WO1993004581A1 - Synergistic interaction of herbicidal aryloxypropionic acid derivatives and cyclohexanediones - Google Patents

Synergistic interaction of herbicidal aryloxypropionic acid derivatives and cyclohexanediones Download PDF

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Publication number
WO1993004581A1
WO1993004581A1 PCT/US1992/007709 US9207709W WO9304581A1 WO 1993004581 A1 WO1993004581 A1 WO 1993004581A1 US 9207709 W US9207709 W US 9207709W WO 9304581 A1 WO9304581 A1 WO 9304581A1
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Prior art keywords
alkyl
substituted
alkoxy
halogen
hydrogen
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PCT/US1992/007709
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French (fr)
Inventor
S. Robert Colby
John Stephen Casey
James Anderson
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Zeneca Limited
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Priority to US07/758,038 priority
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Publication of WO1993004581A1 publication Critical patent/WO1993004581A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Abstract

A synergistic herbicidal composition comprising: (a) an aryloxypropionic acid derivative of formula (I) and (b) a cyclohexanedione derivative of formula (II).

Description

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 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:

(a) An aryloxypropionic acid derivative of the formula

Figure imgf000004_0001

in which

X is hydrogen or halogen;

R1 is hydrogen, C1-C8 alkyl, C1-C6 alkoxyalkyl; and

(b) a cyclohexanedione derivative of the formula

Figure imgf000004_0002

in which R is independently hydrogen; halogen; nitro; cyano; C1-C6 alkyl; C1-C6 alkyl substituted with a substituent

selected from the group consisting of halogen, nitro, hydroxy, C1-C6 alkoxy and C1-C6 alkylthio; C2-C6 alkenyl; C2-C6 alkynyl; hydroxy; C1-C6 alkoxy; C1-C6 alkoxy substituted with a substituent selected from halogen and C1-C6 alkoxy; C2-C6 alkenyl- oxy; C2-C6 alkynyloxy; C2-C6 alkanoyloxy; (C1-C6 alkoxy)- carbonyl; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkyl- sulfonyl; sulfamoyl; N-C(1-C6 alkyl) sulfamoyl; N,N-di (C1-C6 alkyl) sulfamoyl; benzyloxy, substituted benzyloxy wherein the benzene ring is substituted with from one to three substi- tuents selected from the group consisting of halogen, nitro, C1-C6 alkyl, C1-C6 alkoxy and C1-C6 haloalkyl; the group

NR9R10 wherein R9 and R10 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 alkanoyl, benzoyl and benzyl; the groups formyl and C2-C6 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, C1-C6 alkyl and C1-C6 alkoxy;

R2 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, a substituted C1-C6 alkyl, substituted with halogen, C1-C6 alkoxy, C1-C6 alkylthio, phenyl, substituted phenyl wherein the phenyl is substituted with halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl,

C1-C6 alkoxy and C1-C6 alkylthio;

R3 is hydrogen, C1-C6 alkyl, C1-C6 fluoroalkyl,

C2-C6 alkenyl, C2-C6 alkynyl and phenyl;

R4 is hydrogen or the keto tautomer; C1-C6 alkyl;

C2-C6 alkenyl; C2-C6 alkynyl; substituted C1-C6 alkyl wherein the alkyl group is substituted with C1-C6 alkoxy, C1-C6

alkylthio, C1-C6 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, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, and C1-C6 alkylthio; C1-C6 (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, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy and C1-C6 alkylthio; an acyl group and an inorganic or organic cation; and

n is an integer chosen from 2 to 5.

The terms "alkyl", "alkoxy", "alkenyl", "alkylthio", and the like are used herein to embrace both straight-chain and branched-chain radicals.

Examples of aryloxypropionic acid derivatives useful in the present invention are:

(D) -butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)- phenoxy]-propionate, (fluazifop-butyl);

(fluazifop);

(R) -2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy] propionic acid, (fluazifop-P and fluazifop-P-butyl) ;

(RS) -2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy] propionic 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- [1-(ethoxy- imino) -propyl]-3-hydroxycyclohex-2-en-1-one; and

2-[1-(ethoxyimino) propyl] -3-hydroxy-5- (2 ,4,6-tri- methyl-3-butyrylphenyl) cyclohex-2-enone. 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 aryloxy- propionic 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 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-[1-(ethoxyimino)- propyl]-5-(2,4,6-trimethyl-3-butyryl phenyl)-1,3-cyclohexane- dione 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-1,2- dicarboximide (Captan®) and 17-17-17 fertilizer (percentages of N-P2O5-K2O on a weight basis). Each pot was seeded to a single plant species. The plant species included giant

foxtail (Setaria faberi) and shattercane (Sorghum vulgare). The pots were placed in a greenhouse for approximately two weeks where they were watered regularly. The greenhouse temperature was approximately 85° F. day and 80° 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. 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 "O" (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 "E", 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, i.e., where the observed result exceeds 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.

