WO2023023812A1

WO2023023812A1 - Highly loaded solo cyclanilide formulations

Info

Publication number: WO2023023812A1
Application number: PCT/AU2022/051040
Authority: WO
Inventors: Andrew HORSFIELD; Peter Vaughan
Original assignee: Adama Australia Pty Ltd
Current assignee: Adama Australia Pty Ltd
Priority date: 2021-08-25
Filing date: 2022-08-25
Publication date: 2023-03-02
Anticipated expiration: 2024-02-25
Also published as: AU2022332715A1; AR126861A1; AU2021221827A1; UY39911A

Abstract

The invention provides a highly loaded stable solo cyclanilide formulation, in which cyclanilide is present in a concentration of at least 250 g ai/L or at least 250 g ai/kg. In some embodiments, the formulation of the invention is particularly useful as a harvest aid in cotton crops.

Description

Highly Loaded Solo Cyclanilide Formulations

Technical Field

The invention relates to cyclanilide formulations. In particular, the invention is concerned with solo cyclanilide formulations which have advantages over prior art formulations.

Background Art

Cyclanilide (l-(2,4-dicholoroanilinocarbonyl) cyclopropanecarboxylic acid) is a plant growth regulator that inhibits polar auxin transport.

Uses for cyclanilide include: application in cotton in a mixture with ethephon to promote boll opening, defoliation and terminal regrowth; application in cotton in a mixture with mepiquat chloride to reduce plant height and ensure a more manageable crop; and use in nurseries and plant production (ornamentals) to inhibit meristematic tissue, reduce apical dominance and increase branching of trees.

Use rates of cyclanilide in cotton typically range between 29 to 225 g ai/ha when applied as a defoliant and 3 to 5 g ai/ha when applied with mepiquat. In ornamentals, cyclanilide is used as a dilute application in 5 to 200 mg a i/L of spray solution.

Formulations of cyclanilide generally include suspension concentrate (SC) co-formulations with either ethephon e.g., ethephon 720 g/L + cyclanilide 90 g/L SC or with mepiquat e.g., mepiquat 67 g/L + cyclanilide 22 g/L SC, for cotton or as a solo SC e.g., cyclanilide 240 g/L SC - formulation for use in ornamentals.

Commercial cyclanilide formulations currently used in cotton are generally low concentration, with less than 100 grams of cyclanilide per litre or kilogram of formulated product and in a fixed ratio with another active ingredient (Al) such as ethephon or mepiquat. Ethephon and mepiquat have high water solubility and can be formulated in efficient, high loaded solo formulations. Co-formulations are usually suspension concentrates, with the cyclanilide in the dispersed phase and the ethephon or mepiquat dissolved in water in the continuous phase. The maximum loading achievable in a cyclanilide co-formulation is lower for both cyclanilide and the partner Al/s due to their different solubilities. Additionally, to apply cyclanilide in a more active and efficient form such as an emulsifiable concentrate is more complicated and costly to co-formulate with ethephon or mepiquat, due to the need for suitable solvents to ensure stability.

Emulsifiable concentrates (EC) of cyclanilide are mentioned in prior art, primarily in mixtures with other active ingredients. The concentration of EC formulations of cyclanilide are not disclosed at high concentrations e.g., at or more than 100 g ai/L.

Cyclanilide co-formulations may reduce the flexibility of uses of both cyclanilide and the partner Al/s. Depending on the situation, the need to add cyclanilide to an application of ethephon or mepiquat may not be required, because a solo (and high loaded) product would be sufficient. For example, the addition of solo cyclanilide as a tank mix option in cotton, under specific situations with either mepiquat earlier in the season or ethephon close to harvest, provides greater flexibility for the end user. Additionally, a solo formulation provides greater opportunity to vary the dose applied, as the use of a fixed ratio in a co-formulation may not always be desirable, as lower rates of the partner Al/s may produce similar efficacy at a given cyclanilide rate.

