AU2021106990B4 - Highly Loaded Florasulam Formulations - Google Patents

Abstract

The invention provides a florasulam solo formulation containing a florasulam concentration of above 50 g ai/L as a liquid formulation or above 200 g ai/kg as a solid formulation. Preferably, the florasulam concentration is between about 200 g ai/L and about 500 g ai/L 5 The formulation may be used on its own, or tank mixed with one or more other active ingredients, to control weeds in crops. 41

Description

Highly Loaded Florasulam Formulations

Technical Field

The invention relates to novel florasulam formulations. In particular, the invention is concerned with highly loaded florasulam formulations containing more than 200 g ai/L

as a liquid formulation. The formulation of the invention is a solo formulation. The

formulation having florasulam as the only active ingredient may be tank mixed with one or more other active ingredients (co-formulations/tank mixtures), suitable for use to control weeds.

Background Art

Florasulam (N-(2,6-Difluorophenyl)-8-fluoro-5-methoxy-[1,2,4]triazolo[1,5-c]

pyrimidine-2-sulfonamide) is an acetolactate synthase (ALS) inhibitor herbicide suitable for the control of a wide range of weeds. It has been found to be particularly

useful for the control of broadleaved weeds and is often used in winter cereals (wheat,

barley, oats, triticale), corn and in fallow between crops. Use rates typically range between 2.5 to 7.5 g of florasulam per hectare.

Florasulam has been marketed by several suppliers globally as solo formulations or in co-formulations or tank mixtures with a wide range of other active ingredients including, for example: 2,4-D ester, 4-chloro-2-methylpenoxyacetic acid (MCPA), clopyralid, fluroxypyr, bifenox, pinoxaden, flucarbazone, halauxifen-methyl,

diflufenican. However, the solo formulations currently available are generally low concentration liquid formulations with 50 grams of florasulam per litre. The co

formulations or tank mixtures include similar low concentrations of florasulam in

addition to one or more active ingredients e.g., as listed above. For example, co formulations with fluroxypyr or 2,4-D contain florasulam 2.5 g/L + fluroxypyr 100 g/L

suspo-emulsion (SE), require relatively high use rates i.e., 1 L/ha. Others include florasulam 6.25 g/L + 2,4-D ester 300 g/L with a use rate of 500 mL/ha; or 50 g/L

I suspension concentrate (SC) solo formulation with a use rate of 50-100 mL/ha, usually tank mixed with another herbicide.

High concentration formulations are generally desirable: a highly loaded formulation

can deliver the required quantity of active ingredient to a user in a smaller volume and

lower weight. For formulators, higher concentration formulations reduce the quantity of formulated product to be produced. There is a saving in packaging, freight costs,

storage volume and energy costs and a reduction of waste.

The only existing higher concentrated formulations are co-formulations like Paradigm©

(florasulam 200 g/kg + halauxifen-methyl 200 g/kg water-dispersible granules (WG)). While this formulation requires relatively low use rates per hectare of formulated

product, it cannot be applied without halauxifen-methyl as the partner. Further tank mixing with other active ingredients is limited e.g., particular recommendations are

LVE (low-volatile ester) MCPA or clopyralid. However, such co-formulations like

Paradigm are not suitable in situations where halauxifen-methyl is not required, and

these products do not provide flexibility nor the opportunity to apply florasulam solo at a lower use rate, or in a range of alternative tank mix combinations of florasulam

and other active ingredients to control the spectrum of weeds present.

As such, higher loaded solo florasulam formulations are not currently available nor

provided commercially and there is a need for providing such formulations. It would be desirable and beneficial to provide highly loaded florasulam formulations which have

acceptable storage stability for effective use and dosing and which can be used as a

solo formulation or in a tank mixture with a wider range of alternative other active ingredients to control a larger spectrum of weeds, as desired. Accordingly, there

remains a need to develop such higher loaded solo florasulam formulations that are also commercially more desirable.

Reference to any prior art in the specification is not an acknowledgment or suggestion that this prior art forms part of the common general knowledge in any jurisdiction or that this prior art could reasonably be understood, regarded as relevant, and/or combined with other pieces of prior art by a skilled person in the art.

Summary of the Invention

The invention is broadly directed to highly loaded liquid florasulam formulations.

Accordingly, in one aspect of the present invention, there is provided a liquid storage

stable florasulam formulation containing florasulam as sole active ingredient, the concentration of florasulam being above 200 g ai/L, wherein the formulation does not

include any sodium salt of condensed sulfonated naphthalene.

It has been found that the ability to increase the maximum loading of florasulam in a

liquid formulation above 200 g ai/L has the advantage over existing formulations prior to this invention by significantly reducing the volume of material to be formulated,

transported and applied by the end user, respectively.

In preferred embodiments, the formulation according to the invention contains a florasulam concentration of at least 300 g ai/L, or at least 400 g ai/L, or at least 500 g

ai/L, or more than 200, to 500 g ai/L, or preferably is about 205 g ai/L or is about 500 g ai/L.

The liquid florasulam formulation according to the invention has florasulam as the sole active ingredient, but the formulation may be tank mixed with one or more other

active ingredients.

The highly loaded liquid florasulam formulation according to the invention may be

applied to a crop or plant in a tank mixture optionally further comprising one or more other active ingredients.

The highly loaded liquid florasulam formulation according to the invention may be

applied pre-sowing, preferably being incorporated by sowing (IBS), optionally combined in a mix with one or more other active ingredients.

The one or more other active ingredients which may be tank-mixed with the florasulam formulation according to the invention is preferably another herbicide. The

herbicide will be readily selected by one skilled in the art according to the spectrum of weeds that it is desired to control. For example, the one or more other active

ingredients is selected from the group consisting of: 2,4-D, 4-chloro-2 methylpenoxyacetic acid (MCPA), fluroxypyr, dicamba, picloram, bifenox, pinoxaden,

flucarbazone, halauxifen-methyl, cloquintocet-mexyl, diflufenican, picolinafen,

bromoxynil, paraquat, glyphosate and the effective esters or salts of any of the

foregoing.

Examples of commercially available herbicides containing one or more such active ingredients include Flagship, Cutlass®, Bronco®, Picoflex*, Zulu XT, Triathlon*,

Quadrant*, Spraytop© 250, WipeOut* Pro, Roundup Ultra©MAX, Weedmaster Argo,

Weedmaster DST, Crucial 600 and Axial.

It is contemplated that the liquid florasulam formulation according to the invention may be any suitable liquid formulation. For example, the liquid formulation may be,

but is not limited to, a suspension concentrate (SC), a suspo-emulsion (SE), an emulsion in oil or water, an emulsifiable concentrate (EC), a dispersible concentrate or

an oil dispersion. Preferably, the florasulam formulation is an SC.

The liquid florasulam formulation of the invention is useful for controlling a large

spectrum of weeds that are susceptible to florasulam and/or the one or more other active ingredients, if present in the tank mix.

Accordingly, in another aspect of the present invention there is provided a method for

controlling weeds comprising applying the florasulam formulation according to the invention to a crop or plant and/or in fallow between crops to control the weeds. One

skilled in the art would readily be able to select a suitable crop or plant that would benefit from this application. For example, the suitable crop or plant includes, but is

not limited to, wheat, barley, oats, cereal rye, triticale and corn. In this aspect, the use of the solo florasulam formulation, alone or tank mixed with one or more other active

ingredients, may be readily selected by one skilled in the art according to the weeds it is desired to control.

In one example, the application of the florasulam formulation according to the

invention is at a rate of less than 25 mL/ha, or about 5 to 10 mL/ha, or about 12.5 to

25 mL/ha.

In one example, the florasulam formulation according to the invention is applied with an adjuvant suitable for greater leaf absorption and efficacy. For example, the

adjuvant is an oil adjuvant such as commercially available adjuvants such as, Uptake

Spray or Adigor*. Other adjuvants may also be suitable.

As used herein, except where the context requires otherwise, the term "comprise" and

variations of the term, such as "comprising", "comprises and "comprised", are not

intended to exclude further additives, components, integers or steps.

