AU2021105775A4 - Pesticide formulation comprising etoxazole - Google Patents

Abstract

The present invention relates to a pesticide formulation comprising: etoxazole, a synergist, a surfactant, and optionally a solvent. The invention also relates to an emulsifiable concentrate formulation, a dispersible concentrate formulation, 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 ETOXAZOLE FIELD OF THE INVENTION

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

present invention relates to a pesticide formulation containing etoxazole 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

Etoxazole is a member of the diphenyl oxazoline class of

insecticides and acaracides. It is a contact insecticide and acaricide (also

known as a miticide) which is effective against agricultural pests such as

mites and aphids during the egg, larvae and nymph stages, with no activity

against adults. It acts by inhibiting chitin synthesis, resulting in the

inhibition of moulting in affected organisms.

Etoxazole is commonly obtained and used as a racemic mixture of

the two active stereoisomers (R)-5-tert-butyl-2-[2-(2,6-dichlorophenyl)-4,5

dihydro-1,3-oxazol-4-yl]phenetole and (S)-5-tert-butyl-2-[2-(2,6

dichlorophenyl)-4,5-dihydro-1,3-oxazol-4-yl]phenetole. It is commonly used

to control many phytophagous mites such as Tetranychus and

Panonychus spp.

It is a known problem that acaricides such as etoxazole, 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 etoxazole 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 etoxazole

formulations, there remains a need for improved etoxazole-based

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

of the inherent limitations of commercially available etoxazole

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:

etoxazole;

a synergist;

a surfactant, which is preferably a mixture of a non-ionic surfactant

and an anionic surfactant; and optionally, a solvent.

In a second aspect, the invention provides an emulsifiable

concentrate formulation comprising:

etoxazole at a concentration of at least about 10 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.

In a third aspect, the invention provides a dispersible concentrate

formulation comprising:

etoxazole 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; and

a solvent.

In one embodiment, etoxazole 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 40 g/L. More particularly, the surfactant is suitably present in

an amount ranging between about 40 g/L to about 120 g/L.

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

alkylphenol, a polyoxyalkylene ether, an alkylbenzenesulphonate, an alkoxylated styryl phenol and any combination thereof. Preferably, 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.

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 800 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, ethyl benzoate, MIBK, propylene carbonate,

isophorone, N,N-Dimethylacetamide, N,N-Dimethylformamide, xylene,

cyclohexanone, and any combination thereof.

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

pesticide formulation including the steps of:

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

surfactant and a solvent, wherein etoxazole is present at a 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

emulsifiable concentrate formulation of the second aspect or the

dispersible concentrate of the third aspect.

In a fifth aspect, the invention provides a pesticide formulation

prepared by the method of the fourth aspect.

In a sixth 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 or fifth aspects or the emulsifiable concentrate formulation of the

second aspect or the dispersible concentrate formulation of the third

aspect, 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

concentrated liquid form, 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. By way of example, the treatment of a given volume of produce or

target area (e.g., crop, land, commercial or residential premises etc) can

be achieved with a reduced amount of 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 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, the active ingredient in emulsifiable concentrate formulations and dispersible concentrate formulations 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 or dispersible concentrate formulation.

In view of the foregoing, the present invention advantageously

provides an etoxazole composition or formulation suitable for the

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

agricultural or horticultural setting. Further, the etoxazole formulation may

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

dispersible concentrate.

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

formulation comprising:

etoxazole;

a synergist;

a surfactant; and

optionally, a solvent.

The term "etoxazole" refers to a racemic mixture of (R)-5-tert-butyl

2-[2-(2,6-dichlorophenyl)-4,5-dihydro-1,3-oxazol-4-yl]phenetole and (S)-5

tert-butyl-2-[2-(2,6-dichlorophenyl)-4,5-dihydro-1,3-oxazol-4-yl]phenetole.

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 etoxazole 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

"etoxazole" 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

diphenyl oxazoline like etoxazole. 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 etoxazole and thus advantageously increases the biological

effectiveness thereof, while achieving substantial savings on the cost of

the composition formulation. It is understood that whilst piperonyl butoxide

does not have any acaricidal activity per se, when used in conjunction with

etoxazole it does slow the affected pest's capacity to degrade and

eliminate (that is, metabolise) the etoxazole, thereby amplifying the

acaricidal effect of the applied composition, relative to the same amount of

etoxazole applied without a synergist such as piperonyl butoxide.