There is therefore a need to provide a solo cyclanilide formulation that is more highly loaded than previously known and that can be formulated as either a liquid or solid formulation.

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

This invention provides a stable, high loaded solo cyclanilide formulation, wherein cyclanilide is present in a concentration of at least 250 g ai/L or at least 250 g ai/kg. The formulation of the invention may be any agriculturally acceptable formulation type, including a suspension concentrate (SC), an emulsifiable concentrate (EC), a suspo-emulsion (SE), an oil-dispersion (OD), a capsule-suspension (CS), a dispersible concentrate (DC), an oil-in- water emulsion (EW), water soluble granules (SG), water dispersible granules (WG) and emulsifiable granules (EG).

In preferred embodiments, the formulation is an SC or an EC.

In the embodiment where the formulation of the invention is an EC, it may include excipients such as one or more of emulsifiers, solvents and anti-foaming agents. The embodiment is not limited to these.

In the embodiment where the formulation of the invention is an SC, it may include one or more adjuvants and one or more excipients such as one or more of chelating agents, dispersants, wetting agents, adhesive aids, humectants, rheology modifiers and anti-foaming agents. The embodiment is not limited to these.

It has been found that embodiments of the solo formulation of the invention may be advantageous when used for vegetative or fruiting management of cotton, including reducing crop height, reducing internode length, destroying of terminal buds and improving yield and quality.

It has also been found that embodiments of the solo formulation of the invention may be used as a harvest aid for cotton defoliation and boll opening.

Embodiments of a solo formulation of the invention may be used in tank mixtures with tank mix partners such as, but not limited to, mepiquat for vegetative or fruiting management of cotton or with thidiazuron, ethephon, herbicides, ammonium sulfate and other water conditioners and oil adjuvants used as a harvest aids for cotton.

In this use, it is preferred that when the tank mix partner is mepiquat, for a tank mix with high loaded vegetative or fruiting management cotton plant growth regulators, the concentration of mepiquat is 250 g a i/L or more. When solo cyclanilide in a tank mix, with harvest aid plant growth regulator/defoliant products and a tank mix partner is ethephon, it is preferred that the concentration of ethephon is at least 900 g a i/L.

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 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 Cyclanilide EC Formulation

By way of example, an EC formulation containing a cyclanilide concentration of about 250 g/L was prepared. The formulation was designated as AD-AU-1806. The components are as set out in Table 1: Table 1: ADAMA AD-AU-1806 Components

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

Table 2: Component Detail

Method of Preparation.

Note: TERMUL 200 is solid at ambient temperatures and requires melting. 1. Heat the required amount of TERMUL 200 in a water bath at 60 °C and maintain it in a completely molten state prior to addition.

2. Add the HALLCOMID® 1025 into a suitable vessel equipped with a propeller type stirrer. 3. Commence mixing and add TERMUL 200.

4. Continue mixing and add Cyclanilide Technical.

5. Maintain mixing for 45 mins until the Cyclanilide Technical is completely dissolved.

6. Maintain mixing and add NANSA EVM 70/2E.

7. Maintain mixing and add the Gensil 2000. Continue mixing for a further 15 mins.

8. Confirm the active ingredient content by Analytical Method QCM-165.02

9. Adjust with HALLCOMID 1025 as required.

Cold Storage Stability.

After seeded cold storage for 7 days at 0 °C, the product was noted to be cloudy and viscous however no separation or crystallisation was observed. Upon equivalence to ambient temperature, the product returned to a clear liquid without requiring agitation.

Example 2: Highly Loaded Cyclanilide SC Formulation

By way of further example, an SC formulation containing a cyclanilide concentration of about 250 g/L was prepared. The formulation was designated as AD-AU-1807. The components are as set out in Table 3:

Table 3: ADAMA AD-AU-1807 Components

Details of the components are as set out in Table 4:

Table 4: Component Detail

Method of Preparation

Note: Dissolution of the Citric Acid requires the use of water heated to 60 °C.

