US 201402421.99A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0242199 A1 Manhas et al. (43) Pub. Date: Aug. 28, 2014

(54) PEST CONTROL FORMULATIONS AND AOIN 43/90 (2006.01) METHODS OF MAKING AND USING SAME AOIN 65/28 (2006.01) (71) Applicant: 0903608 B.C. Ltd., Vancouver (CA) AOIN 6.5/22 (2006.01) AOIN 6.5/36 (2006.01) (72) Inventors: Karan Manhas, Vancouver (CA); AOIN 25/02 (2006.01) Annett Rozek, Port Moody (CA) AOIN 65/26 (2006.01) (21) Appl. No.: 14/347,219 AOIN37/36 (2006.01) (52) U.S. Cl. (22) PCT Filed: Oct. 4, 2012 CPC ...... A0IN 65/42 (2013.01); A0IN 65/26 86) PCT No.: PCT/B2O12/OSS348 (2013.01); A0IN35/04 (2013.01); A0IN 65/24 (86) O (2013.01); A0IN37/36 (2013.01); A0IN 65/28 S371 (c)(1), (2013.01); A0IN 65/22 (2013.01); A0IN 65/36 (2), (4) Date: Mar. 25, 2014 (2013.01); A0IN 25/02 (2013.01); A0IN 43/90 Related U.S. Application Data (2013.01) (60) Provisional application No. 61/652,110, filed on May USPC ...... 424/736: 424/761; 424/739; 424/778: 25, 2012, provisional application No. 61/622,893, 424/745; 424/754; 514/450 filed on Apr. 11, 2012, provisional application No. 61/542,993, filed on Oct. 4, 2011. (57) ABSTRACT Publication Classification (51) Int. Cl Compositions useful for controlling pests are disclosed. In A. oiN 65/42 (2006.01) Some embodiments, the composition includes a pesticidal AOIN35/04 (2006.01) natural oil and a polar aromatic solvent. Methods of making ADIN 65/24 (2006.01) and using the compositions are disclosed. Patent Application Publication Aug. 28, 2014 Sheet 1 of 2 US 2014/0242199 A1

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PEST CONTROL FORMULATIONS AND higher concentrations it has been reported to demonstrate METHODS OF MAKING AND USING SAME repellency activity against Some insects for up to six months after application (see Daniel & Smith). These repellency TECHNICAL FIELD characteristics limit neem oils insecticidal activity signifi cantly, since insects are repelled from exposure to the very 0001. Some embodiments of the present invention pertain product that is intended to be insecticidal. Neem oil has been to compositions that can be used to control a variety of pests. shown to prevent egg emergence of Some insects when eggs Some embodiments of the present invention can be used to are treated directly with the oil: See Rahman & Talukder; control arthropods, including insects and arachnids, and/or Ahmed, et al. Neem oil also demonstrates some prevention of other pests. Some embodiments of the present invention can oviposition—of a limited Subset of insects—at higher con be used to control Sucking and biting pests, including e.g. bed centrations (including the maize weevil; see M K Khattak). bugs, mosquitoes, ticks, lice, Stink bugs, flies, cockroaches 0006 Current hypotheses suggest that neem oil may work and moths. Some embodiments of the invention pertain to as a contact killer, as an antifeedant, as an insect-growth methods of using compositions to control pests. Other regulator, a sterilizing agent, a gut motility inhibitor, and/or as embodiments of the invention pertain to methods of making a chitin inhibitor. Azadirachting an important active ingredi compositions to control pests. ent in neem oil has been reported to exhibit antifeedant, repellent, and sterilization activities under certain circum BACKGROUND stances and has been used as a pest control chemical in the 0002 Pest control is an ongoing, worldwide problem. In past (see U.S. Pat. No. 4,556,562). addition to physical means of control that have been practiced 0007 Neem oil and azadirachtin are believed to exhibit for centuries, recent decades have witnessed the emergence complex mechanisms of insect toxicity, including activity and widespread use of hundreds of chemically developed pest upon insect hormonal systems, antifeedant activity, anti repellents, growth regulators, and insecticides. These prod molting activity, and numerous other activities. Neem oil as a ucts are frequently synthetic varieties that are heavily refined pesticide is biodegradable and of low environmental and prior to commercialization—the list includes the pyrethroids human toxicity, exempted from the tolerance requirement by (including deltamethrins, cyfluthryns, etc), DEET and other the United States EPA (see United States Federal Register, aromatic amides, organophosphates, and carbamates. The Volume 60, Number 239, 1995). usefulness of these products is often limited by factors includ 0008 Neem oil has drawbacks as an insecticide. While ing human or environmental toxicity, insect resistance (par effective at preventing molting and exhibiting certain repel ticularly to pyrethroids; see e.g. Romero, et al.), limited dry lency characteristics in Some insects, reports of neem oils residue activity, repellancy and physical factors that make knockdown capability are inconsistent (see e.g. Schumutter), them inappropriate for indoor use (odor, staining). For these and some studies find it less efficient at killing adult insects reasons and due to shifting consumer preference paradigms, than related pesticides (see Pavela). Neem oil has been there is consistently increasing demand for naturally-derived, reported to have poor dry residue pesticidal activity against effective pest control products that overcome these limita most insects, and poor dry residual prevention of egg emer tions. gence and prevention of oviposition against most species of 0003. Some pesticide products are derived from botanical insects. Neem oil has an odor that is offensive to Some people, and other natural Sources; for example the pyrethrin classes of and its odor does not rapidly disperse. pesticides are derived from the pyrethrum daisy, Chrysanthe 0009. Other natural oils have been reported to exhibit mum cinerariaefolium. Other examples include: rotenone, insecticidal or other pest control activities, as are described from the roots of Derris Lonchocarpus; ryania, from the further below. stems of Ryania speciosa; and neem, derived from the leaves, 0010 Pests are a considerable annoyance and health risk. bark, and seeds of Azadirachta indica. For example, in recent years, there has been a resurgence of 0004. The tree Azadirachta indica—in some cases bed bug (Cimex lectularius L.) infestations across North referred to as the “Sacred Tree' or “Nature's Pharmacy” America. Bedbugs cause sleeplessness, anxiety, and discom has long been recognized as a source of a wide variety of fort for those affected. Bedbugs are troublesome pests. They useful bioactive compounds. Neem derivatives have demon live and hide in crevices, seams and other Small spaces. They strated effectiveness as moisturizing agents, and neem oil are hard to identify and locate, and can Survive dormant for itself has been used as a treatment for various skin conditions months or a year or more without feeding. They spread by including acne, psoriasis, and chickenpox. It is also used in clinging to Suitcases, furniture and clothing which people toothpastes, as a cooking ingredient, and in pharmaceuticals bring with them from place to place. Current methods of bed for treating a range of symptoms including fever, earache, bug control are expensive and have various limitations, par headache, and serious disorders including diabetes (see e.g. ticularly because products must be applied in sleeping areas Brachmachari). In the agricultural sector, neem oil is consid where the affected individuals are subject to close and lengthy ered an effective measure for the prevention of mildew, exposure. anthracnose, rust, leaf spot, botrytis, scab and alternaria. Its 0011. There remains a need for improved pesticides derivatives have furthermore been described variously as derived from natural sources, pesticides that can prevent egg antiviral, antimicrobial, antifungal, and antiseptic. Neem oil eclosion, and pesticides having improved dry residue and and many of its derivatives have also been recognized and prolonged residual activity. used as insect control agents and pesticides. 0005 Neem oil contains dozens of active compounds that SUMMARY kill or repel insects, with demonstrated efficacy against more 0012 Some embodiments of the present invention provide than 375 insect species. It has been recognized as a repellent pesticidal compositions containing a pesticidal natural oil of many pests, particularly insects (see e.g. Mishra, et al). At and/or a component thereof and/or a derivative thereof and a US 2014/0242199 A1 Aug. 28, 2014

polar aromatic solvent. Some embodiments can be used to 0019. Unless defined otherwise, all technical and scien control pests by killing the pests, preventing or reducing tific terms used herein have the same meaning as commonly feeding, preventing or reducing oviposition, preventing or understood by one of ordinary skill in the art to which this reducing eclosion of their eggs, or the like. Some embodi invention belongs. Although any methods and materials simi ments exhibit effective or more rapid knockdown pesticidal lar or equivalent to those described herein can also be used in activity, dry residue pesticidal activity and/or prolonged the practice or testing of embodiments of the present inven residual pesticidal activity. Some embodiments can be used to tion, preferred methods and materials are described to avoid control pests including insects and/or arachnids, including unnecessarily obscuring the disclosure. arthropods such as bed bugs. 0020. As used herein, “comprises' or “comprising are to 0013. In some embodiments, the pesticidal natural oil is be interpreted in their open-ended sense, i.e. as specifying neem oil, clove oil, peppermint oil, mint oil, cinnamon oil, that the stated features, elements, steps or components thyme oil, oregano oil, and/or garlic oil and/or derivatives or referred to are present, but not excluding the presence or extracts thereof. In some embodiments, the polar aromatic addition of further features, elements, steps or components. Solvent is selected from the group consisting of: aryl alcohols, 0021. As used herein, singular forms include plural refer aryl-alkyl alcohols, aryl aldehydes, aryl-alkyl ketones, aryl ences unless the context clearly dictates otherwise. For aryl ketones, aryl carboxylic acids, aryl esters, aryl-alkyl example, "a fungus' also encompasses “fungi'. esters, aryl-aryl esters, aryl-alkyl ethers, and aryl-aryl ethers. 0022. As used herein, the term "pest” refers to organisms In some embodiments, the polar aromatic solvent is an aryl that negatively affect a host—such as a plant or an animal ketone such as acetophenone. In some embodiments, the Such as a mammal—by colonizing, damaging, attacking, polar aromatic solvent is acetophenone, benzyl alcohol, ethyl competing with them for nutrients, or infecting them. This benzoate and/or benzoic acid. In some embodiments, the includes arthropods including insects and arachnids, and pesticidal natural oil is neem oil and the polar aromatic Sol includes Sucking and biting pests such as bed bugs, mites, vent is acetophenone. ticks, ants, lice, and cockroaches. 0014. In some embodiments, the combination of the natu 0023. As used herein, the term "pesticide” refers to an ral pesticidal oil and the polar aromatic solvent exhibits a agent that can be used to control and/or kill apest. The term is synergistic level of pesticidal activity. In some embodiments, understood to encompass, but is not limited to, naturally the combination of the pesticidal natural oil and the polar occurring or synthetic chemical insecticides (larvicides, adul aromatic solvent is effective as a pesticide wherein each of the ticides, ovicides), acaricides (miticides), fungicides, nemati pesticidal natural oil and the polar aromatic solvent are cides, parasiticides, or other control agents. “Pesticidal activ present at a concentration below the concentration at which ity refers to an agent that is active as a pesticide. the pesticidal natural oil or the polar aromatic solvent would 0024 AS used herein, the term "egg emergence” means exhibit similar pesticidal activity if used alone. In some such eclosion; that is, the emergence of an adult insect from its embodiments, the polar aromatic solvent is acetophenone and pupal case or the hatching of an insect larva/nymph from an the pesticidal natural oil is neem oil, clove oil, cinnamon oil, egg. “Preventing eclosion' or “preventing egg emergence' thyme oil, oregano oil and/or garlic oil. means preventing or delaying the emergence of an adult insect from its pupal case or the hatching of an insect larva BRIEF DESCRIPTION OF THE DRAWINGS from an egg. 0015 FIG. 1 shows the results of an example testing the 0025. As used herein, the terms “control’ or “controlling prevention of egg emergence by a composition in accordance are meant to include, but are not limited to, any killing, growth with one embodiment of the invention. regulating, or pestistatic (inhibiting or otherwise interfering with the normal life cycle of the pest) activities of a compo 0016 FIG. 2 shows the results of an example testing the sition against a given pest. These terms include for example ability of a composition in accordance with one embodiment sterilizing activities which prevent the production of ova or of the invention to kill pyrethroid-resistant bed bugs. sperm, cause death of sperm or ova, or otherwise cause severe injury to the genetic material. Further activities intended to be DETAILED DESCRIPTION encompassed within the scope of the terms “control” or “con 0017. Throughout the following description specific trolling include preventing larvae from developing into details are set forth in order to provide a more thorough mature progeny, modulating the emergence of pests from understanding to persons skilled in the art. However, well eggs including preventing eclosion, degrading the egg mate known elements may not have been shown or described in rial, Suffocation, reducing gut motility, inhibiting the forma detail to avoid unnecessarily obscuring the disclosure. tion of chitin, disrupting mating or sexual communication, Accordingly, the description and drawings are to be regarded and preventing feeding (antifeedant) activity. in an illustrative, rather than a restrictive, sense. 0026. As used herein, the terms “repellent” or “repelling 0018 Where a range of values is provided, it is understood mean that a composition discourages pests from landing or that each intervening value, to the tenth of the unit of the lower climbing on a Surface to which the composition has been limit unless the context clearly dictates otherwise, between applied or incorporated, and/or that the composition encour the upper and lower limit of that range and any other stated or ages pests to move away from a surface to which the compo intervening value within that stated range is encompassed sition has been applied or incorporated. within embodiments of the invention. The upper and lower 0027. As used herein, a "pesticidal natural oil is a natural limits of these Smaller ranges may independently define a oil or oils, for example derived from plant material, that Smaller range of values, and it is to be understood that these exhibits pesticidal activity either on its own or in combination Smaller ranges are intended to be encompassed within with a solvent. As used herein, "pesticidal natural oil embodiments of the invention, Subject to any specifically includes other materials derived, extracted or otherwise excluded limit in the Stated range. obtained from natural sources, for example, powdered US 2014/0242199 A1 Aug. 28, 2014