Further aspects of the present invention and further embodiments of the aspects

described in the preceding paragraphs will become apparent from the following description, given by way of embodiments and/or examples.

Detailed Description of Preferred Embodiments

Reference will now be made in detail to certain embodiments of the invention. While

the invention will be described in conjunction with the embodiments and/or examples,

it will be understood that the intention is not to limit the invention to those

embodiments/examples. On the contrary, the invention is intended to cover all alternatives, modifications, and equivalents, which may be included within the scope

of the present invention.

One skilled in the art will recognize many methods and materials similar or equivalent

to those described herein, which could be used in the practice of the present invention. The present invention is in no way limited to the methods and materials

described. It will be understood that the invention disclosed and defined in this specification extends to all alternative combinations of two or more of the features

mentioned or evident from the text. All of these different combinations constitute

various alternative aspects of the invention.

For the purposes of interpreting this specification, terms used in the singular will also

include the plural and vice versa.

Example 1: Highly Loaded Florasulam Formulations.

By way of example, a highly loaded aqueous SC formulation containing a florasulam concentration of above 200g/L was prepared. The components are as set out in Table

1:

Table 1: Components

Content Component Purposein Supplier g/L Formulation 203.46 Florasulam Technical 98.3 % active ingredient Jiangsu Agrochem Laboratory Co, Ltd 30.00 Tersperse 2500 steric stabilizer Huntsman Australia Pty. Ltd 20.00 Tersperse 4894 dispersant Huntsman Australia Pty. Ltd 12.00 Attagel 50 rheology modifier BASF Australia

Content Component Purposein Supplier g/L Formulation Limited 4.00 Xanthum Gum TSFT rheology modifier Brenntag Australia Pty. Ltd. 80.00 Glycerine humectant Jungbunziauer Austria AG 4.00 Proxel GXL preservative Arch Chemicals Inc.

1.00 Gensil 2030 antifoam Solvay Chemicals Pty. Ltd 0.83 Citric Acid Monohydrate pH adjustment Redox Pty Ltd 745.71 Water diluent Potable water

Details of the components are as set out in Table 2:

Table 2: Component Details

Trade Name IUPAC NAME CAS#

Florasulam Technical 98.3 % N-(2,6-Difluorophenyl)-8-fluoro- 145701-23-1 5-methoxy-[1,2,4]triazolo[1,5 c]pyrimidine-2-sulfonamide Tersperse 2500 methyl methacrylate-methacrylic 119724-54-8 acid-monomethoxy polyethylene glycol methacrylate copolymer solution Tersperse 4894 nonionic proprietary surfactant N.A blend, composition undisclosed Attagel 50 modified fullers earth 8031-18-3

Xanthum Gum TSFT 6-[6-[6-(acetyloxymethyl)-2-[3- 11138-66-2 (technical grade, fine, salt [3,4-dihydroxy-6 tolerant) (hydroxymethyl)-5 phosphanyloxyoxan-2-yl]oxy-5 hydroxy-2-(hydroxymethyl)-6 (phosphanylmethyl)oxan-4 yl]oxy-4,5-dihydroxyoxan-3 yl]oxy-2-carboxy-4,5 dihydroxyoxan-3-yl]oxy-7,8 Glycerine propane-1,2,3-triol 56-81-5

Trade Name IUPAC NAME CAS

# Proxel GXL aqueous dipropylene glycol 2634-33-5 solution of 1,2-benzisothiazol-3 Gensil2030 polydimethysiloxane aqueous 63148-62-9 Citric Acid Monohydrate 2-hydroxypropane-1,2,3- 5949-29-1 tricarboxylic acid hydrate Water water 7732-18-5

To prepare the formulation, by way of example, the following method and the

sequence of operations were followed:

1. 60% of the water was charged into a suitable vessel equipped with high shear

saw tooth dispersion blade mixer.

2. Mixing was commenced and 50% of the Gensil 2030 was added.

3. Mixing was maintained and Citric Acid was added.

4. Mixing was maintained and Tersperse 4894 was added.

5. Mixing was maintained and Tersperse 2500 was added.

6. Mixing was maintained and Attagel 50 was added.

7. Mixing was maintained and Florasulam Technical was gradually incorporated.

The mixture was dispersed until homogenous and free from agglomerates.

8. Recirculation milling was commenced using a Dyno-Mill KD or similar bead

mill. The mill temperature was maintained below 35 °C.

9. The mill base was ground until a particle size D (v, 0.5) 3.0 - 5.0 microns and D

(v, 0.9) < 15 micron was achieved as determined by CIPAC MT 187.

10. The mill base was transferred to another suitable vessel equipped with a

propeller type stirrer. Agitation was maintained at all times.

11. The remaining Gensil 2030 and the remaining water were added.

12. The Glycerine, less the portion for premix (see 13) with Xanthum Gum TSFT,

wasadded.

13. A premix was prepared by mixing a suitable portion of Glycerine with the

Xanthum Gum TSFT and Proxel GXL in a separate vessel. This premix was then added to the mill base and agitation was continued until the xanthum gum

was completely hydrated and dispersed.

14. The product was examined according to the specification and adjustments were made as required.

The resultant highly loaded SC formulation containing a florasulam concentration of 205 g/L, identified as AD-AU-1826 SC formulation, was analysed as described further

below. The analysis is in Table 3:

Table 3: Analysis

Determination Method Specification Analysis Result Appearance, Visual White flowable White flowable PASS Physical State & suspension suspension Colour Odour Olfactory Characteristic Characteristic PASS

pH 1% v/v CIPAC MT 75.3 3.00-6.00 4.8 PASS 1.0 mL/ 100 mL Density @ 20 °C CIPAC MT 3.3.2 1.085 - 1.115 1.104 g/mL PASS g/mL Wet Sieve Test CIPAC MT 185 <0.1% Trace PASS (100 g) 38 pm sieve Spontaneity of CIPAC MT 160 > 60% and < 102% PASS Dispersion 12.5 mL/ 250 105% Standard Water mL after 5 min C at 23 °C Suspensibility CIPAC MT 184 > 60% and < 94% PASS Standard Water 0.50 mL / 250 105% D at 23 °C mL after 30 min Persistent CIPAC MT 47.2 max 60 mL foam After 10 sec 30 mL PASS Foam Standard 2.0 mL/ 200 after 1 min After 1 min 5mL Water C mL After 3 min 1mL After 12 min OmL

Determination Method Specification Analysis Result Viscosity @ 20 CIPAC MT 192 800 - 1200 cps 900 cps @ 20 °C PASS °C Brookfield RVT S2 20 rpm Particle Size CIPAC MT 187 Dv (50) 3.0 - 5.0 Dv (50) 4.63 pm PASS Malvern pm Dv (90) 12.1 am Dv (90) < 15.0 prm Content QCM-174.02 188 - 212 g/L 205 g/L PASS Florasulam

Packaging Stability

A sample of the product in HDPE was weighed and then maintained at 54 °C for a period of 14 days.

Table 4: Analysis of Packaging Stability in HDPE

Sample Pre-Storage Weight Post-Storage Weight Weight Difference

Tol 1113.6 g 1113.5 g 0.1g

TAS1 1061.3 g 1060.7 g 0.6 g

The formulation was suitable for packaging in a HDPE container with a screw cap

closure. The meaning of each of Tol and TAS1 in Table 4 is explained below.

Analysis Methods

The relevant test parameters for suspension concentrate (SC) formulations may be

found in Section 3.2 Table 25 of the Australian Pesticides & Veterinary Medicines Authority (APVMA) Guidelines for the Generation of Storage Stability Data for

Agricultural Chemical Products (Version 2, 22 July 2015). An outline summary of each method employed follows:

- Appearance, Physical State & Colour

These tests were performed visually and are described in descriptive terms.

- Odour

This test was performed organoleptically and involves the use of descriptive terms.

- Density MT 3.3.2

A portion of sample was accurately weight into a density bottle and diluted with water

containing an anti-foam agent, using vacuum, if necessary, to remove occluded air. The volume of sample taken was then found by making up to capacity with the anti-foam

solution and weighing.

