WO2024121275A1 - Ant-repellent composition - Google Patents

Abstract

The present invention relates to a composition having ant-repelling characteristics comprising as an active ingredient a compound of the formula (I), or a salt or crystal thereof: formula (I). Moreover, the present invention relates to the use of the compound of formula (I) for reducing ant infestation, as well as methods of reducing ant infestation using the composition containing the compound of formula (I).

Description

Ant-Repellent Composition

Ants, such as the fire ant So/enopsis invicta and little fire ant Wasmannia auropunctata, are serious and at times invasive pests. When a fire ant mound is disturbed, hundreds of worker fire ants will emerge from the mound to defend the colony by attacking and stinging the intruder. Fire ant mound-building activity can damage plant roots and lead to loss of ornamental and crop plants. It is estimated that ants cause approximately $750 million in damages annually to agricultural assets, including veterinarian bills, livestock and crop loss. Invasive ants are particularly harmful, with 5 of the 19 listed among the "100 worst invasive alien species in the world". They invade human homes, destroy crops, and harm native species at huge annual cost. For example, the estimated costs of So/enopsis invicta and Wasmannia auropunctata are $37 billion and $20 billion, respectively.

The most commonly used method to control invasive ant species is chemical control. Examples of chemical control compounds include methoprene and pyriproxyfen, which are insect growth regulators that affect the reproductive capabilities of the colony but have no acute toxicity to fire ant workers. Over'N Out!® and TopChoice® are further chemical controls, which both contain fipronil as the active ingredient. Since fipronil is a slow-acting insecticide, worker ants transfer the insecticide into the colony before being killed. However, due to the slow-acting nature of fipronil, the products are not suitable for rapid control of ants on, for example, a surface. Thus, ant control is not immediately visible to a consumer applying the product. Systemic insecticides, i.e., insecticides absorbed by and transported through plants, such as hydramethylnon, are also used. Hydramethylnon is typically formulated as granules or incorporated into materials such as baits or gels against pests. Hydramethylnon is a slow-acting poison due to its delayed toxicity and needs to be eaten to be effective. Research into the biological control of invasive ants is practically non-existent and the control of invasive ants with organic products is mostly ineffective.

In a recent publication by Pattrick et al. (Arthropod-Plant Interactions, 2017, 11, 623- 627) the floral volatile 4-methoxybenzaldehyde (also referred to, inter alia, as 4- anisealdehyde or para-anisealdehyde) was examined as an ant-repellent volatile, specifically and only for the ant Formica aquilonia. The researchers found that in olfactometer trials, the ants avoided 4-methoxybenzaldehyde and remained in the treatment airspace (±SE) 20.5% ± 7.7 less than the 50% observed in the control treatment airspace (randomization test, p = 0.004, percentage time in treatment airspace (±SE). The researchers moreover highlighted that investigations into the structures of the repellent volatiles have failed to reveal any clear patterns in their function. With regard to the ant species, Formica aquilonia is a wood ant widely distributed across Europe, living mainly in coniferous forests but also in some deciduous woodlands. This ant species is not considered invasive and is a priority species for conservation in the UK.

Surprisingly, it has now been found that excellent ant control can be achieved using orf/?o-substituted benzaldehyde derivatives. Surprisingly, the ant-repellent effect was improved using many o/t/?o-substituted benzaldehyde compounds compared to 4- methoxybenzaldehyde for the ant Lasius niger. This effect is unexpected given that many of the tested orf/?o-substituted benzaldehydes are not found in plants. For example, 2-methoxybenzaldehyde is found in insects such as beetle larvae. The present invention provides a new and improved ant-repellent composition which is able to deter a wide variety of ant species, including invasive and destructive species Solenopsis invicta and Wasmannia auropunctata.

Accordingly, the present invention, inter alia, relates to the following embodiments:

1. A composition having ant-repelling characteristics comprising as an active ingredient a compound of the formula (I), or a salt or crystal thereof:

wherein R is independently selected from halogen, -C1-6 alkyl, -C2-6 -alkenyl, C2- 6-alkynyl, -O(Ci-₆ alkyl), -O(aryl), -CHO, -C(O)(Ci-₆ alkyl), -C(O)-NH₂, - C(O)-NH(CI-₆ alkyl), -C(O)-N(CI-₆ alkyl)(Ci-₆ alkyl), -NH₂, -NH(CI-₆ alkyl), -N(Ci- 6 alkyl)(Ci-₆ alkyl), -NH-CO(CI-₆ alkyl), -N(CI-₆ alkyl)-CO(Ci-₆ alkyl), - NH-COO(CI-₆ alkyl), -N(CI-₆ alkyl)-COO(Ci-₆ alkyl), -SH, -S-(Ci-₆ alkyl), -(aryl), - (heteroaryl). The composition of item 1 , wherein R is independently selected from -Br, - methyl, -methoxy, -ethoxy, -propoxy and -butoxy, preferably wherein R is - methoxy. The composition of item 1 or 2 further comprising at least one solvent or solid acceptable carrier. An agricultural composition comprising the compound of formula (I) of item 1 or 2, further comprising at least one solvent or solid agriculturally acceptable carrier. The composition of item 3 or the agricultural composition of item 4, wherein the at least one solvent is ethanol, the composition preferably further comprising one or more of an antioxidant, UV-absorbent or fixative. The composition of item 3 or 5 or the agricultural composition of item 4 or 5, wherein the solvent is 60wt% ethanol, preferably further comprising the fixatives 30wt% isopropyl myristate, 7.5wt% dipropylene glycol and 1wt% methyl hydrogenated rosinate, the UV-absorbent 1wt% ethylhexyl methoxycinnamate and the antioxidant 0.5wt% butylated hydroxytoluene. The composition of claim of any one of items 1 to 3, 5 or 6 or the agricultural composition of any one of items 4, 5 or 6, wherein the amount of the compound of formula (I) is about 0.01wt% to 20wt%, preferably about 0.1wt% to 10wt%, more preferably about 0.5wt% to 5wt%. The composition of claim of any one of items 1 to 3 or 5 to 7 or the agricultural composition of any one of items 4 or 5 to 7, wherein the composition or agricultural composition is in the form of a spray, gel, foam, patch, powder, solid, sponge, tape, vapor, paste, tincture, lotion, cream or ointment. Use of the composition of claim of any one of items 1 to 3 or 5 to 8 or the agricultural composition of any one of items 4 or 5 to 8, for controlling and/or combating populations of ants, preferably ants belonging to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum. 10. Use of the composition of claim of any one of items 1 to 3 or 5 to 8 or the agricultural composition of any one of items 4 or 5 to 8, for reducing an infestation of ants, preferably ants belonging to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum.

