AU2021106962B4 - Highly Loaded Clodinafop Formulation - Google Patents

Abstract

The invention concerns highly loaded herbicide formulation containing clodinafop propargyl at a concentration of above 240 g ai/L and a suitable safener. The safener is preferably cloquintocet-mexyl. 5 The formulation may be an emulsifiable concentrate having a single solvent, preferably acetophenone. Optionally, there is more than one solvent. An example is an aromatic hydrocarbon. The formulation is suitable for weed control in a variety of agricultural, commercial and industrial situations. 39

Description

Highly Loaded Clodinafop Formulation

Technical Field

The invention relates to novel clodinafop-propargyl formulations. In particular, the

invention is concerned with a highly loaded formulation containing clodinafop-propargyl formulated with a safener and application of the same to control weeds.

Background Art

Clodinafop-propargyl (prop-2-ynyl (2R)-2-[4-(5-chloro-3- fluoropyridin-2-yl)

oxyphenoxy]propanoate) is an aryloxy phenoxy propionate herbicide. Clodinafop

propargyl has been marketed by several suppliers globally as solo formulations or co formulations (mixtures). These formulations are used for control of weeds in a range of

agricultural, commercial and industrial situations. They have been useful to treat grass weeds in crops of all varieties of wheat e.g., autumn-sown spring wheat, rye, triticale and

durum wheat, amongst other crop varieties and gardens.

Clodinafop-propargyl acts as a systemic herbicide on post-emergent weeds and has been

typically applied to the foliar parts of the weeds. It is absorbed through the leaves and

shoots and is rapidly translocated to and accumulates in the meristematic tissues where it acts to inhibit the enzyme acetyl CoA carboxylase (ACC-ase) and interferes with the

production of fatty acids required for plant growth. It has typically been used to control grass weeds including wild oats, annual rye-grass, rough meadow-grass, green foxtail,

barnyard grass, Persian darnel, volunteer canary seed and paradoxa.

Clodinafop-propargyl has been formulated with safeners and such formulations are

commercially available. Herbicide safeners are chemical compounds used in combination with herbicides to make them "safer" i.e., to reduce the effect of the herbicide on crop

plants, protecting them from herbicidal injury and hence improving selectivity between crop plants vs. weed species being targeted by the herbicide. Safeners are

thought to enhance crop tolerance by inducing the expression of proteins involved in the metabolism of herbicides, thus accelerating their detoxification.

Cloquintocet-mexyl ((RS)-1-methylhexyl (5-chloroquinolin-8-yloxy) acetate) is a quinolinoxycarboxylic acid that has been used as a safener with Clodinafop-propargyl for

crops such as wheat. Existing formulations containing safener are usually emulsifiable concentrate (EC) formulations and typically contain an active ingredient concentration of

clodinafop-propargyl (240 g/L) and cloquintocet-mexyl (60 g/L) (e.g., Mandate).

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.

Generally, the EC is a liquid homogenous formulation commonly applied as an emulsion after dilution in water and is a formulation type used for many agricultural products. ECs

are mixtures of an oil-soluble active ingredient and emulsifying agents dissolved in

organic solvent. The emulsifying agent enables the emulsifiable concentrate to disperse

easily in water, thereby forming a "milky" and homogenous emulsion. Such typical ECs usually require tank agitation to form the emulsion and maintain it during spraying. However, many challenges exist with preparing higher loaded EC formulations, e.g., being

able to load one or more active ingredients at the desired higher concentration that provides the described benefits of higher concentration formulations whilst maintaining a

stable formulation during use. It is also desirable to keep the total solvent concentration in EC formulation low, due to their potential adverse effects on crops, cultivated plants

and the environment generally.

In view of the above described limitations, there remains a need for a highly loaded formulation containing clodinafop-propargyl co-formulated with a safener that addresses

one or more of the described limitations.

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

Until the present invention, highly loaded stable formulations containing clodinafop

propargyl and a safener were not commercially available.

Accordingly, in one aspect of the present invention, there is provided an emulsifiable

concentrate herbicide formulation including:

- clodinafop-propargyl at a concentration of at least 304 g ai/L;

- a safener being cloquintocet-mexyl; and

- either a single aromatic hydrocarbon solvent or a mixture of a first aromatic

hydrocarbon solvent and a second aromatic hydrocarbon solvent;

wherein the total solvent is less than 600 g/L.

It has been found that the ability to increase the maximum loading of clodinafop

propargyl + safener in a formulation at least 304 g ai/L has the advantages over existing formulations prior to this invention of significantly reducing the volume of material to be

formulated, transported and applied by the end user.

In preferred embodiments, the formulation according to the invention contains a

clodinafop-propargyl concentration of at least 305 g ai/L, or at least 310 g ai/L, or at least 315 g ai/L, or at least 320 g ai/L, or at least 330 g ai/L, or at least 335 g ai/L, or at least 340

g ai/L, or at least 345 g ai/L, or at least 350 g ai/L. In some preferred embodiments the

clodinafop-propargyl concentration is about 304 to 336 g ai/L or about 304 g ai/L, or about 320 g ai/L or about 336 g ai/L.

It is contemplated that the safener of the highly loaded formulation of the invention may be any safener, selected by one skilled in the art, that is suitable to enhance crop or

cultivated plant tolerance and/or reduce/inhibit herbicidal injury from clodinafop propargyl. For example, the safener may be selected from a group of compounds that inhibit the enzyme acetyl CoA carboxylase. It will be appreciated that the selection

depends upon the crop or cultivated plant one desires to protect. For example, in treating

a wheat crop, herbicide safeners may be selective for wheat. In this example, the safener may be cloquintocet mexyl, fenchlorazole ethyl or mefenpyr diethyl. Preferably, the safener is cloquintocet mexyl.

In preferred embodiments, the formulation according to the invention contains a safener concentration of at least 65 g ai/L, or at least 70 g ai/L, or at least 75 g ai/L, or at least 80 g

ai/L, or at least 85 g ai/L, or at least 90 g ai/L, or at least 95 g ai/L, or at least 100 g ai/L, or about 65 to 100 g ai/L, or about 70 to 100 g ai/L or about 70 to 90 g ai/L. In especially

preferred embodiments, the safer concentration may be about 72 to 88 g ai/L, or about 72 g ai/L, or about 80 g ai/L or about 88 g ai/L.

It is preferred that the proportion of clodinafop-propargyl to the safener is about 4:1.

It has been found that in developing the highly loaded formulation of the invention the use of aromatic hydrocarbon solvents is advantageous in achieving a low solvent

concentration of the formulation of less than 600 g/L.

Preferably, the formulation of the invention comprises less than 590 g/L, or less than 585

g/L, or less than 580 g/L, or less than 550 g/L or is about 583 g/L, or is about 505 g/L, or is about 500 g/L.

The formulation of the invention comprises a primary solvent and a co-solvent, or a primary solvent alone.

The primary solvent or the co-solvent of the highly loaded formulation of the invention

may be an aromatic hydrocarbon useful for preparing herbicidal formulations. For example, the primary solvent or co-solvent of the highly loaded formulation of the

invention may be chosen from aromatic ketones, or the aromatic hydrocarbons known as

Solvesso@ series. Preferably, the solvent is acetophenone or a mixture of acetophenone

with Solvesso@ 200.