1. Charge the heated water into a suitable vessel equipped with a high shear saw tooth impeller.

2. Commence dispersing and add Citric Acid. Continue to disperse until complete dissolution.

3. Continue dispersing and add EDTA.

4. Continue dispersing and add Gensil 2030.

5. Continue dispersing and add Kraftsperse 25M.

6. Continue dispersing and add Geropon SDS.

7. Continue dispersing and add Geropon T/36.

8. Continue dispersing and add Agrimer 30.

9. Disperse on high speed for 30 mins until homogeneous and free from agglomerates.

10. Continue dispersing and slowly incorporate the Cyclanilide Technical.

11. Disperse on high speed for 30 mins until homogeneous and free from agglomerates.

12. Bead mill by recirculation through a Dyno®KD Grinding Mill or equivalent until a CIPAC MT 187 measured mean particle size < 3.0 microns and 90 % < 8.0 microns is achieved.

13. Transfer the mill base into a separate vessel and when the level permits commence stirring on slow speed.

14. Prepare a premix of the Propylene Glycol and Rheozan SH.

15. Add the Propylene Glycol; Rheozan SH premix when the Cyclanilide SC mill base has completed milling. Maintain stirring for a further 30 mins to ensure complete hydration. Conduct cyclanilide content analysis as per QCM-165.02 and adjust to with water to meet the specification as required.

Cold Storage Stability.

Following cold temperature storage for 7 days at 0 °C, the product was clear of any crystalline residue when passed through a 75 pm sieve. These formulations were tested successfully in cotton for the following uses: defoliation and boll opening in tank mixtures with ethephon, thidiazuron and oil adjuvants; and for control of fruiting and vegetative growth in a tank mixture with mepiquat.

Example 3: Field Trials

Field Trial 1: Narrabri, New South Wales, Australia, Site 1.

One small plot replicated field trial was conducted to evaluate experimental formulations for cotton defoliation. The trial was conducted near Narrabri in the Lower Namoi Valley region of New South Wales, Australia.

Treatments were applied broadcast over the crop using a handheld boom incorporating TT11015 flat fan nozzles. At an application speed of 1.5 metres per second and a pressure of 300 kPa, treatments were applied in a total volume of 134 L/ha and a medium quality. The trial was established as a complete block design with three replicates. Plot size was 6 metres wide by 10 metres long. The crop was planted in a double skip row configuration, so each plot consisted of 4 planted rows and 2 unplanted skip rows. All assessments were conducted on the centre 2 planted rows.

The treatments and results are in Table 5.

At treatment, the crop was physiologically ready for defoliation. It was 1.2 to 1.5 m in height, with a heavy canopy density and 100% row closure between the adjacent planted rows. The cotton plants also filled 50-60% of the one metre skip row space. With the heavy boll load plants were bent over which increased the canopy density with respect to spray penetration. 39% of bolls were open and natural senescence had commenced, with leaf discolouration and a low proportion of desiccated leaves present. The prevailing temperatures dictated that the defoliation conditions were "cold" according to industry guidelines.

Leaf drop on the untreated cotton continued over the duration of the trial, with the level being 20% at the final assessment made 11 days after application (DAA). At this time 76% of bolls were open. This result reflected the physiological condition of the crop. Detailed assessments were conducted pre-spray and, 4, 7 and 11 DAA. These included counts of fresh and desiccated leaf, and bolls counts on the same marked plants in each plot.

Generally, all treatments increased the presence of desiccated/frozen leaf.

No treatment improved boll opening over that which occurred naturally on the untreated cotton.

Evaluations of AD-AU-1806 have demonstrated that the EC form of cyclanilide is highly active when applied solo and can help defoliate cotton and increase boll opening. Additionally, solo applications of cyclanilide can reduce cotton growth by reducing the number of nodes, crop height and terminal bud destruction. When applied in combination with other cotton defoliants/boll openers such as thidiazuron and ethephon, AD-AU-1806 can improve defoliation and boll opening to a similar or superior level compared with thidiazuron tank mixed with an SC co-formulation of ethephon + cyclanilide.

