AU737523B2 - Herbicidal mixtures - Google Patents

Description

P/00/011 Regulation 3.2

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT a.

a. a a

ORIGINAL

TO BE COMPLETED BY APPLICANT Name of Applicant: E.I. DU PONT DE NEMOURS AND COMPANY Actual Inventor(s): Kofi Sam Amuti; Loston Rowe; and Marc Sam Ruggiero Address for Service: CALLINAN LAWRIE, 278 High Street, Kew, 3101, Victoria, Australia Invention Title: "HERBICIDAL MIXTURES" The following statement is a full description of this invention, including the best method of performing it known to me:- 1- 9A-91 18 1A

TITLE

HERBICIDAL MIXTURES FIELD OF THE INVENTION The present invention relates to mixtures of herbicides that have a synergistic effect on weeds.

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, barley, corn (maize), oats, peanut (groundnut), potato, rape, rice, sorghum, soybean, sugar beet, tomato, wheat, vegetables, perennial plantation crops including banana, citrus, cocoa, coffee, grapes, hops, plantain, pineapple, oil palm, Srubber, 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 control of 15 undesired vegetation in noncrop areas is also important. The need for finding products that achieve such results continues to be commercially important.

Combinations of herbicides are typically used to broaden the spectrum of plant control or enhance the level of control of any given species through additive effect.

.Certain rare combinations surprisingly give a greater-than-additive or synergistic effect.

Several such valuable combinations have now been discovered.

U.S. 4,213,773 discloses 2-[2,4-dichloro-5-(2-propynyloxy)phenyl]-5,6,7,8-tetra- S hydro-l,2,4-triazolo[4,3-a]pyridin-3(2H)-one, and U.S. 5,332,718 discloses the utility of this compound for selective control of weeds in plantation crops. These references do not specifically disclose the particular mixtures of the present invention, nor do they 25 describe or suggest the unexpected synergistic utility of said mixtures.

SUMMARY OF THE INVENTION This invention relates to mixtures of herbicides that produce synergistic results.

The herbicidal mixtures comprise herbicidally effective amounts of the compound of Formula I in admixture with herbicidally effective amounts of one of the compounds of Formulae II through IX. 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 applying to the locus of the undesired vegetation herbicidally effective amounts of the aforesaid mixtures.

The mixtures of the invention comprising the Formula I and Formulae II-IX compounds are described below: 0

OCH

2

C=-CH

Nf-N N NO ci 2 -[2,4-dichloro-5-(2-propynyloxy)phenyl].5 8-tetrahyciro- l, 2 4 -triazolo[4,3-a].

pyridin-3(2N)-one

,CO

2

CH

3 4, *4 4 44444.

4 methyl 2-[[46dmty--yiiiy~aiocroy].aiosloy] benzoate (sulfometuron methyl, H) and its agriculturally useful salts; ill

OCH

3 methyl 2 -[[[[(4-methoxy-6-methyl- l, 3 ,S-triazin--yl)amino]arbonyl]mio]sulfonyl]benzoate (metsulfuron methyl, HDI and its agriculturally usefu salts; 0 0

HOCCH

2

-N-CH

2

P(OH.)

2

H

IV

N-(phosphonomethyl)glycine (glyphosate, MV and its agriculturally useful salts; 0

CH

3

PCH

2

CH

2

CHCO

2

H

I I OH 11

V

(±--mn--hdoyetypopiilbtni acid (glufosinate, V) and its agriculturally useful salts; 3

CH

3 -N N- CH 3

VI

1,1 '-dimethyl-4,4'-bipyridinium (paraquat, VI) in the form of agriculturally useful salts;

O

czNHCN(CH 3 2 Cl

VII

N-(3, 4 -dichlorophenyl)-N,N-dimethylurea (diuron, VII);

H

CH

3 0 Br Br.

SCHCH

2

CH

3

VIII

5-bromo-6-methyl-3-(1-methylpropyl)-2,4(lH,3H)-pyrimidinedione (bromacil,

VIII);

and

CH

3

(CH

3 2 N N

Y

IX

3 -cyclohexyl-6-(dimethylamino)-1-methyl-l, 3 ,5-triazine-2,4(1H,3H)-dione (hexazinone,

IX).

The compounds of Formulae H-V and VIII 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 Formulae II-V and VIII is to be understood as including both the free compounds and their agriculturally useful salts, where appropriate and expedient. Similarly, the dication of Formula VI is a salt component, and the counterions present will exchange under physiological and environmental conditions. Therefore hereinbefore and hereinafter any reference to Formula VI is to be understood as including all agriculturally useful salts comprising Formula VI, where appropriate and expedient.

The mixtures of the invention preferred for enhanced herbicidal activity include: Sa) the compound of Formula I and the compound of Formula II, b) the compound of Formula I and the compound of Formula III, c) the compound of Formula I and the compound of Formula IV, d) the compound of Formula I and the compound of Formula V, e) the compound of Formula I and the compound of Formula VI, f) the compound of Formula I and the compound of Formula VII, g) the compound of Formula I and the compound of Formula VIII, and h) the compound of Formula I and the compound of Formula IX.

The herbicidal compositions of the invention preferred for enhanced herbicidal activity include:_ a) the compound of Formula I and the compound of Formula II, b) the compound of Formula I and the compound of Formula III, c) the compound of Formula I and the compound of Formula IV, 15 d) the compound of Formula I and the compound of Formula V, e) the compound of Formula I and the compound of Formula VI, f) the compound of Formula I and the compound of Formula VI, "f g) the compound of Formula I and the compound of Formula VII, and h the compound of Formula I and the compound of Formula IX.

The preferred crops for application of the mixtures of the invention are perennial plantation crops including banana, citrus, coffee, cocoa, grapes, hops, oil palm, plantain, pineapple, rubber, sugarcane, tea, fruit trees, nut trees and forests such as eucalyptus and conifers loblolly pine), and turf Kentucky bluegrass, St. Augustine grass, Kentucky fescue, Bermuda grass).

DETAILS OF THE INVENTION The Formula I compound can be prepared as described in U.S. 4,213,773. The synthesis involves reacting the phenol 1 with 3-chloropropyne in the presence of a base such as anhydrous potassium carbonate in a suitable solvent, such as dry acetonitrile.

0

OH

C ClCH 2 -CH I Cl 1 2 Mixtures of the Formula I compound with several specific commercially available herbicides (Formulae II-IX) has now been discovered to demonstrate surprising synergistic control of key weeds.

Sulfometuron methyl (Formula II) is sold by DuPont as the active ingredient in Oust® herbicide. Although sulfometuron methyl is most conveniently obtained as a commercial product, it and its agriculturally useful salts can be prepared by methods described in U.S. 4,394,506.

Metsulfuron methyl (Formula III) is sold by DuPont as the active ingredient in Ally® herbicide and Escort® herbicide. Although metsulfuron methyl is most conveniently obtained as a commercial product, it and its agriculturally useful salts can be prepared by methods described in U.S. 4,383,113.

