AU720032B2

AU720032B2 - Herbicide

Info

Publication number: AU720032B2
Application number: AU37500/97A
Authority: AU
Inventors: Stephen John Stewart
Original assignee: MACSPRED Pty Ltd
Current assignee: MACSPRED Pty Ltd
Priority date: 1996-09-11
Filing date: 1997-09-11
Publication date: 2000-05-18
Anticipated expiration: 2017-09-11
Also published as: AU3750097A

Description

P/00/011 Regulation 3.2

AUSTRALIA

PATENTS ACT 1990 COMPLETE

SPECIFICATION

FOR A STANDARD

PATENT

ORIGINAL

a a TO BE COMPLETED BY APPLICANT Name of Applicant: Actual Inventor: Address for Service: Invention Title: MACSPRED PTY LTD Stephen John Stewart CALLINAN LAWRIE, 278 High Street, Kew, 3101, Victoria, Australia

"HERBICIDE"

The following statement is a full description of this invention, including the best method of performing it known to me:- The present invention relates to herbicides comprising uracil herbicides in combination with sulfonyl urea herbicides.

Uracil herbicides such as 3-tert-butyl-5-chloro-6-methyluracil having the common name terbacil and commercially available under the trade mark "Sinbar" are "post-emergent" herbicides. They are absorbed by plant roots and used for the selective control of many annual and some perennial weeds in crops such as apple, citrus, lucerne, peaches and sugar cane.

There is a limit to the amount of terbacil that can be applied to a crop to control weeds before growth of the crop may be suppressed. In addition, with increasing environmental concerns, it is desirable to lower the rates of herbicide that are applied to a crop.

Sulfonylurea herbicides such as 2-(4,6-dimethylpyrimidin-2-ylcarbamoyl sulfamoyl) benzoic acid commonly known as sulfometuron which is sold under the trade mark "Oust" are broad range pre-emergent herbicides which are used to control annual and perennial grasses and broad-leafed weeds. They suppress plant growth by arresting cell division in the growing tips of roots and plants.

':9020 They are rapidly taken up by the foliage and roots of sensitive herbaceous species, being translocated throughout the plant. It is reported that sulfonylurea herbicides have a little or poor post-emergent effects: see "SULPHOMETURON- METHYL (OUST) -DOES IT HAVE A PLACE IN THE ESTABLISHMENT OF E.GLOBULUS OF PLANTATIONS?" R. R. A. Fremlin, Department of Conservation and Land Management, Busselton, Western Australia, 6280.

It has now been surprisingly found that sulfonylurea herbicides which were not previously thought to have significant post-emergent activity enhance the post-emergent activity of uracil herbicides.

11/9/97msap8875.spe, -3- According to a first aspect the present invention relates to a herbicidal mixture comprising a uracil herbicide and a sulfonylurea herbicide wherein said uracil herbicide has the following formula:

O

RN

N R2

H

where R is selected from the group consisting of alkyl of 1 through

C

carbon atoms, substituted alkyl of 1 through 8 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, and cyano, aryl of 5 through 10 carbon atoms, substituted phenyl, wherein said substituent is selected from the

C

group consisting of chlorine, bromine, fluorine, alkoxy of 1-5 carbon atoms, :alkyl of 1-6 carbon atoms, nitro, trifluoromethyl, 1,2-tetramethylene, and 1,2trimethylenylene, aralkyl of 5 through 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl, and alkoxy, tetrahydronaphthylalkyl, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, 24/03/00,cf8875.speci,3 3asubstituted cycloalkyl of 3 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkenyl of 4 through 12 carbon atoms, substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of through 13 carbon atoms, (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, (substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and cyano;

R

1 is selected from the group consisting of chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, 15 butoxy, nitro alkoxymethyl of 2 through 6 carbon atoms, hydroxy alkyl of 1 i I through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms, thiocyanato, cyano, thiolmethyl, alkylthio of 1 through 4 carbon atoms, bromomethyl, fluoromethyl, chloromethyl, methylthiomethyl, phenylthiomethyl, and carboxymethyl-thiomethyl;

R

2 is selected from the group consisting of chlorine, bromine, alkyl of 1 through 5 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, bromoalkyl of 1 through 4 carbon atoms, and alkoxy of 1 through 5 carbon atoms; and 24/03/00,cf8875.speci,3 3b- X is selected from the group consisting of oxygen and sulfur; and the sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese, and quaternary ammonium salts of the above compounds and wherein said sulfonylurea herbicide has the following formula: 0 11

COR

I I S02N C- NRi R4 4 6e** 9 9 6 4. 9 a a a.

9*4 a a at..

a 99a6 a.

ta *9 96 a a a 9 a 9 a. 9.

wherein Q isO0; Wiso; R is Cl-C 4 alkyl;

R

2 is H;

R

3 is H;

R

4 isH, is H or CH 3 R, is 24/03100,Mf875.speci.3 3c-

X

N

Z

N y

Y

X is H, CH 3

OCH

3 or OC 2

H

5 Y is H, Cl, CH 3

OCH

3 or OC 2

H

5 and ZisCH.

Any reference herein to uracil and sulfonylurea is understood to also include those salts thereof that are agriculturally useful. That is, the uracil and 10 sulfonylurea herbicides can be present in the form of salts.

