RU2809540C2 - Synergistic pesticide compositions and methods for delivering active ingredients - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: means of pest control. The synergistic pesticide composition contains in effective amounts a pesticide active ingredient selected from strobilurins, azoles, fludioxonil, chlorothalonil, cyprodinil, metalaxyl, chlorfenapyr, mancozeb, isopyrazam, oxathiapiproline, penthiopyrad or a mixture thereof, chlorantraniliprole or cyantraniliprole, and saturated or unsaturated C6-C10-aliphatic acid or an agriculturally compatible salt thereof, wherein the weight ratio of the concentration values of the pesticide active ingredient and the saturated or unsaturated C6-C10-aliphatic acid or an agriculturally compatible salt thereof is from 1:10000 to 10000:1. The pesticide active ingredient selected from strobilurins includes at least one selected from azoxystrobin, dimoxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin. The pesticide active ingredient selected from triazoles includes at least one selected from difenoconazole, epoxiconazole, propiconazole, prothioconazole, tebuconazole. A saturated or unsaturated C6-C10-aliphatic acid is a straight chain acid.

EFFECT: proposed synergistic pesticide composition increases the activity of the specified pesticide ingredients and enhances control over agricultural pests.

15 cl, 120 tbl, 21 ex

Description

LINK TO RELATED APPLICATIONS

This application claims the priority and benefit of U.S. Provisional Patent Applications No. 62/566,269, filed September 29, 2017; No. 62/580964, filed November 2, 2017; and No. 62/585827, filed November 14, 2017, which are all entitled SYNERGIC PESTICIDE COMPOSITIONS AND METHODS OF DELIVERY OF ACTIVE INGREDIENTS, all of which are incorporated by reference herein in their entirety.

TECHNICAL FIELD

One embodiment of the present invention relates to compositions and methods for increasing the effectiveness of pesticide compositions. More specifically, some embodiments relate to synergistic pesticide compositions and methods for delivering pesticide active ingredients. Some embodiments of the present invention are directed to compositions and methods for increasing the effectiveness of fungicides. Some embodiments of the present invention are directed to compositions and methods for increasing the effectiveness of nematicides. Some embodiments of the present invention are directed to compositions and methods for increasing the effectiveness of insecticides. Additional embodiments of the present invention are directed to methods for increasing the activity of pesticide active ingredients in pesticide compositions.

BACKGROUND OF THE ART

Pesticides, including fungicides, herbicides, nematicides and insecticides, are important compositions for use in household, agricultural, industrial and commercial settings, for example, to provide control of unwanted pests and/or pathogens. Ensuring effective pest control is critical in many such settings because pests and/or other pathogens, if left uncontrolled, can cause the loss and or destruction of crops or other plants, or cause harm to animals, humans, or other beneficial or essential organisms . There still remains a need for environmentally safe and effective pesticides, including fungicides, nematicides and insecticides, or compounds that increase the effectiveness of pesticides, including fungicides, nematicides and insecticides, and methods for increasing the effectiveness of pesticides, including fungicides , nematicides and insecticides, so that pesticides can be applied in a more environmentally friendly and effective way.

In agricultural settings, for example, a variety of plant pests such as insects, worms, nematodes, fungi, and plant pathogens such as viruses and bacteria are known to cause significant damage to seeds as well as ornamental and crop plants. Chemical pesticides are commonly used, but many are expensive and potentially toxic to people, animals and/or the environment and can persist long after application. Therefore, it is generally beneficial for farmers, consumers and the environment to use the least amount of chemical pesticides possible while still maintaining pest control to ensure maximum crop yield. In an increasing number of cases, chemical pesticide use has also resulted in pests developing resistance to some chemical pesticides, resulting in reduced effectiveness, the need for larger doses of pesticide chemicals, or even the cessation of some types of pesticides as effective controls. As a result, many chemical pesticides are no longer used or are otherwise limited in use.

Natural pesticide compounds or biologically derived pesticide compounds have been proposed for use in place of some chemical pesticides in an attempt to reduce the toxicity, health and environmental risks associated with the use of chemical pesticides. However, some natural or bio-derived pesticides have demonstrated lower efficacy or durability of their performance compared to competing chemical pesticides, limiting their introduction into the pesticide market as control agents.

Therefore, there still remains a need to provide improved pesticides and pesticide compositions that provide effective, cost-effective and environmentally safe control of pests that include insects, plants, fungi, nematodes, molluscs, mites, viruses and bacteria . In particular, there still remains a need for pesticide compositions that suitably minimize the amount of pesticide agents or pesticide active ingredients required to provide required or acceptable levels of pest control upon application.

Accordingly, there still remains a need to provide synergistic pesticide compositions that suitably minimize the use of pesticide agents or pesticide active ingredients as a result of synergistic effectiveness to provide desired pest control properties upon application. However, large-scale studies of experimental drug combinations in engineering fields other than agriculture have shown that synergistic combinations of drug pairs are extremely difficult and rare, where the probability of finding synergistic drug pairs is only 4-10% [Yin et al., PLOS 9:e93960 (2014); Cokol et al., Mol. Systems Biol. 7:544 (2011)]. In fact, a systematic screening of approximately 120,000 two-drug combinations based on reference drugs found less than 10% synergistic pairs, and only 5% synergistic two-drug pairs for fluconazole, a triazole-based fungicidal compound that is related to some azole-based agricultural fungicidal compounds [Borisy et al., Proc. Natl Acad. Sci. 100:7977-7982 (2003)].

It is intended that the foregoing prior art examples and the limitations that apply thereto are illustrative and not exclusive. Other limitations of the prior art will become apparent to those skilled in the art upon consideration of the present invention.

BRIEF DESCRIPTION OF THE INVENTION

In one embodiment, the present invention provides a synergistic pesticide composition comprising a pesticide active ingredient and an unsaturated C6-C10 aliphatic acid (including an unsaturated C6, C7, C8, C9 or C10 aliphatic acid) or an agriculturally compatible salt, wherein the unsaturated C6-C10 aliphatic acid contains at least one unsaturated C-C bond, and wherein the concentration ratio by weight of said pesticidal active ingredient and said saturated or unsaturated C6-C10 aliphatic acid or agriculturally compatible salt thereof is from about 1:5000 to 5000:1, and more particularly from about 1:2000 to 2000:1. In another embodiment, a synergistic pesticide composition is provided comprising a pesticide active ingredient and a saturated C6-C10 aliphatic acid (including a saturated C6-, C7-, C8-, C9- or C10-aliphatic acid) or an agriculturally compatible one thereof. salt, wherein the concentration ratio by weight of said pesticide active ingredient and said saturated C6-C10 aliphatic acid or agriculturally compatible salt thereof is from about 1:5000 to 5000:1 and more particularly from about 1:2000 to 2000:1. In yet another embodiment, a synergistic pesticide composition is provided comprising a pesticide active ingredient and an unsaturated or saturated C11 aliphatic acid or an agriculturally compatible salt thereof, wherein the ratio of the concentration values by weight of said pesticide active ingredient and said unsaturated or saturated C11 aliphatic acid or agriculturally compatible salt thereof is from about 1:5000 to 5000:1, and more particularly from about 1:2000 to 2000:1. In yet another further embodiment, a synergistic pesticide composition is provided comprising a pesticide active ingredient and an unsaturated or saturated C12 aliphatic acid or an agriculturally compatible salt thereof, wherein the ratio of the concentration values by weight of said pesticide active ingredient and said unsaturated or saturated C12- aliphatic acid or an agriculturally compatible salt thereof is from about 1:5000 to 5000:1, and more particularly from about 1:2000 to 2000:1.

In a further embodiment, there is provided a method for synergistically increasing the pesticidal activity of at least one pesticidal active ingredient adapted to control at least one target pest organism, comprising providing at least one pesticidal active ingredient that is active against said pesticidal active ingredient. at least one target pest; adding, in a synergistically effective concentration, at least one unsaturated C6-C10 aliphatic acid containing at least one unsaturated C-C bond, or an agriculturally acceptable salt thereof, to said pesticide active ingredient to obtain a synergistic pesticide composition and using said a synergistic pesticide composition at a pesticide-effective concentration to control said at least one target pest organism. In another embodiment, instead of an unsaturated C6-C10 aliphatic acid, a saturated C6-C10 aliphatic acid or agriculturally compatible salts thereof may be provided to provide a synergistic pesticide composition. In yet another embodiment, an unsaturated or saturated C11 aliphatic acid or agriculturally compatible salts thereof may be provided to provide a synergistic pesticide composition. In yet another further embodiment, an unsaturated or saturated C12 aliphatic acid or agriculturally compatible salts thereof may be provided to provide a synergistic pesticide composition. In some embodiments, the synergistic pesticide composition may comprise an unsaturated or saturated C6-C10 aliphatic acid or a biocompatible salt thereof, wherein said salt comprises, for example, at least one agriculturally, aquatically or mammalian compatible salt. In other embodiments, an unsaturated or saturated C11 aliphatic acid or a biocompatible salt thereof or an unsaturated or saturated C12 aliphatic acid or a biocompatible salt thereof may be provided.

In another embodiment, the present invention provides a pesticide composition comprising one or more pesticide agents and one or more unsaturated C6-C10 aliphatic acids or agriculturally compatible salts thereof containing at least one unsaturated C-C bond . In some other embodiments, a pesticide composition is provided comprising one or more pesticide agents and one or more saturated C6-C10 aliphatic acids or agriculturally compatible salts thereof. In some embodiments, one or more saturated or unsaturated C6-C10 aliphatic acids impart synergistic pesticidal activity to the pesticide composition relative to the pesticidal activity of the pesticide agent alone, and are present at an appropriate synergistically active concentration ratio by weight of about 1:5000 to 5000:1 and more specifically from about 1:2000 to 2000:1. In some such embodiments, an unsaturated or saturated C11 aliphatic acid or agriculturally compatible salts thereof may be provided. In some additional such embodiments, an unsaturated or saturated C12 aliphatic acid or agriculturally compatible salts thereof may be provided.

In a further embodiment, there is provided a method for synergistically increasing the pesticidal activity of at least one pesticidal active ingredient adapted to control at least one target pest organism, comprising providing at least one pesticidal active ingredient that is active against said pesticidal active ingredient. at least one target pest; adding, in a synergistically effective concentration, at least one unsaturated or saturated C6-C10 aliphatic acid or an agriculturally acceptable salt thereof to form a synergistic pesticide composition; mixing said synergistic pesticide composition with at least one surfactant-containing composition component to form a synergistic pesticide concentrate; diluting said synergistic pesticide concentrate with water to form a synergistic pesticide emulsion and applying said synergistic pesticide emulsion at a pesticide effective concentration and application rate to control said at least one target pest organism. In some such embodiments, an unsaturated or saturated C11 aliphatic acid or an agriculturally compatible salt thereof may be provided. In some additional such embodiments, an unsaturated or saturated C12 aliphatic acid or an agriculturally compatible salt thereof may be provided.

In some embodiments, the synergistic pesticide composition may comprise a concentration ratio by weight of said pesticide active ingredient and said at least one saturated or unsaturated C6-C10 aliphatic acid or agriculturally compatible salts thereof, being in about at least one from the following ranges: from 1:10000 to 10000:1, from 1:5000 to 5000:1, from 1:2500 to 2500:1, from 1:1500 to 1500:1, from 1:1000 to 1000, from 1: 750 to 750:1, 1:500 to 500:1, 1:400 to 400:1, 1:300 to 300:1, 1:250 to 250:1, 1:200 to 200:1 , from 1:150 to 150:1, from 1:100 to 100:1, from 1:90 to 90:1, from 1:80 to 80:1, from 1:70 to 70:1, from 1:60 up to 60:1, from 1:50 to 50:1, from 1:40 to 40:1, from 1:30 to 30:1, from 1:25 to 25:1, from 1:20 to 20:1, 1:15 to 15:1, 1:10 to 10:1, 1:9 to 9:1, 1:8 to 8:1, 1:7 to 7:1, 1:6 to 6:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1, 1:1.5 to 1.5 :1, and from 1.25 to 1.25:1. In a particular such embodiment, the concentration ratios of the pesticide active ingredient and said at least one saturated or unsaturated C6-C10 aliphatic acid or agriculturally compatible salt thereof in the synergistic pesticide composition are advantageously selected to provide a synergistic effect with respect to at least one target pest or target pathogen. In some embodiments, the concentration ratios of the pesticide active ingredient(s) and the at least one unsaturated or saturated C11 aliphatic acid or agriculturally compatible salts thereof in the synergistic pesticide composition may be advantageously selected to provide a synergistic effect against at least one target pest or target pathogen. In some further embodiments, the concentration ratios of the pesticide active ingredient(s) and the at least one unsaturated or saturated C11 aliphatic acid or agriculturally compatible salts thereof in the synergistic pesticide composition may be advantageously selected to provide a synergistic effect against at least one target pest or target pathogen.

In some embodiments, the synergistic pesticide composition comprises a pesticide active ingredient and an unsaturated C6-C10 aliphatic acid that contains at least one of an unsaturated C-C trans bond and an unsaturated C-C cis bond. In a further such embodiment, the unsaturated C6-C10 aliphatic acid contains at least one of a trans-2-, trans-3-, trans-4-, trans-5-, trans-6-, trans-7-, trans -8- and trans-9-unsaturated bonds. In yet another embodiment, a synergistic pesticide composition is provided comprising a pesticide active ingredient and an unsaturated C6-C10 aliphatic acid containing at least one of cis-2-, cis-3-, cis-4-, cis-5-, cis -6-, cis-7-, cis-8- and cis-9-unsaturated bonds. In some such embodiments, the pesticide composition comprises an unsaturated C11 aliphatic acid or an agriculturally compatible salt thereof containing at least one of trans-2-, trans-3-, trans-4-, trans-5-, trans -6-, trans-7-, trans-8-, trans-9-, trans-10-, cis-2-, cis-3-, cis-4-, cis-5-, cis-6-, cis -7-, cis-8-, cis-9- and cis-10-unsaturated bonds. In some additional such embodiments, the pesticide composition comprises an unsaturated C12 aliphatic acid or an agriculturally compatible salt thereof containing at least one of trans-2-, trans-3-, trans-4-, trans-5-, trans-6-, trans-7-, trans-8-, trans-9-, trans-10-, trans-11-, cis-2-, cis-3-, cis-4-, cis-5-, cis-6-, cis-7-, cis-8-, cis-9-, cis-10- and cis-11-unsaturated bonds. In some embodiments, the synergistic pesticide composition may contain at least one saturated C6-C10 aliphatic acid, such as one or more of hexanoic, heptanoic, octanoic, nonanoic and decanoic acid. In some additional embodiments, the synergistic pesticide composition may further comprise at least one second saturated or unsaturated C6-C10 aliphatic acid. In some further embodiments, the pesticide composition may further comprise at least one second unsaturated or saturated C11 or C12 aliphatic acid or an agriculturally compatible salt thereof.

In some embodiments, the at least one saturated or unsaturated C6-C10 aliphatic acid may include a naturally occurring aliphatic acid, such as an acid that may be present in natural plant or animal material or may be extracted, fractionated, or derived from him. In one such embodiment, the at least one saturated or unsaturated C6-10 aliphatic acid may include one or more naturally occurring aliphatic acids provided in the plant extract or fraction thereof. In another such embodiment, the at least one saturated or unsaturated C6-C10 aliphatic acid may include one or more naturally occurring aliphatic acids provided in the animal extract or product or a fraction thereof. In one such embodiment, the at least one saturated or unsaturated C6-C10 aliphatic acid may include a naturally occurring aliphatic acid contained in a plant oil extract such as one or more of coconut oil, palm oil, palm kernel oil, corn oil or fractions or extracts based thereon. In another such embodiment, the at least one saturated or unsaturated C6-C10 aliphatic acid may include a naturally occurring aliphatic acid contained in an extract or product of animal origin, for example, such as one or more of cow's milk, goat's milk, beef tallow and/or cow or goat butter or fractions or extracts thereof. In a specific embodiment, at least one saturated C6-C10 aliphatic acid may be provided in an extract or fraction of one or more vegetable oil extracts, such as one or more of coconut oil, palm oil, palm kernel oil, corn oil or fractions or extracts based on them. In some additional embodiments, the pesticidal composition may contain at least one saturated or unsaturated C11 or C12 aliphatic acid provided in an extract or fraction of one or more plant or animal materials.

In some embodiments, the synergistic pesticide composition exhibits synergistic inhibition of the growth of at least one target pest organism. In some embodiments, the synergistic pesticide composition contains a pesticide active ingredient at a pesticidal effective concentration and one or more saturated or unsaturated C6-C10 aliphatic acids. In some further embodiments, the synergistic pesticide composition contains a pesticide active ingredient and one or more saturated or unsaturated C6-C10 aliphatic acids at a synergistic concentration. In some embodiments, the synergistic pesticide composition has an FIC index (Fractional Inhibition Concentration Index value) of less than 1 according to a growth inhibition assay for inhibiting the growth of at least one target pest or pathogen. In some embodiments, the synergistic pesticide composition has a FIC index value of less than 0.75. In a further embodiment, the synergistic pesticide composition has a FIC index value of 0.5 or less. In some such embodiments, the one or more saturated or unsaturated aliphatic acids may include an unsaturated or saturated C11 aliphatic acid or an agriculturally compatible salt thereof. In some additional such embodiments, the one or more saturated or unsaturated aliphatic acids may include an unsaturated or saturated C12 aliphatic acid or an agriculturally compatible salt thereof.

In some embodiments, the pesticide active ingredient may include at least one of a chemical pesticide and a naturally occurring pesticide oil or extract. In a further aspect, the pesticide active ingredient may include at least one of a fungicide, a nematicide, an insecticide, an acaricide, a herbicide, and a bactericide.

In any such embodiment, the synergistic pesticide composition may contain one or more saturated or unsaturated C6-C10 aliphatic acids containing at least one carboxylic acid group, which may be linear or branched. In some embodiments, the one or more saturated or unsaturated C6-C10 aliphatic acids may include a linear monocarboxylic acid. In some embodiments, the unsaturated C6-C10 aliphatic acid may have one or more cis and trans isomers. In one embodiment, one or more saturated or unsaturated C6-C10 aliphatic acids may be unsubstituted or substituted. In some embodiments, the one or more saturated or unsaturated C6-C10 aliphatic acids may include an unsaturated aliphatic acid that may be monounsaturated or polyunsaturated, i.e. contain one, two or more unsaturated carbon-carbon (C-C) bonds, respectively. In some embodiments, the one or more unsaturated C6-C10 aliphatic acids may include an unsaturated aliphatic acid with at least one of an unsaturated C-C trans bond, an unsaturated C-C cis bond, and more than one conjugated C-C unsaturation. In some such embodiments, the one or more saturated or unsaturated aliphatic acids may include an unsaturated or saturated C11 aliphatic acid, which may be linear or branched, substituted or unsubstituted, have one or more cis and trans isomers, be monounsaturated or polyunsaturated, or contain at least one of an unsaturated C-C trans bond, an unsaturated C-C cis bond, and several conjugated C-C unsaturated bonds. In some additional such embodiments, the one or more saturated or unsaturated aliphatic acids may include an unsaturated or saturated C12 aliphatic acid, which may be linear or branched, substituted or unsubstituted, have one or more cis and trans isomers, be monounsaturated or polyunsaturated or contain at least one of an unsaturated C-C trans bond, an unsaturated C-C cis bond, and more than one conjugated C-C unsaturated bond.