Glyphosate (Formula IV) is sold in the form of the isopropylammonium salt (Formula IVa) by Monsanto as the active ingredient in Roundup® herbicide and Sting® herbicide. Glyphosate is sold in the form of the trimesium salt (Formula IVb) by Zeneca as the active ingredient in Touchdown® herbicide. Although glyphosate is most conveniently obtained as a commercial product, it and its agriculturally useful salts can be prepared by.methods described in U.S. 4,315,765 and U.S. 4,405,531.

15 Glufosinate (Formula V) is sold in the form of the ammonium salt (Formula Va) by AgrEvo as the active ingredient in Basta® herbicide. Although glufosinate is most Sconveniently obtained as a commercial product, it and its agriculturally useful salts can be prepared by methods described in U.S. 4,168,963.

''Paraquat (Formula VI) is always present as the dication in a salt. The salt anions 20 typically used are chloride, forming paraquat dichloride (Formula VIa). Paraquat dichloride is sold by Zeneca as the active ingredient in Gramoxone® herbicide.

S" "Although paraquat is most conveniently obtained as a commercial product, the agriculturally suitable salts comprising it can be prepared by methods described in U.S. 2,972,528 and U.S. 3,793,335.

Diuron (Formula VII) is sold by DuPont as the active ingredient in Karmex® herbicide, along with bromacil as the active ingredient in Krovar® herbicide, and along with hexazinohe as the active ingredient in Velpar® K herbicide. Although diuron is most conveniently obtained as a commercial product, it can be prepared by the methods described in U.S. 2,655,445.

Bromacil (Formula VIII) is sold by DuPont as the active ingredient in Hyvar® X herbicide and Hyvar® DF herbicide, as the lithium salt (bromacil-lithium, Formula VIIIa) as the active ingredient in Hyvar XL herbicide, and along with diuron as the active ingredient in Krovar® herbicide. Although bromacil is most conveniently obtained as a commercial product, it can be prepared by the methods described in U.S. 3,352,862.

Hexazinone (Formula IX) is sold by DuPont as the active ingredient in Velpar® herbicide and along with diuron as the active ingredient in Velpar® K herbicide.

Although hexazinone is most conveniently obtained as a commercial product, it can be prepared by the methods described in U.S. 3,902,997.

Formulation/Utility The mixtures of the Formula I and Formulae II-IX compounds can be formulated in a number of ways: the Formula I and Formulae II-IX compounds can be formulated separately and applied separately or applied simultaneously in an appropriate weight ratio, as a tank mix; or the Formula I and Formulae II-IX compounds can be formulated together in the proper weight ratio.

Mixtures of the Formula I and Formulae II-IX 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, 15 moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions 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 watersoluble. 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- 25 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 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, 15 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, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- S* 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. Chemically stabilized aqueous sulfonylurea or agriculturally suitable .25 sulfonylurea salt dispersions are taught in U.S. 4,936,900. Solution formulations of sulfonylureas.with improved chemical stability are taught in U.S. 4,599,412. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding 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 numbers are as described in the Index Table on page 13.

Example A High Strength Concentrate Compound 1 78.8% Compound 2 19.7% 15 silica aerogel synthetic amorphous fine silica Example B Wettable Powder Compound 1 39.0% Compound 3 26.0% S dodecylphenol polyethylene glycol ether sodium ligninsulfonate sodium silicoaluminate montmorillonite (calcined) 23.0%.

25 Example C High Strength Concentrate Compound 1 24.6% Compound 4 73.9% silica aerogel synthetic amorphous fine silica Example D High Strength Concentrate Compound 1 32.8% Compound 5 65.7% silica aerogel synthetic amorphous fine silica Example E High Strength Concentrate Compound 1 24.6% Compound 6 73.9% silica aerogel synthetic amorphous fine silica Example F High Strength Concentrate Compound 1 24.6% Compound 7 73.9% silica aerogel synthetic amorphous fine silica Example G Granule Compound 1 1.1% Compound 8 8.9% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.

Example H Aqueous Suspension Compound 1 Compound 9 20.0% hydrated attapulgite crude calcium ligninsulfonate 10.0% 25 sodium dihydrogen phosphate water 61.5%.

Example I Extruded Pellet Compound 1 Compound 10 20.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate sodium alkylnaphthalenesulfonate calcium/magnesium bentonite 59.0%.

Test results indicate that mixtures of Formula I with Formulae II-IX are highly active herbicides, providing unexpected synergistic control of selected grass and broadleaf weeds.

The mixtures of the invention are valued for their utility for selective weed control in perennial plantation crops including banana, citrus, coffee, cocoa, grapes, hops, oil palm, plantain, pineapple, rubber, sugarcane, tea, fruit trees, nut trees and forests such as eucalyptus and conifers loblolly pine), and turf Kentucky bluegrass, St.

Augustine grass, Kentucky fescue, Bermuda grass). These mixtures are also valued for their utility for enhanced broad-spectrum pre- and/or postemergence weed control in areas around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, billboards and railroad structures, and along fence rows and highways.

The mixtures of Formula I with Formula II or III are particularly valued, because they retain acceptable levels of selectivity in crops such as banana, coffee, cocoa, hops, oil palm, plantain, pineapple, rubber, sugarcane, tea, forests and turf. The mixtures of Formula I with Formula IV, V or VI are particularly valued, because they retain acceptable levels of selectivity in crops such as banana, citrus, coffee, cocoa, grapes, hops, oil palm, plantain, pineapple, rubber, tea, fruit trees, nut trees and forests. The 15 mixtures of Formula I with Formula VI are particularly valued, because they retain acceptable levels of selectivity in crops such as banana, grapes, oil palm, plantain, rubber, sugarcane, fruit trees and nut trees. The mixtures of Formula I with Formula VIII are particularly valued, because they retain acceptable levels of selectivity in crops such as citrus. The mixtures of Formula I with Formula IX are particularly valued, because they retain acceptable levels of selectivity in crops such as sugarcane and forests.

Many of the mixtures provide useful weed control when applied in sequential applications. Sequential applications of the mixtures may be particularly useful for controlling weeds that have germinated after the initial application or for improving 25 control of larger weeds that may not be entirely controlled by a single application. In particular, sequential applications of the mixtures may be preferred in certain crop and noncrop utilities.

The Formula I and Formulae II-IX 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 II-IX mixtures of this invention may be particularly useful for weed control.

Examples of other herbicides as mixture partners are: alachlor, ametryn, asulam, atrazine, cinmethylin, cyanazine, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, dalapon, dalapon-sodium, 2,4-DB and its dimethylammonium, potassium and sodium salts, dicamba and its dimethylammonium, potassium and sodium salts, EPTC, fluazifop-butyl, fluazifop-P-butyl, fosamine-ammonium, imazamethabenz-methyl, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, lenacil, linuron, mefluidide, metribuzin, norflurazon, oxadiazon, oxyfluorfen, pendimethalin, picloram, picloram-potassium, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, simazine, tebuthiuron, terbacil, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, and trifluralin. Furthermore, the herbicides bromacil, diuron, glufosinate, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, hexazinone, metsulfuron methyl, paraquat dichloride and sulfometuron methyl are useful as additional mixture partners in combination with other of the Formulae

II-IX

herbicidal compounds in admixture with the Formula I herbicidal compound.