The mixtures of the present invention may also include additives such Sas surfactants, solid or liquid diluents, adjuvants, excipients, carriers or even other active ingredients such as herbicidal active ingredients.

According to a second aspect the invention relates to a method of

C

controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a uracil herbicide and a sulfonylurea herbicide.

C

According to a third aspect the present invention relates to a method of controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a uracil herbicide and a sulfonylurea herbicide wherein said uracil herbicide has the following formula: 24/03/00,cf8875.speci,3 3dwhere ~t* q

S.

#5

S

S. 59

S

U

*5 5- 6 R is selected from the group consisting of alkyl of I through carbon atoms, substituted alkyl of I through 8 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, and cyano, aryl of 5 through carbon atoms, substituted phenyl, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, alkoxy of carbon atoms, alkyl of 1-6 carbon atoms, nitro, trifluoromethyl, 1 ,2tetramethylene, and 1,2-trimethylenylene, aralkyl of 5 through 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl, and alkoxy, tetrahydronaphthylalkyl, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, substituted cycloalkyl of 3 24/03/00,cf8875.speci.3 3e- 4 4 444* 44**, 4 4 '9 4 4

U

*9 *9 4.

I

through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkenyl of 4 through 12 carbon atoms, substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of through 13 carbon atoms, (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, (substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and cyano;

R

1 is selected from the group consisting of chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro alkoxymethyl of 2 through 6 carbon atoms, hydroxy alkyl of I through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms, thiocyanato, cyano, thiolmethyl, alkylthio of I through 4 carbon atoms, bromomethyl, fluoromethyl, chloromethyl, methylthiomethyl, phenylthiomethyl, and carboxymethyl-thiomethyl;

R

2 is selected from the group consisting of chlorine, bromine, alkyl of I through 5 carbon atoms, chloroalkyl of I through 4 carbon atoms, bromoalkyl of I through 4 carbon atoms, and alkoxy of I through 5 carbon atoms; and X is selected from the group consisting of oxygen and sulfur; 4 44*9 *9.

9 24103/00,cf8875.speci,3 3f and the sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese, and quaternary ammonium salts of the above compounds and wherein said sulfonylurea herbicide has the following formula: 0 11

CQR

w I I R4

Y

0~ i 10 q. 0= p p *0 wherein QisO; WisO; R is Cl-C 4 alkyl;

FR

2 is H;

R

3 is H;

R

4 isH;

FR

5 is H or OH 3 R, is 24103100,cf8875.sPeci,3 3g x N X is H, CH 3

OCH

3 or 0C 2

H

5 Y is H, Cl, OH 3

OCH

3 or 00 2

H

5 and Z is CH.

Uracil herbicides and processes for their production are disclosed in United States Patent Nos. 3,235,357, 3,352,562 and 3,574,214, the disclosures of which are incorporated herein by reference. US 3,235,357 discloses compounds of the formula: 0 RN R x R2 9U*N/

H

24/03/00cf8875.speci,3 where R is selected from the group consisting of alkyl of 1 through carbon atoms, substituted alkyl of 1 through 8 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, and cyano, aryl of 5 through 10 carbon atoms, substituted phenyl, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, alkoxy of 1-5 carbon atoms, alkyl of 1-6 carbon atoms, nitro, trifluoromethyl, 1,2-tetramethylene, and 1,2trimethylenylene, aralkyl of 5 through 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl, and alkoxy, tetrahydronaphthylalkyl, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, substituted cycloalkyl of 3 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkenyl of 4 through 12 carbon atoms, substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbon atoms, (substituted cycloalkyl)alkyl of through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, 25 (substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and cyano;

R

1 is selected from the group consisting of chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro alkoxymethyl of 2 through 6 carbon atoms, hydroxy 11/9/97msap8875.spe, alkyl of 1 through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms, thiocyanato, cyano, thiolmethyl, alkylthio of 1 through 4 carbon atoms, bromomethyl, fluoromethyl, chloromethyl, methylthiomethyl, phenylthiomethyl, and carboxymethylthiomethyl;

R

2 is selected from the group consisting of chlorine, bromine, alkyl of 1 through 5 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, bromoalkyl of 1 through 4 carbon atoms, and alkoxy of 1 through 5 carbon atoms; and X is selected from the group consisting of oxygen and sulfur; and the sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese, and quaternary ammonium salts of the above compounds.

All uracil herbicides falling within the above disclosures may be used in the compositions and methods of the present invention. In a preferred embodiment of the present invention, 3-tert-butyl-5-chloro-6-methyluracil commonly known as terbacil and sold under the trade mark "Sinbar" is used in the compositions of the present invention. Terbacil has the following formula: Cl CH3 N 0 I N C C(CH3)3

O

c 0 Sulfonylurea herbicides are disclosed in United States Patent Nos.

4,394,506, 4,238,621 and 4,564,384 the disclosures of which are i incorporated herein by reference. United States Patent Nos 4,564,384 and 4,394,506 both disclose compounds of the formula: 11/9/97msap8875.spe, -6- 0 11

CQR

R

W

I I S02N C NRi R3R4 Rs wherein Q isO0; W isO0; R is Cl-C 4 alkyl;

R

2 is H;

R

3 is H; is H,

R

5 is H or CH 3 RR is a x

N

X is H, CH 3 or 0C 2

H-

5 Y is H, Cl, CH 3

OCH

3 or OC 2 Hs1; and Z is CH.