In one embodiment, the highly loaded formulation according to any aspect, embodiment or example of the invention is further co-formulated and/or mixed with one or more

other active ingredients.

In another embodiment, the highly loaded formulation according to any aspect, embodiment or example of the invention is applied to a crop or plant, optionally mixed with one or more other active ingredients, for example as a tank mix. Suitable other active ingredients will be apparent to one skilled in the art.

The highly loaded formulation according to the invention is useful for controlling a large spectrum of weeds that are susceptible to clodinafop-propargyl and/or the one or more

other active ingredients, if present. For example, the weeds include, but are not limited to grasses, including wild oats, annual rye-grass, rough meadow-grass, green foxtail,

barnyard grass, Persian darnel, volunteer canary seed and paradoxa.

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

controlling weeds comprising applying the highly loaded formulation according to the

invention to a crop or plant 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, any species and/or variety of wheat, barley, oats, cereal rye, triticale and corn. In this aspect, the method of

application may be readily selected by one skilled in the art according to the weeds it is desired to control. For example, the crop is any species and/or variety of wheat.

In one example, the application of the highly loaded formulation according to the invention is at a rate of 20 to 290 mL/ha, or about 50 to 210 mL/ha, or about 30 mL/ha, or

about 40 mL/ha, or about 50 mL/ha, or about 60 mL/ha, or about 70 mL/ha, or about 80

mL/ha, or about 90 mL/ha or about 100 mL/ha or about 120 mL/ha.

In one example, the highly loaded formulation according to the invention is applied with

an adjuvant suitable for greater leaf absorption and efficacy. For example, the adjuvant

may be an oil adjuvant such as commercially available under the trademark Hasten.

Other adjuvants may also be suitable. One example is a non-ionic surfactant.

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.

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

include the plural and vice versa.

Example 1: Highly loaded emulsifiable concentrate (EC) formulation of Clodinafop

propargyl with safener.

By way of example, components of a highly loaded emulsifiable concentrate (EC)

formulation of Clodinafop-propargyl with safener, having acetophenone as solvent, identified as AD-AU-1609 EC are set out in Table 1:

Table 1: Components

Content Component Purposein Supplier g/L Formulation 328.54 Clodinafop-propargyl TGAC active ingredient Nutrichem Co., Ltd 97.4 %

81.47 Cloquintocet-mexyl TGAC herbicide safener Nutrichem Co., Ltd 98.2 %

160.00 Soprophor BSU emulsifier Solvay Interox Pty Ltd

40.00 NANSA EVM 70 2/E emulsifier Huntsman Australia Pty Ltd 505.35 Acetophenone solvent Solvay Interox Pty Ltd

0.10 Gensil 2000 antifoam Solvay Interox Pty Ltd

Details of the components of Table 1 are as set out in Table 2:

Table 2: Component Details

Trade Name IUPAC NAME CAS

# Clodinafop-propargyl prop-2-ynyl (2R)-2-[4-(5-chloro-3- 105512-06-9 TGAC 97.4 % fluoropyridin-2-yl)oxyphenoxy]propanoate

Cloquintocet-mexyl TGAC (RS)-1-methylhexyl (5-chloroquinolin-8- 99607-70-2 98.2% yloxy) acetate

Soprophor BSU ethoxylated tristyrylphenol 99734-09-5

NANSA EVM 70 2/E benzenesulfonic acid, 4-C10-14-alkyl 90194-26-6 derivs., calcium salt

Acetophenone 1-phenylethanone 98-86-2

Gensil2000 polydimethylsiloxane 63148-62-9

By way of another example, the components of the highly loaded emulsifiable concentrate (EC) formulation of Clodinafop-propargyl with safener, having acetophenone

with a co-solvent, identified as AD-AU-1715 EC, are set out in Table 3:

Table 3: Components

Content Component Purposein Supplier g/L Formulation 328.54 Clodinafop-propargyl active ingredient Nutrichem Co., Ltd TGAC 97.4 %

81.47 Cloquintocet-mexyl herbicide safener Nutrichem Co., Ltd TGAC 98.2 %

75.00 Soprophor BSU emulsifier Solvay Interox Pty Ltd

25.00 NANSA EVM 70 2/E emulsifier Huntsman Australia Pty Ltd

150.00 Acetophenone solvent Solvay Interox Pty Ltd

432.70 Solvesso 200 (B) co-solvent Australasian Solvents &

Chemicals Company Pty Ltd 0.03 Gensil2000 antifoam Solvay Interox Pty Ltd

Details of the components of Table 3 are as set out in Table 4 (most components being the same as in Table 2 but repeated for convenience):

Table 4: Component Details

Trade Name IUPAC NAME CAS

# Clodinafop-propargyl prop-2-ynyl (2R)-2-[4-(5-chloro-3- 105512-06-9 TGAC 97.4 % fluoropyridin-2-yl)oxyphenoxy]propanoate Cloquintocet-mexyl TGAC (RS)-1-methylhexyl (5-chloroquinolin-8- 99607-70-2 98.2% yloxy) acetate Soprophor BSU ethoxylated tristyrylphenol 99734-09-5

NANSA EVM 70 2/E benzenesulfonic acid, 4-C10-14-alkyl 90194-26-6 derivs., calcium salt Acetophenone 1-phenylethanone 98-86-2

Solvesso 200 (B) solvent naphtha (petroleum), heavy 64742-94-5 aromatic Gensil2000 polydimethylsiloxane 63148-62-9

By way of example, to prepare the highly loaded EC formulation, for example AD-AU 1715 EC or AD-AU-1609 EC, the following method and the sequence of operations were

followed:

1. The required amount of Acetophenone was heated in a water bath at 600 C and maintained at a temperature of 350 C prior to addition. (Acetophenone is a solid at temperatures below 200 C. Heating the solvent is also required for the

dissolution of the active ingredient which is an endothermic process.)

2. The heated Acetophenone was charged into a suitable vessel equipped with a stirrer.

3. Stirring was commenced then Solvesso 200 (B) was added (this step was omitted for AD-AU-1609 EC).

4. Stirring was continued then Cloquintocet-mexyl Technical was added.

5. Stirring was continued for 15-30 mins until complete dissolution was achieved.

6. Whilst stirring was maintained, Clodinafop-propargyl Technical was added.

7. Stirring was continued for 15-30 mins until complete dissolution was achieved.

8. Whilst stirring was maintained, NANSA EVM 70 2/E was added.

9. Soprophor BSU was added and stirring was maintained.

10. Gensil 2000 was added and the formulation was blended for 15-30 mins.

11. Active ingredient content was confirmed by QChem Laboratories Analytical Method QCM110.01

12. Acetophenone and Solvesso 200 (B) (the latter omitted for AD-AU-1609 EC) were adjusted as required.

It has been found that, in developing the highly loaded formulation of the invention while

maintaining a low solvent concentration, the use of Acetophenone was advantageous. The AD-AU-1609 formulation advantageously has the lowest solvent concentration (505

g/L) of any formulation currently on the market with an ai loading of >300g/L. Alternatively, Solvesso 200 may be added as a co-solvent to reduce costs, as in the AD

AU-1715 formulation, which contains 582.7 g/L total solvent.

The resultant highly loaded EC formulations of these examples were analysed as

described further below.