11. A method of controlling, combating and/or reducing an infestation of ants comprising applying the composition of any one of items 1 to 3 or 5 to 8 or the agricultural composition of any one of items 4 or 5 to 8 onto a surface, object and/or fabric.

12. The method of item 11 , wherein the surface, object and/or fabric comprise(s) (a) plant, fungi, soil, wall, floor, window, furniture, clothing item or packaging material.

13. A method of controlling and/or reducing an infestation of ants comprising applying the composition of claim of any one of items 1 to 3 or 5 to 8 or the agricultural composition of any one of items 4 or 5 to 8 to an animal, preferably a mammal, in particular a human, dog, cat, cattle, horse or sheep.

14. A method of protecting a plant, seed and/or object from the attack of ants comprising treating said plant, seed and/or object with the composition of claim of any one of items 1 to 3 or 5 to 8 or the agricultural composition of any one of items 4 or 5 to 8.

15. The method of any one of items 11 to 14, wherein the ants belong to the subfamily Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum.

Accordingly, the present invention provides a composition having ant-repelling characteristics comprising as an active ingredient a compound of the formula (I), or a salt or crystal thereof:

wherein R is independently selected from hydrogen, halogen, -C1-6 alkyl, -C2-6 -alkenyl, C₂-6-alkynyl, -OH, -O(Ci-₆ alkyl), -O(aryl), -CHO, -C(O)(Ci-₆ alkyl), -C(O)-NH₂, - C(O)-NH(CI-₆ alkyl), -C(O)-N(CI-₆ alkyl)(Ci-e alkyl), -NH₂, -NH(CI-₆ alkyl), -N(CI-₆ alkyl)(Ci-₆ alkyl), -NH-CO(CI-₆ alkyl), -N(CI-₆ alkyl)-CO(Ci-₆ alkyl), -NH-COO(CI-₆ alkyl), -N(CI-6 alkyl)-COO(Ci-6 alkyl), -SH, -S-(Ci-6 alkyl), -(aryl), -(heteroaryl).

The inventors have surprisingly and unexpectedly found that the compounds of formula (I) and compositions thereof have an improved ant-repellent effect which thus can result in a reduction of ant infestation. As shown in the appended Examples, the effect of the compounds of formula (I) and compositions thereof are particularly improved over the effect of 4-methoxybenzaldehyde, which is considered in the prior art as an effective benzaldehyde ant-repellent. Moreover, the inventors found that the substitution of the benzaldehyde in the ortho- or exposition results in an improved antrepelling effect compared to the corresponding meta- and para-substituted derivatives. As can be seen from the appended examples, a comparison of 2- hydroxybenzaldehyde, 3-hydroxybenzaldehyde and 4-hydroxybenzaldehyde was conducted using the ant species Lasius niger. The inventors found that 3- and 4- hydroxybenzaldehyde have similar and weak ant-repelling capabilities. The best result was obtained with 2-hydroxybenzaldehyde, which showed a 6-fold improvement in repellence. Accordingly, the present invention, inter alia, relates to compositions of the compounds of formula (I) for repelling ants and reducing the infestation of ants.

The term “ant-repellent” and grammatical variations thereof, as used herein, refers to a spatial repellent effect against ants which reduces the infestation of ants and/or controls and/or combats any population of ants. It is preferred within the present invention that a reduction of infestation of at least 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% is achieved. Within the present invention, reducing the infestation with ants may be achieved through the repelling activity of the composition or compound of formula (I) of the invention. Repelling activity may be determined using methods provided herein, in particular methods as employed herein below and in the examples section. In some embodiments, the present invention relates to a composition comprising the compound of formula (I), wherein R is independently selected from -hydroxy (formula (la)), -Br (formula (lb)), -methyl (formula (Ic), -methoxy (formula (Id)), -ethoxy (formula

(le)), -propoxy (formula (If)) and -butoxy (formula (lg)), preferably -methoxy (formula (Id)). The compounds of formula (I) therefore have the following structure:

formula (le) formula (If) formula (lg)

As can be seen from the appended examples, the inventors of the present invention found that a composition comprising the compound of formula (I), wherein R is independently selected from -hydroxy (formula (la)), -Br (formula (lb)), -methyl (formula

(lc), -methoxy (formula (Id)), -ethoxy (formula (le)), -propoxy (formula (If)) and -butoxy (formula (lg)) are particularly effective at repelling ants and thus reducing the infestation of ants. These compounds display ant-repelling properties across a broad spectrum of ants, including, but not limited to, ants belonging to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum. In preferred embodiments, the invention relates to a composition comprising the compound of formula (I), wherein R is -methoxy (formula

(ld)), corresponding to the compound 2-methoxybenzaldehyde. As highlighted in the appended examples, 2-methoxybenzaldehyde was the most effective ant-repellent across a broad spectrum of ants, including, but not limited to, ants belonging to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum.

As will be understood by the person skilled in the art, depending on the ant species the efficacy of each of the herein above-described compounds may vary and may also be affected by the concentration used. The appended examples also highlight this potential for variation, for example, Table 1 shows that 2-ethoxybenzaldehyde is most effective in repelling Wasmannia auropunctata compared to, for example, 2- hydroxybenzaldehyde, however 2-hydroxybenzaldehyde is more effective at repelling Lasius n/gerthan 2-ethoxybenzaldehyde. The skilled person is capable of running the routine experiments required to determine the optimal active ingredient and/or optimal concentration for a particular ant species to prepare a composition specifically targeting that species should the need arise. It is also envisaged to provide compositions comprising more than one, two, three or more of the components in an optimal form to be used against one or more ant species.

In some embodiments, the invention relates to a composition of the compound of formula (I) and at least one solvent or solid acceptable carrier.

The solvent or solid acceptable carrier that is suitable for the preparation of the composition of the compound of formula (I) according to the invention is known per se. Solvents which may be used include, but are not limited to: water, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, (such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol), toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n- octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, ethylene glycol, propylene glycol, glycerol, N- methyl-2-pyrrolidone and the like. In some embodiments, at least two different solvents are used for the preparation of the composition of the compound of formula (I) according to the invention.