In some further embodiments, one or more saturated or unsaturated C6-C10- (including C6-, C7-, C8-, C9- or C10-) aliphatic acids may include at least one of trans-hexenoic acid, cis- hexenoic acid, hexadienoic acid, hexinoic acid, trans-heptenoic acid, cis-heptenoic acid, heptadienoic acid, heptinoic acid, trans-octenoic acid, cis-octenoic acid, octadienoic acid, octanoic acid, trans-nonenoic acid, cis-nonenoic acid , nonadienoic acid, noninic acid, trans-decenoic acid, cis-decenoic acid, decadienoic acid and decinoic acid. In another embodiment, the one or more saturated or unsaturated C6-C10 aliphatic acids may include at least one of trans-hexenoic acid, cis-hexenoic acid, hexadienoic acid other than 2,4-hexadienoic acid, hexynic acid, trans- heptenoic acid, cis-heptenoic acid, heptadienoic acid, heptinoic acid, trans-octenoic acid, cis-octenoic acid, octadienoic acid, octanoic acid, trans-nonenoic acid, cis-nonenoic acid, nonadienoic acid, noninic acid, trans-decenoic acid , cis-decenoic acid, decadienoic acid and decinoic acid. In some embodiments, the one or more saturated or unsaturated aliphatic acids may include at least one unsaturated C11 or C12 aliphatic acid, such as cis-undecenoic, trans-undecanoic, cis-dodecenoic, trans-dodecenoic, undecadienoic, dodecadienic, undecynic or dodecic acid.

In some further embodiments, one or more saturated or unsaturated C6-C10- (including C6-, C7-, C8-, C9- or C10-) aliphatic acids may include at least one of hexanoic, heptanoic, octanoic, nonanoic and decanoic acid. In some embodiments, the one or more saturated or unsaturated aliphatic acids may include at least one of undecanoic acid or dodecanoic acid.

In some embodiments, the synergistic pesticide composition may contain one or more compatible or agriculturally acceptable salts of one or more saturated or unsaturated C6-C10 aliphatic acids. In one such embodiment, such compatible or agriculturally acceptable salts may include, for example, one or more of potassium, sodium, calcium, aluminum, other suitable metals, ammonium, and other agriculturally acceptable salts of one or more saturated or unsaturated C6-C10 aliphatic acids. In another embodiment, the synergistic pesticide composition may contain one or more saturated or unsaturated C6-C10 aliphatic acids or biocompatible salts thereof, wherein said salt comprises, for example, at least one agriculturally, aquatically or mammalian compatible salt . In some embodiments, the pesticide composition may contain one or more compatible or agriculturally acceptable salts of one or more saturated or unsaturated C11 or C12 aliphatic acids.

However, in some other embodiments, the synergistic pesticide composition may comprise

pesticide active ingredient and one or more saturated or unsaturated C6-C10 aliphatic acids, wherein the unsaturated C6-C10 aliphatic acid contains at least one unsaturated C-C bond, and wherein the ratio of the concentration values of said pesticide active ingredient and said saturated or unsaturated C6-C10 aliphatic acid by weight is from about 1:5000 to 5000:1 and more particularly from about 1:2000 to 2000:1. In one such embodiment, the one or more saturated or unsaturated C6-C10 aliphatic acids may not include agriculturally acceptable salts or other salt forms of the one or more saturated or unsaturated C6-C10 aliphatic acids. In a particular such embodiment, the synergistic pesticide composition may not include such salts for the desired applications, for which the acid forms of one or more saturated or unsaturated C6-C10 aliphatic acids may be preferred. In one such application, it is known that the accumulation of undesirably high concentrations of salts in some soils can have a negative impact on the productivity or fertility of the soil, such as in particular applications in salt-sensitive soils. Accordingly, in some embodiments, it may be particularly preferred to specifically exclude salt forms of one or more saturated or unsaturated C6-C10 aliphatic acids.

In another embodiment, the synergistic pesticide composition may contain a pesticide active ingredient and at least one saturated C6-C10 aliphatic acid, such as at least one of hexanoic, heptanoic, octanoic, nonanoic and decanoic acid. In an alternative embodiment, the synergistic pesticide composition may contain a pesticide active ingredient and at least one unsaturated C6-C10 aliphatic acid, but specifically excluding 2,4-hexadienoic acid. In some such embodiments, the one or more saturated or unsaturated aliphatic acids may include an unsaturated or saturated C11 aliphatic acid. In some additional such embodiments, the one or more saturated or unsaturated aliphatic acids may include an unsaturated or saturated C12 aliphatic acid.

In some embodiments of the present invention, the synergistic pesticide composition may

contain at least one saturated or unsaturated C6-C10 aliphatic acid and at least one pesticide active ingredient selected from the list including:

A) inhibitors of respiratory chain components, selected from:

complex III inhibitors acting on the Q _o site: azoxystrobin (II-1), coumethoxystrobin, cumoxystrobin, dimoxystrobin (II-2), enestroburin, phenaminestrobin, phenoxystrobin/flufenoxystrobin, fluoxastrobin (II-3), kresoxim-methyl (II-4 ), metominostrobin, orysastrobin (II-5), picoxystrobin (II-6), pyraclostrobin (II-7), pyramethostrobin, pyroxystrobin, trifloxystrobin (II-8), 2-[2-(2,5-dimethylphenoxymethyl) methyl ester )phenyl]-3-methoxyacrylic acid and 2-(2-(3-(2,6-dichlorophenyl)-1-methylallylideneaminooxymethyl)phenyl)-2-methoxyimino-N-methylacetamide, piribencarb, trichloropyricarb/chlordincarb, famoxadone, fenamidone;

complex III inhibitors acting on the Q _i site: cyazofamide, amisulbrom, [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxypyridine-2-carbonyl)amino]-6- methyl 4,9-dioxo-1,5-dioxonan-7-yl]-2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4- methoxypyridin-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]-2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3 -[(3-isobutoxycarbonyloxy-4-methoxypyridin-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]-2-methylpropanoate, [(3S,6S,7R ,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxypyridin-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5 -dioxonan-7-yl]-2-methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1, 5-dioxonan-7-yl-2-methylpropanoate;

complex II inhibitors: benodanil, benzovindiflupyr (II-9), bixafen (II-10), boscalid (II-11), carboxin, fenfuram, fluopyram (II-12), flutolanil, fluxapyroxad (II-13), furamethpyr, isofetamide , isopyrazam (II-14), mepronil, hydroxycarboxin, penflufen (II-15), penthiopyrad (II-16), sedaxane (II-17), teclophthalam, tifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethylbutyl)phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide , 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazol-4-carboxamide, 3-(trifluoromethyl)-1-methyl-N-(1,1,3 -trimethylindan-4-yl)pyrazol-4-carboxamide, 1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazol-4-carboxamide, 3-(trifluoromethyl)-1,5- dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazol-4-carboxamide, 1,3,5-trimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazol-4- carboxamide, N-(7-fluoro-1,1,3-trimethylindan-4-yl)-1,3-dimethylpyrazol-4-carboxamide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methylethyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide;

other inhibitors of respiratory chain components: diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)phenyl]ethyl}amine; binapacryl, dinobuton, dinocap, fluazinam (II-18); ferimzone; fentine salts such as fentine acetate, fentine chloride or phenyte hydroxide; ametoctradine (II-19) and silthiopham;

B) sterol biosynthesis inhibitors (SBI fungicides) selected from:

C14-demethylase inhibitors (DMI fungicides): azaconazole, bitertanol, bromuconazole, cyproconazole (II-20), difenoconazole (II-21), diniconazole, diniconazole-M, epoxiconazole (II-22), fenbuconazole, fluquinconazole (II-23) , flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole (II-24), myclobutanil, oxpoconazole, paclobutrazol, penconazole, propiconazole (II-25), prothioconazole (II-26), simeconazole, tebuconazole (II-27), tetraconazole a , triadimefon, triadimenol, triticonazole, uniconazole; imazalil, pefurazoate, prochloraz, triflumizole; fenarimol, nuarimol, pyrifenox, triforin, [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol;

delta 14-reductase inhibitors: aldimorph, dodemorph, dodemorphacetate, fenpropimorph, tridemorph, fenpropidine, piperaline, spiroxamine;

3-ketoreductase inhibitors: fenhexamide;

C) nucleic acid synthesis inhibitors selected from:

fungicides based on phenylamides or acylamino acids: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam) (II-38), ofuras, oxadixil;

other inhibitors of nucleic acid synthesis: hymexazole, octylinone, oxolinic acid, bupyrimate, 5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidine-4 -amine;

D) inhibitors of cell division and polymerization of cytoskeletal proteins, selected from:

tubulin inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl (II-39); 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,

other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone (II-40), pyriophenone;

E) amino acid and protein synthesis inhibitors selected from:

inhibitors of methionine synthesis (anilinopyrimidines): cyprodinil, mepanipyrim, pyrimethanil (II-41);

protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride hydrate, mildiomycin, streptomycin, oxytetracycline, polyoxin, validamycin A;

F) signal transduction inhibitors selected from:

MAP/histidine kinase inhibitors: fluorimide, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;

G-protein inhibitors: quinoxifene;

G) lipid and membrane synthesis inhibitors selected from:

phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane; propamocarb, propamocarb hydrochloride;

inhibitors of lipid peroxidation: dichlorane, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;

inhibitors of phospholipid biosynthesis and cell wall growth: dimethomorph (II-42), flumorph, mandipropamide (II-43), pyrimorph, benthiavalicarb, iprovalicarb, valifenalate, (4-fluorophenyl) ester N-(1-(1-(4- cyanophenyl)ethanesulfonyl)-but-2-yl)carbamic acid;

acid amide hydrolase inhibitors: oxathiapiproline;

H) inhibitors with multi-site action, selected from:

inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride (II-44), basic copper sulfate, sulfur;

thio- and dithiocarbamates: ferbam, mancozeb (II-45), maneb, metam, metiram (II-46), propineb, thiram, cineba, cyram;

organochlorine compounds: anilazine, chlorothalonil (II-47), captafol, captan, folpet, dichlorofluanide, dichlorophen, hexachlorobenzene, pentachlorophenol and its salts, phthalide, tolylfluanide, N-(4-chloro-2-nitrophenyl)-N-ethyl-4 -methylbenzenesulfonamide;

guanidines and others: guanidine, dodine, dodine in the form of a free base, guazatine, guazatin acetate, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), dithianone, 2,6-dimethyl-1H,5H-[1,4] dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (II-48);

I) cell wall synthesis inhibitors selected from:

glucan synthesis inhibitors: validamycin, polyoxin B;

melanin synthesis inhibitors: pyroquilone, tricyclazole, carpropamide, dicyclomet, fenoxanil;

J) plant defense stimulants selected from:

acibenzolar-S-methyl, probenazole, isothianil, tiadinil, prohexadione-calcium; fosetyl, fosetyl aluminum, phosphoric acid and its salts (II-49);

K) substances with an unknown mechanism of action, selected from: bronopol, quinomethionate, cyflufenamide, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamine, fenpyrazamine, flumetover, flusulfamide, flutianil, metasulfocarb, nitrapyrine, nitrotal-isopropyl, oxatia piproline , tolprocarb, 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl ]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, 2-[3,5-bis(difluoromethyl)-1H -pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2- oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4 -(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazole -2-yl)piperidin-1-yl]ethanone, oxine copper, proquinazide, tebufloquin, teclophthalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoromethoxy- 2,3-difluorophenyl)methyl)-2-phenylacetamide, N'-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidine, N'-(4- (4-fluoro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl -N-methylformamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl-N-methylformamidine, 6-tert-butyl-8-fluoro-2,3-dimethylquinoline -4-yl ester of methoxyacetic acid, 3-[5-(4-methylphenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3 -yl]pyridine (pyrisoxazole), N-(6-methoxypyridin-3-yl)cyclopropanecarboxylic acid amide, 5-chloro-1-(4,6-dimethoxypyrimidin-2-yl)-2-methyl-1H-benzoimidazole, 2 -(4-chlorophenyl)-N-[4-(3,4-dimethoxyphenyl)isoxazol-5-yl]-2-prop-2-inyloxyacetamide, ethyl-(Z)-3-amino-2-cyano-3- phenylprop-2-enoate, tert-butyl-N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate, pentyl-N-[6 -[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate, 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl )oxy]-6-fluorophenyl]propan-2-ol, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, 3-( 5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl )quinoline, 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline;

L) antifungal biopesticides selected from: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus pumilus (II-50), Bacillus subtilis (II-51), Bacillus subtilis var. amyloliquefaciens (II-52), Candida oleophila I-82, Candida saitoana, Clonostachys rosea f. catenulata, also called Gliocladium catenulatum, Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Metschnikowia fructicola, Microdochium dimerum, Phlebiopsis gigantea, Pseudozyma flocculosa, Pythium oligandrum DV74, Reynoutria sachlinensis, Talaromyces flavus V117b, Tri choderma asperellum SKT-1, T. atroviride LC52, T. harzianum T-22, T. harzianum TH 35, T. harzianum T-39; T. harzianum and T. viride, T. harzianum ICC012 and T. viride ICC080; T. polysporum and T. harzianum; T. stromaticum, T. virens GL-21, T. viride, T. viride TV1, Ulocladium oudemansii HRU3;

M) growth regulators selected from: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimetipine, 2,6-dimethylpuridine, ethephon, flumetralin, Flurpimidol, fluiaceta, perekhlorphenurone, gibberellinic acid, inabenfitis, indol-3-acetic acid, maleic hydrazide, mefluidide, mepycwate (II-54), naphtalinuxic acid, N-6-Benzidheninine, Pacificure, Podx Diona (Calcium Progosadion , II-55), prohydrojasmone, thidiazuron, triapentenol, tributyl phosphorotrithioate, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and uniconazole;

N) herbicides selected from:

acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, petoxamide, pretilachlor, propachlor, tenylchlor;

amino acid derivatives: bilanaphos, glyphosate, glufosinate, sulfosate;

aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;

bipyridyls: diquat, paraquat;

(thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;

cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;

dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;

diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; hydroxybenzonitriles: bromoxynil, dichlobenil, ioxynil;

imidazolinones: imazamethabenza, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;

phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop;

pyrazines: chloridazon, flufenpyr-ethyl, flutiacet, norflurazon, pyridate;

pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;

sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuronethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flusetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, met sulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propylimidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4, 6-dimethoxypyrimidin-2-yl)urea;

triazines: ametrine, atrazine, cyanazine, dimethamethrin, etiosine, hexazinone, metamitron, metribuzin, prometrin, simazine, terbutylazine, terbutryn, triaziflame;

ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metabenzthiazuron, tebuthiuron;

other acetolactate synthase inhibitors: bispiribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxulam, propoxycarbazone, piribambenz-propyl, pyribenzoxime, pyrifthalide, pyriminobac-methyl, pyrimisulfan, pyrithiob aka, pyroxasulfone, pyroxsulam;

other herbicides: amicarbazone, aminotriazole, anilofos, beflubutamide, benazoline, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclone, bicyclopyrone, bromacil, bromobutide, butafenacil, butamiphos, cafenstrol, carfentrazone, cinidone-ethyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide , dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, etofumezate, etobenzanide, phenoxasulfone, phentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacyl, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methylarsenous acid, napthalam, oxadiargyl, oxadiazone, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazoxifene, pyrazolinate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiene carbazone, topramazone, ethyl ester (3 -[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)phenoxy]pyridin-2-yloxy)acetic acid, 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)pyridazin-4-ol, 4-amino-3-chloro -6-(4-chlorophenyl)-5-fluoropyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid methyl ester and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluorophenyl)pyridine-2-carboxylic acid methyl ester;

O) insecticides selected from:

(thio)organophosphorus compounds: acephate, azametifos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phentoate, fosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, protiophos, sulprofos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;

carbamates: alanicarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furatiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;

pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrins I and II , resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, trans fluthrin, profluthrin, dimefluthrin;

insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazine, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diophenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramate;

nicotinic receptor agonist/antagonist compounds: clothianidin, dinotefuran, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chlorothiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3 ,5]triazinane;

GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pirafluprole, pyriprole, 5-amino-1-(2,6-dichloro-4-methylphenyl)-4-sulfinamoyl-1H-pyrazole-3-thiocarboxylic acid amide;

acaricides, which are mitochondrial electron transport inhibitors (METI) type I: phenazaquin, pyridabene, tebufenpyrad, tolfenpyrad, flufenerim;

compounds that are METI types II and III: acequinocyl, fluacyprim, hydramethylnon;

uncoupling agents: chlorfenapyr;

inhibitors of oxidative phosphorylation: cyhexatin, diafenthiuron, phenbutatin oxide, propargite;

compounds that disrupt shedding: cryomazine;

mixed-function oxidase inhibitors: piperonyl butoxide;

sodium channel blockers: indoxacarb, metaflumizone;

ryanodine receptor inhibitors: chlorantraniliprole, cyantraniliprole, flubendiamide, N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanilidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methylphenyl]-2-(3-chloro-2-pyridyl)-5-trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-methylphenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazol- 3-carboxamide; N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3 -carboxamide; N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5-(difluoromethyl)pyrazole-3-carboxamide; N-[4,6-dibromo-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3 -carboxamide; N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-cyanophenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazol- 3-carboxamide; N-[4,6-dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;

others: benclotiase, biphenazate, cartap, flonicamide, pyridalyl, pymetrozine, sulfur, thiocyclam, cyenopyrafen, flupyrazophos, cyflumetofen, amidoflumet, imitsiaphos, bistrifluron, pyrifluquinazone, ester 1,1'-[(3S,4R,4aR,6S,6aS ,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4, 6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl]cyclopropaneacetic acid; fluensulfone, fluoroalkenyl thioethers; And

P) ribonucleic acid (RNA) and related compounds, including double-stranded RNA (dsRNA), microRNA (miRNA) and small interfering RNA (siRNA); bacteriophages.

In some such embodiments, the synergistic pesticide composition may contain one or more pesticide active ingredients, such as those selected from the list above, and one or more unsaturated or saturated C11 aliphatic acids or agriculturally acceptable salts thereof. In some additional such embodiments, the synergistic pesticide composition may contain one or more pesticide active ingredients, such as those selected from the list above, and one or more unsaturated or saturated C12 aliphatic acids or agriculturally acceptable salts thereof.