Analysis Methods

The relevant test parameters for emulsifiable concentrate (EC) formulations may be

found in Section 3.2 Table 19 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 Anton Paar DMA 48 Density Meter

The Anton Paar density meter was used to calculate the density of liquids and gases based on an electronic measurement of the frequency of oscillation of a U-tube

containing the sample at a specified temperature.

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

The pH value of a mixture of a sample with water was determined by means of a pH meter and electrode system.

- Emulsion Characteristics CIPAC MT 36.3

An emulsion of known concentration in standard water was prepared. The stability of this

emulsion was then assessed in terms of amounts of free "oil" or "cream" which separates

whilst the emulsion was allowed to stand undisturbed for 24 hrs. The ability of the system to re-emulsify at the end of the 24 hrs period was also determined.

- 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.

- Active Constituent Content - QChem Laboratories Analytical Method QCM

157.01

Clodinafop-propargyl and cloquintocet-mexyl content were determined by gas

chromatography using flame ionization detection and internal standardisation. The method is appropriately validated as per the APVMA Guidelines for the Validation of

Analytical Methods for Active Constituents and Agricultural Products (Revision 1, July 1 2014).

The analysis of highly loaded EC formulation AD-AU-1609 is in Table 5:

Table 5: Analysis of AD-AU-1609

Determination Method Specification Analysis Result

Appearance, Visual Clear amber liquid Clear amber liquid PASS Physical State & Colour

Determination Method Specification Analysis Result

Odour Olfactory Distinctive sweet Distinctive sweet PASS

pH - 1% v/v CIPAC 6.5-7.5 7.25 PASS dilution MT 75.3

Density @ CIPAC 1.110 - 1.120 g/mL 1.115 g/mL @ 200C PASS 20oC MT 3.3.2

Initial Initial emulsification Emulsion CIPAC emulsification uniform Characteristics MT 36.3 uniform PASS Standard 2.0 mL/ 30 mins < 2.OmL 30 mins < 0.05 mL Water D 100 mL cream, trace oil 24 cream, nil oil 24 h re Ambient h re-emulsification emulsification complete Temp. 230C complete 24.5 h < 0.05 mL cream, 24.5h <2.0m niloil cream, trace oil

Initial 38 mL Persistent CIPAC max 60 ml foam After 10 sec 21 mL foam Standard MT 47.2 after 1 min After 1 min OmL PASS Water C 1.0 mL/ After3min OmL 200 mL After 12 min OmL

Low CIPAC Nil separated Nil separated material PASS Temperature MT 39.3 material Stability

Crystallization QChem < 0.010 % 0.005% PASS upon dilution PM 085

Active Clodinafop- Clodinafop-propargyl Ingredient Nominal propargyl 304 - 320 g/L PASS Content 336g/L Cloquintocat-mexyl Cloquintocet-mexyl 80 72.0 - 88.0 g/L g/L

The analysis of highly loaded EC formulation AD-AU-1715 is in Table 6:

Table 6: Analysis of AD-AU-1715

Determination Method Specification Analysis Result

Appearance, Visual Clear amber liquid Clear amber liquid PASS Physical State & Colour

Odour Olfactory Sweet ester odour Sweet ester odour PASS

pH 1% v/v CIPAC 5.50-7.50 6.14 PASS dilution MT 75.3

Density @ 20 oC CIPAC 1.088 - 1.098 g/mL 1.093 g/mL PASS MT 3.2

Initial Initial emulsification Emulsion CIPAC emulsification uniform Characteristics MT 36.3 uniform 30 min < 0.10 mL PASS CIPAC Standard 0.5 mL/ 30 min < 2.0 mL cream, nil oil Water D 100 mL cream, trace oil 2 h < 0.10 mL cream, nil Ambient Temp. 2h <2.0mL oil 23 oC cream, trace oil

24 h re- 24 h re emulsification emulsification complete complete 24.5 h < 2.0 mL 24.5 h < 0.10 mL cream, trace oil cream, nil oil

Initial 29 mL Persistent Foam CIPAC max 60 mL foam After 10 sec 22 mL Standard Water MT 47.2 after 1 min After 1 min 10 mL PASS C 1.0 mL/ After 3 min 7mL 200 mL After 12 min 7mL

Crystallisation PM-085 < 0.01 % Nil PASS upon dilution

Content Nominal 304 - 336 g/L 320 g/L PASS Clodinafop propargyl

Determination Method Specification Analysis Result

Content Nominal 72.0 - 88.0 g/L 80 g/L PASS Cloquintocet mexyl

Initial 38 mL Persistent foam CIPAC max 60 ml foam After 10 sec 21 mL Standard Water MT 47.2 after 1 min After 1 min omL PASS C 1.0 mL/ After 3 min 0mL 200 mL After 12 min 0mL

Low CIPAC Nil separated Nil separated material PASS Temperature MT 39.3 material Stability

Crystallization QChem < 0.010 % 0.005% PASS upon dilution PM 085

Clodinafop- Clodinafop-propargyl

Active Nominal propargyl 304 - 320 g/L PASS Ingredient 336 g/L Content Cloquintocat-mexyl Cloquintocet-mexyl 72.0 - 88.0 g/L 80 g/L

The formulation was suitable for packaging in a level 3 Fluorinated HDPE container with a

screw cap closure.

Stability Testing

By way of example, a sample of the product AD-AU-1715 EC, packaged in Level 3

Fluorinated screw cap HDPE containers, was subjected to stability analysis as described

below.

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:

Two 250 mL specimens were packaged into Level 3 Fluorinated screw-cap, HDPE containers (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 highly loaded EC formulations Clodinafop-propargyl with safener, for example AD-AU-175 EC, were prepared and analysed as described above and the results are as follows:

Table 7: Analysis of Time Zero (Ambient) Sample (Tol)

Determination Method Acceptable Limits Analysis Result

Appearance, Visual Clear amber liquid Clear amber liquid PASS Physical State &

Colour

Odour Olfactory Sweet ester Sweet ester PASS

pH 1% v/v CIPAC MT 4.50- 7.00 5.67 PASS dilution 75.3

Density @ 20 °C Density 1.090 - 1.105 1.098 g/mL PASS Meter g/mL

Anton Paar DMA 48

Initial Initial emulsification

Emulsion CIPAC MT emulsification uniform

Characteristics 36.3 uniform PASS CIPAC Standard 0.5 mL/ 30 mins < 2.0 mL 30 mins 0.05 mL Water D Ambient 100 mL cream, trace oil cream, trace oil Temp. 23 °C 2 hr < 2.0 mL 2hr 0.05mL cream, trace oil cream, trace oil 24 hr re- 24 hr re emulsification emulsification complete complete 24.5 hr < 2.0 mL 24.5 hr 0.10 mL cream, trace oil cream, trace oil

Initial 28 mL

Persistent Foam CIPACIMT max60mLfoam After 10 sec 22 mL Standard Water C 47.2 after 1 min After 1 min 9mL PASS 1.0 mL/ After 3 min 9mL 200 mL After 12 min 9mL

Determination Method Acceptable Limits Analysis Result

Content QCM- 304 - 336 g/L 323 g/L PASS Clodinafop- 157.01 propargyl

Content QCM- 72.0 - 88.0 g/L 78.6 g/L PASS Cloquintocet- 157.01 mexyl

The 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. Table 8 shows the Analysis for AD-AU

1715.