- pH Collaborative International Pesticides Analytical Council (CIPAC) MT 75.3

The pH value of a 1% v/v dilution of the formulation was determined by means of a pH

meter and electrode system

- Brookfield RV Viscosity CIPAC MT 192

The viscosity of the formulation was measured in a standard measuring system using a Brookfield RV Viscometer

- Spontaneity of dispersion CIPAC MT 160

The method was broadly similar to that used to determine suspensibility (CIPAC MT

184), except that the preparation of the suspension of known concentration employs only one inversion and a 5 min standing time. The top 9/10ths were then drawn off

and the remaining 1/10th was then assayed chemically and the spontaneity of

dispersion calculated.

- Suspensibility CIPAC MT 184

A suspension of known concentration in CIPAC Standard Water was prepared, placed in a prescribed measuring cylinder at a constant temperature, and allowed to remain

undisturbed for a specific time (30 minutes). The top 9/10ths were then drawn off and the remaining 1/10th was then assayed chemically and the suspensibility calculated.

- Wet Sieve Test CIPAC MT 185

A sample of the formulation was dispersed in water and the suspension formed was transferred to a sieve and washed. The amount of the material retained on the sieve

was determined by drying and weighing.

- Persistent Foam CIPAC MT 47.2

The sample was diluted in a measuring cylinder of standard dimensions which was inverted 30 times and the amount of foam created and remaining after certain times

was measured.

- Cold Temperature Stability of Liquid Formulations CIPAC MT 39.3

A sample was maintained at 0 ±2 C for 7 days and the nature and quantity of any

separated material retained following wet sieving through a 75 Im sieve was determined.

- Active Constituent Content - QChem Laboratories Analytical Method QCM

174.02

Florasulam content was determined by reversed phase high performance liquid chromatography using UV detection and external standardisation. The method was

appropriately validated as per the APVMA Guidelines for the Validation of Analytical Methods for Active Constituents and Agricultural Products (Revision 1, July 12014).

- Observation of Packaging Stability

A sample of the product in a container of the same material and construction to that of

the marketed product was weighed and then maintained at 54 C for a period of 14

days. Any loss or gain in weight was recorded and the container examined, recording observations of any significant interaction with the formulation.

Storage Stability Methods

The APVMA Guidelines for the Generation of Storage Stability Data for Agricultural

Chemical Products (Version 2, 22 July 2015) gives a comprehensive guide to the conduct of stability testing for agricultural chemical products. The procedures contained therein were followed to prepare ambient temperature, elevated temperature (accelerated stability) and cold temperature storage samples as follows:

5000 mL of highly loaded florasulam SC was formulated. Two 1000 mL specimens were packaged into HDPE containers with screw cap closure (commercial packaging

material). The specimens remained in their containers and were stored in an air conditioned facility at approximately 21 °C for the period prior to ambient

temperature and elevated temperature storage.

On the day of initiation of the accelerated storage trial, each of the specimens in their

unopened containers were weighed on a top pan balance (Mettler PJ3600 Delta

Range: SNR J29589) to determine a starting weight (for use as a comparison with weights at the conclusion of the storage period).

The specimen designated for elevated temperature storage (Accelerated Stability sample TAs1) was placed into a thermostatically controlled oven (VWR Mini Incubator:

SNR 0811V1169), heated to 54 2 C, for a period of 14 days. At the end of this period, the sample was removed from the oven and placed into a desiccation chamber to

allow cooling to ambience.

The remaining formulation specimen (Time Zero sample Tol) was stored at air

conditioned ambient temperatures (~21°C) in a locked cabinet for the duration of the

elevated temperature storage period.

A sample of the formulation was prepared for low temperature stability testing by

placing 100 mL of the post accelerated storage stability formulation specimen (TAS1)

into 100 mL ASTM D96 graduated centrifuge tubes and storing it in a refrigerated

cabinet (Esatto Model EBF93W: SNR 5G386) at a temperature of 0 ±2 C for a total of 7 days.

The storage stability samples of AD-AU-1826 SC formulation were analysed as

described above and the results are as follows:

Analyses obtained for Time Zero (Ambient) sample Tol of AD-AU-1826 SC are as

provided in Table 5 below.

Table 5: Analysis of Time Zero (Ambient) Sample Tol of AD-AU-1826 SC

Determination Method Specification Analysis Result Appearance, Physical State Visual White White suspension PASS & Colour suspension Odour Olfactory Characteristic Characteristic PASS

pH - 1% v/v CIPAC MT 75.3 3.00-6.00 4.82 PASS dilution Density @ 20 CIPAC MT 1.085 - 1.115 1.104 g/mL @ 20 °C PASS °C 3.3.2 g/mL Pourability < 5 % residue 1.74 % residue 700 mL Kilner CIPAC MT 148 < 0.25 % rinsed 0.02 % rinsed residue PASS jar residue Brookfield RV Viscosity 20 °C CIPAC MT 192 800 - 1200 cps 980 cps PASS Spindle 2 @ 20 rpm Spontaneity of CIPAC MT 160 > 60 %and < dispersion 12.5 mL/ 250 105% 102% PASS Standard mL after 5 mins water C 23 °C Suspensibility CIPAC MT 184 > 60 %and < Standard 0.50 mL / 250 105% 94% PASS water D 23 °C mL after 30 mins CIPAC MT 185 Wet sieve test 75 pm sieve < 2.0 % 0.00% PASS After 10 sec 30 mL Persistent CIPAC MT 47.2 max 60 ml foam After 1 min 5 mL PASS foam 2.00 mL / 200 after 1 min After 3 min 1 mL CIPAC mL After 12 min 0 mL Standard Water C Content QCM-174.02 188 - 212 g/L 206 g/L PASS Florasulam

Analyses obtained for Accelerated Stability sample TAs1 of AD-AU-1826 SC are as provided in Table 6 below.

Table 6: Analysis of Accelerated Stability Sample TAS1 of AD-AU-1826 SC

Determination Method Specification Analysis Result Appearance, Physical State Visual White White suspension PASS & Colour suspension Odour Olfactory Characteristic Characteristic PASS

pH - 1% v/v CIPAC MT 75.3 3.00-6.00 4.92 PASS dilution Density @ 20 CIPAC MT 1.085 - 1.115 1.105 g/mL @ 20 °C PASS °C 3.3.2 g/mL Pourability < 5 % residue 1.54 % residue 700 mL Kilner CIPAC MT 148 < 0.25 % rinsed 0.01 % rinsed residue PASS jar residue

Brookfield RV Viscosity 20 °C CIPAC MT 192 800 - 1200 cps 980 cps PASS Spindle 2 @ 20 rpm Spontaneity of CIPAC MT 160 > 60 %and < dispersion 12.5 mL / 250 105% 99% PASS Standard mL after 5 mins water C 23 °C

Suspensibility CIPAC MT 184 > 60 %and < Standard 0.50 mL / 250 105% 90% PASS water D 23 °C mL after 30 mins

CIPAC MT 185 Wet sieve test 75 pm sieve < 2.0 % 0.00% PASS After 10 sec 30 mL Persistent CIPAC MT 47.2 max 60 ml foam After 1 min 5 mL PASS foam 2.00 mL / 200 after 1 min After 3 min 1 mL CIPAC mL After 12 min 0 mL Standard Water C

Content QCM-174.02 188 - 212 g/L 205 g/L PASS Florasulam

The AD-AU-1826 SC formulation was determined to be stable to heat for 2 weeks at 54°C for all parameters according to the standard CIPAC accelerated testing regime

and therefore is expected to be shelf stable for at least 2 years.

Cold Temperature Stability of Liquid Formulations CIPAC MT 39.3

The AD-AU-1826 SC formulation was subjected to cold storage condition at 0 ±2 C for 7 days and the volume and nature of any separated material was recorded. Analyses

obtained for Cold Stability sample TCD1 of AD-AU-1826 SC are as provided in Table 7 below.

Table 7: Analysis of Cold Stability sample TCD1 of AD-AU-1826 SC

Determination Method Specification Analysis Result

LowTemperature CIPACIMT <0.05gseparated Nilseparatedmaterial PASS Stability 39.3 After material retained 7 Days by a 75 pm sieve

The absence of any separation or crystal growth indicates the formulation to be cold

storage stable.