In some embodiments, synergistic pesticide compositions may be provided, wherein the pesticide active ingredient comprises at least one pesticidal natural oil selected from margosa oil, karanja oil, clove oil, clove leaf oil, peppermint oil, spearmint oil, mint, cinnamon oil, thyme oil, oregano oil, rosemary oil, geranium oil, lime oil, lavender oil, anise oil, lemongrass oil, tea tree oil, apricot kernel oil, bergamot oil, carrot seed oil, cedar needle oil , citronella oil, clove bud oil, coriander oil, coconut oil, eucalyptus oil, evening primrose oil, fennel oil, ginger oil, grapefruit oil, nutkatone(+), grape seed oil, lavender oil, marjoram oil, pine oil, Scots pine oil, and/or garlic oil and/or components, derivatives and/or extracts of one or more pesticidal natural oils or combinations thereof. In some additional embodiments, synergistic pesticide compositions may be provided that contain additional active ingredients other than one or more primary pesticide active ingredients, wherein such additional active ingredients may provide one or more of additional levels of effectiveness and/or synergistic effects with respect to the pesticide. the effectiveness of the composition, for example, such as, but not limited to, excipients, synergists, agonists, activators, or combinations thereof. In one such embodiment, such additional active components may optionally include naturally occurring compounds or extracts or derivatives thereof. In other embodiments, the pesticide active ingredient may comprise, for example, at least one US Department of Agriculture ("USDA") certified organic, National Organic Program ("NOP compliant") organic, such as one that may be included in the US Environmental Protection Agency's FIFRA 25b list of ingredients published in December 2015. US EPA entitled "Active Ingredients Acceptable in Minimum Risk Pesticide Products" in the US EPA's FIFRA 4a list published in August 2004 entitled "List 4A - Minimal Risk Inert Ingredients", or the US EPA's FIFRA 4b list published in August 2004 entitled "List 4B - Other Ingredients for Which EPA Has Sufficient Information" for example, an Organic Materials Institute-listed (“OMRI-listed”) or natural pesticide active ingredient.

In some embodiments, the pesticidal active ingredient may include at least one of margosa oil, karanja oil, and extracts or derivatives thereof. In additional illustrative such embodiments, the pesticidal active ingredient may include at least one extract or active component of margosa oil or karanja oil, such as, for example, but not limited to azadirachtin, azadiradione, azadiron, nimbin, nimbidin, salannin, deacetylsalannin, salannol, maliantriol, gedunin , karanjin, pongamol or their derivatives.

BRIEF DESCRIPTION OF GRAPHIC MATERIALS

Exemplary embodiments are illustrated with reference to the figures shown in the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative and not limiting.

In fig. 1 illustrates the general structures of carbonylalkenes (1), (2), (3), (4), (5), (6) and (7) associated with illustrative saturated or unsaturated C6-C10 aliphatic acids or their acceptable from an agricultural perspective with salts in accordance with one embodiment of the present invention.

In fig. 2 illustrates an exemplary 96-well microtiter plate showing the color transition of a resazurin dye between colors indicating the absence and presence of growth of an exemplary pest or pathogen in accordance with a synergistic growth inhibition assay in accordance with one embodiment of the present invention.

In fig. Figures 3-5 illustrate the observed survival rate (percentage of the initial number of insects that still survive) for Trichoplusia ni (the cutworm caterpillar) as a function of time for in-vitro testing on modified McMorran's artificial culture medium, which was treated with a separate insecticide treatment Pylon® (containing chlorfenapyr as a pesticide active ingredient) and exemplary unsaturated aliphatic acids (and salts), compared with the corresponding survival rates when treated with a synergistic pesticide composition combining Pylon® insecticide with each of the exemplary unsaturated aliphatic acids (and salts) ) at three concentration levels (shown in FIGS. 3, 4 and 5, respectively) in accordance with one embodiment of the present invention.

DETAILED DESCRIPTION OF SEVERAL IMPLEMENTATION OPTIONS

Throughout the following description, specific details are presented in order to provide a more complete understanding to those skilled in the art. However, well-known elements may not be shown or described in detail to avoid unnecessary complexity of the disclosure. Accordingly, the description and graphics should be considered in an illustrative and not restrictive sense.

DEFINITIONS

Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which the present invention belongs. Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described herein.

All applications, publications, patents and other literature references herein are incorporated by reference in their entirety. In case of discrepancy, the description, including definitions, will control.

As used herein, the singular forms include the plural entities defined unless the context clearly indicates otherwise.

All numeric values or numeric ranges used herein include integers within such ranges and fractions of values or integers within ranges unless the context clearly indicates otherwise. Thus, for example, reference to the range 90-100% includes 91%, 92%, 93%, 94%, 95%, 95%, 97%, etc., as well as 91.1%, 91.2 %, 91.3%, 91.4%, 91.5%, etc., 92.1%, 92.2%, 92.3%, 92.4%, 92.5%,, and etc., etc.

As used herein, the term “plant” includes individual plants or groups of plants of any type of plant, particularly agricultural, silvicultural and ornamental plants.

As used herein, the terms "pest" or "pests" or their grammatical equivalents are intended to refer to organisms, for example including pathogens, that adversely affect a host or other organism, such as a plant or animal, by colonizing, damaging , destruction, competition with them for nutrients, their damage or infection, as well as unwanted organisms that affect man-made structures, living quarters, useful areas or food products. Pests include, but are not limited to, fungi, weeds, nematodes, mites and arthropods, including insects, arachnids and cockroaches. It is understood that the terms "pest" or "pests" or their grammatical equivalents can mean organisms that cause negative effects by attacking plants and seeds, as well as commodities such as stored grain.

As used herein, the terms “pesticide” or “pesticidal” or their grammatical equivalents are intended to mean any composition or substance that can be used in the control of any agricultural, environmental and household pests. The terms “control” or “control” are intended to include, without limitation, any of the killing, suppressive, growth regulating, or pesticidal effects of the composition on a particular pest. Such terms include, for example, a sterilizing effect that prevents the production or normal development of seeds, eggs, sperm or spores, causes the destruction of seeds, sperm, eggs or spores, or otherwise causes serious damage to genetic material. Additional effects which are intended to be within the scope of the terms "control" or "exerting control" include preventing the development of larvae into mature offspring, modulating the emergence of pests from eggs, including preventing hatching, destroying egg material, marinating, inhibiting mycelial growth, decreased intestinal motility, suppression of chitin formation, disruption of mating or sexual communication, antifeeding effects, and inhibition of finding hosts, mates, or nutrient sources. The term "pesticide" includes fungicides, herbicides, nematicides, insecticides and the like. The term "pesticide" includes, without limitation, naturally occurring compounds, as well as so-called "synthetic chemical pesticides" characterized by structures or compositions that do not occur in nature, where pesticides can be produced in a variety of ways, including, but not limited to, extraction from biological sources, chemical synthesis of a compound, and chemical modification of naturally occurring compounds derived from biological sources.

As used herein, the terms “insecticidal” and “acaricidal” or “aphicide” or their grammatical equivalents are intended to mean substances having pesticidal activity against organisms included in the taxonomic classification of the root term, and also mean substances having pesticidal activity against organisms included in the colloquial uses of the root term, where such colloquial uses may not correspond strictly to taxonomic classifications. The term "insecticidal" is intended to mean substances having pesticidal activity against organisms commonly known as insects of the phylum Arthropods, class Insects. In addition, it is also intended that the term as used herein means substances having pesticidal activity against other organisms colloquially referred to as "insects" or "bugs" included in the phylum Arthropods, although the organisms may be classified as belonging to the taxonomic a class other than the class Insects. According to this interpretation, the term "insecticidal" can be used to mean substances having activity against arachnids (class Arachnidae), particularly mites (subclass Mites), given the colloquial use of the term "insect". The term "acaricidal" is intended to mean substances having pesticide activity against mites (Mites) of the phylum Arthropods, class Arachnida, subclass Mites. The term "aphicide" is intended to mean substances having pesticidal activity against aphids (True aphids) of the phylum Arthropods, class Insects, family True aphids. All such terms are intended to be covered by the term “pesticide” or “pesticide” or grammatical equivalents. It is understood that such terms are not necessarily mutually exclusive, so substances known as "insecticides" may have pesticidal activity against organisms in any family of the class Insects, including aphids, and organisms that are covered by other colloquial uses of the term "insect" or "bug", including arachnids and mites. It will be understood that "insecticides" may also be known as acaricides if they have pesticidal activity against mites, or aphicides if they have pesticidal activity against aphids.

As used herein, the terms "control" or "control" or their grammatical equivalents are intended to cover any pesticidal effects (killing) or pestistatic effects (suppression, deterrence, containment and generally interfering with the activity of a pest to prevent damage to the host plant). ) pesticide composition against a specific pest. Thus, the terms "control" or "exerting control" or their grammatical equivalents not only include destruction, but also include such effects as repelling, restraining, suppressing or stopping the development or hatching of an egg, suppressing maturation or development, and chemical sterilization of larvae or adults individuals. Repellent or deterrent effects can be obtained using compounds that are toxic, mildly toxic or non-toxic to pests or that can act as pheromones in the environment.

As used herein, the term “pesticidal effective amount” generally means the amount of mixtures of the present invention, or compositions containing mixtures, necessary to achieve an observable effect on growth, including the effects of necrosis, killing, stunting, prevention and removal, destruction or otherwise. way of reducing the frequency and activity of the target pest. The pesticide effective amount may vary for different mixtures/compositions used in the present invention. The pesticidal effective amount of mixtures/compositions will also vary according to prevailing conditions, such as desired pesticide effect and duration, weather, target species, habitat, method of application, and the like.

As used herein, compatible or agriculturally acceptable salts, the aquatic or mammalian compatible salt may be, for example, one or more of potassium, sodium, calcium, aluminum, other suitable metals, ammonium, and other agriculturally acceptable salts. From the point of view of agriculture, salts of saturated or unsaturated C6-C10 aliphatic acids.

As used herein, the presented range of values implies that every intermediate value up to a tenth of a unit lower limit, unless the context clearly requires otherwise, between the upper and lower limits of that range and every other specified or intermediate value within that specified range is covered by embodiments of the present invention. The upper and lower limits of such smaller ranges may independently define a smaller range of values, and it should be understood that such smaller ranges are intended to be covered by embodiments of the present invention to the exclusion of any specifically excluded limit within said range.

In one embodiment, in accordance with the present invention, the synergistic pesticide composition contains a saturated or unsaturated C6-C10 aliphatic acid (or an agriculturally acceptable salt thereof) and at least one pesticide active ingredient. All references used herein to saturated or unsaturated C6-C10 aliphatic acid include all saturated or unsaturated aliphatic acids containing from 6 to 10 carbon atoms, for example, C6-, C7-, C8-, C9- or C10-, and any combination or subcombination of them, for example, C6- and C8-, C7- and C10-, C6-, C9- and SY-, etc. In some embodiments, the effective dose of the pesticide active ingredient when used in combination with one or more saturated or unsaturated C6-C10 aliphatic acids is lower than the effective dose of the pesticidal active ingredient when used alone (i.e., less pesticide active ingredient is all may also provide pest control when used in a synergistic composition with one or more saturated or unsaturated C6-C10 aliphatic acids). In some embodiments, a pesticidal active ingredient that is not effective against a particular pest species may become effective against that particular species when used in a synergistic composition with one or more saturated or unsaturated C6-C10 aliphatic acids. In some such embodiments, the pesticide composition may contain a saturated or unsaturated C11 aliphatic acid or an agriculturally compatible salt thereof. In some additional such embodiments, the pesticide composition may contain a saturated or unsaturated C12 aliphatic acid or an agriculturally compatible salt thereof.

Without wishing to be bound by any particular theory, it is believed that one or more saturated or unsaturated C6-C10 aliphatic acids in accordance with some embodiments of the present invention act as cellular permeabilization agents and, when combined with a suitable pesticide active ingredient, can suitably promote the passage pesticide active ingredient into the cells of the target pest or target pathogen, thereby suitably providing synergistic activity of such synergistic pesticide composition. All eukaryotic cell membranes, including, for example, fungal cell membranes and insect and nematode cell membranes, are biochemically similar in that they all contain a lipid bilayer, which consists of phospholipids, glycolipids and sterols, as well as a large number of proteins (Cooper & Hausmann 2013). The amphipathic structure of the lipid bilayer and the polarity of membrane proteins limit the passage of extracellular compounds through the membrane and ensure the separation of internal organelles from the intracellular environment. Without limiting any theory, it is believed that one or more saturated or unsaturated C6-C10 aliphatic acids, in accordance with some embodiments disclosed herein, will act as cellular permeabilization agents and, when combined with a suitable pesticide active ingredient, can suitably act as facilitating the passage of an active ingredient (such as, but not limited to, fungicidal, insecticidal, acaricidal, molluscicidal, bactericidal and nematicidal active ingredients) into cells and/or intracellular organelles or intracellular bodies of a target pest or target pathogen (such as, but not limited to fungi, insects, mites, mollusks, bacteria and nematodes, respectively). In a further embodiment, without being bound by any theory, it is believed that the size and/or polarity of many pesticide molecules prevents and/or limits the passage of the pesticide active ingredient through the cell membrane, but the addition of one or more saturated or unsaturated C6-C10 aliphatic acids in accordance with In some embodiments, the present disclosure may suitably reduce or disrupt the integrity of the lipid bilayer or protein organization of the pest's cell membrane by creating gaps in the membrane and/or increasing membrane fluidity to allow, for example, more efficient passage of the pesticide active into the cell and/or intracellular organelles of the cells pest

In another aspect, without being bound by any theory, it is believed that one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) in accordance with some embodiments of the present invention act as at least one of a potentiator, synergist, excipient and/or agonist when combined with a suitable pesticide active ingredient, thereby suitably providing synergistic activity of such synergistic pesticide composition against the target pest or target pathogen.

In some embodiments, the synergistic pesticide composition of the present invention contains one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) as an exemplary cellular permeabilization agent in combination with pesticide. In some embodiments, the synergistic composition contains one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) as an exemplary cell permeabilization agent in combination with a fungicide. In some embodiments, the synergistic composition contains one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) as an exemplary cell permeabilization agent in combination with a nematicide. In some embodiments, the synergistic composition contains one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) as an exemplary cell permeabilization agent in combination with an insecticide.

In one such embodiment, without being bound by any theory, it is believed that one or more saturated or unsaturated C6-C10 aliphatic acids can act as a cell membrane delivery vehicle by improving the passage and/or bioavailability or systemic distribution of the pesticide active ingredient into cell of the target pest and/or in an intracellular organelle of the pest and thus, for example, facilitate the passage of the pesticide active ingredient into the mitochondria of the pest cells. In some other embodiments, without being limited by any theory, one or more saturated or unsaturated C6-C10 aliphatic acids may further provide a synergistic interaction with one or more additional compounds provided as part of the pesticide composition, such as one or more additional saturated C6-C10 aliphatic acids, or one or more unsaturated C6-C10 aliphatic acids, or one or more additional active ingredients or excipients, providing, for example, a synergistic improvement in the pesticidal effect provided by the at least one pesticidal active ingredient.

In another aspect, without being bound by any theory, it is believed that one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) in accordance with some embodiments of the present invention act as at least one of a potentiator, synergist, excipient and/or agonist when combined with a suitable pesticide ingredient, thereby suitably providing synergistic activity of such synergistic pesticide composition against the target pest or target pathogen.

Without being limited to any particular theory, in some embodiments of the present invention it is believed that one or more saturated or unsaturated C6-C10 aliphatic acids act to reduce or alter the integrity of the lipid bilayer and the organization of cell membrane proteins in target pest organisms. In addition, it is also believed that in some embodiments, one or more saturated or unsaturated C6-C10 aliphatic acids are particularly suited for combining to form synergistic pesticide compositions in accordance with embodiments of the present invention that demonstrate synergistic effectiveness with pesticide actives , which are characterized by a pesticide mechanism of action dependent on interaction with one or more components of the cell membrane of the target pest. In some such embodiments, one or more saturated or unsaturated C6-C10 aliphatic acids may be particularly suited to combine to form a synergistic pesticide composition exhibiting synergistic effectiveness with pesticide actives that have a mechanism of action dependent on interaction with a cell membrane protein . In one such embodiment, the cell membrane protein may comprise one or more cytochrome complexes, such as, for example, a cytochrome bc1 complex or a cytochrome p450 complex. Accordingly, in one aspect, synergistic pesticide compositions in accordance with some embodiments of the present invention may be suitably selected to include one or more saturated or unsaturated C6-C10 aliphatic acids and one or more pesticide actives having a pesticidal mode of action dependent on interaction with one or more components of the cell membrane of the target pest, such as, for example, a cell membrane protein. In one aspect, one or more saturated or unsaturated C11 or C12 aliphatic acids are provided in combination with one or more pesticidal actives having a pesticidal mechanism of action dependent on interaction with one or more components of the cell membrane of the target pest, e.g. cell membrane protein.

In a specific embodiment, one or more saturated or unsaturated C6-C10 aliphatic acids are particularly adapted to be combined to form synergistic pesticide compositions in accordance with embodiments of the present invention that demonstrate synergistic effectiveness, with pesticide actives having a pesticidal mechanism of action that involves interaction (such as inhibition of one or more receptor sites) with the cytochrome bc1 complex of the cell membrane (also known as the cytochrome III complex), such as fungicidal actives, collectively referred to by the Fungicide Resistance Prevention Committee (FRAC) as group 11 actives, including, for example, azoxystrobin, cumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, trichloropyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, phenaminstrobin, metominostrobin, orysastrobin, famoxadone, fluoxastrobin, fenamidone or pyr ibenkar. In one such embodiment, the synergistic pesticide composition may be selected to include one or more saturated or unsaturated C6-C10 aliphatic acids and a pesticide active agent having a pesticidal mechanism of action that involves interaction with the cytochrome bc1 cellular complex, such as a pesticide active agent on based on strobilurin. In alternative such embodiments, the synergistic pesticide composition contains one or more saturated or unsaturated C11 or C12 aliphatic acids.

In another specific embodiment, one or more saturated or unsaturated C6-C10 aliphatic acids are particularly adapted to be combined to form synergistic pesticide compositions in accordance with embodiments of the present invention that demonstrate synergistic effectiveness with pesticide actives having a pesticidal mode of action, which involves interaction (such as inhibition of one or more receptor sites) with the cytochrome p450 complex of the cell membrane, such as inhibition of sterol biosynthesis, as is the case with exemplary fungicidal actives collectively referred to as FRAC Group 3 actives, including, for example, triforin, pyrifenox, pirizoxazole, fenarimol, nuarimol, imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizole, aconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole , imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole or prothioconazole. In one such embodiment, the synergistic pesticide composition may be selected to include one or more saturated or unsaturated C6-C10 aliphatic acids and a pesticidal active agent having a pesticidal mechanism of action that involves interaction with the cytochrome p450 cellular complex, for example, such as a pesticide active azole or triazole based substance. In alternative such embodiments, the synergistic pesticide composition contains one or more saturated or unsaturated C11 or C12 aliphatic acids.

In another specific embodiment, one or more saturated or unsaturated C6-C10 aliphatic acids are particularly adapted to be combined to form synergistic pesticide compositions in accordance with embodiments of the present invention that demonstrate synergistic effectiveness with pesticide actives having a pesticidal mode of action, which involves interaction (such as inhibition of one or more receptor sites) with the cell membrane, such as uncoupling of oxidative phosphorylation, as is the case with exemplary insecticidal actives collectively referred to by the Insecticide Resistance Prevention Committee (IRAC) Group 13 actives including , for example, quinoxifene or proquinazide. In one such embodiment, the synergistic pesticide composition may be selected to include one or more saturated or unsaturated C6-C10 aliphatic acids and a pesticidal active agent having a pesticidal mode of action that involves interaction with the cell membrane, such as a pyrrole-based insecticidal active agent , an example of which is chlorfenapyr. In alternative such embodiments, the synergistic pesticide composition contains one or more saturated or unsaturated C11 or C12 aliphatic acids.