Table 8: Analysis of Accelerated Stability sample TAS1

Determination Method Acceptable Limits Analysis Result

Appearance, Visual Clear amber liquid Clear amber liquid PASS Physical State & Colour

Odour Olfactory Sweet ester Sweet ester PASS

pH 1% v/v CIPAC MT 4.50- 7.00 5.07 PASS dilution 75.3

Density @ 20 Density 1.090 - 1.105 1.099 g/mL PASS 0C Meter g/mL Anton Paar DMA 48

Initial Initial emulsification

Emulsion CIPAC MT emulsification uniform

Characteristics 36.3 uniform PASS CIPAC 0.5 mL/ 100 30 mins < 2.0 mL 30 mins 0.05 mL Standard mL cream, trace oil cream, trace oil Water D 2 hr < 2.0 mL

Determination Method Acceptable Limits Analysis Result

Ambient cream, trace oil 2 hr 0.10 mL Temp. 23 °C 24 hr re- cream, trace oil

emulsification 24 hr re complete emulsification

24.5 hr < 2.0 mL complete cream, trace oil 24.5 hr 0.10 mL cream, trace oil

Initial 28 mL

Persistent CIPAC MT max 60 mL foam After 10 sec 22 mL Foam Standard 47.2 after 1 min After 1 min 9mL PASS Water C 1.0 mL/ 200 After 3 min 9mL mL After 12 min 9mL

Content QCM-157.01 304 - 336 g/L 328 g/L PASS Clodinafop propargyl

Content QCM-157.01 72.0 - 88.0 g/L 78.0 g/L PASS Cloquintocet mexyl

A 100 mL sample of the formulation which has been subjected to accelerated storage conditions as above was then moved to a centrifuge tube and subjected to seeded cold

storage conditions for 7 days at0°C. Table 9 below shows the results for AD-AU-1715. The absence of any separated material indicated that the highly loaded emulsifiable

concentrate (EC) formulation of Clodinafop-propargyl with safener of the invention was cold storage stable.

Table 9: Cold Temperature Stability sample Tcdl

Determination Method Specification Analysis Result

CIPAC MT

Low Temperature 39.3 < 0.05 mL < 0.05 mL separated PASS Stability After 7 separated material days material

Packaging Stability

A sample of the product in a Level 3 Fluorinated screw-cap, HDPE containers 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. The Analysis for AD-AU-1715 EC were as set out in Table 10.

Table 10: Analysis of Packaging Stability in Level 3 Fluorinated HDPE containers

Sample Pre-Storage Weight Post-Storage Weight Weight Difference

Tol 302.04 g 301.97 g 0.07 g

TAS1 296.74g 296.68 g 0.06 g

The highly loaded emulsifiable concentrate (EC) formulation of Clodinafop-propargyl with

safener was suitable for packaging in a Level 3 Fluorinated HDPE container with a screw

cap closure.

In conclusion, the invention has provided a novel highly loaded emulsifiable concentrate

(EC) formulation containing a clodinafop-propargyl + safener at a concentration of above 300 g ai/L, which is higher than currently available formulations and allows for less

volume of material to be formulated, transported and applied by the end-user. The safener in this example is cloquintocet mexyl. The co-solvents for AD-AU-1715 are

Acetophenone and Solvesso 200.

Example 2: Field Tests

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

formulations of clodinafop-propargyl with safener of Example 1, identified as AD-AU-1609 EC and AD-AU-1715 EC.

Field Test 1: Millmerran, QLD

At Millmerran, QLD, a trial was conducted to evaluate AD-AU-1609 and AD-AU-1715

bioequivalence with Mandate© for the control of paradoxa grass (Phalaris paradoxa) and crop safety in wheat. The product details are in Table 11:

Table 11: Products

Product name Active ingredient (ai) + Concentration of Formulation Safener ai+ Safener Clodinafop-Propargyl + 240 g/L + Emulsifiable Mandate Cloquintocet-mexyl 60 g/L concentrate

Clodinafop-Propargyl + 320 /L + Emulsifiable AD-AU-1609 Cloquintocet-mexyl 80 g/L concentrate Clodinafop-Propargyl + 320 g/L + Emulsifiable AD-AU-1715 Cloquintocet-mexyl 80 gL concentrate

Treatments are set out in Table 12:

Table 12: Treatments

Trt Treatment Active Rate (g ai/ha) Rate No. (mL/ha)

1 Untreated

2 Mandate^ Clodinafop + cloquintocet 38.4+9.6 160

3 AD-AU-1609^ Clodinafop + cloquintocet 38.4+9.6 120

4 AD-AU-1715^ Clodinafop + cloquintocet 38.4+9.6 120

^0.5% v/v Hasten Spray Adjuvant included

Treatments used a hand held boom fitted with 4 Hardi MiniDrift Green air induction nozzles, calibrated for an output of 100 L/ha at a ground speed of 5.4 kph and an

operating pressure of 250 kPa. Treatments were arranged in a Randomized Complete Block Design with a plot size of 2 x 10 metres and 4 replicates.

Weed control assessments were conducted at 14, 28 and 97 days after application (DAA). Panicle counts were carried out at 97 DAA. Crop safety assessments were conducted at

14 and 18 DAA. Crop yields were also assessed.

Percentage weed control in wheat is shown in Table 13:

Table 13: % control of paradoxa grass

Trt Treatment Rate 14 DAA 28DAA 41DAA No. (mLpr/ha) 1 Untreated - Oe Of 0i 2 Mandate + Hasten 160 36d 56 cd 70 ef 3 AD-AU-1609 HtADA 6120 40cd 65 abc 80cd +

Hasten 4 AD-AU-1715 120 35 d 64 bcd 78 de +

Hasten

In Table 13 and tables below, DAA = Days after application and treatments separated by

different letters are significantly different at the 5% level of probability.

Paradoxa grass panicle counts at 97 DAA are shown in Table 14:

Table 14: Paradoxa grass panicle counts

Trt Treatment Rate Panicles %

2 No. (mLpr /ha) /M reduction

1 Untreated - 27.1a 0 2 Mandate + Hasten 160 0.9 c 97 3 AD-AU-1609 + Hasten 120 0.1 c 99 4 AD-AU-1715 + Hasten 120 0.0 c 100

Crop safety assessments are summarised in Table 15:

Table 15: %Crop Phytotoxicity

Trt Treatment Rate 14 DAA 28 DAA No. (mLpr /ha) 1 Untreated - 1cd Oa 2 Mandate + Hasten 160 5 ab 0a 3 AD-AU-1609+ Hasten 120 4abc 0a 4 AD-AU-1715+ Hasten 120 4abc 0a

Crop yields are summarised in Table 16:

Table 16: Crop Yield

Trt Treatment Rate Kg/ha % of No. (mLpr/ha) Untreated

1 Untreated - 1347 a 100 2 Mandate + Hasten 160 1465 a 109 3 AD-AU-1609 + Hasten 120 1498 a 111 4 AD-AU-1715 + Hasten 120 1431 a 106

The high load formulation of clodinafop (AD-AU-1609) provided significantly better control (80%) compared to the commercial standard of 160 mL/ha Mandate + Hasten

(70%) when assessed 41 DAA. High load formulations of AD-AU-1609 and AD-AU-1715 provided 99 and 100% reduction in panicle production relative to untreated. Minor and

non-specific phytotoxicity was evident at the initial assessment 14 DAA. No phytotoxicity was evident 28 DAA in any treatment. No significant differences in crop yield were

recorded.

