AU2021105774A4 - Pesticide formulation comprising hexythiazox - Google Patents

Abstract

The present invention relates to a pesticide formulation comprising: hexythiazox, a synergist, a surfactant, and optionally a solvent. The invention also relates to a concentrate formulation, an emulsion-in-water formulation, an emulsifiable concentrate, a method of preparing a pesticide formulation of the invention, and a method of preventing and/or controlling a pest infestation in a target area using the pesticide formulation of the invention.

Description

PESTICIDE FORMULATION COMPRISING HEXYTHIAZOX FIELD OF THE INVENTION

This invention relates to a pesticide formulation. In particular, the

present invention relates to a pesticide formulation containing hexythiazox

as an active agent and piperonyl butoxide as a synergist and to methods of

preparing and using said formulation. However, it will be appreciated that

the invention is not limited to this particular field of use.

BACKGROUND TO THE INVENTION

Hexythiazox is a member of the thiazolidine class of insecticides

and acaricides. It is a growth regulator with ovicidal, larvicidal and

nymphicidal activities, which means it is effective against agricultural pests

such as mites and aphids during the egg stage or during the very early

phases of development. Hexythiazox has little to no activity during later

growth phases. The biological target and mechanism of action of

hexythiazox remains unknown, although recent studies suggest activity as

a chitin synthesis inhibitor.

Hexythiazox is commonly obtained and used as a racemic mixture

of two active stereoisomers (4R,5R)-5-(4-chlorophenyl-N-cyclohexyl-4

methyl-2-oxo-1,3-thiazolidine-3-carboxamide and (4S,5S)-5-(4

chlorophenyl-N-cyclohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide.

It is commonly used to control many phytophagous mites such as

Tetranychus, Panonychus, and Eotetranychus spp. It is commonly used to control mites on a wide variety of agriculturally relevant crops. It has a relatively long residual activity when applied to crops.

It is a known problem that acaricides such as hexythiazox, when

administered alone, can display reduced efficacy in populations of target

pests that are treated multiple times, as the populations tend to build

resistance to the active ingredient. One approach to counteract such

resistance is to combine the hexythiazox with another active ingredient.

However, the efficacy of this active ingredient can also diminish over time

and with repeated exposure of the population. Accordingly, it would be

preferable, and a significant advance in the art, to provide an acaricide

composition that does not display reduced efficacy over time or with

repeated exposure to a target population.

Notwithstanding the commercial availability of a range of

hexythiazox formulations, there remains a need for improved hexythiazox

based formulations for use in an agricultural setting that overcomes one or

more of the inherent limitations of commercially available hexythiazox

formulations.

It is an object of the present invention to overcome or ameliorate at

least one of the disadvantages of the prior art, or to provide a useful

alternative.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides a pesticide formulation

comprising: hexythiazox; a synergist; a surfactant; and optionally, a solvent.

In a second aspect, the invention provides a concentrate

formulation comprising:

hexythiazox at a concentration of at least about 50 g/L;

piperonyl butoxide or an analogue or derivative thereof at a

concentration of at least about 10 g/L;

a non-ionic surfactant and an anionic surfactant; and

optionally, a solvent,

wherein the concentrate formulation is an emulsifiable concentrate

or a dispersible concentrate.

In a third aspect, the invention provides an emulsion-in-water

formulation comprising:

hexythiazox at a concentration of at least about 10 g/L;

piperonyl butoxide at a concentration of at least about 10 g/L;

a non-ionic surfactant and an anionic surfactant;

a solvent; and

water.

In one embodiment, hexythiazox is present at a concentration of at

least about 100 g/L of the total weight of the formulation.

In certain embodiments, piperonyl butoxide is present at a

concentration of at least about 100 g/L of the total weight of the formulation.

In some embodiments, the surfactant is present in an amount of at

least about 20 g/L. More particularly, the surfactant is suitably present in

an amount ranging between about 20 g/L to about 150 g/L.

Suitably, the surfactant is selected from the group consisting of an

alkylphenol, a polyoxyalkylene ether, an alkylbenzene sulphonate, an

alkoxylated styryl phenol, a vegetable oil ethoxylate, and any combination

thereof. Preferably, the surfactant is selected from the group consisting of

an alkoxylated alkylphenol, an alkyl polyoxyalkalene ether, calciumC10-16

alkylbenzyl sulphonate, an ethoxylated tristyryl phenol and any

combination thereof.

In one embodiment, the solvent is present in an amount of at least

about 400 g/L. More particularly, the solvent can be present in an amount

ranging between about 400 g/L to about 1000 g/L.

Suitably, the solvent is selected from the group consisting of a

petroleum derivative, a carboxamide, a benzoate, a ketone and any

combination thereof. Preferably, the solvent is selected from the group

consisting of a heavy aromatic solvent naphtha (petroleum), N-methyl

pyrrolidone, methyl benzoate, isophorone, N,N-Dimethylacetamide, N,N

Dimethylformamide, xylene, acetophenone, 1-butylpyrrolidin-2-one and

any combination thereof.

In a fourth aspect, the invention provides an emulsifiable

concentrate, comprising:

hexythiazox at a concentration of at least about 100 g/L; piperonyl butoxide at a concentration of at least about 250 g/L; a non-ionic surfactant comprising a vegetable oil ethoxylate; an anionic surfactant comprising a calcium salt of an alkylbenzene sulfonate; and a solvent comprising methyl benzoate.

In a fifth aspect, the invention provides a method of preparing a

pesticide formulation including the steps of:

(a) combining hexythiazox, a synergist such as piperonyl butoxide,

a surfactant and a solvent, wherein hexythiazox is present at a

concentration of at least 10 g/L; and

(b) mixing the mixture of step (a) to thereby prepare the pesticide

formulation.

Suitably, the pesticide formulation is that of the first aspect, the

concentrate formulation of the second aspect.

The method of the fifth aspect may further comprise the step of

adding water or a water-containing liquid to the mixture before or during

step (b).

In a sixth aspect, the invention provides a pesticide formulation

prepared by the method of the fifth aspect.

In a seventh aspect, the invention provides a method of preventing

and/or controlling a pest infestation in a target area, including the step of

applying a pesticidally effective amount of the pesticide formulation of the

first, third or sixth aspects, or the emulsifiable concentrate formulation of

the second or fourth aspects mixed with water or a water-containing liquid to the target area to thereby prevent and/or control the pest infestation. In some cases, it may be preferable to sequentially, or concurrently apply the inventive pesticide formulation described herein, with the emulsifiable or dispersible concentrate formulations described herein (mixed with water or a water-containing liquid).

In one embodiment, the method of the present aspect further

includes the initial step of mixing the pesticide formulation or the

emulsifiable concentrate formulation with water or the water-containing

liquid.

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

elements, components, integers or steps but may include one or more

unstated further elements, components, integers or steps.

It will be appreciated that the indefinite articles "a" and "an" are not

to be read as singular indefinite articles or as otherwise excluding more

than one or more than a single subject to which the indefinite article refers.

For example, "a" surfactant includes one surfactant, one or more

surfactants and a plurality of surfactants.

DETAILED DESCRIPTION OF THE INVENTION

There is an advantage in providing pesticide products in a liquid

form, either as a concentrate having a relatively high concentration of

active ingredient/s in proportion to other excipients within the formulation, which are stable in concentrate form but readily dispersible in water when diluted for use, or as a stable ready-to-use formulation. By way of example, using a concentrate liquid formulation allows for the treatment of a given volume of produce or target area (e.g., crop, land, commercial or residential premises etc) with a reduced amount of the concentrated pesticide product being used. As such, these concentrated pesticide products afford a broadly better economic outcome together with reduced costs (e.g., reduced non-active ingredients, packaging, handling, storage, freight, labour, regulatory licensing and disposal costs) and less environmental impact (e.g., reduced non-active ingredients, such as solvents, surfactants, preservatives, anti-oxidants, dyes and consumption deterrents, and packaging, such as containers, closures, labels/booklets, pallets and pallet liners/boxes/wrapping).

In addition to the above, providing an emulsifiable concentrate,

emulsion-in-water or dispersible concentrate form of a pesticide product

can further alleviate some or all of the deficiencies of other product

formulations or preparations of the pesticide in question, such as

suspensions or suspoemulsions. To this end, in emulsifiable concentrate

formulations, emulsion-in-water concentrate formulations and dispersible

concentrate formulations, the active ingredient is not in the solid phase but

is dissolved in a liquid phase, and thereby is not subject to settling or

physical phase separation of solid from liquid. Furthermore, the selection

of appropriate solvents and other excipients typically requires careful consideration so as to achieve a passable emulsifiable concentrate, emulsion-in-water or dispersible concentrate formulation.

Notwithstanding the above, in some situations there may also be an

advantage in providing pesticide formulations in 'ready to use' form, such

as an emulsion-in-water formulation that can be applied without any further

dilution or mixing required. This approach may be particularly useful for

active ingredients that have low solubility in water (such as, for instance,

hexythiazox) in order to ensure a safe and efficacious product is used,

rather than relying on proper dilution and mixing of an emulsifiable or

dispersible concentrate by the user. Alternatively, provision of an

emulsion-in-water concentrate formulation may provide the benefits of a

concentrated formulation, whilst also being readily dilutable in water or a

water-containing liquid.

In view of the foregoing, the present invention advantageously

provides an hexythiazox composition or formulation suitable for the

prevention, control or treatment of a range of pest infestations in an

agricultural or horticultural setting. Further, the hexythiazox formulation

may be ready for direct use, or it may be an emulsifiable concentrate, an

emulsion-in-water concentrate or a dispersible concentrate.

Accordingly, in one broad form the invention resides in a pesticide

formulation comprising:

hexythiazox;

a synergist;

a surfactant; and optionally, a solvent.

The term "hexythiazox" refers to a racemic mixture of (4R,5R)-5-(4

chlorophenyl-N-cyclohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide

and (4S,5S)-5-(4-chlorophenyl-N-cyclohexyl-4-methyl-2-oxo-1,3

thiazolidine-3-carboxamide. By "racemic", it is meant that the proportions

of the two stereoisomers are relatively equivalent (i.e., the (R) and (S)

isomers are each approximately equal, or about 50% (R) and about 50%

(S)) although some variation may occur. It is generally appreciated that the

two stereoisomers of hexythiazox are both biologically active as

acaricides. Recent research suggests that the two stereoisomers may

have different biological activity against different species and degradation

characteristics in vivo, however products containing increased or enriched

amounts of one isomer over the other have not yet been developed. It will

be appreciated that use of the term "hexythiazox" herein can refer to one

or both of these stereoisomers, including specific mixtures and/or ratios

thereof, such as racemic mixtures.

The term "synergist" as generally used herein refers to an agent

that synergizes the activity of a pesticide or an insecticide, such as a

thiazolidine like hexythiazox. Synergists may include any that are known in

the art, such as, for instance, piperonyl butoxide (PBO), N-octyl

bicycloheptene dicarboximide (MGK-264), piprotal, propyl isome,

sesamex, sesamolin, sulfoxide and inclusive of any analogues or

derivatives thereof.