In conclusion, the new AD-AU-1826 SC formulation containing a florasulam

concentration of about 200 g/L performs excellently in all requisite tests.

A highly loaded aqueous SC formulation containing a florasulam concentration of

about 500g/L, identified as AD-AU-1818-SC, was also prepared and analysed using similar methods to those described above.

Analyses obtained for Time Zero (Ambient) sample Tol and for Accelerated Stability sample TAs1 of AD-AU-1818-SC are as provided in Table 8 and Table 9 below.

Table 8: Analysis of Time Zero (Ambient) Sample Tol of AD-AU-1818-SC

Determination Method Specification Analysis Result Appearance, Physical State Visual White White suspension PASS & Colour suspension

Determination Method Specification Analysis Result Odour Olfactory Characteristic Characteristic PASS

pH - 1% v/v CIPAC MT 75.3 3.00-5.00 3.70 PASS dilution Density @ 20 CIPAC MT 1.085 - 1.230 1.210 g/mL @ 20 PASS °C 3.3.2 g/mL °C Pourability < 5 % residue 3.18 % residue 700 mL Kilner CIPAC MT 148 < 0.25 % rinsed 0.22 % rinsed PASS jar residue residue Brookfield RV Viscosity 20 °C CIPAC MT 192 2400 - 3000 cps 2820 cps PASS Spindle 2 @ 20 rpm Spontaneity of CIPAC MT 160 > 60 %and < dispersion 12.5 mL / 250 105% 101% PASS Standard mL after 5 mins water C 23 °C Suspensibility CIPAC MT 184 > 60 %and < Standard 0.50 mL / 250 105% 100% PASS water D 23 °C mL after 30 mins CIPAC MT 185 Wet sieve test 75 pm sieve < 2.0 % 0.06% PASS After 10 sec 0 mL Persistent CIPAC MT 47.2 max 60 ml foam After 1 min 0 mL PASS foam 2.00 mL / 200 after 1 min After 3 min 0 mL CIPAC mL After 12 min 0 mL Standard Water C Content QCM-174.02 475 - 525 g/L 495 g/L PASS Florasulam

Table 9: Analysis of Accelerated Stability Sample TAS1 of AD-AU-1818-SC

Determination Method Specification Analysis Result Appearance, Physical State Visual White White suspension PASS & Colour suspension Odour Olfactory Characteristic Characteristic PASS

pH - 1% v/v CIPAC MT 75.3 3.00-5.00 3.75 PASS dilution

Determination Method Specification Analysis Result Density @ 20 CIPAC MT 1.085 - 1.230 1.207 g/mL @ 20 PASS °C 3.3.2 g/mL °C Pourability < 5 % residue 3.00 % residue 700 mL Kilner CIPAC MT 148 < 0.25 % rinsed 0.19 % rinsed PASS jar residue residue Brookfield RV Viscosity 20 °C CIPAC MT 192 2400 - 3000 cps 2640 cps PASS Spindle 2 @ 20 rpm Spontaneity of CIPAC MT 160 > 60 % and < dispersion 12.5 mL/ 250 105% 101% PASS Standard mL after 5 mins water C 23 °C Suspensibility CIPAC MT 184 > 60 % and < Standard 0.50 mL / 250 105% 97% PASS water D 23 °C mL after 30 mins CIPAC MT 185 Wet sieve test 75 pm sieve < 2.0 % 0.13% PASS After 10 sec 0 mL Persistent CIPAC MT 47.2 max 60 ml foam After 1 min 0 mL PASS foam 2.00 mL / 200 after 1 min After3min omL CIPAC mL After 12 min 0 mL Standard Water C Content QCM-174.02 475 - 525 g/L 493 g/L PASS Florasulam

The AD-AU-1818 SC formulation was determined to be stable to heat for 2 weeks at

54°C for all parameters according to the standard CIPAC accelerated testing regime.

In conclusion, the inventors have created a novel higher loaded florasulam formulation

containing a florasulam concentration above that of currently available formulations. In this example, the ability to increase the maximum loading in a liquid formulation

from 50 g ai/L to more than 200 and up to 500 g/L represents a 75 to 90% reduction in

the volume of material to be formulated, transported and applied by the end user, respectively. The solo liquid florasulam SC formulations are more versatile than

existing co-formulated products such as Paradigm@, as they can be applied on susceptible weeds or pre-sowing without additional herbicides that are co-formulated or without an additional tank mix partner or adjuvant.

Example 2: Compatibility Profile of Highly Loaded Florasulam SC Formulations

Compatibility tests were conducted to evaluate the suitability of using the highly loaded liquid florasulam formulation of Example 1, identified as AD-AU-1826 SC, with

additional herbicides containing one or more other active ingredients along with adjuvants as tank mix partners. The compatibility profile of AD-AU-1826 are provided

in Table 10 below.

Table 10: Compatibility Profile of AD-AU-1826

AD-AU-1826 SC Uptake© Spraytop© 250 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L 2.0 L/Ha 50 pL / 100 mL CIPAC C 500 pL 4.0 mL Water Compatible - Homogeneous 30 min. Re disperses 24 h. AD-AU-1826 SC Uptake@ Spraytop@ 330 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L 1.5 L/Ha 50 pL / 100 mL CIPAC C 500 pL 3.0 mL Water Compatible - Homogeneous 30 min. Re disperses 24 h. AD-AU-1826 SC Uptake@ Quadrant@ 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L 1.2 L/Ha 50 pL / 100 mL CIPAC C 500 pL 2.4 mL Water Compatible - Homogeneous 30 min. Re disperses 24 h. AD-AU-1826 SC Uptake@ WipeOut@ Pro 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L 1.5 L/Ha 50 pL / 100 mL CIPAC C 500 pL 3.0 mL Water Compatible - Homogeneous 30 min. Re disperses 24 h.

AD-AU-1826 SC Uptake@ Roundup 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L Ultra@MAX 1.5 L/Ha 50 pL / 100 mL CIPAC C 500 pL 3.0 mL Water

Compatible - Homogeneous 30 min. Re disperses 24 h. AD-AU-1826 SC Uptake@ Weedmaster Argo 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L 1.5 L/Ha 50 pL / 100 mL CIPAC C 500 pL 3.0 mL Water Compatible - Homogeneous 30 min. Re disperses 24 h. AD-AU-1826 SC Uptake@ Weedmaster DST 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L 2.0 L/Ha 50 pL / 100 mL CIPAC C 500 pL 4.0 mL Water Compatible - Homogeneous 30 min. Re disperses 24 h. AD-AU-1826 SC Uptake@ Crucial 600 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L 1.35 L/Ha 50 pL / 100 mL CIPAC C 500 pL 2.7 mL Water Compatible - Homogeneous 30 min. Re disperses 24 h. AD-AU-1826 SC Adigor@ Axial 25 mL/Ha Water Volume 50 L/Ha 500 mL/100 L 300 mL/Ha 50 pL / 100 mL CIPAC C 500 pL 600 pL Water Compatible - Homogeneous 30 min. Re disperses 24 h. Adjuvants

Uptake: paraffinic oil and alkoxylated alcohol non-ionic surfactants.

Adigor*: methyl esters of canola oil fatty acids.

Other Herbicides (active ingredients)

Spraytop© 250: paraquat.

Spraytop© 330:paraquat.

Quadrant®: picolinafen, diflufenican, bromoxynil, MCPA.

WipeOut®Pro: glyphosate present as MEA salt.

Roundup Ultra©MAX: high-load glyphosate.

Weedmaster Argo: glyphosate present as the potassium and isopropylamine salts.

Weedmaster DST: glyphosate present as the potassium and mono ammonium salts.

Crucial 600: glyphosate.

Axial: pinoxaden + cloquintocet-mexyl.

Example 3: Field Tests

Field Trials analyses were conducted to evaluate the efficacy of the highly loaded

florasulam SC formulations of Example 1, identified as AD-AU-1826 SC (200 g ai/L).