All sulfonyl urea herbicides falling within the above disclosure may be used in the compositions and methods of the present invention. In a preferred embodiment of the pres nento, 2-(4,6-dimethylpyrimidin-2ylcarbamnoylsulfamoyl) benzioc commonly known as sulfometuron methyl and sold 24103100,of 8875.speci,6 -7under the trade mark "Oust" is used in the compositions and methods of the present invention. Sulfometuron methyl has the following formula:

CO.OH

SO2.NH.CO.NH CH3 CH3 *999 9 9 -9 9- 9.- 9 9 9 9 9 9 9 *9* 99j9 99 9 9-.

9 Preferably the mixture contains 44g/kg terbacil and 2g/kg sulfometuron methyl based on the total weight of the mixture.

Sinbar contains 800g/kg terbacil. It is advertised for selective weed control in apples, peaches, seed lucerne and peppermint. It is a soil residual herbicide, mainly entering weeds though their roots. In Table 1 are provided recommended dosage rates for certain weeds in Australia. In the first column 2.2kgs to 4.5kgs equates to 1.76 kgai/ha to 3.6 kgai/ha (ai active ingredient). It has been found that when terbacil is mixed with an amount of sulfometuron, this rate can be substantially decreased.

TABLE 1 CROP WEEDS CONTROLLED RATE kg/ha Light Medium Heavy Soils Soils Soils APPLES PEACHES ANNUAL WEEDS: (At least 3 years old) Amaranthus, Barley grass, Barnyard 2.2 kg 4.5 kg grass, Bathurst Burr, Brome grasses, Capeweed, Fat-hen, Innocent weed, Milk Thistle, Paterson's Curse, Pigweed, 3.3 kg 4.5 kg Shepherd's Purse, Threecorered jack (Spiny Emex, Doublegee), Whorled Pigeon grass, Wild Lettuce, Wild Oats, Wild Radish, Wild Turnip PEACHES As above 2.2 3.5 kg (At least 3 years old) APPLES PEACHES PERENNIAL WEEDS: 4.5 kg (At least 8 years old) Couch grass, Kikuyu, Johnson grass, 200 g/100 L Nutgrass 24/03/00,cf8875.speci,7 CROP WEEDS CONTROLLED RATE kg/ha Light Medium Heavy Soils Soils Soils LUCERNE SEED Annual ryegrass, Charlock, 1 kg 1.4 kg 1.75 kg CROPS Chickweed, Deadnettle, Fat-hen (At least 1 year old) Fumitory, Melilorus, Milk Thistle, Mustard, Rough Poppy, Paterson's Curse, Sheepweed, Shepherd's Purse, Soursob, Storksbill (Geranium), Three Cornered Jack(s) (Spiny Emex, Doublegee), Wild Oats, Wild Radish, Wild Turnip, Wireweed, Yellow Burrweed PEPPERMINT Amaranthus, Barley grass, Brome 2 kg grasses, Barnyard grass, Capeweed, Fat-hen, Shepherd's Purse, Sowthistle, Whorled Pigeon grass, Wild Eats, Wild Radish, Wild Turnip In mixtures and methods of the present invention the uracil herbicide may be applied in rates up to what is known in the art for application of such herbicides. In practice, however the rate may be reduced because of the synergistic effect of the sulfonyl urea herbicide. In the mixtures and methods of the present invention the uracil herbicide is preferably applied in the range of about 1 to about 4,000 gai/ha more preferably about 500 to about 3,000 gai/ha. Amounts in the range of about 1.3 kgai/ha have been found to be particularly effective.

Oust® contains 750 grams per kilogram sulfometuron methyl. It is advertised for the control of certain annual and perennial grasses and broad leaf weeds in commercial and industrial areas. It is a soil residual herbicide with some knock down action. Although it is advertised as a pre-emergence herbicide, the instructions for use state that best results are obtained if application is made before or during the early stages of weed growth. It is stated that for weeds advanced beyond the 4-leaf stage or when more rapid knock down is required, mixtures with Roundup herbicide should be used. This knock down is required, mixtures with Roundup® herbicide should be used. This 11/9/97msap8875.spe, implies that Oust® only has good efficacy against very small weeds, ie: less than or at the 4-leaf stage. In addition the Fremlin paper referred to above states that Oust® is ineffective as a post-emergence herbicide. Table 2 sets out recommended dosages for certain weeds in Australia. The recommended rates of Oust® are in the range of 200-400 g/ha which equates to 150-300 gai/ha.

Again, rates up to what is known in the art for application of such herbicides may be used but lower rates than these may be used in practice in the mixtures and methods of the present invention. The sulfonyl urea herbicide is preferably applied in the range of about 1 to about 400 gai/ha preferably about 1 to about 200 gai/ha. Amounts in the range of about 60 gai/ha have been found to be particularly effective. It has been found that this rate of Oust® alone, would not provide the level of control that has been obtained from the mixture of terbacil and Oust®. The terbacil/Oust® mixture also controls large weeds, advanced beyond the 4-leaf stage.

