WO2014149207A2 - Benzimidazole-based insecticidal compositions and related methods - Google Patents

Abstract

Pesticidal composition comprising a benzimidazole compound of general formula I, or any agriculturally acceptable salt thereof, wherein Ar, R₂, R₄, R₅, R6 and R₇ are as described herein. Disclosed also is the pesticidal composition, comprising a benzimidazole compound of general formula I or any agriculturally acceptable salt thereof. Further disclosed are the methods of preparing such pesticidal compositions and the method of controlling insects using such pesticidal compositions.

Description

BENZIMIDAZOLE-BASED PESTICIDAL COMPOSITIONS

AND RELATED METHODS PRIORITY CLAIM

This application claims the benefit of U.S. Provisional Patent Application Serial No. 61/798,307 filed March 15, 2013, the entire disclosure of which is hereby expressly incorporated by reference. TECHNICAL FIELD

Various aspects and embodiments relate generally to pesticidal compositions and to methods of preparing and using such pesticidal compositions. Particular aspects and embodiments generally relate to benzimidazole-based pesticidal compositions and the methods of producing and using such pesticidal compositions.

BACKGROUND

Controlling insect populations is essential to modern agriculture, food storage, and hygiene. There are more than ten thousand species of insects that cause losses in agriculture. The world-wide agricultural losses amount to billions of U.S. dollars each year. Accordingly, there exists a continuous need for new insecticides and for methods of producing and using such insecticides.

DISCLOSURE

Embodiments of the present disclosure include benzimidazole compounds and pesticidal compositions comprising such benzimidazole compound.

Embodiments of the present disclosure further include methods of producing benzimidazole compounds and benzimidazole-based pesticidal compositions.

Further embodiments of the present disclosure include methods of controlling insects that comprise applying a benzimidazole-based pesticidal composition near a population of insects.

MODE(S) FOR CARRYING OUT THE INVENTION As used herein, the term "alkyl" refers to an acyclic, saturated, branched or unbranched, substituenf consisting of carbon and hydrogen, for example, methyl, ethyl, propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 2-methylbutyl, 1 ,1 -dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl.

As used herein the term "cycloalkyl" means a monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, bicycle[2.2.2]octyl, and decahydronapthyl.

As used herein, the term "alkenyl" means and includes a straight, branched, or cyclic hydrocarbon containing at least one carbon-carbon double bond. Examples may include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.

As used herein the term "cycloalkenyl" means a cyclic hydrocarbon containing at least one carbon-carbon double bond, such as, for example, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and cyclodecenyl.

As used herein, the term "alkynyl" means and includes a straight, branched, or cyclic hydrocarbon containing at least one carbon-carbon triple bond. Examples may include, but are not limited to, ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, or decynyl.

As used herein, the term "aryl" means and includes an aromatic ring compound with or without any substitution, such as, for example, phenyl and naphthyl.

As used herein, the term "alkoxy" means and includes an alkyl or a cycloalkyl group containing at least one carbon-oxygen single bond. Non-limiting examples may include methoxyl, ethoxy, propoxy, butoxy, cyclopropxy, cyclobutoxy, or cyclopentoxy.

As used herein, the term "alkylthio" means and includes an alkyl group containing at least one carbon-sulfur single bond.

As used herein, the term "haloalkylthio" means and includes an alkyl group containing at least one carbon-sulfur single bond and halogen atom.

As used herein, the terms "halo" and "halogen" mean and include fluorine, chlorine, bromine, or iodine.

As used herein, the terms "haloalkyl" and "haloalkoxy," respectively, mean and include, an alkyl group and an alkoxy group substituted with at least one halogen atom or halothio group.

As used herein, the term "heteroatom" means and includes sulfur (S), oxygen (O) or nitrogen (N) atom. As used herein, the term "heteroaryT means and includes an aromatic moiety containing at least one sulfur (S), oxygen (O), or nitrogen (N) atom in the aromatic ring. Non-limiting examples may include furyl, pyridyl, pyrimidyl, thienyl, isothiazolyl, imidazolyl, tetrazolyl, pyrazinyl, benzofuranyl, benzothiophenyl, quinolyl, isoquinolyl, benzothienyl, isobenzofuryl, pyrazolyl, indolyl, isoindolyl, benzimidazolyl, purinyl, carbozolyl, oxazolyl, thiazolyl, isothiazolyl, 1 ,2,4-thiadiazolyl, isooxazolyl, pyrrolyl, pyrazolyl, quinazolinyl, pyridazinyl, pyrazinyl, cinnolinyl, phthalazinyl, quinoxalinyl, xanthinyl, hypoxanthinyl, pteridinyl, 5-azacytidinyl, 5-azauracilyl, triazolopyridinyl, imidazolopyridinyl, pyrrolopyrimidinyl, or pyrazolopyrimidinyl.

As used herein, the term "heteroalkyF^" means and includes an alkyl moiety as defined herein containing at least one sulfur (S), oxygen (O), or nitrogen (N) atom.

As used herein, the term "cyano" means and includes a functional group containing a carbon-nitrogen triple bond.

As used herein, the term "nitro" means and includes a functional group containing a nitrogen atom joined to two oxygen atoms.

As used herein the term, "pesticidally effective amount" means and includes an amount of active material that causes an adverse effect to the at least one insect, wherein the adverse effect may include deviations from natural development, killing, regulation, or the like.

As used herein, the term "control" or grammatical variations thereof means and includes regulating the number of living insects or regulating the number of viable eggs of the insects.

The pesticidal composition may comprise a benzimidazole compound of general formula I, or any agriculturally acceptable salt thereof:

I

wherein Ar may be any aryl or heteroaryl moiety including, but not limited to, phenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, pyrazolo, imidazolo, thiophenyl, furyl or any other heteroaromatic ring system. Ar may be substituted or unsubstituted. Ar may be substituted at any open position with hydrogen, halogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, or combinations thereof; and the alkyl, alkenyl, or alkynyl group may be substituted with one or more heteroatoms such as N, O, Si, or SO,, (n = 0, 1, 2) at any position. Additionally, Ar may be substituted with alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, unsubstituted amines, substituted amines, unsubstituted aryloxy, substituted aryloxy; or combinations thereof;

R₂, R4, R₅, R₆ and R each may independently be selected from:

(a) hydrogen, halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or halothio;

(b) C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl;

(c) 0-C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl;

(d) C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted with one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1 , 2) at any position;

(e) amine, alkoxyamine, or cyano amine;