The ant-repellent composition of the present invention may also be combined with a solid acceptable carrier. Combination with a solid acceptable carrier has the advantages of ease of use, no fear of liquid leakage, and a low risk of the liquid solution touching the hand. In some embodiments, the ant-repellent composition of the present invention is combined with a solid acceptable carrier wherein the ant-repellent composition may be volatilized from the carrier into a space. The solid acceptable carrier is not particularly limited and may include one or more of a plant powder such as wood flour, flour, base fabrics (such as paper, woven fabric and non-woven fabric), porous organic molded bodies (such as visco pearl, kaolin, talc, calcium carbonate, silica, silica sand), Inorganic carriers (such as ceramics, polyethylene, polypropylene, ethylene I vinyl acetate copolymer (EVA), ethylene I methyl methacrylate copolymer (EMMA), styrenic diblock polymer, styrenic triblock polymer, thermoplastic elastomer (TPE)). Examples of TPE include, but are not limited to, a plastic resin film or molded article composed of TPE, thermoplastic polyolefinelastomers (TPO) and silicone rubber. A solid acceptable carrier may be prepared using a plastic resin film, a molded body or a silicone rubber molded body as a solid acceptable carrier which exhibits an efficient space repellent effect against ants. In some embodiments more than one, that is, at least two, at least three, at least four and so on, solid acceptable carriers are combined with the ant-repellent composition of the present invention.

Also, when the ant-repellent composition is contained in a solid acceptable carrier, a solvent, a surfactant or other components as described herein may be added as necessary, and a conventionally known method for its preparation can be appropriately adopted. For example, when the carrier is a non-woven fabric, the ant-repellent composition may be carried by a chemical solution dispensing method or a coating method or may be embedded with paraffin wax. It is suitable to adopt a method or a method in which an ant-repellent composition is sprayed or dripped together with a solvent as needed to permeate the formed body. Alternatively, a silicone rubber molded article containing a high concentration of ant-repellent composition and an untreated silicone rubber molded article are mixed in a closed container and allowed to stand for an appropriate time to allow the ant-repellent composition to be spread over the entire silicone rubber molded article. In the present invention, other functional components such as, for example, a repellent component against insects other than ants, an insecticidal component, a deodorizing component, and a disinfectant I antibacterial component may be added to the antrepellent composition, as long as the effects of the present invention are not impaired. The additional functional components may be mixed and/or blended and comprised with the ant-repellent composition. Among these functional components, repellent components against insects other than ants include, but are not limited to, dimethyl phthalate. Exemplary insecticidal components include but are not limited to empentrin, transfluthrin, metfluthrin, profluthrin etc. However, the products comprising the composition of the present invention may also be substantially free of an insecticidal component to suit consumers who do not wish to use such components. Moreover, deodorizing components such as plant extract selected from the group consisting of grasses, camellias, lemon, mint, cucumber, fruit and herb extracts may be included. Furthermore, it is also possible to impart a relaxing effect by adding green leaf alcohol, green leaf aldehyde or the like called "green scent". Furthermore, the composition or compound of formula (I) may be admixed with one or more fragrance compounds, fragrance compositions and the like. Such fragrance compounds may be of natural and/or synthetic origin, examples for such natural and synthetic fragrance ingredients can be found e. g. in, Perfume and Flavor Materials of Natural Origin", S. Arctander, Ed., Elizabeth, N. J., 1960 and "Perfume and Flavor Chemicals", S. Arctander, Ed., Vol. I & II, Allured Publishing Corporation, Carol Stream, USA, 1994.

The compositions of the present invention may comprise other ingredients often used in the formulation of said compositions. In some embodiments, additional components may be combined with the composition of the invention to improve overall rheological and processing properties, and to ensure microbiological integrity during storage. Such components include, without limitation, absorbents, antifoaming agents, acidifiers, alkalizers, buffers, antimicrobial agents, antioxidants, binders, biological additives, chelating agents (for example, disodium EDTA, tetrasodium EDTA, sodium metasilicate, and the like), denaturants, preservatives (for example imidazolidinyl urea, diazolidinyl urea, phenoxyethanol, methylparaben, ethylparaben, propylparaben, and the like), reducing agents, solubilizing agents, viscosity modifiers, humectants, thickening agents, and combinations thereof. These additional components may be present in an amount from about 0.001 % by weight to about 10% by weight of the dispersion, in embodiments from about 0.1 % by weight to about 1 % by weight of the dispersion.

Examples of suitable humectants which may be added to the formulation or composition of the invention include, but are not limited to, polyols and polyol derivatives, including glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol (sometimes referred to herein as 1 ,2-pentane diol), isopreneglycol (1 ,4-pentane diol), 1 ,5-pentane diol, hexylene glycol, erythritol, 1 ,2,6- hexanetriol, polyethylene glycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20, and combinations thereof. Moreover, the formulation may include sugars and sugar derivatives (including fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbityl silanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and salts thereof), ethoxylated sorbitol (Sorbeth-6, Sorbeth-20, Sorbeth-30, Sorbeth-40), and combinations thereof. In some embodiments, a commercially available 1 ,2-pentane diol such as HYDROLITE-5® pentylene glycol (commercially available from Symrise GmbH) may be utilized. In other embodiments, a propylene glycol may be utilized. Where utilized, such humectants may be present in amounts from about 0.1 % by weight to about 20% by weight of the dispersion, in embodiments from about 3% by weight to about 10% by weight of the dispersion.

In some embodiments, a preservative such as phenoxyethanol and a humectant such as butylene glycol, hexylene glycol, pentylene glycol and/or propylene glycol may both be added to the formulation. In embodiments, the pentylene glycold and/or propylene glycol may provide humectancy and assist in the preservation of the concentrate when combined with phenoxyethanol. The phenoxyethanol and pentylene glycol and/or propylene glycol mix should be water soluble and non-volatile.

The term “carrier” as used herein refers to an organic or inorganic material, natural or synthetic, with which the ant-repellent composition is combined in order to facilitate its application. The carrier is therefore generally inert and has no detrimental effect on the ant-repellent capabilities of the present invention.

In some embodiments, the invention relates to an agricultural composition comprising the compound of formula (I) and at least one solvent or solid agriculturally acceptable carrier.

Within the present invention, agricultural applications for the compositions of the compounds of formula (I) are also encompassed. The solvent or solid agricultural acceptable carrier is therefore suitable for application to (a) plant, fruit, seed, or soil. The carrier may be solid (such as clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like) or as described hereinabove. It is preferred that the composition of the present invention releases the active agent, i.e. , the compound of formula (I) rapidly. Therefore, in preferred embodiments, the compounds of formula (I) are combined with a solid acceptable carrier to form (a) granule(s). Granules are suitably designed to rapidly disintegrate and disperse in the presence of free moisture. Granules may be distributed by various means, for example by hand. For more effective and even distribution the granules may be distributed using a rotary spreader, shaker can or drop spreader.