Without being limited to any particular theory, in certain additional embodiments of the present invention, one or more saturated or unsaturated C6-C10 aliphatic acids are believed to act to reduce or alter the integrity of the lipid bilayer and the organization of cell membrane proteins in target pest organisms , and are thus effective in increasing at least one of the fluidity and permeability of the cell membrane of the target pest, which, for example, may suitably increase the permeability and/or transport of the pesticide active substance across the cell membrane. In addition, it is also believed that in some embodiments, one or more saturated or unsaturated C6-C10 aliphatic acids are particularly suited for combining to form synergistic pesticide compositions in accordance with embodiments of the present invention that demonstrate synergistic effectiveness with pesticide actives , which are characterized by a pesticidal mechanism of action dependent on transport across one or more cell membranes of the target pest, such as interaction with a target site within a cell or intracellular organelle of the target pest. In some such embodiments, a synergistic pesticide composition in accordance with one embodiment of the present invention demonstrating synergistic effectiveness may contain one or more saturated or unsaturated C6-C10 aliphatic acids and one or more pesticide actives characterized by a transport-dependent mechanism of action through the cell membrane. Accordingly, in one aspect, synergistic pesticide compositions in accordance with some embodiments of the present invention may be suitably selected to include one or more saturated or unsaturated C6-C10 aliphatic acids and one or more pesticide actives having a pesticidal mode of action dependent on interaction with a target site within a cell or intracellular organelle of the target pest, such as, for example, a cell membrane protein. In alternative such embodiments, the synergistic pesticide composition contains one or more saturated or unsaturated C11 or C12 aliphatic acids.

In a specific embodiment, one or more saturated or unsaturated C6-C10 aliphatic acids are particularly adapted to be combined to form synergistic pesticide compositions in accordance with embodiments of the present invention that demonstrate synergistic effectiveness, with pesticide actives having a pesticidal mechanism of action that involves interaction (such as inhibition of one or more receptors) with a target site through the cell membrane of the target pest, for example, such as fungicidal active substances, collectively called FRAC group 9 and group 12 active substances, including, for example, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil or fludioxonil. In one such embodiment, the synergistic pesticide composition may be selected to include one or more saturated or unsaturated C6-C10 aliphatic acids and a pesticidal active agent having a pesticidal mechanism of action that involves interaction with a target site within the cell membrane of the target pest, e.g. , such as one or more of an anilinopyrimidine such as cyprodinil, and a phenylpyrrole such as fludioxonil. In alternative such embodiments, the synergistic pesticide composition contains one or more saturated or unsaturated C11 or C12 aliphatic acids.

Without being limited to any particular theory, in some further embodiments of the present invention, it is believed that one or more saturated or unsaturated C6-C10 aliphatic acids act to reduce or alter the integrity of the lipid bilayer and the organization of cell membrane proteins in pest organisms representing the target, and are thus effective in increasing at least one of the fluidity and permeability of the cell membrane of the target pest, which, for example, may suitably increase the permeability and/or transport of the pesticide active substance across the cell membrane. In addition, it is also believed that in some preferred embodiments, one or more unsaturated C6-C10 aliphatic acids containing unsaturated C-C bonds at one or more of the second (2-), third (3-), and terminal ((n -1)-) positions of the aliphatic acid carbon chain are particularly suited for combining to form synergistic pesticide compositions in accordance with embodiments of the present invention that demonstrate synergistic effectiveness with pesticide actives. In some specific such embodiments, one or more C6-C10 aliphatic acids containing an unsaturated C-C bond at one or more of the 2-, 3-, and (n-1)- positions (where n is the number of carbon atoms in the unsaturated aliphatic acid) may be suitably particularly adapted to form synergistic pesticide compositions in combination with one or more pesticide active substances characterized by a pesticidal mechanism of action dependent on interaction with a component of the cell membrane of the target pest or dependent on transport across one or more cell membranes target pest (such as interaction with a target site within a cell or intracellular organelle of the target pest). In some such embodiments, a synergistic pesticide composition in accordance with one embodiment of the present invention demonstrating synergistic effectiveness may contain one or more unsaturated C6-C10 aliphatic acids containing an unsaturated C-C bond at one or more of the 2-, 3-positions - and a terminal position ((n-1)-) in the carbon chain of the aliphatic acid, and one or more pesticide active substances characterized by a mechanism of action dependent on interaction with a component of the cell membrane of the target pest or on transport across the cell membrane of the target pest. In alternative such embodiments, the synergistic pesticide composition comprises one or more unsaturated C11 or C12 aliphatic acids containing an unsaturated C-C bond at one or more of the 2-, 3-, and terminal ((n-1)- positions).

In some embodiments, the one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) provide an aliphatic carbonylalkene. In some embodiments, the one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) comprise at least one unsaturated C6-C10 aliphatic acid containing at least one carboxylic acid group and at least one unsaturated C-C bond. In another embodiment, the unsaturated C6-C10 aliphatic acid (or an agriculturally acceptable salt thereof) comprises at least two unsaturated C6-C10 aliphatic acids containing at least one carboxylic acid group and at least one unsaturated bond S-S. In yet another embodiment, the unsaturated C6-C10 aliphatic acid (or an agriculturally acceptable salt thereof) contains at least one carboxylic acid group and at least one of a C-C double and triple bond. In a further embodiment, a synergistic pesticide composition is provided comprising at least one pesticide active ingredient and at least one unsaturated C6-C10 aliphatic acid (or an agriculturally acceptable salt thereof) containing at least one carboxylic acid group and at least one unsaturated C-C bond, in combination with at least one saturated C6-C10 aliphatic acid (or an agriculturally acceptable salt thereof). In yet another embodiment, the saturated or unsaturated C6-C10 aliphatic acid may be in the form of a plant extract or oil or fraction thereof containing, for example, at least one saturated or unsaturated C6-C10 aliphatic acid.

In some embodiments, the one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) provide an aliphatic carbonylalkene characterized by one of the general structures (1), (2), (3), (4 ), (5), (6) or (7) shown in FIG. 1. In some embodiments, the saturated or unsaturated C6-C10 aliphatic acid may be provided in an agriculturally acceptable salt form.

In some embodiments, the composition contains one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) and a fungicidal active ingredient. In some embodiments, the effective dose of the fungicidal active ingredient when used in combination with one or more saturated or unsaturated C6-C10 aliphatic acids is lower than the effective dose of the fungicidal active ingredient when used alone (i.e., less fungicidal active ingredient is all may also provide fungal control when used in a composition with one or more saturated or unsaturated C6-C10 aliphatic acids). In some embodiments, a fungicidal active ingredient that is not effective against a particular fungal species (e.g., at a certain concentration that is less than the lower limit of effectiveness for a particular fungus or for a particular fungal species that may be at least partially resistant or tolerant to a particular fungicidal active ingredient when used alone) may become effective against that particular species when used in a composition with one or more saturated or unsaturated C6-C10 aliphatic acids.

In some embodiments, the composition contains one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) and a nematicidal active ingredient. In some embodiments, the effective dose of the nematicidal active ingredient when used in combination with one or more saturated or unsaturated C6-C10 aliphatic acids is lower than the effective dose of the nematicidal active ingredient when used alone (i.e., less of the nematicidal active ingredient is all may also control nematodes when used in a composition with one or more saturated or unsaturated C6-C10 aliphatic acids). In some embodiments, a nematicidal active ingredient that is not effective against a particular nematode species (e.g., at a certain concentration that is less than the lower limit of effectiveness for a particular nematode or for a particular nematode species that may be at least partially resistant or tolerant against specific nematicidal active ingredient when used alone) may become effective against that specific species when used in a composition with one or more saturated or unsaturated C6-C10 aliphatic acids.

In some embodiments, the composition contains one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) and an insecticidal active ingredient. In some embodiments, the effective dose of the insecticidal active ingredient when used in combination with one or more saturated or unsaturated C6-C10 aliphatic acids is lower than the effective dose of the insecticidal active ingredient when used alone (i.e., less insecticidal active ingredient is all may also provide insect control when used in a composition with one or more saturated or unsaturated C6-C10 aliphatic acids). In some embodiments, an insecticidal active ingredient that is not effective against a particular insect species (e.g., at a certain concentration that is less than the lower limit of effectiveness for a particular insect or for a particular insect species that may be at least partially resistant or tolerant against a particular insecticidal active ingredient when used alone) may become effective against that particular species when used in a composition with one or more saturated or unsaturated C6-C10 aliphatic acids. In further embodiments, one or more saturated or unsaturated C6-C10 aliphatic acids may suitably provide a synergistic increase in the effectiveness of at least one of the acaricidal, molluscicidal, bactericidal or virucidal active ingredient such that the composition is pesticidally effective against one or more of pests such as mites, shellfish, bacteria or viruses.

In some embodiments, the composition contains one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) and a pesticidal natural or essential oil, such as margosa oil. In some embodiments, the pesticidal natural oil may include, for example, one or more of margosa oil, karanja oil, clove oil, peppermint oil, peppermint oil, cinnamon oil, thyme oil, oregano oil, geranium oil, lime oil, lavender oil, anise oil and/or garlic oil and/or components, derivatives and/or extracts of one or more pesticidal natural oils or combinations of the above. In some embodiments, the pesticidal natural oil is margosa oil or a component or derivative thereof. In another embodiment, the pesticidal natural oil comprises karanja oil or a component or derivative thereof. In another embodiment, the pesticidal natural oil comprises thyme oil or a component or derivative thereof.

In other embodiments, the pesticidal natural oil may include any natural oil or mixture of oils that includes one or more constituents common to two or more pesticidal natural oils listed above (i.e., margosa oil, karanji oil, clove oil, peppermint oil pepper, cinnamon oil, thyme oil, oregano oil, garlic oil, anise oil, geranium oil, lime oil, lavender oil), including but not limited to thymol (found in oregano oil and thyme oil), p-cymene (found in oil oregano and thyme oil), 1,8-cineole (found in thyme oil and peppermint oil), eugenol (found in clove oil and cinnamon oil), limonene (found in cinnamon oil, peppermint oil and lime oil), alpha- pinene (found in cinnamon oil, geranium oil and lime oil), carvacrol (found in oregano oil, thyme oil and clove oil), gamma-terpinene (found in oregano oil and lime oil), geraniol (found in thyme oil and geranium oil ), alpha-terpineol (found in thyme oil and anise oil), beta-caryophyllene (found in clove oil, cinnamon oil, and peppermint oil), and linalool (found in thyme oil, cinnamon oil, and geranium oil, among others). In other embodiments, the pesticidal natural oil may include any oil containing as a constituent one or a combination of the following compounds: azadirachtin, nimbin, nimbinin, salannin, gedunin, geraniol, geranial, gamma-terpinene, alpha-terpineol, beta-caryophyllene , terpinen-4-ol, myrcenol-8, thuyanol-4, benzyl alcohol, cinnamaldehyde, cinnamyl acetate, alpha-pinene, geranyl acetate, citronellol, citronellyl formate, isomenthone, 10-epi-gamma-eudesmol, 1,5-dimethyl-1 -vinyl-4-hexenylbutyrate, 1,3,7-octatriene, eucalyptol, camphor, diallyl disulfide, methylallyl trisulfide, 3-vinyl-4H-1,2-dithiin, 3-vinyl-1,2-dithiol-5-cyclohexane, diallyl trisulfide , anethole, methyl chavicol, anisaldehyde, estragole, linalyl acetate, geranial, beta-pinene, thymol, carvacrol, p-cymene, beta-myrcene, alpha-myrcene, 1,8-cineol, eugenol, limonene, alpha-pinene, menthol, menthone and linalool.

In additional embodiments, the pesticidal natural oil may include one or more suitable plant-derived essential oils or extracts or fractions thereof disclosed herein, including, without limitation, alpha or beta pinene; alpha-campholenic aldehyde; alpha-citronellol; alpha-isoamyl cinnamaldehyde (eg amyl cinnamaldehyde); alpha-pinene oxide; alpha-cinnamon terpinene; alpha-terpineol (eg 1-methyl-4-isopropyl-1-cyclohexen-8-ol); lambda terpinene; yarrow oil; C16-aldehyde (pure); allicin; alpha-phellandrene; amylcinnamaldehyde; amyl salicylate; anethole; anise oil; anise seed oil; anisealdehyde; basil oil; laurel oil; benzyl acetate; benzyl alcohol; bergamot oil (e.g. Monardia fistulosa, Monarda didyma, Citrus bergamia, Monarda punctata); orange peel oil; black pepper oil; borneol; calamus oil; camphor; ylang-ylang oil (such as Javanese); cardamom oil; oil of cloves (eg Dianthus caryophyllus); carvacrol; carveol; cassia oil; Castor oil; cedar oil (for example, blunt-leaved cypress); cedar tree oil; chamomile oil; cineole; cinnamaldehyde; cinnamon alcohol; cinnamon oil; cis-pinane; citral (eg 3,7-dimethyl-2,6-octadienal); citronella oil; citronellal; dextro-citronellol (eg 3,7-dimethyl-6-octen-1-ol); citronellol; citronelli acetate; citronellylnitrile; Unshiu mandarin oil; clary sage oil; clove oil (eg Eugenia caryophyllus); clove bud oil; coriander oil; corn oil; cotton seed oil; d-dihydrocarvone; decylaldehyde; diallyl disulfide; diethyl phthalate; dihydroanethole; dihydrocarveol; dihydrolinalool; dihydromyrcene; dihydromyrcenol; dihydromyrcenyl acetate; dihydroterpineol; dimethyl salicylate; dimethyloctanal; dimethyloctanol; dimethyloctanylacetate; diphenyl oxide; dipropylene glycol; d-limonene; d-pulegone; estragole; ethyl vanillin (eg 3-ethoxy-4-hydrobenzaldehyde); eucalyptol (eg cineole); Eucalyptus citriodora oil; Eucalyptus globulus oil; eucalyptus oil; eugenol (eg 2-methoxy-4-allylphenol); evening primrose oil; fenchol; fennel oil; ferniol.TM.; fish fat; florazone (eg, 4-ethyl-alpha, alpha-dimethylbenzenepropanal); galaxolide; geraniol (eg 2-trans-3,7-dimethyl-2,6-octadiene-8-ol); geraniol; geranium oil; geranyl acetate; geranylnitrile; ginger oil; grapefruit oil; guaiacol; guaiac tree oil; Guryun balsam; heliotropin; herbanate (eg 3-(1-methylethyl)bicyclo(2,2,1)-hept-5-ene-2-carboxylic acid ethyl ester); Japanese arborvitae oil; hydroxycitronellal; i-carvone; i-methyl acetate; ionone; isobutylquinolein (eg 6-sec.butylquinoline); isobornyl acetate; isobornyl methyl ether; isoeugenol; isolongifolene; jasmine oil; jojoba oil; juniper oil; lavender oil; lavandin; lemongrass oil; lemon oil; lime oil; limonene; linalooloxide; linalool; linalyl acetate; linseed oil; Litsea cubeba oil; I-methyl acetate; longifolene; tangerine oil; mint oil; menthane hydroperoxide; menthol crystals; levomenthol (eg 5-methyl-2-isopropylcyclohexanol); menthol; levomentone (eg 4-isopropyl-1-methylcyclohexan-3-one); methyl anthranilate; methyl cedryl ketone; methylchavicol; methylhexyl ether; methylionone; mineral oil; mint oil; amber musk; musk ketone; musk-xylene; mustard oil (also known as allyl isothiocyanate); myrcene; nerol; neryl acetate; nonylaldehyde; nutmeg oil (for example, nutmeg); orange oil (eg Citrus aurantium dulcis); orris root oil (eg Iris florentina); para-cymene; para-hydroxyphenylbutanone crystals (eg 4-(4-hydroxyphenyl)-2-butanone); Palmosa oil (for example, Cymbopogon martini); patchouli oil (eg Pogostemon cablin); p-cymene; flea mint oil; pepper oil; peppermint oil (eg Mentha piperita); perillaldehyde; petitgrain oil (eg Citrus aurantium amara); phenylethyl alcohol; phenylethyl propionate; phenylethyl 2-methylbutyrate; allspice oil; allspice leaf oil; pinane hydroperoxide; pinanol; ester from pine oil; oil and pine needles; pine oil; pinene; piperonal; piperonyl acetate; piperonyl alcohol; plinol; plinyl acetate; pseudoionone; Rodinol; rhodinyl acetate; Rosalyn; rose oil; rosemary oil (eg Rosmarinus officinalis); Ophiopogon japonica oil; sage oil; sandalwood oil (for example, Santalum album); sandenol; sassafras oil; Sesame oil; soybean oil; peppermint oil; herb oil; Lavender lavender oil; spiranthol; borage oil; tangerine oil; Camellia oleifera oil; tea tree oil; terpenoid; terpineol; terpinolene; terpinyl acetate; tert-butylcyclohexyl acetate; tetrahydrolinalool; tetrahydrolinyl acetate; tetrahydromyrcenol; fine basil oil; thyme oil; thymol; tomato oil; trans-2-hexenol; trans-anethole and its metabolites; turmeric oil; turpentine; vanillin (eg 4-hydroxy-3-methoxybenzaldehyde); vetiver oil; vitalizair; occidental thuja oil; white grapefruit oil; wintergreen oil (methyl salicylate), etc.

In some embodiments, the effective dose of the pesticidal natural oil when used in combination with one or more saturated or unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof) is lower than the effective dose of the pesticidal natural oil when used alone (i.e., a smaller amount of pesticidal natural oil can still provide pest control when used in a composition with one or more saturated or unsaturated C6-C10 aliphatic acids). In some embodiments, an essential oil that is not effective against a particular pest species may become effective against that particular species when used in a composition with one or more saturated or unsaturated C6-C10 aliphatic acids.

In some embodiments, the at least one saturated or unsaturated C6-C10 aliphatic acid may include a naturally occurring aliphatic acid, such as an acid that may be present in natural plant or animal material or may be extracted, fractionated, or derived from him. In one such embodiment, the at least one saturated or unsaturated C6-C10 aliphatic acid may include one or more naturally occurring aliphatic acids present in the plant extract or fraction thereof. In another such embodiment, the at least one saturated or unsaturated C6-C10 aliphatic acid may include one or more naturally occurring aliphatic acids provided in the animal extract or product or a fraction thereof. In one such embodiment, the at least one saturated or unsaturated C6-C10 aliphatic acid may include a naturally occurring aliphatic acid contained in a plant oil extract such as one or more of coconut oil, palm oil, palm kernel oil, corn oil or fractions or extracts based thereon. In another such embodiment, the at least one saturated or unsaturated C6-C10 aliphatic acid may include a naturally occurring aliphatic acid contained in an extract or product of animal origin, for example, such as one or more of cow's milk, goat's milk, beef tallow and/or cow or goat butter or fractions or extracts thereof. In a specific embodiment, the at least one saturated or unsaturated C6-C10 aliphatic acid may be present as a component of one or more natural materials of plant or animal origin or an extract or fraction thereof. In a particular such embodiment, at least one saturated C6-C10 aliphatic acid may be present in an extract or fraction of one or more vegetable oil extracts, such as one or more of coconut oil, palm oil, palm kernel oil, corn oil, or fractions or extracts based on them.