(f) C(0)R', C(0)OR', or C(0)NR' where R' may be alkyl optionally substituted with one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1 , 2) at any position, aryl or heteroaryl with at least one substituent being any combination of hydrogen, halo, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide or substituted amine group, unsubstituted aryloxy and substituted aryloxy;

(g) SO_n (n = 0, 1 , 2) substituted with C1-C8 alkyl that may include one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1 , 2) at any position, aryl or heteroaryl with at least one substituent being any combination of hydrogen, halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide or substituted amine group, unsubstituted aryloxy and substituted aryloxy; (h) aryl or heteroaryl substituted with any combination of hydrogen, halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, unsubstituted or substituted amine group, unsubstituted aryloxy, substituted aryloxy; and the alkyl, alkenyl, or alkynyl group may be optionally substituted with one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1, 2) at any position;

(i) an amino moiety substituted with hydrogen, C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl moiety that may be substituted with one or more heteroatoms, such as N, O, Si, or SO_n (n = 0, 1, 2), halo, alkoxy, haloalkyl, or haloalkoxy; C(0)R', C(0)OR', C(0)NR' where R' is selected from the group consisting of an alkyl moiety which may be substituted with at least one heteroatom such as N, O, Si, or SO_n (n = 0,1 , 2) at any position, halo, alkoxy, haloalkyl, or haloalkoxy, or R' may be an aryl or heteroaryl with at least one substituent being any combination of hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl moiety that may be substituted with one or more heteroatoms, such as N, O, Si, or SO_n (n = 0, 1, 2) at any position , halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, amine, substituted or unsubstituted amine group, unsubstituted aryloxy and substituted aryloxy; «

(j) an amino moiety substituted with any combination of hydrogen, alkyl, alkenyl, alkynyl moiety, wherein the alkyl, alkenyl, or alkynyl group is optionally substituted with at least one of heteroatom, halo, alkoxy, haloalkyl, and haloalkoxy.

In one embodiment, the pesticidal composition may comprise a benzimidazole compound of formula I or any agriculturally acceptable salt thereof, wherein:

Ar, R₂, R₅ and R₇ are as described above,

R₄ iTiay be selected from the group consisting of hydrogen, halogens, C1-C8 alkyl substituted with at least two halogen atoms, C3-C8 cycloalkyl substituted with at least two halogen atoms, 0-(Cl-C8) alkyl that may be substituted with two halogen atoms, 0-(C3- C8) cycloalkyl that may be substituted with at least one halogen atom, phenyl optionally substituted with at least one of halogen, haloalkyl, haloalkoxy, and heteroaryl optionally substituted with substituted with at least one of halogen, haloalkyl and haloalkoxy, and R₆ may be selected from the group consisting of C1-C8 alkyl, C1 -C8 alkyl substituted with at least two halogen atoms, C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with at least two halogen atoms, 0-(Cl-C8) alkyl , 0~(C1-C8) alkyl that may be substituted with two halogen atoms, 0-(C3-C8) cycloalkyl, 0-(C3-C8) cycloalkyl that may be substituted with at least one halogen atom, phenyl optionally substituted with at least one halogen, haloalkyl and haloalkoxy, heteroaryl optionally substituted with at least one halogen, haloalkyl and haloalkoxy, O-phenyl optionally substituted with at least one halogen, haloalkyl and haloalkoxy, O-heteroaryl optionally substituted with at least one halogen, haloalkyl and haloalkoxy, S-{C1 -C8)alkyl, S-phenyl optioanlly substituted with at least one halogen, haloalkyl and haloalkoxy, S- substituted with at least one halogen, haloalkyl and haloalkoxy.

In one embodiment, the pesticidal composition may comprise a benzimidazole compound having general formula II or any agriculturally acceptable salt thereof, wherein Ar, R4, R₅, R6 and R₇ are as described previously.

II

The benzimidazole compound of the general formula II may exist in various tautomeric forms. Non-limiting examples of such tautomeric forms may include, but are not limited to, compounds II-A to II-F as shown below. The benzimidazole compound of the present disclosure may include at least one of these tautomeric forms.

II-A II-C

In one embodiment, the pesticidal composition may comprise a benzimidazole compound having general formula II-2 or any agriculturally acceptable salt thereof, wherein Ar, R₅ and R₇ are as described previously.

II-2

One embodiment of a method of producing the benzimidazole compound of formula I may be as shown in Scheme 1. The method may include reacting the substituted benzene- 1,2-diamine compound of forumula IV with an aldehyde compound V to provide the benzimidazole compound I. Scheme l

V The method of Scheme 1 may include reacting the substituted benzene- 1,2- diamine compound of forumula IV with the aldehyde compound V in a dry polar aprotic solvent, such as DMF, at temperature from about 80° C to 100° C to provide the benzimidazole compound of formula I.

Scheme 2

IV V-l I-l

In some embodiments, the benzimidazole compound of formula I may be produced by the method of Scheme 2, wherein R4, R₅, and R₇ each may independently be halogen (e.g., F, CI, Br or I), (Cl-C8)alkyl substituted with at least two or more halogen atoms, (C3-C8)cycloalkyl substituted with at least two or more halogen atoms, substituted aryl or substituted hetroaryl, R₆ may be (Cl-C8)alkyl with or without substituent, (C3- C8)cycloalkyl with or without substituent, substituted phenyl or substituted hetroaryl, 0(C1-C8)alkyl substituted with at least two or more halogen atoms, O-phenyl substituted, O-heteroaryl substituted, S(Cl -C8)alkyl substituted with at least two or more halogen atoms, S-phenyl substituted, S-heteroaryl substituted, where the substituent of the aryl or heteroaryl may be at least one of halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, substituted amine, and cyano group. As shown in Scheme 2, the benzimidazole compound of formula I-l may be produced from the reaction of benzene- 1 ,2-diamine compound IV with Ar-substituted aldehyde of formula V-l, substituted phenyl or substituted hetroaryl and chlorotrimethylsilane, in a dry polar aprotic solvent, such as N,N-dimethylformamide (DMF), at temperatures between 80 °C and 100 °C for one hour (h) to two h to provide benzimidazole compound of formula 1-1, wherein Ar may be aryl or hetroaryl substituted at any position with at least one of halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, substituted amine, and cyano group.

The pesticidal composition comprising a benzimidazole compound of formula I may be used to control a wide variety of pests. As a non-limiting example, in one or more embodiments, the pesticidal composition comprising the benzimidazole compound of formula I may be used to control one or more members of at least one of Phylum Arthropoda, Phylum Nematoda, Subphylum Chelicerata, Subsphylum Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida, and Class Symphyla. In at least some embodiments, the method of the present disclosure may be used to control one or more members of at least one of Class Insecta and Class Arachnida.