Granular formulations for use in the present invention include both extrudates and relatively coarse particles. In addition to the ant-repellent of the present invention, generally, the granules can include fillers (also referred to as a carrier herein), surface active agents (which term can include dispersants and wetting agents) and auxiliary agents such as binders, stabilizers and buffering agents. The filler can be inert, or can serve a biological function, such as acting as a fertilizer. The filler, as well as the other components, preferably should not degrade the ant-repelling compound of formula (I) during the granule preparation or on long term storage or use in the field. Those of skill in the art can readily select appropriate granule components to satisfy these criteria. Typical carriers for granular forms include fertilizer, sand, limestone, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, chalk, zeolite, calcite, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb, or which can be coated with, a pesticide.

The granular substrate material can be one of the typical carriers mentioned above and/or can be a fertilizer material such as urea/formaldehyde fertilizers, urea, potassium compounds (such as potassium sulphate, nitrate, chloride, oxide, metaphosphate), ammonium compounds (such as ammonium nitrate, sulphate, phosphate), phosphorus compounds (such as phosphoric acid), sulfur, plant nutrients and micronutrients and mixtures or combinations thereof. The ant-repellent may be homogeneously distributed throughout the granule, spray impregnated or absorbed onto the granule substrate after the granules are formed or coated onto the surface of the granule.

A binder may be used to agglomerate the components of the granules. When present, the binder can be typically used in amounts up to about 20% by weight (dry basis) of the granular composition, more typically between about 2 to about 20% by weight. The binder binds the ingredients into a granular substrate and maintains particle size during handling. Examples of suitable binders include brewers’ condensed solubles, lignosulfonate, sodium carbonate lignin, cane molasses, beet syrup, beet molasses, desugared beet molasses, whey, starch, soy solubles, cane molasses, hydrolyzed collagen, amino acid solutions, cellulose derivatives, or cellulose based polymer binders. Other water-soluble binders having equivalent properties to, for example, brewer's condensed solubles, can also be used.

Additional auxiliary agents such as surfactants, dispersants, disintegrating agents, wetting agents and the like, can be added where desired to modify the properties of the granules. Additional active ingredients may also be present in the formulations, including surface-active agents such as heavy aromatic naphthol, kerosene and other petroleum fractions, or vegetable oils; and/or adhesives such as dextrin, glue or synthetic resins. The compounds of formula (I) and compositions thereof may be formulated with insecticides so that after losing the repellent activity the treated area will still not be safe for ants.

Contemplated for treatment herein are plants having agricultural value such as fruits, vegetables, grains, ornamental stock plants and turf. The compound and composition of the present invention can be used for soil amendment of potting or field soil, spraying of plant parts such as the base, trunk or stem, decontamination of irrigation water and soil drenches.

In some embodiments, the invention relates to the composition or the agricultural composition of the compound of formula (I), wherein the at least one solvent is ethanol, preferably further comprising one or more of an antioxidant, UV-absorbent or fixative. Said antioxidant is preferably butylated hydroxytoluene, said UV-absorbent is preferably ethylhexyl methoxycinnamate and said fixative is preferably one or more of a methyl hydrogenated rosinate, isopropyl myristate and dipropylene glycol.

The inventors of the present invention found that a solvent comprising an alcohol such as those described hereinabove, an antioxidant, a UV-absorbent and a fixative (including a perfume fixative) is particularly suitable for the application of the composition of the present invention. The antioxidant is not particularly limited and may be one selected from tocopherol, butylated hydroxytoluene (BHT), polyphenols and phytic acid, preferred is BHT. UV-absorbents may also be advantageously added to the composition of the invention to prevent degradation of the composition as a result of UV-exposure. UV absorbents include, but are not limited to, avobenzone, 4- methylbenzylidene camphor, polysillicone-15, ethylhexyl methoxycinnamate, ethylhexyl triazone and similar compounds easily identified by a person skilled in the art, preferred is ethylhexyl methoxycinnamate. Moreover, fixatives, including perfume fixatives, may be added to the composition of the present invention in order to equalize vapor pressure, and increase persistence. Fixatives or perfume fixatives include, but are not limited to, resinoids (benzoin, labdanum, myrrh, olibanum, storax, tolu balsam), ambroxide, civetone, muscone, diphenylmethane, dipropylene glycol (DPG), cyclopentadecanolide, ambroxide, benzyl salicylate, benzyl benzoate, diethyl phthalate, triethyl citrate, methyl hydrogenated rosinate, methyl myristate, isopropyl myristate and dipropylene glycol. Preferred (perfume) fixatives are methyl hydrogenated rosinate, methyl myristate, isopropyl myristate and dipropylene glycol or a combination thereof.

In some embodiments, the invention relates to a composition or agricultural composition, wherein the wherein the solvent is 60wt% ethanol, preferably further comprising the fixatives 30wt% isopropyl myristate, 7.5wt% dipropylene glycol and 1wt% methyl hydrogenated rosinate, the UV-absorbent 1wt% ethylhexyl methoxycinnamate and the antioxidant 0.5wt% butylated hydroxytoluene.

In some embodiments, the invention relates to a composition or agricultural composition, wherein the amount of the compound of formula (I) is about 0.01wt% to 20wt%, preferably about 0.1 wt% to 10wt%, more preferably about 0.5wt% to 5wt%.

Although the quantity of the compound of formula (I) in the ant-repellent composition of this invention may be suitably determined by the use application of said ant-repellent composition, use period, use specification, etc., in the case of a liquid formulation, an amount of about 0.01 % to 20% by weight, preferably about 0.1 % to 10% by weight, more preferably about 0.5% to 5% by weight is appropriate. In addition, when the composition is comprised with a solid carrier, which is used for 8 to 12 hours per time, the ant-repellent active agent is preferably used in an amount of about 10 to 50 mg per carrier, while in uses for 15 to 30 days, the ant-repellent active agent may be used in an amount of about 100 to 2000 mg per carrier. The amount of active ant-repelling agent or compositions thereof should be determined in order to reduce ant infestation quickly enough to meet consumer expectations.

In some embodiments, the invention relates to the composition or agricultural composition of the invention, wherein the composition or agricultural composition is in the form of a spray, gel, foam, patch, powder, solid, sponge, tape, vapor, paste, tincture, lotion, cream or ointment. These forms are commonly utilized, for example in consumer or agricultural use products due to, inter alia, the ease of use, containment, application and packaging of the product.