In some embodiments, an emulsifier or other surfactant may be used in the preparation of pesticide compositions in accordance with aspects of the present invention. Suitable surfactants can be selected by one skilled in the art. Examples of surfactants that may be used in some embodiments of the present invention include, but are not limited to, sodium lauryl sulfate, saponin, ethoxylated alcohols, ethoxylated fatty acid esters, alkoxylated glycols, ethoxylated fatty acids, ethoxylated castor oil, glyceryl oleates, carboxylated alcohols, carboxylic acids, ethoxylated alkylphenols, fatty acid esters, sodium dodecyl sulfide, other natural or synthetic surfactants and combinations thereof. In some embodiments, the surfactant(s) are non-ionic surfactants. In some embodiments, the surfactant(s) are cationic or anionic surfactants. In some embodiments, the surfactant may include two or more surfactants used in combination. The selection of a suitable surfactant depends on the respective application routes and conditions of use, and selection of suitable surfactants is known to those skilled in the art.

In one aspect, a pesticide composition in accordance with some embodiments of the present invention contains one or more suitable carrier or diluent components. A suitable carrier or diluent component may be selected by one skilled in the art depending on the particular application required and the conditions under which the composition is used. Commonly used carriers and diluents may include ethanol, isopropanol, isopropyl myristate, other alcohols, water and other inert vehicles, such as, but not limited to, vehicles listed by the EPA as "minimal risk inert pesticide ingredients" (4A) (list of ingredients published in December 2015 US EPA in FIFRA 4a as part of the list published in August 2004 under the title "List 4A - inert ingredients with minimal risk") or, for example, "inert pesticide ingredients" (4B) (list published in August 2004 US EPA in FIFRA 4b entitled "List 4B - Other Ingredients for Which EPA Has Sufficient Information") or as required by EPA 40 CFR 180.950 dated May 24, 2002, each of which is hereby incorporated herein into in its entirety for all purposes, including, for example, citric acid, lactic acid, glycerin, castor oil, benzoic acid, carbonic acid, ethoxylated alcohols, ethoxylated amides, glycerides, benzene, butanol, 1-propanol, hexanol, other alcohols , dimethyl ether and polyethylene glycol.

In one embodiment, the present invention provides a method for increasing the effectiveness of a pesticide. In one aspect, there is provided a method for increasing the effectiveness of a fungicide. In another aspect, there is provided a method for increasing the effectiveness of a nematicide. In a further aspect, there is provided a method for increasing the effectiveness of an insecticide.

In one such embodiment, the method comprises providing a synergistic pesticide composition comprising a pesticidal active ingredient and at least one saturated or unsaturated C6-C10 aliphatic acid, and causing the resulting synergistic composition to act on a pest. In a particular illustrative embodiment, without being limited by any particular theory, at least one saturated or unsaturated C6-C10 aliphatic acid can suitably function as a cell permeabilizing agent or cell membrane disruptor. In one aspect, the method involves providing a fungicidal composition comprising a fungicidal active ingredient and at least one saturated or unsaturated C6-C10 aliphatic acid, and causing the resulting synergistic composition to act on a fungus. In another aspect, the method comprises providing a nematicidal composition comprising a nematicidal active ingredient and at least one saturated or unsaturated C6-C10 aliphatic acid, and causing the resulting synergistic composition to act on a nematode. In a further aspect, the method comprises providing an insecticidal composition comprising an insecticidal active ingredient and at least one saturated or unsaturated C6-C10 aliphatic acid, and causing the resulting synergistic composition to act on an insect.

In one embodiment in accordance with the present invention, at least one saturated or unsaturated C6-C10 aliphatic acid present in the pesticidal composition comprises an unsaturated aliphatic carbonylalkene. In a particular such embodiment, without being limited by any particular theory, the at least one saturated or unsaturated C6-C10 aliphatic acid may suitably function as a cell permeabilizing agent or cell membrane disruptor. In one such embodiment, the cell permeabilization agent comprises a carbonylalkene characterized by one of the general structures (1), (2), (3), (4), (5), (6) or (7) shown in FIG. 1. In a further embodiment, the cell permeabilization agent comprises at least one unsaturated aliphatic acid containing at least one carboxyl group and containing at least one unsaturated C-C bond.

In one illustrative embodiment, the method comprises providing a synergistic pesticide composition comprising a pesticidal active ingredient and at least one saturated or unsaturated C6-C10 aliphatic acid that functions as a cellular permeabilization agent, and causing the synergistic pesticide composition to target the pest with increasing amounts of pesticide active ingredient that passes into the pest cells. In some such embodiments, the pesticidal active is a fungicide and the pest is a fungus, and without being limited to any particular theory, the cell permeabilization agent that is at least one saturated or unsaturated C6-C10 aliphatic acid provides easier passage of the fungicide through the cell walls and membranes of the fungus. In some such embodiments, the pesticide is a nematicide and the pest is a nematode, and without being limited to any particular theory, the cell permeabilization agent that is at least one saturated or unsaturated C6-C10 aliphatic acid provides easier passage of nematicide through nematode cell membranes. In some such embodiments, the pesticide is an insecticide, and without being limited to any particular theory, the cell permeabilization agent that is at least one saturated or unsaturated C6-C10 aliphatic acid allows the insecticide to more easily pass through the cuticle of the insect, chitinous membrane or cellular or intracellular membranes.

In some embodiments, in addition to actually being synergistic in pesticidal activity, certain synergistic pesticide compositions according to embodiments of the present invention may also suitably have additional unexpected beneficial properties. Examples of such additional advantageous properties may include one or more of improved environmental degradation; improved toxicological and/or ecotoxicological properties, for example, such as reduced toxicity to aquatic organisms or toxicity to beneficial insects.

In a further aspect, for any of the embodiments described above or below, wherein a synergistic pesticide composition is provided comprising at least one pesticidal active and one or more saturated or unsaturated C6-C10 aliphatic acids or salts thereof, in an alternative embodiment The synergistic pesticide composition may alternatively contain at least one pesticide active substance and one or more saturated or unsaturated C11 aliphatic acids or salts thereof. In another aspect, for any of the embodiments described above, wherein a synergistic pesticide composition is provided comprising at least one pesticide active ingredient and one or more saturated or unsaturated C6-C10 aliphatic acids or salts thereof, in an alternative embodiment, the synergistic pesticide the composition may alternatively contain at least one pesticide active substance and one or more saturated or unsaturated C12 aliphatic acids or salts thereof.

EXPERIMENTAL METHODS

In accordance with one embodiment of the present invention, the combination of at least one saturated or unsaturated C6-C10 aliphatic acid and a pesticidal active ingredient provides a synergistic pesticide composition exhibiting a synergistic pesticidal effect. In some embodiments, the synergistic effect between the pesticide active ingredient and the components of pesticide compositions based on at least one saturated or unsaturated C6-C10- (or alternatively C11- or C12-) aliphatic acid in accordance with embodiments of the present invention was tested using a synergistic growth inhibition assay, which was developed based on and related to the checkerboard assay known in the art, for testing combinations of antimicrobial agents. In a synergistic growth inhibition assay used in accordance with certain embodiments of the present invention, multiple dilutions of combinations of a pesticide active ingredient and at least one saturated or unsaturated C6-C10 aliphatic acid were tested in separate wells for inhibitory activity against the organism. pest or pathogen that is the target. In one such embodiment, combinations of pesticidal active ingredient and saturated or unsaturated C6-C10- (or alternatively C11- or C12-) aliphatic acid agents may preferably be tested at decreasing concentration values. In a further such embodiment, combinations of pesticidal active ingredient and saturated or unsaturated C6-C10- (or alternatively C11- or C12-) aliphatic acid agents can be tested at increasing concentrations. Such multiple combinations of pesticidal active ingredient and agents based on at least one saturated or unsaturated C6-C10- (or alternatively C11- or C12-) aliphatic acid can be prepared in 96-well microtiter plates. In one such embodiment, the synergistic growth inhibition assay then comprises arrays each containing a pesticidal active ingredient and agents based on one or more saturated or unsaturated C6-C10- (or alternatively C11- or C12-) aliphatic acids with gradually decreasing concentration values to test the MIC of agents in combination at which the growth of the target pest or target pathogen is inhibited. Thus, each well of a microtiter plate provides a unique combination of two agents, in which the effectiveness of the combination against a target pest or pathogen can be determined.

A method for determining and quantifying synergistic efficacy is by calculating the "fractional inhibition concentration index" or FIC index, known in the art for determining synergy between two antibiotic agents (see, for example, M. J. Hall et al., "The fractional inhibitory concentration (FIC) index as a measure of synergy", J Antimicrob Chem., 11 (5):427-433, 1983, for example). In one embodiment, in accordance with the present invention, for each row of wells of a microtiter plate in a synergistic growth inhibition assay, the FIC index is calculated from the lowest concentration of pesticide active ingredient and agents based on one or more saturated or unsaturated C6-C10 aliphatic acids required for inhibition growth of the target pest or target pathogen. Obtain the FIC for each component by dividing the concentration of the agent present in a given well of the microtiter plate by the minimum inhibitory concentration (MIC) of that agent alone required to inhibit the growth of the target pest or target pathogen. In this case, the FIC index is the sum of these values for both agents in a given well of the microtiter plate. The FIC index is calculated for each series as follows:

FIC _index =MIC _a +MIC _A +MIC _b /MIC _B ,

wherein MIC _a , MIC _b are the minimum inhibitory concentration (MIC) of compounds A and B, respectively, when combined as a composition, and MIC _A , MIC _B are the MICs of compounds A and B, respectively, when used alone. Fractional concentration suppression indices can then be used as a measure of synergy. If the lowest FIC index in the microtiter plate thus obtained is less than 1 (FIC _index <1), the combination of the pesticide active ingredient and agents based on one or more saturated or unsaturated C6-C10- (or alternatively C11- or C12-) aliphatic acids exhibits synergism, and this indicates a synergistic pesticide composition. If the FIC index is 1, the combination is additive. FIC index values greater than 4 are considered to indicate antagonism.

In a particular embodiment, if the FIC index is 0.5 or less, the combination of a pesticidal active ingredient and one or more saturated or unsaturated C6-C10 (or alternatively C11 or C12-) aliphatic acids exhibits significant synergy. For example, in one embodiment, an FIC index of 0.5 may correspond to a synergistic pesticide composition comprising a pesticide agent in Va from its MIC separately and an agent based on one or more saturated or unsaturated (or alternatively C11- or C12-) C6-C10 -aliphatic acids in from its MIC separately.

In some embodiments of the present invention, an exemplary synergistic growth inhibition assay was conducted starting with a starting composition containing an agent based on a pesticidal active ingredient (Compound A) at its MIC alone and an agent based on one or more saturated or unsaturated C6-C10- (or in alternatively, C11- or C12-) aliphatic acids (compound B) at its MIC separately in the first well of a row of a 96-well microtiter plate. Serial dilutions of these starting compositions were then used in subsequent wells of a row of a microtiter plate to analyze the pesticide composition under the same conditions to determine the concentration of the composition in which the two agents were combined corresponding to the well of the microtiter plate at which inhibition of the growth of the target pest or target organism ceased. The minimum inhibitory concentration of each individual pesticidal active ingredient product (Compound A) and each one or more saturated or unsaturated C6-C10 aliphatic acid product (as Compound B) were determined in parallel with formulations combining the two agents.

In some embodiments, Fusarium oxysporum is used as an exemplary pest or pathogen to determine synergy in pesticide compositions containing a pesticide active ingredient (Compound A) product and one or more saturated or unsaturated C6-C10- ( or alternatively C11- or C12-) aliphatic acids (compound B). Resazurin dye (also known as alamar blue dye) was used as an indicator to determine the presence of growth or growth inhibition of Fusarium oxysporum in the wells of 96-well microtiter plates used in the illustrative synergistic growth inhibition assay. In addition to the color change of the resazurin dye if Fusarium oxysporum growth is present, optical or visual assessment of the microtiter plate well can also be performed to further determine the presence of growth or inhibition of Fusarium oxysporum growth.

In other embodiments, Botrytis cinerea is used as an exemplary pest or pathogen to determine synergy in pesticide compositions containing a pesticide active ingredient (compound A) and an agent based on one or more saturated or unsaturated C6-C10- (or as alternatives to C11- or C12-) aliphatic acids (compound B). As described above, resazurin was used as an indicator of growth or growth inhibition of Botrytis cinerea in an illustrative synergistic growth inhibition assay. In addition to the color change of resazurin, optical or visual assessment of the microtiter plate well can also be performed to further determine whether Botrytis cinerea is growing or inhibiting growth.

In additional embodiments, Sclerotinia sclerotiorum is used as an exemplary pest or pathogen to determine synergy in pesticide compositions containing a pesticide active ingredient (compound A) and an agent based on one or more saturated or unsaturated C6-C10- (or as alternatives to C11- or C12-) aliphatic acids (compound B). As described above, resazurin was used as an indicator of growth or growth inhibition of Sclerotinia sclerotiorum in an illustrative synergistic growth inhibition assay. In addition to the color change of resazurin, optical or visual assessment of the microtiter plate well can also be performed to further determine the presence of growth or inhibition of growth of Sclerotinia sclerotiorum.

Alternatively, other suitable exemplary pest or pathogen organisms may be used to determine the synergy of combinations of pesticide active ingredient products and products based on one or more saturated or unsaturated C6-C10- (or alternatively C11- or C12-) aliphatic acids in accordance with embodiments of the present invention. For example, other exemplary fungal pathogens may be used, such as, but not limited to, Leptosphaeria maculans, Sclerotinia spp. and Verticillium spp. In yet other examples, suitable exemplary pests or pathogens other than fungi may be used, such as an insect, mite, nematode, bacterial pathogens, viral pathogens, mollusc, or other pests or pathogens suitable for use in the MIC inhibition assay testing method. growth.

All examples detailed below were tested in accordance with the illustrative synergistic growth inhibition assay described above using conventional techniques for determining MICs known to those skilled in the art. Stock solutions of pesticide active ingredient products and products based on one or more saturated or unsaturated C6-C10- (or alternatively C11- or C12-) aliphatic acids were initially prepared in 100% dimethyl sulfoxide (“DMSO”) and diluted to 10 % DMSO using sterile Potato Dextrose Broth (PDB) followed by further serial dilution to provide test solution concentrations for use in microtiter plate wells, except for specific experimental examples detailed below. Accordingly, the maximum concentration of DMSO in the test solutions was limited to 10% DMSO or less, which was specifically determined not to provide growth inhibition of the exemplary fungal pests used in the test.

A culture of an illustrative fungal pathogen, namely Fusarium oxysporum, Botrytis cinerea or Sclerotinia sclerotiorum, for example, is grown to exponential phase in potato dextrose broth (PDB). Transfer a 20 µl aliquot of the homogenized mycelium from the culture to a well of a 96-well microtiter plate and incubate for a period ranging from 1 day to 7 days (depending on the pathogen and specific assay reagents, as described in the example descriptions below) with 180 µl test solution containing pesticides and aliphatic acid-based products in combination in a range of dilutions to ensure mycelial growth. After the incubation period, 10 μl of resazurin dye is added to each well and the color in the solution is observed and compared with the color of the test solution with the same concentration values in wells without mycelium culture inoculum to monitor the effects of the test solution separately. The resazurin dye appears blue for wells with only the initial 20 µl of culture where growth was inhibited, and appears pink for wells where mycelial growth occurred, as shown in FIG. 2, where the transition from blue to pink color can be clearly seen in each of the top 4 rows of microtiter plate wells (labeled 1-4 in Fig. 2) as the concentration of pesticide agents and the agent based on one or more saturated or unsaturated The C6-C10- (or alternatively C11- or C12-) aliphatic acids in the test solution decrease from left to right. In addition to the color change of the resazurin dye, the growth or lack of growth of the mycelial culture was also observed visually or optically.

According to this assay, the minimum inhibitory concentration is the lowest concentration at which growth is inhibited and corresponds to a well of a microtiter plate in which the color of the dye is the same as in the control without culture and without growth, and/or in which confirm by visual and/or optical inspection that growth is inhibited.

EXAMPLES

Example 1 Inhibition of Fusarium oxysporum using pyraclostrobin in combination with several exemplary unsaturated C6-C10 aliphatic acids (or agriculturally acceptable salts thereof)

Receiving a sample

Dissolve 10 mg of pyraclostrobin (available from Santa Cruz Biotechnology, Dallas, TX, under stock number 229020) in 10 ml of dimethyl sulfoxide (DMSO) and the resulting solution was diluted 2-fold in DMSO to provide a concentration of 0.5 mg/ml. This solution was diluted 10-fold in potato dextrose broth (PDB) to provide a concentration of 0.05 mg/ml in 10% DMSO/90% PDB. Using high performance liquid chromatography (HPLC), the solubility of pyraclostrobin in 10% DMSO/90% PDB was determined to be 0.0154 mg/ml.

A solution of (2E,4E)-2,4-hexadienoic acid potassium salt was prepared by dissolving 2 g of (2E,4E)-2,4-hexadienoic acid potassium salt in 20 ml PDB, which was further diluted by serial dilution in PDB. A solution of (2E,4E)-2,4-hexadienoic acid (available from Sigma-Aldrich under stock #W342904) was prepared by dissolving 20 mg (2E,4E)-2,4-hexadienoic acid in 1 ml DMSO and adding 0. 1 ml to 0.9 ml PDB to obtain a solution of 2 mg/ml (2E,4E)-2,4-hexadienoic acid in 10% DMSO/90% PDB, which was further diluted by serial dilution in PDB.

A solution of trans-2-hexenoic acid (available from Sigma-Aldrich under stock #W316903) was prepared by dissolving 100 mg trans-2-hexenoic acid in 1 ml DMSO and adding 0.1 ml to 0.9 ml PDB to obtain solution 10 mg/ml in 10% DMSO/90% PDB, which was further diluted by serial dilution in PDB. A solution of trans-3-hexenoic acid (available from Sigma-Aldrich under stock no. W317004) was prepared by adding 20 μl of trans-3-hexenoic acid to 1980 μl of PDB and the resulting solution was serially diluted in PDB. The density of trans-3-hexenoic acid was assumed to be 0.963 g/mL.

Combinations of pyraclostrobin and one or more illustrative saturated or unsaturated C6-C10 aliphatic acids (and agriculturally acceptable salts thereof) were prepared by adding 0.5 ml of 0.0308 mg/ml pyraclostrobin to 0.5 ml of 1.25 mg /ml potassium salt (2E,4E)-2,4-hexadienoic acid (combination 1), 0.5 ml 0.25 mg/ml (2E,4E)-2,4-hexadienoic acid (combination 2), 0, 5 ml 0.625 mg/ml (2E,4E)-2,4-hexadienoic acid (combination 3), 0.5 ml 1.25 mg/ml trans-2-hexenoic acid (combination 4) or 0.5 ml 0, 6019 mg/ml trans-3-hexenoic acid (combination 5). Each combination was tested over a 2-fold dilution range in the synergistic growth inhibition assay detailed above, observed after an incubation period of 24 hours, and the FIC index for each combination was calculated as shown below in Table 1.