TABLE 2

*C*

*r WEEDS _RATE BOOM HANDGUN KNAPSACK g/ha g/100 L g/15 L Easy-to-kill Annual Weeds Grasses Annual Ryegrass, Barnyard grass, 200 or 400 20 or 40 3 or 6 Summer grass/Crabgrass, Wild Oats, Winter grass Broadleafs Blue Billygoat Weed, Capeweed, Corkscrew/Erodium, Paterson's Curse/Salvation Jane, Subterranean Clover and Turnip weed Easy-to-kill Perennial Weeds Grasses Prairie grass Broadleafs Dandelion, Dock, White Clover 99* 9* I1/9/97msap8875.spe, *qq i WEEDS IRATE Hard-to-kill Annual Weeds 200 or 400 20 or 40 3 or 6 Grasses Rat's Tail Fescue, Squirrel Tail Fescue Broadleaf Black Thistle/Spear Thistle Hard-to-kill Perennial Weeds 400 or 800 40 or 80 6 or 12 Grasses African Lovegrass, Columbus grass, Couch, Elastic grass, Guinea grass, Johnson grass, Kikuyu, Paspalum and Phalaris Therefore, the amounts of uracil herbicide and sulfonyl urea herbicide used in the methods and mixtures of the present invention may be applied in rates up to what is known in the art for applications of each of the herbicides separately. In practice, however, the rates of each may be substantially reduced due to the synergistic effect of the two herbicides in combination.

The ratio of uracil herbicide to sulfonyl urea herbicide may be in any suitable ratio such that the two herbicides exhibit a synergistic effect.

Preferably the ratio of sulfonyl urea herbicide to uracil herbicide is in the range of about 1:800 to about 1:1.6, more preferably about 1:300 to about 1:10 most preferably about 1:150 to about The mixtures of herbicides will normally be formulated with an agriculturally suitable diluent, carrier and/or excipient. Preferably the mixture is formulated according to the prevailing conditions of use required such that its mode of application, the environment and target are taken into consideration.

The herbicides of the present invention may be applied in any suitable S manner known for the application of herbicides. They may be applied in a liquid formulation or as a granular herbicide formulation. Useful formulations of the uracil and sulfonylurea with or without one or more other herbicides include: 11/9/97msap8875.spe, -11solids such as granules, tablets, powders, and dusts which may also be water-soluble or dispersible; or liquids such as solutions, emulsions and suspensions.

The herbicides and/or the diluent, carrier and/or excipient may be encapsulated.

The following Table 3 sets out preferred ranges of ingredients of mixtures according to the present invention in both liquid and granular formulations.

TABLE 3 999.

9 9 .9 9 9999 99..

9.

99 9 9999 ACTIVE INGREDIENTS (WEIGHT PERCENT) FORMULATION TERBACIL SULFOMETURON INERT CARRIER DILUENTS ADHESIVES SURFACTANT

METHYL

Granules Pellets 1.32 13.2 0.06 0.6 70 90 5-14.2 2 3.62 Wettable Powder/Dry 9.55 85.91 0.45 4.09 0- 74 -1 Flowables/Water Dispersible Granules The uracil and sulfonyl urea herbicides may be pre-mixed or preformulated and applied as a mixture or part of a mixture. They may, however, be applied separately but within time frame sufficient to allow the two herbicides to exhibit synergy.

The mixtures and methods of the present invention may be used with any suitable crop. These include all crops for which Sinbar® is recommended as well as all trees including all hardwoods and Eucalyptus varieties such as Eucalyptus globulus, Eucalyptus regnans and Eucalyptus nitens, and also woody crops such as vines including grape vines.

The mixtures and methods of the present invention have a particular application in use with eucalypt species but is not limited thereto. Over the 11/9/97msap8875.spe, -12past decade in Australia, the planting of eucalypts such as Eucalyptus Globulus have dramatically increased. The demand for high quality paper and export wood chips has driven this growth. Eucalypt forestry has largely relied upon effective pre-plant weed control using predominantly tank mixes of glyphosate and simazine. When no pre-plant weed control has been carried out or where weeds re-establish following planting there has been some use of grass specific non-residual herbicides, however success has often been limited due to incomplete control of the weed spectrum and lack of residual effect. The mixtures and methods of the present invention offer knockdown of established weed growth, broad spectrum weed control, moderate residual activity and are safe to the Eucalyptus. Indeed, it has surprisingly been found that the mixtures and methods of the present invention offer better survival and better diameter and volume growth of the Eucalyptus than untreated controls. The mixtures and methods of the present invention allow a reduction in the amount of herbicide that needs to be applied to a crop which is of cost and environmental benefit.

The invention will now be more particularly described with reference to the following non-limiting examples: ooo.

Example 1 Formulation Process Preparation of Granules The ingredients are blended in a rotating mixer, and adhesives are sprayed onto that blend so as to effect granulation. When most of the granules have reached an average of 1.0 mm in size, they are removed, dried, and screened, oversize material is crushed to produce additional material in the S desired range. The resulting granules contain a total of 4.6% of the active ingredients.

11 /9/97msap8875.spe, -13- Example 2 Formulation The granules are formulated as described in Example 1.

INGREDIENT BY WEIGHT Terbacil 4.4 Sulfometuron Methyl 0.2 Inert Carrier 80.0 Solid diluents (eg. Talc) 12.9 Adhesives 9*W 999 9..

9 .9 *9 9 .4 9 Example 3 A trial was established to evaluate various liquid and granular formulations of herbicide compositions of the present invention.