Suitable forms may be a spray or an aerosol form. The aerosol form may use a liquid or a gas as a propellant. These include, for example, conventional propellant gases required for spray cans, such as propane, butane, dimethyl ether, CO2, or halogenated lower alkyl gases (for example, halogenated C1-4 alkyls), and mixtures of two or more thereof. In particular, the composition comprising the compound of formula (I) according to the present invention is preferably formulated such that it can be sprayed directly in an area of infestation, it can be bound to a solid support or encapsulated in a time release material.

In some embodiments, the invention relates to the use of the composition or agricultural composition of the invention for controlling and/or combating populations of ants, preferably ants belonging to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum.

The ant-repellent composition of the present invention exhibits a practical spatial repellent effect against ants thus controlling and combating any population of ants. The inventors of the present invention examined a variety of ant species showing the effectiveness of the composition against the infestation of any ant species. Exemplary ant species include, but are not limited to, Lasius niger (or black garden ant), which can infest buildings, particularly foundation forms in contact with soil. A further exemplary species is Wasmannia auropunctata, also referred to as the little fire ant, which is an invasive species which eliminates native ants and other insects, strips nutrients from agricultural plants, causes injury such as blindness to animals through its sting and eats animal hatchlings. This species is thought to have caused the decline of populations of tortoises, scorpions, spiders and native ants. Wasmannia auropunctata is also known to sting humans. Solenopsis invicta or red imported fire ant, is another exemplary ant species which is particularly harmful. Solenopsis are stinging ants which secrete a venom that results in a local burning sensation that is particularly painful to the victim. The sting site swells into bumps on humans leading to further pain, irritation and potentially infection. It is estimated that 30-60% of the people living in fire ant-infested areas of the US are stung each year. Solenopsis invicta are invasive species which cause serious harm to their habitats. Further invasive ant species include Paratrechina longicornis and Tapinoma magnum. In further embodiments, the invention relates to the use of the composition or agricultural composition of the invention for reducing an infestation of ants, preferably ants belonging to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum.

In some embodiments, the invention provides a method of controlling, combating and/or reducing an infestation of ants comprising applying the composition or agricultural composition of the invention onto a surface, object and/or fabric.

In some embodiments, the invention provides a method, wherein the surface, object and/or fabric comprise(s) (a) plant, fungi, soil, wall, floor, window, furniture, clothing item or packaging material.

The composition of the present invention may be applied to various use situations depending on its formulation. If the composition is comprised in product such as a liquid, aerosol, powder or granule, it can be used in the entrance, kitchen, toilet, living room, bedroom, warehouse, car, veranda, porch, garden, around the house, indoors etc. It is possible to form a space in which ants do not approach by spraying or placing a predetermined amount of the composition or agricultural composition of the invention. When the solid acceptable carrier is a plastic resin molded product or a silicone rubber molded product, it may be wound around an ankle or shoes as a foot band, or the molded product may be used by attaching it to shoes using a fixture such as a clip. If the carrier is like a seal, it is convenient to provide an adhesive layer on the underside of the film-like carrier and stick it to the lower part of the pants, shoes or the like.

The compound of formula (I) or compositions or agricultural compositions thereof may be used for protecting wooden materials such as trees, board fences, sleepers, etc., and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants, and for preventing ants from doing harm to crops, animals or human beings (e. g. when the ants invade houses and public facilities). The composition of the invention may be applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it may also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywood, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant control composition of the present invention is directly applied to the nest of the ants or to its surroundings.

The present invention also provides a method for protecting objects from the infestation of ants. The method, in one embodiment, may comprise contacting or covering the surface of an object with a treatment composition comprising the compound of formula (I), in particular 2-methoxybenzaldedye (formula (Id)). Contacting or covering the surface of the object may be achieved, for example, by employing a spraying device comprising the composition of the invention. As such, the invention also provides antrepellent objects, such as, for example, fabrics or clothes. The fabrics may have the ant-repellent composition of the invention absorbed in the fibres of the fabrics. The fabrics are suitable for use in clothing and, more particularly, are suitable for use in protective garments designed to be worn by individuals, who may be at risk of exposure to ants, in particular So/enopsis invicta. The repellent compounds and compositions of the invention may be incorporated into the fabrics in a variety of ways including, but not limited to, immersing the fibres or fabrics in a bath containing the compound of formula (I), providing a spray to the fibres or fabrics or washing the fibres or fabrics. Within the present invention, amounts of the formulation of the invention to the fibres or fabrics may be varied by the skilled person in order to achieve the desired effect of reducing infestation with ants.

In some embodiments, the invention relates to a method of controlling or reducing an infestation of ants comprising applying the composition or agricultural composition of the invention to an animal, preferably a mammal, in particular a human, dog, cat, cattle, horse or sheep.

Given that certain ants, in particular Solenopsis invicta and Wasmannia auropunctata may infest and cause physical harm to animals through their sting, the composition of the present invention may also be directly applied to animals including a farm animal, such as a cattle, horse, pig, sheep, goat, poultry (such as chicken, turkeys and geese), fur-bearing animals (such as mink, foxes, chinchillas, rabbits and the like), as well as companion animals (such as cats and dogs), but also humans.

In some embodiments, the invention provides a method of protecting a plant, seed and/or object from the attack of ants comprising treating said plant, seed and/or object with the composition or agricultural composition of the invention. The compounds or compositions of the invention can also be applied preventively to places at which occurrence of the ants is expected. In some embodiments, the invention provides a method according to the invention, wherein the ants belong to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular wherein the ants belong to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum, preferably wherein the ants are Solenopsis invicta and/or Wasmannia auropunctata.

The following definitions apply throughout the present specification and the claims, unless specifically indicated otherwise.

As used herein, the term “alkyl” refers to a monovalent saturated acyclic (i.e., non- cyclic) hydrocarbon group which may be linear or branched. Accordingly, an “alkyl” group does not comprise any carbon-to-carbon double bond or any carbon-to-carbon triple bond. A “C1-6 alkyl” denotes an alkyl group having 1 to 6 carbon atoms. Preferred exemplary alkyl groups are methyl, ethyl, propyl (e.g., n-propyl or isopropyl), or butyl (e.g., n-butyl, isobutyl, sec-butyl, or tert-butyl). Unless defined otherwise, the term “alkyl” preferably refers to C1-4 alkyl, more preferably to methyl or ethyl, and even more preferably to methyl.