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

concentrates, emulsions 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

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

piperonyl butoxide. In some embodiments, the synergist (such as

piperonyl butoxide), alone or in combination with at least one surfactant,

may also act as a solvent and solubilise the etoxazole loading to produce

an emulsifiable concentrate. 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.

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 one aspect, the invention provides an emulsifiable concentrate

formulation comprising:

etoxazole at a concentration of at least about 10 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.

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

pesticide formulation including the steps of:

(a) combining etoxazole, a synergist such as piperonyl butoxide or

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

etoxazole 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 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.

The statements which follow apply equally to the aforementioned

aspects of the invention.

For the present invention, etoxazole is suitably present in a

concentration (e.g., at least about 10 g/L) that provides a pesticide

formulation, or in a higher concentration (e.g., such as about 100 g/L) that

provides a concentrated pesticide formulation, such as an emulsifiable

concentrate formulation 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 or dispersible concentrate formulations,

etoxazole may be present in an amount from about 10 g/L to about 300

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

250 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, etoxazole 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 g/L, or any range therein, of the liquid pesticide formulation. In certain embodiments of the present invention, etoxazole is present in an amount of about 25 g/L to about 200 g/L of the liquid pesticide formulation.

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

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

pyrethrins, pyrethroids, diphenyl oxazolines, 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 emulsifiable

concentrate formulations or dispersible concentrate formulations, 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 10 g/L to about 250 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. The ratio of etoxazole to 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.

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. 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 benxoates (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, ethyl benzoate, MIBK, propylene carbonate, isophorone, N,N-Dimethylacetamide, N,N-Dimethylformamide, xylene, cyclohexanone and any combination thereof.

In a particular embodiment, the synergist may also act, alone or in

concert with a surfactant, to solubilise the active ingredient. In other words,

the synergist may also act as a solvent to form an emulsifiable

concentrate.

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.

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

solvent is suitably about 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 and any range

therein. In one preferred embodiment, the ratio of the first solvent to the

second solvent is in the range of about 3:1 to about 1:3.

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

including an emulsifiable concentrate formulation or dispersible

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

amount from about 200 g/L to about 800 g/L or any range therein such as, but not limited to, 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 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 300 g/L to about 800 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 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.

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 etoxazole pesticide

formulation, such as an emulsifiable concentrate formulation, or

dispersible concentrate formulation, or a direct use formulation. 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 or dispersible concentrate formulations, the

surfactant may be present in an amount from about 20 g/L to about 300

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, 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, 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

25 g/L to about 100 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 or 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-, -S3H, -SO3-, -OS03H, -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, 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 know 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., T1285)), 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 20:1 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 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 etoxazole

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, 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, 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 etoxazole, 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 emulsifiable concentrate formulation of the second mentioned aspect or dispersible concentrate formulation of the third mentioned aspect mixed with water or a water-containing liquid 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 etoxazole

formulation or the dispersible concentrate etoxazole formulation with water

or the water-containing liquid.

The terms "treat", "treat" 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 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 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 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 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 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 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 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 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 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 or an emulsifiable concentrate formulation or

dispersible concentrate formulation comprising etoxazole 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 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. and Panonychus 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 and tea.

The pesticide formulation or the emulsifiable concentrate

formulation or dispersible concentrate formulation 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 emulsifiable concentrate

formulation or the dispersible concentrate 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

are applied at a rate of about 150 to 1100mL per hectare (e.g., about

150mL, 155mL, 160mL, 165mL, 170mL, 175mL, 180mL, 185mL, 190mL,

195mL, 200mL, 205mL, 210mL, 215mL, 220mL, 225mL, 230mL, 235mL,

240mL, 245mL, 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, 10OOmL, 1025mL, 1050mL, 1075mL, and 11OOmL per hectare

and any range therein) and more preferably at a rate of about 175mL to

about 1050mL per hectare subsequent to dilution thereof in a suitable

spray liquid. Obviously, the amount of the pesticide formulation or the

emulsifiable concentrate to be applied per hectare will depend, at least in

part, upon the concentration of etoxazole 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 etoxazole 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 may be between

about 3:1 and about 1:3 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 to the total amount

of surfactant may be between about 20:1 and about 1:20 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 a Etoxazole Emulsifiable

Concentrate and Dispersible Concentrate Formulations

A number of embodiments of emulsifiable concentrate formulations

or dispersible concentrate formulations across a range of etoxazole

concentrations, a range of overall etoxazole and piperonyl butoxide

concentrations/proportions, and a range of solvents and surfactants are

provided below.