Example 2 Inhibition of Fusarium oxysporum using fludioxonil in combination with several exemplary unsaturated aliphatic acids (or agriculturally acceptable salts thereof)

Receiving a sample

20 mg of fludioxonil (available from Shanghai Terppon Chemical Co. Ltd., Shanghai, China) was dissolved in 10 ml of dimethyl sulfoxide (DMSO) and the resulting solution was diluted 2-fold in DMSO to provide a concentration of 1 mg/ml. This solution was diluted 10-fold in potato dextrose broth (PDB) to provide a concentration of 0.1 mg/ml in 10% DMSO/90% PDB. Using HPLC, the solubility of fludioxonil in 10% DMSO/90% PDB was determined to be 0.0154 mg/ml.

A solution of (2E,4E)-2,4-hexadienoic acid potassium salt was prepared by dissolving 2 g of (2E,4E)-2,4-hexadienoic acid potassium salt in 20 ml PDB, which was further diluted by serial dilution in PDB. A solution of (2E,4E)-2,4-hexadienoic acid (available from Sigma-Aldrich as part number W342904) was prepared by dissolving 20 mg (2E,4E)-2,4-hexadienoic acid in 1 ml DMSO and adding 0.1 ml to 0.9 ml PDB to obtain a solution of 2 mg/ml (2E,4E)-2,4-hexadienoic acid in 10% DMSO/90% PDB, which was further diluted by serial dilution in PDB.

A solution of trans-2-hexenoic acid (available from Sigma-Aldrich under stock #W316903) was prepared by dissolving 100 mg trans-2-hexenoic acid in 1 ml DMSO and adding 0.1 ml to 0.9 ml PDB to obtain solution 10 mg/ml in 10% DMSO/90% PDB, which was further diluted by serial dilution in PDB. A solution of trans-3-hexenoic acid (available from Sigma-Aldrich under stock number W317004) was prepared by adding 20 μl of trans-3-hexenoic acid to 1980 μl of PDB and the resulting solution was serially diluted in PDB. The density of trans-3-hexenoic acid was assumed to be 0.963 g/mL.

Combinations of compounds A and B, shown below in Table 2, were prepared by adding 0.5 ml of 9.63 x 10-4 mg/ml fludioxonil to each of 0.5 ml of 0.625 mg/ml potassium salt (2E,4E)-2 ,4-hexadienoic acid, (combination 1), 0.5 ml 0.25 mg/ml (2E,4E)-2,4-hexadienoic acid (combination 2), 0.5 ml 0.625 mg/ml trans-2- hexenoic acid (combination 3) and 0.5 ml of 0.6019 mg/ml trans-3-hexenoic acid (combination 4). Each combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 24 hours, and the FIC index for each combination was calculated as shown in Table 2 below.

Example 3 Inhibition of Fusarium oxysporum by Fludioxonil in Combination with Several Exemplary Unsaturated Aliphatic Acids

Receiving a sample

20 mg of fludioxonil (available from Shanghai Terppon Chemical Co. Ltd., Shanghai, China) was dissolved in 10 ml of dimethyl sulfoxide (DMSO) and the resulting solution was diluted 2-fold in DMSO to provide a concentration of 1 mg/ml. This solution was diluted 10-fold in potato dextrose broth (PDB) to provide a concentration of 0.1 mg/ml in 10% DMSO/90% PDB. Using HPLC, the solubility of fludioxonil in 10% DMSO/90% PDB was determined to be 0.0154 mg/ml.

Stock solutions of several illustrative unsaturated C6-C10 aliphatic acids as Compound B for testing individual MICs were prepared at a concentration of 25 μl/ml in DMSO by adding 25 μl of each compound B in 975 μl DMSO followed by 10-fold dilution in the PDB for each 3-octenic acid (available from Sigma-Aldrich under stock #CDS000466), trans-2-octenic acid (available from Sigma-Aldrich), 9-decenoic acid (available from Sigma-Aldrich under stock #W366005), 3-decenoic acid ( available from Sigma-Aldrich under stock #CDS000299) and trans-2-decenoic acid (available from TCI America under stock #D0098).

To test in combination with fludioxonil, solutions of 0.78 μl/ml 3-octenic acid, trans-2-octenic acid and 9-decenoic acid in DMSO were prepared by adding 3.125 μl of each compound B in 2 ml DMSO followed by 2× dilution in DMSO to ensure a concentration of 0.78 µl/ml. Solutions of 3-decenoic acid and trans-2-decenoic acid were prepared in a similar manner, but using an additional 2-fold dilution in DMSO to provide a concentration of 0.39 μl/ml in DMSO.

Each of these resulting stock solutions was then diluted 10-fold in the PDB to yield 0.078 μL/mL solutions for each of 3-octenoic acid, trans-2-octenoic acid, and 9-decenoic acid, and to obtain 0.039 μL/mL solutions for each of 3-decenoic acid and trans-2-decenoic acid, all in 10% DMSO/90% PDB.

Combinations of exemplary components of Compound B with fludioxonil were prepared by adding 0.5 ml of 0.078 μl/ml each of 3-octenic acid, trans-2-octenic acid and 9-decenoic acid or 0.039 μl/ml each of 3-decenoic acid acid and trans-2-decenoic acid to 0.5 ml of 4.813 x 10 ^-4 mg/ml fludioxonil prepared by serially diluting 0.0154 mg/ml fludioxonil in 10% DMSO/90% PDB obtained above using PDB. The density of 3-octenic acid was assumed to be 0.938 g/ml. The density of trans-2-octenic acid was assumed to be 0.955 g/ml. The density of 3-decenoic acid was assumed to be 0.939 g/ml. The density of trans-2-decenoic acid was assumed to be 0.928 g/mL. The density of 9-decenoic acid was assumed to be 0.918 g/ml.

Each combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 24 hours, and the FIC index for each combination was calculated as shown below in Table 3.

Example 4 Inhibition of Fusarium oxysporum using thyme oil in combination with several exemplary unsaturated aliphatic acids

Receiving a sample

Dissolve 12.5 mg of thyme oil (available from Sigma-Aldrich under stock #W306509) in 1 g of dimethyl sulfoxide (DMSO) and the resulting solution was diluted 10-fold in PDB to provide a concentration of 1.25 mg/ml in 10% DMSO/90% P.D.B.

Stock solutions of several illustrative unsaturated C6-C10 aliphatic acids as Compound B for testing individual MICs were prepared at a concentration of 25 μl/ml by adding 25 μl each of 3-octenic acid (available from Sigma-Aldrich under stock #CDS000466), trans- 2-octenic acid (available from Sigma-Aldrich under stock #CDS000466), 9-decenoic acid (available from Sigma-Aldrich under stock #W366005), 3-decenoic acid (available from Sigma-Aldrich under stock #CDS000299) and trans- 2-decenoic acid (available from TCI America under stock #D0098) in 975 µl DMSO followed by a 10-fold dilution in the PDB.

Stock solutions of illustrative unsaturated C6-C10 aliphatic acids as Compound B to be tested in combination with thyme oil were prepared by adding 3.125 µl each of 3-octenic acid, trans-2-octenic acid and 9-decenoic acid in 2 ml DMSO followed by 2-fold dilution in DMSO to obtain a stock solution with a concentration of 0.78 µl/ml. Solutions of 3-decenoic acid and trans-2-decenoic acid were prepared in a similar manner, but using an additional 2-fold dilution in DMSO to provide a concentration of 0.39 μl/ml.

Each of these resulting stock solutions was then diluted 10-fold in the PDB to produce 0.078 μL/mL solutions (for each of 3-octenic acid, trans-2-octenic acid, and 9-decenoic acid) and 0.039 μL/mL solutions ( for 3-decenoic acid and trans-2-decenoic acid) in 10% DMSO/90% PDB.

Combinations of exemplary Compound B with thyme oil were prepared by adding 0.5 ml of 0.078 μl/ml each of 3-octenic acid, trans-2-octenic acid and 9-decenoic acid or 0.039 μl/ml each of 3- decenoic acid and trans-2-decenoic acid to 0.5 ml of 1.25 mg/ml thyme oil in 10% DMSO/90% PDB. The density of 3-octenic acid was assumed to be 0.938 g/ml. The density of trans-2-octenic acid was assumed to be 0.955 g/ml. The density of 3-decenoic acid was assumed to be 0.939 g/ml. The density of trans-2-decenoic acid was assumed to be 0.928 g/mL. The density of 9-decenoic acid was assumed to be 0.918 g/ml.

Each combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 24 hours, and the FIC index for each combination was calculated as shown below in Table 4.

Example 5 Inhibition of Botrytis cinerea by Margosa oil limonoid extract (isolated from cold pressed margosa oil) and Fortune Aza Technical (azadirachtin extract) in combination with various illustrative unsaturated aliphatic acids

Receiving a sample

Limonoid extract was prepared from cold pressed margosa oil using solvent extraction with hexane and methanol to obtain limonoid extract from margosa oil. Fortune Aza Technical, a pesticide containing 14% azadirachtin (isolated from margosa seed/kernel source), was obtained from Fortune Biotech Ltd., Secunderabad, India.

Solutions of margosa oil limonoid extract and Fortune Aza Technical were prepared at a concentration of 5 mg/ml in DMSO followed by tenfold dilution in PDB to provide a concentration of 0.5 mg/ml in 10% DMSO/90% PDB.

Stock solutions of 3-octenic acid and trans-2-octenic acid as Compound B for individual MIC testing were prepared at 25 μL/mL by adding 25 μL of each Compound B in 975 μL DMSO followed by 10-fold dilution in PDB.

For testing in combination with margosa oil limonoid extract and Fortune Aza Technical, stock solutions of 3-octenic acid and trans-2-octenic acid were prepared at a concentration of 6.25 μl/ml by adding 62.5 μl of the corresponding compound in 937.5 μl DMSO followed by 10-fold dilution in PDB (ratio 11.7). Stock solutions of 3-octenic acid and trans-2-octenic acid were prepared at a concentration of 3.125 μl/ml for combination testing by adding 31.25 μl of the corresponding compound in 968.75 μl DMSO followed by a 10-fold dilution in PDB (ratio 6. 0 or 5.9). Stock solutions of 3-octenic acid and trans-2-octenic acid at a concentration of 0.625 μl/ml for combination testing were prepared by adding 6.25 μl of the corresponding compound in 993.75 μl DMSO followed by a 10-fold dilution in PDB (ratio 1, 2). The density of 3-octenic acid was assumed to be 0.938 g/ml. The density of trans-2-octenic acid was assumed to be 0.955 g/ml.

Combinations were prepared by adding 0.5 ml of 6.25 µl/ml, 3.125 µl/ml or 0.625 µl/ml 3-octenic acid or trans-2-octenic acid obtained above (as Compound B) to 0.5 ml margosa oil limonoid extract or Fortune Aza Technical at a concentration of 0.5 mg/ml in 10% DMSO/90% PDB (as Compound A) for testing in a synergistic growth inhibition assay. Each combination was observed after an incubation period of 24 hours, and the FIC index for each combination was calculated as shown in Tables 5 and 6 below.

Example 6 Inhibition of Fusarium oxysporum growth using fludioxonil in combination with various exemplary saturated aliphatic acids

Receiving a sample

20 mg of fludioxonil was dissolved in 10 ml of dimethyl sulfoxide (DMSO) and the resulting solution was diluted 2-fold in DMSO to provide a concentration of 1 mg/ml. This solution was diluted 10-fold in potato dextrose broth (PDB) to provide a concentration of 0.1 mg/ml in 10% DMSO/90% PDB. Using high performance liquid chromatography, the solubility of fludioxonil in 10% DMSO/90% PDB was determined to be 0.0154 mg/ml. A solution of 0.000963 mg/ml fludioxonil was prepared by adding 625 μl of 0.0154 mg/ml fludioxonil to 9375 μl PDB.

To test individual MICs, stock solutions of hexanoic acid or octanoic acid as component B were prepared by adding 100 μL hexanoic acid (93 mg) or octanoic acid (91 mg) to 900 μL PDB, providing concentration values of 9.3 mg/mL and 9. 1 mg/ml respectively. A stock solution of decanoic acid was prepared at a concentration of 10 mg/mL in DMSO, followed by a 10-fold dilution in PDB to provide a concentration of 1 mg/mL in 10% DMSO/90% PDB. Decanoic acid potassium salt stock solution was prepared by adding 100 mg to 10 mL PDB to provide a concentration of 10 mg/mL. A stock solution of dodecanoic acid was prepared at a concentration of 1 mg/mL in DMSO, followed by a 10-fold dilution in PDB to provide a concentration of 0.1 mg/mL in 10% DMSO/90% PDB.

To test MIC combinations, a 0.29 mg/mL hexanoic acid solution was prepared by adding 156 μL of a 9.3 mg/mL stock solution to 4844 μL PDB. Similarly, a solution of octanoic acid was prepared at a concentration of 1.14 mg/mL by diluting the stock solution of 9.1 mg/mL in PDB. A solution of decanoic acid at a concentration of 0.5 mg/ml was prepared by diluting the original solution 2 times to 1 mg/ml. Decanoic acid potassium salt solution at a concentration of 0.156 mg/mL was prepared by adding 78 μL of a 10 mg/mL stock solution to 4922 μL PDB. A solution of dodecanoic acid at a concentration of 0.2 mg/ml was prepared by dissolving 2 mg in 1 ml of DMSO, followed by 10-fold dilution in PDB at 40°C.

The combinations for which the results are shown in Table 7 were prepared by adding 0.5 ml of 0.0154 mg/ml fludioxonil to 0.5 ml of each stock solution. Each combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 24 hours, and the FIC index for each combination was calculated as shown below in Table 7.

The combinations for which the results are shown in Table 8 were prepared by adding 0.5 ml of 0.000963 mg/ml fludioxonil to 0.5 ml of each stock solution.

Example 7 Inhibition of Fusarium oxysporum by Cold-Pressed Margosa Oil Limonoid Extract and Fortune Aza Technical (Azadirachtin Extract) in Combination with Various Illustrative Saturated Aliphatic Acids

Receiving a sample

Limonoid extract was prepared from cold pressed margosa oil using solvent extraction with hexane and methanol to obtain limonoid extract from margosa oil. Fortune Aza Technical, a pesticide containing 14% azadirachtin (isolated from margosa seed/kernel source), was obtained from Fortune Biotech Ltd., Secunderabad, India (also called "Azatech"). Solutions of margosa oil limonoid extract and Fortune Aza Technical were prepared at a concentration of 5 mg/ml in DMSO followed by tenfold dilution in PDB to provide a concentration of 0.5 mg/ml in 10% DMSO/90% PDB. These solutions were used to test individual MICs.

For single octanoic acid MIC testing, a solution was prepared by adding 100 μL octanoic acid (91 mg) to 900 μL PDB to provide concentration values of 9.1 mg/mL. A stock solution of decanoic acid was prepared at a concentration of 10 mg/mL in DMSO, followed by a 10-fold dilution in PDB to provide a concentration of 1 mg/mL in 10% DMSO/90% PDB.

Octanoic acid combinations were prepared by dissolving 5 mg of margosa or Fortune Aza Technical oil limonoid extract in 1 mL of DMSO and adding 6.25 μL of octanoic acid (d=0.91 g/mL) followed by 10-fold dilution in PDB. A solution was thus obtained containing 0.5 mg/ml limonoid extract from margosa oil or Fortune Aza Technical and 0.56875 mg/ml octanoic acid. Decanoic acid combinations were prepared by dissolving 5 mg of limonoid extract from margosa oil or Fortune Aza Technical in 1 mL of DMSO and adding 2.5 mg of decanoic acid, followed by a 10-fold dilution in PDB. A solution was thus obtained containing 0.5 mg/ml limonoid extract from margosa oil or Fortune Aza Technical and 0.25 mg/ml decanoic acid.

Each combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 24 hours, and the FIC index for each combination was calculated as shown below in Table 9.

Obtaining samples for examples 8-19

For each of Experimental Examples 8-19 described below, concentrated stock solutions and diluted working solutions were prepared for each of the exemplary pesticide active ingredients as component A and each of the illustrative unsaturated and saturated aliphatic acids as component B in accordance with the following descriptions.

Pesticide active ingredients as compound A

Concentrated stock solutions were prepared by dissolving the pesticide active ingredient in 100% dimethyl sulfoxide (DMSO), which were then diluted 10-fold in potato dextrose broth (PDB) to obtain the working stock solution described below.

Pyraclostrobin (available from Santa Cruz Biotech, Dallas, TX, USA, stock #SC-229020). A stock solution of 0.5 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.05 mg/mL, for which the effective concentration in the solubilized state was confirmed using high performance liquid chromatography (HPLC). which was 0.015 mg/ml. This working stock solution, at an effective concentration of 0.015 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Azoxystrobin (available from Sigma-Aldrich, St. Louis, MO, USA, stock #31697). A stock solution of 1.75 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.175 mg/mL, for which the effective solubilized concentration was confirmed by HPLC to be 0.15 mg/ml. This working stock solution, at an effective concentration of 0.15 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Chlorothalonil (available from Chem Service Inc., West Chester, PA, USA, under stock #N-11454). A stock solution of 0.5 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.05 mg/mL, for which the effective concentration in the solubilized state was confirmed using high performance liquid chromatography (HPLC). which was 0.002 mg/ml. This working stock solution, at an effective concentration of 0.002 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Fludioxonil (available from Shanghai Terppon Chemical Co. Ltd., Shanghai, China). A stock solution of 1.05 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.105 mg/mL, for which the effective solubilized concentration was confirmed using HPLC to be 0.021 mg/ml. This working stock solution, at an effective concentration of 0.021 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Cyprodinil (available from Shanghai Terppon Chemical Co. Ltd., Shanghai, China). A stock solution of 1.37 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.137 mg/mL, for which the effective solubilized concentration was confirmed using HPLC to be 0.009 mg/ml. This working stock solution, at an effective concentration of 0.009 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Metalaxyl. A stock solution of 3.32 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.332 mg/mL, for which the effective solubilized concentration was confirmed using HPLC to be 0.316 mg/ml. This working stock solution, at an effective concentration of 0.316 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Difenoconazole (available from Santa Cruz Biotech, Dallas, TX, USA, under stock number SC-204721). A stock solution of 1.3 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.13 mg/mL, for which the effective concentration in the solubilized state was confirmed using high performance liquid chromatography (HPLC). which was 0.051 mg/ml. This working stock solution, at an effective concentration of 0.051 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Propiconazole (available from Shanghai Terppon Chemical Co. Ltd., Shanghai, China). A stock solution of 1.0 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.10 mg/mL, for which the effective concentration in the solubilized state was confirmed using high performance liquid chromatography (HPLC). which was 0.089 mg/ml. This working stock solution, at an effective concentration of 0.089 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Epoxiconazole (available from Shanghai Terppon Chemical Co. Ltd., Shanghai, China). A stock solution of 2.5 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.25 mg/mL, for which the effective concentration in the solubilized state was confirmed using high performance liquid chromatography (HPLC). which was 0.03 mg/ml. This working stock solution, at an effective concentration of 0.025 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Tebuconazole (available from Shanghai Terppon Chemical Co. Ltd., Shanghai, China). A stock solution of 5.0 mg/mL in 100% DMSO was diluted 10-fold in PDB to obtain a working stock solution with a nominal concentration of 0.50 mg/mL, for which the effective concentration in the solubilized state was confirmed using high performance liquid chromatography (HPLC). which was 0.45 mg/ml. This working stock solution, at an effective concentration of 0.45 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Thyme Oil (available from Sigma-Aldrich, St. Louis, MO, USA, stock #W306509), Garlic Oil (available from New Directions Aromatics, Mississauga, ON, Canada), Lemongrass Oil (available from Xenex Labs, Coquitlam, UK Columbia, Canada, stock no. OL123), wintergreen oil (available from Xenex Labs, Coquitlam, British Columbia, Canada, stock no. OW134), peppermint oil (available from Xenex Labs, Coquitlam, British Columbia, Canada, stock no. OP1531), spearmint oil (available from Xenex Labs, Coquitlam, British Columbia, Canada, stock #AS132), clove leaf oil (available from New Directions Aromatics, Mississauga, Ontario, Canada), cinnamon leaf oil ( available from Xenex Labs, Coquitlam, British Columbia, Canada, under stock #OC2131), tea tree oil (available from Newco Natural Technology, Calgary, Alberta, Canada), geranium oil (available from Xenex Labs, Coquitlam, British Columbia, Canada, stock #OW134), peppermint oil (available from Xenex Labs, Coquitlam, British Columbia, Canada, stock #OG1042), rosemary oil (available from Xenex Labs, Coquitlam, British Columbia, Canada, stock #OR131) and oil oregano (available from New Directions Aromatics, Mississauga, Ontario, Canada). A 100 mg/mL stock solution in 100% DMSO was diluted 10-fold in PDB to obtain a 10 mg/mL working stock solution. This working stock solution at an effective concentration of 10 mg/mL was used for further serial dilution in the PDB to the required individual concentration values shown in Tables 10-111 below.