Materials and Method The trial was established in early August 1994 on an undulating site just east of Ballarat in Australia on red gradational soils. Surface soil texture was clay loam with moderate to high permeability and pH of 5.5-6. The site had been used as pasture prior to the establishment of E. Gobulus. At the time of :20 application, weed growth was well established and occupied 100 per cent of S the soil surface. Major weeds present included spear thistle (Cirsium vulgare), wild radish (Raphanus raphanistrum), subterranean clover (Trifolium subterraneum ribwort (Plantago lanceolata sorrel (rumex acetosella), annual ryegrass (Lolium rigidum) and fog grass (Holcus lanatus).

Grasses were fully tillered and broadleaf weeds were typically 10-15 cm S in height and diameter. Average weed biomass height was in the order of cm at the time of treatment.

The herbicides which were evaluated are detailed in Table 4.

11/9/97msap8875.spe, -14- TABLE 4 HERBICIDE TREATMENTS Liquid Treatments Granular Treatments Treatment No 1 Treatment No 2 Terbacil Sulfometuron Terbacil Sulfometuron Methyl Methyl Treatment No 3 Terbacil Treatment No 4 Untreated Control The trial was established based on a randomised replicated block design.

There was a total of ten treatments of which four were granular formulations.

Each treatment contained five trees and was replicated three times. The liquid 1 5 treatments were applied as a strip treatment using a CO 2 pressurised backpack sprayer with a 2 m boom applying herbicide in a water volume of 100 It/ha.

Granular treatments were applied with their formulated state directly to the ground using a hand operated Weed-A-Metre® applicator which treats a one metre diameter (circle) with a calibrated dose of granulated product. Each tree received four spots to result in a total treated area of 2 m x 2 x (4m 2 Care was taken to avoid excessive overlap of spot treatments.

Assessments of weed control were made at one, three and six months after treatment. These assessments were recorded as a percentage of live weed cover present to assess biomass reduction.

0 11/9/97msap8875.spe, The height, diameter, and survival were recorded at the commencement of the trial and again at twelve months after treatment. Height was measured at tallest point and diameter was measured 30 cm above ground level.

Tree growth response was assessed at twelve months after treatment by comparing the increase in height, diameter and a tree volume index (ie. D 2

H

where D represents diameter and H represents height).

Growth Responses Table 5 below outlines the growth responses from the various granular herbicide treatments.

TABLE Treatment Diameter Height Volume cm m cm 3 1. Terbacil Sulfometuron Methyl 2.2 1.4 95.3 2. Terbacil Sulfometuron Methyl 3.1 1.7 119.9 3. Terbacil 2.5 1.6 100.7 4. Untreated control 1.8 1.4 75.5 Diameter Significant differences were observed between the treatments in diameter growth. Using Dunnett's test the Treatment two was significantly different from the control.

Height No significant differences were observed between the treatments.

11/9/97msap8875.spe, -16- Volume Volume growth, which is predominantly a function of diameter, demonstrated significant differences between treatments. Using Dunnett's test Treatment two was significantly different from the control.

Conclusion Significant increases in diameter, and volume growth results from the application of the trialed herbicide treatments comprising terbacil and sulfometuron methyl when applied to one year old Eucalyptus Globulus.

Treatment 2 (terbacil sulfometuron methyl), resulted in the greatest growth response with diameter and volume measure 172.2% and 158.8% respectively of the untreated control when measured twelve months after treatment and was the only significantly different treatment when Dunnett's test was applied.

Treatment 1 (terbacil sulfometuron methyl) liquid formulation was not compared with a terbacil liquid formulation so no conclusion can be drawn. It can be seen however that liquid formulations results in increases in diameter and volume growth when compared with the untreated control.

SExample 4 25 o' o oooo• DESCRIPTION OF TRIALS Site Trial Location Species No. of Description No. Treatments #1 Traralgon, Vic E.globulus 9 Treatments applied to 12 month old trees #2 Mt Gambier SA E.globulus 20 Treatments applied to 12 month old trees 11/9/97msap8875.spe, -17- 9 DESCRIPTION OF TRIALS Site Trial Location Species No. of Description No. Treatments #3 Albany, WA E. globulus 8 Treatments applied to 12 month old trees #4 Tasmania E.regnans 8 Treatments applied to 12 month old trees Tasmania E.regnans 8 Treatments applied to 12 month old trees #6 Tasmania E.nitens 8 Treatments applied 12 month old trees #7 Mt Barker, WA E.globulus 8 Treatments applied 1 month after trees were planted Treatments

TREATMENTS

Trial Formulation Rate a.i Active Comment No. Kg/ha 1 Terbacil 1.6 8.045 Spot application 2* Terbacil 2.4 8.045 Spot application 3* Terbacil Sulfometuron 1.31 4.352 Spot application Methyl 0.006 0.198 4* Untreated (control) N/A N/A N/A Response Parameters Weed efficacy: 1. Percentage ground cover at installation for all weeds combined, 1, 2, 3 and 6 months after treatment. Assessment is based on the percentage weed cover (total and percentage ground cover for each 11/9/97msap8875.spe, -18selected species) reduction from assessment 1 to assessment 3, unless otherwise indicated.