Embodiment 1 - Recipe for an emulsifiable concentrate combining 11Og/L

Etoxazole and 11Og/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 and dispersion properties upon

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

(including a cold temperatures of 20C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life. These are significant advantages of the concentrate described

herein, and are a significant improvement over the prior art.

Composition of embodiment 1 is as follows in Table 1:

Table 1:

Ingredient Role Concentration Etoxazole Active 113.4g/L (CAS# 153233-91-1, Technical acaricidal (yields 110.0g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 119.6g/L (CAS# 51-03-6, Technical material, synergist (yields 112.4g/L 94.0%) Piperonyl butoxide)

Alkyl polyoxyalkylene ether Surfactant 17.Og/L (CAS# Proprietary, e.g. Termul 203) Alkoxylated alkylphenol Surfactant 50.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium Surfactant 50.1g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Propylene carbonate Solvent 158.6g/L (CAS# 108-32-7) Methyl benzoate Solvent 587.8g/L (CAS# 93-58-3) (to 1096g/L total)

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 brown liquid liquid Assay: 111.6g/L 109.2g/L Require 103.5g/L ! Etoxazole 116.5g/L Assay: 110.2g/L 109.2g/L Require 103.5g/L Piperonyl butoxide 116.5g/L pH1% 7.1 7.2 Nominally: 5.5 to 9.5 Persistent foaming 9mL 8mL 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 Re- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h

Embodiment 2 - Recipe for an emulsifiable concentrate combining 11Og/L

Etoxazole and 11Og/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 a 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 2 is as follows in Table 3:

Table 3:

Ingredient Role Concentration Etoxazole Active 113.0g/L (CAS# 153233-91-1, Technical acaricidal (yields 109.6g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 119.9g/L (CAS# 51-03-6, Technical material, synergist (yields 111.9g/L 94.0%) Piperonyl butoxide) Alkyl polyoxyalkylene ether Surfactant 17.1g/L (CAS# Proprietary, e.g. Termul 203) Alkoxylated alkylphenol Surfactant 49.9g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium Surfactant 50.1g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Propylene carbonate Solvent 155.1g/L (CAS# 108-32-7) Ethyl benzoate Solvent 573.7g/L (CAS# 93-89-0) (to 1079g/L total)

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

4:

Table 4:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown brown liquid liquid Assay: 107.9g/L 106.8g/L Require 103.5g/L Etoxazole 116.5g/L Assay: 108.5g/L 109.6g/L Require 103.5g/L Piperonyl butoxide 116.5g/L pH1% 7.4 7.0 Nominally: 5.5 to 9.5 Persistent foaming 5mL 11mL 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- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h

Embodiment 3 - Recipe for an emulsifiable/dispersible concentrate

combining 220g/L Etoxazole and 11Og/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 a 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 3 is as follows in Table 5:

Table 5:

Ingredient Role Concentration Etoxazole Active 227.9g/L (CAS# 153233-91-1, Technical acaricidal (yields 221.1g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 120.9g/L (CAS# 51-03-6, Technical material, synergist (yields 113.6g/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.3g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium Surfactant 30.1g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) 4-Methylpentan-2-one (MIBK) Solvent 261.3g/L (CAS# 108-10-1) N-methyl-2-pyrrolidone Solvent 326.6g/L (CAS# 872-50-4) (to 997g/L total)

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

6:

Table 6:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown brown liquid liquid Assay: 225.9g/L 217.4g/L Require 207g/L Etoxazole 233g/L Assay: 113.5g/L 116.7g/L Require 103.5g/L Piperonyl butoxide 116.5g/L pH1% 7.1 7.6 Nominally: 5.5 to 9.5 Persistent foaming 9mL 6mL Require: 60mL foam after 1 min Emulsion characteristics/ Dispersion Trace of cream; Nil cream; stability No oil; No oil; Require: 2mL cream after 30 min, Re- Re-emulsifies/24h trace of oil after 30 min and emulsifies/24h complete re-emulsion after 24h