Field Test 1: Roseworthy, South Australia

At Roseworthy, SA, a trial was conducted to evaluate the crop safety and efficacy of

AD-AU-1826 SC (205 g ai/L) for the pre-emergent control of volunteer lentils (Lens culinaris), volunteer field pea (Pisum sativum arvense) and volunteer chickpea (Cicer

arietnum) in wheat cv. Other products were also tested. The product details are in Table 11:

Table 11: Products

Active ingredient Concentration Product name (ai) of Active Formulation ingredient Florasulam 205 g/L Suspension AD-AU-1826 SC (205) concentrate Mesotrione 480 g/L Suspension Callisto 480 SC concentrate

Gallery 750 DF Isoxaben 750 g/kg Dry flowable

Clopyralid 600 g/L Suspension Victory 600 SC concentrate

Treatments are set out in Table 12:

Table 12: Treatments

Rate Product Active Application No. Product Ingredient timing (mL or g/ha) (g Al/ha) 1 Untreated control Nil Nil

2 AD-AU-1826 SC 15 mL 3 IBS

3 AD-AU-1826 SC 25 mL 5

4 Callisto 100 mL 48

5 Gallery 140 g 105

6 Victory 600 75 mL 45

7 AD-AU-1826 SC 15 mL 3 PSPE 8 AD-AU-1826 SC 25 mL 5 IBS = Treatments incorporated by sowing PSPE = Treatments applied post sowing, pre-emergent

Mean crop emergence of wheat is shown in Table 13:

Table 13. Crop emergence of wheat cv.

Rate Appl. Crop emergence No. Treatment (g timing (mean no./m row) ai/ha) 25DAS 1 Untreated control Nil 51 2 AD-AU-1826 SC 3 51 3 AD-AU-1826 SC 5 52 4 Callisto 48 IBS 50 5 Gallery 105 50 6 Victory 600 45 50 7 AD-AU-1826 SC 3 PSPE 51

Rate Al Crop emergence No. Treatment (g Appl. (mean no./m row) ai/ha) timing25DAS 8 AD-AU-1826 SC 5 49 P-value 0.3252 CV 6.91 IBS = Treatments incorporated by sowing PSPE = Treatments applied post sowing, pre-emergent DAS = Days after sowing NSD = No significant difference due to a P-value > 0.05

Percent volunteer lentil control is shown in Table 14:

Table 14: Volunteer lentil (Lens culinaris) control in wheat cv

Rate Lentil control No Treatment (g ti. (mean % relative to untreated control) ai/ha) timing 26DAS 56DAS 83DAS

1 Untreated Nil 0 d 0 f 0 f control 2 AD-AU-1826 SC 3 95 a 87 abc 85 bc 3 AD-AU-1826 SC 5 95 a 93 ab 89 abc 4 Callisto 48 IBS 87 a 86 abcd 84 bc 5 Gallery 105 58 b 71 bcd 60 d 6 Victory 600 45 98 a 99 a 99 a 7 AD-AU-1826 SC 3 58 b 60 d 81 c PSPE 8 AD-AU-1826 SC 5 58 b 65 cd 66 d P-value 0.0001* 0.0001* 0.0001* CV 9.65 19.82 11.64 tA IBS = Treatments incorporated by sowing PSPE =Treatments applied post sowing, pre-emergent DAS= Days after sowing * = Data failed Bartlett's test and cannot be transformed for homogeneity Means followed by the same letter are not significantly different (P = 0.05, Duncan's) tA = Data transformed using x = Arcsine square root percent (y), original means presented

Mean percent field pea control is shown in Table 15:

Table 15: Volunteer field pea (Pisum sativum arvense) control in wheat cv

Rate Field pea control No Treatment (g Appi. (mean %relative to untreated control) ai/ha) 26DAS 56DAS 83DAS

1 Untreated Nil 0 f 0 f 0 d control 2 AD-AU-1826 SC 3 98 ab 100 a 100 a 3 AD-AU-1826 SC 5 98 ab 100 a 100 a 4 Callisto 48 IBS 96 abc 80 c 79 b 5 Gallery 105 59 d 45 d 43 c 6 Victory 600 45 97 abc 94 a 94 a 7 AD-AU-1826 SC 3 91 bc 91 ab 97 a PSPE 8 AD-AU-1826 SC 5 59 d 84 bc 80 b P-value 0.0001 0.0001 0.0001 CV 9.12 7.98 6.86 tA IBS = Treatments incorporated by sowing PSPE =Treatments applied post sowing, pre-emergent DAS =Days after sowing Means followed by the same letter are not significantly different (P = 0.05, Duncan's) tA = Data transformed using x = Arcsine square root percent (y), original means presented

Mean field pea density is shown in Table 16:

Table 16: Volunteer field pea (Pisum sativum arvense) density in wheat cv

Rate Field pea density No Treatment (g Appi. (mean no./m2 )

ai/ha) 26DAS 56DAS 83DAS

1 Untreated Nil 16 a 24 a 24 a control 2 AD-AU-1826 SC 3 1 c 0 d 0 fg 3 AD-AU-1826 SC 5 0 c 1 d 0 g IBS 4 Callisto 48 1 c 4 d 5 de 5 Gallery 105 5 b 16 bc 10 b

Rate Field pea density No Treatment (g Appl. (mean no./m2

) ai/ha) timing 26DAS 56DAS 83DAS

6 Victory 600 45 1 c 5 d 3 def

7 AD-AU-1826 SC 3 1 c 4 d 8 de PSPE 8 AD-AU-1826SC 5 7 b 4 d 7 cd

P-value 0.0001 0.0001 0.0001

CV 79.92 61.99 49.66

tL tL IBS = Treatments incorporated by sowing PSPE = Treatments applied post sowing, pre-emergent DAS = Days after sowing Means followed by the same letter are not significantly different (P = 0.05, Duncan's) tL = Data transformed using x = Log (y + 1), original means presented

Mean percent chickpea control is shown in Table 17:

Table 17: Volunteer chickpea (Cicer arietinum) control in wheat cv

Rate AppI. Chickpea control No Treatment (g timing (mean % relative to untreated control) ai/ha) 56DAS 83DAS

1 Untreated Nil 0 f 0 g control 2 AD-AU-1826 SC 3 71 bcd 84 abc

3 AD-AU-1826 SC 5 82 b 93 ab

4 Callisto 48 IBS 53 cde 45 ef

5 Gallery 105 33 e 33 f

6 Victory 600 45 100 a 100 a

7 AD-AU-1826 SC 3 63 bcd 73 cd PSPE 8 AD-AU-1826 SC 5 68 bcd 58 de

P-value 0.0001* 0.0001

CV 22.28 18.01

tA IBS = Treatments incorporated by sowing PSPE =Treatments applied post sowing, pre-emergent DAS =Days after sowing * = Data failed Bartlett's test and cannot be transformed for homogeneity

Means followed by the same letter are not significantly different (P = 0.05, Duncan's) tA = Data transformed using x = Arcsine square root percent (y), original means presented

Chickpea density in wheat is shown in Table 18:

Table 18: Volunteer chickpea (Cicer arietinum) density in wheat cv

Rate Chickpea density No Treatment (g i. (mean no./m 2

) ai/ha) timing 26DAS 56DAS 83DAS

1 Untreated Nil 3 7 ab 9 ab control 2 AD-AU-1826 SC 3 1 2 cd 4 bcde

3 AD-AU-1826 SC 5 2 4 abcd 3 cde

4 Callisto 48 IBS 1 9 ab 14 a

5 Gallery 105 2 6 abcd 6 abcd

6 Victory 600 45 2 0 d 0 e

7 AD-AU-1826 SC 3 1 8 ab 6 abcd PSPE 8 AD-AU-1826 SC 5 1 6 abcd 7 abcd

P-value 0.5560 0.0023 0.0024

CV 115.79 62.10 57.14

tL tL

IBS = Treatments incorporated by sowing PSPE =Treatments applied post sowing, pre-emergent DAS =Days after sowing Means followed by the same letter are not significantly different (P = 0.05, Duncan's) NSD = No significant difference due to a P-value > 0.05 tL = Data transformed using x = Log (y + 1), original means presented

Moderate crop vigour reductions were recorded for AD-AU-1826 applied at 5 g ai/ha

standalone IBS and PSPE.