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. Generally, the herbicidally effective amounts of the compounds of Formulae I-IX in the mixtures will vary depending on the specific compounds selected, environmental 15 conditions, formulation, method of application, amount and type of vegetation present, etc. The herbicidally effective amounts of Formula I relative to Formula II is generally in a ratio of 64:1 to 1:2, preferably in a ratio of 32:1 to 1:1, and most preferably in a ratio of 8:1 to 2:1. The herbicidally effective amounts of Formula I relative to Formula III is generally in a ratio of 16:1 to 1:8, preferably in a ratio of 8:1 to 1:4, and 20 most preferably in a ratio of 4:1 to 1:2. The herbicidally effective amounts of Formula I relative to Formula IV is generally in a ratio of 2:1 to 1:10, preferably in a ratio of 1:1 to 1:8, and most preferably in a ratio of 1:1 to 1:5. The herbicidally effective amounts of Formula I relative to Formula V is generally in a ratio of 1:1 to 1:10, preferably in a ratio of 1:1 to 1:8, and most preferably in a ratio of 1:1 to 1:5. The herbicidally 25 effective amounts of Formula I relative to Formula VI is generally in a ratio of 2:1 to 1:10, preferably in a ratio of 1:1 to 1:8, and most preferably in a ratio of 1:1 to 1:5. The herbicidally effective amounts of Formula I relative to Formula VII is generally in a ratio of 1:4 to 1:24, preferably in a ratio of 1:4 to 1:16, and most preferably in a ratio of to 1:12. The herbicidally effective amounts of Formula I relative to Formula VIII is generally in a ratio of 1:1 to 1:16, preferably in a ratio of 1:1 to 1:10, and most preferably in a ratio of 1:1 to 1:8. The herbicidally effective amounts of Formula I relative to Formula IX is generally in a ratio of 1:1 to 1:12, preferably in a ratio of 1:1 to 1:10, and most preferably in a ratio of 1:1 to 1:8.

Generally a herbicidally effective amount of the Formula I compound is applied at a rate from 5 to 5000 g ai/ha, preferably at a rate from 10 to 2000 g ai/ha, and most preferably at a rate from 10 to 1000 g ai/ha. Generally a herbicidally effective amount of the Formula II compound is applied at a rate from 0.25 to 840 g ai/ha, preferably at a rate from 2 to 420 g ai/ha, and most preferably at a rate from 3 to 260 g ai/ha. Generally a herbicidally effective amount of the Formula III compound is applied at a rate from 0.25 to 350 g ai/ha, preferably at a rate from 2 to 200 g ai/ha, and most preferably at a rate from 3 to 175 g ai/ha. Generally a herbicidally effective amount of the Formula IV compound is applied at a rate from 140 to 9000 g ai/ha, preferably at a rate from 320 to 6700 g ai/ha, and most preferably at a rate from 500 to 4500 g ai/ha. Generally a herbicidally effective amount of the Formula V compound is applied at a rate from 100 to 5000 g ai/ha, preferably at a rate from 250 to 2500 g ai/ha, and most preferably at a rate from 500 to 2000 g ai/ha. Generally a herbicidally effective amount of the Formula VI compound is applied at a rate from 25 to 2000 g ai/ha, preferably at a rate from 50 to 1000 g ai/ha, and most preferably at a rate from 100 to 500 g ai/ha.

Generally a herbicidally effective amount of the Formula VII compound is applied at a rate from 200 to 10000 g ai/ha, preferably at a rate from 500 to 5000 g ai/ha, and most preferably at a rate from 500 to 4000 g ai/ha. Generally a herbicidally effective amount of the Formula VIII compound is applied at a rate from 200 to 10000 g ai/ha, preferably 15 at a rate from 500 to 4000 g ai/ha, and most preferably at a rate from 500 to 3000 g ai/ha. Generally a herbicidally effective amount of the Formula IX compound is applied at a rate from 100 to 10000 g ai/ha, preferably at a rate from 100 to 3000 g ai/ha, and most preferably at a rate from 100 to 1000 g ai/ha. One skilled in the art can readily determine herbicidally effective application rates and ratios of the herbicide of Formula I to the herbicides of Formulae II-IX as well as timing necessary for the desired level of weed control and crop safety.

The Formula I triazinone (Compound 1) was tested in combination with the Formula II sulfonylurea (Compound the Formula III sulfonylurea (Compound 3), the Formula IV phosphonate (Compounds 4 and the Formula V phosphonate (Compound the Formula VI pyridinium salt (Compound the Formula VII urea (Compound the Formula VIII triazinedione (Compound 9) and the Formula IX triazinedione (Compound 10). The compounds of Formulae I-IX are listed in the Index Table below by number referred to in the following test data: *9999* 0 09 09 99 9 *0 99

S

9 9 0 INDEX TABLE Compound Number Formula Name 1 I 2 2 4 -dichloro-5-(2-propynyloxy)phenyl]-5,6,7,8-tetrahydro- 1, 2 ,4-triazolo[4,3-a]pyridin-3(2H)-one 2 II sulfometuron methyl 3 III metsulfuron methyl 4 IVa glyphosate-isopropylammonium IVb glyphosate-trimesium 6 Va glufosinate-ammonium 7 VIa paraquat dichloride 8 VII diuron 9 VIII bromacil IX hexazinone The data in the following Tables A and B demonstrate the efficacy of the Formula I and Formula II mixtures of this invention against specific weeds. The weed 5 control afforded by the mixtures of this invention are not limited, however, to these species. Compound numbers are as described in the Index Table on page 13.

Test A Protocol 10-cm square plastic pots were partially filled with sandy loam soil and planted with seeds of large crabgrass (Digitaria sanguinalis), which were covered with 0.5 cm 10 of soil. Preemergence treatments were applied by diluting dry flowable formulations of the compounds in a non-phytotoxic solvent containing a surfactant and then spraying the treatments onto the soil surface using a stationary laboratory circulating belt sprayer calibrated to deliver 327 L/ha through a single nozzle. Compound 1 was applied at 1, 2, 4 and 8 g ai/ha. Compound 2 was applied at 1 g ai/ha. Mixtures of Compound 1 at 1, 2, 4 and 8 g ai/ha and Compound 2 at 1 ai/ha were also applied. Individual treatments were replicated four times. Treatments were positioned in a greenhouse in a randomized complete block design. The greenhouse was maintained at a 26 °C average daily temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 30 days after spraying, the plants were evaluated for injury as compared to control plants that were sprayed preemergence with a non-phytotoxic solvent containing a surfactant. Injury was evaluated visually using a 0 to 100% scale where 0 indicates no effect and 100 indicates complete control.

For Test A, the mean response of each treatment was determined. Colby's equation was used to calculate the expected additive herbicidal effect of the mixtures of Compound 1 and Compound 2. Colby's equation (Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967)) calculates the expected additive effect of herbicidal mixtures, and for two active ingredients is of the form: Pa+b Pa Pb (PaPb 100) wherein Pa+b is the percentage effect of the mixture expected from additive contribution of the individual components, Pa is the observed percentage effect of the first active ingredient at the same use rate as in the mixture, and Pb is the observed percentage effect of the second active ingredient at the same use rate as in the mixture.