As a non-limiting example, in one or more embodiments, the method of the present disclosure may be used to control one or more members of at least one of Phylum Arthropoda, Phylum Nematoda, Subphylum Chelicerata, Subsphylum Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida, and Class Symphyla. In at least some embodiments, the method of the present disclosure may be used to control one or more members of at least one of Class Insecta and Class Arachnida.

In additional embodiments, the method of the present disclosure may be used to control members of the Order Coleoptera (beetles) including, but not limited to, Acanthoscelides spp. (weevils), Acanthoscelides obtectus (common bean weevil), Agrilus planipennis (emerald ash borer), Agriotes spp. (wireworms), Anoplophora glabripennis (Asian longhorned beetle), Anthonomus spp. (weevils), Anthonomus grandis (boll weevil), Aphidius spp., Apion spp. (weevils), Apogonia spp. (grubs), Ataenius spretulus (Black Turfgrass Ataenius), Atomaria linearis (pygmy mangold beetle), Aulacophore spp., Bothynoderes punctiventris (beet root weevil), Bruchus spp. (weevils), Bruchus pisorum (pea weevil), Cacoesia spp., Callosobruchus maculatus (southern cow pea weevil), Carpophilus hemipteras (dried fruit beetle), Cassida vittata, Cerosterna spp., Cerotoma spp. (chrysomelids), Cerotoma trifurcata (bean leaf beetle), Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis (cabbage seedpod weevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp. (chrysomelids), Colaspis spp. (soil beetles), Conoderus scalaris, Conoderus stigmosus, Conotrachelus nenuphar (plum curculio), Cotinus nitidis (Green June beetle), Crioceris asparagi (asparagus beetle), Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes pusillus (flat grain beetle), Cryptolestes turcicus (Turkish grain beetle), Ctenicera spp. (wireworms), Curculio spp. (weevils), Cyclocephala spp. (grubs), Cylindrocpturus adspersus (sunflower stem weevil), Deporaus marginatus (mango leaf- cutting weevil), Dermestes lardarius (larder beetle), Dermestes maculates (hide beetle), Diabrotica spp. (chrysomelids), Epilachna varivestis (Mexican bean beetle), Faustinus cubae, Hylobius pales (pales weevil), Hypera spp. (weevils), Hypera postica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil), Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers), Lasioderma serricorne (cigarette beetle), Leptinotarsa decemlineata (Colorado potato beetle), Liogenys fuscus, Liogenys suturalis, Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (wood beetles/powder post beetles), Maecolaspis joliveti, Megascelis spp., Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle), Melolontha melolontha (common European cockchafer), Oberea brevis, Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilus mercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothed grain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cereal leaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp. (May/June beetle), Phyllophaga cuyabana (chrysomelids), Phynchites spp., Popillia japonica (Japanese beetle), Prostephanus truncates (larger grain borer), Rhizopertha dominica (lesser grain borer), Rhizotrogus spp. (European chafer), Rhynchophorus spp. (weevils), Scolytus spp. (wood beetles), Shenophorus spp. (Billbug), Sitona lineatus (pea leaf weevil), Sitophilus spp. (grain weevils), Sitophilus granaries (granary weevil), Sitophilus oryzae (rice weevil), Stegobium paniceum (drugstore beetle), Tribolium spp. (flour beetles), Tribolium castaneum (red flour beetle), Tribolium confusum (confused flour beetle), Trogoderma variabile (warehouse beetle), and Zabrus tenebioides.