This is demonstrated in Table 5, where the addition of AD-AU-1806 at a higher cyclanilide dose (60 g ai/ha) with the lower rate of ethephon (238 g ai/ha) provided similar or greater defoliation and boll opening compared with the full ethephon dose (applied either as Escalate 500 + AD-AU-1804 or + AD-AU-1806 + Promote Plus 900).

AD-AU-1807 performed similarly to AD-AU-1806.

Table 5. Evaluation varying combinations of thidiazuron, ethephon and cyclanilide on cotton defoliation and boll opening cv. Sicot 754B3F. Narrabri, New South Wales, Australia

* Applied with D-C Tron oil adjuvant at 1 L/ha

Means within the same column with a letter in common are not significantly different (P>0.05)

Field Trial 2: Brookstead, Queensland, Australia, Site 2 One small plot replicated field trial was conducted between April and May to evaluate experimental formulations for cotton defoliation. The trial was conducted near Brookstead in the Inner Darling Downs region of Queensland, Australia.

Treatments were applied broadcast over the crop using a handheld boom incorporating TT11001 flat fan nozzles. At an application speed of 1 metre per second and a pressure of 200 kPa, treatments were applied in a total volume of 117 L/ha and a medium quality. The trial was established as a complete block design with three replicates. Plot size was 4 metres (rows) wide by 10 metres long.

At treatment, the crop was physiologically ready for defoliation. It was 1.0 to 1.2 m in height, with medium canopy density, 70-90% row closure and 79% bolls open. Natural senescence had commenced with leaf discolouration and a low proportion of desiccated leaves present. Leaf drop on the untreated cotton continued over the duration of the trial, with the level being 38% at the final assessment made 14 days after application (DAA). At this time 88% of bolls were open. This result reflected the physiological condition of the crop.

Detailed assessments were conducted pre-spray and 3, 8 and 14 DAA. These included counts of fresh and desiccated leaf, and bolls counts on the same marked plants in each plot. An assessment of regrowth was made 14 DAA.

The treatments and results are set out in Table 6.

Cyclanilide did not provide defoliation of this cotton crop and did not appear to add to or synergise the defoliant activity of ethephon.

When applied alone, both cyclanilide and ethephon generally enhanced boll opening over that occurring naturally on the untreated cotton. Combinations of AD-AU-1806 or AD-AU-1807 with thidiazuron an ethephon enhanced boll opening.

No differences in regrowth were observed.

Table 6. Evaluation varying combinations of thidiazuron, ethephon and cyclanilide on cotton defoliation and boll opening cv. Sicot 746B3F. Brookstead, Queensland, Australia

* Applied with D-C Tron oil adjuvant at 1 L/ha

Field Trial 3: Macalister, Queensland, Australia, Site 3 A similar trial was carried out at this site. The treatments and results are shown in Table 7, below. Table 7: Evaluation varying combinations of thidiazuron tank mixtures on cotton defoliation and boll opening cv. Sicot 748B3F. Macalister, Queensland, Australia Site 3

Application of AD-AU-1806 in the tank mix with Escalate 500 + Promote improved defoliation and boll opening. The addition of AD-AU-1806 to Escalate 500 + Promote as significantly improved boll opening.

Field Trial 4: Macalister, Queensland, Australia, Site 4

A similar trial was carried out at this site. The treatments and results are shown in Table 8, below. Table 8: Evaluation varying combinations of thidiazuron tank mixtures on cotton defoliation and boll opening cv. Sicot 748B3F. Macalister, Queensland, Australia 2021. Site 4.

* Applied with Hasten adjuvant at 0.5 L/ha

Application of AD-AU-1806 in the tank mix with Escalate 500 + Promote improved defoliation and boll opening compared with Escalate 500 + Promote.