It is well established that the use of synergists such as piperonyl

butoxide (PBO) can enhance pesticidal, insecticidal, acaricidal, fungicidal,

molluscicidal and vermicidal activity in vitro and/or in vivo, by, for example,

inhibiting the activity of certain insect metabolic enzymes involved in

detoxification and resistance or by other mechanisms of action (see, e.g.,

Gunning R.V. et al., "Piperonyl Butoxide", pages 215-225, Academic Press

(1998); Benchaoui H.A. et al. J. Pharm. Pharmacol. 1996, 48, 753-759;

Wen Z. et al., Pest. Science 1997, 49, 367-371; Zhao J-Z J. Econ.

Entomol. 2000, 93,1508-1514; Nishiwaki H. et al., J. Pest. Science 2004,

29,1 10-1 16 and the patent applications DE 4426942, EP 617890). By

way of example, piperonyl butoxide is capable of interacting with and

inhibiting phase 1 metabolic enzymes, specifically esterases and

cytochrome P450s.

The addition of a synergist, such as piperonyl butoxide, to the

present pesticide formulation thereby facilitates or potentiates the activity

of hexythiazox and thus advantageously increases the biological

effectiveness thereof, while achieving substantial savings on treatment

cost. It is understood that whilst piperonyl butoxide does not have any

acaricidal activity per se, when used in conjunction with hexythiazox it

does slow the affected pest's capacity to degrade and eliminate (that is,

metabolise) the hexythiazox, thereby amplifying the acaricidal effect of the

applied composition, relative to the same amount of hexythiazox applied

without a synergist such as piperonyl butoxide.

As will be shown herein, it is understood that the emulsifiable

concentrates, emulsions (including emulsion concentrates) and dispersible

concentrates of the present invention are stabilized as a result of the

interaction between the surfactants and solvents present within the

formulations. The surfactant(s) and solvent(s) advantageously and

surprisingly provide an end product that achieves and maintains

homogeneity after manufacture and during storage, even at the equivalent

of up to two years of storage under accelerated conditions, even though

the active constituents are at or near their solubility limits.

The solvent of the pesticide formulations herein may comprise one

solvent, or they may comprise two or more solvents. It is understood that

at least one of the solvents of the formulation dissolves at least the

hexythiazox. In some embodiments, the solvent may also dissolve the

piperonyl butoxide. In some embodiments, the solvent may also comprise

water. Each solvent may be aprotic (i.e., they are unable to donate a

hydrogen atom). Each solvent may be polar or it may be non-polar. In

some embodiments, an emulsion may be formed between a polar solvent

and a non-polar solvent, or between a polar solvent/water mixture and a

non-polar solvent, or between a polar solvent/water mixture and the

synergist, or between water and a non-polar solvent. Formulations of the

present invention that comprise water as the most abundant component by

weight are referred to herein as "emulsion-in-water" formulations.

Emulsion-in-water formulations described herein can comprise

concentrations of hexythiazox suitable for direct use, or they can comprise higher concentrations of hexythiazox suitable for use as a concentrate

(i.e., that requires dilution with water before application).

The surfactant of the pesticide formulations herein may comprise

one surfactant, or they may comprise two or more surfactants. The

surfactant may be an anionic surfactant, or it may be a non-ionic

surfactant. In one embodiment, the surfactant of the present invention may

comprise both an anionic surfactant and a non-ionic surfactant. It is

understood that a surfactant comprises a hydrophobic portion and

hydrophilic portion, whereby an anionic surfactant has a negative charge

on the hydrophilic portion, and a non-ionic surfactant has no formal

charge. Anionic surfactants are regularly obtained as a salt with a metal

cation, such as a sodium, potassium or calcium salt. It is expected that any

surfactant suitable for use in pesticide formulations may be suitable for use

in the formulations of the present invention. Suitable surfactants may be

mixtures. They may be proprietary products.

It is envisaged that the pesticide formulation may take the form of

any liquid formulation known in the art. Exemplary liquid formulations

include oil-miscible liquids, soluble concentrates, ultra-low-volume (ULV)

liquids, dispersible concentrates, emulsifiable concentrates, emulsions

including oil-in-water and micro-emulsions, suspension concentrates and

suspoemulsions.

In one particular embodiment, the pesticide formulation is or

comprises an emulsifiable concentrate.

It will be well understood that the term "emulsifiable concentrate formulation" or "emulsifiable concentrate" (EC) refers to a homogenous liquid formulation or concentrate of an active agent, such as a pesticide, which, on dilution in water or a water-containing liquid, forms an emulsion such as a spontaneous milky white emulsion comprising a dispersed water immiscible phase. By way of example, a water insoluble active ingredient is typically dissolved in a largely water insoluble solvent that upon combination with water or the like and agitation forms an emulsion being a distribution of droplets of the water insoluble solvent and active ingredient amongst a water matrix stabilised by surfactants. The term "emulsion", as used herein, refers to a fine dispersion of minute droplets of one liquid in another in which it is not soluble or miscible and includes microemulsions and macroemulsions.

In another particular embodiment, the pesticide formulation is or

comprises a dispersible concentrate.

It will be well understood that the term "dispersible concentrate

formulation" or "dispersible concentrate" (DC) refers to a homogenous

liquid formulation or concentrate of an active agent, such as a pesticide,

which, on dilution with water or a water-containing liquid, forms a

suspension or a solid dispersion phase within the water-based matrix. In

other words, the active agent, which is in liquid form in the dispersible

concentrate formulation, precipitates on contact with water or water

containing liquids and is dispersed throughout the water-containing phase

as solid particles. By way of example, a water insoluble active ingredient is

typically dissolved in a solvent that may be miscible, or at least partially miscible, in water, which when in contact with water or the like and agitated, the solvent mixes and dissolves into the water phase, leaving the water insoluble active ingredient to contact the water and precipitate as solid particles. The solid active ingredient may be dispersed in the water matrix and suspended by action of the surfactant or surfactants also present in the formulation.

In one aspect, the invention provides a concentrate formulation

comprising:

hexythiazox at a concentration of at least about 50 g/L;

piperonyl butoxide or an analogue or derivative thereof at a

concentration of at least about 10 g/L;

a non-ionic surfactant and/or an anionic surfactant; and

optionally, a solvent,

wherein the concentrate formulation is an emulsifiable concentrate

formulation or a dispersible concentrate formulation.

In a related aspect, the invention provides a method of preparing a

pesticide formulation including the steps of:

(a) combining hexythiazox, a synergist such as piperonyl butoxide

or an analogue or derivative thereof, a surfactant and a solvent, wherein

hexythiazox is present at a concentration of at least 10 g/L; and

(b) mixing the mixture of step (a) to thereby prepare the pesticide

formulation.

In another particular embodiment, the pesticide formulation is an

emulsion-in-water formulation.

By "emulsion-in-water" as used herein, it is meant that the pesticide

formulation is a homogeneous liquid formulation of an active agent, such

as a pesticide. An emulsion-in-water pesticide formulation comprises a

water-immiscible phase in which the active agent or agents are dissolved,

which is dispersed throughout a water-containing matrix. In other words, it

is understood that such formulations comprise an oily organic phase

dispersed as small droplets throughout a bulk water-containing, or

aqueous, phase. An alternate term for an emulsion-in-water formulation

may be an oil-in-water formulation. Such formulations may be in ready-to

use form (i.e., comprising a concentration of hexythiazox low enough for

use without further dilution) or in concentrate form (i.e., comprising a high

enough concentration of hexythiazox that requires dilution before

application).

The statements which follow apply equally to the aforementioned

aspects of the invention.

For the present invention, hexythiazox is suitably present in a

concentration (e.g., at least about 20 g/L) that provides a pesticide

formulation, or in a higher concentration (e.g., such as about 50 g/L) that

provides a concentrated pesticide formulation, such as an emulsifiable

concentrate formulation, an emulsion-in-water concentrate or a dispersible

concentrate, suitable for use in the effective prevention, control and/or

treatment of a pest infestation.

In relation to liquid pesticide formulations, such as emulsifiable

concentrate formulations, emulsion-in-water concentrate formulations or dispersible concentrate formulations, hexythiazox may be present in an amount from about 5 g/L to about 300 g/L or any range therein such as, but not limited to, about 10 g/L to about 275 g/L, about 25 g/L to about 175 g/L, about 50 g/L to about 150 g/L, or about 75 g/L to about 125 g/L of the liquid pesticide formulation. In particular embodiments of the present invention, hexythiazox is present in an amount of about 5, 10, 15, 20, 25,

30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115,

120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185,

190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255,

260, 265, 270, 275, 280, 285, 290, 295, 300 g/L, or any range therein, of

the liquid pesticide formulation. In certain embodiments of the present

invention, hexythiazox is present in an amount of about 20 g/L to about

150 g/L of the liquid pesticide formulation. When the liquid pesticide

formulation is prepared in a ready-to-use emulsion formulation,

hexythiazox may be present in an amount of at least 0.01 g/L, or at a

range between 0.01 g/L and 5 g/L or any range therein, such as but not

limited to between about 0.01 g/L and about 0.5 g/L, or about 0.025 g/L

and about 0.75 g/L, or about 0.5 g/L and about 2.5 g/L. In particular

embodiments of the present invention, the hexythiazox may be present in

an amount of about 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045,

0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1,

1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8,

2.9, 3, 3.1, 3.2, 3..3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5,

4.6,4.7, 4.8, 4.9, 5 g/L or any range therein, of the liquid pesticide

formulation.

Piperonyl butoxide (PBO) is a well-known pesticide synergist that

can enhance the potency of certain pesticides, such as carbamates,

pyrethrins, pyrethroids, diphenyl oxazolines, thiazolidines and rotenone.

An analogue or derivative of piperonyl butoxide may be any as are known

in the art and include, for example, a range of additional side chains and

moieties (e.g., alkyl side chains, alkynyl side chains). Examples of

piperonyl butoxide analogues are described in Panini et al., Pest

Management Science, 2017, v73(2); 371-379 and Philippou et al. (2010),

Imperial College London, PhD Thesis (Thesis:519289), which are

incorporated by reference herein. Suitably, the piperonyl butoxide

analogue or derivative retains at least partly the synergist activity of PBO.

In relation to liquid pesticide formulations, such as emulsion-in

water formulations (including concentrates), emulsifiable concentrate

formulations or dispersible concentrate formulations, the synergist (e.g.,

piperonyl butoxide) may be present in an amount from about 10 g/L to

about 600 g/L or any range therein such as, but not limited to, about 25

g/L to about 300 g/L, about 100 g/L to about 500 g/L, or about 200 g/L to

about 400 g/L of the liquid pesticide formulation. In particular embodiments

of the present invention, piperonyl butoxide is present in an amount of

about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,

100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165,

170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235,

240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305,

310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375,

380, 385, 390, 395, 400, 405, 410, 415, 420, 425, 430, 435, 440, 445,

450, 455, 460, 465, 470, 475, 480, 485, 490, 495, 500, 505, 510, 515,

520, 525, 530, 535, 540, 545, 550, 555, 560, 565, 570, 575, 580, 585,

590, 595, 600 g/L, or any range therein, of the liquid pesticide formulation.