As used herein, the term “alkenyl” refers to a monovalent unsaturated acyclic hydrocarbon group which may be linear or branched and comprises one or more (e.g., one or two) carbon-to-carbon double bonds while it does not comprise any carbon-to- carbon triple bonds. The term “C2-6 alkenyl” denotes an alkenyl group having 2 to 6 carbon atoms. Preferred exemplary alkenyl groups are ethenyl, propenyl (e.g., prop-1 - en-1 -yl, prop-1 -en-2-yl, or prop-2 -en-1-yl), butenyl, butadienyl (e.g., buta-1 ,3-dien-1-yl or buta-1 , 3-dien-2-yl), pentenyl, or pentadienyl (e.g., isoprenyl). Unless defined otherwise, the term “alkenyl” preferably refers to C2-4 alkenyl.

As used herein, the term “alkynyl” refers to a monovalent unsaturated acyclic hydrocarbon group which may be linear or branched and comprises one or more (e.g., one or two) carbon-to-carbon triple bonds and optionally one or more (e.g., one or two) carbon-to-carbon double bonds. The term “C2-6 alkynyl” denotes an alkynyl group having 2 to 6 carbon atoms. Preferred exemplary alkynyl groups are ethynyl, propynyl (e.g., propargyl), or butynyl. Unless defined otherwise, the term “alkynyl” preferably refers to C2-4 alkynyl.

As used herein, the term “aryl” refers to an aromatic hydrocarbon ring group, including monocyclic aromatic rings as well as bridged ring and/or fused ring systems containing at least one aromatic ring (e.g., ring systems composed of two or three fused rings, wherein at least one of these fused rings is aromatic; or bridged ring systems composed of two or three rings, wherein at least one of these bridged rings is aromatic). If the aryl is a bridged and/or fused ring system which contains, besides one or more aromatic rings, at least one non-aromatic ring (e.g., a saturated ring or an unsaturated alicyclic ring), then one or more carbon ring atoms in each non-aromatic ring may optionally be oxidized (i.e., to form an oxo group). “Aryl” may, e.g., refer to phenyl, naphthyl, dialinyl (i.e., 1 ,2-dihydronaphthyl), tetralinyl (i.e., 1 ,2,3,4- tetrahydronaphthyl), indanyl, indenyl (e.g., 1 H-indenyl), anthracenyl, phenanthrenyl, 9H-fluorenyl, or azulenyl. Unless defined otherwise, an “aryl” preferably has 6 to 14 ring atoms, more preferably 6 to 10 ring atoms, even more preferably refers to phenyl or naphthyl, and most preferably refers to phenyl.

As used herein, the term “heteroaryl” refers to an aromatic ring group, including monocyclic aromatic rings as well as bridged ring and/or fused ring systems containing at least one aromatic ring (e.g., ring systems composed of two or three fused rings, wherein at least one of these fused rings is aromatic; or bridged ring systems composed of two or three rings, wherein at least one of these bridged rings is aromatic), wherein said aromatic ring group comprises one or more (such as, e.g., one, two, three, or four) ring heteroatoms independently selected from 0, S and N, and the remaining ring atoms are carbon atoms, wherein one or more S ring atoms (if present) and/or one or more N ring atoms (if present) may optionally be oxidized, and further wherein one or more carbon ring atoms may optionally be oxidized (i.e., to form an oxo group). For example, each heteroatom-containing ring comprised in said aromatic ring group may contain one or two 0 atoms and/or one or two S atoms (which may optionally be oxidized) and/or one, two, three or four N atoms (which may optionally be oxidized), provided that the total number of heteroatoms in the corresponding heteroatom-containing ring is 1 to 4 and that there is at least one carbon ring atom (which may optionally be oxidized) in the corresponding heteroatom-containing ring. “Heteroaryl” may, e.g., refer to thienyl (i.e., thiophenyl), benzo[b]thienyl, naphtho[2,3- b]thienyl, thianthrenyl, furyl (i.e., furanyl), benzofuranyl, isobenzofuranyl, chromanyl, chromenyl (e.g., 2H-1 -benzopyranyl or 4H-1 -benzopyranyl), isochromenyl (e.g., 1 H-2- benzopyranyl), chromonyl, xanthenyl, phenoxathiinyl, pyrrolyl (e.g., 1 H-pyrrolyl), imidazolyl, pyrazolyl, pyridyl (i.e., pyridinyl; e.g., 2-pyridyl, 3-pyridyl, or 4-pyridyl), pyrazinyl, pyrimidinyl, pyridazinyl, indolyl (e.g., 1 H-indolyl), isoindolyl, indazolyl, indolizinyl, purinyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, cinnolinyl, pteridinyl, carbazolyl, [3-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl (e.g., [1 ,10]phenanthrolinyl, [1 ,7]phenanthrolinyl, or

[4,7]phenanthrolinyl), phenazinyl, thiazolyl, isothiazolyl, phenothiazinyl, oxazolyl, isoxazolyl, oxadiazolyl (e.g., 1 ,2,4-oxadiazolyl, 1 ,2,5-oxadiazolyl (i.e., furazanyl), or 1 .3.4-oxadiazolyl), thiadiazolyl (e.g., 1 ,2,4-thiadiazolyl, 1 ,2,5-thiadiazolyl, or 1 ,3,4- thiadiazolyl), phenoxazinyl, pyrazolo[1 ,5-a]pyrimidinyl (e.g., pyrazolo[1 ,5-a]pyrimidin- 3-yl), 1 ,2-benzoisoxazol-3-yl, benzothiazolyl, benzothiadiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzo[b]thiophenyl (i.e., benzothienyl), triazolyl (e.g., 1 H-1 ,2,3-triazolyl, 2H-1 ,2,3-triazolyl, 1 H-1 ,2,4-triazolyl, or 4H-1 ,2,4-triazolyl), benzotriazolyl, 1 H-tetrazolyl, 2H-tetrazolyl, triazinyl (e.g., 1 ,2,3-triazinyl, 1 ,2,4-triazinyl, or 1 ,3,5-triazinyl), furo[2,3-c]pyridinyl, dihydrofuropyridinyl (e.g., 2,3-dihydrofuro[2,3- c]pyridinyl or 1 ,3-dihydrofuro[3,4-c]pyridinyl), imidazopyridinyl (e.g., imidazo[1 ,2- a]pyridinyl or imidazo[3,2-a]pyridinyl), quinazolinyl, thienopyridinyl, tetrahydrothienopyridinyl (e.g., 4,5,6,7-tetrahydrothieno[3,2-c]pyridinyl), dibenzofuranyl, 1 ,3-benzodioxolyl, benzodioxanyl (e.g., 1 ,3-benzodioxanyl or