In conclusion, the highly loaded clodinafop formulations AD-AU-1609 and AD-AU-1715

provided improved control of paradoxa grass compared to the commercial standard of

Mandate. The data supports the commercial substitution of high load formulations of

clodinafop of the invention for the standard Mandate© containing 240 g ai/L

Field Test 2: Moonie, QLD

At Moonie, QLD, a trial was conducted to evaluate a high load formulation of clodinafop

propargyl (AD-AU-1609) on weed control compared with stand-alone treatments of Mandate herbicide and crop safety in wheat cv. Gregory.

Treatments are set out in Table 17:

Table 17: Treatments

Trt Treatment Active Rate Rate (product/ha) No. (gac/ha) 1 Untreated

2 Mandate Clodinafop-propargyl 20.4 85 mL Hasten 0.5% v/v 3 Mandate Clodinafop-propargyl 38.4 160 mL Hasten 0.5% v/v 4 AD-AU-1609 Clodinafop-propargyl 20.8 65 mL Hasten 0.5% v/v 5 AD-AU-1609 Clodinafop-propargyl 38.4 120 mL Hasten 0.5% v/v

Treatments used a handheld boom fitted with 4 Hardi MiniDrift Green air induction

nozzles, calibrated for an output of 100 L/ha at a ground speed of 5.4 kph and an operating pressure of 250 kPa. Treatments were arranged in a Randomized Complete

Block Design with a plot size of 2 x 10 metres and 4 replicates.

Weed control assessments were conducted at 15, 35 and 56 days after application (DAA).

Crop safety assessments were conducted at 8 and 15 DAA.

Assessments of control of paradoxa grass (Phalaris paradoxa) is shown in Table 18:

Table 18: % control of paradoxa grass

Trt No. Treatment Rate 15 DAA 35 DAA 56 DAA (product /ha) 1 Untreated - 0 0 0 2 Mandate 85 mL 38 cde 75 bcd 75 de Hasten 0.5% v/v 3 Mandate 160 mL 24 ef 82 bc 84 bcd Hasten 0.5% v/v 4 AD-AU-1609 65 mL 35 c-f 94 ab 90 a-d Hasten 0.5% v/v 5 AD-AU-1609 120 mL 35 c-f 85 bc 70 cde Hasten 0.5% v/v

Wild oats were an incidental weed in this experiment with a number of plots having very few plants present. Higher numbers tended to occur where paradoxa grass numbers

were low.

Wild oat control ratings are shown in Table 19:

Table 19: % Control of wild oats at 15 and 35 DAA

Trt No. Treatment Rate 15 DAA 35 DAA (product/ha) 1 Untreated - 0 0 2 Mandate 85 mL 48 abc 83 abc Hasten 0.5% v/v 3 Mandate 160 mL 44 bcd 95 a Hasten 0.5% v/v 4 AD-AU-1609 65 mL 45 a-d 95 a Hasten 0.5% v/v 5 AD-AU-1609 120 mL 50 ab 95 a Hasten 0.5% v/v

Crop safety assessments are summarised in Table 20:

Table 20: %Crop Phytotoxicity

Trt No. Treatment Rate 7 DAA 15 DAA (product /ha) 1 Untreated - 0 0 2 Mandate 85 mL 3 bc 4a Hasten 0.5% v/v 3 Mandate 160 mL 1 c 4a Hasten 0.5% v/v 4 AD-AU-1609 65 mL 1 c 3a Hasten 0.5% v/v 5 AD-AU-1609 120 mL 4 abc 4a Hasten 0.5% v/v The high load formulation of clodinafop AD-AU-1609 + Hasten provided statistically

similar control of paradoxa grass 56 DAA at 20.4 and 38.4 ga/ha clodinafop compared to equivalent rates of Mandate + Hasten with treatments providing 75-90% control of wild

oats 49 DAA. Commercially acceptable control (95%) of wild oats (Avena sterilis ssp. ludoviciana) was obtained with 160 mL/ha Mandate and 65 and 120 mL/ha AD-AU-1609

35 DAA. No treatment caused unacceptable crop injury. All treatments were safe to wheat cv. Gregory. In addition, no significant differences in phytotoxicity to wheat were

noted comparing Mandate with the high load clodindafop-propargyl formulation AD-AU 1609.

In conclusion, the highly loaded clodinafop formulation AD-AU-1609 provided excellent

control of wild oats and statistically similar control of paradoxa grass compared to the

equivalent rates of Mandate@. The data supports the substitution of high load

formulations of clodinafop of the invention for the current Mandate@ formulation with

equivalent amounts of active constituent applied.

Field Test 3: Moonie, QLD

At Moonie, QLD, a trial was conducted to evaluate a high load formulation of clodinafop propargyl (AD-AU-1609) on weed control compared with stand-alone treatments of

Mandate, Atlantis OD (mesosulfuron) and Axial (pinoxaden), and crop safety in wheat cv. Spitfire. Treatments are set out in Table 21:

Table 21: Treatments

Trt No. Treatment Active Rate Rate (gac/ha) (product /ha) 1 Untreated - - 2 Mandate Clodinafop- 20.4 85 mL Hasten propargyl 0.5% v/v 3 Mandate Clodinafop- 38.4 160 mL Hasten propargyl 0.5% v/v 4 AD-AU-1609 Clodinafop- 20.8 65 mL Hasten popargyl 0.5% v/v 5 AD-AU-1609 Clodinafop- 38.4 120 mL Hasten propargyl 0.5% v/v

Treatments used a handheld boom fitted with 4 Hardi MiniDrift Green air induction nozzles, calibrated for an output of 100 L/ha at a ground speed of 6 kph and an operating

pressure of 250 kPa. Treatments were arranged in a Randomized Complete Block Design with a plot size of 2 x 10 metres and 4 replicates.

Weed control assessments were conducted at 28 and 49 days after application (DAA). Counts of wild oat panicles were taken at 93 DAA. Crop safety assessments were

conducted at 8 DAA and crop biomass reduction relative to untreated control plots were undertaken at 49 DAA.