Results of Test A are shown in Table A, which lists the observed response of a specific weed to-Compound 1 and Compound 2 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 2, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 2 (Colby's equation).

TABLE A* *i Effect of Compound 1 and Compound 2 as Active Ingredients Alone and in Mixture 0

SO

C. S fS

S

5655Se 5 Compound Compound Crabgrass 1 2 Mean Expectedt Alone 1 0 0- 2 0 4 0 42- 8 0 84 0 1 31 Mixtures 1 1 48 31 2 1 76 4 1 75 8 1 92 89 Rates are expressed in g ai/ha for Compound I and Compound 2. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test B Protocol square plastic pots were partially filled with sandy loam soil and planted with seeds of southern sandbur (Cenchrus echinatus), which were covered with 0.5 cm of soil. Preemergence treatments were applied by diluting dry flowable formulations of the compounds in a non-phytotoxic solvent containing a surfactant and then spraying the treatments onto the soil surface using a stationary laboratory circulating belt sprayer calibrated to deliver 327 L/ha through a single nozzle. Compound 1 was applied at 1, 2 and 4 g ai/ha. Compound 2 was applied at 0.5 g ai/ha. Mixtures of Compound 1 at 1, 2 and 4 g ai/ha and Compound 2 at 0.5 ai/ha were also applied. Individual treatments were replicated four times. Treatments were positioned in a greenhouse in a randomized complete block design. The greenhouse was maintained at a 26 OC average daily temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 30 days after spraying, the plants were evaluated for injury as compared to control plants that were sprayed preemergence with 15 a non-phytotoxic solvent containing a surfactant. Injury was evaluated visually using a to 100% scale where 0 indicates no effect and 100 indicates complete control.

Results of Test B are shown in Table B, which lists the observed response of a specific weed to Compound 1 and Compound 2 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 2, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 2 (Colby's equation).

TABLE B* Effect of Compound 1 and Compound 2 as Active Ingredients Alone and in Mixture Compound Compound Sandbur 1 2 Mean Expectedt Alone 1 0 2 0 12 4 0 31 0 0.5 Mixtures 1 0.5 65 62 2 0.5 85 4 0.5 86 72 Rates are expressed in g ai/ha for Compound 1 and Compound 2. Data are reported as percent control.

16 t. "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Weeds other than those specifically listed in Tables A and B are also controlled by mixtures of Compound 1 and Compound 2. Different ratios of Compound 1 to Compound 2, and different formulation types, also provide useful weed control from the combination of the two herbicides.

The data in the following Tables C and D demonstrate the efficacy of the Formula I and Formula III mixtures of this invention against specific weeds. The weed control afforded by the mixtures of this invention are not limited, however, to these species. Compound numbers are as described in the Index Table on page 13.

Test C Protocol 10-cm square plastic pots were partially filled with sandy loam soil and planted with seeds of large crabgrass (Digitaria sanguinalis), which were covered with 0.5 cm 15 of soil. Preemergence treatments were applied by diluting dry flowable formulations of the compounds in a non-phytotoxic solvent containing a surfactant and then spraying the treatments onto the soil surface using a stationary laboratory circulating belt sprayer calibrated to deliver 327 L/ha through a single nozzle. Compound 1 was applied at 1, 2 and 4 g ai/ha. Compound 3 was applied at I and 2 g ai/ha. Mixtures of Compound 1 at 1, 2 and 4 g ai/ha and Compound 3 at 1 and 2 ai/ha were also applied. Individual treatments were replicated four times. Treatments were positioned in a greenhouse in a randomized complete block design. The greenhouse was maintained at a 24 °C average daily temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 33 days after spraying, the plants were i 25 evaluated for injury as compared to control plants that were sprayed preemergence with a non-phytotoxic solvent containing a surfactant. Injury was evaluated visually using a 0 to 100% scale where 0 indicates no effect and 100 indicates complete control.

Results of Test C are shown in Table C, which lists the observed response of a specific weed to Compound 1 and Compound 3 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 3, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 3 (Colby's equation).

17 TABLE C* Effect of Compound 1 and Compound 3 as Active Ingredients Alone and in Mixture Compound Compound Crabgrass 1 3 Mean Expectedt Alone 1 0 0 2 0 11- 4 0 61 0 1 8- 0 2 31 Mixtures 1 1 9 8 2 1 50 18 4 1 72 64 1 2 54 31 2 2 66 39 4 2 84 73 Rates are expressed in g ai/ha for Compound 1 and Compound 3. Data are reported as 5 percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test D Protocol 10-cm square plastic pots were partially filled with sandy loam soil and planted with seeds of pitted momingglory (Ipomoea lacunosa), which were covered with 0.5 cm of soil. Preemergence treatments were applied by diluting dry flowable formulations of the compounds in a non-phytotoxic solvent containing a surfactant and then spraying the treatments onto the soil surface using a stationary laboratory circulating belt sprayer calibrated to deliver 327 L/ha through a single nozzle. Compound 1 was applied at 1, 2 and 4 g ai/ha. Compound 3 was applied at 1 g ai/ha. Mixtures of Compound 1 at 1, 2 and 4 g ai/ha and Compound 3 at 1 g ai/ha were also applied. Individual treatments were replicated four times. Treatments were positioned in a greenhouse in a randomized complete block design. The greenhouse was maintained at a 24 °C average daily temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 33 days after spraying, the plants were evaluated for injury as compared to control plants that were sprayed preemergence with r a non-phytotoxic solvent containing a surfactant. Injury was evaluated visually using a 0 to 100% scale where 0 indicates no effect and 100 indicates complete control.

Results of Test D are shown in Table D, which lists the observed response of a specific weed to Compound 1 and Compound 3 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 3, and the expected additive effect of the herbicidal mixtures of Compound I and Compound 3 (Colby's equation).

TABLE D* Effect of Compound I and Compound 3 as Active Ingredients Alone and in Mixture Compound Compound Morningglory 1 3 Mean Expectedt Alone 1 0 0_ 2 0 0 4 0 13 8 0 18 0 1 86 Mixtures.

1 1 91 86 2 1 92 86 4 1 95 88 8 1 95 89 Rates are expressed in g ai/ha for Compound 1 and Compound 3. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Weeds other than those specifically listed in Tables C and D are also controlled by mixtures of Compound 1 and Compound 3. Different ratios of Compound 1 to Compound 3, and different formulation types, also provide useful weed control from the combination of the two herbicides.

The data in the following Tables E-H demonstrate the efficacy of the Formula I and Formula IV mixtures of this invention against specific weeds. The weed control afforded by the mixtures of this invention are not limited, however, to these species.

Compound numbers are as described in the Index Table on page 13.

19 Test E Protocol Guineagrass (Panicum maximum) was grown 21 days in a greenhouse to approximately 24-cm height in 18-cm round pots containing a 60:40 mixture of sterilized sandy loam soil and Metro-Mix® 350 potting soil. Treatments were applied to the test species by diluting the formulated compounds in a non-phytotoxic solvent containing a surfactant, and spraying the treatments onto the plants using a stationary laboratory circulating belt sprayer calibrated to deliver 311 L/ha through a single nozzle.