In certain embodiments of the present invention, piperonyl butoxide is

present in an amount of about 15 g/L to about 400 g/L of the liquid

pesticide formulation. In other embodiments, piperonyl butoxide is present

at a concentration of at least about 100 g/L, preferably at least about 200

g/L, more preferably at least about 300 g/L and even more preferably at

least about 400 g/L of the total weight of the formulation. When the liquid

pesticide formulation is prepared in a ready-to-use emulsion formulation,

the synergist (e.g., piperonyl butoxide) may be present in an amount of at

least 0.01 g/L, or at a range between 0.01 g/L and 10 g/L or any range

therein, such as but not limited to between about 0.01 g/L and about 0.5

g/L, or about 0.025 g/L and about 0.75 g/L, or about 0.5 g/L and about 2.5

g/L, or about 1 g/L and about 7.5 g/L. In particular embodiments of the

present invention, the piperonyl butoxide may be present in an amount of

about 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.06, 0.07,

0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4,

1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1,

3.2, 3..3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6,4.7, 4.8,

4.9, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, 8, 8.2,

8.4, 8.6, 8.8, 9, 9.2, 9.4, 9.6, 9.8, 10 g/L or any range therein, of the liquid

pesticide formulation. The ratio of hexythiazox to synergist (e.g., piperonyl

butoxide) may be between about 20:1 and about 1:20 or any range

therein, such as between 10:1 and 1:1, or between 5:1 and 1:5, or

between 2:1 and 1:10, or between 1:1 and 1:15, or it may be about 20:1,

19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1,

5:1, 4:1, 3:1, 2:1, 1.9:1 , 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1,

1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:3, 1:4,

1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18,

1:19, 1:20 or any range therein in the liquid pesticide formulation. In

certain embodiments of the present invention, the ratio of hexythiazox to

synergist (e.g. piperonyl butoxide) may be between 1:10 and 10:1.

The term "solvent" refers to any liquid capable of maintaining

another substance in solution. Examples of solvents include, but are not

limited to, organic solvents and water. It will be apparent to the skilled

artisan that the solvent may include any appropriate solvent as are known

in the art. By way of example, the solvent may comprise a petroleum

derivative or hydrocarbon, such as a heavy aromatic solvent naphtha

(petroleum) (e.g., Recosol 150), a carboxamide having an amidoalkyl

structure (i.e., R-CO-NR'R" structure wherein R, R' and R" are

independent an organic moiety or hydrogen) inclusive of lactams and

pyrrolidones, such as N-substituted pyrrolidones (e.g., N-methyl

pyrrolidone, N-butylpyrrolidone and N-octylpyrrolidone), N,N

dimethylformamide and N,N-dimethylacetamide, an acetic acid C6-C8 branched alkyl ester (including the material sold under the trade name

Exxate 700), a ketone inclusive of cyclic ketones, aromatic ketones,

alkylketones (e.g., isophorone) and arylketones (e.g., acetophenone), a

benzoate, inclusive of alkyl benzoates (e.g., methyl benzoate, ethyl

benzoate), cyclohexanone, acetone, glycols, inclusive of glycol ethers

such as diethylene glycol monomethyl ether (including the material sold

under the trade name Carbitol), ethylene glycol monobutyl ethers

(including the material sold under the trade name Butyl Glysolv), propylene

glycol monomethyl ether (including the material sold under the trade name

Glysolv PM), methanol, ethanol, isopropanol, decanol and paraffins.

In one particular embodiment, the solvent is selected from the

group consisting of a petroleum derivative, a carboxamide, a benzoate, a

ketone and any combination thereof. More particularly, the solvent is

selected from the group consisting of a heavy aromatic hydrocarbon, a

pyrrolidone, an alkyl benzoate, an alkyl ketone, and any combination

thereof. Even more particularly, the solvent is selected from the group

consisting of a heavy aromatic solvent naphtha (petroleum), N-methyl

pyrrolidone, methyl benzoate, isophorone, N,N-Dimethylacetamide, N,N

Dimethylformamide, xylene, acetophenone, 1-butylpyrrolidin-2-one and

any combination thereof. In some embodiments, the solvent may comprise

water.

Such solvents may be used in isolation or in combination as a

mixture of two, three, four, five or more solvents. In one particular

embodiment, the solvent comprises first and second solvents. It will be appreciated that the first and second solvents may be or comprise any solvent known in the art, including water.

For the present aspect, the ratio of the first solvent to the second

solvent may suitably be between 1 and 15 parts of the first solvent, and

between 1 and 15 parts of the second solvent. For example, the ratio may

be about 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1,

2.9:1, 2.8:1, 2.7:1, 2.6:1, 2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.9:1, 1.8:1,

1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1,1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4:,

1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6,

1:2.7, 1:2.8, 1:2.9, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13,

1:14, 1:15 and any range therein. In one preferred embodiment, the ratio

of the first solvent to the second solvent is in the range of about 11:1 to

about 1:11.

In another particular embodiment, the solvent may comprise a first

solvent, a second solvent, and a third solvent. It will be appreciated that

the first, second and third solvents may be or comprise any solvent known

in the art, including water.

For the present aspect, the ratio of the first solvent to the second

solvent to the third solvent may suitably be between 1 and 15 parts of the

first solvent, between 1 and 15 parts of the second solvent, and between

about 1 and 15 parts of the third solvent, for example the ratio may be

between 15:1:1, 1:15:1, 1:1:15, 15:1:15, 15:15:1, 1:15:15, or any range

therein. In one particular embodiment the solvent may be about 7 or 8

parts of the first solvent, about 7 or 8 parts of the second solvent, and about 1 part of the third solvent. Put differently, the ratio of the first solvent to the second solvent to the third solvent may be about 7:7:1, or about

8:8:1, or about 7.5:7.5:1, or any range therein.

For the above aspects, the solvent of a liquid pesticide formulation,

including an emulsifiable concentrate formulation, a dispersible

concentrate formulation and an emulsion-in-water formulation or

concentrate formulation, of the present invention, may be present in an

amount from about 200 g/L to about 1000 g/L or any range therein such

as, but not limited to, about 250 g/L to about 900 g/L, about 350 g/L to

about 650 g/L, or about 400 g/L to about 550 g/L of the liquid pesticide

formulation. In particular embodiments of the present invention, the solvent

is present in an amount of about 200, 210, 220, 230, 240, 250, 260, 270,

280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410,

420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550,

560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690,

700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830,

840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970,

980, 990 and 1000 g/L, or any range therein, of the liquid pesticide

formulation. In certain embodiments of the present invention, the solvent is

present in an amount of at least about 300 g/L of the liquid pesticide

formulation. More particularly, the solvent is present in an amount ranging

between about 425 g/L to about 900 g/L of the liquid pesticide formulation.

Further to the above, the solvent provided herein is preferably an

agriculturally acceptable solvent. The term "agriculturally acceptable solvent" as used herein refers to a solvent that is not unacceptably damaging to a plant and/or its environment, and/or not unsafe to the user or others that may be exposed to the solvent when used as described herein.

As used herein, the term "surfactant" or surface-active agent refers

to an agent, usually an organic chemical compound that is at least partially

amphiphilic (i.e., typically containing a hydrophobic tail group and

hydrophilic polar head group). Given their structure, surfactants are

generally capable of lowering the surface tension (or interfacial tension)

between two liquids or between a liquid and a solid. Further to this, these

properties typically allow solubility of the surfactant in organic solvents as

well as in water, and allow the surfactant to promote solubilization or at

least dispersal of fatty/waxy materials in water and water-containing

solutions. In this regard, a surfactant may act as a detergent, a wetting

agent, an emulsifying agent, a foaming agent, a solubilising agent and/or a

dispersing agent.

Accordingly, in particular embodiments, the surfactant is or

comprises an emulsifying agent. As generally used herein, the term

"emulsifying agent" or "emulsifier" refers to a chemical agent, compound,

or substance capable of producing an emulsion by reducing the interfacial

tension between the two insoluble liquids. In some embodiments, the

surfactant may be a solubilising agent and act as a solvent in the

formulations described herein. In such embodiments, the surfactant may

replace at least a portion of the solvent required to form a stable formulation. In some embodiments, the surfactant may replace a substantial portion of solvent, or it may replace all of the solvent (e.g., the formulation may comprise minimal or no solvent).

Similar to that for the solvents provided above, the surfactant

provided herein is preferably an agriculturally acceptable surfactant. The

term "agriculturally acceptable surfactant" as used herein refers to a

surfactant that is not unacceptably damaging to a plant and/or its

environment, and/or not unsafe to the user or others that may be exposed

to the surfactant when used as described herein.

The surfactant, including one or a plurality of surfactants (e.g., 1, 2,

3, 4, 5 etc. surfactants), are suitably present in a high enough

concentration that allows for the production of an hexythiazox pesticide

formulation, such as an emulsifiable concentrate formulation, or

dispersible concentrate formulation, or an emulsion-in-water formulation

for either direct use or as a concentrate. In this regard, it will be apparent

that an amount of the surfactant of the pesticide formulation can vary, for

example, depending on the specific form of the pesticide formulation (e.g.,

liquid or solid formulation), the particular active ingredient and/or synergist

concentration(s) and the particular surfactant to be included therein.

With regard to liquid pesticide formulations, such as emulsifiable

concentrate formulations, dispersible concentrate formulations or

emulsion-in-water formulations, the surfactant may be present in an

amount from about 20 g/L to about 1000 g/L or any range therein such as,

but not limited to, about 25 g/L to about 200 g/L, or about 30 g/L to about

100 g/L thereof. In particular embodiments of the present invention, the

surfactant is present in an amount of about 20, 25, 30, 35, 40, 45, 50, 55,

60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135,

140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 210,

220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350,

360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490,

500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630,

640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770,

780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910,

920, 930, 940, 950, 960, 970, 980, 990, 1000 g/L, or any range therein, of

the liquid pesticide formulation. In certain embodiments of the present

invention, the surfactant is present in an amount of at least about 20 g/L of

the liquid pesticide formulation. More preferably, the surfactant is present

in an amount ranging between about 20 g/L to about 150 g/L of the liquid

pesticide formulation.

For the present invention, the surfactant is suitably selected from

the group consisting of non-ionic surfactants, anionic surfactants, cationic

surfactants, zwitterionic surfactants, cation-anion composite surfactants

and any combination thereof. Suitable non-ionic surfactants may include

polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers,

polyoxyethylene polyoxypropylene ethers, polyoxyethylene alkyl esters,

polyoxyethylene sorbitan alkyl esters, polyoxyethylene polyoxypropylene

block copolymers, sorbitan alkyl esters, higher fatty acid alkanolamides

and any combination thereof. Suitable cationic surfactants may include alkylamine salts, quaternary ammonium salts and combinations thereof.

Further, suitable anionic surfactants may include naphthalenesulfonic acid

polycondensate, alkenylsulfonate, naphthalenesulfonate, formalin

condensate of a naphthalenesulfonate, formadehyde condensate of an

alkylnaphthalenesulfonate, lignin sulfonate, alkylarylsulfonate, alkylaryl

sulfonate sulfate, polystyrene sulfonate, polycarboxylate,

polyoxyethylenealkyl ether sulfate, polyoxyethylenealkylaryl ether sulfate,

alkylsulfosuccinate, alkyl sulfate, alkyl ether sulfonate, a higher fatty acid

alkali salt and any combination thereof.