extracts and the like. A "derivative' is a compound or com ethoxylated amides, glycerides, benzene, butanol, 1-pro position that can be obtained from a natural oil. A "constitu panol, hexanol, other alcohols, dimethyl ether, and polyeth ent’ or "component' is a compound or composition found in ylene glycol. a natural oil. 0036 Some embodiments of the present invention provide 0028. As used herein, "neem oil” refers to oil derived from compositions and methods useful in the control of a variety of the seeds, leaves, and bark of Azadirachta indica. Methods pests. Some embodiments of the present invention can be for obtaining neem oil, azadirachtin extract or other deriva used to control insects, arachnids, and/or other pests. Some tives purified from neem oil are known in the art. One exem embodiments of the present invention can be used to control plary method for obtaining neem oil is cold pressing. Sucking and biting pests, including e.g. bedbugs, mosquitoes, 0029. As used herein, “dry residue activity” refers to com ticks, lice, fleas, Stink bugs, flies, cockroaches, spiders and/or positions that exhibit pesticidal activity and/or prevention of moths. egg emergence after the composition has dried for at least two 0037. In some embodiments, the composition includes a hours from application before pests are exposed to the dry combination of a pesticidal natural oil and a polar aromatic reside. Solvent. In some embodiments, the combination of the pesti 0030. As used herein, “prolonged residual activity” refers cidal natural oil and the polar aromatic solvent is effective to to compositions that exhibit pesticidal activity and/or preven control pests. In some embodiments, the combination of the tion of egg emergence up to several days after the composi pesticidal natural oil and the polar aromatic solvent is effec tion has been applied to a target Surface. In some embodi tive to prevent eclosion. In some embodiments, the combina ments, “prolonged residual activity” refers to compositions tion of the pesticidal natural oil and the polar aromatic Solvent that exhibit pesticidal activity and/or prevention of egg emer is effective to prevent oviposition. In some embodiments, the gence up to one week, two weeks, three weeks, or more after combination of the pesticidal natural oil and the polar aro the composition has dried after being applied to a target matic solvent exhibits effective knockdown pesticidal activ Surface. Higher prolonged residual pesticidal activity can ity. In some embodiments, the combination of the pesticidal extend the interval between re-treatments of a target surface natural oil and the polar aromatic solvent exhibits prolonged necessary to achieve an acceptable level of pest control. In residual pesticidal activity. Some embodiments, prolonged residual activity refers to 0038. In some embodiments, the combination of the pes compositions that exhibit pesticidal activity and/or preven ticidal natural oil and the polar aromatic solvent exhibits tion of egg emergence up to at least 7 days, 8 days, 9 days, 10 markedly improved ability to control pests and/or an days, 11 days, 12 days, 13 days, 14 days, 15 days, 16 days, 17 expanded range of pesticidal activity as compared with either days, 18 days, 19 days, 20 days, or 21 days after treatment, the pesticidal natural oil or the polar aromatic solvent alone. meaning that a composition does not need to be re-applied to In some embodiments, a composition including a combina pests or to Surfaces where the pests or their eggs may contact tion of a pesticidal natural oil and a polar aromatic Solvent or otherwise be exposed to the composition for at least such exhibits improved dry residue pesticidal activity as compared period of time. with either the pesticidal natural oil or the polar aromatic 0031. As used herein, “knockdown activity refers to the Solvent used alone. In some embodiments, a composition pesticidal activity of a composition as applied directly to a including a combination of a pesticidal natural oil and a polar pest. aromatic Solvent acts to prevent eclosion when used under conditions at which the pesticidal natural oil or the polar 0032. As used herein, “surface' or “target surface' aromatic solvent used alone would not prevent eclosion to a includes a surface to which a pesticide is applied or is to be significant level. In some embodiments, a composition applied. Such surfaces may include, for example, a Surface including a combination of a pesticidal natural oil and a polar where pests are likely to contact or otherwise be exposed to aromatic solvent acts to prevent oviposition when used under the applied pesticide, to lay their eggs, and/or a surface that conditions at which the natural oil or the polar aromatic has been or is suspected to be infested by pests. Solvent used alone would not prevent oviposition to a signifi 0033. As used herein, “preventing oviposition” means that cant level. In some embodiments, a composition including a a composition prevents a pest from laying eggs, and/or combination of a pesticidal natural oil and a polar aromatic decreases the number of eggs typically laid by a pest. solvent exhibits improved or more rapid knockdown of a pest 0034. As used herein, the term “stability” means the abil as compared with either the pesticidal natural oil or the polar ity of a composition to retain its pesticidal activity after appli aromatic solvent used alone. In some embodiments, a com cation to a surface to be treated with insecticide. position including a combination of a pesticidal natural oil 0035. The term “carrier as used herein refers to an inert and a polar aromatic solvent exhibits prolonged residual pes material, organic or inorganic, with which an active ingredi ticidal activity as compared with either the pesticidal natural ent can be mixed or formulated to facilitate its application, oil or the polar aromatic solvent used alone. In some embodi storage, transport, and/or handling, or improve various prod ments, a composition including a combination of a pesticidal uct characteristics such as its odor. Commonly used carriers natural oil and a polar aromatic solvent exhibits prolonged include, but are not limited to, ethanol, isopropanol, other residual egg eclosion prevention activity, while the pesticidal alcohols, and water. Exemplary carriers that can be used in natural oil or the solvent used alone do not exhibit such some embodiments of the invention include inert carriers activity. listed by the U.S. EPA as a Minimal Risk Inert Pesticide 0039. In some embodiments, a composition including a Ingredients (4A), Inert Pesticide Ingredients (4B) or under combination of a polar aromatic solvent with a pesticidal EPA regulation 40 CFR 180.950, each of which is hereby natural oil shows a lesser degree of repellency than the repel incorporated herein by reference in its entirety for all pur lency of the pesticidal natural oil used alone. Under certain poses, including for example, citric acid, lactic acid, glycerol, experimental conditions described herein, dry residues of castor oil, benzoic acid, carbonic acid, ethoxylated alcohols, exemplary combinations comprising neem oil in combination US 2014/0242199 A1 Aug. 28, 2014

with a polar aromatic solvent demonstrate significantly less wherein R can be: repellency to adult bed bugs than dry residues of neem oil alone, and exhibit comparable levels of repellency when com pared with an untreated control. In some embodiments, the OH O O combination of a polar aromatic solvent with a pesticidal natural oil appears to mitigate the repellency of the natural oil --- uk R u R ul O -R7 (that is, the repellency of a target surface treated with the combination is the same as the repellency of the untreated target Surface). In some embodiments, the combination of a and wherein R. R. R. Rs and R can independently be —H. polar aromatic solvent with a pesticidal natural oil appears to or an alkyl group, alkenyl group or alkynyl group, including mitigate the repellency and improve the attractancy of the e.g. a methyl, ethyl, propyl, isopropyl, butyl, or pentyl group natural oil (that is, a target Surface treated with the combina or the like, oran—OH group or a halo functional group, oran tion is more attractive than the untreated target Surface and/or alkyl, alkenyl or alkynyl group including an alcohol, halo or the treatment flushes pests out of hiding spots and crevices). other polar functional group; and wherein R, and Rs can 0040 Decreasing the repellency of a pesticidal natural oil independently be —H or an alkyl group, including e.g. a (or acting as an attractant) can increase the effectiveness of a methyl, ethyl, propyl, isopropyl, butyl, or pentyl group or the composition as a pesticide, because pests will remain in an like, or an aromatic group. In some embodiments, R, and/or area where the composition has been applied (or can be Rs can have other substituents. In some embodiments R. R. flushed from hiding areas), rather than moving to untreated R. Rs and/or R can have other Substituents. Other polar areas due to the repellency of the pesticidal natural oil, and aromatic compounds could be used in Some embodiments. thereby avoiding or being otherwise unaffected by the prop 0044. In some embodiments, the polar aromatic solvent is erties of the pesticide. In some cases, applying a product with benzyl alcohol, 3,4-dimethylbenzyl alcohol, alpha-4-dimeth a high degree of repellency can result in the spread of pests, as ylbenzyl alcohol. 2-phenyl-2-propanol. 1-phenylethanol, the pests move away from the location to which the repellent benzaldehyde, 2-hydroxy-5-methylbenzaldehyde, acetophe product has been applied. For example, if there is a localized none, 4'-methylacetophenone, 2-hydroxyacetophenone, infestation of pests in a residential dwelling and a repellent 2',4'-dimethylacetophenone, 3',4'-dimethylacetophenone, product is applied to the area where the infestation is local propiophenone, 4'-methylproppiophenone, butyrophenone, ized, the pests may simply move on and infest other areas of isobutryophenone, Valerophenone, 4'-hydroxyvalerophe the residential dwelling. none, cyclohexyl phenyl ketone, hexanophenone, 2.2',4,4'- tetrahydroxybenzophenone, benzoic acid, 4-hydroxy ben 0041. In some embodiments, a pesticidal composition Zoic acid, ethylbenzoate, isobutylbenzoate, benzylbenzoate, includes two or more natural oils and apolar aromatic solvent. propyl-4-hydroxybenzoate, phenol, butyl phenyl ether, trans In some embodiments, at least one of the natural oils is a pesticidal natural oil, and at least one of the natural oils is an anethole, dibenzyl ether, diphenyl ether, and/or a combina oil or fragrance selected to decrease the repellency of the one tion thereof. or more pesticidal natural oils in the composition. In some 0045. In some embodiments, the polar aromatic solvent is embodiments, the natural oils are selected to provide a com replaced by an alkyl alcohol. In some embodiments, the Sol position that has an odor to humans that is more pleasant than vent is 2-ethyl-1-hexanol. 1-nonanol. 2-butyl-1-octanol, the odor of the pesticidal natural oil alone, i.e. the natural oil 2-hexyl-1-decanol. 1-dodecanol, 2-octanol. 1-decanol, and/ is an additive that masks the odor of the pesticidal natural oil. or a combination thereof. 0046. In some embodiments, compositions including a 0042. In some embodiments, the polar aromatic solvent is pesticidal natural oil and a polar aromatic solvent exhibit a ketone. In some embodiments, the polar aromatic solvent is significantly improved Stability and dry residue pesticidal a simple ketone. In some embodiments, the polar aromatic activity as compared to the dry residue pesticidal activity of Solvent is acetophenone. In some embodiments, the polar the pesticidal natural oil or the polar aromatic solvent alone. aromatic solvent is an alcohol, an aldehyde, an ester, or a In one embodiment, the addition of acetophenone or other carboxylic acid. In some embodiments, the polar aromatic polar aromatic organic solvent to neem oil or a component or Solvent is an aryl alcohol, an aryl-alkyl alcohol, an aryl alde derivative of neem oil provides a composition with signifi hyde, an aryl-alkyl ketone, an aryl-aryl ketone, an aryl car cantly improved stability and dry residue pesticidal activity as boxylic acid, an aryl-alkyl ester, an aryl-aryl ester, an aryl compared with neem oil or its components or derivatives alkyl ether, an aryl-aryl ether and/or a combination thereof. alone, and as compared with the dry residue pesticidal activ 0043. In some embodiments, the polar aromatic solvent ity of the solvent alone. has the general structure 0047. In some embodiments, compositions including a pesticidal natural oil and a polar aromatic solvent prevent egg emergence (i.e. prevent eclosion). In some embodiments, (I) compositions including a pesticidal natural oil and a polar aromatic solvent exhibit prolonged egg eclosion prevention activity. 0048. In some embodiments, a composition including a combination of a pesticidal natural oil and a polar aromatic Solvent exhibits improved prevention of oviposition as com pared with either the pesticidal natural oil or polar aromatic Solvent alone. 0049. In some embodiments, a composition including a combination of a pesticidal natural oil and a polar aromatic US 2014/0242199 A1 Aug. 28, 2014

solvent exhibits improved or more rapid knockdown of pests TABLE 1-continued as compared with either the pesticidal natural oil or polar aromatic solvent alone. Chemical Constituents of Pesticidal Natural Oils 0050. In some embodiments, compositions including a Essential oil Chemical Constituent Reference pesticidal natural oil and apolar aromatic solvent exhibit both Thyme oil Thymol; Geraniol; Thompson; Granger & improved or more rapid knockdown of pests as compared Carvacrol; Linalool; Passet; Shabnum & Wagay with either the pesticidal natural oil or the polar aromatic alpha-Terpineol; p Cymene; 1,8-Cineole: Solvent used alone, and also prolonged dry residual pesticidal terpinen-4-ol; Myrcenol activity. 8; Thuyanol-4, mycrene; gamma-terpinene; alpha 0051. In some embodiments, the pesticidal natural oil is terpinene neem oil or a component or derivative thereof. In other Clove oil Eugenol; benzyl alcohol: Chaieb embodiments, the pesticidal natural oil is neem oil, clove oil, carvacrol; thymol; peppermint oil, cinnamon oil, thyme oil, oregano oil, garlic cinnamaldehyde; beta caryophyllene oil, anise oil, geranium oil, lime oil, lavender oil, components Cinnamon oil Linalool; cinnamyl Kaul; Simic or derivatives thereof including for example geraniol acetate; beta derived from geranium oil and eugenol derived from clove caryophyllene; alpha oil—or a combination of the foregoing. Table 1 presents a pinene; eugenol; cinnamaldehyde; Summary of major chemical constituents (i.e. components) of limonene Some pesticidal natural oils. In some embodiments, the pes Geranium oil Geraniol; linalool; geranyl Rajeswara Rao ticidal natural oil is any oil that includes one or more con acetate; citronellol; stituents common to two or more of the pesticidal natural oils citronellyl formate; isomenthone; alpha listed in Table 1 (i.e. neem oil, clove oil, peppermint oil, pinene; 10-epi-gamma cinnamon oil, thyme oil, oregano oil, garlic oil, anise oil, eudesmol geranium oil, lime oil, lavender oil), including, but not limited Peppermint oil Menthol; Menthone; 1.8- Gochev; Clark & Menary to, thymol (found in oregano oil and thyme oil), p-cymene Cineole: Methyl acetate; Limonene; beta (found in oregano oil and thyme oil), 1,8-cineole (found in caryophyllene thyme oil and peppermint oil), eugenol (found in clove oil and Lavender oil ,5-Dimethyl-1-vinyl-4- Hui; Shellie, Mondello, cinnamon oil), limonene (found in cinnamon, peppermint, hexenylbutyrate; 1,3,7- Marriott, & Dugo and lime oil), alpha-pinene (found in cinnamon oil, geranium Octatriene: eucalyptol; camphor oil, and lime oil), carvacrol (found in oregano oil, thyme oil, Garlic oil Diallyl disulfide; Methyl Kimbaris; Avato and clove oil), gamma-terpinene (found in oregano oil and allyl trisulfide: 3-Vinyl lime oil), geraniol (found in thyme oil and geranium oil), 4H-1.2 dithiin; 3-Vinyl alpha-Terpineol (found in thyme oil and anise oil), beta 2 dithiole-5- cyclohexane; Diallyl caryophyllene (found in clove oil, cinnamon oil, and pepper trisulfide mint oil) and linalool (found in thyme oil, cinnamon oil and Anise oil Anethole; methyl Santos; Arslan geranium oil, amongst others). In other embodiments, the chavicol; anisaldehyde; pesticidal natural oil is any oil having as a constituent one of estragole; alpha the following compounds, or a combination of the following Terpineol; linalool Lime oil d-limonene; linallyl Vasudeva & Sharma: compounds: azadirachtin, nimbin, nimbinin, salannin, gedu acetate; beta-myrcene: Lota, M.-L. nin, geraniol, geranial, gamma-terpinene, alpha-terpineol, linalool; alpha-pinene; beta-caryophylene, terpinen-4-ol, myrcenol-8, thuyanol-4, geranial; beta-pinene; benzyl alcohol, cinnamaldehyde, cinnamyl acetate, alpha gamma-terpinene pinene, geranyl acetate, citronellol, citronellyl formate, iso menthone, 10-epi-gamma-eudesmol, 1,5-dimethyl-1-vinyl 0.052 Table 2 presents a summary of known pesticidal 4-hexenylbutyrate, 1.3.7-octatriene, eucalyptol, camphor, activities (including insecticidal, acaricidal, ovicidal, larvi diallyl disulfide, methyl allyl trisulfide, 3-vinyl-4H-1.2 cidal, reducing growth rate, and pupation inhibiting activi dithiin, 3-vinyl-1,2 dithiole-5-cyclohexane, diallyl trisulfide, ties) of constituents of Some pesticidal natural oils. In some anethole, methyl chavicol, anisaldehyde, estragole, linallyl embodiments, the pesticidal natural oil is any oil or any con acetate, geranial, beta-pinene, thymol, carvacrol, p-cymene, stituent that comprises a significant quantity (i.e. an amount beta-myrcene, alpha-myrcene, 1,8-cineole, eugenol, of the constituent sufficient to provide the natural oil with limonene, alpha-pinene, menthol, menthone, and linalool. pesticidal activity) of one or more constituents possessing insecticidal activity. In some embodiments, the pesticidal natural oil is any oil that comprises a significant quantity (i.e. TABLE 1. an amount of the constituent sufficient to provide the natural Chemical Constituents of Pesticidal Natural Oils oil with pesticidal activity) of one or more of the constituents listed in Table 2, namely thymol, p-cymene, eugenol, cinna Essential oil Chemical Constituent Reference maldehyde, linalool, cinnamyl acetate, menthol, d-limonene, Oregano oil Thymol; Carvacrol; p- Vokou: Toncer anethole, carvacrol, alpha-pinene, geraniol, 1,8-cineole, cymene; gamma myrcene, anisaldehyde, alpha-terpineol, alpha-terpinene, terpinene; alpha gamma-terpinene, terpinen-4-ol, and beta-myrcene. In some terpinene; linalool Neem oil Azadirachtin; Nimbin; Schmutterer embodiments, the constituent known to possess insecticidal Nimbinin; Salannin; activity is a terpene, for example, azadirachtin. In some Gedunin embodiments, the constituent of the pesticidal natural oil is present in an amount greater than or equal to about 0.1%, US 2014/0242199 A1 Aug. 28, 2014

