herbicidal compound and additionally containing one or more surface active agents. The surface active agent promotes rapid dispersion of the powder in aqueous medium to form stable, sprayable suspensions. A wide variety of surface active agents can be used, for example, long chain fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, omega-substituted polyethylene glycols of relatively long chain length.

Granules comprise the herbicidal composition impregnated on a particulate inert carrier having a particle size of about 1 to 2 millimeters in diameter. The granules can be made by spraying a solution of the active ingredient in a volatile solvent onto the granular carrier. Suitable carriers in preparation of granules include clay, vermiculite, sawdust, granular carbon, etc.

WO 93/04581 PCr/US92/07709 Microcapsules and other slow release formulations are advantageous as formulations to deliver and distribute the active ingredients. Microcapsules consist of fully enclosed droplets or granules containing the active materials in which the enclosing material is an inert porous membrane, arranged to allow escape of the enclosed materials to the surrounding medium at controlled rates over a specified per-iod of time.

Encapsulated droplets are typically about 1 to 50 microns in diameter. The enclosed liquid typically constitutes about to 95% of the weight of the entire capsule, and may contain an amount of solvent in addition to the active materials.

Encapsulated granules are characterized by porous membranes sealing the openings of the granule carrier pores, trapping the liquid containing the active components inside for controlled release. A typical granule size ranges from 1 millimeter to 1 centimeter in diameter. In agricultural usage, the granule size is generally about 1 to 2 millimeters in diameter.

Granules formed by extrusion, agglomeration or prilling are useful in the present invention as well as materials in their naturally occurring form. Examples of such carriers are vermiculite, starch sintered clay granules, kaolin, attapulgite clay, sawdust and granular carbon. Useful encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

The herbicidal compositions can also be applied to the soil in the form of a solution in a suitable solvent.

Solvents frequently used in herbicidal formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene, and aromatic petroleum fractions rich in methylated naphthalenes.

Emulsifiable concentrates consist of an oil solution of the herbicide along with an emulsifying agent. Prior to use, the concentrate is diluted with water to form a suspended emulsion of oil droplets. The emulsifiers used are usually a mixture of anionic and nonionic surfactants. Other additives WO 93/04581 PCT/US92/07709 16 such as spreading agents and stickers can be included in the emulsifiable concentrate.

It is not necessary that the compositions be admixed with the soil particles. After application by the abovediscussed methods, they may be distributed below the soil surface to a depth of at least one-half inch by conventional means such as discing, dragging, or mixing.

Claims (12)

1. A synergistic herbicidalcopstn An aryloxypropionic acid derivative of the formula x CF 30 O--CH-COORI -N -H 3 1 in which X is hydrogen or halogen; Ris hydrogen, C 1 -c 6 alkyl, cI-C 6 alkoxyalkyl; and a cyclohexanedione. derivative of the formula ~OR 2 OR 4 in which R is independently hydrogen; halogen; nitro; cyano; C 1 -C 6 alky;l; C 1 -C 6 alkyl. substituted with a substituent selected from the group consisting of halogen, nitro, hydroxy, C -C 6alkxanC 1- 6 alkylthio; C 2 -C 6 alkenyl; C 2-C 6alknj hydroxy; C 1 -C 6 alkoxy; C 1 -C 6 alkoxy substituted with a substi- tuent selected from halogen and C alkoyy; C 2 -C 6 alkenyl- oxy, lyyoy 2- 6 alkanoyioxy; (C alkoxy)- carbonyl; C-C 6 alkylthio; C-C 6 alkylsulf inyl; C-C 6 alkyl- sulfonyl; sulfamoyl; N-(C 1 -0 6 alkyl)sulfamoyl; N,N-di(C 1 -C 6 alkyl) sulfanoyl; benzyloxy, substituted benzyloxy wherein the benzene ring is substituted with from one to three substi- tuents selected from the group consisting of halogen, nitro, -WBSTi TUIP SHEET 18 C -C alkyl, C -C 6 alkoxy and C -C haloalkyl; the group 9 o1 9 and R10 1 NR R0 wherein R and R are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 2 kanoyl, benzoyl and benzyl; the groups formyl and C 2 -C 6 .'J'noxyl and the oxime, imine and Schiff base derivatives there, R 2 is C1-C 6 alkyl, C2-C 6 alkenyl, C 2 -C 6 haloalkenyl, C2-C 6 alkynyl, C 2 -C 6 haloalkynyl, a substituted C -C 6 alkyl, substituted with halogen, C -C 6 alkoxy, C 1 -C 6 alkylthio, phenyl, substituted phenyl wherein the phenyl is substituted with halogen, nitro, cyano, C -C 6 alkyl, C-C6 haloalkyl, C 1 -C 6 alkoxy and C -C 6 alkylthio; R 3 is hydrogen, C -C 6 alkyl, C 1 -C 6 fluoroalkyl, C -C b JL b C -C6 alkenyl, C 2 -C 6 alkynyl and phenyl; R 4 is hydrogen or the keto tautomer; C -C 6 alkyl; C2-C6 alkenyl; C 2 -C 6 alkynyl; substituted C -C 6 alkyl wherein the alkyl group is substituted with C 1 -C 6 alkoxy, C1-C6 alkylthio, C 1 -C 6 alkoxycarbonyl, phenyl, and substituted phenyl wherein the benzene ring is substituted with 1 to 3 substituents selected from the group consisting of halogen, nitro, cyano, C -C6 alkyl, C-C 6 haloalkyl, C 1 -C 6 alkoxy, and C-C6 alkylthio; C 1 -C 6 (alkyl) sulfonyl; benzene sulfonyl; substituted benzene sulfonyl wherein the benzene ring is substituted with 1 to 3 substituents selected from the group consisting of halogen, nitro, cyano, C -C 6 alkyl, C1-C6 haloalkyl, C -C 6 alkoxy and C 1 -C 6 alkylthio; an acyl group and an inorganic or organic cation; and o n is an integer chosen fron; wherein the weight ratio of to is in the range of to 30:1. to a te S M 1)A NII .cH-2 H 1 1- ;1U+ 0:144 481 112- +1l U W-)Hc~ ~r. PR-8659