AD-AU-1826 treatments applied standalone IBS recorded equivalence in control of

volunteer lentil (Lens culinaris), volunteer field pea (Pisum sativum arvense) and volunteer chickpea (Cicer arietinum).

Callisto and Victory recorded significantly lower volunteer lentil densities compared to the untreated control. However, these were not always lower than other treatments.

Treatments containing AD-AU-1826 applied standalone IBS recorded equivalent and significant reductions in volunteer field pea densities compared to the untreated

control. Accordingly, standalone AD-AU-1826 performed well.

Applying AD-AU-1826 IBS at 3 g ai/ha and 5 g ai/ha significantly reduced volunteer field

pea densities compared to the same active ingredient rate applied PSPE.

AD-AU-1826 treatments applied standalone IBS and PSPE were equivalent for

volunteer chickpea (Cicer arietinum) density.

Field Test 2: Elmore, Victoria At Elmore, Victoria, a trial was conducted in wheat Triticum aestivum cv. to:

- compare the equivalence on volunteer pulses of AD-AU-1826 + fluroxypyr

Victory with Outshine ±Victory;

- compare the bioequivalence of Vortex and AD-AU-1826 + 2,4-D ester 680;

- evaluate AD-AU-1826 when applied with other tank mix partners including LVE MCPA 570, Zulu XT or Triathlon;

- compare with another registered standard product, Paradigm + LVE MCPA 570;

- determine the crop safety of all treatments on cereals.

Herbicide treatments were applied by gas powered hand boom at Zadocks (Z) 13/22 14/23 crop growth stage (GS). Herbicide treatments were applied across the direction

of sowing with a three metre width handheld propane powered spray boom.

A mixed volunteer pulse weed complex was targeted comprising:

- faba bean Viciafaba at 2-3 nodes/leaf pairs GS (UTC mean 12 plants/m2);

- tame vetch Vicia sativa at 3-5 nodes/leaflets GS (UTC mean 27 plants/m2);

- field pea Pisum sativum at 3-5 nodes GS (UTC mean 14 plants/m2); spineless burr medic Medicago polymorpha cv. Cavalier at 3-5 trifoliate leaves

GS (UTC mean 11 plants/m2).

Volunteer pulse seeds were spread evenly along trial replicates prior to crop sowing.

Treatments are set out in Table 19:

Table 19: Treatments

Trt Treatment Active ingredient Rate Product rate No. (g ai/ha) mL or g/ha 1 Untreated - 2 Paradigm halauxifen-methyl 200 5 25 g/kg florasulam 200 g/kg 5 LVE MCPA570 MCPA570g/L 359 630 Uptake Spray Oil Adjuvant 0.5%v/v 3 Vortex 2,4-D 300 g/L 246 820 florasulam 6.25g/L 5.1 Uptake Spray Oil adjuvant 0.5%v/v 4 Outshine fluroxypyr 100g/L 100 1000 florasulam 2.5g/L 2.5 Uptake Spray Oil adjuvant 0.5%v/v 5 Outshine fluroxypyr 100g/L 200 2000 florasulam 2.5g/L 5 Uptake Spray Oil adjuvant 0.5%v/v 6 Outshine fluroxypyr 100g/L 100 1000 florasulam 2.5g/L 2.5 Victory clopyralid 300 g/L 30 100 Uptake Spray Oil adjuvant 0.5%v/v 7 Triathlon diflufenican 25 g/L 25 MCPA 250 g/L 250 1000 bromoxynil 150 g/L 150 8 AD-AU-1826 florasulam 205 g/L 5 25 Uptake Spray Oil adjuvant 0.5%v/v 9 AD-AU-1826 florasulam 205 g/L 5 25 2,4-D ester 680 2,4-D 680 g/L 245 360 Uptake Spray Oil adjuvant 0.5%v/v 10 AD-AU-1826 florasulam 205 g/L 5 25 LVE MCPA 570 MCPA ester 570 g/L 251 440 Uptake Spray Oil adjuvant 0.5%v/v 11 AD-AU-1826 florasulam 205 g/L 5 25 Zulu XT 2,4-D 720 g/L 360 500 Uptake Spray Oil adjuvant 0.5%v/v 12 AD-AU-1826 florasulam 205 g/L 5 25 Flagship 400 fluroxypyr 400 g/L 100 250 Uptake Spray Oil adjuvant 0.5%v/v

Trt Treatment Active ingredient Rate Product rate No. (g ai/ha) mL or g/ha 13 AD-AU-1826 florasulam 205 g/L 5 25 Flagship 400 fluroxypyr 400 g/L 200 500 Uptake Spray Oil adjuvant 0.5%v/v 14 AD-AU-1826 florasulam 205 g/L 5 25 Flagship 400 fluroxypyr 400 g/L 200 500 Victory clopyralid 300 g/L 30 100 Uptake Spray Oil adjuvant 0.5%v/v 15 AD-AU-1826 florasulam 205 g/L 5 25 Triathlon diflufenican 25 g/L 25 MCPA 250 g/L 250 1000 bromoxynil 150 g/L 150 Wetspray 1000 non-ionic surfactant 0.2%v/v

Crop safety and volunteer pulse efficacy of trial treatments were assessed at 15 DAA,

43 DAA and grain yield was assessed at 126 DAA.

AD-AU-1826 tank-mixes with fluroxypyr ±Victory compared to Outshine ±Victory gave equivalent final efficacy comprising commercially acceptable control of volunteer

pulses.

AD-AU-1826 tank-mix with fluroxypyr + Victory gave significantly higher efficacy of faba bean, vetch and field-pea at second assessment compared to Outshine + Victory

tank-mix.

Vortex & AD-AU-1826 tank-mixes with 2,4-D ester 680, LVE MCPA 570, Zulu XT &

Triathlon all gave equivalent efficacy comprising commercially acceptable control of volunteer pulses at final assessment.

Commercial standard treatment of Paradigm + LVE MCPA 570 gave commercially acceptable control of all volunteer pulses at final assessment.

Triathlon applied alone gave control of faba bean and burr medic, borderline

commercially acceptable control of tame vetch and weak suppression of field peas.

All treatments gave excellent wheat crop safety.

Field Test 3: Bridgewater, Victoria At Bridgewater Victoria, a trial was conducted in wheat in oats Avena sativa cv. to:

- compare the equivalence on fumitory and hedge mustard of AD-AU-1826

+ fluroxypyr + LVE MCPA with Outshine + LVE MCPA;

- evaluate AD-AU-1826 when applied with other tank mix partners including Affinity + MCPA 750, Quadrant or Triathlon;

- compare with another registered standard product, Paradigm & Precept; and

- determine the crop safety of all treatments on oats.

Herbicide treatments were applied by gas powered hand boom at the Zadocks (Z) 23 25 crop growth stage.

There was a moderate density weed complex at application comprising:

- Indian hedge mustard Sisymbrium orientale at 2-5 leaf G.S. (UTC mean 27 plants/m2);

- denseflower fumitory Fumaria densflora at 6-20 leaf G.S. (UTC mean 28

plants/m2);

- volunteer sub-clover Trifolium subterraneum, at 2-7 trifoliate leaf G.S. (UTC

mean 61 plants/m 2 ); and

- wireweed Polygonum aviculare at 2-6 leaf G.S. (UTC mean 12 plants/m 2 ).

Prior barley crop stubble groundcover was minimal (z5%) due to very poor crop

germination and subsequent maintenance as chemical fallow over the 2018 season.

Sub-clover was established uniformly across the site by seeding with a separate shallow sowing pass to the oat crop.

Treatments are set out in Table 20.