2. ground cover of: Annual Ryegrass (Lolium rigidum) Fog grass (Holcus lanatus) Capeweed (Arctotheca calendula) Clover (Trifolium spp) Sorrel (Rumex acestosella) Flat weed (Hypochoeris radicata) Tree vigour: Assessed out at installation, 1, 2, 3 and 6 months after treatment on a 1 to 4 scale: 1 healthy; 2 moderately healthy; 3 poor health; 4 dead.

Tree growth: Collar diameter and height of each tree was measured at installation and at 6 months after treatment. The increment between installation and 6 months was used to analyse for differences between treatments. Tree :volume was calculated based on the formula: /3(TnD- 4) x H; where H height and D Volume. Comparisons of growth between 9 treatments was based on the growth (increment) between installation and the measurement at 6 months.

Method of Analysis Weed efficacy: Weed reduction between assessments was analysed for total weed Scover and each of the main weed species.

4 Percentage weed reduction of total ground cover (GC) between assessments 1 and 3 was calculated as follows: Sll/9/97msap8875.spe, -19- Total weed reduction (Total GC at assessment 3) x 100 (total GC at assessment 1) where total GC total GC in percentage.

Percentage reduction for each weed species between assessments 1 and 3 was calculated as follows: firstly the proportion GC of each weed species was calculated; For example, of GC by species 1 of species 1) x total GC 100, where of species 1 is the proportion of species 1.

Then: Percentage Reduction GC by species 1 in assessment 3) x 100 (by species 1 in assessment) where GC is the of ground covered by species 1 as calculated above.

Percentage reductions were transformed using Arcsin in degrees.

Analysis of variance was carried out on the transformed reduction for total weed cover and for selected weed species.

For sorrel the actual ground cover was analysed rather than the reduction as sorrel percentages tended to increase over subsequent assessments.

Tree vigour: Plot means were used in this analysis. Variables analysed included vigour for each assessment (where assessed) and the variation (increment) between assessments 1 and 2, 1 and 3 (and 1 and 4 where applicable).

11/9/97msap8875.spe, Vigour means were transformed using the inverse formula; ie.

1 mean vigour rating.

Tree growth: Plot means for diameter, height and volume at assessment 1 and 4 (6 months), as well as the increments, were analysed.

No transformation was required.

Analysis of Individual Trial (Site not included as a variable) The results of the trails are set out in Figures 1 to 16 as detailed below.

Site 1 (Traralgon, Victoria) Weed efficacy: Determination is based on the difference in total weed cover between assessments 1 and 3.

Figure 1 Percentage reduction in the ground cover of capeweed between assessment 1 and 2 for site 1.

Figure 2 Percentage reduction in cover of fog grass between assessments 1 and 2 for site 1.

a Figures 1 and 2 illustrate the synergistic effect of the compositions of the present invention over terbacil in reduction of ground cover of capeweed and fog grass.

ll/9/97msap8875.spe, -21- Site 2 (Mt Gambier, South Australia) Weed efficacy: Determination is based on the difference in weed cover between Assessment 1 and 3.

Figure 3 Percentage weed cover reduction between assessment 1 and 3 for site 2.

Figure 4 Percentage increase in the ground cover of capeweed between assessment 1 and 3 for site 2.

Figure Percentage change in ryegrass cover between assessment 1 and 3 for site 2.

Figure 6 1 5 Differences in volume increment over 6 months associated with different herbicide treatments at site 2.

Figures 3 to 5 illustrate the synergistic effect of the compositions of the present invention over terbacil in percentage weed cover reduction, percentage increase in ground cover of capeweed and percentage change in ryegrass.

Although the percentage change in ryegrass in Figure 5, treatments 2 and 3 appear similar, the amount of terbacil used in treatment 3 is significantly lower than treatment 2. Figure 6 illustrates the increase in volume increment when the compositions of the present invention are used.

Site 3 (Albany, Western Australia) Weed efficacy: Figure 7 Percentage change in weed cover between assessment 1 and 3 for site 3.

ll/9/97msap8875.spe, -22- Figure 8 Change in the percentage ground cover associated with clover between assessments 1 and 3 for site 3.

Figure 9 Volume increment over 6 months associated with different herbicide treatments at site 3.

Figures 7 and 8 illustrate the synergistic effect of compositions of the present invention over terbacil in percentage change in weed cover and change in percentage ground cover of clover. Figure 9 illustrates the increase in volume increment when the compositions of the present invention are used. It also illustrates that increasing the amount of terbacil eventually results in a suppression of growth of the crop.

Site 4 (Tasmania) Figure Volume increment over 6 months associated with different herbicide treatments at site 4.

Figure 10 again illustrates the volume increment increase when compositions of the present invention are used. It also illustrates the growth suppression associated with increasing the amount of terbacil.

Site 5 (Tasmania) Figure 11 Volume increment over 6 months associated with different herbicide treatments at site Figure 11 illustrates the volume increment increase when compositions of the present invention are used.

11/9/97msap8875.spe, Site 6 (Tasmania) Figure 12 Change in the percentage ground cover of annual grasses between assessments 1 and 3 for site 6.

Site 7 (Mt Barker, Western Australia) Figure 13 Percentage change in weed cover between assessment 1 and 3 for site 7.

Figure 14 Percentage change in the ground cover of capeweed between assessment 1 and 3 for site 7.