Figure imgf000010_0001
Figure imgf000011_0001

Example II

In this example, the following formulations were prepared from 2-[1-ethoxyimino)propyl]-3-hydroxy-5-(2,4,6- trimethyl-3-butyrylphenyl)cyclohex-2-enone (Herbicide A), and the D isomer of butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)- phenoxy]-propionate (Herbicide B).

Formulation (a): Herbicide (A), 125 g/l;

nonionic emulsifier (methyl capped derivative of Renex 650), 20 g/l; Aerosol OT 100, 30 g/l; and Teneco 500/100 to 1 liter.

Formulation (b): Herbicide (B), 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 ryegras (Lolium perenne) and annual bluegrass (Poa annua). At the time of spraying, the oilseed rape was at the 2-true leaf growth stage, the annual bluegrass was at the 3-leaf, 2-tille stage of growth, and the ryegrass was at the 2-leaf growth stage. Formulations (a) and (b) 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 "O" (indicating the "observed" results). These results are compared with the expected results, shown in the columns headed by the symbol "E", as determined by the Colby formula.

The Colby formula is utilized to demonstrate the presence or absence of synergism (Colby, R. S., "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 demonstration by comparison with the Colby formula is that Herbicide (A) tested alone will kill a proportion of the target weeds and leave a proportion (a%) as survivors. Similarly, Herbicide (B) tested alone will leave (b%) 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, 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.

Figure imgf000013_0001
Example III

This example demonstrates the synergistic response of Herbicide (B) used in Example I and 5-(3-acetyl-2,4,6- trimethylphenyl)-2-[1-(ethoxyimino)-propyl]-3-hydroxycyclohe 2-en-1-one (Herbicide C).

The following formulations were prepared: Formula tion (b) included Herbicide (B) , 125 g/l; emulsifier 50 g/l; made up to 1.0 liter with Solvesso 100; and formulation (c) included Herbicide (C), 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 sanguinalis), barnyardgrass (Echinochloa crusgalli), goosegrass (Eleusine indica), guineagrass (Panicum maximum), and johnsongrass (Sorghum halepense).

At the time of spraying, each plant species had 4 - 5 leaves per plant. The above formulations were blended and the final solution blended with 0.1% by weight of AGRAL 90 an 1.0% 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% representin 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.

Figure imgf000015_0001

The compositions of this invention are useful as 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. 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 pyrophyl lite. 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. 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 period of time. Encapsulated droplets are typically about 1 to 50 microns in diameter. The enclosed liquid typically constitutes about 50 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, attapul- gite 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 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 above- discussed 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