Table 20: Treatments

Trt Treatment Active ingredient Rate Product rate No. (g ai/ha) mL or g/ha 1 Untreated - 2 Paradigm halauxifen-methyl 200 g/kg 5 25 florasulam 200 g/kg 5 Uptake Spray Oil Adjuvant 0.5%v/v 3 Affinity Force carfentrazone-ethyl 240 g/L 20.4 85

Trt Treatment Active ingredient Rate Product rate No. (g ai/ha) mL or g/ha MCPA 750 MCPA 750 g/L 247.5 330

4 Outshine fluroxypyr 100g/L 100 1000 florasulam 2.5g/L 2.5 LVE MCPA 570 MCPA 570 g/L 180 315 Uptake Spray Oil Adjuvant 0.5%v/v Outshine fluroxypyr 100g/L 150 1500 florasulam 2.5g/L 3.75 LVE MCPA 570 MCPA 570 g/L 359 630 Uptake Spray Oil Adjuvant 0.5%v/v 6 Triathlon diflufenican 25 g/L 18.25 750 MCPA 250 g/L 187.5 bromoxynil 150 g/L 112.5 7 Quadrant picolinafen 10 g/L 6 600 diflufenican 20 g/L 12 MCPA 250 g/L 150 bromoxynil 150 g/L 144 8 AD-AU-1826 florasulam 205g/L 5 25 Uptake Spray Oil Adjuvant 0.5%v/v 9 AD-AU-1826 florasulam 205 g/L 5 25 Flagship 400 fluroxypyr 400 g/L 100 250 LVE MCPA 570 MCPA 570 g/L 180 315 Uptake Spray Oil Adjuvant 0.5%v/v AD-AU-1826 florasulam 205 g/L 5 25 Flagship 400 fluroxypyr 400 g/L 150 375 LVE MCPA 570 MCPA 570 g/L 359 630 Uptake Spray Oil Adjuvant 0.5%v/v 11 Precept pyrasulfotole 25 g/L 37.5 1500 MCPA EHE 250 g/L 375 Hasten Adjuvant 0.5%v/v 12 Affinity Force carfentrazone-ethyl 240 g/L 20.4 85 MCPA 750 MCPA 750 g/L 247.5 330 AD-AU-1826 florasulam 205 g/L 5 25 13 AD-AU-1826 florasulam 205 g/L 5 25 Triathlon diflufenican 25 g/L 18.25 750 MCPA 250 g/L 187.5 bromoxynil 150 g/L 112.5 Wetspray 1000 non-ionic surfactant 0.2%v/v 14 AD-AU-1826 florasulam 205 g/L 5 25 Quadrant picolinafen 10 g/L 6 600 diflufenican 20 g/L 12 MCPA 250 g/L 150 bromoxynil 150 g/L 144 Wetspray 1000 non-ionic surfactant 0.2%v/v

Crop safety and weed efficacy of trial treatments were assessed at 12 DAA, 18 DAA, 31 DAA and 87 DAA and plant counts were done.

Trial data was analysed using a 95% confidence level. Means were compared using Duncan's New Multiple Range Test.

AD-AU-1826 + fluroxypyr + LVE MCPA 570 gave commercially acceptable control of Indian hedge mustard, denseflower fumitory and sub-clover, equivalent to matched

rates of Outshine + LVE MCPA 570.

AD-AU-1826 + Affinity Force + MCPA 750 gave equivalent, commercially acceptable

control of Indian hedge mustard and denseflower fumitory, compared to Affinity Force

+ MCPA 750.

AD-AU-1826 + Affinity Force + MCPA 750 gave significantly higher, commercially

acceptable control of sub-clover compared to Affinity Force + MCPA 750 which gave strong suppression.

AD-AU-1826 tank-mixes with Triathlon and Quadrant gave improved mean efficacy against denseflower fumitory compared to Triathlon and Quadrant applied alone, lifting efficacy from good to very strong suppression.

AD-AU-1826 tank-mixes with Triathlon and Quadrant gave significantly improved

efficacy against sub-clover, lifting efficacy from good suppression to commercially

acceptable control.

Paradigm gave excellent control of Indian hedge mustard, denseflower fumitory and

sub-clover.

Precept gave excellent control of Indian hedge mustard and denseflower fumitory and

suppression of sub-clover.

All treatments were safe to the crop.

AD-AU-1826 applied alone always gave greater crop biomass reduction with some

differences statistically separated, compared to when applied in tank-mixes.

Paradigm and AD-AU-1826 applied alone gave similar biomass reduction.

Field Test 4: Greymare, Queensland Post-emergence control of Mexican poppy in winter cereals has relied upon 2,4-D and more recently upon Paradigm + MCPA.

A field trial was conducted at Jandowae, QLD to compare a 25 mL/ha AD-AU-1826 in combination with LVE MCPA, LVE MCPA + Flagship, LVE 2,4-E ester 680, Zulu XT,

Triathlon, Bronco MA-X, Flagship 400 + LVE 2,4-D ester 680 and Bronco MA-X

+ Flagship. Finally, the experiment had the objective of determining the crop safety of

the various treatments in oats cv. Warrego.

Treatments were applied using a hand-held spray boom equipped with 4 x HMD green low-pressure air-induction nozzles and operated at a pressure of 250 kPa to deliver a

spray volume of 100 L/ha in dryland oats at GS 23 to 27 under conditions of good soil moisture. Treatments were arranged in a Randomized Complete Block Design with a

plot size of 2 x 10 metres and 4 replicates.

Soil type was a pebbly sandy clay loam. The weed spectrum was dominated by

Mexican poppy and wireweed with lower numbers of small-flowered mallow, sowthistle and pimpernel.

Weed and crop details at application are summarised in Table 21:

Table 21: Weed Details

Common name Scientific name Growth stage Weed size

Mexican poppy Argemone Mexicana 2 leaf - rosette 2-10cm

Wireweed Polygonum aviculare Multi-leaf 3- 10cm

Small-flowered mallow Malva parviflora 4 leaf - multi-leaf 5 - 25 cm

Treatments are summarised in Table 22:

Table 22: Treatments

Trt No. Treatment Active g ai/ha Rate (product mL/ha) 1 Untreated -

2 Paradigm^ 5+5 25 g LVE MCPA 570 359 630

3 Bronco MA-X 140+140 1000

4 Triathlon 25+250+150 1000

5 AD-AU-1826^ 5 25 LVE MCPA 570 570 630

6 AD-AU-1826^ 5 25 LVE 2,4-D ester 680 245 360

7 AD-AU-1826^ 5 25 Zulu XT 360 500

8 AD-AU-1826^ 5 25 Bronco MA-X 140+140 1000

9 AD-AU-1826^^ 5 25 Triathlon 25+250+150 1000

10 AD-AU-1826^ 5 25 Flagship 400 200 500 LVE MCPA 570 359 630

11 AD-AU-1826^ 5 25 Flagship 400 200 500 LVE 2,4-D ester 680 245 360

12 AD-AU-1826^ 5 25 Flagship 400 150 375 Bronco MA-X 70+70 500

^ applied with 0.5% v/v Uptake Spraying Oil ^^ applied with 0.2% v/v Wetspray

Weed control was assessed on 4 occasions using a subjective 0-100 percentage scale where 0=no effect and 100=complete control. Assessments were undertaken August 4

(7 DAA), August 11 (14 DAA), August 25 (29 DAA) and September 21 (55 DAA). Crop Safety was assessed on August 4 and 11 with a subjective % estimate of injury where

0=no effect and 100=complete crop destruction.

Data was analysed at a Randomized Complete Block separately for each crop using

ARM 9 statistical software. AOV tables were prepared with treatment values identified by different letters being significant according to the Duncan's New Multiple Range

test at the 5% level of probability.

Percent control of Mexican Poppy is shown in Table 23.