Figures 13 and 14 illustrate the synergistic effect of compositions of the present invention over terbacil in percentage change in weed cover and percentage change in capeweed.

Figure Change in observed vigour between assessments 1 and 3 at site 7.

Figure 16 Volume increment over 6 months associated with different herbicide treatments at site 7.

a Figures 15 and 16 illustrate the increase in vigour of the Eucalyptus and S volume increment when compositions of the present invention are used. They illustrate that increasing terbacil suppresses Eucalyptus growth.

11/9/97msap8875.spe, -24- Summary Weed efficacy Total weed cover: only treatment 3 reduced overall weed cover where the dominant weed was capeweed with some ryegrass. Against these two species a combination of terbacil and sulfometuron methyl was effective.

Capeweed: when applied alone, terbacil had a marginal impact on capeweed. However, when applied in combination with sulfometuron methyl up to 80% reduction can be expected.

Fog grass: reductions between 50% and 100% can be expected with mixtures of terbacil and sulfometuron methyl.

Ryegrass: there appeared to be a trend for the low rate of terbacil, applied alone, to be less effective than either the high rate, or when mixed with sulfometuron methyl. Terbacil mixed with sulfometuron S: methyl provided between 70% and 100% reduction in ryegrass.

C.

C

Clover: treatments containing terbacil and sulfometuron methyl can be expected to reduce clover cover by between 65% and 100%.

Sorrel: herbicide mixtures that contain sulfometuron methyl will provide useful reductions in sorrel cover.

SVigour: Trees in treatment 3 (terbacil at 1.3 kg/ha mixed with sulfometuron at gm/ha) were the most vigorous.

11/9/97msap8875.spe, Growth: At site 7 where treatments were applied over newly planted E.globulus seedlings the trend was for the trees in treatments with the highest weed efficacy to grow fastest.

Finally it is to be understood that the aforegoing description refers merely to preferred embodiments of the invention and that variations and modifications will be possible thereto without departing from the spirit and scope of the invention.

a a °co o ooooo* 11/9/97msap8875.spe, Where the terms "comprise", "comprises" 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.

*e e 0 6/10/97GV8875.SPE.1

Claims

1. A herbicidal mixture comprising a uracil herbicide and a sulfonylurea herbicide wherein uracil herbicide has the following formula: i 9