Assessments of control of wild oats is shown in Table 22:

Table 22: % control of wild oats

Trt No. Treatment Rate 28 DAA 49 DAA (product/ha) 1 Untreated - 0 0 2 Mandate 85 mL 97 a 99 ab Hasten 0.5% v/v 3 Mandate 160 mL 99 a 100 a Hasten 0.5% v/v 4 AD-AU-1609 65 mL 94 a 100 ab Hasten 0.5% v/v 5 AD-AU-1609 120 mL 98 a 100 ab Hasten 0.5% v/v

Wild oat panicle counts are shown in Table 23:

Table 23: % Wild oat panicle count (panicle/0.25m2) [% reduction] 94 DAA Trt No. Treatment Rate Panicle

% (product /ha) /0.25m 2 reduction 1 Untreated - 14.4 a 0 2 Mandate 85 mL 0.2 d 99 Hasten 0.5% v/v 3 Mandate 160 mL 0.1 d 99 Hasten 0.5% v/v 4 AD-AU-1609 65 mL 0.4 cd 97 Hasten 0.5% v/v 5 AD-AU-1609 120 mL 0.0 d 100 Hasten 0.5% v/v

Crop safety assessments are summarised in Table 24:

Table 24: % Crop safety - % Phytotoxicity 8 DAA, % Biomass Reduction 49 DAA

Trt No. Treatment Rate 8 DAA 49 DAA (product/ha) 1 Untreated - 1def 0d 2 Mandate 85 mL 2 def 1 cd Hasten 0.5% v/v 3 Mandate 160 mL 1 ef 1 cd Hasten 0.5% v/v 4 AD-AU-1609 65 mL 0f 1 bcd Hasten 0.5% v/v 5 AD-AU-1609 120 mL 0f 0d Hasten 0.5% v/v

The high load formulation of clodinafop AD-AU-1609 + Hasten provided statistically similar control of wild oats (Avena sterilis ssp. ludoviciana) 28 and 49 DAA at 20.4 and

38.4 ga/ha clodinafop compared to equivalent rates of Mandate + Hasten with all treatments providing 99-100% control of wild oats 49 DAA.

Mandate and AD-AU-1609 provided less than 1% biomass reduction 49 DAA and between 0 and 2% phytotoxicity 8 DAA.

Weed control assessed 49 DAA showed 100% for Mandate and 100% for both rates of AD AU-1609.

In conclusion, the highly loaded clodinafop formulation AD-AU-1609 provided excellent control of wild oats that was statistically equivalent to that provided by the standard of

Mandate@. The data supports the substitution of high load formulations of clodinafop of

the invention for the current Mandate@ formulation with equivalent amounts of active constituent applied.

Field Test 4: Muresk, WA

At Muresk, WA, a trial was conducted to evaluate AD-AU-1609 and AD-AU-1715

bioequivalence with Mandate@ for the control of Annual Ryegrass (Lolium rigidum, ARG) in wheat (Triticum aestivum) and crop safety. Other products were also tested. The

product details are in Table 25:

Table 25: Products

Active ingredient Active ingredient Formulation Product rate (g/L or kg) type

Mandate clodinafop-propargyl, Cloquintocet- 300 EC mexyl

Hasten ethyl and methyl esters of fatty 704 EC acids

AD-AU-1609 clodinafop-propargyl, cloquintocet- 400 EC mexyl

AD-AU-1715 clodinafop-propargyl, cloquintocet- 400 EC mexyl Treatments are set out in Table 26:

Table 26: Treatments

Trt Treatment Form Form Rate Other Other No. Name Conc Unit Rate Unit Rate Rate Unit

1 Untreated Control

2 Mandate 300 g/L 210 ml/ha 63 g ai/ha Hasten 500 ml/100 1 500 ml/1001

3 AD-AU-1609 400 g/L 158 ml/ha 63.2 g ai/ha Hasten 500 ml/100 1 500 ml/1001

4 AD-AU-1715 400 g/L 158 ml/ha 63.2 g ai/ha Hasten 500 ml/100 1 500 ml/1001

Weed counts were conducted the day before application and again at 63 and 83 days after application (DAA). Crop phytotoxicity, crop vigour reduction and visual ARG control

was assessed at 13, 27, 45 and 63 DAA. Yield was also assessed.

Crop Phytotoxicity is shown in Table 27:

Table 27: %Crop Phytotoxicity

Rating Type PHYGEN Rating Unit

% Trt-Eval Interval 13 DAA 27 DAA 45 DAA 63 DAA Trt Treatment Rate No. Name Rate Unit 1 Untreated Control 0.Og 0.Od 0.Od 0.Od 2 Mandate 210 ml/ha 5.Oc 0.8d 0.Od 0.Od Hasten 500 ml/100 1 3 AD-AU-1609 158 ml/ha 3.5cd 0.Od 0.Od 0.Od Hasten 500 ml/100 1 4 AD-AU-1715 158 ml/ha 4.5cd 0.Od 0.Od 0.Od Hasten 500 ml/100 I LSD P=.05 N/A N/A 2.44 N/A Standard Deviation 1.88 2.86t 1.71 0.16t CV 34.86 57.9t 49.97 106.4t Bartlett's X2 21.82 3.778 2.248 5.775 P(Bartlett's X2) 0.009* 0.437 0.523 0.123 Replicate F 0.862 1.292 3.896 1.568 Replicate Prob(F) 0.4676 0.2887 0.0147 0.2102 TreatmentF 76.560 68.982 153.031 18.074 reatment Prob(F) 0.0001 0.0001 0.0001 0.0001

Crop vigour reduction is shown in Table 28:

Table 28: % Crop Vigour

Rating Type VIGOR Rating Unit %

Trt-Eval Interval 13 DAA 27 DAA 45 DAA 63 DAA Trt Treatment Rate No. Name Rate Unit 1 Untreated Control 0.Od 0.Oc 0.Od 0.0 2 Mandate 210 ml/ha 0.Od 0.Oc 0.Od 0.0 Hasten 500 ml/100 1 3 AD-AU-1609 158 ml/ha 0.Od 0.5c 0.Od 0.0 Hasten 500 ml/100 1

Rating Type VIGOR Rating Unit

% Trt-Eval Interval 13 DAA 27 DAA 45 DAA 63 DAA Trt Treatment Rate No. Name Rate Unit 4 AD-AU-1715 158 ml/ha 0.Od 0.Oc 0.Od 0.0 Hasten 500 ml/100 I LSD P=.05 0.59 0.52 N/A Standard Deviation 0.42 0.37 0.04t 0.00 CV 70.18 102.27 68.28t 0.0 Bartlett's X2 3.336 2.595 2.05 0.0 P(Bartlett's X2) 0.503 0.762 0.152 Replicate F 1.320 2.892 1.256 0.000 Replicate Prob(F) 0.2796 0.0456 0.3009 1.0000 TreatmentF 28.776 16.527 59.751 0.000 reatment Prob(F) 0.0001 0.0001 0.0001 1.0000

Annual ryegrass (Lolium rigidum) count per m2 at -1, 63 and 83 DAA is shown in Table 29:

Table 29: Annual ryegrass (Lolium rigidum) count per m2

Rating Type COUNT Rating Unit m2 Trt-Eval Interval -1 DAA 63 DAA 83 DAA Pest Stage Majority 13 31 51 Pest Stage Minimum/Maximum 10 14 20 55 20 71 Trt Treatment Rate No. Name Rate Unit 1 Untreated Control 169- 86a 84a 2 Mandate 210 ml/ha 187- 20f-i 22cde Hasten 500 ml/100 1 3 AD-AU-1609 158 ml/ha 190- 26e-h 19de Hasten 500 ml/100 I 4AD-AU-1715 158 ml/ha 185- 24e-i 17de Hasten 500 ml/100 I LSD P=.05 23.60 17.42 18.02 Standard Deviation 16.57 12.23 12.65 CV 9.15 34.45 40.71 Bartlett's X2 23.76 38.39 39.713 P(Bartlett's X2) 0.069 0.001* 0.001* Replicate F 0.018 2.949 6.457 Replicate Prob(F) 0.9966 0.0428 0.0010 reatmentF 0.762 14.359 10.040 Treatment Prob(F) 0.7094 0.0001 0.0001

*Significant Bartlett's relates to skewness/kurtosis, not variance, and therefore the data was not transformed.