Compound 1 was applied at 31 and 62 g ai/ha. Compound 4 was applied at 125 and 250 g ai/ha. Mixtures of Compound 1 at 31 and 62 g ai/ha with Compound 4 at 125 and 250 g ai/ha were also applied. Individual treatments were replicated three times.

Treatments were positioned in a greenhouse in a randomized complete block design.

*i The greenhouse was maintained at a 28 °C average daily temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 28 days after spraying, the plants were evaluated for injury as compared to 15 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 control.

Results of Test E are shown in Table E, which lists the observed response of a specific weed to Compound 1 and Compound 4 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 4, and the expected additive effect of the herbicidal mixtures of .Compound I and Compound 4 (Colby's equation).

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TABLE E* Effect of Compound 1 and Compound 4 as Active Ingredients Alone and in Mixture Compound Compound Guineagrass 1 4 Mean Expectedt Alone 31 0 37 62 0 73 0 125 0 0 250 0 Mixtures 31 125 53 37 62 125 80 73 31 250 70 37 62 250 78 73 Rates are expressed in g ai/ha for Compound 1 and Compound 4. Data are reported as 5 percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test F Protocol Guineagrass (Panicum maximum) seeds were planted in 18-cm round fiber pots filled with a 60:40 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture. The plants were treated postemergence at the 6- to 8-leaf stage with test compounds formulated with a non-phytotoxic solvent. Compound 1 was applied at 250 and 500 g ai/ha. Compound 4 was applied at 250 and 500 g ai/ha. Mixtures of Compound 1 at 250 and 500 g ai/ha with Compound 4 at 250 and 500 g ai/ha were also applied. The treated plants were grown in a greenhouse. At the end of the tests, the plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results of Test F are shown in Table F, which lists the observed response of a specific weed to Compound 1 and Compound 4 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound I and Compound 4, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 4 (Colby's equation).

TABLE F* Effect of Compound 1 and Compound 4 as Active Ingredients Alone and in Mixture Compound Compound Guineagrass 1 4 Mean Expectedt Alone 250 0 90 500 0 95 0 250 10 0 500 30 Mixtures 250 250 95 91 250 500 95 93 500 250 100 96 500 500 100 96.

Rates are expressed in g ai/ha for Compound 1 and Compound 4. Data are reported as 5 percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test G Protocol Pitted momingglory (Ipomoea lacunosa) was grown 21 days in a greenhouse to approximately 16-cm height in 18-cm round pots containing a 60:40 mixture of sterilized sandy loam soil and Metro-Mix® 350 potting soil. Treatments were applied to the test species by diluting the formulated compounds in a non-phytotoxic solvent containing a surfactant, and spraying the treatments onto the plants using a stationary laboratory circulating belt sprayer calibrated to deliver 311 L/ha through a single nozzle.

Compound 1 was applied at 31, 62 and 125 g ai/ha. Compound 4 was'applied at 125, 250 and 500 g ai/ha. Mixtures of Compound 1 at 31, 62 and 125 g ai/ha with Compound 4 at 125, 250 and 500 g ai/ha were also applied. Individual treatments were replicated three times. Treatments were positioned in a greenhouse in a randomized complete block design. The greenhouse was maintained at a 28 °C average daily temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 28 days after spraying, the plants were evaluated for injury as compared to control plants that were sprayed only with nonphytotoxic solvent. Injury was evaluated visually using a 0 to 100% scale. where 0 indicates no effect and 100 indicates complete control.

x 22 Results of Test G are shown in Table G, which lists the observed response of a specific weed to Compound I and Compound 4 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 4, and the expected additive effect of the herbicidal mixtures of Compound I and Compound 4 (Colby's equation).

TABLE G* Effect of Compound 1 and Compound 4 as Active Ingredients Alone and in Mixture Compound Compound Momingglory 1 4 Mean Expectedt Alone 31 0 47 62 0 77 125 0 0 125 0 0 250 0 0 500 17- Mixtures 31 125 70 47 62 125 100 77 125 125 100 31 250 77 47 62 250 85 77 125 250 100 31 500 83 56 62 500 87 81 125 500 93 92 Rates are expressed in g ai/ha for Compound I and Compound 4. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test H Protocol Pitted momingglory (Ipomoea lacunosa) was grown 21 days in a greenhouse to approximately 16-cm height in 18-cm round pots containing a 60:40 mixture of sterilized sandy loam soil and Metro-Mix@ 350 potting soil. Treatments were applied to the test species by diluting the formulated compounds in a non-phytotoxic solvent

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containing a surfactant, and spraying the treatments onto the plants using a stationary laboratory circulating belt sprayer calibrated to deliver 311 L/ha through a single nozzle.

Compound 1 was applied at 31, 62 and 125 g ai/ha. Compound 5 was applied at 125, 250 and 500 g ai/ha. Mixtures of Compound 1 at 31, 62 and 125 g ai/ha with Compound 5 at 125, 250 and 500 g ai/ha were also applied. Individual treatments were replicated three times. Treatments were positioned in a greenhouse in a randomized complete block design. The greenhouse was maintained at a 28 oC average daily temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 28 days after spraying, the plants were evaluated for injury as compared to control plants that were sprayed only with nonphytotoxic solvent. Injury was evaluated visually using a 0 to 100% scale where 0 indicates no effect and 100 indicates complete control.

Results of Test H are shown in Table H, which lists the observed response of a specific weed to Compound 1 and Compound 5 applied alone as single active 15 ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 5, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 5 (Colby's equation).

TABLE H* Effect of Compound 1 and Compound as Active Ingredients Alone and in Mixture *c Compound Compound Moringglory 1 5 Mean Expectedt Alone 31 0 47 62 0 77 125 0 90 0 125 0- 0 250 3 0 500 17 Mixtures 31 125 95 47 31 250 90 49 31 500 98 56 62 250 90 78 125 125 100 Rates are expressed in g ai/ha for Compound 1 and Compound 5. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Weeds other than those specifically listed in Tables E-H are also controlled by mixtures of Compound 1 with Compounds 4 and 5. Different ratios of Compound 1 to Compounds 4 and 5, and different formulation types, also provide useful weed control from the combination of the herbicides.

The following protocol was used for the test in Table I. Compound numbers are as described in the Index Table on page 13. The data demonstrate the efficacy of the Formula I and Formula V mixtures of this invention against a specific weed. The weed control affordecdby the mixtures of this invention are not limited, however, to this species.

Test I Protocol Pitted momingglory (Ipomoea lacunosa) was grown 21 days in a greenhouse to approximately 16-cm height in 18-cm round pots containing a 60:40 mixture of sterilized sandy loam soil and Metro-Mix® 350 potting soil. Treatments were applied to the test species by diluting the formulated compounds in a non-phytotoxic solvent containing a surfactant, and spraying the treatments onto the plants using a stationary laboratory circulating belt sprayer calibrated to deliver 311 L/ha through a single nozzle.