2. s 5ynsrqistic herbicidal composition kmm3.k-z An aryloxypropionic acid derivative of the formula O-CH-cooR I I in which X is hydrogen or halogen- R Iis hydrogen, C 1 -C 6 alkyl, C -C alkcoxyakyl; and a cyclohexanedione of the formula 'OR4 in which R is fcrmyl or C 2-c alkanexyl; R is CI-C 6 alkyl; R is C C6 alkyl; R 4 is hydrogen or the keto tautomer at a weiqht ratio of to of from about about'5R1.

3. A composition according to Claim oeemp.r- djuvants. 1:.5 to 2 further

4. A composition according to~-e-aim 2 in w.hich (a) is the D isomer of butyl 2-*4-(5-trifluoromsthyl-2-pyridyloxy)- phenoxy]-propionate. 19 A composition according to Claim 4 in which (b) is 2-[l-(ethoxyimino)propyl]-3-hydroxy-5-(2,4,6-trimethyl-3- butyrylphenyl)cyclohex-2-enone or the keto tautomer.

6. A composition according to Claim 4 in which (b) is 2-[l-(ethoxyimino)propyl]-3-hydroxy-5-(2,4,6-trimethyl-3- acetylphenyl)cyclohex-2-enone.

7. A composition according to Claim 2 in which X is hydrogen or chlorine and R1 is hydrogen.

8. A composition according to Claim 7 in which R is acetyl or butyryl; R 2 and R 3 are ethyl; R 4 is hydrogen or the keto tautomer.

9. A composition according to Claim 8 in which the weight ratio of to is from about 1:2 to about 8:1. A composition according to Claim 9 further including adjuvants.

11. A synergistic herbicidal composition according to claim 1 wherein the weight ratio of component to component (b) is about 1:2 to about 8:1. I* (A U\ A \11 %C1Hl\ 0 1 :22 9 8 1 1 12-- +40 89 2,410,1405:n; 3: H PR-8659

12. A method of controlling undesirabla vegetation whih eemp 4 -5.japplying to thlocus where control is desired an herbicidal composition mixture of: An aryloxypropionic acid derivative of the formula O-c-COOH3 in which X is hydrogen or halogen; RI is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxyalkyl; and a cyclohexanedione of the formula 3 ,OR 4 in which R is formyl or c 2 -C 6 alkanoxyl; R 2 is C 1 -C 6 a~kyl; X3 is C 1 -C 6 alkyl; R 4 is hydrogen or the keto tautomer at a weight ratio of to of from about about i5:1.