1 .4-benzodioxanyl), or coumarinyl. Unless defined otherwise, the term “heteroaryl” preferably refers to a 5 to 14 membered (more preferably 5 to 10 membered) monocyclic ring or fused ring system comprising one or more (e.g., one, two, three or four) ring heteroatoms independently selected from 0, S and N, wherein one or more S ring atoms (if present) and/or one or more N ring atoms (if present) are optionally oxidized, and wherein one or more carbon ring atoms are optionally oxidized; even more preferably, a “heteroaryl” refers to a 5 or 6 membered monocyclic ring comprising one or more (e.g., one, two or three) ring heteroatoms independently selected from 0, S and N, wherein one or more S ring atoms (if present) and/or one or more N ring atoms (if present) are optionally oxidized, and wherein one or more carbon ring atoms are optionally oxidized. Moreover, unless defined otherwise, particularly preferred examples of a “heteroaryl” include pyridinyl (e.g., 2-pyridyl, 3-pyridyl, or 4-pyridyl), imidazolyl, thiazolyl, 1 H-tetrazolyl, 2H-tetrazolyl, thienyl (i.e., thiophenyl), or pyrim idinyl.

As used herein, the term “halogen” refers to fluoro (-F), chloro (-CI), bromo (-Br), or iodo (-I).

The terms “bond” and “covalent bond” are used herein synonymously, unless explicitly indicated otherwise or contradicted by context.

As used herein, the terms “optional”, “optionally” and “may” denote that the indicated feature may be present but can also be absent. Whenever the term “optional”, “optionally” or “may” is used, the present invention specifically relates to both possibilities, i.e., that the corresponding feature is present or, alternatively, that the corresponding feature is absent. For example, the expression “X is optionally substituted with Y” (or “X may be substituted with Y”) means that X is either substituted with Y or is unsubstituted. Likewise, if a component of a composition is indicated to be “optional”, the invention specifically relates to both possibilities, i.e., that the corresponding component is present (contained in the composition) or that the corresponding component is absent from the composition.

As used herein, unless explicitly indicated otherwise or contradicted by context, the terms “a”, “an” and “the” are used interchangeably with “one or more” and “at least one”. Thus, for example, a composition comprising “a” compound of formula (I) can be interpreted as referring to a composition comprising “one or more” compounds of formula (I).

It is to be understood that wherever numerical ranges are provided/disclosed herein, all values and subranges encompassed by the respective numerical range are meant to be encompassed within the scope of the invention. Accordingly, the present invention specifically and individually relates to each value that falls within a numerical range disclosed herein, as well as each subrange encompassed by a numerical range disclosed herein.

As used herein, the term “about” preferably refers to ±10% of the indicated numerical value, more preferably to ±5% of the indicated numerical value, and in particular to the exact numerical value indicated.

As used herein, the term “comprising” (or “comprise”, “comprises”, “contain”, “contains”, or “containing”), unless explicitly indicated otherwise or contradicted by context, has the meaning of “containing, inter alia”, i.e., “containing, among further optional elements, ...”. In addition thereto, this term also includes the narrower meanings of “consisting essentially of” and “consisting of”. For example, the term “A comprising B and C” has the meaning of “A containing, inter alia, B and C”, wherein A may contain further optional elements (e.g., “A containing B, C and D” would also be encompassed), but this term also includes the meaning of “A consisting essentially of B and C” and the meaning of “A consisting of B and C” (i.e., no other components than B and C are comprised in A).

It will be appreciated that the compounds of formula (I) may exist in the form of different isomers, in particular stereoisomers (including, e.g., geometric isomers (or cis/trans isomers), enantiomers and diastereomers) or tautomers (including, in particular, prototropic tautomers, such as keto/enol tautomers or thione/thiol tautomers). Complexes of any such isomers of the compounds of formula (I) are contemplated as being part of the present invention, either in admixture or in pure or substantially pure form. As for stereoisomers, the invention embraces complexes of the isolated optical isomers of the compounds of formula (I) as well as any mixtures thereof (including, in particular, racemic mixtures/racemates). The racemates can be resolved by physical methods, such as, e.g., fractional crystallization, separation or crystallization of diastereomeric derivatives, or separation by chiral column chromatography. The individual optical isomers can also be obtained from the racemates via salt formation with an optically active acid followed by crystallization. It will be understood that some compounds may exhibit tautomerism. In such cases, the formulae provided herein expressly depict only one of the possible tautomeric forms. The formulae and chemical names as provided herein are intended to encompass any tautomeric form of the corresponding compound and not to be limited merely to the specific tautomeric form depicted by the drawing or identified by the name of the compound.

It is to be understood that the present invention specifically relates to each and every combination of features and embodiments described herein, including any combination of general and/or preferred features/embodiments. In particular, the invention specifically relates to each combination of meanings (including general and/or preferred meanings) for the various groups and variables comprised in formula (I).

In this specification, a number of documents including patent applications and scientific literature are cited. The disclosure of these documents, while not considered relevant for the patentability of this invention, is herewith incorporated by reference in its entirety. More specifically, all referenced documents are incorporated by reference to the same extent as if each individual document was specifically and individually indicated to be incorporated by reference.

The reference in this specification to any prior publication (or information derived therefrom) is not and should not be taken as an acknowledgment or admission or any form of suggestion that the corresponding prior publication (or the information derived therefrom) forms part of the common general knowledge in the technical field to which the present specification relates.

The invention is also illustrated by the appended figure.

Figure 1 : Measurement of the ant-repellent effect of 2-methoxybenzaldehyde (2- methoxyBA) and 4-methoxybenzaldehyde (2-methoxyBA) applied with 5% concentration in a common solvent composition against Lasius niger (100 replicates, p = 0.03).

Examples To make inferences about the structure of the odorant receptor underlying the behavioral response of the ants to 2-hydroxybenzaldehyde the effect of various structural modifications on the strength of the behavioral response was investigated.

- the hydroxy- group was moved around the benzene ring, testing 3- hydroxybenzaldehyde and 4-hydroxybenzaldehyde.