greater than or equal to about 0.5% or greater than or equal to TABLE 2-continued about 1% by weight in the pesticidal natural oil. Known Pesticidal Activities of Chemical Constituents of Pesticidal Natural Oils TABLE 2 Compound Activity Reference Known Pesticidal Activities of Chemical Constituents of Pesticidal Natural Oils Anisaldehyde insecticidal activity - Marcus & Lichtenstein house fly Compound Activity Reference alpha-Terpineol Reduce growth rate - Karr & Coats B. germanica Thymol Insecticidal activity - Lee alpha-Terpineol Antifeedant activity - Hummelbrunner & Isman M. domestica & S. iiiura S. iiiura alpha-Terpinene Larvicidal activity - Cheng (2009) Thymol Insecticidal activity - Franzios A. aegypti & D. melanogaster A. albopictus Thymol Insecticidal activity - Traboulsi gamma-terpinene Larvicidal activity - Cheng (2009) C. pipiens moiesii is A. aegypti & p-Cymene Antifeedant activity - Salom A. albopictus pales weevil gamma-terpinene Larvicidal activity - Abbassy Eugenol Antifeedant activity - Jones & Firn A.fabae & P. Brassicae larvae S. ittorais Eugenol Insecticidal activity - Yang et al. (2003) Terpinen-4-ol Larvicidal activity - Abbassy P. capitis A.fabae & Eugenol Insecticidal activity - Trongtokit S. ittorais A. dirtis mosquitoes p-cymene Larvicidal activity - Cheng (2009) Eugenol Acaricidal activity - Kim, Kim, & Ahn A. aegypti & D.farina & A. albopictus D. pteronyssinus beta-myrcene Larvicidal activity - Cheng (2009) Cinnamaldehyde Insecticidal activity - Samarasekera A. aegypti & C. quinquefasciaius & A. albopictus A. tessellatus Cinnamaldehyde Acaricidal activity - Chang & Cheng termites Linalool Insecticidal activity - Yang et al. (2005) 0053 Other oils that can be used, alone or in combination, Philimantis capitis as additives in some embodiments of the present invention Linalool Acaricidal activity - Perrucci can be derived from plant, animal or mineral sources, or be P clinicui synthetic. Such oils may be added as a carrier and/or for Linalool Antifeedant activity - Hummelbrunner, & Isman S. iiiura various other purposes, including but not limited to, improv Linalool Reduce growth rate - Karr & Coats ing odor characteristics (e.g. acting as an odor-masking B. germanica agent), improving properties of another oil used as an active Cinnamyl acetate Insecticidal activity - Yang et al. (2005) ingredient, decreasing repellency, acting as a pesticide, and/ Philimantis capitis Menthol Insecticidal activity - Ellis & Baxendale or improving other properties of the formulation. Such oils Tracheal mites include, but are not limited to, castor oil, orange oil, citrus oil, Menthol Inhibit pupation - Harwood, Modenke, & Berry cedar oil, linseed oil, soybean oil, licorice oil, mint oil, Sweet Psaticia Menthol Insecticidal activity - Tripathi birch oil, canola oil, jojoba oil, lavandin oil, mustard seed oil, T. Castaneim & coconut oil, eue oil, tulsi oil, almond oil, cottonseed oil, corn C. machiatus oil, germanium oil, sesame oil, tung oil, rosemary oil, basil d-limonene Insecticidal activity - Lee (1997); Don-Pedro oil, fennel oil, ginger oil, grapefruit oil, mandarin oil, pepper M. domestica, D. virgifera, oil, rose oil, tangerine oil, tea tree oil, tea seed oil, pine oil, S. iiii tra, cardamom oil, Cassia oil, celery oil, cognac oil, dill weed oil, Some cockroaches juniper oil, guiacwood oil, parsley oil, pimento leaf oil, apri d-limonene Reduce growth rate - Karr & Coats cot oil. Origanum oil, betel leafoil, ajowan oil, chilly seed oil, B. germanica cubeb oil, curry oil, frankincense oil, ginger grass oil, heeng Anethole insecticidal activity - Chang & Ahn oil, jamrosa oil, kalaunji oil, citronella oil, linaloe berry oil, B. germanica Anethole insecticidal activity - Fuhremann, et al. bantulasi oil, bursera oil, lemon balm oil, karanja oil, nepeta house fly lactone oil, mink oil, limba pine oil, litsea cubeba oil, lovage Carvacrol insecticidal activity - Hierro, et al. (2004) oil, manuca oil, marjoran oil, milfoil oil, myrrh oil, myrtle oil, A. Simplex neroli oil, niauli oil, cumin seed oil, cyperiol oil, gereniol oil, Carvacrol insecticidal activity - Traboulsi grape seed oil, hinoki oil, laurel berry oil, lichen oil, mace oil, C. pipiens moiesii is mango ginger oil, mentha pipereta oil, paprika oil, Vetivert alpha-pinene insecticidal activity - Traboulsi C. pipiens moiesii is oil, wheat germ oil, macassar oil, mentha citreta oil, musk Geraniol insecticidal activity - Hierro melon oil, narkachur oil, palmarosa oil, patchouli oil, pome A. Simplex granate oil, pumpkin oil, tomar seed oil, cananga oil, avocado 1,8-Cineole Acaricidal activity - Miresmailli, Bradbury & oil, safflower oil, abies alba needle oil, ambrette seed oil, house dust mites Isman amyris oil angelica root oil, artemisia oil, estragon oil, fir 1,8-Cineole Reduce growth rate - Obeng-Ofori & Reichmuth Coleopteran sp. needle oil, galangal oil, galbanum oil, olibanum oil, palma 1,8-Cineole insecticidal activity - Tripathi, Prajanpati, rosa oil, patchouli oil, birch oil, cajeput oil, calamus oil, T. Castianet in Aggarwal, & Kumar cedarwood oil, wintergreen oil, carrot oil, costus oil, cypress Myrcene Reduce growth rate - Karr & Coats oil, davana oil, dwarf pine needle oil, elemi oil, guajac oil, hop B. germanica oil, hyssop oil, chamomile oil, jasmine oil, larch oil, rose wood oil, oil, Sassafras oil, tagetes oil, thuja oil, Valerian oil, US 2014/0242199 A1 Aug. 28, 2014

verbena oil, vervain oil, Vetiver oil, wormwood oil, ylang tants, other natural or synthetic Surfactants, and combinations ylang oil, olive oil, evening primrose oil, hazelnut oil, grape thereof. In some embodiments, the Surfactant(s) are non-ionic core oil, peach core oil, walnut oil, Sunflower oil, sandalwood Surfactants. In some embodiments, the Surfactant(s) are ionic oil, turmeric oil, nutmeg oil, soy oil, vegetable oils, menthol Surfactants. The selection of an appropriate Surfactant oil, eucalyptol, camphor oil, cedar leaf oil, laurel leaf oil, depends upon the relevant applications and conditions of use, balsam oil, bay oil, capsicum oil, spearmint oil, caraway seed and appropriate Surfactants are known to those skilled in the oil, lemon eucalyptus oil, lemongrass oil, sage oil, penny art royal oil, bergamot oil, mineral oil, other natural or essential 0060. In some embodiments, a pesticidal composition oils, or combinations thereof. includes a suitable carrier. A suitable carrier can be selected 0054. In some embodiments, the additive is an odor-mask by one skilled in the art, depending on the particular applica ing agent or compound. In some embodiments, the odor tion desired and the conditions of use of the composition. masking agent is vanilla extract, wintergreen oil, spearmint Commonly used carriers include ethanol, isopropanol, other oil, clove oil, lemongrass oil, and/or a combination thereof. alcohols, water and other inert carriers listed by the EPA as a 0055. In some embodiments, the additive can be a second Minimal Risk Inert Pesticide Ingredients (4A), Inert Pesticide pesticidal natural oil or other material having pesticidal activ Ingredients (4B) or under EPA regulation 40 CFR 180.950, ity, including for example cinnamon oil, thyme oil, clove oil, each of which is hereby incorporated herein in its entirety for clove leaf oil, clove bud oil, eugenol, lime oil, oregano oil, all purposes including for example, citric acid, lactic acid, thyme oil, mint oil (including spearmint or peppermint oil), or glycerol, castor oil, benzoic acid, carbonic acid, ethoxylated the like. alcohols, ethoxylated amides, glycerides, benzene, butanol, 0056. In some embodiments, the additive can be an odor 1-propanol, hexanol, other alcohols, dimethyl ether, and neutralizing agent. In some embodiments, the odor-neutral polyethylene glycol. izing agent can be an odor-absorbent material. In some 0061 Some embodiments of the present invention include embodiments, the additive is zeolite and/or other natural or combinations of a pesticidal natural oil (and/or components synthetic odor absorbent material. and/or derivatives thereof) with a polar aromatic solvent and 0057 Derivatives and/or components of neem oil that can one or more other natural oils (plant, animal or mineral be used in embodiments of the present invention include, but derived), synthetic oils, and/or chemical derivatives of any of are not limited to, neem oil, palmitoleic acid, alpha-linolenic the foregoing. acid, Stearic acid, palmitic acid, oleic acid, linoleic acid, 0062. In some embodiments, a pesticidal composition campesterol, beta-sitosterol, stigmasterol, azadirachtin, comprises a pesticidal natural oil at a concentration of meliantriol, melianone, gedunin, amoorastatin, Vepinin, mar between 0.25% and 99.3% by weight, including any concen rangin, Vilasinin, nimbin, nimbolide, nimbolinin, ohchino tration therebetween e.g. 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, lide, nimbolinin, Salannin, meliacarpin, meliacquinal, nimban 0.8%, 0.9%, 1%, 2%, 5%, 7.5%, 10%, 15%, 20%, 25%, 30%, diol, nimbinene, nimbocinone, kulactone, limocinol, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, limocinone, nimolinone, azadirachnol, or other triterpenoids, 85%,90%.95%.98% or 99% by weight; and apolar aromatic azadirone, azadiradione, azadirachtol, epoxyazadiradione, solvent at a concentration between 0.7% and 99.75% by other compounds derived from neem, related to neem, com weight, including any concentration therebetween e.g. 0.8%, binations thereof, and their active derivatives. 0.9%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 3%, 4%, 5%, 0058. Derivatives and/or components of other pesticidal 7.5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, natural oils that can be used in some embodiments of the 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or present invention include, but are not limited to, thymol. 99% by weight. In some embodiments, the polar aromatic p-cymene, 1,8-cineole, eugenol, limonene, carvacrol, men Solvent is presentata concentration between 0.13 mol/kg and thol, alpha-pinene, linalool, menthone, carvacrol, gamma 8.3 mol/kg or any value therebetween, e.g. 0.2,0.4,0.6, 0.8. terpinene, geraniol, alpha-terpineol, beta-caryophyllene, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, linalool, gedunin, geraniol, geranial, terpinen-4-ol, myr or 8.0 mol/kg. cenol-8, thuyanol-4, benzyl alcohol, cinnamaldehyde, cin 0063. In some embodiments, a pesticidal composition is namyl acetate, geranyl acetate, citronellol, citronellyl for provided in which the weight ratio of polar aromatic solvent mate, isomenthone, 10-epi-gamma-eudesmol. 1,5-dimethyl to pesticidal natural oil is in the range of 1.5:1 to 7:1, or any 1-vinyl-4-hexenylbutyrate, 1.3.7-octatriene, eucalyptol, range therebetween including e.g. 2:1, 2.5:1, 3:1, 4:1, 5:1, or camphor, diallyl disulfide, methylallyltrisulfide, 3-vinyl-4H 6:1. 1.2 dithin, 3-vinyl-1,2 dithiole-5-cyclohexane, diallyl trisul 0064 One exemplary composition according to one fide, anethole, methyl chavicol, anisaldehyde, estragole, lina embodiment includes neem oil or a component or derivative lyl acetate, beta-pinene, beta-myrcene, alpha-myrcene, thereof, acetophenone or another polar aromatic solvent, and menthol, and other compounds derived from pesticidal natu optionally includes a Surfactant, additional insect controlling ral oils, combinations thereof, and their active derivatives. compounds and/or additional natural oils or other products to 0059. In some embodiments, a surfactant is used in pre add fragrance, decrease repellency, or extend the range of paring pesticidal compositions or pest control agents. Suit insects Susceptible to the composition. In one embodiment, able surfactants can be selected by one skilled in the art. Such a composition includes neem oil (or a derivative thereof) Examples of Surfactants that can be used in Some embodi at a concentration between 0.1% and 99% by weight, includ ments of the present invention include, but are not limited to, ing any concentration therebetween e.g. 0.2%, 0.25%, 0.3%, ethoxylated castor oil, Sodium lauryl Sulfate, Saponin, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 5%, 7.5%, ethoxylated alcohols, ethoxylated fatty esters, alkoxylated 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, glycols, ethoxylated fatty acids, carboxylated alcohols, car 60%. 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99% by boxylic acids, fatty acids, ethoxlylated alkylphenols, fatty weight; and acetophenone at a concentration between 0.7% esters, sodium dodecylsulfide, other fatty acid-based surfac and 99.75% by weight (between 0.13 mol/kg and 8.3 mol/kg US 2014/0242199 A1 Aug. 28, 2014