Embodiment 4 - Recipe for a dispersible concentrate combining 220g/L

Etoxazole and 11Og/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 a 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 4 is as follows in Table 7: Table 7:

Ingredient Role Concentration Etoxazole Active 229.1g/L (CAS# 153233-91-1, Technical acaricidal (yields 222.2g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 123.0g/L (CAS# 51-03-6, Technical material, synergist (yields 115.6g/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.3g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium Surfactant 31.1g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Cyclohexanone Solvent 601.9g/L (CAS# 108-94-1) (to 1015g/L total)

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 brown liquid liquid Assay: 219.9g/L 211.1g/L Require 207g/L Etoxazole 233g/L Assay: 117.9g/L 115.0g/L Require 103.5g/L Piperonyl butoxide 116.5g/L pH1% 6.7 7.5 Nominally: 5.5 to 9.5 Persistent foaming 12mL 7mL Require: 60mL foam after 1 min Dispersion stability Trace of cream; Nil 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 5 - Recipe for an emulsifiable concentrate combining 160g/L

Etoxazole and 80g/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 a 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 5 is as follows in Table 9:

Table 9:

Ingredient Role Concentration Etoxazole Active 165.9g/L (CAS# 153233-91-1, Technical acaricidal (yields 160.9g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 87.8g/L (CAS# 51-03-6, Technical material, synergist (yields 82.5g/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.1g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium Surfactant 30.5g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Isophorone Solvent 665.2g/L (CAS# 78-59-1) (to 1015g/L total)

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

10:

Table 10:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown brown liquid liquid Assay: 158.4g/L 154.7g/L Require 151g/L Etoxazole 69g/L Assay: 85.2g/L 79.2g/L Require 72g/L Piperonyl butoxide 88g/L pH1% 7.6 6.8 Nominally: 5.5 to 9.5 Persistent foaming 4mL 9mL Require: 60mL foam after 1 min Emulsion characteristics Trace of 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 6 - Recipe for an emulsifiable concentrate combining 11Og/L

Etoxazole and 11Og/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 a 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 6 is as follows in Table 11:

Table 11:

Ingredient Role Concentration Etoxazole Active 112.9g/L (CAS# 153233-91-1, Technical acaricidal (yields 109.5g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 120.2g/L (CAS# 51-03-6, Technical material, synergist (yields 113.Og/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.6g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Nonylphenol, ethoxylated Surfactant 10.1g/L (CAS# 127087-87-0, e.g. Teric N30) Alkylbenzenesulfonic acid, calcium Surfactant 40.Og/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) N-methyl-2-pyrrolidone Solvent 253.0g/L (CAS# 872-50-4) Solvent naphtha (petroleum), heavy Solvent 415.5g/L aromatic (to 982g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

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

12:

Table 12:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown brown liquid liquid Assay: 114.5g/L 109.3g/L Require 103.5g/L Etoxazole 116.5g/L Assay: 105.5g/L 107.5g/L Require 103.5g/L Piperonyl butoxide 116.5g/L pH1% 7.1 6.6 Nominally: 5.5 to 9.5 Persistent foaming 5mL 1mL Require: 60mL foam after 1 min Emulsion characteristics 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- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h

Embodiment 7 - Recipe for an emulsifiable concentrate combining 11Og/L

Etoxazole and 11Og/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 a 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 7 is as follows in Table 13:

Table 13:

Ingredient Role Concentration Etoxazole Active 113.1g/L (CAS# 153233-91-1, Technical acaricidal (yields 109.7g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 119.9g/L (CAS# 51-03-6, Technical material, synergist (yields 112.7g/L 94.0%) Piperonyl butoxide) Alkyl polyoxyalkylene ether Surfactant 15.Og/L (CAS# Proprietary, e.g. Termul 203) Alkoxylated alkylphenol Surfactant 50.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium Surfactant 50.2g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Propylene carbonate Solvent 155.0g/L (CAS# 108-32-7) Solvent naphtha (petroleum), heavy Solvent 488.1g/L aromatic (to 991g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