Control of annual ryegrass (Lolium rigidum) control at 13, 27, 45 and 63 DAA is shown in Table 30:

Table 30: % Control of Annual Ryegrass

Rating Type CONTROL Rating Unit ° Trt-Eval Interval 13 DAA 27 DAA 45 DAA 63 DAA Pest Stage Majority 29 21 30 31 Pest Stage Minimum/Maximum 13 29 12 29 13 36 20 55 Trt Treatment Rate No. Name Rate Unit 1 Untreated Control Og Oj Oh Of 2 Mandate 210 ml/ha 43cde 70a-d 60de 63bcd Hasten 500 ml/100 1 3 AD-AU-1609 158 ml/ha 38def 45efg 65b-e 75abc Hasten 500 ml/100 1 4 AD-AU-1715 158 ml/ha 40def 53cde 73a-d 65bcd Hasten 500 ml/100 I LSD P=.05 13.63 21.22 N/A N/A Standard Deviation 9.57 14.90 13.92 19.39 CV 23.29 32.59 28.24 40.71 Bartlett's X2 25.175 7.481 22.548 25.124 P(Bartlett's X2) 0.022* 0.876 0.047* 0.022*

Replicate F 0.381 0.800 1.238 0.413 Replicate Prob(F) 0.7671 0.5006 0.3071 0.7446 reatmentF 18.201 13.316 19.533 10.679 reatment Prob(F) 0.0001 0.0001 0.0001 0.0001

Crop yield t/ha at 133 DAA is shown in Table 31:

Table 31: Crop Yield

Rating Type YIELD Rating Unit T-MET Trt-Eval Interval 133 DAA Trt Treatment Rate No. Name Rate Unit 20 1 Untreated Control 2.129de 2 Mandate 210 ml/ha 2.791ab Hasten 500 ml/100 1 3 AD-AU-1609 158 ml/ha 2.828ab Hasten 500 ml/100 1 4 AD-AU-1715 158 ml/ha 3.059a Hasten 500 ml/100 I LSD P=.05 0.4401 Standard Deviation 0.3090 CV 11.46 Bartlett's X2 4.879 P(Bartlett's X2) 0.993 Replicate F 13.231 Replicate Prob(F) 0.0001 reatmentF 5.304 reatment Prob(F) 0.0001

The high load clodinafop-propargyl formulations AD-AU-1609 and AD-AU-1715 applied at 158 mL/ha (63 gai/ha) performed in a similar manner to Mandate when applied at the

same active rate of 210 mL/ha (63 g.ai/ha). The three products showed no significant

difference in ARG density at 63 or 83 DAA or in visual control at 13, 45 and 63 DAA. Clodinafop-propargyl provided good control of ARG with ARG density 73-80% lower than

the untreated 83 DAA. AD-AU-1715 yielded significantly higher than the untreated and was the highest yielding treatment in the trial at 3.06 t/ha, 0.93 t/ha higher than the

untreated. AD-AU-1609 and Mandate also yielded significantly higher than the untreated and were statistically similar to AD-AU-1715. The increase in yield above the untreated

can be attributed to reduced weed competition.

High load clodinafop-propargyl formulations AD-AU-1609 and AD-AU-1715 performed

similarly to Mandate with statistically equivalent annual ryegrass density at 63 and 83 DAA and visual control at 13, 45 and 63 DAA when applied at the same active rate of 63 g

ai/ha.

Field Test 5: Rand, NSW

At Rand, NSW, a trial was conducted to evaluate a high load formulation of clodinafop

propargyl (AD-AU-1609) on wild oats, spp, Avenafatua, in wheat, cv Gregory, compared with the commercial standard Mandate.

The product details are in Table 32:

Table 32: Products

Active ingredient Active ingredient Form Product rate (g/L or kg) type

Hasten Ethyl and methyl esters of vegetable oil 900 EC and non-ionic surfactants Mandate Clodinafop-propargylCloquintocet-mexyl 300 EC

AD-AU-1609 Clodinafop-propargyl Cloquintocet-mexyl 400 EC

AD-AU-1715 Clodinafop-propargyl Cloquintocet-mexyl 400 EC

Treatments are set out in Table 33:

Table 33: Treatments

Trt Treatment Form Conc. Rate/ Al Rate/ No. Name g/L Rate Unit Rate Unit

1 Untreated Control 2 Mandate 300 EC 65 ml/ha 19.5 g ai/ha Hasten EC 500 ml/100 I 500 ml/1001

3 AD-AU-1609 400 EC 50 ml/ha 20 g ai/ha Hasten EC 500 ml/100 I 500 ml/1001

4 AD-AU-1715 400 EC 50 ml/ha 20 g ai/ha Hasten EC 500 ml/100 I 500 ml/1001

Crop phytotoxicity, crop vigour reduction and visual weed control were assessed at 10, 31

and 42 days after application (DAA). Weed counts were assessed at 0 and 49 DAA.

Wild oat (Avenafatua) plant counts per m2 at 49 DAA and control at 10, 31 and 42 DAA are shown in Table 34:

Table 34: Wild oat plant counts

Rating Type COUNT CONTROL Rating Unit M2

% Trt-Eval Interval 49 DAA 10 DAA 31 DAA 42 DAA Trt Treatment Rate No. Name Rate Unit 1 Untreated Control 84.Oa 0.Of 0.Of 0.Og 2 Mandate 65 ml/ha 4.7ef 8.3a-d 81.7a 90.Oab Hasten 500 ml/100 I 3 AD-AU-1609 50 ml/ha 5.3ef 13.3a 75.Oab 85.Oabc Hasten 500 ml/100 I 4 AD-AU-1715 50 ml/ha 0.0f 11.7ab 80.Oab 91.7a Hasten 500 ml/100 I LSD P=.05 N/A 5.30 10.57 7.94 Standard Deviation 0.36t 3.18 6.36 4.77 CV 53.55t 45.11 11.03 7.29 Bartlett's X2 19.396 3.193 7.94 11.954 P(Bartlett's X2) 0.196 0.999 0.635 0.367

Replicate F 0.112 0.435 0.910 1.572 Replicate Prob(F) 0.8941 0.6510 0.4128 0.2232 Treatment F 8.117 3.547 64.960 138.964 Treatment Prob(F) 0.0001 0.0011 0.0001 0.0001

Crop phytotoxicity and vigour reduction at 10, 31and 42 DAA are shown in Table 35:

Table 35: % Crop Phytotoxicity and Vigour Reduction

Rating Type PHYGEN VIGRED Rating Unit % %

Trt-Eval Interval 10 DAA 31 DAA 42 DAA 10 DAA 31 DAA 42 DAA Trt Treatment Rate No. Name Rate Unit Untreated 1 Control 0.0- 0.0- 0.0- 0.0- 0.0- 0.0

2 Mandate 65 ml/ha 0.0- 0.0- 0.0- 0.0- 0.0- 0.0 Hasten 500 ml/100 I 3 AD-AU-1609 50ml/ha 0.0- 0.0- 0.0- 0.0- 0.0- 0.0 Hasten 500ml/100 I

Rating Type PHYGEN VIGRED Rating Unit %

% Trt-Eval Interval 10 DAA 31 DAA 42 DAA 10 DAA 31 DAA 42 DAA Trt Treatment Rate No. Name Rate Unit 4 AD-AU-1715 50 ml/ha 0.0- 0.0- 0.0- 0.0- 0.0- 0.0 Hasten 500 ml/100 I LSD P=.05 Standard Deviation 0.00 0.00 0.00 0.00 0.00 0.00 CV 0.0 0.0 0.0 0.0 0.0 0.0 Bartlett's X2 0.0 0.0 0.0 0.0 0.0 0.0 P(Bartlett's X2) . .