or any value therebetween, e.g. 0.2,0.4,0.6,0.8, 1.0, 1.5, 2.0, embodiments of the present invention can also be used to 2.5.3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, or 8.0 mol/kg), control other arachnids upon which they are expected to be including any concentration therebetween e.g. 0.8%, 0.9%, effective, including, but not limited to, Scorpions and other 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 3%, 4%, 5%, 7.5%, 10%, species of spiders. This disclosure is intended to encompass 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, uses against all of the above, as well as uses against other 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99% by pests, including other insects and arachnids, and other organ weight. The exemplary composition optionally includes one isms including fungi, bacteria, viruses, and nematodes. or more Surfactants, other pesticidal ingredients, stabilizers, 0069. In some embodiments, the pesticidal compositions carriers, diluents, or other non-pesticidal ingredients, and/or described herein are effective to kill and/or control pests other natural oils. and/or prevent or reduce oviposition and/or prevent or reduce 0065. In one exemplary embodiment, a pesticidal compo eclosion of their eggs. In some embodiments, the pesticidal sition includes a combination of neem oil at a concentration of compositions described herein exhibit effective knockdown 5.5% by weight, acetophenone at a concentration of 15.5% by pesticidal activity, exhibit effective dry residue pesticidal weight, natural oils (lemongrass oil, spearmint oil, clove oil, activity, and/or exhibit effective prolonged residual pesticidal and wintergreen oil) at 8% or 3.4% by weight and a surfactant activity. at a concentration of 5.0% by weight. In one exemplary 0070. In some embodiments, the pesticidal compositions embodiment, a pesticidal composition includes a combina described herein are effective to kill and/or control pests tion of neem oil at a concentration of 5.5% by weight, and/or prevent oviposition and/or prevent eclosion of their acetophenone at a concentration of 18.25% by weight, and eggs, or exhibit improved knockdown of a pest, dry residue 1.25% ethoxylated castor oil by weight. pesticidal activity, and/or prolonged residual pesticidal activ 0066 Exemplary formulations according to one exem ity, when the concentration of each of the pesticidal natural oil plary embodiment comprising neem oil as the pesticidal natu and the polar aromatic solvent is below a level at which the ral oil and acetophenone as the solvent were shown to dem pesticidal natural oil and the polar aromatic solvent used onstrate improved dry residue pesticidal activity as compared alone would be effective to achieve the same function. In with neem oil alone when neem oil and acetophenone are Some embodiments, the pesticidal compositions described present at a concentration of at least 0.55% and 1.55% by herein exhibit a synergistic pesticidal effect as compared with weight, respectively. the activity the pesticidal natural oil or the polar aromatic 0067 Formulations according to another exemplary Solvent used alone. In some embodiments, the pesticidal embodiment were found to demonstrate improved dry resi compositions described herein exhibit significantly improved due prevention of egg eclosion as compared with neem oil pesticidal effect as compared with the activity of the pesti alone when neem oil and acetophenone were present at con cidal natural oil or the polar aromatic solvent used alone at the centrations of at least 0.25% and 0.7% by weight, respec same concentration. tively. 0071. Some embodiments of the present invention can be 0068. Some embodiments of the present invention can be used to control pests that affect humans and non-human mam used to control pests such as arthropods, including insects and mals including bedbugs, cockroaches, lice, fleas, ticks, mites, arachnids. Exemplary embodiments of the present invention and Scabies. Some embodiments of the present invention can have been demonstrated to have efficacy against arthropods be used to control pests that affect plants or agriculture. Such including insects and spiders including bed bugs, German as aphids or nematodes. In some embodiments, any of the cockroaches (Blattella germanica), Smoky Brown cock compositions described above may be used in any situation in roaches (Periplaneta fuliginosa), American cockroaches which a neem oil-based insect control agent is currently (Periplaneta americana), cat fleas (Ctenocephalides felis), employed. fire ants (Solenopsis Invicta), black carpenterants (Campono 0072. In some embodiments, any of the compositions tus pennsylvanicus), pavement ants (Tetramorium caespi described above are formulated in a deliverable form suited to tum), field ants (Formica sp.), moisture ants (Lasius sp.), a particular application. Deliverable forms that can be used in wood ants (Formica rufa), house flies (Musca domestica), accordance with embodiments of the present invention bottle flies (Lucilia sericata), giant silverfish (Ctenolepisma include, but are not limited to, liquids, emulsions, Solids, longicaudata), firebrats (Thermobia domestica), bean aphids waxes, dusts, fumigants, aqueous Suspensions, oily disper (Aphis fabae), pea aphids (Acyrthosiphon pisum), and ter sions, pastes, powders, dusts, emulsifiable concentrates, mites (Reticulitermes flavipes). Some embodiments of the aerosol sprays, wood fillers, varnishes, wood treatments or present invention can also be used to control insects or arthro furniture oils, detergents, drywall mixtures, fumigating pods upon which they are expected to be effective based on candles, caulking compositions, crack and crevice fillers, their demonstrated activity, including, but not limited to, sealing agents, and mattress and mattress cover treatments. whiteflies, mosquitoes, other species of flies, other species of Suitable deliverable forms can be selected and formulated by aphids, other species of silverfish, lice, Stink bugs, moths, those skilled in the art using methods currently known in the beetles, lace bugs, whiteflies, green peach aphids, western art floral thrips, diamondback moths, leafminers, grasshoppers, 0073. Some embodiments of the present invention dem crickets, locusts, leafhoppers, planthoppers, psyllids, Scale onstrate effective insect control activity on surfaces where insects, midges, fruit flies, earworms, bollworms, army pest products are commonly employed, including, but not worms, budworms, hornworms, milkweed bugs, mealy bugs, limited to, carpet, mattresses, wood, and fabrics. In some weevils, botflies, face flies, sawflies, rice bugs, coffee bugs, embodiments, any of the compositions described above are Vegetable bugs, corn borers, horn flies, blowflies, Sowbugs, applied to Surfaces inside a household, residence or building. pillbugs, and centipedes. Exemplary embodiments of the In some embodiments, any of the compositions described present invention have been demonstrated to have efficacy above are applied to mattresses, sheets, fabrics, travel bags/ against arachnids including cellar spiders and ticks. Some Suitcases, carpets, painted or unpainted hard Surfaces, wood, US 2014/0242199 A1 Aug. 28, 2014

flooring, furniture and/or buildings. In some embodiments, allowing the solvent to solvate the oil before addition of other any of the compositions described herein are applied out ingredients. In some embodiments in which the pesticidal doors or to plants or agricultural areas and/or inside or outside natural oil is neem oil, the formulation is prepared by warm Structures. ing neem oil to a temperature of 25-30°C. before any further 0.074. Some embodiments are effective as an insect control components of the formulation are added. The solvent is then agent against insects resistant to pyrethrins (eg. pyrethrum) added to the oil, allowing the solvent to solvate the oil before and pyrethroids (eg. deltamethrin, bifenthrin, w-cyhalothrin, addition of other ingredients. Optionally, a surfactant and/or etc.). In some embodiments, the pyrethrin-resistant insect is a other ingredients (which may include additional natural oils bed bug (Cimex lectularius L.). or other pesticides) are then added. In some embodiments, a 0075 Some embodiments provide methods of using any surfactant is added prior to addition of the solvent. Once all of the compositions described above to control populations of ingredients are completely Solvated, they may optionally be bed bugs and/or other insects, arachnids and/or other arthro combined with an appropriate amount of a conventional dilu pods. Some embodiments provide a method of killing and/or ent and/or additional solvent (including different types of controlling pests and/or preventing oviposition and/or eclo Solvents). Other carriers, Solvents, Surfactants, pesticides, fra sion of their eggs by applying any of the compositions grances or odor neutralizers may optionally be added. Appro described herein directly to the pests or to surfaces where the priate preservatives or stabilizers may optionally be added. pests or their eggs may contact the composition. In some Materials that encapsulate, hold, transport, delay release or embodiments, the pests are insects and/or arachnids. In some otherwise improve delivery may optionally be added. embodiments, the insects are of the orders hemiptera, hymenoptera, blattodea, isopteran, diptera or lepidoptera. In EXAMPLES Some embodiments, the pests are bed bugs. 0079 Embodiments of the present invention are further 0076. In some embodiments, the methods of use of any of described with reference to the following examples, which the compositions described herein include combination with are intended to be illustrative and not limiting. natural oils for direct application, dilution with an appropriate 0080. In the examples that follow, the neem oil used was carrier for delivery as a ready-to-use spray, or in a concen cold pressed neem seed oil ("C.P. neem oil’). trated form to be diluted and applied. Other methods of use include, but are not limited to, use as a wood treatment or Example 1 furniture oil, as a laundry detergent, as a gel or paste which can be applied to a target location, as an oily emulsion, as a Dry Residue Pesticidal Activity dust formulation, as a component in drywall mixture, as a crack or crevice filler or other sealing agent, as a foam, as a I0081 Solution A containing neem oil at 5.5% by weight, component in caulking compositions, as a fumigating mist or 15.5% acetophenone by weight, 8% natural oils (lemongrass candle, as an aerosol or aerosol bomb, or in a formulation oil, spearmint oil, clove oil, and wintergreen oil) by weight, employed for treating mattresses or mattress covers. In some and 5.0% ethoxylated castor oil by weight was prepared with embodiments, any of the compositions described above are isopropyl alcohol (isopropanol) as a carrier diluent. A serial used for indoor domestic or commercial uses in dispersible dilution was performed, comprising 100% Solution A, 50% forms against a range of pests. Some embodiments of the Solution A in isopropanol, 25% Solution A in isopropanol, present invention can be used in dispersible forms in agricul and 10% Solution A in isopropanol. 1.0 mL of each solution tural or other outdoor settings to control pests. was applied to 90-millimetre filter paper substrates in petri 0077. In some embodiments, the compositions described dishes. Substrates were allowed to air dry for two hours, then herein exhibit prolonged residual pesticidal activity, enabling were infested with adult bed bugs (approximately half male a period of time to pass between re-treatment of target Sur and half female). Replicates of each treatment group and of a faces. In one embodiment, pests are killed or controlled, negative Control Group were tested concurrently. Mortality and/or oviposition and/or eclosion are prevented by applying was observed at specified intervals after infestation. Adultbed any of the compositions described herein directly to the pests bugs were counted dead if they were unresponsive when or to Surfaces where the pests or their eggs may contact or stimulated. otherwise be exposed to the composition. A period of time I0082. The percentage of dead adult bed bugs was mea greater than about a week, e.g. 7 days, 8 days, 9 days, 10 days, sured at 1-, 2-, 4-, 8-, 12-, 24-, 48-, 72-, and 480-hour intervals 11 days, 12 days, 13 days, 14 days, 15 days, 16 days, 17 days, after infestation and compared against controls. The data 18 days, 19 days, 20 days, or 21 days or longer is allowed to collected are summarized in Table 3. At levels as low as pass. Then any of the compositions described herein are re 0.55% neem oil and 1.55% acetophenone by weight the com applied to the pests or to Surfaces where the pests or their eggs bination demonstrated improved insecticidal activity over an may contact or otherwise be exposed to the composition. untreated control group. No insecticidal activity, relative to a 0078 Formulations according to some embodiments can control, was observed at concentrations of 0.055% neem oil be prepared in any Suitable manner. Some embodiments of and 0.155% acetophenone by weight. the present invention provide methods for preparing pesti cidal formulations comprising mixing a pesticidal natural oil TABLE 3 and/or a component and/or a derivative thereof and a polar Dry Residue Pesticidal Activity. aromatic solvent. In some embodiments, the pesticidal for mulation is prepared by heating one or more pesticidal natural Control 100% SO% 25%. 10% 190 oils (or component or derivative thereof) in a water bath % Concentration O 5.5 2.75 1.375 0.55 0.055 before any further components of the formulation are added. C.P. Neem Oil The surfactant is added to the pesticidal natural oil, and then (by weight) one or more solvents are added to the pesticidal natural oil, US 2014/0242199 A1 Aug. 28, 2014 10

TABLE 3-continued TABLE 4-continued

Dry Residue Pesticidal Activity. LT50 and Maximum Mortality of Formulations Incorporating Control 100% SO% 25%. 10% 190 Pesticidal Natural Oils. % Concentration O 15.5 7.76 3.875 1.55 0.155 Pesticidal LTso Max Acetophenone Natural Oil Solvent (hrs.) 95% C.I. (hrs.) mortality (by weight) Time (Hours) % Mortality Thyme Oil Ethyl Lactate 17.24 16.65 to 17.82 OO% Garlic Oil Acetophenone 11.98 1086 to 13.09 90% O O.OO O.OO O.OO O.OO O.OO O.OO Garlic Oil Ethyl Lactate 24.54 7.27 to 41.80 OO% 1 O.OO 2.08 O.OO O.OO O.OO O.OO Anise Oil Acetophenone 17.79 16.56 to 19.01 OO% 2 O.OO 8.71 2.SO O.OO O.OO O.OO 4 O.OO 41.14 15.00 2.78 O.OO O.OO Anise Oil Ethyl Lactate 227.8 NA* 30% 8 O.OO 90.45 SO.83 5.56 O.OO O.OO Geranium Oil Acetophenone 2.00 Interrupted ** OO% 12 O.OO 97.50 65.83 8.06 O.OO O.OO Geranium Oil Ethyl Lactate 16.93 NA* 90% 24 O.OO 100.OO 100.OO 43.76 2.SO O.OO Lime Oil Acetophenone 6.628 NA* 89% 48 2.SO 100.OO 100.OO 73.41 S.OO O.OO 72 2.SO 100.OO 100.OO 85.68. 14.77 O.OO Lime Oil Ethyl Lactate 93.35 NA* 45% 480 16.82 100.OO 10O.OO 97.50 70.91 11.67 Peppermint Oil Acetophenone 2.18 2.15 to 2.22 OO% Peppermint Oil Ethyl Lactate NA* NA* 559, Lavender Oil Acetophenone 3.57 3.01 to 4.14 OO% Lavender Oil Ethyl Lactate NA* NA* 40% Example 2 Neem Oil Acetophenone 6.54 6.07 to 7.02 OO% Neem Oil Ethyl Lactate NA* NA* 40% Dry Residue Pesticide Activity of Various Pesticidal Control None NA* NA* 30% Natural Oils *NA: LTso and 95% C.I. cannot be reliably calculated for formulations that do not reach 100% maximum mortality 0083. This example illustrates the dry residual pesticidal **Interrupted: 95% C.I. cannot be reliably calculated when the LT50 is below two hours activity of formulations containing a variety of pesticidal natural oils as active ingredients. Solutions were prepared by combining 2.5% by weight of the pesticidal natural oil as Example 3 active ingredient, 2.5% by weight sodium lauryl Sulphate, 5.0% by weight solvent (either ethyl lactate or acetophenone Dry Residual Insecticidal Activity of Various as noted), and an appropriate amount of water as a diluent. 1.0 Solvents mL of each solution was applied to three replicates of filter paper, 90 millimetres in diameter, contained in petri dishes I0085. This example illustrates the dry residual pesticidal (Treated Groups). Treated Groups and three replicates of an activity of formulations including neem oil and various untreated Control Group were allowed to dry for two hours organic solvents including alcohols, ketones, esters and car prior to infestation with a known number of adult bed bugs boxylic acids. Solutions were prepared using 5.5% by weight (approximately half male and half female). neem oil; the percent by weight of organic solvent indicated 0084 Bedbug mortality was assessed immediately after in Table 5 and an appropriate amount of isopropanol as a infestation and at 2-, 4-, 8-, 12-, and 24-hour intervals after carrier diluent. The percent by weight of each solvent was infestation, and daily thereafter until 33 days after infestation. varied to ensure a consistent molar quantity of solvent in each Adult bedbugs were counted dead if they were unresponsive solution (final concentration of 1.5 mol/kg). Treated Groups when stimulated. Table 4 Summarizes the LTs (the mean for each solution were prepared by treating filter paper, 90 point of time at which 50% of bed bugs had died), the 95% mm in diameter, with 1.0 mL of solution and allowing it to air Confidence Interval (C.I.) and the maximum mortality dry for four hours. A known number of adults were added to observed for each formulation. each treated dish, four hours after treatment. Bedbug mor tality was assessed immediately after infestation and at TABLE 4 1-hour, 2-hour, 4-hour, 6-hour, 8-hour, 10-hour, 12-hour, and 24-hour intervals, and at 24-hour intervals thereafter until 14 LT50 and Maximum Mortality of Formulations Incorporating days after infestation. Adult bed bugs were counted dead if Pesticidal Natural Oils. they were unresponsive when stimulated. Table 5 shows the Pesticidal LTso Max maximum 96 mortality of all treated groups and the time taken Natural Oil Solvent (hrs.) 95% C.I. (hrs.) mortality to reach maximum mortality. Cinnamon Oil Acetophenone 3.06 2.77 to 3.36 100% I0086 A number of the tested organic solvents, from the Cinnamon Oil Ethyl Lactate 14.OO 1316 to 15.05 100% Clove Oil Acetophenone 5.25 4.90 to S.S9 100% classes of alcohols, ketones, esters and carboxylic acids, Clove Oil Ethyl Lactate 10.58 10.03 to 11.11 100% proved effective in combination with neem oil. Solvents that Eugenol Acetophenone 2.82 2.62 to 3.02 100% included at least one aryl group were generally more effective Eugenol Ethyl Lactate 9.91 9.73 to 10.12 100% Oregano Oil Acetophenone 2.00 Interrupted 100% than solvents that contained only alkyl groups. Alkyl aryl Oregano Oil Ethyl Lactate 9.53 9.32 to 9.74 100% ketones were consistently effective solvents, and Small aryl Thyme Oil Acetophenone 3.10 2.89 to 3.31 100% alcohols, arylalkyl alcohols, aryl aryl ketones, and alkylaryl esters also proved effective in combination with neem oil.