Compound 1 was applied at 31, 62 and 125 g ai/ha. Compound 6 was applied at 125, 250 and 500 g ai/ha. Mixtures of Compound 1 at 31, 62 and 125 g ai/ha with Compound 6 at 125, 250 and 500 g ai/ha were also applied. Individual treatments were replicated three times. Treatments were positioned in a greenhouse in a randomized complete block design. Thegreenhouse was maintained at a 28 'C average daily 25 temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 28 days after spraying, the plants were evaluated for injury as compared to control plants that were sprayed only with nonphytotoxic solvent. Injury was evaluated visually using a 0 to 100% scale where 0 indicates no effect and 100 indicates complete control.

Results of Test H are shown in Table I, which lists the observed response of a specific weed to Compound 1 and Compound 6 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 6, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 6 (Colby's equation). Weeds other than that specifically listed are also controlled by mixtures of Compound 1 and Compound 6. Different ratios of Compound 1 to Compound 6, and different formulation types, also provide useful weed control from the combination of the two herbicides.

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99999 6 TABLE I* Effect of Compound 1 and Compound 6 as Active Ingredients Alone and in Mixture Compound Compound Momingglory 1 6 Mean Expected? Alone 31 0 47 62 0 77 125 0 90 0 125 0 0 250 7 0 500 80 Mixtures 31 125 80 47 62 125 93 77 125 125 93 31 250 90 51 62 250 100 79 125 250 97 91 62 500 100 125 500 100 98 Rates are expressed in g ai/ha for Compound 1 and Compound 6. Data are reported as 5 percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

The data in the following Tables J and K demonstrate the efficacy of the Formula I and Formula VI mixtures of this invention against specific weeds. The weed control afforded by the mixtures of this invention are not limited, however, to these species. Compound numbers are as described in the Index Table on page 13.

Test J Protocol Pitted momingglory (Ipomoea lacunosa) was grown 21 days in a greenhouse to approximately 16-cm height in 18-cm round pots containing a 60:40 mixture of sterilized sandy loam soil and Metro-Mix® 350 potting soil. Treatments were applied to the test species by diluting the formulated compounds in a non-phytotoxic solvent containing a surfactant, and spraying the treatments onto the plants using a stationary laboratory circulating belt sprayer calibrated to deliver 311 L/ha through a single nozzle.

Compound I was applied at 31, 62 and 125 g ai/ha. Compound 7 was applied at 125, 250 and 500 g ai/ha. Mixtures of Compound I at 31, 62 and 125 g ai/ha with Compound 7 at 125, 250 and 500 g ai/ha were also applied. Individual treatments were replicated three times. Treatments were positioned in a greenhouse in a randomized complete block design. The greenhouse was maintained at a 28 °C average daily temperature, and natural light in the greenhouse was supplemented with artificial light to achieve a photoperiod of 14 hours. At 28 days after spraying, the plants were evaluated for injury as compared to control plants that were sprayed only with nonphytotoxic solvent. Injury was evaluated visually using a 0 to 100% scale where 0 indicates no effect and 100 indicates complete control.

Results-of-Test J are shown in Table J, which lists the observed response of a specific weed to Compound I and Compound 7 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and .i Compound 7, and the expected additive effect of the herbicidal mixtures of 15 Compound 1 and Compound 7 (Colby's equation).

TABLE J* Effect of Compound 1 and Compound 7 as Active Ingredients Alone and in Mixture c Compound Compound Momingglory 1 7 Mean Expected" Alone 31 0 47 62 0 77 125 0 0 125 7 0 250 37 0 500 57 Mixtures 31 125 70 51 62 125 100 79 125 125 100 91 31 250 88 67 62 250 100 86 31 500 100 77 Rates are expressed in g ai/ha for Compound 1 and Compound 7. Data are reported as percent control.

27 t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test K Protocol Guineagrass (Panicum maximum) seeds were planted in 18-cm round fiber pots filled with a 60:40 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture. The plants were treated postemergence at the 6- to 8-leaf stage with test compounds formulated with a non-phytotoxic solvent. Compound 1 was applied at 500 g ai/ha. Compound 7 was applied at 250 g ai/ha. A mixture of Compound 1 at 500 g ai/ha with Compound 7 at 250 g ai/ha were also applied. The treated plants were grown in a greenhouse. At the end of the tests, the plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results of Test K are shown in Table K, which lists the observed response of a 15 specific weed to Compound 1 and Compound 7 applied alone as single active ingredients, the observed responses of the specific weed to mixtures of Compound 1 and Compound 7, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 7 (Colby's equation).

"TABLE K* Effect of Compound 1 and Compound 7 as Active Ingredients Alone and in Mixture Compound Compound Guineagrass 1 7 Mean Expected" SAlone 500 0 0 250 Mixture 500 250 100 98 Rates are expressed in g ai/ha for Compound I and Compound 7. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Weeds other than those specifically listed in Tables J and K are also controlled by mixtures of Compound 1 and Compound 7. Different ratios of Compound 1 to Compound 7, and different formulation types, also provide useful weed control from the combination of the two herbicides.

The data in the following Tables L and M demonstrate the efficacy of the Formula I and Formula VII mixtures of this invention against specific weeds. The weed control afforded by the mixtures of this invention are not limited, however, to these species. Compound numbers are as described in the Index Table on page 13.

Test L Protocol Pitted momingglory (Ipomoea lacunosa), common ragweed (Ambrosia artemisiifolia) and purslane (Portulaca oleracea) seeds were planted in 10-cm square plastic pots filled with a 60:40 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture. The plants were treated postemergence with the test compounds formulated with a non-phytotoxic solvent. Compound 1 was applied at 64 g ai/ha.

Compound 8 was applied at 250 and 500 g ai/ha. Mixtures of Compound 1 at 64 g ai/ha with Compound 8 at 250 and 500 g ai/ha were also applied. The treated plants were grown in a greenhouse. At the end of the tests, the plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect 15 and 100 indicates complete control.

Results of Test L are shown in Table L, which lists the observed response of specific weeds to Compound 1 and Compound 8 applied alone as single active ingredients, the observed responses of specific weeds to mixtures of Compound 1 and Compound 8, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 8 (Colby's equation).

TABLE L* Effect of Compound 1 and Compound 8 as Active Ingredients Alone and in Mixture a Cmpd Cmpd Moringglory Ragweed Purslane S8 Mean Expectedt Mean Expected Mean Expected Alone 64 0 20 80 0 250 0 0 0 0 500 0 0 0 Mixtures 64 250 60 20 100 80 90 64 500 30 20 100 80 80 Rates are expressed in g ai/ha for Compound 1 and Compound 8. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

29 Test M Protocol Bermudagrass (Cynodon dactylon), guineagrass (Panicum maximum), and johnsongrass seeds were planted in 10-cm square plastic pots filled with a 60:40 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture. The plants were treated postemergence with the test compounds formulated with a non-phytotoxic solvent.

Compound 1 was applied at 125 g ai/ha. Compound 8 was applied at 500 g ai/ha.

Mixtures of Compound 1 at 125 g ai/ha with Compound 8 at 500 g ai/ha were also applied. The treated plants were grown in a greenhouse. At the end of the tests, the plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results. ofTest M are shown in Table M, which lists the observed response of specific weeds to Compound 1 and Compound 8 applied alone as single active ingredients, the observed responses of specific weeds to mixtures of Compound 1 and i. Compound 8, and the expected additive effect of the herbicidal mixtures of 15 Compound 1 and Compound 8 (Colby's equation).