99.. q .9 9 9 *r 9,*9 9.9 9 *999 9,r 1 where R is selected from the group consisting of alkyl of 1 through carbon atoms, substituted alkyl of 1 through 8 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, and cyano, aryl of 5 through 10 carbon atoms, substituted phenyl, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, alkoxy of 1-5 carbon atoms, alkyl of 1-6 carbon atoms, nitro, trifluoromethyl, 1,2-tetramethylene, and 1,2- trimethylenylene, aralkyl of 5 through 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl, and alkoxy, tetrahydronaphthylalkyl, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, substituted cycloalkyl of 3 through 12 carbon atoms, wherein said 24/03/00,cf8875.claims,26 0 0c 0* *i 0 p 1 0 p q *r Oi*0 substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkenyl of 4 through 12 carbon atoms, substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of through 13 carbon atoms, (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, (substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and cyano; R 1 is selected from the group consisting of chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro alkoxymethyl of 2 through 6 carbon atoms, hydroxy alkyl of 1 through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms, thiocyanato, cyano, thiolmethyl, alkylthio of 1 through 4 carbon atoms, bromomethyl, fluoromethyl, chloromethyl, methylthiomethyl, phenylthiomethyl, and carboxymethyl-thiomethyl; R 2 is selected from the group consisting of chlorine, bromine, alkyl of 1 through 5 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, bromoalkyl of 1 through 4 carbon atoms, and alkoxy of 1 through 5 carbon atoms; and X is selected from the group consisting of oxygen and sulfur; and 24/03/00,cf8875.claims,27 28 the sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese, and quaternary ammonium salts of the above compounds and wherein said sulfonylurea herbicide has the following formula: 0 11 CQR R w S02N C NRt 53 R4 wherein Q is0 QisO; R44 isH RisO *6 N 0. z N 24/03100f8875. claims, 28 29 X is H, CH 3 OCH 3 or OC 2 H 5 Y is H, Cl, CH 3 OCH 3 or OC 2 H 5 and Z is CH. 2. A mixture according to claim 1 wherein said uracil herbicide is chloro-6-methyluracil and said sulfonylurea herbicide is 2-(4,6-dimethylpyridmidin- 2-ylcarbamoylsulfamoyl) benzoic acid. 3. A mixture according to claim 2, wherein 3-tert-butyl-5-chloro-6-methyluracil is in an amount of 44g/kg based on the total weight of the mixture and said 2-(4,6- dimethylpyridmidin-2-ylcarbamoylsulfonyl) benzoic acid is in an amount of 2g/kg based on the total weight of the mixture. 4. A mixture according to claim 1 or claim 2, wherein the ratio of uracil it: herbicide to sulfonylurea herbicide is in the range of about 1:800 to about 1:1.6. A mixture according to claim 1 or claim 2, wherein the ratio of uracil herbicide to sulfonylurea herbicide is in the range of about 1:300 to about 1:10. 6. A mixture according to claim 1 or claim 2, wherein the ratio of uracil *oo SI.. herbicide to sulfonylurea herbicide is in the range of about 1:150 to about 4 S 7. A mixture according to any one of claims 1 to 6, wherein the mixture has S.. been formulated into a powder, a dry flowable, water dispersible granules or a 4 liquid composition. 8. A mixture according to claims 1 to 7, further comprising one or more of an agriculturally acceptable surfactant, solid or liquid diluent, carrier, excipient, adjuvant and/or other active ingredients including herbicides. 9. A method of controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a uracil herbicide and a sulfonylurea herbicide. 24/03/00,cf8875.claims,29 A method of controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a uracil herbicide and a sulfonylurea herbicide wherein said uracil herbicide has the following formula: a a a 9 I 10 C a C 9 CCCV 'S where R is selected from the group consisting of alkyl of I through carbon atoms, substituted alkyl of I through 8 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, and cyano, aryl of 5 through carbon atoms, substituted phenyl, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, alkoxy of carbon atoms, alkyl of 1-6 carbon atoms, nitro, trifluoromethyl, 1,2- tetramethylene, and 1,2-trimethylenylene, aralkyl of 5 through 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl, and alkoxy, tetrahydronaphthylalkyl, alkenyl of 3 24/03/00,cf8875.claims,30 0 U 0 *000 56 0* 0 0* S 065 S 0* 6 0 U 5 0 S 0 6*0* 00 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, substituted cycloalkyl of 3 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkenyl of 4 through 12 carbon atoms, substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of through 13 carbon atoms, (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, (substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and cyano; R 1 is selected from the group consisting of chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro alkoxymethyl of 2 through 6 carbon atoms, hydroxy alkyl of I through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms, thiocyanato, cyano, thiolmethyl, alkylthio of I through 4 carbon atoms, bromomethyl, fluoromethyl, chloromethyl, methylthiomethyl, phenylthiomethyl, and carboxymethyl-thiomethyl; R 2 is selected from the group consisting of chlorine, bromine, alkyl of I through 5 carbon atoms, chloroalkyl of I through 4 carbon atoms, bromoalkyl of I through 4 carbon atoms, and alkoxy of I through 5 carbon atoms; and 24/03/00,cf8875.claims,31 X is selected from the group consisting of oxygen and sulfur; and the sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese, and quatemnary ammonium salts of the above compounds and wherein said sulfonylurea herbicide has the following formula: 0 11 CQR R w I I S02N C NRi RsR4 100 :000*0 io 0 S; R isC0C4akl *R isH whRein H R0isH FR isHorS3 Qis; 24103100 ,Mf875.claims,32 N X Z N Y X is H, CH 3 OCH 3 or OC 2 H 5 Y is H, Cl, OH 3 OCH 3 or 00 2 H 5 and Z is CH. 11. A method according to claim 9 or claim 10, wherein the uracil herbicide is applied in the range of about 1 to about 3,600 gai/ha. 10 12. A method according to claim 9 or claim 10, wherein the uracil herbicide is applied in the range of about 1 to about 4,000 gai/ha. 13. A method according to claim 9 or claim 10, wherein the uracil herbicide is applied in the range of about 500 to about 3,000 gai/ha. 14. A method according to claim 9 or claim 10, wherein the uracil herbicide is 15 applied in the range of about 1,300 gai/ha. 15. A method according to any one of claims 9 to 14, wherein said sulfonylurea herbicide is applied in the range of about 1 to about 400 gai/ha. 16. A method according to claim 9 or claim 10, wherein said sulfonylurea herbicide is applied in the range of about 1 to about 200 gai/ha. 17. A method according to claim 9 or claim 10, wherein said sulfonylurea herbicide is applied in the range of about 60 gai/ha. 24/03/00,cf8875. claims,33 34 18. A method according to any one of claims 9 to 17, wherein the locus to be protected is selected from apple, citrus, lucerne, peaches, sugar cane, grape vines and all tree species including hardwoods and eucalyptus varieties. 19. A method according to claim 18, wherein said eucalyptus variety is selected from Eucalyptus globulus, Eucalyptus regnans and Eucalyptus nitens. A method according to any one of claims 9 to 19, wherein the uracil and sulfonylurea herbicides are premixed and applied as a composition. 21. A method according to any one of claims 9 to 19, wherein the uracil and sulfonylurea herbicides are applied separately but within a time frame to sufficient to allow the two herbicides to exhibit synergy. 22. A method according to claim 9 or claim 10, wherein said uracil herbicide is 3-tert-butyl-5-chloro-6-methyluracil and said sulfonylurea herbicide is 2- .go :oo (4,6)dimethylpyridmidin-2-ylcarbamoylsulfamoyl benzoic acid. 23. A method according to claim 22 wherein said uracil herbicide is 3-tert-butyl- 15 5-chloro-6-methyluracil is in an amount of 44g/kg based on the total weight of the mixture and dimethylpyridmidin-2-ylcarbamoylsulfamoyl benzoic acid is in an amount of 2g/kg based on the total weight of the mixture. 24. Mixtures, compositions and methods substantially as hereinbefore described with reference to any one of the drawings and/or examples but o 20 excluding any comparative drawings or examples. DATED this 2 4 t h day of March 2000. MACSPRED PTY LTD By their Patent Attorneys: CAkLINAN LAWRIE 24103/00,cf8875.claims,34