US 2014/0242199 A1 Aug. 28, 2014 12

TABLE 5-continued Maximum 90 Mortality of Formulations with Differing Organic Solvents. Time to Class of % Solvent Max. Max Solvent Formula (wfw) Compound name Mortality Mortality Aryl acid Ar-X-H Ar = phenyl 18.55 Benzoic acid 100% 48 hr Aryl-alkyl Ar-X-Alk ester Ar = 4-hydroxyphenyl 27.27 Propyl-4-hydroxybenzoate 100% 24hr Alk = propyl

Example 4 four hours in a highly-ventilated room. A known number of adults were added to each treated dish, four hours after treat Dry Residual Insecticidal Activity of Various ment. Bed bug mortality was assessed immediately after Solvents infestation and at 1-hour, 2-hour, 4-hour, 6-hour, 8-hour, 10-hour, 12-hour, and 24-hour intervals, and at 24-hour inter 0087. This example illustrates the dry residual pesticidal vals thereafter until 14 days after infestation. Adult bed bugs activity of formulations including neem oil and various were counted dead if they were unresponsive when stimu organic solvents including alcohols, ketones, esters and car lated. Table 6 shows the maximum '% mortality of all treated boxylic acids. Solutions were prepared using 5.5% by weight groups and the time taken to reach maximum mortality. neem oil; 1.5 mol/kg organic solvent; and an appropriate I0088 A number of the tested organic solvents, from the amount of isopropanol as a carrier diluent. The percent by classes of alcohols, ketones, esters, ethers, aldehydes and weight of each solvent was varied to ensure a consistent molar carboxylic acids, proved effective in combination with neem quantity of solvent in each Solution. Treated Groups for each oil. Solvents that included at least one aryl group were gen solution were prepared by treating filter paper, 90 mm in erally more effective than solvents that contained only alkyl diameter, with 1.0 mL of solution and allowing it to airdry for groups. TABLE 6 Maximum 90 Mortality of Formulations with Differing Organic Solvents. Time to Max. Max Class Formula and ID Compound name Mortality Mortality Alcohol X = CH(OH) Alkyl alcohol Alk-X-H Alk = nonyl 1-Nonanol 100% 48 hr Alk = butyl-heptyl 2-Butyl-1-octanol 100% 8 d (Branched alkyl) Alk = dodecyl 1-dodecanol 90% 14 d Alk = hexyl-nonyl 2-hexyl-1-decanol 100% 14 d (Branched alkyl) Isoalcohol Alk-X-Alk Alk1 = butyl 3-Heptanol 30% 14 d Alk = ethyl Alk = hexyl 2-Octanol 100% 48 hr Alk = methyl Alk = isobutyl 2,6-Dimethyl-4-heptanol 20% 14 d Alk2 = isobutyl Aryl alcohol Ar-X-H Ar = 3,4-dimethylphenyl 3,4-dimethylbenzyl alcohol 100% 14 d Aryl-alkyl Ar-X-Alk alcohol Ar = 4-methylphenyl Alpha-4-dimethylbenzyl alcohol 100% 24 hr Alk = methyl Ar = phenyl Alk = dimethyl 2-Phenyl-2-propanol 100% 24 hr Aldehyde and Ketone X = (C=O) Aryl-Aldehyde Ar-X-H Ar = 4-methylphenyl p-Tolualdehyde SO% 6d Ar = 2-hydroxy-5- 2-hydroxy-5-methylbenzaldehyde 100% 24 hr methylphenyl Aryl-Alkyl Ar-X-Alk ketone Ar = 4-hydroxyphenyl 4'-Hydroxyacetophenone SO% 9d Alk = methyl US 2014/0242199 A1 Aug. 28, 2014

TABLE 6-continued Maximum 90 Mortality of Formulations with Differing Organic Solvents. Time to Max. Max Class Formula and ID Compound name Mortality Mortality Ar = 2-hydroxyphenyl 2'-Hydroxyacetophenone 100% 24 hr Alk = methyl Ar = 4-hydroxyphenyl 4'-Hydroxyvalerophenone 70% 14 d Alk = butyl Ar-phenyl Alk = cyclohexyl Cyclohexyl phenylketone 90% 8 d Carboxylic Acids and Esters X = (C=O)—O Aryl acid Ar-X-H Ar = 4-hydroxyphenyl 4-Hydroxybenzoic acid 100% 24 hr Ar = 4-hydroxy-3- 4-Hydroxy-3-methyl benzoic acid 60% 14 d methylphenyl Aryl-alkyl Ar-X-Alk ester Ar = phenyl Alk = ethyl Ethylbenzoate 100% 48 hr Ar = phenyl Alk = isobutyl Isobutylbenzoate 90% 8 d Aryl-aryl ester Ar-X-Ar Ar = phenyl Alk = benzyl Benzyl benzoate 100% 8 d Phenol and Ethers X = O

Ar-X-H Phenol 100% 24 hr Aryl-Alkyl Ar-X-Alk ether Ar = benzyl Alk = methyl Benzyl methyl ether 60% 8 d Ar = phenyl Alk = butyl Butyl phenyl ether 100% 6d Ar = 4-(1-propenyl)benzyl Trans-anethole 100% 5 di Alk = methyl Aryl-Aryl Ar-X-Air ether Ar = benzyl Ar = benzyl Dibenzyl ether 90% 7 d Ar = phenylAr2 = phenyl Diphenyl ether 100% 72 hr Benzenes

Benzene 40% 14 d Toluene 50%. 14 d p-Xylene 30% 14 d *Solvent tested in separate study from other solvents in table (under same experimental conditions)

Example 5 TABLE 7 Dry Residual Insecticidal Activity Mean 90 Mortality of 4-Hour Dry Residues. 10 24 0089. Three solutions were prepared, each containing iso O HR 2 HR, 4 HR 8 HR HR HR propanol as a carrier diluent: Solution A included 5.5% Control No Treatment O% O% 0% O% O% 0% neem oil and 1.25% castor oil by weight: Solution B Solution A 5.5% Neem Oil O% O% O% O% O% 9% included 18.25% acetophenone and 1.25% castor oil by Solution B 18.25% O% O% O% O%. 10% 70% weight; and Solution C included 5.5% neem oil, 18.25% Acetophenone Solution C 5.5% Neem Oil + O%. 30% 40% 60% 70% 90% acetophenone, and 1.25% castor oil by weight. 1.0 mL of each 18.25% solution was applied to one replicate of filter paper, 90 milli Acetophenone metres in diameter, contained in petri dishes (Treated Groups). An untreated Control Group was tested concur rently. All Treated Groups were allowed to dry for four hours prior to infestation with adult bed bugs. Example 6 0090 Bedbug mortality was assessed immediately after infestation and at 2-, 4-, 8-,10-, and 24-hour intervals after Dry Residual Insecticidal Activity infestation. Adult bed bugs were counted dead if they were 0092 Six solutions were prepared, each containing iso unresponsive when stimulated. Table 7 Summarizes the mean propanol as a carrier diluent: Solution A included 5.5% mortality data of all formulations at the stated observation neem oil by weight, 15.5% acetophenone by weight, 1.8% intervals. natural oils (lemongrass oil and wintergreen oil) by weight 0091 Solution C demonstrated significantly higher pesti and 1.25% surfactant by weight; Solution B included 5.5% cidal activity at all observed intervals, than a solution of neem oil by weight, 15.5% acetophenone by weight, and acetophenone alone (Solution B) or neem oil alone (Solution 5.0% surfactant by weight; Solution C included 5.5% neem A). oil alone by weight; Solution D included 15.5% acetophe US 2014/0242199 A1 Aug. 28, 2014 14 none alone by weight: Solution E included 1.8% natural oils example facilitates assessment of the necessary retreatment (lemongrass oil and wintergreen oil) by weight; and Solution interval for a pesticidal composition. A Solution comprising F included 5.5% neem oil by weight and 15.5% acetophe 5.5% neem oil by weight, 15.5% acetophenone by weight, none by weight. 1.0 mL of each solution was applied to filter 8% natural oils (lemongrass oil, spearmint oil, clove oil, and paper, 90 millimetres in diameter, contained in petri dishes wintergreen oil) by weight and 5.0% ethoxylated castor oil by (the Treated Groups). The surfactant used in all solutions was weight was prepared and combined with an appropriate ethoxylated castor oil. Two replicates for each Treated Group amount of isopropyl alcohol as a carrier diluent. 1.0 mL of and two replicates of a negative Control Group were tested each Solution was applied to unpainted plywood Surfaces, 90 concurrently. Treated surfaces were sealed in petri dishes millimetres in diameter, contained in petri dishes. Five repli with a plastic paraffin film and allowed to sit for eight days, cates were done as a Treated Group, and five replicates were then were exposed to the air for four hours, prior to infestation done for an untreated negative Control Group tested concur with a known number of adult bed bugs. rently. All Treated Group substrates were treated at the begin 0093. Immediately after infestation and at 4-8-, 12-, 24-, ning of the experiment, then allowed to air dry until the time 48-, 72-, 96-, 120-, and 144-hour intervals after infestation, of infestation. On Day 1, adult bedbugs were infested either the number of bed bugs killed in the intervening period was immediately after treatment, or two hours after treatment assessed. Adult bed bugs were counted dead if they were (when the substrate was dry). On following days until Day 30, unresponsive when stimulated. The mean percentage of dead adult bed bugs were infested onto replicates of substrates adult bedbugs was calculated for each interval and compared treated on Day 1 and air-dried since. At intervals after infes for efficacy to the data from all other formulations. Table 8 tation of bed bugs each day, the number of bed bugs killed in Summarizes the mean mortality data of all formulations at the the intervening period was counted. Adult bed bugs were stated observation intervals. counted dead if unresponsive when stimulated. 0094 Solutions A, B and F demonstrated a similar level of 0096. The percentage of dead adult bed bugs was calcu activity, and all demonstrated markedly improved dry residue lated for each daily interval and compared for efficacy to the pesticidal activity relative to both neem oil alone (Solution data from the Control Group. Table 9 presents the mean C), acetophenone alone (Solution D), and essential oils alone mortality data for the Treated and Control Groups for up to 27 (Solution E), particularly at earlier time points between 12 days after the Day 1 treatment, at the 15-day observation hours and 120 hours. interval. While the Controls in this experiment exhibited TABLE 8 Mean 90 Mortality of 8-Day Old Residues.

OHR. 4 HR 8 HR 12 HR 24 HR 48 HR 72 HR 96 HR 120 HR 144 HR

Control O.0% O.0% O.0% 0.0% O.0% 0.0% O.0% O.0% O.0% O.0% Solution. A 0.0% 0.0% 10.0% 40.0% 65.0% 75.0% 90.0% 95.0% 95.0% 100.0% Solution B O.0% 0.0%. 10.0%. 25.0% SS.0% 80.0% 90.0% 90.0% 90.0% 90.0% Solution C O.0% 0.0% 0.0% 0.0% 0.0% S.0% S.0% S.0% S.0% S.O% Solution D. O.0% 0.0% S.0% S.0%. 10.0%. 25.0% 45.0% 45.0% 65.0% 80.0% Solution E 0.0% 0.0% 0.0% 0.0% 0.0% 10.0% 10.0% 25.0%. 30.0%. 30.0% Solution F O.0%. 10.0%. 20.0%. 35.0% 65.0% 75.0% 90.0% 100.0% 100.0% 100.0%

Example 7 higher than normal mortality (perhaps because of contami nation of treated Substrates or due to glue epoxy used to seal Prolonged Residual Pesticidal Activity the substrates within petri dishes) the Treated Groups none 0095. This example illustrates the prolonged residual pes theless exhibited significantly improved pesticidal activity ticidal activity of combinations of neem oil, acetophenone, when compared with the Control Groups for treatments up to and a Surfactant against bed bugs. The method used in this 27 days old. TABLE 9 Mean % Mortality of Compositions after Prolonged Dry Times, Observed 15 Days after Infestation Days After Treatment, Prior to Infestation 1 2 3 4 5 6 7 8 9 10 11 12 13 14

% Treated 1OO 100 1OO 100 100 100 100 100 100 100 100 83 97 87 Mortality Group Control 40 57 40 13 23 43 O 23 7 10 30 37 10 O Group Days After Treatment, Prior to Infestation

15 16 17 18 19 2O 21 22 23 24 25 26 27

% Treated 1OO 97 1OO 100 90 87 90 77 NA* 70 90 53 60 Mortality Group US 2014/0242199 A1 Aug. 28, 2014 15

TABLE 9-continued Mean % Mortality of Compositions after Prolonged Dry Times, Observed 15 Days after Infestation Control 19 36 17 32 33 43 50 13 10 24 12 6 37 Group

NA = data not available

Example 8 0100 Table 10 summarizes the prolonged dry residual egg emergence data from a similar study of the same formulation Prevention of Egg Emergence as described above, over alonger period of time. 1.0 mL of the 0097. This example illustrates the prevention of egg emer composition was dried for two hours prior to introduction of gence by a composition including neem oil, acetophenone, bed bug eggs, and completely prevented egg eclosion up to 19 and an appropriate Surfactant. The dry residue prevention of days after its application to a filter paper Substrate. TABLE 10 Mean % Bed Bug Egg Eclosion Observed 15 days after Infestation. Days After Treatment

2 3 4 5 6 7 8 9 1O 11 12 13

% Treated O O O O O O O O O 2 O O O Eclosion Group Control 59 56 39 49 51 33 55 53 66 81 72 70 67 Group Days After Treatment

14 1S 16 17 18. 19 20 21 22 23 24 25

% Treated O O O O O O 7 27 33 NA* 100 100 Eclosion Group Control 100 1OO 99 100 100 100 100 100 97 100 100 100 Group

NA = data not available bed bug egg emergence is compared among different meth Example 9 ods of applying the composition and to an untreated control group. A solution comprising 5.5% neem oil by weight, Prevention of Oviposition and Egg Emergence 15.5% acetophenone by weight, 8% natural oils (lemongrass oil, spearmint oil, clove oil, and wintergreen oil) by weight 0101 This example illustrates the prevention of egg emer and 5.0% ethoxylated castor oil by weight was prepared and gence of a combination of neem oil and acetophenone, as combined with an appropriate amount ofisopropyl alcohol as compared with neem oil alone. a carrier diluent. Three different Treated Groups were pre 0102. A concentrated solution, Solution B. including pared, one of filter paper treated with 1.0 mL of solution and 25% neem oil by weight, 70% acetophenone by weight, and allowed to air dry prior to introduction of eggs, one of filter 5.0% ethoxylated castor oil by weight was prepared. paper with eggs laid on it treated with 1.0 mL of solution 0103 Dilutions of this concentrated solution were pre added to the edge of the substrate and allowed to wick under pared, each containing ethanol as the carrier diluent. Dilu neath the eggs, and one where eggs were sprayed directly. tions containing 15% of Solution B (final concentration of Five replicates for each Treated Group, and five negative 3.75% neem oil and 10.5% acetophenone by weight)—or Control Group were tested concurrently. greater killed 100% of adults infested on the treated surface 0098. At daily intervals, the numbers of hatched and and no eggs were laid. Dilutions of 10% or less of Solution B unhatched eggs present in the sealed dishes were counted and were insufficient to kill adult bed bugs before eggs were laid compared to other Treated Groups and the Control Group. on the treated Substrates in these groups; these dilutions were One egg was counted as "hatched for every new nymph monitored for oviposition and eclosion, and are compared to present in the petri dish when compared with the prior inter positive control treatments of neem oil alone (10% solution in val. diluent) and negative controls treated only with the carrier 0099 While the eggs in the Control Group hatched at the diluent. Formulation A included 10% neem oil by weight predicted interval of approximately 7 days, none of the eggs diluted in ethanol, Formulation B contained 10% by volume in any of the Treated Groups had hatched by experiments end of the concentrated Solution B described above diluted in 16 days post-treatment. No difference was observed between ethanol (final concentration of 2.5% neem oil and 7% spray treatments, wet treatments, and dry residue treatments. acetophenone by weight); Formulation C included 1% by FIG. 1 shows the egg emergence data of the treated groups at volume of the concentrated Solution B (final concentration of the stated daily intervals (the three treated groups having 0.25% neem oil and 0.7% acetophenone by weight); and identical data sets) as compared to the Untreated Control. Formulation D included 0.1% by volume of the concen US 2014/0242199 A1 Aug. 28, 2014

trated Solution B (final concentration of 0.025% neem oil and cinnamon oil, thyme oil, garlic oil, anise oil, geraniol, and 0.07% acetophenone by weight). geranium oil with 5.0% acetophenone by weight resulted in 0104 Table 11 Summarizes egg emergence and oviposi complete prevention of egg eclosion across all observation tion observations for the tested compositions and controls. intervals. Combinations of 2.5% by weight clove oil, eugenol, Oviposition was seen on 10-day-old dry treatments of all the and oregano oil exhibited some increased prevention of egg above solutions and controls, but was significantly reduced on emergence relative to Solutions of ethyl lactate, although the sample treated with a 10% dilution of Solution B (Formu Some egg emergence was observed. Solutions with 2.5% lation B). Eclosion was observed on both negative controls clove oil, eugenol, and oregano oil all exhibited complete and Formulation A (neem oil only) treatments, and on dilu prevention of egg eclosion when combined with 15.5% tions of the concentrated Solution B of 0.1% (Formulation D) acetophenone by weight. Among those tested, the natural oils and lower concentrations. No egg emergence was exhibited that exhibited stronger insecticidal activity on adult bedbugs on dilutions of 1.0% of the concentrated Solution B or more also generally exhibited stronger ovicidal activity and pre (Formulation B and C). Vention of egg emergence. TABLE 11 Eclosion and Oviposition Observations of a Serial Dilution of an Exemplary Composition, Compared with Control and Neem Oil Alone, Observed 10-13 Days after Infestation. 10 Day 11 Day 12 Day 13 Day # eggs # emerged # eggs # emerged # eggs if emerged # eggs # emerged Negative Control 29 O 31 O 31 11 31 11 Formulation A 22 O 23 O 25 8 25 8 (10% Neem Oil) Formulation B 4 O 4 O 4 O 4 O (2.5% Neem Oil + 7% Acetophenone) Formulation C 18 O 19 O 18 O 18 O (0.25% Neem Oil + 0.7% Acetophenone) Formulation D 35 O 36 O 34 9 34 9 (0.025% Neem Oil + 0.07% Acetophenone)