In certain preferred embodiments, the one or more surfactants to be

included in the pesticide formulation, including the emulsifiable

concentrate formulation described herein, the dispersible concentrate

described herein, may comprise an anionic surfactant. As generally used

herein, the term "anionic surfactant" refers to a surfactant comprising, as

ionic or ionizable groups, only anionic groups. Such anionic groups may

include, for example, -CO2H, -C2-, -SO3H, -S3-, -OSO3H, -OSO3-,

H2PO3, -HP03-, -P03 2 -, -H2PO2, =HPO2, -HP2-, =P02-, =POH, and =PO

groups. Suitable anionic surfactants may include those hereinbefore

described. Such anionic surfactants may be used alone or in combination

as a mixture of two, three, four, five or more anionic surfactants. In certain

embodiments, the one or more surfactants to be included in the pesticide

formulation, including the emulsifiable concentrate formulation described

herein or the dispersible concentrate formulation described herein or the

emulsion-in-water formulations described herein, may comprise a non ionic surfactant. As generally used herein, the term "non-ionic surfactant" refers to a surfactant that does not contain or comprise an ionic or ionizable group. Suitable non-ionic surfactants may include those hereinbefore described. Such non-ionic surfactants may be used alone or in combination as a mixture of two, three, four, five or more non-ionic surfactants. In certain embodiments, the surfactant may comprise a combination of one or more anionic surfactant and one or more non-ionic surfactant. In such embodiments, the ratio by weight of total anionic surfactant to total non-ionic surfactant may be between about 20:1 and about 1:20, or between 10:1 and 1:10, or between 15:1 and 1:1, or between 5:1 and 1:15, or between 5:1 and 1:5, or between 3:1 and 1:1, or between 2:1 and 1:2, or between 2:1 and 1:3, or about 1:1 or any range therein, or it may be about 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1,

12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2.9:1, 2.8:1, 2.7:1, 2.6:1,

2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1,

1.3:1, 1.2:1, 1.1:1, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4:, 1:1.5, 1:1.6, 1:1.7, 1:1.8,

1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3,

1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17,

1:18, 1:19, 1:20, or any range therein, in the liquid pesticide formulation.

It will be appreciated that the surfactant may be any suitable

surfactant known in the art. Exemplary surfactants include an alkylphenol

alkoxylate (e.g., Termul 200), a polyoxyalkylene ether (e.g., Termul 203),

an alkoxylated oil (e.g., -54 x ethoxylated (e.g., Termul 1285)), an

alkylphenol alkoxylate (e.g., -10 x ethoxylated (e.g., TericNl10)), an alkoxylated alcohol (Alcohol C12 - C15, -23 x ethoxylated (e.g. Teric

12A23); Alcohol C12, -3 x ethoxylated (e.g. Surfactant 12A3)), an

alkoxylated polyaryl phenol (e.g., Tristyryl Phenol, -16 x ethoxylated (e.g.

TSP15)), an alkoxylated block co-polymer (Ethoxylate-Propoxylate

copolymer (e.g. Teric PE64)), an alkylbenzenesulphonate (e.g., Calcium

C10-16 alkylbenzyl sulphonate, branched or linear chain in solvent (e.g.

Ninate 60E, NANSA EVM70/2E, Kemmat HF60)), an alcohol ether

sulphate (e.g. Toximul TANS-5), an alkylamine ethoxylate (e.g. Toximul

TAABS-5), a silicone polymer, inclusive of polysiloxanes (e.g., Evonik

Break-Thru OE 446, Evonik Break-Thru AF 9903, Jiangxi Tiansheng QS

302) and silicone glycol copolymers (e.g., Xiameter OFX-5211), a block

co-polymer (e.g., Teric PE64), an alkoxylated nonylphenol (e.g., Teric

N10), an alkoxylated alcohol (e.g., Teric BL8), an alkyl polyglucoside (e.g.,

Croda AL-2575), an ethoxylate-propoxylate copolymer, a C10-16

alkylbenzenesulphonate (branched or linear in solvent), a branched

alcohol ether sulphate, a tallowamine alkoxylated salt, and a mineral oil

(e.g., Rhodoline DF5888).

In particular embodiments, the surfactant is selected from the group

consisting of an alkylphenol alkoxylate (e.g., Termul 200), a

polyoxyalkylene ether (e.g., Termul 203), an alkylbenzenesulphonate (e.g.,

Ninate 60E, NANSA EVM70/2E, Kemmat HF60), an alkoxylated styryl

phenol (e.g., alkoxylated monostyryl phenols, alkoxylated distyryl phenols,

alkoxylated tristyryl phenols, such as Termul 3150), an alkoxylated oil,

such as an alkoxylated vegetable oil (e.g., Termul 1284 and Termul 1285) and any combination thereof.

More particularly, the surfactant can be selected from the group

consisting of an alkoxylated alkylphenol (e.g., Termul 200), an alkyl

polyoxyalkalene ether (e.g., Termul 203), calcium C10-16 alkylbenzyl

sulphonate (branched or linear chain in solvent) (e.g., Ninate 60E, NANSA

EVM70/2E, Kemmat HF60), an ethoxylated tristyryl phenol (e.g., Termul

3150), and any combination thereof.

In particular embodiments, the ratio by weight of the total amount of

solvent to the total amount of surfactant may be between about 30:1 and

about 1:1, or between about 15:1 and about 3:1, or between about 10:1

and about 5:1 or any range therein, or it may be about 30:1, 29:1, 28:1,

27:1, 26:1, 25:1, 24:1, 23:1, 22:1, 21:1, 20:1, 19:1, 18:1, 17:1, 16:1, 15:1,

14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4.9:1, 4.8:1, 4.7:1,

4.6:1, 4.5:1, 4.4:1, 4.3:1, 4.2:1, 4.1:1, 4:1, 3.9:1, 3.8:1, 3.7:1, 3.6:1, 3.5:1,

3.4:1, 3.3:1. 3.2:1, 3.1:1. 3:1, 2:1, 1:1 or any range therein.

It will be apparent in light of the foregoing that one or more

surfactants may be introduced into the formulation of the invention as a

soluble concentration in a further solvent (e.g., calcium dodecylbenzene

sulfonate in ethyl hexanol) and the latter may equate, for example, to

amounts up to about 10 g/L to about 25 g/L or more of the formulation.

Given the above, it will be appreciated that such amounts of the further

solvent may make little or no contribution to the solvency of hexythiazox

within the formulation of the invention.

One or more additional auxiliary agents, such as adjuvants, preservatives, colouring agents (e.g., dyes), odourants, embittering agents and other deterrents and the like, as are known in the art, can also be added where desired to modify the properties of the pesticide formulation, including the emulsifiable concentrate formulation, emulsion-in-water formulations and the dispersible concentrate formulation as required.

It will be understood that it is desirable for liquid forms of the

pesticide formulation, including the emulsifiable concentrate formulation or

dispersible concentrate formulation or emulsion-in-water formulations,

provided herein to be readily or easily pumped or poured from a storage

vessel. Preferably, the liquid pesticide formulation has a viscosity at room

temperature (i.e., 20 0C) of no more than 2000 cPs (e.g., 1, 5, 10, 20, 30,

40, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200,

1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 cPs and any range

therein), as viscosities above this typically make it difficult or impractical to

pump or pour the formulation. Preferably, the liquid pesticide formulation of

the invention has a viscosity at room temperature of about or less than 400

cPs.

With respect to the aforementioned aspect of preparing pesticide

formulation of hexythiazox, it will be appreciated that this method may be

performed using methods and commercially available equipment, such as

formulation vessels and the like, known in the art.

In another aspect, the invention provides a pesticide formulation

prepared by the method of the aforementioned aspect.

In a further aspect, the invention resides in a method of preventing and/or controlling a pest infestation in a target area, including the step of applying a pesticidally effective amount of the pesticide formulation of the first mentioned aspect or the concentrate formulation of the second mentioned aspect mixed with water or a water-containing liquid, or the emulsion-in-water formulation of the third mentioned aspect, to the target area to thereby prevent and/or control the pest infestation.

Suitably, the method of this aspect further includes the initial step of

mixing the pesticide formulation or the emulsifiable concentrate

hexythiazox formulation, the dispersible concentrate hexythiazox

formulation or the emulsion-in-water concentrate formulation with water or

the water-containing liquid.

The terms "treat", "treating" and "treatment" are broadly intended to

include preventing or controlling a pest infestation. Treating the pest

infestation preferably results in at least maintaining, more preferably

maintaining or reducing, and even more preferably reducing the degree or

severity of the pest infestation in a target area. In one embodiment,

treatment with the pesticide formulation or the emulsifiable concentrate

formulation or the dispersible concentrate or the emulsion-in-water

formulation provided herein is able to substantially eradicate an existing

pest infestation.

As used herein, "preventing" (or "prevent" or "prevention") refers to

a course of action (such as administering an effective amount of the

pesticide formulation or the emulsifiable concentrate formulation described

herein) initiated prior to the onset of a symptom, aspect, or characteristic of the pest infestation (e.g., plant or crop damage) so as to prevent, reduce or delay the symptom, aspect, or characteristic thereof. It is to be understood that such preventing need not be absolute to be beneficial to a plant, crop or the like.

As generally used herein, "control" (or "controlled" or "controlling")

refers to an intervention with the pesticide formulation or the emulsifiable

concentrate formulation or the emulsion-in-water formulations or the

dispersible concentrate formulation that reduces or ameliorates a

symptom, aspect, or characteristic of the pest infestation after it has begun

to develop. The term "ameliorating", with reference to a pest infestation,

refers to any observable beneficial effect thereto as a result of the

administration of the pesticide formulation or the emulsifiable concentrate

formulation or the emulsion-in-water formulations (including in concentrate

form) or the dispersible concentrate formulation. The beneficial effect can

be determined using any methods or standards known to the ordinarily

skilled artisan. Accordingly, these terms are meant to include any lethal

(i.e., pesticidal) or inhibitory (i.e., pestistatic) activities of the pesticide

formulation or the emulsion-in-water formulation (including concentrate

form) or the emulsifiable concentrate formulation or the dispersible

concentrate formulation against a given pest, including those hereinafter

described.

Herein, the terms "target area", "locus" or "space" refer to any area,

location or habitat where the prevention, control and/or eradication of a

pest infestation is needed or expected to be needed.

As used herein, the terms "effective amount", "pesticidally effective

amount" and "insecticidally effective amount" refer to an amount of the

pesticide formulation or the emulsifiable concentrate formulation or

dispersible concentrate formulation that is effective to cause such

prevention, control, and/or eradication of the pest infestation. By way of

example, an effective amount means an amount necessary to produce an

observable pesticidal and/or pestistatic effect on unwanted pests (e.g.,

insects), including the effects of death, growth inhibition, reproduction

inhibition, inhibition of proliferation, and removal, destruction, or otherwise

diminishing the occurrence and activity of these unwanted pests. An

effective amount of the pesticide formulation or the emulsifiable

concentrate formulation or dispersible concentrate formulation or

emulsion-in water formulations of the invention may vary according to the

prevailing conditions such as desired pesticidal and/or pestistatic effect

and duration, weather, target species, habitat, mode of application, and

the like.