In additional embodiments, the method of the present disclosure may be used to control members of the Order Dermaptera (earwigs).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Dictyoptera (cockroaches) including, but is not limited to, Blattella germanica (German cockroach), Blatta orientalis (oriental cockroach), Parcoblatta pennylvanica, Periplaneta americana (American cockroach), Periplaneta australoasiae (Australian cockroach), Periplaneta brunnea (brown cockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselus suninamensis (Surinam cockroach), and Supella longipalpa (brownbanded cockroach).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Diptera (true flies) including, but is not limited to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfa blotch leafminer), Agromyza spp. (leaf miner flies), Anastrepha spp. (fruit flies), Anastrepha suspensa (Caribbean fruit fly), Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies), Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (oriental fruit fly), Ceratitis spp. (fruit flies), Ceratitis capitata (Mediterranea fruit fly), Chrysops spp. (deer flies), Cochliomyia spp. (screwworms), Contarinia spp. (Gall midges), Culex spp. (mosquitoes), Dasineura spp. (gall midges), Dasineura brassicae (cabbage gall midge), Delia spp., Delia platura (seedcorn maggot), Drosophila spp. (vinegar flies), Fannia spp. (filth flies), Fannia canicularis (little house fly), Fannia scalaris (latrine fly), Gasterophilus intestinalis (horse bot fly), Gracillia perseae, Haematobia irritans (horn fly), Hylemyia spp. (root maggots), Hypoderma lineatum (common cattle grub), Liriomyza spp. (leafminer flies), Liriomyza brassica (serpentine leafminer), Melophagus ovinus (sheep ked), Musca spp. (muscid flies), Musca autumnalis (face fly), Musca domestica (house fly), Oestrus ovis (sheep bot fly), Oscinella frit (frit fly), Pegomyia betae (beet leafminer), Phorbia spp., Psila rosae (carrot rust fly), Rhagoletis cerasi (cherry fruit fly), Rhagoletis pomonella (apple maggot), Sitodiplosis mosellana (orange wheat blossom midge), Stomoxys calcitrans (stable fly), Tabanus spp. (horse flies), and Tipula spp. (crane flies).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Hemiptera (true bugs) including, but is not limited to, Acrosternum hilare (green stink bug), Blissus leucopterus (chinch bug), Calocoris norvegicus (potato mirid), Cimex hemipterus (tropical bed bug), Cimex lectularius (bed bug), Dagbertus fasciatus, Dichelops furcatus, Dysdercus suturellus (cotton stainer), Edessa meditabunda, Ewygaster maura (cereal bug), Euschistus heros, Euschistus servus (brown stink bug), Helopeltis antonii, Helopeltis theivora (tea blight plantbug), Lagynotomus spp. (stink bugs), Leptocorisa oratorius, Leptocorisa varicornis, Lygus spp. (plant bugs), Lygus hesperus (western tarnished plant bug), Maconellicoccus hirsutus, Neurocolpus longirostris, Nezara viridula (southern green stink bug), Phytocoris spp. (plant bugs), Phytocoris californicus, Phytocoris relativus, Piezodorus guildingi, Poecilocapsus Hneatus (fourlined plant bug), Psallus vaccinicola, Pseudacysta perseae, Scaptocoris castanea, and Triatoma spp. (bloodsucking conenose bugs/kissing bugs).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Homoptera (aphids, scales, whiteflies, leaflhoppers) including, but is not limited to, Acrythosiphon pisum (pea aphid), Adelges spp. (adelgids), Aleurodes proletella (cabbage whitefly), Aleiirodicus disperses, Aleurothrixus floccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutella bigutella, Aphrophora spp. (leafhoppers), Aonidiella aurantii (California red scale), Aphis spp. (aphids), Aphis gossypii (cotton aphid), Aphis pomi (apple aphid), Aulacorthum solani (foxglove aphid), Bemisia spp. (whiteflies), Bemisia argentifolii, Bemisia tabaci (sweetpotato whitefly), Brachycolus noxius (Russian aphid), Brachycorynella asparagi (asparagus aphid), Brevennia rehi, Brevicoryne brassicae (cabbage aphid), Ceroplastes spp. (scales), Ceroplastes rubens (red wax scale), Chionaspis ¾¾9.(scales), Chrysomphalus spp. (scales), Coccus spp. (scales), Dysaphis plantaginea (rosy apple aphid), Empoasca spp. (leafhoppers), Eriosoma lanigerum (woolly apple aphid), Icerya purchasi (cottony cushion scale), Idioscopus nitidulus (mango leafhopper), Laodelphax striatellus (smaller brown planthopper), Lepidosaphes spp., Macrosiphum spp., Macrosiphum euphorbiae (potato aphid), Macrosiphum granarium (English grain aphid), Macrosiphum rosae (rose aphid), Macrosteles quadrilineatus (aster leafhopper), Mahanarva frimbiolata, Metopolophium dirhodum (rose grain aphid), Mictis longicornis, Myzus spp., Myzus persicae (green peach aphid), Nephotettix spp. (leafhoppers), Nephotettix cinctipes (green leafhopper), Nilaparvata lugens (brown planthopper), Parlatoria pergandii (chaff scale), Parlatoria ziziphi (ebony scale), Peregrinus maidis (corn delphacid), Philaenus spp. (spittlebugs), Phylloxera vitifoliae (grape phylloxera), Physokermes piceae (spruce bud scale), Planococcus spp. (mealybugs), Pseudococcus spp. (mealybugs), Pseudococcus brevipes (pine apple mealybug), Quadraspidiotus perniciosus (San Jose scale), Rhapalosiphum spp. (aphids), Rhapalosiphum maida (corn leaf aphid), Rhapalosiphum padi (oat bird-cherry aphid), Saissetia spp. (scales), Saissetia oleae (black scale), Schizaphis graminum (greenbug), Sitobion avenae (English grain aphid), Sogatella furcifera (white-backed planthopper), Therioaphis spp. (aphids), Toumeyella spp. (scales), Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies), Trialeurodes vaporariorum (greenhouse whitefly), Trialeurodes abutiloneus (bandedwing whitefly), Unaspis spp. (scales), Unaspis yanonensis (arrowhead scale), and Zulia entreriana. In at least some embodiments, the method of the present disclosure may be used to control Myzus persicae.

In additional embodiments, the method of the present disclosure may be used to control members of the Order Hymenoptera (ants, wasps, and bees) including, but not limited to, Acromyrrmex spp., Athalia rosae, Atta spp. (leafcutting ants), Camponotus spp. (carpenter ants), Diprion spp. (sawflies), Formica spp. (ants), Iridomyrmex humilis (Argentine ant), Monomorium ssp., Monomorium minumum (little black ant), Monomorium pharaonis (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex spp. (harvester ants), Polistes spp. (paper wasps), Solenopsis spp. (fire ants), Tapoinoma sessile (odorous house ant), Tetranomorium spp. (pavement ants), Vespula spp. (yellow jackets), and Xylocopa spp. (carpenter bees).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Isoptera (termites) including, but not limited to, Coptotermes spp., Coptotermes curvignathus, Coptotermes frenchii, Coptotermes formosanus (Formosan subterranean termite), Cornitermes spp. (nasute termites), Cryptotermes spp. (drywood termites), Heterotermes spp. (desert subterranean termites), Heterotermes aureus, Kalotermes spp. (drywood termites), Incistitermes spp. (drywood termites), Macrotermes spp. (fungus growing termites), Marginitermes spp. (drywood termites), Microcerotermes spp. (harvester termites), Microtermes obesi, Procornitermes spp., Reticulitermes spp. (subterranean termites), Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes flavipes (eastern subterranean termite), Reticulitermes hageni, Reticulitermes hesperus (western subterranean termite), Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes tibialis, Reticulitermes virginicus, Schedorhinotermes spp., and Zootermopsis spp. (rotten-wood termites).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Lepidoptera (moths and butterflies) including, but not limited to, Achoea janata, Adoxophyes spp., Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (black cutworm), Alabama argillacea (cotton leafworm), Amorbia cuneana, Amyelosis transitella (navel orangeworm), Anacamptodes defectaria, Anarsia lineatella (peach twig borer), Anomis sabulifera (jute looper), Anticarsia gemmatalis (velvetbean caterpillar), Archips argyrospila (fruittree leafroller), Archips rosana (rose leaf roller), Argyrotaenia spp. (tortricid moths), Argyrotaenia citrana (orange tortrix), Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaf folder), Bucculatrix thurberiella (cotton leafperforator), Caloptilia spp. (leaf miners), Capua reticulana, Carposina niponensis (peach fruit moth), Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneura rosaceana (obliquebanded leafroller), Chrysodeixis spp., Cnaphalocerus medinalis (grass leafroller), Colias spp., Conpomorpha cramerella, Cossus cossus (carpenter moth), Crambus spp. (Sod webworms), Cydiafunebrana (plum fruit moth), Cydia molesta (oriental fruit moth), Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darna diducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers), Diatraea saccharalis (sugarcane borer), Diatraea graniosella (southwester corn borer), Farias spp. (bollworms), Earias insulata (Egyptian bollworm), Earias vitella (rough northern bollworm), Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalk borer), Epiphysias postruttana (light brown apple moth), Ephestia spp. (flour moths), Ephestia cautella (almond moth), Ephestia elutella (tobbaco moth), Ephestia kuehniella (Mediterranean flour moth), Epimeces spp., Epinotia aporema, Erionota thrax (banana skipper), Eupoecilia ambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltia spp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (oriental fruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp. (noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothis virescens (tobacco budworm), Hellula undalis (cabbage webworm), Indarbela spp. (root borers), Keiferia ly coper icella (tomato pinworm), Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella, Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp. (noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantria dispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasena corbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars), Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean pod borer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm), Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis (rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis (European corn borer), Oxydia vesulia, Pandemis cerasana (common currant tortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus, Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms), Peridroma saucia (variegated cutworm), Perileucoptera coffeella (white coffee leafminer), Phthorimaea operculella (potato tuber moth), Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris rapae (imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indian meal moth), Plutella xylostella (diamondback moth), Polychrosis viteana (grape berry moth), Prays endocarpa, Prays oleae (olive moth), Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm), Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophaga incertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stem borer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella (Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp. (armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda (fall armyworm), Spodoptera oridania (southern armyworm), Synanthedon spp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineola bisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper), Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), and Zeuzera pyrina (leopard moth). In at least some embodiments, the method of the present disclosure may be used to control Spodoptera exigua.