Example 10 TABLE 12 Prevention of Egg Emergence by Various Pesticidal Mean % Eclosion of Formulations Incorporating Various Natural Oils. Natural Oils Pesticidal % Eclosion (3 0105. This example illustrates the prevention of egg emer Natural Oil Solvent Max mortality weeks post-infest.) gence of formulations including a natural oil and acetophe Cinnamon Oil Acetophenone OO% O% none. Solutions were prepared according to Table 12 below, Cinnamon Oil Ethyl Lactate OO% 40% comprising 2.5% by weight active oil ingredient, 5.0% by Clove Oil Acetophenone OO% 20% Clove Oil Ethyl Lactate OO% 80% weight solvent (either ethyl lactate or acetophenone), and an Eugenol Acetophenone OO% 20% appropriate amount of water as a carrier diluent. Treated Eugenol Ethyl Lactate OO% 40% Groups for each solution were prepared by treating filter Oregano Oil Acetophenone OO% 20% paper, 90 mm in diameter, with 1.0 mL of solution and Oregano Oil Ethyl Lactate OO% 40% Thyme Oil Acetophenone OO% O% allowed to air dry for two hours. Five bed bug eggs were Thyme Oil Ethyl Lactate OO% 80% added to each treated dish, two hours after treatment. Imme Garlic Oil Acetophenone 90% O% diately after infestation, and at 1-, 2-, and 3-week intervals Garlic Oil Ethyl Lactate OO% 80% thereafter, the numbers of hatched and unhatched eggs Anise Oil Acetophenone OO% O% Anise Oil Ethyl Lactate 30% 40% present in the sealed dishes were counted and compared to Geranium Oil Acetophenone OO% O% other Treated Groups. One egg was counted as “hatched for Geranium Oil Ethyl Lactate 90% 60% every new nymph present in the petri dish when compared Lime Oil Acetophenone 89% O% with the prior interval. Table 12 compares the mean % egg Lime Oil Ethyl Lactate 45% 80% eclosion of the treated groups at three weeks post-infestation. Peppermint Oil Acetophenone OO% O% Peppermint Oil Ethyl Lactate 55% 60% The maximum mortality data obtained in Example 2, above, Lavender Oil Acetophenone OO% O% are included for each formulation, for comparison purposes. Lavender Oil Ethyl Lactate 40% 80% 0106 All dishes treated with 2.5% by weight natural oils Neem Oil Acetophenone OO% NA** and 5.0% by weight ethyl lactate exhibited some eclosion at Neem Oil Ethyl Lactate 40% NA** all weekly observation intervals (up to 80% eclosion for com Control None 30% 100% binations of ethyl lactate with clove oil, thyme oil, garlic oil, **NA: Test not performed lavender oil, and lime oil). Combinations of 2.5% by weight US 2014/0242199 A1 Aug. 28, 2014

Example 11 every new nymph present in the petri dish when compared with the prior interval. Table 13 compares the 96 egg eclosion Prevention of Egg Emergence with Various Solvents of the treated groups at the 3-week observation interval. The maximum mortality data obtained in Example 3, above, are 0107 This example illustrates the dry residual pesticidal included for comparison purposes. activity of formulations including neem oil and various 0108. A number of the tested organic solvents, from the organic solvents including alcohols, ketones, esters and car classes of alcohols, ketones, esters and carboxylic acids, boxylic acids. Solutions were prepared using 5.5% by weight proved effective at preventing egg eclosion in combination neem oil; the percent by weight of organic solvent indicated with neem oil. Solvents that included at least one aryl group in Table 13 and an appropriate amount of isopropanol as a were generally more effective at preventing egg emergence carrier diluent. Treated Groups for each solution were pre than solvents that contained only alkyl groups. Alkyl aryl pared by treating filter paper, 90 mm in diameter, with 1.0 mL ketones were consistently effective solvents, and Small aryl of solution and allowing it to air dry for four hours. Five eggs alcohols, arylalkyl alcohols, aryl aryl ketones, and alkylaryl were added to each treated dish, four hours after treatment. esters also proved effective at preventing emergence in com Immediately after infestation, and at 1-, 2-, and 3-week inter bination with neem oil. Among those tested, the organic Sol vals thereafter, the numbers of hatched and unhatched eggs vents that exhibited stronger insecticidal activity on adult bed present in the sealed dishes were counted and compared to bugs generally also exhibited stronger ovicidal activity and other Treated Groups. One egg was counted as “hatched for prevention of egg emergence. TABLE 13 % Bed Bug Egg Eclosion Observed 3 Weeks after Infestation. Class of % Solvent Max. % Solvent Formula (wfw) Compound name Mortality Eclosion Alcohol X = CH(OH) Alkyl Alk-X-H alcohols Alk = butyl 11.26 1-Butanol 40% 100% Alk = hexyl 15.52 1-Hexanol 40% O% Alk = ethyl-pentyl 19.78 2-Ethyl-1-hexanol 100% O% (Branched alkyl) Alk = decyl 24.04 1-Decanol 100% O% Isoalcohols Alk-X-Alk Alk = ethyl 11.26 2-Butanol 20% 100% Alk2 = methyl Cyclohexanol 15.21 Cyclohexanol 60% 60% Aryl alcohol Ar-X-H Ar = phenyl 16.42 Benzyl alcohol 100% O% Aryl-alkyl Ar-X-Alk alcohol Ar = phenyl 18.56 1-Phenylethanol 100% O% Alk = methyl Aldehyde and Ketone X = (C=O) Aldehyde Ar-X-H Ar = phenyl 16.12 Benzaldehyde 100% O% Alkyl-Alkyl Alk-X-Alk ketone Alk1 = methyl 19.17 Methylcyclohexylketone 70% 80% Alk = cyclohexyl Cyclohexanone 14.91 Cyclohexanone SO% 40% Aryl-Alkyl Ar-X-Alk ketone Ar = phenyl 18.25 Acetophenone OO% O% Alk = methyl Ar = 4-methylphenyl 20.38 4'-Methylacetophenone OO% O% Alk = methyl Ar = 24- 22.51 2',4'-Dimethylacetophenone OO% O% dimethylphenyl Alk = methyl Ar = 3,4- 22.51 3',4'-Dimethylacetophenone OO% O% dimethylphenyl Alk = methyl Ar = phenyl 20.69 Propiophenone OO% O% Alk = ethyl Ar = 4-methylphenyl 22.51 4-Methylpropiophenone OO% O% Alk = ethyl Ar = phenyl 22.51 Butyrophenone OO% O% Alk = propyl Ar = phenyl 22.51 Isobutyrophenone OO% O% Alk = isopropyl US 2014/0242199 A1 Aug. 28, 2014

TABLE 13-continued % Bed Bug Egg Eclosion Observed 3 Weeks after Infestation. Class of % Solvent Max. % Solvent Formula (wfw) Compound name Mortality Eclosion Ar = phenyl 24.64 Valerophenone 100% O% Alk = butyl Ar = phenyl 26.77 Hexanophenone 100% O% Alk = pentyl Aryl-aryl Ar-X-Ara ketone Ar = 2,4- 37.4 2,2'-44 100% O% dihydroxyphenyl Tetrahydroxybenzophenone Ar = 2,4- dihydroxyphenyl Carboxylic Acids and Esters X = (C=O)—O Alkyl-alkyl Alk-X-Alk ester Alk = methyl 13.38 Ethyl acetate 30% 100% Alk = ethyl Alk = methyl 30.12 2-tert-Butylcyclohexylacetate 100% 20% Alk = 2-tert butylcyclohexyl Aryl acid Ar-X-H Ar = phenyl 18.55 Benzoic acid 100% O% Aryl-alkyl Ar-X-Alk ester Ar = 4-hydroxyphenyl 27.27 Propyl-4-hydroxybenzoate 100% O% Alk = propyl

Example 12 1.25% ethoxylated castor oil by weight%. 18.25% acetophe none by weight, and water as a carrier solvent; and Solution Insecticidal Knockdown Activity F included 0.3% azadirachtin A by weight, 1.25% ethoxy lated castor oil by weight, and water as a carrier solvent. Adult 0109. This example illustrates the insecticidal knockdown bed bugs were infested on to petri dishes containing filter activity of combinations of neem oil or derivatives thereof paper, 90 millimetres in diameter. Bedbugs were treated by with acetophenone against bed bugs, when compared with applying 5 microliters of each solution to the Ventral side. knockdown activity of neem oil or derivative alone and Mortality was assessed at intervals of 30 minutes, and 1-, 2-, acetophenone alone. Six solutions were prepared: Solution 4-, 6-, 8-,10-, 24-, 100-, and 342-hours after treatment. Bed A included 5.5% neem oil by weight, 1.25% ethoxylated bugs were counted dead if unresponsive when stimulated. castor oil by weight and 18.25% acetophenone by weight, and The percentage of dead adult bed bugs was calculated and isopropanol as a carrier solvent; Solution B included 5.5% compared to data from all other formulations. Table 14 sum neem oil by weight, 1.25% ethoxylated castor oil by weight, marizes mortality data of respective formulations at the stated 18.25% acetophenone by weight, and water as a carrier sol intervals. vent; Solution C included 5.5% neem oil by weight, 1.25% 0110. The neem/acetophenone (Solutions A and B) and ethoxylated castor oil by weight, and water as a carrier Sol azadirachtin/acetophenone (Solution C) combinations per vent; Solution D included 18.25% acetophenone by weight, formed better as knockdown killers than neem alone (Solu 1.25% ethoxylated castor oil by weight, and water as a carrier tion D), acetophenone alone (Solution E), and azadirachtin solvent; Solution Fincluded 0.3% azadirachtin Aby weight, alone (Solution F). TABLE 1.4

% Mortality of Neem Oil and Azadirachtin as Knockdown Killers of Adult Bed Bugs.

Time (hours)

O O.S 1 2 4 6 8 10 24 100 342

% Mortality Solution A (5.5% neem oil, O 80 80 80 8O 90 90 100 100 100 100 18.25% acetophenone, 75% isopropanol) Solution B (5.5% neem oil, 18.25% O 60 60 60 60 7O 8O 8O 90 80 100 acetophenone, 75% water) Solution C (0.3% azadirachtin A, O 30 30 30 30 40 7O 80 100 100 100 18.25% acetophenone, 80.2% water) US 2014/0242199 A1 Aug. 28, 2014 19

TABLE 14-continued %. Mortality of Neem Oil and Azadirachtin as Knockdown Killers of Adult Bed Bugs. Time (hours

O O.S 1 2 4 6 8 10 24 100 342 Solution D (5.5% neem oil, O 3O 40 40 SO SO SO SO SO 6O SO 93.25% water) Solution E (18.25% O 40 40 40 40 40 40 40 30 30 100 acetophenone, 80.5% water) Solution F (0.3% azadirachtin A, O O O O O O O O O O 10 98.45% water) Water O O O O O O O O O O O Untreated Control O O O O O O O O O O O

Example 13 TABLE 1.5 Broad Spectrum Pesticide Activity Mean 90 Mortality of 2-Hour Dried Compositions Against Arthropods. Mean 90 Mortality 0111. This example illustrates the dry residue pesticidal activity of a combination of natural oil and solvent against Insect reated/Control Ohrs 1 hrs 4 hrs 24 hrs arthropods (including insects) other than bedbugs. The tested Smoky Brown cockroach Treate O O 45 OO arthropods were German cockroach (Blattella germanica), Silsby reach E. g g o Smoky Brown cockroach (Periplanetafuliginosa). American German cockroach Contro O O O O cockroach (Periplaneta americana), cellar spider (Pholcus American cockroach Treate O O 66 OO phalangiodes) cat flea (Ctenocephalides felis), tick (Ixodidea Ackroach Contro O O O O family), fire ant (Solenopsis Invicta), termite (Reticulitermes la R (N, g 3. flavipes), black carpenterant (Camponotus pennsylvanicus), Cat Flea Treate O OO 100 OO pavement ant (Tetramorium caespitum), field ant (Formica Cat Flea Contro O O O O sp.), moisture ant (Lasius sp.), wood ant (Formica rufa), Tick Treate O 7 100 OO Tick Contro O O O O house fly (Musca domestica), bottle fly (Lucilia sericata), Fiire Ant (8c O OO OO OO giant silverfish (Ctenolepisma longicaudata), firebrat (Ther- Fire Ant Contro O O 10 OO mobia domestica), bean aphid (Aphis fabae), and pea aphid Termite Treate O OO 100 OO (Acyrthosiphon pisum). A solution of 5.5% neem oil by CNN An Contro g 18 . 3. weight, 15.5% acetophenone- - - - by weight, 2.65% natural oils arpenterE. Antt Contro(8c O O O O (lemongrass oil, Vanillin, and wintergreen oil) by weight and Pavement Ant Treate O OO 100 OO 1.25% ethoxylated castor oil by weight was combined with an Pavement Ant Contro O O O O appropriate amount of isopropyl alcohol as a carrier diluent. Field Ant Treate O OO 100 OO Field Ant Contro O O O O 1.0 mL of the solution was applied to filter paper surfaces, 90 Moisture Ant Treate O OO 100 OO millimetres in diameter, contained in petridishes (the Treated Moisture Ant Contro O O O 70 Groups). Untreated Control replicates were tested concur- Wood Ant Treate O OO 100 OO rently. Treated substrates were allowed to air dry for two y Contro O O O O hours prior to infestation with a known number of adult East ER (N, g s o . arthropods. Dishes were infested according to the following Bottle Fly Treate O 95 100 OO schedule: three replicates of three adults apiece were pre- Bottle Fly Contro O O O O pared for American and Smoky Brown cockroaches; three Giant Silverfish Treate O O 22 OO replicates of five adults apiece were prepared for German GiantFirebrat Silverfish ControTreate O O 40O OOO cockroaches; nine replicates of one adult apiece were pre- Firebrat Contro O O O O pared for cellar spiders; and three replicates of 10 adults Bean aphid Treate O 10 25 OO apiece were prepared for ticks, ants, termites, flies, aphids, s Contro g g 5. silverfish, firebrats, and cat fleas. At 1-, 4-, and 24-hour inter- N.d t O O O 33 vals following the addition of arthropods, the number of arthropods killed in the intervening period was observed. The adult arthropods were counted dead if they were unresponsive when stimulated. Example 14 0112 The percentage of dead adult arthropods was calcu Dry Residual Pesticide Activity Against lated for 1-, 4-, and 24-hour intervals following infestation Insecticide-Resistant Insects and compared for efficacy to the data of the Control Groups. Table 15 summarizes the mean mortality data of the treatment 0113. This example illustrates the dry residue pesticidal against each arthropod at the Stated intervals. The tested com activity of exemplary compositions against bedbugs resistant position killed 100% of all arthropods by the 24-hour obser to pyrethroid insecticides, a recognized problem in eliminat Vation interval, and exhibited strong pesticidal activity ing bedbug infestations (see Romero). A formulation of 5.5% against Some species at the 4-hour observation interval. neem oil by weight, 15.5% acetophenone by weight, 8% US 2014/0242199 A1 Aug. 28, 2014 20 natural oils (lemongrass oil, spearmint oil, clove oil, and wintergreen oil) by weight and 5.0% surfactant by weight; wintergreen oil) by weight and 5.0% ethoxylated castor oil by Solution B included 5.5% neem oil by weight, 15.5% weight was prepared and combined with an appropriate acetophenone by weight, and 5.0% surfactant by weight; amount of isopropyl alcohol as a carrier diluent (the Treated Solution C included 5.5% neem oil by weight, and 5.0% Group). A concentrate formulation of the common pyrethroid surfactant by weight; and Solution D included 5.5% neem insecticide SuspendR SC containing 4.75% deltamethrin by oil alone by weight. The Surfactant used in all solutions was weight diluted according to the highest (strongest) rate ethoxylated castor oil. Ninety-millimetre diameter filter paper Substrates were prepared in petridishes, on which were allowed by the label was employed as a Positive Control affixed small wooden blocks notched on one side, the notch Group. 1.0 mL of each solution was applied to filter paper forming a small crevice out of contact with the filter paper surfaces, 90 millimetres in diameter, contained in petridishes, where insects could shelter. For the Treated Groups 1.0 mL of and allowed to dry for two hours. Five replicates of each each solution was applied to the exterior of the block, leaving Treated Group, Positive Control Group, and a Negative Con the crevice untreated, and 1.0 mL of each solution was trol Group were tested concurrently. Adult bed bugs from a applied directly to the filter paper substrate. A fifth untreated field-collected strain were added to each treated surface. Mor group was tested concurrently as a negative Control Group. tality of bed bugs was observed at specified intervals after Treated substrates were allowed to dry for two hours before infestation on substrates. The adult bed bugs were counted infestation with adult bed bugs. dead if they were unresponsive when stimulated. 0117 Immediately after treatment and at 1-, 4-, and 8-hour intervals after infestation of bed bugs to each group, the bed 0114. The percentage of dead adult bed bugs at 0-,1-, 4-, bugs were observed for mortality and whether they preferred 8-, 12-, 24-, and 72-hour intervals on Treated Group were to stay on the treated filter paper, or locate within the compared against those infested on the Positive Control (del untreated crevice. Table 16 Summarizes the observations of tamethrin-treated) and Negative Control Groups. FIG.2 sum each Group immediately after infestation and at 1-, 4-, and marizes the results as tested on filter paper. Bedbugs infested 8-hour intervals post-infestation. Compositions A and B, on deltamethrin (Positive Control Group) exhibited mean which included neem oil in combination with acetophenone, mortality of 10% by the 72-hour interval, which was statisti exhibited a lesser degree of repellency (i.e. fewer bed bugs cally insignificant in comparison with Negative Controls. The were counted in the untreated crevice) than compositions tested formulation including neem oil and acetophenone pro including neem oil alone, with or without Surfactant (compo duced 100% mortality by the 24-hour interval. sitions C and D). TABLE 16 Mean Repellency Data. 0-hour 1-hour 4-hour 8-hour