- the hydroxy- group was replaced with groups of different volumes: benzaldehyde (i.e., no group), 2-methylbenzaldehyde, 2- aminobenzaldehyde, and 2-bromobenzaldehyde

- the hydroxy- group was replaced with carbon chains of different lengths:

2-methoxybenzaldehyde, 2-ethoxybenzaldeyhde, 2-n- propoxybenzaldehyde, 2-butoxybenzaldehyde, and 2- phenoxybenzaldehyde.

Additionally three chemicals that are structurally similar to benzaldehyde were tested: Trans-2-hexen-1-ol, Cis-2-hexen-1-ol, hexanoic acid, and other chemicals that had previously been shown to have ant-repellent effects: Allyl isothiocyanate, and citrus essential oil.

All chemicals were tested at 5% concentration in a standard solvent composition comprising the solvent 96% ethanol (60wt%), and fixatives: isopropyl myristate (30wt%), hercolyn D-E (dipropylene glycol) (7.5wt%), methyl hydrogenated rosinate (1wt%), UVB absorber: Parsol MVX (ethylhexyl methoxycinnamate) (1wt%), and antioxidant: butylated hydroxytoluene (0.5wt%). This solvent composition alone constituted the control.

In each trial, 300 \ of the chemical solution was applied uniformly to a square paper perimeter, with a width of 5 mm, and internal dimensions of 100 mm x 100 mm. Five worker ants were collected from stock ant colonies with fine insect forceps and transferred to a Fluon-coated Petri dish. The Petri dish was then placed upside down at the center of the paper perimeter. After one minute, the Petri dish was gently lifted. The time until the third individual crossed the perimeter (i.e., the median time until exit) was recorded.

A first experiment assayed the efficacy of all chemicals mentioned above using Lasius niger (100 replicates for each of 2-hydroxybenzaldehyde and 2- methoxybenzaldehyde, and 30 replicates for all other chemicals). A second experiment assayed the four most effective repellents identified in the first experiment (2-hydroxybenzaldehyde, 2-bromobenzaldehyde, 2- ethoxybenzaldehyde, and 2-methoxybenzaldehyde) and the same control using five additional species: Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta, and Tapinoma magnum (20 replicates per chemical per species).

Median values are reported in Table 1.

Table 1. Measurement of repellent effect, in seconds, of substances compared to the negative control (solvent composition) in Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and Tapinoma magnum. The highest values indicate the most efficient products while the lowest values indicate the least efficient products, for each species. The compounds were applied with 5% concentration in a common solvent. (30 replicates were tested in column 2, 20 replicates in column 3-7)

Claims

Claims: A composition having ant-repelling characteristics comprising as an active ingredient a compound of the formula (I), or a salt or crystal thereof:

wherein R is independently selected from halogen, -C1-6 alkyl, -C2-6 -alkenyl, C2- 6-alkynyl, , -O(Ci-₆ alkyl), -O(aryl), -CHO, -C(O)(Ci-₆ alkyl), -C(O)-NH₂, - C(O)-NH(CI-₆ alkyl), -C(O)-N(CI-₆ alkyl)(Ci-₆ alkyl), -NH₂, -NH(CI-₆ alkyl), -N(Ci- 6 alkyl)(Ci-₆ alkyl), -NH-CO(CI-₆ alkyl), -N(CI-₆ alkyl)-CO(Ci-₆ alkyl), - NH-COO(CI-₆ alkyl), -N(CI-₆ alkyl)-COO(Ci-₆ alkyl), -SH, -S-(Ci-₆ alkyl), -(aryl), - (heteroaryl). The composition of claim 1 , wherein R is independently selected from -Br, - methyl, -methoxy, -ethoxy, -propoxy and -butoxy, preferably wherein R is - methoxy. The composition of claim 1 or 2 further comprising at least one solvent or solid acceptable carrier. An agricultural composition comprising the compound of formula (I) of claim 1 or 2, further comprising at least one solvent or solid agriculturally acceptable carrier. The composition of claim 3 or the agricultural composition of claim 4, wherein the at least one solvent is ethanol, the composition preferably further comprising one or more of an antioxidant, UV-absorbent or fixative. The composition of claim 3 or 5 or the agricultural composition of claim 4 or 5, wherein the solvent is 60wt% ethanol, preferably further comprising the fixatives 30wt% isopropyl myristate, 7.5wt% dipropylene glycol and 1wt% methyl hydrogenated rosinate, the UV-absorbent 1wt% ethylhexyl methoxycinnamate and the antioxidant 0.5wt% butylated hydroxytoluene. The composition of claim of any one of claims 1 to 3, 5 or 6 or the agricultural composition of any one of claims 4, 5 or 6, wherein the amount of the compound of formula (I) is about 0.01wt% to 20wt%, preferably about 0.1wt% to 10wt%, more preferably about 0.5wt% to 5wt%. The composition of claim of any one of claims 1 to 3 or 5 to 7 or the agricultural composition of any one of claims 4 or 5 to 7, wherein the composition or agricultural composition is in the form of a spray, gel, foam, patch, powder, solid, sponge, tape, vapor, paste, tincture, lotion, cream or ointment. Use of the composition of claim of any one of claims 1 to 3 or 5 to 8 or the agricultural composition of any one of claims 4 or 5 to 8, for controlling and/or combating populations of ants, preferably ants belonging to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum. Use of the composition of claim of any one of claims 1 to 3 or 5 to 8 or the agricultural composition of any one of claims 4 or 5 to 8, for controlling and/or combating populations of ants, preferably ants belonging to the sub-family Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum. A method of controlling, combating and/or reducing an infestation of ants comprising applying the composition of any one of claims 1 to 3 or 5 to 8 or the agricultural composition of any one of claims 4 or 5 to 8 onto a surface, object and/or fabric. The method of claim 11 , wherein the surface, object and/or fabric comprise(s) (a) plant, fungi, soil, wall, floor, window, furniture, clothing item or packaging material. A method of controlling and/or reducing an infestation of ants comprising applying the composition of claim of any one of claims 1 to 3 or 5 to 8 or the agricultural composition of any one of claims 4 or 5 to 8 to an animal, preferably a mammal, in particular a human, dog, cat, cattle, horse or sheep. A method of protecting a plant, seed and/or object from the attack of ants comprising treating said plant, seed and/or object with the composition of any one of claims 1 to 3 or 5 to 8 or the agricultural composition of any one of claims 4 or 5 to 8. The method of any one of claims 11 to 14, wherein the ants belong to the subfamily Formicinae, Myrmicinae and/or Dolichoderinae, in particular ants belonging to the species Lasius niger, Wasmannia auropunctata, Paratrechina longicornis, Solenopsis invicta and/or Tapinoma magnum. 1