Table 23: Percent Control of Mexican Poppy

Trt No. Treatment Rate 28 DAA 55 DAA (product mL/ha) 1 Untreated - 0 0 2 Paradigm 25 g 94 abc 100 a LVE MCPA 570 630

3 Bronco MA-X 1000 100 a 100 a

4 Triathlon 1000 86 bcd 80 c

5 AD-AU-1826A 25 74e 98 ab LVE MCPA 570 630

6 AD-AU-1826A 25 80 de 100 a LVE 2,4-D ester 680 360

7 AD-AU-1826A 25 85 cde 90 b Zulu XT 500

8 AD-AU-1826A 25 98 ab 100a Bronco MA-X 1000

9 AD-AU-1826AA 25 99 a 100a Triathlon 1000 10 AD-AU-1826A 25 74e 98 a Flagship 400 500 LVE MCPA 570 630

Trt No. Treatment Rate 28 DAA 55 DAA (product mL/ha) 11 AD-AU-1826A 25 80 de 100a Flagship 400 500 LVE 2,4-D ester 680 360

12 AD-AU-1826A 25 95 abc 99 a Flagship 400 375 Bronco MA-X 500

Treatments separated by different letters are significantly different at the 5% level of probability A plus 0.5% v/v Uptake AA plus 0.2% v/v Wetspray

Percent control of wireweed is shown in Table 24:

Table 24: Percent Control of Wireweed

Trt No. Treatment Rate 55 DAA (product mL/ha) 1 Untreated - 0

2 Paradigm 25 g 79 bc LVE MCPA 570 630

3 Bronco MA-X 1000 78 bc

4 Triathlon 1000 73 bcd

5 AD-AU-1826A 25 65 cd LVE MCPA 570 630

6 AD-AU-1826A 25 80 bc LVE 2,4-D ester 680 360

7 AD-AU-1826A 25 58 d Zulu XT 500

8 AD-AU-1826A 25 83 ab Bronco MA-X 1000

Trt No. Treatment Rate 55 DAA (product mL/ha) 9 AD-AU-1826AA 25 98 a Triathlon 1000

10 AD-AU-1826A 25 80 bc Flagship 400 500 LVE MCPA 570 630

11 AD-AU-1826A 25 83 ab Flagship 400 500 LVE 2,4-D ester 680 360

12 AD-AU-1826A 25 71 bcd Flagship 400 375 Bronco MA-X 500

Treatments separated by different letters are significantly different at the 5% level of probability A plus 0.5% v/v Uptake AA plus 0.2% v/v Wetspray

Commercially acceptable control of Mexican poppy was achieved with Bronco MA-X alone and in combination with AD-AU-1826 and AD-AU-1826 + LVE MCPA.

Commercially acceptable control of Mexican poppy was achieved with AD-AU-1826 in

combination with LVE MCPA 570 +- Flagship 400, 2,4-D LVE ester 680 +/- Flagship 400, Triathlon and AD-AU-1826 + Flagship + 500 mL/ha Bronco MA-X.

Excellent control of wireweed was obtained with AD-AU-1826 + Triathlon.

Treatments including Triathlon caused unacceptable injury to oats.

It is apparent from the Field Tests that the formulation of the invention may be used to control one or more weeds chosen from: volunteer lentils (Lens culinaris), volunteer

field pea (Pisum sativum arvense), volunteer chickpea (Cicer arietnum), faba bean (Viciafaba), tame vetch (Vicia sativa), spineless burr medic (Medicago polymorpha cv.

Cavalier), Indian hedge mustard (Sisymbrium orientale), denseflower fumitory

(Fumaria densiflora), volunteer sub-clover (Trifolium subterraneum), wireweed

(Polygonum aviculare), Mexican poppy (Argemone Mexicana) and small-flowered mallow (Malva parviflora).

Other weeds which may also be controlled by the formulation of the invention include: Bedstraw (Galium tricornutum), Turnip weed (Rapistrum rugosum), Bittercress

(Coronopus didymus), Wild radish (Raphanus raphanistrum), Wild turnip (Brassica tournefortii), Shepherd's purse (Bidens Pilosa), Stonecrop (Crassula sieberiana, C.

helsii), Annual Ground Cherry, Wild Gooseberry (Physalis spp.), Thornapples (Datura spp.), Apple of Peru (Nicandra physalodes), Bathurst Burr (Xanthium spinosum), Noogoora Burr (Xanthium strumarium), Doublegee/Spiny emex (Emex australis), Caltrop/ Yellow Vine including (T. maximus and T. micrococcus), Cleavers (Galium aparine), Dwarf amaranth (Amaranthus macrocarpus), Prickly lettuce (Latuca serriola),

Polymeria (Polymeria pusillia), Capeweed (Arctotheca calendula), Rynchosia (Rynchosia minima), Volunteer sunflowers, Pigweed (Portulaca olraceae), Sowthistle (Sonchus

oleraceus), Variegated thistle (Silybum marianum), Vetch Tares (Vicia villosa), volunteer lupins, Climbing buckwheat/ Black bindweed (Fallopia convolvulus), Saffron

thistle (Carthamus lanatus), New Zealand spinach (Tetragonia tetragonioides), Skeleton weed (Chondrilla juncea), Rough poppy (Papaver hybridum), Erodium/

Common Storks Bill (Erodium cicutarium), Volunteer conventional/ triazine tolerant

canola (Brassica napus), Silverleaf Nightshade (Solanum elaeagnifolium), Bellvine (lpomea plebeian, Bladder Ketmia and Cowvine.

It will be appreciated from the data in the above tables that the efficacy of the formulations of the invention is at least comparable to that of prior art formulations.

However, the formulations of the invention, being more concentrated, are more efficient.

Claims (5)

Claims

1. A liquid storage stable formulation containing florasulam as sole active ingredient, the concentration of florasulam being above 200 g ai/L, wherein the formulation does not include any sodium salt of condensed sulfonated naphthalene.

2. The formulation of claim 1, wherein the florasulam concentration is between about 205 g ai/L and about 500 g ai/L.

.0

3. The formulation of claim 1or 2, wherein used in a tank mix with one or more active ingredients chosen from: 2,4-D, 4-chloro-2-methylpenoxyacetic acid (MCPA), fluroxypyr, dicamba, picloram, bifenox, pinoxaden, flucarbazone, halauxifen-methyl, cloquintocet-mexyl, diflufenican, picolinafen, bromoxynil, paraquat, glyphosate and the effective esters or salts of any of the foregoing. -5

4. The formulation of any one of claims 1 to 3, when used to control one or more weeds chosen from: volunteer lentils (Lens culinaris), volunteer field pea (Pisum sativum arvense), volunteer chickpea (Cicer arietnum), faba bean (Vicia faba), tame vetch (Vicia sativa), spineless burr medic (Medicago polymorpha cv. Cavalier), Indian hedge mustard (Sisymbrium orientale), denseflower fumitory (Fumaria densiflora), volunteer sub-clover (Trifolium subterraneum), wireweed (Polygonum aviculare), Mexican poppy (Argemone Mexicana), small-flowered mallow (Malva parviflora), Bedstraw (Galium tricornutum), Turnip weed (Rapistrum rugosum), Bittercress (Coronopus didymus), Wild radish (Raphanus raphanistrum), Wild turnip (Brassica tournefortii), Shepherd's purse (Bidens Pilosa), Stonecrop (Crassula sieberiana, C. helsii), Annual Ground Cherry, Wild Gooseberry (Physalis spp.), Thornapples (Datura spp.), Apple of Peru (Nicandra physalodes), Bathurst Burr (Xanthium spinosum), Noogoora Burr (Xanthium strumarium), Doublegee/Spiny emex (Emexaustralis), Caltrop/Yellow Vine including (T. maximus and T. micrococcus), Cleavers (Galium aparine), Dwarf amaranth (Amaranthus macrocarpus), Prickly lettuce (Latuca serriola), Polymeria (Polymeria pusillia), Ca peweed (Arctotheca calendula), Rynchosia (Rynchosia minima),

Volunteer sunflowers, Pigweed (Portulaca olraceae), Sowthistle (Sonchus oleraceus),

Variegated thistle (Silybum marianum), Vetch Tares (Vicia villosa), volunteer lupins, Climbing buckwheat/ Black bindweed (Fallopia convolvulus), Saffron thistle

(Carthamus lanatus), New Zealand spinach (Tetragonia tetragonioides), Skeleton weed (Chondrilla juncea), Rough poppy (Papaver hybridum), Erodium/ Common

Storks Bill (Erodium cicutarium), Volunteer conventional/ triazine tolerant canola (Brassica napus), Silverleaf Nightshade (Solanum elaeagnifolium), Bellvine (lpomea

plebeia), Bladder Ketmia and Cowvine.

5. The formulation of any one of claims 1 to 4, when applied to a crop area prior to sowing of the crop or by being incorporated by sowing of the crop, or when applied

post sowing but pre-emergently of the crop or when applied post-emergently of the crop.