Field Trial 5: Dalby, Queensland, Australia, Site 5

A vegetative growth trial was carried out at this site. The treatments and results are shown in Table 9, below. Table 9. Evaluation of mepiquat and cyclanilide solo and tank mix applications for fruiting and vegetative growth management in cotton cv. Sicot 75BRF. Dalby, Queensland, Australia, Site 5.

WAA = weeks after application

^A 0 = Green and Active Growing Tips, 10 = Dark and Burnt off Tips There were significantly fewer nodes (NAWF) in the cotton treated with the mixture of AD-AU- 1806 plus AD-AU-1815 than in the untreated cotton. By comparison, the solo application of AD- AU-1815 did not significantly reduce the number of nodes.

All treatments had a significant effect on crop growth at 4 WAA. The reduction in crop growth was also seen at 7 WAA with all treatments except AD-AU-1807 applied alone. All other treatments had a similar effect on crop growth, including a solo application of AD-AU-1806.

All treatments had a significant effect on tip burn. Rate effects were seen with AD-AU-1815. AD-AU-1806 applied solo reduced tip burn. The mixtures of AD-AU-1806 and AD-AU-1807 with AD-AU-1815 did not affect the level of tip burn seen compared with AD-AU-1815 applied alone. Field Trial 6: Condamine, Queensland, Australia, Site 6

A similar trial was carried out at this site. The treatments and results are shown in Table 10, below.

Table 10. Evaluation of mepiquat and cyclanilide solo and tank mix applications for fruiting and vegetative growth management in cotton cv. Sicot 75BRF. Condamine, Queensland, Australia 2019. Site 6.

WAA = weeks after application

^A 0 = Green and Active Growing Tips The only treatment effect seen was in the colour grading of the crop tips which may indicate some tip burn off. AD-AU-1806 and AD-AU-1807 applied solo provided a similar level of tip burn to both the AD-AU-1815 and AD-AU-1815 + AD-AU-1806 or AD-AU-1807.

Industrial Applicability

The cyclanilide formulation of the invention provide a high loading of cyclanilide as a solo active ingredient. The formulations enable more flexibility in use, while field trials have shown that tank mixes which include the formulations of the invention are as effective as, or more effective than, prior art tank mixes.

Claims

1. A stable, high loaded solo cyclanilide formulation, wherein cyclanilide is present in a concentration of at least 250 g a i/L or at least 250 g ai/kg.

2. The formulation of claim 1, which is chosen from the type: suspension concentrate (SC), an emulsifiable concentrate (EC), a suspo-emulsion (SE), an oil-dispersion (OD), a capsule-suspension (CS), a dispersible concentrate (DC), an oil-in-water emulsion (EW), water soluble granules (SG), water dispersible granules (WG) and emulsifiable granules (EG).

3. The formulation of claim 2, which is a suspension concentrate (SC) or an emulsifiable concentrate (EC).

4. The formulation of claim 3 which an EC and which includes excipients such as one or more of emulsifiers, solvents and anti-foaming agents.

5. The formulation of claim 3 which an SC and which include one or more adjuvants and one or more excipients such as one or more of chelating agents, dispersants, wetting agents, adhesive aids, humectants, rheology modifiers and anti-foaming agents.

6. The formulation of any one of claims 1 to 5, when combined in a tank mix with mepiquat.

7. The formulation of claim 6, wherein concentration of mepiquat is 250 g a i/L or more.

8. The formulation of any one of claims 1 to 5, when combined in a tank mix with ethephon.

9. The formulation of claim 8, wherein concentration of ethephon is at least 900 g a i/L.

10. The formulation of any one of claims 1 to 5 when combined in a tank mix with one or more of thidiazuron, ethephon, herbicides, ammonium sulfate, water conditioners and oil adjuvants.

11. A method for vegetative or fruiting management of a cotton crop, including applying to the cotton crop the formulation as claimed in any one of claims 1 to 10. A method for aiding for cotton defoliation and/or boll opening in a cotton crop, including applying to the cotton crop the formulation as claimed in any one of claims 1 to 10.