% % % % % % % Live Live Live 96 Live Live Live Live Live In Out In Out % In Out % In Out % Solution Crew. Crew. Crew. Crew. Dead Crew. Crew. Dead Crew. Crew. Dead

A. O 1OO O 1OO O O 22 78 O O 100 B O 1OO 10 90 O O O 1OO O O 100 C O 1OO 40 60 O 70 30 O 2O 10 70 D O 1OO 100 O O 8O 2O O 60 O 40 Control O 1OO 50 50 O 50 50 O 60 40 O

Example 15 Example 16 Repellency of Exemplary Compositions Testing of Various Substrates 0118. This example illustrates the pesticidal activity of a 0115 This example illustrates the repellency characteris composition according to an exemplary embodiment on a tics of an exemplary composition according to one embodi variety of Surfaces. In particular, the example demonstrates ment. Where it is desired to have an insecticide act by killing the dry residue pesticidal activity of an exemplary formula or otherwise disrupting the life cycle of adult insects, nymphs, tion on several substrates where bed bugs are known to live, and their eggs, rather than merely dispersing them, repellent nest, and reproduce indoors. A Solution including 5.5% neem characteristics of the composition utilized may be reduced or oil by weight, 15.5% acetophenone by weight, 8% natural oils minimized in some embodiments. (lemongrass oil, spearmint oil, clove oil, and wintergreen oil) 0116. In this example, bedbug mortality was evaluated on by weight and 5.0% ethoxylated castor oil by weight was a treated Surface with an untreated crevice harbourage avail prepared and combined with an appropriate amount of iso able, and the percentage of bed bugs that retreated to the propyl alcohol as a carrier diluent. Four substrates were pre untreated crevice was measured to evaluate the repellency of pared: painted plywood, 100% cottonfabric, mattress swatch, the tested compositions. Four Solutions were prepared, each and Berber carpet (glued to the petri dish to prevent the test containing isopropanol as a carrier diluent: Solution A bugs from climbing underneath the carpet to escape the included 5.5% neem oil by weight, 15.5% acetophenone by treated area). Five replicates were constructed for each weight, 8% natural oils (lemongrass oil, spearmint oil, and Treated Group and five replicates were constructed for US 2014/0242199 A1 Aug. 28, 2014

untreated Control Groups of each substrate. 1.0 mL of the maximum 96 mortality of all treated groups and the time taken formulation was applied to each Treated Group and allowed to reach maximum mortality. Combinations of a pesticidal oil to dry for two hours. Adult bedbugs were infested two hours and acetophenone were more effective than either the oil or after treatment. Bedbugs were observed for mortality imme acetophenone alone. diately after infestation and at 1-, 4-, 8-, 12-, 24-, and 72-hour intervals post-infestation. Bed bugs were counted dead if TABLE 1.8 unresponsive when stimulated. 0119 The percentage of dead adult bed bugs was calcu Maximum 90 Mortality of Various Oils Alone or With Acetophenone lated for each interval and compared to the data for all other Solvent Max groups. Table 17 presents the mean mortality data for the Oil Solvent % w/w Mortality Time LTSO Treated and Control Groups over the stated intervals. Mortal ity of adult bed bugs for all Treated Groups was 100% at 24 Oil Controls hours and 100% for all treated surfaces excepting glued car Oregano oil — 100% 72 18 h pet (80% mortality) at 12 hours. This data indicates efficacy Clove oil 100% S3 17 Cinnamon 90% 218 h 22h of the tested composition on a wide range of indoor Surfaces. oil Oil + Acetophenone TABLE 17 Oregano oil Acetophenone 18.25 100% 24h 6h Mean 90 Bed Bug Mortality after Treatment on Various Substrates. Clove oil Acetophenone 18.25 100% 24h 8h Cinnamon Acetophenone 18.25 100% S3 8h Time (Hours oil Acetophenone 18.25 100% S3 17 O 1 4 8 12 24 72

Untreated O 2 6 4 4 6 6 Plywood Treated O 2 58 98 100 1OO 100 Example 18 Plywood Untreated O O 2 2 6 8 16 Residual Activity of Various Oils in Combination Cotton Treated O 28 82 1OO 100 1OO 100 with Acetophenone Cotton Untreated O 2 2 4 4 4 12 I0121 This example illustrates the dry residual pesticidal Mattress activity of formulations comprising further pesticidal natural Treated O 42 98 1OO 100 1OO 100 oils (thyme, garlic and neem oils) with acetophenone as the Mattress Untreated O O O O O O O polar aromatic solvent. Solutions were prepared using 5.5% Glued Carpet by weight natural oil; the percentage by weight of organic Treated Glued O O O 30 8O 1OO 100 solvent indicated in Table 19 and an appropriate amount of Carpet isopropanol as a carrier diluent. Solvent was added to a final concentration of 1.5 mol/kg. Solutions were also prepared of each natural oil alone (5.5% by weight with an appropriate Example 17 amount of isopropanol as a carrier diluent), and of the polar organic solvent alone (the percent by weight indicated in Residual Activity of Various Solvent/Oil Table 19 with an appropriate amount of isopropanol as a Combinations carrier diluent). Treated Groups for each solution were pre pared by treating filter paper, 90 mm in diameter, with 1.0 mL 0120. This example illustrates the dry residual pesticidal of solution and allowing it to air dry for four hours. A known activity of formulations comprising varying pesticidal natural number of adults (usually 10) were added to each treated dish, oils (oregano, clove and cinnamon oils) with acetophenone as four hours after treatment. Bedbug mortality was assessed the polar aromatic solvent. Solutions were prepared using immediately after infestation and at 1-hour, 2-hour, 4-hour, 5.5% by weight natural oil; the percent by weight of 6-hour, 8-hour, 10 hour, 12-hour, and 24-hour intervals, and at acetophenone indicated in Table 18 and an appropriate 24-hour intervals thereafter until 14 days after infestation. amount of isopropanol as a carrier diluent. The percent by Adult bed bugs were counted dead if they were unresponsive weight of Solvent was at a final concentration of 1.5 mol/kg. when stimulated. Table 19 shows the maximum '% mortality Solutions were also prepared of each natural oil alone (5.5% of all treated groups and the time taken to reach maximum by weight with an appropriate amount of isopropanol as a mortality. Combinations of a pesticidal oil and acetophenone carrier diluent), and of acetophenone alone (the percent by were more effective than either the oil or acetophenone alone. weight indicated in Table 18 with an appropriate amount of isopropanol as a carrier diluent). Treated Groups for each TABLE 19 solution were prepared by treating filter paper, 90 mm in diameter, with 1.0 mL of solution and allowing it to airdry for Maximum 90 Mortality of Various Oils Alone or With Acetophenone four hours. A known number of adults (usually 10) were Solvent Max added to each treated dish, four hours after treatment. Bedbug Oil Solvent % w/w Mortality Time LTSO mortality was assessed immediately after infestation and at 1-hour, 2-hour, 4-hour, 6-hour, 8-hour, 10 hour, 12-hour, and Oil Controls 24-hour intervals, and at 24-hour intervals thereafter until 14 Oregano oil — 100% 24h 8h days after infestation. Adult bed bugs were counted dead if Clove oil 100% 1SO 27 they were unresponsive when stimulated. Table 18 shows the US 2014/0242199 A1 Aug. 28, 2014 22

TABLE 19-continued phyllata (Syzigium aromaticum L. Myrtaceae): a short review” (2007) 21:6 Phytotherapy Research 501-506. Maximum 90 Mortality of Various Oils Alone or With Acetophenone 0148 Chang, K. S. and Ahn, Y.T., “Fumigant activity of Solvent Max (E)—anethole identified in Illicium verum fruit against Oil Solvent % w/w Mortality Time LTSO Blattella germanica’ (2001) 58 Pest Manage. Sci. 161 166. Cinnamon 100% 1SO 37h oil 0149 Chang, S.T. and Cheng, S.S., “Antitermitic activity Thyme 100% 1SO 36h of leaf essential oils and components from Cinnamomum Garlic 100% 1SO 22h osmophleum” (2002) 50 J. Agric. Food Chem. 1389–1392. Neem oil 10% 0150 Cheng, S. S., et al., “Variations in insecticidal activ Oil + Acetophenone ity and chemical compositions of leaf essential oils from Thyme Acetophenone 18.25 100% 10 h. 6h Cryptomeria japonica at different ages” (2009) 100:1 Garlic Acetophenone 18.25 100% 10 h. 7h Bioresource Tech. 465-470. Neem oil Acetophenone 18.25 100% 8h 4h 0151. 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0165 Hummelbrunner, A. L. and Isman, M. B., "Acute, mum suvae (wild) against four species of stored product Sublethal, antifeedant and synergistic effects of monoter coleopteran” (1997) 43 Int. J. Pest Manag. 89-94. penoid essential oil compounds on the tobacco cut worm 0182 Pavela, R., Kazda, J., & Herda, G., “Effectiveness of (Lepidoptera: Noctuidae) (2001) 49J. Agric. Food Chem. Neem (azidirachta indica) insecticides against Brassica 715-720. pod midge (Dasimera brassicae Winn.) (2009) 82:3 Jour 0166 Jones, C. & Firn, R. “Some Allelochemicals of nal of Pest Science 235. Ptteridium quilinum and their Involvement in Resistance to 0183 Perrucci, S., Cioni, P. L., Cascella, A., Macchioni, Pieris brassicae'' (1979) 7 Biochem. Syst. Ecol. 187. F., “Therapeutic efficacy of linalool for the topic treatment 0167 Karr, L. L. and Coats, J. R. “Effects of four monot of parasitic otitis caused by Psoroptes cuniculi in the rabbit erpenoids on growth and reproduction of the Germancock and in the goat' (1997) 11 Med. Vet. Entomol. 300-302. roach (Blattodea: Blattellidae)” (1992) 85 J. Econ. Ento 0.184 Rahman, A & Talukder, FA, “Bioefficacy of somer mol. 424-429. plant derivatives that protect grain against the pulse beetle, 0168 Kaul, P.N., et al., “Volatile constituents of essential Callosobruchus maculatus” (2006) 6:3 Journal of Insect oils isolated from different parts of cinnamon (Cinnamo Science. mum zeylanicum Blume), (2003) 83 J. Sci. Food Agri. 0185. Rajeswara Rao, B. R., et al., “Volatile flower oils of 53-55. three genotypes of rose-scented geranium (Pelargonium (0169. Khattak, M. K. “Repellancy and residual effect of sp.) (1999) 15 Flavour Frag. J. 105-107. neem or mineral oil on the distribution and oviposition of 0186 Romero, A, et al., “Insecticide Resistance in the Bed maize weevil, Sitophilus zeamus Motsch (2000) 3 Paki Bug: A Factor in the Pests Sudden Resurgence' (2007) stan Journal of Biological Sciences 2131-2134. 44:2J Med Entomol 175. (0170 Kim E. H. Kim HK, Ahn Y.J., “Acaricidal activity of 0187 Salom, S. M., et al., “Laboratory Evaluation of Bio clove bud oil compounds against Dermatophagoides fari logically-Based Compounds as Antifeedants for the Pales nae and Dermatophagoides pteronyssinus (Acari: Pyro Weevil, Hullobius–Pales (Herbst)' (1994) 29 J. Entomol. glyphidae)” (2003) 51 J Agric Food Chem 885-889. Sci. 407. 0171 Kimbaris, A. C., et al., “Quantitative analysis of 0188 Samarasekera, R. “Mosquitocidal Activity of Leaf garlic (Allium sativum) oil unsaturated acyclic components and Bark Essential Oils of Ceylon Cinnamomum zeylani using FT-Raman spectroscopy” (2006) 94.2 Food Chem cum” (2005) 17:3 Journal of Essential Oil Research 301 istry 287-295. 3O3. 0172 Lee, S., Tsao, R., Peterson, C. and Coats, J. R. (0189 Santos, P. M., et al., “Essential oils from hairy root “Insecticidal activity of monoterpenoids to western corn cultures and from fruits and roots of Pimpinella anisum’ root worm (Coleoptera: Chrysomelidae), spotted spider (1998) 48 Phytochemistry 455-460. mite (Acari: Tetranychidae) and Housefly (Diptera: Mus 0190. Schumutter, H., “Properties and potential of natural cidae) (1997) 90 J. Econ. Entomol. 883-892. pesticides from the neem tree, Azadirachta indica’ (1990) (0173 Lota, M.-L., et al., “Volatile Components of Peel 35 Annu Rev Entomol 271. and Leaf Oils of Lemon and Lime Species” (2002) 50 J. 0191 Shabnum S. Wagay M.. “Essential Oil Composi Agri. Food Chem. 796-805. tion of Thymus Vulgaris L. and their Uses” (2011) Journal 0.174 Marcus, C. & Lichtenstein, P., “Biologically Active of Research & Development, Vol. 11 Components of Anise: Toxicity and Interactions with (0192. Shellie R, Mondello L, Marriott P. Dugo G., “Char Insecticides in Insects” (1979) 27:6 J. Agri. Food Chem. acterisation of lavender essential oils by using gas chro 1217. matography-mass spectrometry with correlation of linear (0175 Miresmailli, S., Bradbury, R. and Isman, M. B., retention indices and comparison with comprehensive "Comparative toxicity of Rosmarinus officinalis L. essen two-dimensional gas chromatography” (2002) 970 J. tial oil blends of its major constituents against Tetranychus Chromatogr. A. 225-234. urticae Koch (Acari: Tetranychidae) on two different host 0193 Simic, A., et al., “The Chemical Composition of plants” (2006) 62 Pest Manag. Sci. 366-371. some Lauraceae Essential Oils and Their Antifungal 0176 Mishra, A K, et al. “Use of neem oil as a mosquito Activities” (2004) 18 Phytother. Res. 713-717. repellent in tribal villages of mandla district, madhya 0194 Thompson, J. et al., “Qualitative and quantitative pradesh' (1995) 32:3 Indian J Malariol 99-103. variation in monoterpene co-occurrence and composition (0177 Momen, FM, et al., “Influence of Mint and Pepper in the essential oil of Thymus vulgaris chemotypes” (2003) minton Tetranychus urticae and Some Predacious Mites of 29 J. Chem. Ecol. 859. the Family Phytoseiidae (Acari: Tetranychidae: Phytosei 0.195 Toncer. O., et al., “Changes in Essential Oil Com idae) (2001) 36 position of Oregano (Origanum onites L.) due to Diurnal 0.178 Acta Phytopathologica et Entomologica Hungarica Variations at Different Development Stages” (2009) Notu 143-153. lae Botanicae Horti Agrobotanici Cluj 37 (2), 177-181. (0179 Naovi, S N H, et al., “Comparative Toxicity of R 0196. Traboulsi, A. F., et al., “Insecticidal properties of B-A Neem Formulation and Malathion Against Bed essential plant oils against the mosquito Culex pipiens Bugs' (1993) 13 Proceedings of Pakistan Congress of molestus (Diptera: Culicidae) (2002) 58:5 Pest Manag. Zoology 369. Sci. 491-495. 0180 National Research Council, Board on Science and 0.197 Tripathi, A. K., et al., Effects of volatile oil constitu Technology for International Development, Ad Hoc Panel ents of Mentha species against stored grain pests, Calloso Report, Neem: A Tree for Solving Global Problems (Wash brunchus maculatus and Tribolium castanum' (2000) 22 J. ington: National Academy Press, 1992). Med. Arom. Plant Sci. 549-556. 0181. Obeng-Ofori, D. and Reichmuth, C. H., “Bioactiv 0198 Tripathi, A. K., Prajanpati, V., Aggarwal, K. K. and ity of eugenol, a major component of essential oil of Oci Kumar, S., “Toxicity, feeding deterrence, and effect of US 2014/0242199 A1 Aug. 28, 2014 24