Nutkatone(+) (available from Alfa Aesar, Ward Hill, MA, USA, stock #A19166). A 10 mg/mL stock solution in 100% DMSO was diluted 10-fold in PDB to obtain a 1.0 mg/mL working stock solution. This working stock solution at an effective concentration of 1.0 mg/mL was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Limonoid extract from margosa oil. Limonoid extract was prepared from cold pressed margosa oil using solvent extraction with hexane and methanol to obtain limonoid extract from margosa oil. A stock solution of 5 mg/mL margosa oil limonoid extract in 100% DMSO was diluted 10-fold in PDB to obtain a 0.5 mg/mL working stock solution. This working stock solution, at an effective concentration of 0.5 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values shown in Tables 10-111 below.

Fortune Aza Technical. Fortune Aza Technical™, a pesticide containing 14% azadirachtin (isolated from margosa seed/kernel source), was obtained from Fortune Biotech Ltd., Secunderabad, India. A 5 mg/mL stock solution of Fortune Aza Technical in 100% DMSO was diluted 10-fold in PDB to obtain a 0.5 mg/mL working stock solution. This working stock solution, at an effective concentration of 0.5 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values shown in Tables 10-111 below.

Flavonoid extract from karanja oil. The flavonoid extract was obtained from cold-pressed karanja oil through solvent extraction. A stock solution of 5 mg/mL karanji oil flavonoid extract in 100% DMSO was diluted 10-fold in PDB to obtain a 0.5 mg/mL working stock solution. This working stock solution, at an effective concentration of 0.5 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values shown in Tables 10-111 below.

Salannin. Salannin was isolated and purified from cold-pressed margosa oil through solvent extraction. A stock solution of 1 mg/mL salannin in 100% DMSO was diluted 10-fold in PDB to obtain a 0.1 mg/mL working stock solution. This working stock solution, at an effective concentration of 0.1 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Unsaturated aliphatic acids as compound B

Concentrated stock solutions were prepared by dissolving each illustrative unsaturated aliphatic acid in 100% dimethyl sulfoxide (DMSO), which were then diluted 10-fold in potato dextrose broth (PDB) to obtain the working stock solution described below.

trans-2-hexenoic acid, trans-3-hexenoic acid, cis-3-hexenoic acid, 5-hexenoic acid, 3-heptenoic acid, trans-2-octenic acid, trans-3-octenic acid, 3-octenic acid, 7-octenoic acid, 3-decenoic acid, cis-3-decenoic acid, 9-decenoic acid, trans-2-nonenoic acid, 3-nonenoic acid, (9Z)-octadecenoic acid (oleic acid) (all available from Sigma- Aldrich, St. Louis, MO, USA), trans-2-decenoic acid (available from TCI America, Portland, OR, USA, stock #D0098), cis-2-decenoic acid (available from BOC Sciences, Shirley, New York, USA) and trans-2-undecenoic acid (available from Alfa Aesar, Ward Hill, MA, USA, stock no. L-11579). A 50 mg/mL stock solution in 100% DMSO was diluted 10-fold in PDB to obtain a 5 mg/mL working stock solution. This working stock solution at an effective concentration of 5 mg/mL was used for further serial dilution in the PDB to the required individual concentration values shown in Tables 10-111 below.

(2E,4E)-2,4-Hexadienoic acid (available from Sigma-Aldrich, St. Louis, MO, USA). A 20 mg/mL stock solution in 100% DMSO was diluted 10-fold in PDB to obtain a 2 mg/mL working stock solution. This working stock solution, at an effective concentration of 2 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Saturated aliphatic acids as compound B

Concentrated stock solutions were prepared by dissolving each illustrative saturated aliphatic acid in 100% dimethyl sulfoxide (DMSO), which were then diluted 10-fold in potato dextrose broth (PDB) to obtain the working stock solution described below.

Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid (all available from Sigma-Aldrich, St. Louis, MO, USA). A 50 mg/mL stock solution in 100% DMSO was diluted 10-fold in PDB to obtain a 5 mg/mL working stock solution. This working stock solution, at an effective concentration of 5 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values shown in Tables 10-111 below.

Decenoic acid (available from Sigma-Aldrich, St. Louis, MO, USA). A 10 mg/mL stock solution in 100% DMSO was diluted 10-fold in PDB to obtain a 1 mg/mL working stock solution. This working stock solution at an effective concentration of 1 mg/mL was used for further serial dilution in the PDB to the required individual concentration values shown in Tables 10-111 below.

Dodecenoic acid (available from Sigma-Aldrich, St. Louis, MO, USA). A 1 mg/mL stock solution in 100% DMSO was diluted 10-fold in PDB to obtain a 0.1 mg/mL working stock solution. This working stock solution, at an effective concentration of 0.1 mg/mL, was used for further serial dilution in the PDB to the required individual concentration values listed in Tables 10-111 below.

Working stock solutions for each Compound A and Compound B component were then serially diluted to test the individual MIC of each pesticide active ingredient (as Compound A), each unsaturated or saturated aliphatic acid (as Compound B), and the combined MIC of each combination Compound A and Compound B according to the synergistic growth inhibition assay described above.

Example 8 Inhibition of Fusarium oxysporum with pyraclostrobin, azoxystrobin, chlorothalonil, fludioxonil, cyprodinil, difenoconazole and tebuconazole in combination with various exemplary saturated aliphatic acids

Working solutions of pyraclostrobin, azoxystrobin, chlorothalonil, fludioxonil, cyprodinil, difenoconazole, and tebuconazole were each prepared as described above (as Compound A) and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 10-15 below. Each of the working solutions of hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid and decanoic acid (as compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 10- 15 below.

Each individual compound and combination was tested over a range of 2-fold dilutions in a synergistic growth inhibition assay, observed after an incubation period of 48 hours, and the FIC index for each combination was calculated as shown in Tables 10-15 below.

Example 9 Inhibition of the growth of Sclerotinia sclerotiorum by pyraclostrobin, azoxystrobin, propiconazole, epoxiconazole, tebuconazole and difenoconazole in combination with various exemplary saturated aliphatic acids

Each of the working solutions of pyraclostrobin, azoxystrobin, propiconazole, epoxiconazole, tebuconazole and difenoconazole were prepared as described above (as Compound A) and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 16-20 below. Working solutions of hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and dodecanoic acid (as Compound B) were each prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in tables 16-20 below.

Each individual compound and combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 7 days, and the FIC index for each combination was calculated as shown in Tables 16-20 below.

Example 10 Inhibition of Botrytis cinerea growth using pyraclostrobin, azoxystrobin, cyprodinil, metalaxyl, epoxiconazole, tebuconazole, propiconazole and difenoconazole in combination with various exemplary saturated aliphatic acids

Each of the working solutions of pyraclostrobin, azoxystrobin, cyprodinil, metalaxyl, epoxiconazole, tebuconazole, propiconazole and difenoconazole were prepared as described above (as Compound A) and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 21 -26 below. Working solutions of hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and dodecanoic acid (as Compound B) were each prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in tables 21-26 below.

Each individual compound and combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 48 hours, and the FIC index for each combination was calculated as shown in Tables 21-26 below.

Example 11 Inhibition of Fusarium oxysporum growth using pyraclostrobin, azoxystrobin, fludioxonil, cyprodinil, difenoconazole, epoxiconazole and tebuconazole in combination with various illustrative unsaturated aliphatic acids

Working solutions of pyraclostrobin, azoxystrobin, fludioxonil, cyprodinil, difenoconazole, epoxiconazole, and tebuconazole were each prepared as described above (as Compound A) and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 27-32 below. Each of the working solutions (2E,4E)-2,4-hexadienoic acid, trans-3-hexenoic acid, 4-hexenoic acid, 5-hexenoic acid, 3-heptenoic acid, trans-2-octenoic acid, trans-3- octenic acid, 7-octenic acid, 3-decenoic acid, 9-decenoic acid, trans-2-nonenoic acid, 3-nonenoic acid, trans-2-decenoic acid and trans-2-undecenoic acid (as compound B) were prepared , as described above, and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 27-32 below.

Each individual compound and combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 48 hours, and the FIC index for each combination was calculated as shown in Tables 27-32 below.

Example 12 Inhibition of the growth of Sclerotinia sclerotiorum by pyraclostrobin, azoxystrobin, chlorothalonil, fludioxonil, difenoconazole, propiconazole, epoxiconazole and tebuconazole in combination with various illustrative unsaturated aliphatic acids

Working solutions of pyraclostrobin, azoxystrobin, chlorothalonil, fludioxonil, difenoconazole, propiconazole, epoxiconazole, and tebuconazole were each prepared as described above (as Compound A) and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 33 -42 below. Each of the working solutions of (2E,4E)-2,4-hexadienoic acid, trans-2-hexenoic acid, trans-3-hexenoic acid, 5-hexenoic acid, 3-heptenoic acid, trans-2-octenoic acid, trans- 3-octenic acid, 3-octenic acid, 7-octenic acid, 3-decenoic acid, cis-3-hexenoic acid, 9-decenoic acid, trans-2-nonenoic acid, 3-nonenoic acid, (9Z)-octadecenoic acid , trans-2-decenoic acid, cis-2-decenoic acid, and trans-2-undecenoic acid (as Compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in tables 33-42 below.

Each individual compound and combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 7 days, and the FIC index for each combination was calculated as shown in Tables 33-42 below.

Example 13 Inhibition of Botrytis cinerea growth by pyraclostrobin, azoxystrobin, chlorothalonil, cyprodinil, metalaxyl, epoxiconazole and tebuconazole in combination with various illustrative unsaturated aliphatic acids

Working solutions of pyraclostrobin, azoxystrobin, chlorothalonil, cyprodinil, metalaxyl, epoxiconazole, and tebuconazole were each prepared as described above (as Compound A) and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 43-50 below. Each of the working solutions of (2E,4E)-2,4-hexadienoic acid, trans-2-hexenoic acid, trans-3-hexenoic acid, 5-hexenoic acid, 3-heptenoic acid, trans-2-octenoic acid, trans- 3-octenic acid, 3-octenic acid, 7-octenic acid, 3-decenoic acid, 9-decenoic acid, trans-2-nonenoic acid, 3-nonenoic acid, (9Z)-octadecenoic acid, trans-2-decenoic acid and trans-2-undecenoic acid (as Compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 43-50 below.

Each individual compound and combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 48 hours, and the FIC index for each combination was calculated as shown in Tables 43-50 below.

Example 14 Inhibition of Fusarium oxysporum with Thyme Oil, Garlic Oil, Wintergreen Oil, Peppermint Oil, Spearmint Oil, Clove Leaf Oil, Tea Tree Oil, Oregano Oil, Nootkatone(+) and Azadirachtin Extract, Fortune Aza Technical (also known as Fortune Azatech) in combination with various illustrative saturated aliphatic acids

Each of the working solutions of Thyme Oil, Garlic Oil, Wintergreen Oil, Peppermint Oil, Spearmint Oil, Clove Leaf Oil, Tea Tree Oil, Oregano Oil, Nutkatone(+) and Azadirachtin Extract - Fortune Aza Technical (also known as Fortune Azatech) - was prepared as described above (as Compound A) and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 51-61 below. Each of the working solutions of hexanoic, heptanoic, octanoic, nonanoic, decanoic, and dodecanoic acid (as Compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 51-61 below .

Each individual compound and combination was tested over a range of 2-fold dilutions in a synergistic growth inhibition assay, observed after an incubation period of either 24 hours or 4 days as indicated below, and the FIC index was calculated for each combination as shown in Tables 51- 61 below.

Example 15 Inhibition of Sclerotinia sclerotiorum with Thyme Oil, Garlic Oil, Lemongrass Oil, Wintergreen Oil, Peppermint Oil, Spearmint Oil, Clove Leaf Oil, Cinnamon Leaf Oil, Rosemary Oil, Oregano Oil, Limonoid Extract margosa and salannin oils in combination with various illustrative saturated aliphatic acids

Each of the working solutions of thyme oil, garlic oil, lemongrass oil, wintergreen oil, peppermint oil, spearmint oil, clove leaf oil, cinnamon leaf oil, rosemary oil, oregano oil, margosa oil limonoid extract and salannin were prepared , as described above (as Compound A), and were serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 62-73 below. Each of the working solutions of hexanoic, heptanoic, octanoic, nonanoic, decanoic and dodecanoic acid (as Compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 62-73 below .

Each individual compound and combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 7 days, and the FIC index for each combination was calculated as shown in Tables 62-73 below.

Example 16 Inhibition of Botrytis cinerea with Thyme Oil, Wintergreen Oil, Spearmint Oil, Rosemary Oil, Oregano Oil, Nutkatone(+), Karanja Oil Flavonoid Extract, Fortune Aza Technical, Salannin and Margosa Oil Limonoid Extract in Combination with various illustrative saturated aliphatic acids

Each of the working solutions of thyme oil, wintergreen oil, spearmint oil, rosemary oil, oregano oil, nutkatone(+), karanja oil flavonoid extract, Fortune Aza Technical, salannin and margosa oil limonoid extract were prepared as described above (as compounds A) and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 74-83 below. Each of the working solutions of hexanoic, heptanoic, octanoic, nonanoic, decanoic and dodecanoic acid (as Compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing, as shown in Tables 74-83 below .

Each individual compound and combination was tested over a range of 2-fold dilutions in a growth inhibition assay, observed after an incubation period of 24 hours to 4 days as indicated, and the FIC index for each combination was calculated as shown in Tables 74-83 below.

Example 17 Inhibition of Fusarium oxysporum with Thyme Oil, Garlic Oil, Lemongrass Oil, Wintergreen Oil, Peppermint Oil, Spearmint Oil, Clove Leaf Oil, Cinnamon Leaf Oil, Tea Tree Oil, Geranium Oil, Oregano Oil , rosemary and nutkatone(+) oils in combination with various illustrative unsaturated aliphatic acids

Each of the working solutions of thyme oil, garlic oil, lemongrass oil, wintergreen oil, peppermint oil, spearmint oil, clove leaf oil, cinnamon leaf oil, tea tree oil, geranium oil, oregano oil, rosemary oil and nutkatone (+) was prepared as described above (as Compound A) and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 84-98 below. Each of the working solutions (2E,4E)-2,4-hexenoic acid, trans-2-hexenoic acid, trans-3-hexenoic acid, 4-hexenoic acid, 5-hexenoic acid, 3-heptenoic acid, trans-2- octenic acid, trans-3-octenic acid, 3-octenic acid, 7-octenic acid, 3-decenoic acid, 9-decenoic acid, trans-2-nonenoic acid, 3-nonenoic acid, (9Z)-octadecenoic acid, trans -2-decenoic acid and trans-2-undecenoic acid (as Compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 84-98 below.

Each individual compound and combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 48 hours, and the FIC index for each combination was calculated as shown in Tables 84-98 below.

Example 18 Inhibition of Sclerotinia sclerotiorum with Thyme Oil, Garlic Oil, Lemongrass Oil, Wintergreen Oil, Peppermint Oil, Spearmint Oil, Clove Leaf Oil, Fortune Aza Technical Azadirachtin Extract, and Oregano Oil in Combination with Various Illustrative Unsaturated aliphatic acids

Each of the working solutions of thyme oil, garlic oil, lemongrass oil, wintergreen oil, peppermint oil, spearmint oil, clove leaf oil, Fortune Aza Technical azadirachtin extract, and oregano oil were prepared as described above (as Compound A) , and were serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 99-107 below. Each of the working solutions (2E,4E)-2,4-hexenoic acid, trans-2-hexenoic acid, trans-3-hexenoic acid, 4-hexenoic acid, 5-hexenoic acid, 3-heptenoic acid, trans-2- octenic acid, trans-3-octenic acid, 3-octenic acid, 7-octenic acid, 3-decenoic acid, 9-decenoic acid, trans-2-nonenoic acid, 3-nonenoic acid, (9Z)-octadecenoic acid, trans -2-decenoic acid and trans-2-undecenoic acid (as Compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 99-107 below.

Each individual compound and combination was tested over a 2-fold dilution range in a synergistic growth inhibition assay, observed after an incubation period of 7 days, and the FIC index for each combination was calculated as shown in Tables 99-107 below.

Example 19 Inhibition of the growth of Botrytis cinerea using oregano oil, nutkatone(+), spearmint oil, rosemary oil, thyme oil, salannin, karanja oil flavonoid extract and margosa oil limonoid extract in combination with various illustrative unsaturated aliphatic acids

Each of the working solutions of oregano oil, nutkatone(+), spearmint oil, rosemary oil, thyme oil, salannin, karanja oil flavonoid extract and margosa oil limonoid extract were prepared as described above (as compound A) and serially diluted in the PDB to the individual required concentration values for MIC testing as shown in Tables 108-115 below. Each of the working solutions of (2E,4E)-2,4-hexadienoic acid, trans-2-hexenoic acid, trans-3-hexenoic acid, 5-hexenoic acid, trans-2-octenoic acid, 7-octenoic acid, 3- decenoic acid, 9-decenoic acid, and trans-2-decenoic acid (as Compound B) were prepared as described above and serially diluted in the PDB to the individual required concentrations for MIC testing as shown in Tables 108-115 below.

Each individual compound and combination was tested over a range of 2-fold dilutions in a growth inhibition assay, observed after an incubation period of 48 hours, and the FIC index for each combination was calculated as shown in Tables 108-115 below.

Example 20: In-vitro insecticidal efficacy against Trichoplusia ni chlorfenapyr (active ingredient in Pylon® insecticide) in combination with various illustrative unsaturated aliphatic acids (and their agriculturally acceptable salts)

Receiving a sample

Chlorfenapyr, a synthetic halogenated pyrrole miticide insecticide, is the active ingredient in Pylon® insecticide (available from BASF Corp., Research Triangle Park, North Carolina, USA) and is present as a 21.4% w/w liquid formulation. Pylonr . The Pylon® liquid formulation was diluted in water to form a 2 mg/ml Pylon® stock solution (containing 0.428 mg/ml chlorfenapyr).