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

14:

Table 14:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown brown liquid liquid Assay: 114.6g/L 111.2g/L Require 103.5g/L Etoxazole 5 116.5g/L Assay: 110.Og/L 109.7g/L Require 103.5g/L Piperonyl butoxide 116.5g/L pH1% 7.2 6.8 Nominally: 5.5 to 9.5

Persistent foaming 3mL OmL Require: 60mL foam after 1 min Emulsion characteristics 0.2mL of 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 8 - Recipe for a dispersible concentrate combining 11Og/L

Etoxazole and 11Og/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 a 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 8 is as follows in Table 15:

Table 15:

Ingredient Role Concentration Etoxazole Active 113.4g/L (CAS# 153233-91-1, Technical acaricidal (yields 110.Og/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 120.1g/L (CAS# 51-03-6, Technical material, synergist (yields 112.9g/L 94.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 28.3g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 9.5g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium Surfactant 37.6g/L salt in 2-ethylhexanol (CAS# 68584

23-6, 104-76-7, e.g. Ninate 60E) N,N-Dimethylacetamide Solvent 160.1g/L (CAS#127-19-5) N,N-Dimethylformamide Solvent 110.Og/L (CAS# 68-12-2) Xylenes Solvent 372.9g/L (CAS# 1330-20-7) (to 952g/L total)

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 brown liquid liquid Assay: 109.3g/L 104.4g/L Require 103.5g/L Etoxazole 116.5g/L Assay: 111.9g/L 111.8g/L Require 103.5g/L Piperonyl butoxide 116.5g/L pH1% 7.6 6.9 Nominally: 5.5 to 9.5 Persistent foaming 3mL 2mL Require: 560mL foam after 1 min Emulsion characteristics/ Dispersion No cream; No cream; stability No oil; No oil; Require: 2mL cream after 30 min, Re- Re-emulsifies/24h trace of oil after 30 min and emulsifies/24h complete re-emulsion after 24h

Embodiment 9 - Recipe for an emulsifiable concentrate combining 1Og/L

Etoxazole and 220g/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 a 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 for embodiment 8 is as follows in Table 17:

Table 17:

Ingredient Role Concentration Etoxazole Active 10.3g/L (CAS# 153233-91-1, Technical acaricidal (yields 10.0g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 238.9g/L (CAS# 51-03-6, Technical material, synergist (yields 224.6g/L 94.0%) Piperonyl butoxide) Tristyrylphenol ethoxylate Surfactant 32.1g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium Surfactant 27.9g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 631.2g/L aromatic (to 940g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

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

18:

Table 18:

Test As- AcceleratedAged manufactured Result Presentation Clear, yellow to Clear, yellow to brown brown liquid liquid Assay: 9.3g/L 9.2g/L Require 8.5g/L Etoxazole 11.5g/L Assay: 228.7g/L 221.7g/L Require 207g/L Piperonyl butoxide 233g/L pH1% 6.9 7.8 Nominally: 5.5 to 9.5 Persistent foaming 12mL 4mL Require: 60mL foam after 1 min Emulsion characteristics Nil cream; Nil 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 10 - Recipe for an emulsifiable concentrate combining

11Og/L Etoxazole and 1Og/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 a 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 Etoxazole Active 113.0g/L (CAS# 153233-91-1, Technical acaricidal (yields 109.6g/L material, 97.0%) ingredient Etoxazole) Piperonyl butoxide Acaricidal 10.1g/L (CAS# 51-03-6, Technical material, synergist (yields 9.5g/L Piperonyl 94.0%) butoxide) Alkyl polyoxyalkylene ether Surfactant 15.2g/L (CAS# Proprietary, e.g. Termul 203) Alkoxylated alkylphenol Surfactant 50.1g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P)

Alkylbenzenesulfonic acid, calcium Surfactant 49.8g/L salt in 2-ethylhexanol (CAS# 68584 23-6, 104-76-7, e.g. Ninate 60E) N-methyl-2-pyrrolidone Solvent 350.Og/L (CAS# 872-50-4) Solvent naphtha (petroleum), heavy Solvent 398.4g/L aromatic (to 987g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