In additional embodiments, the method of the present disclosure may be used to control members of the Order Mallophaga (chewing lice) including, but not limited to, Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken body louse), and Menopon gallinea (common hen house).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Orthoptera (grasshoppers, locusts, and crickets) including, but not limited to, Anabrus simplex (Mormon cricket), Gryllotalpidae (mole crickets), Locusta migratoria, Melanoplus spp. (grasshoppers), Microcentrum retinerve (angularwinged katydid), Pterophylla spp. (kaydids), chistocerca gregaria, Scudderia furcata (forktailed bush katydid), and Valanga nigricorni.

In additional embodiments, the method of the present disclosure may be used to control members of the Order Phthiraptera (sucking lice) including, but not limited to, Haematopinus spp. (cattle and hog lice), Linognathus ovillus (sheep louse), Pediculus humanus capitis (human body louse), Pediculus humanus humanus (human body lice), and Pthirus pubis (crab louse).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Siphonaptera (fleas) including, but not limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea), and Pulex irritans (human flea).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Thysanoptera (thrips) including, but not limited to, Frankliniella fusca (tobacco thrips), Frankliniella occidentalis (western flower thrips), Frankliniella shultzei, Frankliniella williamsi (corn thrips), Heliothrips haemorrhaidalis (greenhouse thrips), Riphiphorothrips cruentatus, Scirtothrips spp., Scirtothrips citri (citrus thrips), Scirtothrips dorsalis (yellow tea thrips), Taeniothrips rhopalantennalis, and Thrips spp.

In additional embodiments, the method of the present disclosure may be used to control members of the Order Thysanura (bristletails) including, but not limited to, Lepisma spp. (silverfish) and Thermobia spp. (frebrats).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Acari (mites and ticks) including, but not limited to, Acarapsis woodi (tracheal mite of honeybees), Acarus spp. (food mites), Acarus siro (grain mite), Aceria mangiferae (mango bud mite), Aculops spp., Aculops lycopersici (tomato russet mite), Aculops pelekasi, Aculus pelekassi, Aculus schlechtendali (apple rust mite), Amblyomma americanum (lone star tick), Boophilus spp. (ticks), Brevipalpus obovatus (privet mite), Brevipalpus phoenicis (red and black flat mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks), Dermacentor variabilis (american dog tick), Dermatophagoides pteronyssinus (house dust mite), Eotetranycus spp., Eotetranychus carpini (yellow spider mite), Epitimerus spp., Eriophyes spp., Ixodes spp. (ticks), Metatetranycus spp., Notoedres cati, Oligonychus spp., Oligonychus coffee, Oligonychus Ulcus (southern red mite), Panonychus spp., Panonychus citri (citrus red mite), Panonychus ulmi (European red mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemun latus (broad mite), Rhipicephalus sanguineus (brown dog tick), Rhizoglyphus spp. (bulb mites), Sarcoptes scabiei (itch mite), Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae (twospotted spider mite), and Varroa destructor (honey bee mite).

In additional embodiments, the method of the present disclosure may be used to control members of the Order Nematoda (nematodes) including, but not limited to, Aphelenchoides spp. (bud and leaf& pine wood nematodes), Belonolaimus spp. (sting nematodes), Criconemella spp. (ring nematodes), Dirofilaria immitis (dog heartwom), Ditylenchusspp. (stem and bulb nematodes), Heterodera spp. (cyst nematodes), Heterodera zeae (corn cyst nematode), Hirschmanniella spp. (root nematodes), Hoplolaimus spp. (lance nematodes), Meloidogyne spp. (root knot nematodes), Meloidogyne incognita (root knot nematode), Onchocerca volvulus (hook-tail worm), Pratylenchns spp. (lesion nematodes), Radopholus spp. (burrowing nematodes), and Rotylenchus reniformis (kidney-shaped nematode).

In at least some embodiments, the method of the present disclosure may be used to control at least one insect in one or more of the Orders Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera, Orthoptera, Diptera, Hymenoptera, and Siphonaptera, and at least one mite in the Order Acari.

Example A: Bioassays on Beet Armyworm ("BAW") and Corn Earworm ("CEW") and Cabbage Looper ("CL")

BAW has few effective parasites, diseases, or predators to lower its population.

BAW infests many weeds, trees, grasses, legumes, and field crops. In various places, it is of economic concern upon asparagus, cotton, corn, soybeans, tobacco, alfalfa, sugar beets, peppers, tomatoes, potatoes, onions, peas, sunflowers, and citrus, among other plants. CEW is known to attack corn and tomatoes, but it also attacks artichoke, asparagus, cabbage, cantaloupe, collards, cowpeas, cucumbers, eggplant, lettuce, lima beans, melon, okra, peas, peppers, potatoes, pumpkin, snap beans, spinach, squash, sweet potatoes, and watermelon, among other plants. CEW is also known to be resistant to certain insecticides. CL feeds on a wide variety of cultivated plants and weeds. It feeds readily on crucifers, and has been reported damaging broccoli, cabbage, cauliflower, Chinese cabbage, collards, kale, mustard, radish, rutabaga, turnip, and watercress. Other vegetable crops injured include beet, cantaloupe, celery, cucumber, lima bean, lettuce, parsnip, pea, pepper, potato, snap bean, spinach, squash, sweet potato, tomato, and watermelon. CL is also known to be resistant to certain insecticides. Consequently, because of the above factors control of these pests is important. Furthermore, molecules that control these pests are useful in controlling other pests.