In particular embodiments, an effective amount is the amount of the

pesticide formulation or the emulsifiable concentrate formulation or

dispersible concentrate formulation or the emulsion-in-water formulation of

the invention that has an adverse effect (e.g., reproduction inhibition,

knockdown and/or death) on at least 25% (e.g., 25%, 30%, 35%, 40%,

45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% or

any range therein) of the pests treated or contacted therewith, more

preferably at least 50% of the pests treated or contacted therewith, and even more preferably at least 70% or greater of the pests treated or contacted therewith.

The efficacy of the pesticide formulation or the emulsifiable

concentrate formulation or dispersible concentrate formulation or the

emulsion-in-water formulation of the present invention may be monitored

by determining the mortality of or adverse effect upon treated pests (e.g.,

insects). This includes inhibition or modulation of pest growth, inhibition of

pest reproduction by slowing or arresting its proliferation, or complete

destruction/death of the pest. The actual value of an effective amount for

the pesticide formulation or the emulsifiable concentrate formulation or

dispersible concentrate formulation or the emulsion-in-water formulation is

preferably determined by routine screening procedures employed to

evaluate pesticidal activity and efficacy, such as those methods well

known in the art.

With respect to the above, an effective amount of the pesticide

formulation or the emulsion-in-water formulation or the emulsifiable

concentrate formulation or dispersible concentrate formulation described

herein is preferably administered to the target area or locus of the pest

infestation. By way of example, to prevent or control pest-related damage

to a plant or crop, an effective amount of a pesticide formulation (including

an emulsion-in-water formulation) or an emulsifiable concentrate

formulation or dispersible concentrate formulation or emulsion-in-water

concentrate formulation comprising hexythiazox is administered to an area

adjacent and/or including the plant or crop. As such, a pest, and in particular insects, can be readily contacted with an effective amount of the pesticide formulation or the emulsifiable concentrate formulation or dispersible concentrate formulation or emulsion-in-water formulations of the invention.

The pest infestation to be prevented and/or controlled by the

method of the present aspect may be in respect of any pest, and more

particularly any insect or insects, as are well known in the art. Nonlimiting

examples of pests, and in particular insects, that may be treated by

application of the pesticide formulation of the invention include

grasshoppers, locusts, earwigs, crickets, millipedes, slaters, ants, aphids,

flies, mites, beetles, bugs, moths, springtails, caterpillars, loopers,

bruchids, fleas, mealybugs, midges, thrips, weevils, butterflies and

cockroaches, which can cause significant damage to, for example, a wide

range of agricultural and horticultural crops and plants.

In specific embodiments, the pest or pest infestation to be targeted,

prevented and/or controlled by the method for the present aspect are the

phytophagous mites (such as Tetranychus sp. Panonychus sp. and

Eotetranychus sp.). Phytophagous mites attack a wide variety of

horticultural crops, including citrus (for example, lemon, orange, grapefruit

and the like), pome fruit (for example, apples and pears), vegetables,

strawberries, tea and cotton.

The pesticide formulation or the emulsifiable concentrate

formulation or dispersible concentrate formulation or emulsion-in-water

formulations of the invention may be applied to the target crop or plant of interest, to a part thereof (such as the leaf or seed), or to surroundings thereof. Methods and techniques for applying the pesticide formulation or the ready-to-use emulsion-in-water formulation, or the emulsifiable concentrate formulation, the dispersible concentrate formulation or emulsion-in-water concentrate formulation are known in the art and may include, for example, ground or aerial spraying.

In one embodiment, liquid forms of the pesticide formulation or the

emulsifiable concentrate formulation or dispersible concentrate formulation

or the emulsion-in-water concentrate formulation are applied at a rate of

about 250 to 3750 mL per hectare (e.g., about 250mL, 255mL, 260mL,

265mL, 270mL, 275mL, 280mL, 285mL, 290mL, 295mL, 300mL, 305mL,

310mL, 315mL, 320mL, 325mL, 330mL, 335mL, 340mL, 345mL, 350mL,

355mL, 360mL, 365mL, 370mL, 375mL, 380mL, 385mL, 390mL, 395mL,

400mL, 405mL, 410mL, 415mL, 420mL, 425mL, 430mL, 435mL, 440mL,

445mL, 450mL, 455mL, 460mL, 465mL, 470mL, 475mL, 480mL, 485mL,

490mL, 495mL, 500mL, 510mL, 520mL, 530mL, 540mL, 550mL, 560mL,

570mL, 580mL, 590mL, 600mL, 620mL, 640mL, 660mL, 680mL, 700mL,

720mL, 740mL, 760mL, 780mL, 800mL, 820mL, 840mL, 860mL, 880mL,

900mL, 920mL, 940mL, 960mL, 980mL, 1000mL, 1025mL, 1050mL,

1075mL, and 1100mL, 1150mL, 1200mL, 1250mL, 1300mL, 1350mL,

1400mL, 1450mL, 1500mL, 1600mL, 1700mL, 1800mL, 1900mL,

2000mL, 2100mL, 2200mL, 2300mL, 2400mL, 2500mL, 2600mL,

2700mL, 2800mL, 2900mL, 3000mL, 3250mL, 3500mL, 3750mL per

hectare and any range therein) and more preferably at a rate of about

250mL to about 750mL per hectare subsequent to dilution thereof in a

suitable spray liquid. In another embodiment, whereby the liquid pesticide

formulation is in a ready-to-use preparation, the application rate may be

between about 100 and 6000 L/ha (e.g., about 100, 150, 200, 250, 300,

350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000,

1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100,

2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200,

3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300,

4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400,

5500, 5600, 5700, 5800, 5900, 6000 Litres per hectare and any range

therein). Obviously, the amount of the pesticide formulation, the emulsion

in-water formulation or concentrate formulation, the emulsifiable

concentrate or the dispersible concentrate to be applied per hectare will

depend, at least in part, upon the concentration of hexythiazox therein, the

particular pest infestation to be targeted and the type of target crop to

which the formulation is to be applied.

Throughout the specification the aim has been to describe the

preferred embodiments of the invention without limiting the invention to

any one embodiment or specific collection of features. It will therefore be

appreciated by those of skill in the art that, in light of the instant disclosure,

various modifications and changes can be made in the particular

embodiments exemplified without departing from the scope of the present

invention.

With respect to the terms "comprising", "consisting of', and

"consisting essentially of", where one of these three terms is used herein,

the presently disclosed and claimed subject matter may include the use of

either of the other two terms. Thus, in some embodiments not otherwise

explicitly recited, any instance of "comprising" may be replaced by

"consisting of' or, alternatively, by "consisting essentially of'.

In the foregoing paragraphs, various ratios of components have

been disclosed. It will be appreciated that the following ratios of

components can be combined in any disclosed combination, namely:

• the ratio of hexythiazox to piperonyl butoxide may be between

about 20:1 and about 1:20 or any range therein, and

• the ratio of the first solvent to the second solvent (when present)

may be between about 15:1 and about 1:15 or any range therein,

and

• the ratio of the total anionic surfactant to total non-ionic surfactant

may be between about 20:1 and about 1:20 or any range therein,

and

• the ratio by weight of the total amount of solvent (when present) to

the total amount of surfactant may be between about 30:1 and

about 1:30 or any range therein.

Any reference to publications cited in this specification is not an

admission that the disclosures constitute common general knowledge in

Australia.

In order that the invention may be more readily understood and put into practice, one or more preferred embodiments thereof will now be described, by way of example only.

Example 1: Embodiments of Hexythiazox Emulsifiable

Concentrate, Dispersible Concentrate and Emulsion-in-Water

Formulations (Including Concentrate Formulations Thereof)

A number of embodiments of emulsifiable concentrate formulations,

dispersible concentrate formulations, or emulsion-in-water direct use

formulations across a range of hexythiazox concentrations, a range of

overall hexythiazox and piperonyl butoxide concentrations/proportions,

and a range of solvents and surfactants are provided below.

Embodiment 1 - Recipe for an emulsifiable concentrate combining 100g/L

Hexythiazox and 100g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 1 and, as shown in Table 2, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion properties upon dilution in

water prior to application; and 3) physical and chemical stability (including

at cold temperatures of 2 0C for 7 days), at the point of manufacturing and

again after accelerated aging to approximately two years of shelf life.

Composition of embodiment 1 is as follows in Table 1:

Table 1:

Ingredient Role Concentration Hexythiazox Active 101.8g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 99.9g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 108.0g/L (CAS# 51-03-6, Technical material, synergist (yields 101.5g/L 94.0%) Piperonyl butoxide) Tristrylphenol ethoxylate Surfactant 20.4g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium Surfactant 8.8g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 699.1g/L aromatic (to 938g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

Chemical and physical parameters of embodiment 1 is as follows in Table

2:

Table 2:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 100.1g/L 101.1g/L Require 90g/L Hexythiazox 110g/L Assay: 100.4g/L 99.6g/L Require 90g/L Piperonyl butoxide 110g/L pH1% 6.7 6.8 Nominally: 5.5 to 9.5 Persistent foaming 4mL 4mL Require: 60mL foam after 1 min Emulsion characteristics 0.5mL of cream; 3.OmL of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and Re- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h

Embodiment 2 - Recipe for an emulsifiable concentrate combining 1Og/L

Hexythiazox and 100g/L Piperonyl Butoxide. The concentrate is produced as below in Table 3 and, as shown in Table 4, has been determined via assay as having: 1) adequate active ingredient concentration, even after accelerated aging; 2) acceptable emulsion and dispersion properties upon dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 2 is as follows in Table 3:

Table 3:

Ingredient Role Concentration Hexythiazox Active 102.Og/L (CAS# 78587-05-0, Technical material, acaricidal (yields 100.1g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 108.2g/L (CAS# 51-03-6, Technical material, synergist (yields 101.7g/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 12.2g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 3.2g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium Surfactant 13.1g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Acetophenone Solvent 801.g/L (CAS# 98-86-2) (to 1040g/L total)

Chemical and physical parameters of embodiment 2 is as follows in Table

4:

Table 4:

Test As Accelerated manufactured Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 100.6g/L 100.0g/L Require 90g/L Hexythiazoxl110g/L Assay: 101.6g/L 94.4g/L Require 90g/L Piperonyl butoxide 110g/L pH1% 6.8 6.9 Nominally: 5.5 to 9.5 Persistent foaming 2mL 4mL Require: 60mL foam after 1 min Emulsion characteristics 0.2mL of cream; 0.2mL of cream; Require: 2mL cream after 30 min, trace No oil; No oil; of oil after 30 min and complete re- Re- Re emulsion after 24h emulsifies/24h emulsifies/24h

Embodiment 3 - Recipe for an emulsifiable concentrate combining 1OOg/L

Hexythiazox and 250g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 5 and, as shown in Table 6, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 3 is as follows in Table 5:

Table 5:

Ingredient Role Concentration Hexythiazox Active 102.0g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 100.1g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 271.8g/L (CAS# 51-03-6, Technical material, synergist (yields 255.5g/L 94.0%) Piperonyl butoxide) Vegetable oil ethoxylate Surfactant 20.4g/L (CAS# 61791-12-6, e.g. Termul 1285) Alkylbenzenesulfonic acid, calcium salt Surfactant 36.3g/L in 2-ethylhexanol (CAS# 68584-23-6, 104-76-7, e.g. Ninate 60E) Methyl benzoate Solvent 658.6g/L (CAS# 93-58-3) (to 1089g/L total)

Chemical and physical parameters of embodiment 3 is as follows in Table

6:

Table 6:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 101.9g/L 102.7g/L Require 90g/L Hexythiazox 110g/L Assay: 251.9g/L 248.8g/L Require 235g/L Piperonyl butoxide 265g/L pH1% 6.9 6.6 Nominally: 5.5 to 9.5 Persistent foaming 6mL 8mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; ;trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

Embodiment 4 - Recipe for an emulsifiable concentrate combining 1OOg/L

Hexythiazox and 250g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 7 and, as shown in Table 8, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 4 is as follows in Table 7:

Table 7:

Ingredient Role Concentration Hexythiazox Active 102.Og/L (CAS# 78587-05-0, Technical material, acaricidal (yields 100.1g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 272.1g/L (CAS# 51-03-6, Technical material, 94.0%) synergist (yields 255.8g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 97.9g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 57.1g/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 444.9g/L aromatic (to 974g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

Chemical and physical parameters of embodiment 4 is as follows in Table

8:

Table 8:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 104.2g/L 13.9g/L Require 90g/L Hexythiazox 110g/L Assay: 257.4g/L 252.9g/L Require 235g/L ! Piperonyl butoxide 265g/L pH1% 6.6 6.9 Nominally: 5.5 to 9.5 Persistent foaming 6mL 6mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; <trace of oil after 30 min and complete Re- Re-emulsifies/24h re-emulsion after 24h emulsifies/24h

Embodiment 5 - Recipe for an emulsifiable concentrate combining 100g/L

Hexythiazox and 250g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 9 and, as shown in Table 10, has been determined as

having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2 0C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 5 is as follows in Table 9:

Table 9:

Ingredient Role Concentration Hexythiazox Active 102.0g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 100.1g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 271.9g/L (CAS# 51-03-6, Technical material, 94.0%) synergist (yields 255.6g/L Piperonyl butoxide) Vegetable oil ethoxylate Surfactant 20.4g/L (CAS# 61791-12-6, e.g. Termul 1285) Alkylbenzenesulfonic acid, calcium salt in Surfactant 36.2g/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) 1-Butylpyrrolidin-2-one Solvent 96.2g/L (CAS# 3470-98-2, e.g. Genagen NBP) Solvent naphtha (petroleum), heavy Solvent 443.1g/L aromatic (to 970g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

Chemical and physical parameters of embodiment 5 is as follows in Table

10:

Table 10:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 102.4g/L 103.Og/L Require 90g/L Hexythiazox 110g/L Assay: 254.5g/L 256.9g/L Require 235g/L Piperonyl butoxide 265g/L pH1% 6.7 7.0 Nominally: 5.5 to 9.5 Persistent foaming 4mL 4mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; !trace of oil after 30 min and Re-emulsifies/24h Re-emulsifies/24h complete re-emulsion after 24h

Embodiment 6 - Recipe for an emulsifiable concentrate combining 1OOg/L

Hexythiazox and 250g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 11 and, as shown in Table 12, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 6 is as follows in Table 11:

Table 11:

Ingredient Role Concentration Hexythiazox Active 102.2g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 100.3g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 272.Og/L (CAS# 51-03-6, Technical material, 94.0%) synergist (yields 255.7g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 24.3g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 8.3g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in 2- Surfactant 24.5g/L ethylhexanol (CAS# 68584-23-6, 104-76-7, e.g. Ninate 60E) Xylenes Solvent 526.9g/L (CAS# 1330-20-7) (to 958g/L total)

Chemical and physical parameters of embodiment 6 is as follows in Table

12:

Table 12:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 103.3g/L 102.6g/L Require 90g/L Hexythiazox 110g/L Assay: 250.0g/L 249.4g/L Require 235g/L Piperonyl butoxide 265g/L pH1% 6.8 7.1 Nominally: 5.5 to 9.5 Persistent foaming 4mL 4mL Require: 60mL foam after 1 min Emulsion characteristics 0.5mLof cream; 0.5mLof cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re re-emulsion after 24h emulsifies/24h

Embodiment 7 - Recipe for an emulsifiable concentrate combining 70g/L

Hexythiazox and 350g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 13 and, as shown in Table 14, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 7 is as follows in Table 13:

Table 13:

Ingredient Role Concentration Hexythiazox Active 71.2g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 69.8g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 380.0g/L (CAS# 51-03-6, Technical material, synergist (yields 357.2g/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 21.8g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 8.Og/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 26.4g/L 2-ethylhexanol (CAS# 68584-23-6, 104 76-7, e.g. Ninate 60E) Xylenes Solvent 460.1g/L (CAS# 1330-20-7) (to 967g/L total)

Chemical and physical parameters of embodiment 7 is as follows in Table

14:

Table 14:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 72.7g/L 72.7g/L Require 63g/L Hexythiazox 77g/L Assay: 355.2g/L 359.5g/L Require 333g/L Piperonyl butoxide 367g/L pH1% 6.6 6.7 Nominally: 5.5 to 9.5 Persistent foaming 4mL 4mL Require: 560mL foam after 1 min Emulsion characteristics 1.0mL of cream; 1.OmL of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

Embodiment 8 - Recipe for an emulsifiable concentrate combining 50g/L

Hexythiazox and 400g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 15 and, as shown in Table 16, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 8 is as follows in Table 15:

Table 15:

Ingredient Role Concentration Hexythiazox Active 51.Og/L (CAS# 78587-05-0, Technical material, acaricidal (yields 50.0g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 435.0g/L (CAS# 51-03-6, Technical material, synergist (yields 408.9g/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 12.5g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 8.Og/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium Surfactant 36.2g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 437.2g/L aromatic (to 980g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

Chemical and physical parameters of embodiment 8 is as follows in Table

16:

Table 16:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 52.2g/L 52.3g/L Require 45g/L Hexythiazox 55g/L Assay: 406.Og/L 410.6g/L Require 380g/L Piperonyl butoxide 420g/L pH1% 6.7 7.1 Nominally: 5.5 to 9.5 Persistent foaming 2mL 2mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; 0.3mL of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re- Re-emulsifies/24h re-emulsion after 24h emulsifies/24h

Embodiment 9 - Recipe for an emulsifiable concentrate combining 150g/L

Hexythiazox and 15g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 17 and, as shown in Table 18, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition for embodiment 8 is as follows in Table 17:

Table 17:

Ingredient Role Concentration Hexythiazox Active 153.0g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 150.1g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 16.3g/L (CAS# 51-03-6, Technical material, synergist (yields 15.3g/L 94.0%) Piperonyl butoxide) Tristrylphenol ethoxylate Surfactant 32.5g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in Surfactant 32.6g/L 2-ethylhexanol (CAS# 68584-23-6, 104 76-7, e.g. Ninate 60E) Isophorone Solvent 736.7g/L (CAS# 78-59-1) (to 971g/L total)

Chemical and physical parameters of embodiment 8 is as follows in Table

18:

Table 18:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 149.1g/L 149.4g/L Require 141g/L Hexythiazox 159g/L Assay: 15.3g/L 14.7g/L Require 12.8g/L Piperonyl butoxide 17.2g/L pH1% 6.8 7.1 Nominally: 5.5 to 9.5 Persistent foaming 2mL 4mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

Embodiment 10 - Recipe for an emulsifiable concentrate combining

150g/L Hexythiazox and 15g/L Piperonyl Butoxide. The concentrate is

produced as below in Table 19 and, as shown in Table 20, has been

determined via assay as having: 1) adequate active ingredient

concentration, even after accelerated aging; 2) acceptable emulsion and

dispersion properties upon dilution in water prior to application; and 3)

physical and chemical stability (including at cold temperatures of 20C for 7

days), at the point of manufacturing and again after accelerated aging to

approximate two years of shelf life.

Composition of embodiment 10 is as follows in Table 19:

Table 19:

Ingredient Role Concentration Hexythiazox Active acaricidal 153.2g/L (CAS# 78587-05-0, Technical material, ingredient (yields 150.3g/L 98.1%) Hexythiazox) Piperonyl butoxide Acaricidal 16.4g/L (CAS# 51-03-6, Technical material, synergist (yields 15.4g/L 94.0%) Piperonyl butoxide) Tristrylphenol ethoxylate Surfactant 32.2g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in Surfactant 32.1g/L 2-ethylhexanol (CAS# 68584-23-6, 104 76-7, e.g. Ninate 60E) N-methyl-2-pyrrolidone Solvent 70.1g/L (CAS# 872-50-4) Acetophenone Solvent 751.5g/L (CAS# 98-86-2) (to 1055g/L total)

Chemical and physical parameters of embodiment 10 is as follows in

Table 20:

Table 20:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 150.1g/L 149.8g/L Require 141g/L Hexythiazox 159g/L Assay: 15.1g/L 13.8g/L Require 12.8g/L Piperonyl butoxide 17.2g/L pH1% 6.8 7.0 Nominally: 5.5 to 9.5 Persistent foaming 6mL 6mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; Trace of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re re-emulsion after 24h emulsifies/24h

Embodiment 11 - Recipe for an emulsifiable concentrate combining

150g/L Hexythiazox and 15g/L Piperonyl Butoxide. The concentrate is

produced as below in Table 21 and, as shown in Table 22, has been

determined via assay as having: 1) adequate active ingredient

concentration, even after accelerated aging; 2) acceptable emulsion and

dispersion properties upon dilution in water prior to application; and 3)

physical and chemical stability (including at cold temperatures of 20C for 7

days), at the point of manufacturing and again after accelerated aging to

approximate two years of shelf life.