WHAT IS CLAIMED IS:
1. A synergistic herbicidal composition comprising:
(a) An aryloxypropionic acid derivative of the formula
Figure imgf000019_0001
in which
X is hydrogen or halogen;
R1 is hydrogen, C1-C6 alkyl, C1-C6 alkoxyalkyl; and (b) a cyclohexanedione derivative of the formula
Figure imgf000019_0002
in which
R is independently hydrogen; halogen; nitro; cyano; C1-C6 alkyl; C1-C6 alkyl substituted with a substituent
selected from the group consisting of halogen, nitro, hydroxy, C1-C6 alkoxy and C1-C6 alkylthio; C2-C6 alkenyl; C2-C6 alkynyl; hydroxy; C1-C6 alkoxy; C1-C6 alkoxy substituted with a substituent selected from halogen and C1-C6 alkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; C2-C6 alkanoyloxy; (C1-C6 alkoxy)- carbonyl; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkyl- sulfonyl; sulfamoyl; N-C(1-C6 alkyl) sulfamoyl; N,N-di(C1-C6 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-C6 alkyl, C1-C6 alkoxy and C1-C6 haloalkyl; the group
NR9R10 wherein R9 and R10 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 alkanoyl, benzoyl emd benzyl; the groups formyl and C2-C6 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, C1-C6 alkyl and C1-C6 alkoxy;
R2 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, a substituted C1-C6 alkyl, substituted with halogen, C1-C6 alkoxy, C1-C6 alkylthio, phenyl, substituted phenyl wherein the phenyl is substituted with halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy and C1-C6 alkylthio;
R3 is hydrogen, C1-C6 alkyl, C1-C6 fluoroalkyl, C2-C6 alkenyl, C2-C6 alkynyl and phenyl;
R4 is hydrogen or the keto tautomer; C1-C6 alkyl; C2-C6 alkenyl; C2-C6 alkynyl; substituted C1-C6 alkyl wherein the alkyl group is substituted with C1-C6 alkoxy, C1-C6
alkylthio, C1-C6 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, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, and C1-C6 alkylthio; C1-C6(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, C1-C6 alkyl, C1-C6
haloalkyl, C1-C6 alkoxy and C1-C6 alkylthio; an acyl group and an inorganic or organic cation; and
n is an integer chosen from 2 to 5.
2. A synergistic herbicidal composition comprising: (a) An aryloxypropionic acid derivative of the formula
Figure imgf000021_0001
in which
X is hydrogen or halogen;
R1 is hydrogen, C1-C6 aallkk]yl, C1-C6 alkoxyalkyl; and (b) a cyclohexanedione of the formula
Figure imgf000021_0002
in which
R is formyl or C1-C6 alkanoxyl;
R2 is C1-C6 alkyl;
R3 is C1-C6 alkyl;
R4 is hydrogen or the keto tautomer
at a weight ratio of (a) to (b) of from about 1.0:0.001 to about 20:1.
3. A composition according to Claim 2 further comprising adjuvants.
4. A composition according to Claim 2 in which (a) is the D isomer of butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy) phenoxy]-propionate.
5. A composition according to Claim 4 in which (b) is 2-[1-(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-[1-(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; R2 and R3 are ethyl; R4 is hydrogen or the keto tautomer.
9. A composition according to Claim 8 in which the weight ratio of (a) to (b) is from about 1:2 to about 8:1.
10. A composition according to Claim 9 further comprising adjuvants.
11. A synergistic herbicidal composition comprising:
(a) A 5-trifluoro-substituted-2-pyridyloxy- phenoxy propionic acid derivative optionally substituted at the 3-position with halogen; and
(b) a tetrasubstituted 5-phenyl-[2-(1-alkoxy- iminoalkyl) cyclohexanedione derivative at a weight ratio of (a) to (b) of about 1:2 to about 8:1.
12. A method of controlling undesirable vegetation which comprises applying to the locus where control is desired an herbicidal composition comprising a mixture of :
(a) An aryloxypropionic acid derivative of the formula
Figure imgf000023_0001
in which
X is hydrogen or halogen;
R1 is hydrogen, C1-C6 alkyl, C1-C6 alkoxyalkyl; and (b) a cyclohexanedione of the formula
Figure imgf000023_0002
in which
R is formyl or C2-C6 alkanoxyl;
R2 is C1-C6 alkyl;
R3 is C1-C6 alkyl;
R4 is hydrogen or the keto tautomer
at a weight ratio of (a) to (b) of from about 1.0 to 0.001 to about 20:1.
13. A method according to Claim 12 wherein (a) is the D isomer of butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)- phenoxy]-propionate and (b) is 2-[1-(ethoxyimino)propyl]-3- hydroxy-5-(2,4,6-trimethyl-3-butyrylphenyl) cyclohex-2-enone or the keto tautomer. AMENDED CLAIMS
[received by the International Bureau on 5 January 1993 (05.01.93) ;
original claim 1 amended; remaining claims unchanged (2 pages)]
1. A synergistic herbicidal composition comprising:
(a) An aryloxypropionic acid derivative of the formula
Figure imgf000024_0001
in which
X is hydrogen or halogen;
R1 is hydrogen, C1-C6 alkyl, C1-C6 alkoxyalkyl; and (b) a cyclohexanedione derivative of the formula
Figure imgf000024_0002
in which
R is independently hydrogen; halogen; nitro; cyano; C1-C6 alkyl; C1-C6 alkyl substituted with a substituent
selected from the group consisting of halogen, nitro, hydroxy, C1-C6 alkoxy and C1-C6 alkylthio; C1-C6 alkenyl; C2-C6 alkynyl; hydroxy; C1-C6 alkoxy; C1-C6 alkoxy substituted with a substituent selected from halogen and C1-C6 alkoxy; C2-C6 alkenyl- oxy; C2-C6 alkynyloxy; C2-C6 alkanoyloxy; (C1-C6 alkoxy)- carbonyl; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkyl- sulfonyl; sulfamoyl; N-(C1-C6 alkyl) sulfamoyl; N,N-di(C1-C6 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-C6 alkyl, C1-C6 alkoxy and C1-C6 haloalkyl; the group
NR9R10 wherein R9 and R10 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 alkanoyl, benzoyl and benzyl; the groups formyl and C2-C6 alkanoxyl and the oxime, imine and Schiff base derivatives thereof;
R2 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, a substituted C1-C6 alkyl, substituted with halogen, C1-C6 alkoxy, C1-C6 alkylthio, phenyl, substituted phenyl wherein the phenyl is substituted with halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy and C1-C6 alkylthio;
R3 is hydrogen, C1-C6 alkyl, C1-C6 fluoroalkyl, C2-C6 alkenyl, C2-C6 alkynyl and phenyl;
R4 is hydrogen or the keto tautomer; C1-C6 alkyl; C2-C6 alkenyl; C2-C6 alkynyl; substituted C1-C6 alkyl wherein the alkyl group is substituted with C1-C6 alkoxy, C1-C6
alkylthio, C1-C6 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, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, and C1-C6 alkylthio;C1-C6 (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, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy and C1-C6 alkylthio; an acyl group and an inorganic or organic cation; and
n is an integer chosen from 2 to 5.
PCT/US1992/007709 1991-09-12 1992-09-11 Synergistic interaction of herbicidal aryloxypropionic acid derivatives and cyclohexanediones WO1993004581A1 (en)