Certain molecules disclosed in this document were tested against BAW, CEW and CL using procedures described in the following examples. In the reporting of the results, the "TABLE 2: Mortality Rating for Beet Armyworm (BAW), Corn Earworm (CEW), and Cabbage Looper (CL) Insects" was used (See Table Section).

BIOASSAYS ON BAW (Spodoptera exigua)

Bioassays on BAW were conducted using a 128-well diet tray assay. One to five second instar BAW larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 ng/cm of the test compound (dissolved in 50 μΐ, of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry. Trays were covered with a clear self-adhesive cover, and held at 25 °C, 14:10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the tables entitled "Table 1" (See Table Section).

BlOASSAYS ON CEW (Helicoverpa zed)

Bioassays on CEW were conducted using a 128-well diet tray assay. One to five second instar CEW larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 ^ig /cm² of the test compound (dissolved in 50 xL of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry. Trays were covered with a clear self-adhesive cover, and held at 25 °C, 14:10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the table entitled "Table 1" (See Table Section).

Bioassays on CL {Trichoplusia ni)

Bioassays on CL were conducted using a 128-well diet tray assay. One to five second instar CL larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 μg /cm of the test compound (dissolved in 50 of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry. Trays were covered with a clear self-adhesive cover, and held at 25 °C, 14:10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the table entitled "Table 1" (See Table Section).

Example B: Bioassays on Green Peach Aphid ("GPA") (Myzus persicae).

GPA is the most significant aphid pest of peach trees, causing decreased growth, shriveling of the leaves, and the death of various tissues. It is also hazardous because it acts as a vector for the transport of plant viruses, such as potato virus Y and potato leafroll vims to members of the nightshade/potato family Solanaceae, and various mosaic viruses to many other food crops. GPA attacks such plants as broccoli, burdock, cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce, macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, and zucchini, among other plants. GPA also attacks many ornamental crops such as carnation, chrysanthemum, flowering white cabbage, poinsettia, and roses. GPA has developed resistance to many pesticides.

Certain molecules disclosed in this document were tested against GPA using procedures described in the following example. In the reporting of the results, the "TABLE 3: Mortality Rating for Green Peach Aphid (GPA) Insects^*1 was used (See Table Section).

Cabbage seedlings grown in 3 -inch pots, with 2-3 small (3-5 cm) true leaves, were used as test substrate. The seedlings were infested with 20-50 GPA (wingless adult and nymph stages) one day prior to chemical application. Four pots with individual seedlings were used for each treatment. Test compounds (2 mg) were dissolved in 2 mL of acetone/methanol (1 : 1) solvent, forming stock solutions of 1000 ppm test compound. The stock solutions were diluted 5X with 0.025% Tween 20 in H₂0 to obtain the solution at 200 ppm test compound. A hand-held aspirator-type sprayer was used for spraying a solution to both sides of cabbage leaves until runoff. Reference plants (solvent check) were sprayed with the diluent only containing 20% by volume of acetone/methanol (1 : 1) solvent. Treated plants were held in a holding room for three days at approximately 25 °C and ambient relative humidity (RH) prior to grading. Evaluation was conducted by counting the number of live aphids per plant under a microscope. Percent Control was measured by using Abbott's correction formula (W.S. Abbott, "A Method of Computing the Effectiveness of an Insecticide" J. Econ. Entomol. 18 (1925), pp.265-267) as follows.

Corrected % Control = 100 * (X - Y) / X

where

X = No. of live aphids on solvent check plants and

Y = No. of live aphids on treated plants

The results are indicated in the tables entitled "Table 1" (See Table Section).

Example C: BlOASSAYS ON Yellow Fever Mosquito "YFM" (Aedes aegypti).

YFM prefers to feed on humans during the daytime and is most frequently found in or near human habitations. YFM is a vector for transmitting several diseases. It is a mosquito that can spread the dengue fever and yellow fever viruses. Yellow fever is the second most dangerous mosquito-borne disease after malaria. Yellow fever is an acute viral hemorrhagic disease and up to 50% of severely affected persons without treatment will die from yellow fever. There are an estimated 200,000 cases of yellow fever, causing 30,000 deaths, worldwide each year. Dengue fever is a nasty, viral disease; it is sometimes called "breakbone fever" or "break-heart fever" because of the intense pain it can produce. Dengue fever kills about 20,000 people annually. Consequently, because of the above factors control of this pest is important. Furthermore, molecules that control this pest (YFM), which is known as a sucking pest, are useful in controlling other pests that cause human and animal suffering.

Certain molecules disclosed in this document were tested against YFM using procedures described in the following paragraph. In the reporting of the results, the "TABLE 4: Mortality Rating for Yellow Fever Mosquitos (YFM)" was used (See Table Section).

Master plates containing 400 μg of a molecule dissolved in 100 of dimethyl sulfoxide (DMSO) (equivalent to a 4000 ppm solution) are used. A master plate of assembled molecules contains 15 per well. To this plate, 135 μL of a 90: 10 watenacetone mixture is added to each well. A robot (Biomek® NXP Laboratory Automation Workstation) is programmed to dispense 15 μL aspirations from the master plate into an empty 96-well shallow plate ("daughter" plate). There are 6 reps ("daughter" plates) created per master. The created daughter plates are then immediately infested with YFM larvae.

The day before plates are to be treated, mosquito eggs are placed in Millipore water containing liver powder to begin hatching (4 g. into 400 ml). After the daughter plates are created using the robot, they are infested with 220 xL of the liver powder/larval mosquito mixture (about 1 day-old larvae). After plates are infested with mosquito larvae, a non- evaporative lid is used to cover the plate to reduce drying. Plates are held at room temperature (RT, about 22 °C) for 3 days prior to grading. After 3 days, each well is observed and scored based on mortality.

The results are indicated in Table 1 (See Table Section).

TABLE 1 shows the pesticidal activities of the benzimidazole compounds against several insects: beet armyworm (BAW), corn earworm (CEW), cabbage looper (CL), green peach aphid (GPA), and yellow fever mosquitoes (YFM). The mortality efficiency of the benzimidazole compounds against BAW, CEW, CL and GPA insects is determined after five days of treatment. The mortality efficiency against YFM is determined after three days of treatment. The mortality efficiency is rated as shown in TABLES 2-4.