TABLE M* Effect of Compound 1 and Compound 8 as Active Ingredients Alone and in Mixture Cmpd Cmpd Bermudagrass uineagrass ohnsongrass 1 8 Mean Expectedt Mean Expected Mean Expected lee* 0 0 Alone 125 0 0 30 30 0 500 0 0 0 Mixture 125 500 50 0 70 30 50 Rates are expressed in g ai/ha for Compound 1 and Compound 8. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Weeds other than those specifically listed in Tables L and M are also controlled by mixtures of Compound 1 and Compound 8. Different ratios of Compound 1 to Compound 8, and different formulation types, also provide useful weed control from the combination of the two herbicides.

The data in the following Tables N and O demonstrate the efficacy of the Formula I and Formula VIII mixtures of this invention against specific weeds. The weed control afforded by the mixtures of this invention are not limited, however, to these species. Compound numbers are as described in the Index Table on page 13.

Test N Protocol Dallisgrass (Paspalum dilatatum), broadleaf signalgrass (Brachiaria platyphylla), smooth crabgrass (Digitaria ischaemum), southern sandbur (Cenchrus echinatus) and common ragweed (Ambrosia artemisiifolia) seeds were planted in a growing medium comprising a 75:25 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture and treated preemergence with the test compounds formulated with a nonphytotoxic solvent. Compound 1 was applied at 32 g ai/ha. Compound 9 was applied at 500 g ai/ha. Mixtures of Compound 1 at 32 g ai/ha with Compound 9 at 500 g ai/ha were also applied. The treated plants were grown in a greenhouse until they were rated at the end of the test. The plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

15 Results of Test N are shown in Table N, which lists the observed response of specific weeds to Compound 1 and Compound 9 applied alone as single active ingredients, the observed responses of specific weeds to mixtures of Compound 1 and Compound 9, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 9 (Colby's equation).

TABLE N* Effect of Compound 1 and Compound 9 S as Active Ingredients Alone and in Mixture Cmpd Cmpd Dallisgrass Signalgrass Crabgrass 19 Mean Expectedf Mean Expected Mean Expected Alone 32 -0 80 30 80 0 500 20 40 0 Mixture 32 500 100 84 80 54 90 Cmpd Cmpd Sandbur Ragweed 1 9 Mean Expected Mean Expected Alone 32 0 0 0 0 500 30 20 Mixture 32 500 60 30 80 Rates are expressed in g ai/ha for Compound 1 and Compound 9. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test 0 Protocol Dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), itchgrass (Rottboellia exaltata), johnsongrass (Sorghum halepense), and pitted morningglory (Ipomoea lacunosa) were grown in a greenhouse using a medium comprising a 60:40 10 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture. The plants were treated postemergence with the test compounds formulated with a non-phytotoxic solvent. Compound 1 was applied at 32 and 64 g ai/ha. Compound 9 was applied at 250 g ai/ha. Mixtures of Compound 1 at 32 and 64 g ai/ha with Compound 9 at 250 g ai/ha were also applied. The treated plants were grown in a greenhouse until they were rated at the end of the test. The plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results_of Test O are shown in Table O, which lists the observed response of specific weeds to Compound 1 and Compound 9 applied alone as single active ingredients, the observed responses of specific weeds to mixtures of Compound 1 and Compound 9, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 9 (Colby's equation).

000..: 0** 40 00 0 0 0 oo 0 00 0

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0 TABLE O* Effect of Compound 1 and Compound 9 as Active Ingredients Alone and in Mixture Cmpd Cmpd Dallisgrass Goosegrass Itchgrass 1 9 Mean Expectedt Mean Expected Mean Expected Alone 32 0 0 0 0 64 0 0 30 0 0 250 0 0 Mixtures 32 250 30 0 40 0 20 0 64 250 70 0 70 30 20 0 Cmpd Cmpd Johnsongrass Morningglory 1 9 Mean Expected Mean Expected Alone 32 0 0 0 64 0 20 20 0 250 0 -0 Mixtures 32 250 20 0 50 0 64 250 50 20 70 5 Rates are expressed in g ai/ha for Compound 1 and Compound 9. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Weeds other than those specifically listed in Tables N and O are also controlled by mixtures of Compound 1 and Compound 9. Different ratios of Compound 1 to Compound 9, and different formulation types, also provide useful weed control from the combination of the two herbicides.

The data in the following Tables P-T demonstrate the efficacy of the Formula I and Formula IX mixtures of this invention against specific weeds. The weed control afforded by the mixtures of this invention are not limited, however, to these species.

Compound numbers are as described in the Index Table on page 13.

a 33 Test P Protocol Bermudagrass (Cynodon dactylon), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltata), johnsongrass (Sorghum halepense), peanut (Arachis hypogaea) and ragweed (Ambrosia artemisiifolia) seeds were planted in 10-cm plastic pots containing a 75:25 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture and treated preemergence with the test compounds formulated with a nonphytotoxic solvent. Compound 1 was applied at 64 g ai/ha. Compound 10 was applied at 500 g ai/ha. Mixtures of Compound 1 at 64 g ai/ha with Compound 10 at 500 g ai/ha were also applied. The treated plants were grown in a greenhouse until they were rated at the end of the test. The plants were visually rated and compared with untreated controls using-a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results of Test P are shown in Table P, which lists the observed response of .specific weeds to Compound 1 and Compound 10 applied alone as single active 15 ingredients, the observed responses of specific weeds to mixtures of Compound 1 and Compound 10, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 10 (Colby's equation).

TABLE P* Effect of Compound 1 and Compound as Active Ingredients Alone and in Mixture Cmpd Cmpd Bermudagrass Guineagrass Itchgrass 1 10 Mean Expectedt Mean Expected Mean Expected Alone 64 -0 80 90 0 0 500 90 Mixture 64 500 100 98 100 90 70 0 Cmpd Cmpd Johnsongrass Peanut Ragweed !1 I. Mean Expected Mean Expected Mean Expected Alone 64 0 0 20 40 0 500 0 -_30 Mixture 64 500 90 0 50 44 90 83 Rates are expressed in g ai/ha for Compound 1 and Compound 10. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), 5 pp 20-22 (1967).

Test 0 Protocol Bermudagrass (Cynodon dactylon), goosegrass (Eleusine indica) and pitted momingglory (Ipomoea lacunosa) seeds were planted in a growing medium comprising a 75:25 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture and 10 treated preemergence with the test compounds formulated with a non-phytotoxic solvent. Compound 1 was applied at 32 g ai/ha. Compound 10 was applied at 192 g ai/ha. Mixtures of Compound 1 at 32 g ai/ha with Compound 10 at 192 g ai/ha were also applied. The treated plants were grown in a greenhouse until they were rated at the end of the test. The plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results of Test Q are shown in Table Q, which lists the observed response of specific weeds to Compound 1 and Compound 10 applied alone as single active ingredients, the observed responses of specific weeds to mixtures of Compound 1 and Compound 10, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 10 (Colby's equation).