13. A method according to claim 12 wherein is the D isomer of butyl 2-[4-(5-trifluromehyl-2pyridyloxy phanoxy]-propionate and is 2-(l-(etheodyixino)proPy13- 3 hydroxy-5-(2,4,6-triathyl-3-butyrylp'hnyl) cycloheX-2-eonl or the keto tautomer. COS 1~"-I SUBSTITUTE SHEET 21 -22-

14. A synergistic herbicidal composition as claimed in claim 1 substantially as hereinbefore described with reference to any one of the examples. DATED: 3 February, 1995 PHILLIPS ORMONDE FITZPATRICK Attorneys for: ZENECA LIMITED WN C\WINWORD\WENDYVrTPING26776T DOC INTERNATIONAL SEARCH REPORT International Application No PCT7US 92/07709 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) 6 According to International Patent Classification (IPC) or to both National Classification and IPC A 01 N 43/40, 35/10 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols A 01 N Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in Fields Searched 8 III. DOCUMENTS CONSIDERED TO BE RELEVANTa Category' Citation of Document, 11 with indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 13 A GB, A, 1599121 (ISHIHARA SANGYO KAISHA LTD) 1-13 September 1981, see the claims A EP, A2, 0080301 (ICI AUSTRALIA LIMITED) 1-13 1 June 1983, see the claims X WEED TECHNOLOGY, vol 5, Issue 2(April-June)1991, 1-13 K. Neil Harker\et al: "Synergistic mixtures of sethoxydim and fluazifop on annual grass weeds", pp 310-316 Special categories of cited documents: 1 0 T later dopument published after Ihe lpternational filing date document defining the l state of the art which Is not or priority date and not in conflict with the application but A nt definin them ral sae e a icited t understand the principle or theory underlying the considered to be of pa icular relevance invention earlier document but published on or after the international filing date document of particular relevance, the claimed, invention cannot be considered novel or cannot be considered to doqumpnt which ma throw doubts pn griority claim(s) or involve an inventive step which is cited to esablish the publication date of another d o ime nnt citation or other special reason (as specified) document of particular relevance, the claimed invention cannot be considered to Involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with ne or more other such dlu-d other means ents such combination being obvious to a person sklled other means n the art. Sdocument publishe prior t a te imternational filing date but document member of the same patent family later than the priority date claimed IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report November 1992 1 8 DEC 1992 International Searching Authority Signature of Authorized Officer Gerd Wranne I EUROPEAN PATENT OFFICE Form PCT1SA/210 (second sn (January 18851 International Application No. PCT/IJS 92/07709 I11. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND Caegryf Citation of Document, with indication, where appropriate, 0f the relevant passages I Relevant to Claim No EP, Al, 0004414 (IMPERIAL CHEMICAL INDUSTRIES LIMITED) 3 October 1979, see the claims EP, A2, 0293062 (IMPERIAL tLHEMICAL INDUSTRIES PLC) November 1988, see the claims 1-13 1-13 Form PCT/ISA/210 CExtra shoot) (January 1985) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO.PCT/US 92/07709 SA 64881 This annex lits the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP ile on 30/10/92 The European Patent office is in no way liable for theseparticulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date GB-A- 1599121 30/09/81 AT-B- 359329 10/11/80 AU-B- 527957 31/03/83 AU-B- 574041 30/06/88 AU-D- 3434278 27/09/79 BE-A- 868875 10/01/79 CA-A- 1243321 18/10/88 CH-A- 629487 30/04/82 DE-A-C- 2812571 01/02/79 FR-A-B- 2398059 16/02/79 FR-A- 2501470 17/09/82 FR-A-B- 2501684 17/09/82 GB-A- 1599126 30/09/81 JP-C- 1382152 09/06/87 JP-A- 54022371 20/02/79 LU-A- 80024 12/12/78 NL-A- 7803036 23/01/79 OA-A- 6013 30/06/81 EP-A2- 0080301 01/06/83 AU-D- 9045982 26/05/83 CA-A- 1203543 22/04/86 DE-A- 3278932 29/09/88 GB-A- 2110673 22/06/83 JP-A- 58092634 02/06/83 US-A- 4717418 05/01/88 US-A- 4760192 26/07/88 EP-A1- 0004414 03/10/79 AU-D- 4465879 06/09/79 GB-A- 2026865 13/02/80 JP-A- 54126729 02/10/79 OA-A- 6198 30/06/81 EP-A2- 0293062 30/11/88 AU-B- 596268 26/04/90 AU-D- 1090388 11/08/88 JP-A- 63216801 09/09/88 US-A- 5030269 09/07/91 For more details about this annex: see Official Journal of the European patent Office, No. 12/82 EPO FORM P0479