TABLE 2: Mortality Rating for Beet Armyworm (BAW), Corn Earworm (CEW), and Cabbage Looper (CL) Insects

TABLE 3: Mortality Rating for Green Peach Aphid (GPA) Insects

TABLE 4 : Mortality Rating for Yellow Fever Mosquitos (YFM)

% Control (or Mortality) Rating

> 80 A

More than 0 - Less than 80 B

Not Tested C

No activity noticed in this bioassay D TABLE 1 shows the mortality study results of the benzimidazole compounds 1-27 against several insects: beet armyworm (BAW), corn earworm (CEW), cabbage looper (CL), green peach aphid (GPA), and yellow fever mosquito (YFM).

TABLE 1

Embodiments of the present disclosure further include methods of controlling insects that comprises applying an pesticidal composition comprising a benzimidazole compound of the general formula I near a population of pests. In some embodiments, the pesticidal composition may comprise a benzimidazole compound of the general formula I in a phytologically-acceptable inert carrier (e.g., solid carrier or liquid carrier), and may be applied near a population of pests.

The control of pests may be achieved by applying an pesticidally effective amount of the benzimidazole-based composition in form of sprays, topical treatment, gels, seed coatings, microcapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants aerosols, dusts, or the like.

In some embodiments, the benzimidazole-based pesticidal compositions may be in the form of solid. Non-limiting examples of the solid forms may include power, dust or granular formulations.

In some embodiments, the benzimidazole-based pesticidal compositions may be in the form of liquid formulation. Examples of the liquid forms may include, but not limited to, dispersion, suspension, emulsion or solution in appropriate liquid carrier.

In some embodiments, the benzimidazole-based pesticidal compositions may be in the form of liquid dispersion, wherein the benzimidazole compound may be dispersed in water or other agriculturally suitable liquid carrier.

In some embodiments, the benzimidazole-based pesticidal compositions may be in the form of solution in an appropriate organic solvent. In one embodiment, the spray oils, which are widely used in agricultural chemistry, may be used as the organic solvent for the benzimidazole -based pesticidal compositions.

When desired, the benzimidazole-based pesticidal compositions may be used in conjunction with at least one of other insecticides, fungicides and herbicides to obtain control of a wider variety of pests, diseases and weeds. When used in conjunction with other insecticides or fungicides or herbicides, the benzimidazole-based pesticidal compositions may be formulated with the other insecticides or fungicides or herbicide, or applied sequentially with the other insecticides or fungicides or herbicides.

The following examples serve to explain embodiments of the present invention in more detail. These examples should not be construed as being exhaustive or exclusive as to the scope of this invention. EXAMPLES Example 1

Preparation of 2-substituted-4,6-bis(trifluoromethyl)-lH-benzo[d]imidazole

[Compounds 1-17]

In separate 15 mL pressure tubes, a solution of 3,5-bis(trifluoromethyl)benzene- 1,2-diamine (0.40 mmol) in DMF (3 mL) was mixed with an aldehyde (0.48 mmol). To the mixture was added chlorotrimethylsilane (1.03 mmol) dropwise, and the tube was sealed and heated to 100 °C for 1 h. The mixture was cooled, diluted with ethyl acetate (EtOAc, 15 mL) and washed with water (10 mL). The organic phase was washed with brine (10 mL) and concentrated under vacuum to give a residue that was purified by preparative thin layer chromatography to afford 2-substituted-4,6-bis(trifluoromethyl)-lH- benzo[d]imidazole (Compounds 1-17).

Aldehydes used include: 2,6-dichlorobenzaldehyde, 2,6-dichloro-4-(trifluoro- methyl)benzaldehyde, 2-chloro-5-(trifluoromethyl)benzaldehyde, 3-chlorothiophene-2- carbaldehyde, 2,4-dichlorobenzaldehyde, 2-chloro-4-(dimethylamino)benzaldehyde, 2- chloro-6-methylbenzaldehyde, 2-methoxy-4-(trifluoromethyl)benzaldehyde, 2-fluoro-4- (trifluoromethyl)-benzaldehyde, 2,4,6-trichlorobenzaldehyde, 2,5-dichlorothiophene-3- carbaldehyde, 5-chloro-thiophene-2-carbaldehyde, 5-(trifluoromethyl)picolinaldehyde, 2,6- dichloronicotinaldehyde, 6-(trifluoromethyl)nicotinaldehyde, 3,5- dichloroisonicotinaldehyde, 3-chloropicolinaldehyde.

Compounds 1-17 in TABLE 5 were made in accordance with the procedures disclosed in Example 1. Example 2

Preparation of 2-(6-(trifluoromethyl)pyridin-3-yl)-lH-benzo[d]imidazoles

[Compounds 18-25]

In separate 25 mL vials, a solution of an appropriate phenyl- 1,2-diamine (1 eq) in DMF (10 mL) was mixed with 6-(trifluoromethyl)nicotinaldehyde (1.2 eq). To the mixture was added chlorotrimethylsilane (2.5 eq) dropwise and heated to 115 °C for 1.5 h. Then, the reaction mixture was cooled to RT, and stirred for overnight. The mixture was diluted with EtOAc (50 mL) and washed with brine (4 x 50 mL). The organic phase was dried over sodium sulfate (Na₂S0₄), filtered, and concentrated under vacuum to give a residue that was purified by column chromatography to afford 2-(6-(trifluoromethyl)pyridin-3-yl)- lH-benzo[d]imidazoles (Compounds 18-25).

The phenyl- 1 ,2-diamines used include: 3,5-difluorobenzene-l,2-diamine, 4-

(trifluoromethoxy)benzene- 1 ,2-diamine, 4-chloro-5-fluorobenzene- 1 ,2-diamine, 4-chloro- 5-(trifluoromethyl)benzene- 1 ,2-diamine, 4-fluoro-5-(trifluoromethyl)benzene- 1 ,2-diamine, 4-bromo-5-(trifluoromethoxy)benzene- 1,2-diamine, 3-chloro-5-(trifluoromethyl)benzene- 1 ,2-diamine, 4,5-difluorobenzene- 1 ,2-diamine

Compounds 18-25 in TABLE 5 were made in accordance with the procedures disclosed in Example 2. Example 3

Preparation of 2-(6-(trifluoromethyI)pyridin-3-yl)-lH-benzo[d]imidazoIes

[Compounds 26-27]

Equimolar amounts of a benzaldehyde and 3,4,5,6-tetrachlorophenyl-l,2-diamine were reflux ed together in benzene. The resulting precipitates were filtered and purified by recrystallization from a solvent mixture of tetrahydrofuran (THF) and carbon tetrachloride (CC1₄) to afford 2-substituted-4,5,6,7-tetrachloro-lH-benzo[d]imidazoles (Compounds 26-27).