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BR9206485A BR9206485A (en) 1991-09-12 1992-09-11 Synergistic herbicidal composition and process to control undesirable vegetation
EP19920920871 EP0603336A1 (en) 1991-09-12 1992-09-11 Synergistic interaction of herbicidal aryloxypropionic acid derivatives and cyclohexanediones
AU26776/92A AU658452B2 (en) 1991-09-12 1992-09-11 Synergistic interaction of herbicidal aryloxypropionic acid derivatives and cyclohexanediones
CA 2118794 CA2118794C (en) 1991-09-12 1992-09-11 Synergistic interaction of herbicidal aryloxypropionic acid derivatives and cyclohexanediones

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Publication number Priority date Publication date Assignee Title
WO1997010710A1 (en) * 1995-09-20 1997-03-27 Basf Aktiengesellschaft Synergistic herbicidal mixtures containing cyclohexenone oxime ether
WO1999008520A1 (en) * 1997-08-15 1999-02-25 Zeneca Limited Herbicidal compositions

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EP0004414A1 (en) * 1978-03-01 1979-10-03 Imperial Chemical Industries Plc Mixtures of herbicidal pyridyloxyphenoxypropanoic acid derivatives with other herbicides, and processes of killing unwanted plants therewith
GB1599121A (en) * 1977-07-21 1981-09-30 Ishihara Mining & Chemical Co A-(4-(5-fluoromethyl-2-pyridyloxy)phenoxy)alkane-carboxylic acid derivatives and their use as herbicides
EP0080301A2 (en) * 1981-11-20 1983-06-01 Ici Australia Limited Herbicidal cyclohexane-1,3-dione derivatives
EP0293062A2 (en) * 1987-02-05 1988-11-30 Imperial Chemical Industries Plc Herbicidal composition

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GB1599121A (en) * 1977-07-21 1981-09-30 Ishihara Mining & Chemical Co A-(4-(5-fluoromethyl-2-pyridyloxy)phenoxy)alkane-carboxylic acid derivatives and their use as herbicides
EP0004414A1 (en) * 1978-03-01 1979-10-03 Imperial Chemical Industries Plc Mixtures of herbicidal pyridyloxyphenoxypropanoic acid derivatives with other herbicides, and processes of killing unwanted plants therewith
EP0080301A2 (en) * 1981-11-20 1983-06-01 Ici Australia Limited Herbicidal cyclohexane-1,3-dione derivatives
EP0293062A2 (en) * 1987-02-05 1988-11-30 Imperial Chemical Industries Plc Herbicidal composition

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Title
WEED TECHNOLOGY, vol 5, Issue 2(April-June)1991, K. Neil Harker et al: "Synergistic mixtures of sethoxydim and fluazifop on annual grass weeds", pp 310-316 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997010710A1 (en) * 1995-09-20 1997-03-27 Basf Aktiengesellschaft Synergistic herbicidal mixtures containing cyclohexenone oxime ether
US6103664A (en) * 1995-09-20 2000-08-15 Basf Aktiengesellschaft Synergistic herbicidal mixtures containing cyclohexenone oxime ethers
CN1092021C (en) * 1995-09-20 2002-10-09 巴斯福股份公司 Synergistic herbicidal mixtures contg. cyclohexenone oxime ether
CN1303880C (en) * 1995-09-20 2007-03-14 巴斯福股份公司 Synergistic weedicide mixture containing cyclohexene ketoxime ether
WO1999008520A1 (en) * 1997-08-15 1999-02-25 Zeneca Limited Herbicidal compositions

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AU658452B2 (en) 1995-04-13
EP0603336A1 (en) 1994-06-29
NZ244308A (en) 1995-04-27
MX9205213A (en) 1993-06-01
CA2118794A1 (en) 1993-03-18

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