Composition of embodiment 11 is as follows in Table 21:

Table 21:

Ingredient Role Concentration Hexythiazox Active acaricidal 152.9g/L (CAS# 78587-05-0, Technical material, ingredient (yields 150.0g/L 98.1%) Hexythiazox) Piperonyl butoxide Acaricidal 16.5g/L (CAS# 51-03-6, Technical material, synergist (yields 15.5g/L 94.0%) Piperonyl butoxide) Tristrylphenol ethoxylate Surfactant 32.9g/L (CAS# 99734-09-5, e.g. Termul 3150) Tristyrylphenol ethoxylate phosphate Surfactant 32.0g/L ester (CAS# Proprietary, e.g. Soprophor FLK) N-methyl-2-pyrrolidone Solvent 69.9g/L (CAS# 872-50-4) Acetophenone Solvent 753.7g/L (CAS# 98-86-2) (to 1058g/L total)

Chemical and physical parameters of embodiment 11 is as follows in

Table 22:

Table 22:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 147.5g/L 147.5g/L Require 141g/L Hexythiazox 159g/L Assay: 15.3g/L 15.4g/L Require 12.8g/L Piperonyl butoxide 17.2g/L pH1% 6.8 7.0 Nominally: 5.5 to 9.5 Persistent foaming 4mL 4mL Require: 60mL foam after 1 min Emulsion characteristics 0.5mL of cream; 1.5mL of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re- Re-emulsifies/24h re-emulsion after 24h emulsifies/24h

Embodiment 12 - Recipe for a dispersible concentrate combining 100g/L

Hexythiazox and 100g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 23 and, as shown in Table 24, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2 0C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 12 is as follows in Table 23:

Table 23:

Ingredient Role Concentration Hexythiazox Active 102.2g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 100.3g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 108.4g/L (CAS# 51-03-6, Technical material, synergist (yields 101.9g/L 94.0%) Piperonyl butoxide) D-Glucopyranose, oligomeric, decyl Surfactant 10.1g/L octyl glycosides and hexylene glycol surfactant blend (CAS# 68515-73-1 in 107-41-5, e.g. Croda Atlox 4919) Tristrylphenol ethoxylate Surfactant 27.0g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium Surfactant 23.6g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) N,N-Dimethylformamide Solvent 333.7g/L (CAS# 68-12-2) N-methyl-2-pyrrolidone Solvent 46.1g/L (CAS# 872-50-4) N,N-Dimethylacetamide Solvent 344.0g/L (CAS# 127-19-5) (to 992g/L total)

Chemical and physical parameters of embodiment 12 is as follows in

Table 24:

Table 24:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 100.3g/L 101.0g/L Require 90g/L Hexythiazox 110g/L Assay: 101.4g/L 103.0g/L Require 90g/L ! Piperonyl butoxide 110g/L pH1% 6.8 6.9 Nominally: 5.5 to 9.5 Persistent foaming 2mL 4mL Require: 60mL foam after 1 min Dispersion stability 0.2mL of cream; 0.2mL of cream; Require: 2mL cream after 30 min, No oil; No oil; <trace of oil after 30 min and Re-emulsifies/24h Re-emulsifies/24h complete re-emulsion after 24h

Embodiment 13 - Recipe for a dispersible concentrate combining 50g/L

Hexythiazox and 125g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 25 and, as shown in Table 26, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2 0C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 13 is as follows in Table 25:

Table 25:

Ingredient Role Concentration Hexythiazox Active 50.7g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 49.7g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 135.9g/L (CAS# 51-03-6, Technical material, 94.0%) synergist (yields 127.7 g/L Piperonyl butoxide) Tristrylphenol ethoxylate Surfactant 32.6g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in 2- Surfactant 32.3g/L ethylhexanol (CAS# 68584-23-6, 104-76-7, e.g. Ninate 60E) Cyclohexanone Solvent 728.1g/L (CAS# 108-94-1) (to 980g/L total)

Chemical and physical parameters of embodiment 13 is as follows in

Table 26:

Table 26:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown brown liquid liquid Assay: 48.9g/L 50.0g/L Require 45g/L Hexythiazox 55g/L Assay: 126.5g/L 125.4g/L Require 118g/L Piperonyl butoxide 132g/L pH1% 6.8 6.8 Nominally: 5.5 to 9.5 Persistent foaming 2mL 2mL Require: 560mL foam after 1 min Dispersion stability No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and Re- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h

Embodiment 14 - Recipe for emulsion-in-water/emulsifiable concentrate

combining 30g/L Hexythiazox and 30g/L Piperonyl Butoxide. The

concentrate is produced as below in Table 27 and, as shown in Table 28,

has been determined via assay as having: 1) adequate active ingredient

concentration, even after accelerated aging; 2) acceptable emulsion and

dispersion properties upon dilution in water prior to application; and 3)

physical and chemical stability (including at cold temperatures of 20C for 7

days), at the point of manufacturing and again after accelerated aging to

approximate two years of shelf life.

Composition of embodiment 14 is as follows in Table 27:

Table 27:

Ingredient Role Concentration Hexythiazox Active 30.5g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 29.9g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 32.6g/L (CAS# 51-03-6, Technical material, 94.0%) synergist (yields 30.6g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 29.5g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 17.Og/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 154.1g/L aromatic (CAS# 64742-94-5, e.g. Recosol 150) Water Solvent 727.Og/L (CAS# 7732-18-5) (to 991g/L total)

Chemical and physical parameters of embodiment 14 is as follows in

Table 28:

Table 28:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 30.6g/L 30.8g/L Require 27g/L Hexythiazox 33g/L Assay: 31.2g/L 30.0g/L Require 27g/L ! Piperonyl butoxide 33g/L pH1% 6.9 6.9 Nominally: 5.5 to 9.5 Persistent foaming 6mL 4mL Require: 60mL foam after 1 min Emulsion characteristics No cream; Trace of cream; Require: 2mL cream after 30 min, No oil; No oil; <trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

Embodiment 15 - Recipe for emulsion-in-water/emulsifiable concentrate

combining 20g/L Hexythiazox and 50g/L Piperonyl Butoxide. The

concentrate is produced as below in Table 29 and, as shown in Table 30,

has been determined via assay as having: 1) adequate active ingredient

concentration, even after accelerated aging; 2) acceptable emulsion and

dispersion properties upon dilution in water prior to application; and 3)

physical and chemical stability (including at cold temperatures of 20 C for 7

days), at the point of manufacturing and again after accelerated aging to

approximate two years of shelf life.

Composition of embodiment 15 is as follows in Table 29:

Table 29:

Ingredient Role Concentration Hexythiazox Active 20.4g/L (CAS# 78587-05-0, Technical material, acaricidal (yields 20.0g/L 98.1%) ingredient Hexythiazox) Piperonyl butoxide Acaricidal 56.3g/L (CAS# 51-03-6, Technical material, synergist (yields 52.9g/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 19.6g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 11.5g/L 2-ethylhexanol (CAS# 68584-23-6, 104 76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 96.1g/L aromatic (CAS# 64742-94-5, e.g. Recosol 150) Water (CAS# 7732-18-5) Solvent 790.4g/L (to 994g/L total)

Chemical and physical parameters of embodiment 15 is as follows in

Table 30:

Table 30:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 20.3g/L 20.2g/L Require 17g/L Hexythiazox 23g/L Assay: 51.9g/L 52.5g/L Require 45g/L Piperonyl butoxide 55g/L pH1% 7.1 6.9 Nominally: 5.5 to 9.5 Persistent foaming 4mL 6mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and Re-emulsifies/24h Re complete re-emulsion after 24h emulsifies/24h

Example 2: Hexythiazox 100 g/L + Piperonyl butoxide 250 g/L EC Raw

Material Identities

An example formulation combining 100g/L Hexythiazox and 250g/L

Piperonyl Butoxide is provided below in Table 31, which includes the purity

(where known), source and technical details of the components. The

Hexythiazox technical and Piperonyl Butoxide technical are the same as

that used in the formulations of Example 1.

0 9: C) c : CN (D (D co D o~ -CN C0

0.

0 a))

0 =3 m _z

CD0D

.a0 C l)'0 Uu~CD <N = d5/ -- .9v:C 00 0 C-0 0 CC) o'C 'D 0 a) Co )

2 n -F 0CO Q U,&CV~? C?' C) c'- 0 LC) a) LL aLO 7:' C) )

. CC) a)cIm ~ V LO -a< .2-j0 0 it .20 U) F -o z a) m 0 E' 0)l 0) CuD

E x E02~ E E E E E xo o Cu -C 0

cu N - 0.- ~ - 0 M a) tcu - cu C) Cu Cu c co~u Cu _ o o c =3 (m~l 2= cN C CL- C 0 - CL m) nu 0. mco ~) c 2 c 2 co

E cD

C OO 0 0O m

O- (DCCl)cau CL CDC0)- 0 C) 00 3cn 0N Na)

2 0 Vc

Example 3: Method of Manufacture of Hexythiazox Emulsifiable

Concentrate Formulation

Formulation of a 1,000L batch of product, inclusive of quality control

measures, is as follows:

Formulation Procedure

1. Ensure formulation vessel is empty and clean

2. Charge solvent component(s), holding a small proportion back (e.g.

-10%) for subsequent addition, to the formulation vessel with the

agitator operating

3. Charge active ingredients (hexythiazox and synergists, e.g. piperonyl

butoxide) to the formulation vessel with continuous agitation

4. Charge the surfactant(s) and other excipients clearing residual

components from any pumps or process lines used with the remaining

complement of solvent

5. Continue agitating for a minimum of 30 minutes following the last

ingredient's addition

Quality Control Procedure

1. Sample approximately 1L of product, ensuring it is representative

2. Sub-sample 250mL from the original 1L sample, and subject it to the

following testing regime.

2.1. Specific gravity (CIPAC MT3.1)

If specific gravity is within the bounds of the acceptable range listed in

the specification, record the value and proceed to the next test. If

specific gravity is outside of the bounds of the acceptable range listed in the specification, agitate the formulation charge until specific gravity is constant. If still outside of the bounds of the acceptable range, quarantine batch for further investigations and possible rework.

2.2. pH 1% aqueous (CIPAC MT75.3)

If pH 1% aqueous is satifactory, record results and proceed to the next

test. If pH 1% aqueous is outside the bounds of the acceptable range

listed in the specification, quarantine the batch for further

investigations and possible rework.

2.3. Emulsion characteristics (CIPAC MT36.1)

If emulsion stability in standard hard water is satifactory, record results

and proceed to the next test. If emulsion stability is outside the bounds

of the acceptable range listed in the specification, adjust the contents

of surfactants. After suitable agitation time to ensure homogeneity,

resample and retest. Repeat adjustment process until emulsion

stability is within the bounds of the acceptable range.

2.4. Persistent foam (CIPACMT47.2)

If persistent foaming characteristics are satifactory, record results and

proceed to the next test. If persistent foaming characteristics are

outside the bounds of the acceptable range quarantine the batch for

further investigations and possible rework.

2.5. Active constituent (hexythiazox) content (appropriately

validated method: specificity; linearity of response with correlation

coefficient R>0.99; accuracy of mean measured assay as a proportion of true content 100±2%; reproducibility of response 2% relative standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active

constituent content), or additional hexythiazox technical (for a low

active content). After suitable agitation time to ensure homogeneity,

resample and retest. Repeat adjustment process until active

constituent levels are within the bounds of the acceptable range.

2.6. Active constituent (synergist, e.g. Piperonyl butoxide) content

(appropriately validated method: specificity; linearity of response with

correlation coefficient R>0.99; accuracy of mean measured assay as a

proportion of true content 100±2%; reproducibility of response 2%

relative standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active

constituent content), or additional synergist (for a low active

constituent content). After suitable agitation time to ensure

homogeneity, resample and retest. Repeat adjustment process until

active constituent levels are within the bounds of the acceptable

range.