Chemical and physical parameters of embodiment 10 is as follows in

Table 20:

Table 20:

Test As Accelerated Aged manufactured Result Presentation Clear, yellow to Clear, yellow to brown brown liquid liquid Assay: 111.6g/L 108.1g/L Require 103.5g/L Etoxazole 116.5g/L Assay: 9.2g/L 8.8g/L Require 8.5g/L Piperonyl butoxide 11.5g/L pH1% 7.6 7.1 Nominally: 5.5 to 9.5 Persistent foaming OmL OmL 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- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h

Example 2: Method of Manufacture of Etoxazole 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 (etoxazole 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 (Etoxazole) 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 Etoxazole 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 3: Method of Manufacture of Etoxazole 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 (etoxazole 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 (Etoxazole) 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 Etoxazole 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:

etoxazole;

a synergist;

a surfactant; and

optionally, a solvent.

2. An emulsifiable concentrate formulation comprising:

etoxazole 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; and

optionally, a solvent.

3. A dispersible concentrate formulation comprising:

etoxazole 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; and

a solvent.

4. The emulsifiable concentrate formulation of Claim 2, or the

dispersible concentrate formulation of Claim 3, wherein etoxazole is

present at a concentration of at least about 100 g/L of the total weight of

the formulation.

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

the dispersible concentrate formulation of Claim 3 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 emulsifiable concentrate formulation of any one of Claims 2 to

4 or 5, or the dispersible concentrate formulation of any one of Claims 3 to

5, wherein the surfactant is present in an amount of at least about 40 g/L.

7. The emulsifiable concentrate formulation or the dispersible

concentrate formulation of Claim 6, wherein the surfactant is present in an

amount ranging between about 40 g/L to about 120 g/L.

8. The emulsifiable concentrate formulation of any one of Claims 2 or

4 to 7, or the dispersible concentrate formulation of any one of Claims 3 to

7, wherein the surfactant is selected from the group consisting of an

alkylphenol, a polyoxyalkylene ether, an alkylbenzenesulphonate, an

alkoxylated styryl phenol, and any combination thereof.

9. The emulsifiable concentrate formulation or the dispersible

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 emulsifiable concentrate formulation of any one of Claims 2 or

3 to 9, or the dispersible concentrate formulation of any one of Claims 3 to

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

11. The emulsifiable concentrate formulation or the dispersible

concentrate formulation of Claim 10, wherein the solvent is present in an

amount ranging between about 400 g/L to about 800 g/L.

12. The emulsifiable concentrate formulation of any one of Claims 2 or

4 to 11, or the dispersible concentrate formulation of any one of Claims 3

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 emulsifiable concentrate formulation or the dispersible

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 emulsifiable concentrate formulation or the dispersible

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, ethyl benzoate,

MIBK, propylene carbonate, isophorone, N,N-Dimethylacetamide, N,N

Dimethylformamide, xylene, cyclohexanone and any combination thereof.

15. The emulsifiable concentrate of claim 2, wherein the solvent

comprises propylene carbonate and methyl benzoate.

16. An emulsifiable concentrate, comprising:

etoxazole at a concentration of at least about 110 g/L;

piperonyl butoxide at a concentration of at least about 110 g/L;

a non-ionic surfactant comprising an alkyl polyoxyalkylene ether

and an alkoxylated alkylphenol;

an anionic surfactant comprising a calcium salt of an alkylbenzene

sulfonate; and

a solvent comprising propylene carbonate and methyl benzoate.

17. A method of preparing a pesticide formulation including the steps

of:

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

surfactant and a solvent, wherein etoxazole 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.

18. The method of Claim 17, wherein the pesticide formulation is the

emulsifiable concentrate formulation of any one of Claims 2 or 4 to 16 or

the dispersible concentrate formulation of any one of Claims 3 to 14.

19. A pesticide formulation prepared by the method of Claim 17 or

Claim 18.

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 Claim 1 or Claim 17 and/or the emulsifiable

concentrate formulation of any one of Claims 2 or 4 to 16, or the

dispersible concentrate formulation of any one of Claims 3 to 14, 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 emulsifiable concentrate formulation

with water or the water-containing liquid.