A stock solution was prepared for each of trans-2-hexenoic acid and trans-3-hexenoic acid (both available from Sigma-Aldrich, St. Louis, MO, USA) by dissolving each illustrative unsaturated aliphatic acid in 100% dimethyl sulfoxide (DMSO) with providing a concentration of 20 mg/ml (20,000 ppm). A stock solution for the potassium salt of (2E,4E)-2,4-hexadienoic acid was prepared by dissolving the salt in water to form a 20 mg/mL (20,000 ppm) solution.

An artificial culture medium suitable for Trichoplusia ni (ni caterpillar) was prepared according to the recipe of modified McMorran's artificial culture medium known in the field of entomology (containing agar, casein, potassium hydroxide, Alphacel, Wesson's salt mixture, sugar, roasted wheat germ, choline chloride, ascorbic acid, methylparaben, aureomycin, flaxseed oil and vitamin solution).

Pylon® stock solutions were diluted in 35 ml of artificial culture medium to provide a concentration of 0.0016 mg/ml for each Pylon® treatment and each of the unsaturated aliphatic acids (and salts) stock solutions were diluted in 35 ml of artificial culture medium with concentration values of 0 .05 mg/mL, 0.15 mg/mL, and 0.30 mg/mL for each unsaturated aliphatic acid (and salt) treatment, and the combination of Pylon® and each aliphatic acid (and salt) were added to the artificial culture medium at the same concentration values for each combination treatment. The treated artificial culture medium was then used to fill each well of a 24-well treatment plate with approximately 0.5 ml of artificial culture medium, which was allowed to solidify at room temperature and stored overnight at approximately 4°C. The next day, newly hatched Trichoplusia ni larvae (hatched from eggs obtained from Natural Resource Canada, an insect research center in Sault Ste. Marie, Ontario, Canada) were added to each well of the plate and their survival rate was monitored every 72 hours and every 24 hours for a total of no more than 144 hours (6 days) with the insecticidal effectiveness of Pylon® alone, each unsaturated aliphatic acid (and salt) alone, and each combination of Pylon® and unsaturated aliphatic acid (and salt) determined . Each experiment had 3 replicates and was repeated at least 3 times.

The observed survival rates for larvae at each time interval for the Pylon® and unsaturated aliphatic acid (and salt) treatments are shown in comparison with the corresponding survival rates for the combination treatments for each of the three unsaturated aliphatic acid (and salt) concentrations in Figures 3- 5.

Cumulative results demonstrating insecticidal effectiveness (which equals (100% - (survival rate))) for each treatment are shown below in Tables 116-118 (corresponding to concentrations of unsaturated aliphatic acids and salts of 0.05 mg/ml, 0.15 mg/ ml and 0.30 mg/ml, respectively).

The observed level of effectiveness (1 - (survival rate)) for individual treatments and combination treatments was used to evaluate the effectiveness data in Tables 116-118 for synergistic effects in the combination of Pylon® and exemplary unsaturated aliphatic acids (and salts) using the Colby formula ( also called Abbott's formula) according to S. R. Colby, Calculating Synergistic and Antagonistic Responses of Herbicide Combinations, Weeds, Vol. 15, No. 1 (Jan. 1967), well known in the field of experimental agriculture, to determine the synergism between two or more compounds. According to the Colby formula, the expected effectiveness, E (%), of treatment with a combination of compounds A and B at concentrations a and b, respectively, can be determined by evaluating:

E = x + y - (xy/100), where

x is the effectiveness (%) of compound A alone, applied at concentration a;

y is the effectiveness (%) of compound B alone, applied at concentration b.

The presence and extent of synergy present in the case of a combination treatment can be determined according to Colby's formula by estimating the synergy index, SF = (observed effectiveness)/(expected effectiveness). For values of SF > 1, synergistic effectiveness is demonstrated in the observed effectiveness of the combination of compounds, with the synergy present increasing as SF increases above 1. However, for SF < 1, antagonism is present, and for SF = 1, the effectiveness of the compounds is only additive. Tables 116-118 demonstrate the calculated synergy according to the Colby formula above for the observed insecticidal effectiveness of each treatment with the combination of Pylon® and the illustrative unsaturated aliphatic acids (and salts) tested. As shown in Tables 116-118, the combination of Pylon® insecticide at a concentration of 0.0016 mg/ml (equivalent to 0.00034 mg/ml chlorfenapyr as insecticidal active ingredient) with an exemplary unsaturated aliphatic acid (and salt) with concentration values from 0 .05 mg/ml to 0.30 mg/ml provided synergistic efficacy rates that were 4 to 24 times greater than the expected efficacy of the individual components, thus providing significant evidence of synergistic pesticide efficacy of the combinations in accordance with one embodiment of the present inventions.

Example 21 Insecticidal efficacy of in-planta against Trichoplusia ni chlorfenapyr (active ingredient in Pylon® insecticide) in combination with various illustrative unsaturated aliphatic acids (and their agriculturally acceptable salts)

Receiving a sample

Chlorfenapyr, a synthetic halogenated pyrrole miticide insecticide, was provided as the active ingredient in Pylon® insecticide (available from BASF Corp., Research Triangle Park, North Carolina, USA) and was present as a 21.4% w/w liquid formulation . Pylon®. The liquid Pylon® formulation was diluted in water to form a 0.187 mg/ml Pylon® treatment solution (containing 0.0400 mg/ml chlorfenapyr).

A stock solution was prepared for trans-2-hexenoic acid (available from Sigma-Aldrich, St. Louis, MO, USA) by dissolving trans-2-hexenoic acid in 100% dimethyl sulfoxide (DMSO) to provide a concentration of 20 mg/mL. A stock solution for the potassium salt of (2E,4E)-2,4-hexadienoic acid was prepared by dissolving the salt in water to form a 20 mg/mL (20,000 ppm) solution. Combination treatment solutions were prepared by adding a stock solution of each of the exemplary unsaturated aliphatic acids and salts to the Pylon® treatment solution to obtain a combination treatment solution having a Pylon® concentration of 0.187 mg/mL and exemplary unsaturated aliphatic acid (or salt) concentration values of 0 .06 mg/ml.

Cabbage plants (Brassica oleracea var. capitate, cv. Danish Ballhead) were grown from seed (available from West Coast Seeds, Delta, British Columbia, Canada) in potting soil mix for 4 weeks in a pest-free indoor growing environment. Once 4 weeks of age, each cabbage plant was sprayed with 10 ml of treatment solution using a hand pump sprayer and allowed to dry. After the sprayed treatment solution has dried on the leaves of the cabbage plants, 15-30 first instar Trichoplusia ni larvae (hatched from eggs obtained from Natural Resource Canada, an insect research center in Sault Ste. Marie, Ontario, Canada) were placed directly on the leaves of each cabbage plant. The treated cabbage plants were then placed in a nylon insulation tent and kept in an indoor growing environment, and the larvae were left to feed on the plants. In one set of cabbage plants, larvae were allowed to feed for 48 hours and then the number of surviving larvae was recorded and survival rates (%) were determined. In a second separate set of cabbage plants, the larvae were allowed to feed for 72 hours and the number of surviving larvae was then recorded and survival rates (%) determined. Each experiment was repeated at least 3 times.

Cumulative results demonstrating insecticidal effectiveness (which equals (100% - (observed survival rate))) for each treatment are shown below in Tables 119-120 (corresponding to observation intervals of 48 hours and 72 hours for two sets of plants, both sets of concentration values unsaturated aliphatic acid and salt was 0.06 mg/ml, and the Pylon® concentration was 0.187 mg/ml). The observed percentage insecticidal effectiveness level (equal to 100% (survival rate)) for individual treatments and combination treatments was used to evaluate the effectiveness data in Tables 119-120 for the synergistic effects in the combination of Pylon® and illustrative unsaturated aliphatic acids (and salts) with using the Colby formula (also called the Abbott formula) according to S. R. Colby, Calculating Synergistic and Antagonistic Responses of Herbicide Combinations, Weeds, Vol. 15, No. 1 (Jan. 1967), well known in the field of experimental agriculture, to determine the synergism between two or more compounds. According to the Colby formula, the expected effectiveness, E (%), of treatment with a combination of compounds A and B at concentrations a and b, respectively, can be determined by evaluating:

E = x + y - (xy/100), where

x is the effectiveness (%) of compound A alone, applied at concentration a;

y is the effectiveness (%) of compound B alone, applied at concentration b.

The presence and extent of synergy present in the case of a combination treatment can be determined according to Colby's formula by estimating the synergy index, SF = (observed effectiveness)/(expected effectiveness). For values of SF > 1, synergistic effectiveness is demonstrated in the observed effectiveness of the combination of compounds, with the synergy present increasing as SF increases above 1. However, for SF < 1, antagonism is present, and for SF = 1, the effectiveness of the compounds is only additive. Tables 119 and 120 demonstrate the calculated synergy according to the Colby formula above for the observed insecticidal effectiveness of each treatment with the combination of Pylon® and the exemplary unsaturated aliphatic acid (and salt) tested. As shown in Tables 119-120, the combination of Pylon® insecticide at a concentration of 0.187 mg/ml (equivalent to 0.0400 mg/ml chlorfenapyr as a pesticide active ingredient) with an exemplary unsaturated aliphatic acid (and salt) at a concentration of 0.06 mg/ml ml provided synergistic effectiveness scores of 1.14 to 1.25 relative to the expected effectiveness of the individual components, thus providing evidence of synergistic pesticide effectiveness of the combinations in accordance with one embodiment of the present invention.

Table 120. Expected and observed efficacy (%) in-planta against Trichoplusia ni at concentration values of Pylon® 0.187 mg/ml and illustrative unsaturated aliphatic acid (and salt) 0.06 mg/ml after 72 hours

In some embodiments, in accordance with the present invention, and as illustrated in some illustrative embodiments in the experimental examples described above, a combination of an unsaturated C6-C10 aliphatic acid (and agriculturally acceptable salts thereof in some specific embodiments) and a pesticide active ingredient provides a synergistic pesticide composition exhibiting a synergistic effect. That is, when used in combination, the unsaturated C6-C10 aliphatic acid and the pesticidal active ingredient have an effectiveness that is greater than would be expected from simply adding the effectiveness of the pesticidal active ingredient and the unsaturated C6-C10 aliphatic acid when used alone. In some alternative embodiments, the unsaturated aliphatic acid or agriculturally acceptable salt thereof may include an unsaturated C11 aliphatic acid or agriculturally acceptable salt thereof. In some further alternative embodiments, the unsaturated aliphatic acid or agriculturally acceptable salt thereof may include an unsaturated C12 aliphatic acid or agriculturally acceptable salt thereof.

In some embodiments, in accordance with the present invention, and as illustrated in some illustrative embodiments in the experimental examples described above, a combination of a saturated C6-C10 aliphatic acid (and agriculturally acceptable salts thereof in some specific embodiments) and a pesticide active ingredient provides a synergistic pesticide composition exhibiting a synergistic effect. That is, when used in combination, the saturated C6-C10 aliphatic acid and the pesticidal active ingredient have an effectiveness that is greater than would be expected from simply adding the effectiveness of the pesticidal active ingredient and the saturated C6-C10 aliphatic acid when used alone. In certain specific embodiments, the combination of a saturated C6-C10 aliphatic acid and a margosa seed, kernel, oil, extract, or derivative pesticide active ingredient provides a synergistic pesticide composition exhibiting a synergistic pesticide effect. In some further embodiments, the combination of a saturated CP or C12 aliphatic acid and a margosa seed, kernel, oil, extract or derivative pesticide active ingredient provides a synergistic pesticide composition exhibiting a synergistic pesticide effect. In some alternative embodiments of the present invention, the combination of a saturated C11 or C12 aliphatic acid (and agriculturally acceptable salts thereof in some particular embodiments) and a pesticide active ingredient provides a synergistic pesticide composition exhibiting a synergistic effect.

In the above examples, using illustrative species of fungi and insects, it is demonstrated that a large number of saturated and unsaturated C6-C10-, including C6-, C7-, C8-, C9- and C10-, as well as C11- and C12-aliphatic acids have a synergistic effect when used in combination with an insecticidal or fungicidal active agent. Based on the above results and the fact that the cell membranes of eukaryotic cells have a similar lipid bilayer structure, it can be reasonably assumed that saturated and unsaturated C6-C10 aliphatic acids, as well as saturated and unsaturated C11 and C12 aliphatic acids, will have a synergistic effect when used in combination with active ingredients, including fungicidal, insecticidal, acaricidal, molluscicidal, bactericidal and nematicidal active ingredients, to control target pests including fungi, insects, mites, molluscs, bacteria and nematodes.

While a number of illustrative aspects and embodiments have been discussed above, certain modifications, conversions, additions, and subcombinations thereof will be apparent to those skilled in the art. Accordingly, it is intended that the appended claims and the claims hereinafter be construed in the broadest sense in accordance with the disclosure as a whole.

Claims (18)

1. A synergistic pesticide composition containing a pesticide active ingredient selected from strobilurins, azoles, fludioxonil, chlorothalonil, cyprodinil, metalaxyl, chlorfenapyr, mancozeb, isopyrazam, oxathiapiproline, penthiopyrad or a mixture thereof, chlorantraniliprole or cyantraniliprole; and a saturated or unsaturated C6-C10 aliphatic acid or an agriculturally compatible salt thereof; wherein the weight ratio of the concentration values of said pesticide active ingredient and said saturated or unsaturated C6-C10 aliphatic acid or agriculturally compatible salt thereof is from 1:10,000 to 10,000:1. 2. The synergistic pesticide composition according to claim 1, wherein the synergistic pesticide composition has an FIC index value of less than 1, or preferably less than 0.75, or more preferably less than 0.5. 3. Synergistic pesticide composition according to any one of paragraphs. 1 or 2, wherein the saturated or unsaturated C6-C10 aliphatic acid comprises at least one of a natural plant extract or a natural animal extract, or fractions thereof. 4. Synergistic pesticide composition according to any one of paragraphs. 1 or 2, wherein the saturated or unsaturated C6-C10 aliphatic acid comprises a vegetable oil extract, an animal oil extract, or a fraction or derivative thereof. 5. Synergistic pesticide composition according to any one of paragraphs. 1 or 2, wherein said composition exhibits synergistic inhibition of the growth of at least one target pest organism. 6. Synergistic pesticide composition according to any one of paragraphs. 1 or 2, wherein said composition contains said pesticide active ingredient at a pesticidal effective concentration and said saturated or unsaturated C6-C10 aliphatic acid or an agriculturally compatible salt thereof. 7. Synergistic pesticide composition according to any one of paragraphs. 1 or 2, wherein said pesticide active ingredient selected from strobilurins comprises at least one selected from the list including: azoxystrobin, dimoxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin and wherein said pesticide active ingredient selected from triazoles comprises at least one selected from the list containing difenoconazole, epoxiconazole, propiconazole, prothioconazole, tebuconazole. 8. Synergistic pesticide composition according to any one of paragraphs. 1 or 2, wherein the weight ratio of the concentration values of said pesticide active ingredient and said saturated or unsaturated C6-C10 aliphatic acid or agriculturally compatible salt thereof is in at least one of the following ranges: from 1:10000 to 10000: 1, from 1:5000 to 5000:1, from 1:2500 to 2500:1, from 1:1500 to 1500:1, from 1:1000 to 1000, from 1:750 to 750:1, from 1:500 to 500:1, 1:400 to 400:1, 1:300 to 300:1, 1:250 to 250:1, 1:200 to 200:1, 1:150 to 150:1, from 1:100 to 100:1, 1:90 to 90:1, 1:80 to 80:1, 1:70 to 70:1, 1:60 to 60:1, 1:50 to 50 :1, 1:40 to 40:1, 1:30 to 30:1, 1:25 to 25:1, 1:20 to 20:1, 1:15 to 15:1, 1 :10 to 10:1, 1:9 to 9:1, 1:8 to 8:1, 1:7 to 7:1, 1:6 to 6:1, 1:5 to 5: 1, 1: to 4:1, 1:3 to 3:1, 1:2 to 2:1, 1:1.5 to 1.5:1 and 1.25 to 1.25: 1. 9. Synergistic pesticide composition according to any one of paragraphs. 1-8, wherein said saturated or unsaturated C6-C10 aliphatic acid comprises a straight chain saturated or unsaturated C6-C10 aliphatic acid. 10. A method for synergistically increasing the pesticidal activity of at least one pesticide active ingredient adapted to control at least one target pest, comprising: providing at least one pesticide active ingredient that is active against said at least one target pest organism, wherein the pesticide active ingredient is selected from strobilurins, azoles, fludioxonil, chlorothalonil, cyprodinil, metalaxyl, chlorfenapyr, mancozeb, isopyrazam , oxathiapiproline, penthiopyrad or a mixture thereof, chlorantraniliprole or cyantraniliprole; adding, in a synergistically effective concentration, at least one saturated or unsaturated C6-C10 aliphatic acid or an agriculturally acceptable salt thereof to said pesticide active ingredient to form a synergistic pesticide composition; And using said synergistic pesticide composition at a pesticidal effective concentration to control said at least one target pest organism. 11. The method of claim 10, wherein the weight ratio of said synergistically effective concentration of said saturated or unsaturated C6-C10 aliphatic acid or agriculturally compatible salt thereof and said pesticide active ingredient is within approximately at least one of the following ranges: from 1:10000 to 10000:1, from 1:5000 to 5000:1, from 1:2500 to 2500:1, from 1:1500 to 1500:1, from 1:1000 to 1000, from 1:750 to 750: 1, from 1:500 to 500:1, from 1:400 to 400:1, from 1:300 to 300:1, from 1:250 to 250:1, from 1:200 to 200:1, from 1: 150 to 150:1, 1:100 to 100:1, 1:90 to 90:1, 1:80 to 80:1, 1:70 to 70:1, 1:60 to 60:1 , from 1:50 to 50:1, from 1:40 to 40:1, from 1:30 to 30:1, from 1:25 to 25:1, from 1:20 to 20:1, from 1:15 to 15:1, from 1:10 to 10:1, from 1:9 to 9:1, from 1:8 to 8:1, from 1:7 to 7:1, from 1:6 to 6:1, from 1:5 to 5:1, from 1: to 4:1, from 1:3 to 3:1, from 1:2 to 2:1, from 1:1.5 to 1.5:1 and from 1 .25 to 1.25:1. 12. The method of claim 10, wherein the synergistic pesticide composition has a FIC index value of less than 1, or preferably less than 0.75, or more preferably less than 0.5. 13. The method of claim 10, wherein the saturated or unsaturated C6-C10 aliphatic acid comprises at least one of a natural plant extract or a natural animal extract or fractions thereof. 14. The method according to claim 10, wherein the saturated or unsaturated C6-C10 aliphatic acid comprises a vegetable oil extract, an animal oil extract, or a fraction or derivative thereof. 15. Method according to any one of paragraphs. 10-14, wherein said saturated or unsaturated C6-C10 aliphatic acid comprises a straight chain saturated or unsaturated C6-C10 aliphatic acid.

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