activity of 1,8-cineole from Artemisia annua on progeny sp.), moisture ants (Lasius sp.), wood ants (Formica rufa), production of Tribolium castanaeum (Coleoptera: Tenebri house flies (Musca domestica), bottle flies (Lucilia sericata), onidae)” (2001) 94.J. Econ. Entomol. 979-983. giant silverfish (Ctenolepisma longicaudata), firebrats (Ther 0199 Trongtokit Y. Rongsriyam Y. Komalamisra N, Api mobia domestica), bean aphids (Aphis fabae), and/or pea wathnasorn C. “Comparative repellency of 38 essential aphids (Acyrthosiphon pisum). oils against mosquito bites” (2005) 19 Phytother Res 303 158. A composition as defined in claim 154 wherein the 3.09. arthropods comprise bedbugs, German cockroaches, Ameri 0200 Vasudeva, N. & Sharma, T., "Chemical Composi can cockroaches, Smoky-brown cockroaches, Oriental cock tion and Antimicrobial Activity of Essential Oil of Citrus roaches, house flies, biting flies, filth flies, red imported fire limettoides Tanaka' (2012) 1 Jour. Of Pharm. Tech. & ants, odorous house ants, carpenterants, pharaoh ants, Argen Drug Res. tine ants, mosquitoes, ticks, fleas, Sowbugs, pillbugs, centi 0201 Vokou, D, et al., “Geographic variation of Greek pedes, spiders, silverfish, Scorpions, cockroaches, whiteflies, Oregano (Origanum vulgare ssp. hirtum) essential oils' mosquitoes, flies, aphids, Scabies, lice, Stink bugs, moths, (1993) 21 Biochem. Syst. Ecol. 287-295. beetles, lace bugs, green peach aphids, western floral thrips, 0202 Webb et al. On the penetration of insecticides diamondback moths, leafminers, grasshoppers, crickets, through the insect cuticle (Cooper Technical Bureau: locusts, leafhoppers, planthoppers, psyllids, Scale insects, Berkhamsted, 1945). midges, houseflies, fruit flies, earworms, bollworms, army 0203 Xia, Y, et al., “The molecular and cellular basis of worms, budworms, hornworms, milkweedbugs, mealy bugs, olfactory-driven behaviour in Anopheles gambiae larvae' weevils, botflies, face flies, sawflies, rice bugs, coffee bugs, (2008) 105 Proceedings from the National Academy of vegetable bugs, corn borers, horn flies, blowflies, or mites. Sciences 6433-6438. 159. A composition as defined in claim 153, wherein the 0204 Yang Y C, Lee S H, Lee W J, Choi D H, Ahn Y J, polar aromatic solvent is selected from the group consisting “Ovicidal and adulticidal effects of Eugenia caryophyllata of aryl ketones, aryl alcohols, aryl-alkyl alcohols, aryl alde bud and leaf oil compounds on Pediculus capitis” (2003) hydes, aryl-alkyl ketones, aryl-aryl ketones, aryl carboxylic 51 J Agri. Food Chem. 4884-4888. acids, aryl esters, aryl-alkyl esters, aryl-aryl esters, aryl-alkyl 0205 Yang, Y.C., Lee, H. S. Lee, S. H., Clark, J. M., Ahn, ethers, and aryl-aryl ethers. Y.J., “Ovicidal and adulticidal activities of Cinnamomum 160. A composition as defined in claim 153, wherein the zeylanicum bark essential oil compounds and related com polar aromatic solvent comprises a compound having the pounds against Pediculus humanus capitis (Anoplura: Structure: Pediculidae)” (2005) Int. J. Parasitol 0206. The invention described herein is not to be limited in Scope by the specific aspects herein disclosed, since these (I) aspects are intended as illustrations of several aspects of the invention. Any equivalent aspects are intended to be within the scope of this invention. Various modifications of embodi ments of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims and any claims hereafter introduced. To the extent that they are not mutually exclusive, embodiments described above can be combined with one another to yield further embodi wherein R can be: ments of the invention. 1-152. (canceled) OH O O 153. A pesticidal composition for controlling pests, the composition comprising a pesticidal natural oil and/or a com -O-R- -k Rs ul us R ponent thereof and/or a derivative thereof; and a polar aro R7 R7 O1 matic solvent or an alkyl alcohol solvent. 154. A composition as defined in claim 153, wherein the and wherein R. R. R. Rs and R can independently be —H. pests comprise arthropods. or an alkyl group, alkenyl group or alkynl group, including a 155. A composition as defined in claim 154, wherein the methyl, ethyl, propyl, isopropyl, butyl, or pentyl group, or an arthropods comprise insects, arachnids or centipedes. —OH group or a halo functional group, oran alkyl, alkenyl or 156. A composition as defined in claim 155, wherein the alkynyl group including an alcohol, halo or other polar func insects are of the orders Hemiptera, Hymenoptera, Blattodea, tional group; and wherein R, and Rs can independently be Isoptera, Diptera or Lepidoptera. —H or an alkyl group, including a methyl, ethyl, propyl. 157. A composition as defined in claim 154, wherein the isopropyl, butyl, or pentyl group, or an aromatic group; and arthropods comprise bed bugs (Cimex lectularius), German wherein R, and Rs can optionally have other Substituents; and cockroaches (Blattella germanica), Smoky brown cock wherein R. R. R. Rs and/or R can optionally have other roaches (Periplaneta fuliginosa), American cockroaches Substituents. (Periplaneta americana), cellar spiders (Pholcus phalang 161. A composition as defined in claim 153 wherein the iodes), cat fleas (Ctenocephalides felis), ticks (Ixodidea fam polar aromatic solvent or alkyl alcohol solvent comprises ily), fire ants (Solenopsis invicta), termites (Reticulitermes acetophenone, 2-ethyl-1-hexanol. 1-decanol. 2-propanol, flavipes), black carpenterants (Camponotus pennsylvanicus), cyclohexanol, benzyl alcohol. 1-phenylethanol, benzalde pavement ants (Tetramorium caespitum), field ants (Formica hyde, methylcyclohexylketone, cyclohexanone, 4'-methylac US 2014/0242199 A1 Aug. 28, 2014

etophenone, 2',4'-dimethylacetophenone, 3',4'-dimethylac aldehyde, alpha-terpineol, alpha-terpinene, gamma-ter etophenone, propiophenone, 4'-methylpropiophenone, pinene, terpinen-4-ol, and beta-myrcene. butyrophenone, isobutyrophenone, Valerophenone, 4'-hy 168. A composition as defined in claim 153, wherein the droxyvalerophenone, hexanophenone, 2,2'-4.4" tetrahy pesticidal natural oil and/or component thereofand/or deriva droxybenzophenone, 2-tert-butylcyclohexylacetate, cyclo tive thereof comprises palmitoleic acid, alpha-linolenic acid, hexyl phenyl ketone, isobutyl benzoate, dibenzyl ether, Stearic acid, palmitic acid, oleic acid, linoleic acid, campes benzoic acid, propyl-4-hydroxybenzoate, 1-nonanol. 1-dode terol, beta-sitosterol, Stigmasterol, azadirachtin, meliantriol, canol. 2-butyl-1-octanol, 2-hexyl-1-decanol, 2-octanol, 3,4- melianone, gedunin, amoorastatin, Vepinin, marrangin, dimethylbenzyl alcohol, alpha-4-dimethylbenzyl alcohol, Vilasinin, nimbin, nimbidin, nimbolide, nimbolinin, ohchino 2-phenyl-2-propanol, p-tolualdehyde, 2-hydroxy-5-methyl lide, nimbolinin, Salannin, meliacarpin, meliacquinal, nimban diol, nimbinene, nimbocinone, kulactone, limocinol, limoci benzaldehyde, 4'-hydroxyacetophenone, 2'-hydroxyac none, nimolinone, azadirachnol, or other triterpenoids, etophenone, 4-hydroxybenzoic acid, 4-hydroxy-3-methyl azadirone, azadiradione, azadirachtol, and/or epoxyazadira benzoic acid, ethylbenzoate, benzylbenzoate, phenol, benzyl dione. methyl ether, butyl phenyl ether, trans-anethole, or diphenyl 169. A composition as defined in claim 160, wherein the ether. pesticidal natural oil comprises one or more of neem oil, 162. A composition as defined in claim 153, wherein the oregano oil, clove oil, cinnamon oil, thyme oil or garlic oil. pesticidal natural oil comprises one or more of neem oil, 170. A composition as defined in claim 161, wherein the cinnamon oil, clove oil, eugenol, oregano oil, thyme oil, pesticidal natural oil comprises one or more of neem oil, garlic oil, anise oil, geranium oil, lime oil, peppermint oil or oregano oil, clove oil, cinnamon oil, thyme oil or garlic oil. lavender oil. 171. A composition as defined in claim 153 for preventing 163. A composition as defined in claim 153, wherein the egg eclosion, wherein the pesticidal natural oil comprises one pesticidal natural oil and/or component thereofand/or deriva or more of neem oil, cinnamon oil, clove oil, eugenol, oregano tive thereof comprises thymol, p-cymene, 1,8-cineole, oil, thyme oil, garlic oil, anise oil, geranium oil, lime oil, eugenol, limonene, C-pinene, carvacrol, gamma-terpinene, peppermint oil or lavender oil, and wherein the polar aromatic geraniol, alpha-terpineol, beta-caryophyllene, or linalool. Solvent comprises an aryl ketone. 164. A composition as defined in claim 153, wherein the 172. A composition as defined in claim 153 for preventing pesticidal natural oil comprises any oil having as a major egg eclosion, wherein the pesticidal natural oil comprises one active constituent one or more of azadirachtin, nimbin, nim or more of neem oil, cinnamon oil, clove oil, eugenol, oregano binin, Salannin, gedunin, geraniol, geranial, gamma-ter oil, thyme oil, garlic oil, anise oil, geranium oil, lime oil, pinene, alpha-terpineol, beta-caryophylene, terpinen-4-ol. peppermint oil or lavender oil, and wherein the polar aromatic myrcenol-8, thuyanol-4, benzyl alcohol, cinnamaldehyde, Solvent or alkyl alcohol solvent comprises acetophenone, cinnamyl acetate, alpha-pinene, geranyl acetate, citronellol, 1-hexanol, 2-ethyl-1-hexanol. 1-decanol, cyclohexanol, ben citronellyl formate, isomenthone, 10-epi-gamma-eudesmol. Zyl alcohol. 1-phenylethanol, benzaldehyde, cyclohexanone, 1,5-dimethyl-1-vinyl-4-hexenylbutyrate, 1,3,7-octatriene, 4'-methylacetophenone, 2',4'-dimethylacetophenone, 3',4'- eucalyptol, camphor, diallyl disulfide, methylallyl trisulfide, dimethylacetophenone, propiophenone, 4'-methylpro 3-vinyl-4H-1.2 dithin, 3-vinyl-1,2 dithiole-5-cyclohexane, piophenone, butyrophenone, isobutyrophenone, Valerophe diallyl trisulfide, anethole, methyl chavicol, anisaldehyde, none, hexanophenone, 2,2'-4.4 tetrahydroxybenzophenone, estragole, linallyl acetate, beta-pinene, thymol, carvacrol, 2-tert-butylcyclohexylacetate, benzoic acid, or propyl-4-hy p-cymene, beta-myrcene, alpha-myrcene, 1,8-cineole, droxybenzoate. eugenol, limonene, menthol, menthone, and linalool. 173. A composition as defined in claim 154, wherein the 165. A composition as defined in claim 153, wherein the pesticidal natural oil and/or component thereofand/or deriva pesticidal natural oil and/or component thereofand/or deriva tive thereof comprises neem oil or azadirachtin and the polar tive thereof comprises thymol, p-cymene, myrcene, 1,8-cin aromatic solvent comprises acetophenone. eole, eugenol, limonene, carvacrol, menthol, alpha-pinene, 174. A method of controlling arthropods, the method com linalool, menthone, combinations thereof, and/or their active prising exposing the arthropods and/or their eggs to a pesti derivatives. cidal composition as defined in claim 153. 166. A composition as defined in claim 153, wherein the 175. A method of preventing eclosion of arthropod eggs, pesticidal natural oil and/or component thereofand/or deriva the method comprising exposing the arthropod eggs to a tive thereof comprises a terpene. composition as defined in claim 153. 167. A composition as defined in claim 153, wherein the 176. The method as defined in claim 174, wherein the pesticidal natural oil is a pesticidal natural oil that comprises arthropods comprise bedbugs. one or more of thymol, p-cymene, eugenol, cinnamaldehyde, 177. The method as defined in claim 175, wherein the linalool, cinnamyl acetate, menthol, d-limonene, anethole, arthropods comprise bedbugs. carvacrol, alpha-pinene, geraniol, 1,8-cineole, myrcene, anis k k k k k