TABLE O* Effect of Compound 1 and Compound as Active Ingredients Alone and in Mixture Cmpd Cmpd Bermudagrass Goosegrass Momingglory 1 10 Mean Expectedt Mean Expected Mean Expected Alone 32 0 30 70 0 192 0 0 0 Mixture 32 192 70 30 90 70 80 0 Rates are expressed in g ai/ha for Compound 1 and Compound 10. Data are reported 5 as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating •Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test R Protocol 10 Dallisgrass (Paspalum dilatatum), annual bluegrass (Poa annua), southern sandbur (Cenchrus echinatus), alfalfa (Medicago sativa), and peanut (Arachis hypogaea) seeds were planted in a growing medium comprising a 75:25 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture and treated preemergence with the test compounds formulated with a non-phytotoxic solvent.

Compound 1 was applied at 64 g ai/ha. Compound 10 was applied at 384 g ai/ha.

Mixtures of Compound 1 at 64 g ai/ha with Compound 10 at 384 g ai/ha were also applied. The treated plants were grown in a greenhouse until they were rated at the end of the test. The plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results of Test R are shown in Table R, which lists the observed response of specific weeds to Compound 1 and Compound 10 applied alone as single active ingredients, the observed responses of specific weeds to mixtures of Compound 1 and Compound 10, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 10 (Colby's equation).

TABLE R* Effect of Compound 1 and Compound as Active Ingredients Alone and in Mixture Cmpd Cmpd Dallisgrass Bluegrass Sandbur 1 10 Mean Expectedt Mean Expected Mean Expected Alone 64 0 60 0 0 0 384 30 60 20 Mixture 64 384 100 72 90 60 100 Cmpd Cmpd Alfalfa Peanut 1 10 Mean Expected Mean xpected Alone 64 0 0 0 384 20 30 Mixture 64 384 100 20 50 Rates are expressed in g ai/ha for Compound 1 and Compound 10. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test S Protocol Pitted morningglory (Ipomoea lacunosa) was grown in a greenhouse in plastic pots containing a 60:40 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture. When the plants reached the 5- to 8-leaf stage, they were treated postemergence with the test compounds formulated with a non-phytotoxic solvent.

Compound 1 was applied at 125 g ai/ha. Compound 10 was applied at 250 and 500 g ai/ha. Mixtures of Compound 1 at 125 g ai/ha with Compound 10 at 250 and 500 g ai/ha were also applied. The treated plants were grown in a greenhouse until they were rated at the end of the test. The plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results of Test T are shown in Table T, which lists the observed response of specific weeds to Compound 1 and Compound 10 applied alone as single active n 37 ingredients, the observed responses of specific weeds to mixtures of Compound 1 and Compound 10, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 10 (Colby's equation).

TABLE S* Effect of Compound 1 and Compound as Active Ingredients Alone and in Mixture Cmpd Cmpd omingglory 1 10 Mean Expectedt Alone 125 0 70 0 250 0 0 500 20 Mixtures 125 250 80 125 500 100 76 Rates are expressed in g ai/ha for Compound 1 and Compound 10. Data are reported as percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating 10 Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Test T Protocol Annual bluegrass (Poa annua), southern sandbur (Cenchrus echinatus), goosegrass (Eleusine indica), guineagrass (Panicum maximum), and smooth crabgrass (Digitaria ischaemum) were grown in a greenhouse using a medium comprising a 60:40 ratio of sterilized sandy loam soil and Metro-mix® 350 potting mixture. The plants were treated postemergence with the test compounds formulated with a non-phytotoxic solvent. Compound 1 was applied at 125 g ai/ha. Compound 10 was applied at 750 g ai/ha. Mixtures of Compound 1 at 125 g ai/ha with Compound 10 at 750 g ai/ha were also applied. The treated plants were grown in a greenhouse until they were rated at the end of the test. The plants were visually rated and compared with untreated controls using a scale of 0 to 100 where 0 indicates no effect and 100 indicates complete control.

Results of Test T are shown in Table T, which lists the observed response of specific weeds to Compound 1 and Compound 10 applied alone as single active ingredients, the observed responses of specific weeds to mixtures of Compound 1 and Compound 10, and the expected additive effect of the herbicidal mixtures of Compound 1 and Compound 10 (Colby's equation).

-38- TABLE T* Effect of Compound 1 and Compound as Active Ingredients Alone and in Mixture Cmpd Cmpd Annual Bluegrass Guineagrass Goosegrass 1 10 Mean Expectedt Mean Expected Mean Expected Alone 125 0 0 30 30 0 750 10 80 70 Mixture 125 750 50 10 100 86 80 79 a o Cmpd Cmpd Crabgrass Sandbur 1 10 Mean Expected Mean Expected Alone 125 0 20 20 0 750 60 90 Mixture 125 750 80 68 100 92 Rates are expressed in g ai/ha for Compound 1 and Compound 10. Data are reported as 10 percent control.

t "Expected" are expected responses calculated according to Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967).

Weeds other than those specifically listed in Tables P-T are also controlled by mixtures of Compound 1 and Compound 10. Different ratios of Compound 1 to Compound 10, and different formulation types, also provide useful weed control from the combination of the two herbicides.

Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof 22/06/01 ,cf9339.speci,38

Claims (10)

1. A herbicidally effective synergistic mixture of 2-[2,4-dichloro-5-(2- propynyloxy)phenyl]-5,6,7,8-tetrahydro-1,2,4-triazolo[4,3-a]pyridin-3(2H)-one (Formula I) with a herbicidal compound selected from sulfometuron methyl (Formula II), metsulfuron methyl (Formula III), glyphosate (Formula IV), glufosinate (Formula V), paraquat (Formula VI), diuron (Formula VII), bromacil (Formula VIII), and S* hexazinone (Formula IX), and their agriculturally suitable salts. 15 2. The mixture of Claim 1 which is the compound of Formula I and the *compound of Formula II. S3. The mixture of Claim 1 which is the compound of Formula I and the compound of Formula III.

3. The mixture of Claim 1 which is the compound of Formula I and the compound of Formula IV. The mixture of Claim 1 which is the compound of Formula I and the 2 compound of Formula V.

6. The mixture of Claim 1 which is the compound of Formula I and the o• Scompound of Formula VI.

7. The mixture of Claim 1 which is the compound of Formula I and the compound of Formula VII.

8. The mixture of Claim 1 which is the compound of Formula I and the compound of Formula VIII.

9. The mixture of Claim 1 which is the compound of Formula I and the compound of Formula IX. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the mixture of any one of Claims 1-9 and at least one of the following: surfactant, solid or liquid diluent. 22/06/01 ,cf9339.speci,39

11. 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 one of Claims 1-9.

12. A herbicidally effective synergistic mixture of Claim 1, substantially as herein described with reference to any one of the Examples.

13. An agriculturally suitable composition of Claim 10, substantially as herein described with reference to any one of the Examples.

14. A method of Claim 11 for controlling the growth of undesired vegetation which method is substantially as herein described with reference to any one of the Examples. i DATED this 2 2 nd day of June, 2001. 15 E.I. DU PONT DE NEMOURS AND COMPANY By their Patent Attorney: S. CA LINAN LAWRIE *a 22/06/01,cf9339.speci,40