. Replicate F 0.000 0.000 0.000 0.000 0.000 0.000 Replicate Prob(F) 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 reatmentF 0.000 0.000 0.000 0.000 0.000 0.000 reatment Prob(F) 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 At 31 DAA, Mandate at 65 ml/ha with Hasten gave the highest visual control, however not significantly different from AD-AU-1609 with Hasten or AD-AU-1715 with Hasten.

At 42 DAA, AD-AU-1715 with Hasten gave the highest visual control. However, this was not significantly different to the clodinafop-propargyl formulations Mandate and AD-AU

1609 with Hasten.

At 49 DAA, AD-AU-1715 with Hasten gave the lowest wild oat plant counts. However, this

was not significantly different from the clodinafop-propargyl formulations Mandate and AD-AU-1609 with Hasten.

No crop phytotoxicity or crop vigour reduction was observed in any treatment at any assessment timing.

In conclusion, the clodinafop-propargyl formulation of AD-AU-1715 with Hasten gave high

levels of visual control and similarly the lowest wild oat plant counts, however these were not significantly different to AD-AU-1609 with Hasten and the commercial standard

Mandate with Hasten.

Field Test 7: Thallon, QLD

At Thallon, QLD, a trial was conducted to compare efficacy and crop safety in wheat cv Elmore of a high load formulation of clodinafop-propargyl (AD-AU-1609) on Phalaris

(Phalaris spp) in wheat compared with solo applications of Mandate.

Products details are in Table 36:

Table 36: Products

Content of a.i. Formulation Mode of TreatmentNameActiveIngredient Nominal Type Action

cloquintocet MANDATE mexyl 60 g/L EC Group A HERBICIDE clodinafop- 240 g/L propargyl cloquintocet

AD-AU-1609 clodinap- 3820 g/L EC Group A propargyl

HASTEN SPRAY ethyl and methyl Not ADJUVANT esters of fatty 704 g/L EC applicable acids Group A herbicides inhibit the acetyl-CoA carboxylase (ACCase) enzyme.

Treatments are set out in Table 37:

Table 37: Treatments

Treatment Rate Rate Product/ha g ai/ha 1. Untreated 2. MANDATE + HASTEN 85 mL + 0.5% v/v 20.4 3. MANDATE + HASTEN 160 mL + 0.5% v/v 38.4 4. AD-AU-1609 + HASTEN 65 mL + 0.5% v/v 20.8 5. AD-AU-1609 + HASTEN 120 mL + 0.5% v/v 38.4

Treatments were applied using a hand-held boom incorporating two ALBUZ CVI 110 015

flat fan nozzles per metre. At an application speed of 1.5 m/s and a pressure of 200 kPa, treatments were applied in a total volume of 98 L/ha and a coarse quality.

The trial was established as a randomised complete block design with four replicates.

Detailed assessments were conducted at pre-spray, 10, 21, 36, 49 and 76 (commercial harvest) days after treatment (DAT). These included weed density and control, crop

phytotoxicity, vigour and final grain yield.

No vigour reduction, symptoms of crop phytotoxicity or detrimental effects to grain yield

were observed as a result of the treatments applied in this trial.

Assessment of Phalaris control is shown in Table 38:

Table 38: Mean Phalaris Control (0-100 Scale)

Treatment Rate Rate 10 DAT 21 DAT 36 DAT 49 DAT Product/ha g ai/ha 1. Untreated 0.0 d 0.0 g 0.0 e 0.0 d 2. MANDATE + 85 mL+ 20.4 11.3 abc 30.0 cdef 62.5 cd 82.5 bc HASTEN 0.5% v/v 3. MAN TE + 160 mv/v 38.4 11.3 abc 25.0 def 65.0 bcd 82.5 bc

4. AD-AU-1609 065% v/v 20.8 5.0 cd 25.0 def 55.0 d 85.0 abc

5. AD-AU-1609 120 mv/v 38.4 12.5 abc 30.0 cdef 62.5 cd 86.3 ab

0.045 <0.0 <0.0 <0.00 F Probability 01 01 1 LSD 5 % 8.7 12.6 15.7 10.1

Assessment of Phalaris Counts is shown in Table 39:

Table 39: Mean Phalaris Counts (number/m2) and Grain Yield (t/ha)

Treatment Rate Rate Count49 Yield 76 Product/ha g CountPre DAT DAT ai/ha 1. Untreated 4.3 1.4 1.8 2. MANDATE + 85 mL + 0.5% v/v 20.4 3.0 0.8 2.2 3.ANDTE .MANDATE + 160 mL + 0.5% v/v 38.4 4.0 1.2 2.0 HASTEN

4. U1609+ 65 mL + 0.5% v/v 20.8 4.5 1.8 2.2 HASTEN

Treatment Rate Rate Count 49 Yield 76 Product/ha g DAT DAT ai/ha 5.AD-AU-1609+ 120 mL + 0.5% v/v 38.4 5.8 0.8 2.0 HASTEN F Probability 0.671 0.10 0.191 LSD 5 % ns ns ns

ns = not significant

All treatments were considered safe to wheat cv. Elmore in this trial.

AD-AU-1609 provided very good control of phalaris by 49 DAT. A positive rate response

was observed where AD-AU-1609 was applied, with the higher rate providing better control at all assessment timings.

It will be appreciated from the data in the above tables that the efficacy and safety of the

formulations of the invention are at least comparable to that of prior art formulations. However, the formulations of the invention, being more concentrated, are more efficient,

and expected to be storage stable for at least 2 years.

Claims (5)

1. An emulsifiable concentrate herbicide formulation including:

- clodinafop-propargyl at a concentration of at least 304 g ai/L;

- a safener being cloquintocet-mexyl; and

- either a single aromatic hydrocarbon solvent or a mixture of a first aromatic hydrocarbon solvent and a second aromatic hydrocarbon solvent;

wherein the total solvent is less than 600 g/L.

2. The emulsifiable concentrate herbicide formulation of claim 1, wherein

acetophenone is the single aromatic solvent or the first aromatic solvent.

3. The emulsifiable concentrate herbicide formulation of claim 2, wherein the second aromatic hydrocarbon solvent is solvent naphtha.

4. An emulsifiable concentrate herbicide formulation containing clodinafop-propargyl at a concentration of about 320 g ai/L, a safener being cloquintocet-mexyl at a

concentration of about 80 g ai/L, a solvent being acetophenone and, optionally, a cosolvent being an aromatic hydrocarbon, solvent naphtha, selected from the

Solvesso@ series, wherein the total solvent is less than 600 g/L.

5. A method for controlling weeds comprising applying the emulsifiable concentrate

herbicide formulation of any one of claims 1 to 4 to a crop or plant.