3. Catalogue and store a retention sample of approximately 200mL

4. Generate a certificate of analysis noting results of testing

5. Issue quality clearance giving authority to package goods

6. Package the finished goods ensuring both the batch number and

manufacturing date is noted on the label.

Example 4: Method of Manufacture of Hexythiazox Dispersible

Concentrate Formulation

Formulation of a 1,000L batch of product, inclusive of quality control

measures, is as follows:

Formulation Procedure

1. Ensure formulation vessel is empty and clean

2. Charge solvent component(s), holding a small proportion back (e.g.

-10%) for subsequent addition, to the formulation vessel with the

agitator operating

3. Charge active ingredients (hexythiazox and synergist, e.g. piperonyl

butoxide) to the formulation vessel with continuous agitation

4. Charge the surfactant(s) and other excipients clearing residual

components from any pumps or process lines used with the remaining

complement of solvent

5. Continue agitating for a minimum of 30 minutes following the last

ingredient's addition

Quality Control Procedure

1. Sample approximately 1L of product, ensuring it is representative

2. Sub-sample 250mL from the original 1L sample, and subject it to the

following testing regime.

2.1. Specific gravity (CIPAC MT3.1)

If specific gravity is within the bounds of the acceptable range listed in

the specification, record the value and proceed to the next test. If

specific gravity is outside of the bounds of the acceptable range listed

in the specification, agitate the formulation charge until specific gravity

is constant. If still outside of the bounds of the acceptable range,

quarantine batch for further investigations and possible rework.

2.2. pH 1% aqueous (CIPAC MT75.3)

If pH 1% aqueous is satifactory, record results and proceed to the next

test. If pH 1% aqueous is outside the bounds of the acceptable range

listed in the specification, quarantine the batch for further

investigations and possible rework.

2.3. Dispersion stability (CIPAC MT180)

If dispersion stability in standard hard water is satifactory, record

results and proceed to the next test. If dispersion stability is outside

the bounds of the acceptable range listed in the specification, adjust

the contents of surfactants. After suitable agitation time to ensure

homogeneity, resample and retest. Repeat adjustment process until

dispersion stability is within the bounds of the acceptable range.

2.4. Persistent foam (CIPACMT47.2)

If persistent foaming characteristics are satifactory, record results and

proceed to the next test. If persistent foaming characteristics are outside the bounds of the acceptable range quarantine the batch for further investigations and possible rework.

2.5. Active constituent (hexythiazox) content (appropriately

validated method: specificity; linearity of response with correlation

coefficient R>0.99; accuracy of mean measured assay as a proportion

of true content 100±2%; reproducibility of response 2% relative

standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active

constituent content), or additional hexythiazox technical (for a low

active content). After suitable agitation time to ensure homogeneity,

resample and retest. Repeat adjustment process until active

constituent levels are within the bounds of the acceptable range.

2.6. Active constituent (Synergist, e.g. Piperonyl butoxide) content

(appropriately validated method: specificity; linearity of response with

correlation coefficient R>0.99; accuracy of mean measured assay as a

proportion of true content 100±2%; reproducibility of response 2%

relative standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active constituent content), or additional Synergist (for a low active constituent content). After suitable agitation time to ensure homogeneity, resample and retest. Repeat adjustment process until active constituent levels are within the bounds of the acceptable range.

3. Catalogue and store a retention sample of approximately 200mL

4. Generate a certificate of analysis noting results of testing

5. Issue quality clearance giving authority to package goods

6. Package the finished goods ensuring both the batch number and

manufacturing date is noted on the label.

Example 5: Method of Manufacture of Hexythiazox Emulsion-in

Water Concentrate Formulation

Formulation of a 1,000L batch of product, inclusive of quality control

measures, is as follows:

Formulation Procedure

1. Ensure formulation vessel is empty and clean

2. Charge organic solvent component(s), holding a small proportion back

(e.g. -10%) for subsequent addition, to the formulation vessel with the

agitator operating

3. Charge active ingredients (hexythiazox and synergist, e.g. piperonyl

butoxide) to the formulation vessel with continuous agitation

4. Charge the surfactant(s) and other excipients clearing residual

components from any pumps or process lines used with the remaining

complement of solvent

5. Continue agitating for a minimum of 30 minutes

6. Charge water to the formulation vessel with the agitator operating

7. Continue agitating for a minimum of 30 minutes following the last

ingredient's addition

Quality Control Procedure

1. Sample approximately 1L of product, ensuring it is representative

2. Sub-sample 250mL from the original 1L sample, and subject it to the

following testing regime.

2.1. Specific gravity (CIPAC MT3.1)

If specific gravity is within the bounds of the acceptable range listed in

the specification, record the value and proceed to the next test. If

specific gravity is outside of the bounds of the acceptable range listed

in the specification, agitate the formulation charge until specific gravity

is constant. If still outside of the bounds of the acceptable range,

quarantine batch for further investigations and possible rework.

2.2. pH 1% aqueous (CIPAC MT75.3)

If pH 1% aqueous is satifactory, record results and proceed to the next

test. If pH 1% aqueous is outside the bounds of the acceptable range

listed in the specification, quarantine the batch for further

investigations and possible rework.

2.3. Dispersion stability (CIPAC MT180)

If dispersion stability in standard hard water is satifactory, record

results and proceed to the next test. If dispersion stability is outside

the bounds of the acceptable range listed in the specification, adjust

the contents of surfactants. After suitable agitation time to ensure

homogeneity, resample and retest. Repeat adjustment process until

dispersion stability is within the bounds of the acceptable range.

2.4. Persistent foam (CIPACMT47.2)

If persistent foaming characteristics are satifactory, record results and

proceed to the next test. If persistent foaming characteristics are

outside the bounds of the acceptable range quarantine the batch for

further investigations and possible rework.

2.5. Active constituent (hexythiazox) content (appropriately

validated method: specificity; linearity of response with correlation

coefficient R>0.99; accuracy of mean measured assay as a proportion

of true content 100±2%; reproducibility of response 2% relative

standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active

constituent content), or additional hexythiazox technical (for a low

active content). After suitable agitation time to ensure homogeneity,

resample and retest. Repeat adjustment process until active

constituent levels are within the bounds of the acceptable range.

2.6. Active constituent (Synergist, e.g. Piperonyl butoxide) content

(appropriately validated method: specificity; linearity of response with

correlation coefficient R>0.99; accuracy of mean measured assay as a

proportion of true content 100±2%; reproducibility of response 2%

relative standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active

constituent content), or additional Synergist (for a low active

constituent content). After suitable agitation time to ensure

homogeneity, resample and retest. Repeat adjustment process until

active constituent levels are within the bounds of the acceptable

range.

3. Catalogue and store a retention sample of approximately 200mL

4. Generate a certificate of analysis noting results of testing

5. Issue quality clearance giving authority to package goods

6. Package the finished goods ensuring both the batch number and

manufacturing date is noted on the label.

Claims (21)

1. A pesticide formulation comprising:

hexythiazox;

a synergist;

a surfactant; and

optionally, a solvent.

2. A concentrate formulation comprising:

hexythiazox at a concentration of at least about 50 g/L;

piperonyl butoxide at a concentration of at least about 10 g/L;

a non-ionic surfactant and/or an anionic surfactant; and

optionally, a solvent,

wherein the concentrate formulation is an emulsifiable concentrate

formulation or a dispersible concentrate formulation.

3. An emulsion-in-water formulation comprising:

hexythiazox at a concentration of at least about 10 g/L;

piperonyl butoxide at a concentration of at least about 10 g/L;

a non-ionic surfactant and/or an anionic surfactant;

a solvent; and

water.

4. The concentrate formulation of Claim 2, wherein hexythiazox is present at a concentration of at least about 100 g/L of the total weight of the formulation.

5. The concentrate formulation of Claim 2 or Claim 4, wherein

piperonyl butoxide is present at a concentration of at least about 100 g/L

of the total weight of the formulation.

6. The concentrate formulation of any one of Claims 2, 4 or 5, wherein

the surfactant is present in an amount of at least about 20 g/L.

7. The concentrate formulation of Claim 6, wherein the surfactant is

present in an amount ranging between about 20 g/L to about 150 g/L.

8. The concentrate formulation of any one of Claims 2 or 4 to 7,

wherein the surfactant is selected from the group consisting of an

alkylphenol, a polyoxyalkylene ether, an alkylbenzene sulphonate, an

alkoxylated styryl phenol, a vegetable oil ethoxylate, and any combination

thereof.

9. The concentrate formulation of Claim 8, wherein the surfactant is

selected from the group consisting of an alkoxylated alkylphenol, an alkyl

polyoxyalkalene ether, calcium C10-16 alkylbenzyl sulphonate, an

ethoxylated tristyryl phenol, and any combination thereof.

10. The concentrate formulation of any one of Claims 2 or 3 to 9,

wherein the solvent is present in an amount of at least about 400 g/L.

11. The concentrate formulation of Claim 10, wherein the solvent is

present in an amount ranging between about 400 g/L to about 1000 g/L.

12. The concentrate formulation of any one of Claims 2 or 4 to 11,

wherein the solvent is selected from the group consisting of a petroleum

derivative, a carboxamide, a benzoate, a ketone and any combination

thereof.

13. The concentrate formulation of Claim 12, wherein the solvent is

selected from the group consisting of a heavy aromatic hydrocarbon, a

pyrrolidone, an alkyl benzoate, an alkyl ketone, and any combination

thereof.

14. The concentrate formulation of Claim 12 or Claim 13, wherein the

solvent is selected from the group consisting of a heavy aromatic solvent

naphtha (petroleum), N-methyl pyrrolidone, methyl benzoate, isophorone,

N,N-Dimethylacetamide, N,N-Dimethylformamide, xylene, acetophenone,

1-butylpyrrolidin-2-one and any combination thereof.

15. An emulsifiable concentrate, comprising:

hexythiazox at a concentration of at least about 100 g/L; piperonyl butoxide at a concentration of at least about 250 g/L; a non-ionic surfactant comprising a vegetable oil ethoxylate; an anionic surfactant comprising a calcium salt of an alkylbenzene sulfonate; and a solvent comprising methyl benzoate.

16. A method of preparing a pesticide formulation including the steps

of:

(a) combining hexythiazox, a synergist such as piperonyl butoxide,

a surfactant and a solvent, wherein hexythiazox is present at a

concentration of at least 10 mg/L; and

(b) mixing the mixture of step (a) to thereby prepare the pesticide

formulation.

17. The method of Claim 17, wherein the pesticide formulation is the

concentrate formulation of any one of Claims 2 or 4 to 15.

18. The method of claim 16, further comprising the step of adding water

or a water-containing liquid to the mixture before or during step (b).

19. A pesticide formulation prepared by the method of any one of

Claims 17 to 19.

20. A method of preventing and/or controlling a pest infestation in a target area, including the step of applying a pesticidally effective amount of the pesticide formulation of any one of Claims 1, 3 or 19 and/or the concentrate formulation of any one of Claims 2 or 4 to 15, mixed with water or a water-containing liquid to the target area to thereby prevent and/or control the pest infestation.

21. The method of Claim 20, further including the initial step of mixing

the pesticide formulation and/or the concentrate formulation with water or

the water-containing liquid.