The benzaldehydes used include: 4-nitrobenzaldehyde and 4-chlorobenzaldehyde. Compounds 26-27 in TABLE 5 were made in accordance with the procedures disclosed in Example 3.

MP ESI-MS

Structure 'H NMR

(°C) (m/z)

(400 MHz, DMSO-

Off- d6):

315- 377.9

White δ 14.20 (s, 1H), 8.56

318 ([M+H] +)

Solid (d, J = 9.4, 2H), 8.14

(d, J = 9.4 Hz, 2H)

While this invention has been described in certain embodiments, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.

Claims

What is claimed is:

1. A benzimidazole compound of formula I or a salt thereof:

wherein

Ar is an aryl group, and

R₂, R , R₅, R6 and R₇ each is independently selected from the group consisting of: (a) hydrogen, halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or halothio;

(b) C1-C8 alkyl, C2-C8 alkenyl or alkynyl;

(c) O-C 1 -C8 alkyl, 0-C2-C8 alkenyl or alkynyl;

(d) C1-C8 alkyl, alkenyl or alkynyl moiety optionally substituted with one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1, 2) at any position;

(e) amine, alkoxyamine, or cyano amine;

(f) C(0)R', C(0)OR', or C(0)NR' where R' may be alkyl optionally substituted with one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1 , 2) at any position, aryl or heteroaryl with at least one substituent being any combination of hydrogen, halo, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, unsubstituted amine, substituted amine group, unsubstituted aryloxy and susbstituted aryloxy;

(g) SO_n (n = 0, 1 , 2) substituted with CI -C8 alkyl that may include one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1 , 2) at any position, aryl or heteroaryl with at least one substituent being any combination of hydrogen, halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide or substituted amine group, unsubstituted aryloxy and substituted aryloxy;

(h) aryl or heteroaryl substituted with any combination of hydrogen, halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, unsubstituted or substituted amine group, unsubstituted aryloxy, substituted aryloxy and the alkyl, alkenyl, or alkynyl group may be optionally substituted with one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1, 2) at any position;

(i) an amino moiety substituted with hydrogen, alkyl, alkenyl, alkynyl,

C(0)R', C(0)OR', C(0)NR' where R' is selected from the group consisting of an alkyl moiety optionally substituted with at least one heteroatom, or aryl or heteroaryl with at least one substituent being any combination of hydrogen, halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, amine, and aryloxy;

(j) an amino moiety substituted with any combination of hydrogen, alkyl, alkenyl, alkynyl moiety, wherein the alkyl, alkenyl, or alkynyl group is optionally substituted with at least one of heteroatom, halo, alkoxy, haloalkyl, and haloalkoxy.

2. The compound of claim 1 , wherein the aryl or heteroaryl group is selected from the group consisting of phenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, pyrazolo, imidazolo, thiophenyl, and furyl, wherein the aryl or heteroaryl group is substituted at any open position with at least one hydrogen, halogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, amines, aryloxy, and combinations thereof.

3. The compound of claim 1 , wherein:

R4 is selected from the group consisting of hydrogen, halogen, C1-C8 alkyl substituted with at least two halogen atoms, C3-C8 cycloalkyl substituted with at least two halogen atoms, phenyl optionally substituted with at least one halogen, haloalkyl, haloalkoxy, and heteroaryl optionally substituted with at least one halogen, haloalkyl and haloalkoxy, and

R-6 may be selected from the group consisting of C1-C8 alkyl, C1-C8 alkyl substituted with at least two halogen atoms, C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with at least two halogen atoms, phenyl optionally substituted with at least two halogen atoms, heteroaryl optionally substituted with at least two halogen atoms, 0-(Cl- C8) alkyl that may be substituted with two halogen atoms, 0-(Cl-C8) cycloalkyl that may be substituted with at least one halogen atom, O-phenyl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, O-heteroaryl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, S-(C1-C8)alkyl, S-phenyl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, S-substituted with at least one halogen, haloalkyl and haloalkoxy.

The compound of claim 1 , having formula II or a salt thereof:

II

6. The compound of claim 1 selected from the group consisting Compounds 1-27 as specified in TABLE 5.

7. A method of preparing a benzimidazole compound, comprising:

reacting a substituted benzene- 1,2-diamine compound of forumula IV with an aldehyde compound of formula V:

IV V I wherein

Ar is an aryl or heteraryl group selected from the group consisting of phenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, pyrazolo, imidazolo, thiophenyl, and furyl, wherein the aryl group is substituted at any open position with at least one hydrogen, halogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, unsubstituted or substituted amines, aryloxy, and combinations thereof,

R-2, ¾, R-5, R and R₇ each is independently selected from the group consisting of: (a) hydrogen, halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or halothio;

(b) CI -C8 alkyl, C2-C8 alkenyl or C2-C8alkynyl;

(c) 0-C1-C8 alkyl, 0-C2-C8 alkenyl or 0-C2-C8 alkynyl;

(d) C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl moiety substituted with one or more heteroatoms such as N, O, Si, or SO„ (n = 0, 1 , 2) at any position;

(e) amine, alkoxyamine, or cyano amine;

(f) C(0)R', C(0)OR', or C(0)NR' where R' may be alkyl optionally substituted with one or more heteroatoms such as N, O, Si, or SO_n (n = 0,1 , 2) at any position, aryl or heteroaryl with at least one substituent being any combination of hydrogen, halo, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, amine and aryloxy;

(g) SO_n (n = 0, 1 , 2) substituted with C1-C8 alkyl that may include one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1 , 2) at any position, aryl or heteroaryl with at least one substituent being any combination of hydrogen, halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide or substituted amine group, unsubstituted aryloxy and substituted aryloxy;

(h) aryl or heteroaryl substituted with any combination of hydrogen, halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide or substituted amine group, unsubstituted aryloxy, substituted aryloxy and the alkyl, alkenyl, or alkynyl group may be optionally substituted with one or more heteroatoms such as N, O, Si, or SO_n (n = 0, 1, 2) at any position;

(i) an amino moiety substituted with any combination of hydrogen, C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl moiety that may be substituted with one or more heteroatoms, such as N, O, Si, or SO_n (n = 0, 1, 2), halo, alkoxy, haloalkyl, or haloalkoxy; C(0)R', C(0)OR', C(0)NR' where R' is selected from the group consisting of an alkyl moiety which may be substituted with at least one heteroatom such as N, O, Si, or SO_n (n = 0,1 , 2) at any position, halo, alkoxy, haloalkyl, or haloalkoxy, or R' may be an aryl or heteroaryl with at least one substituent being any combination of hydrogen, C1-C8 alkyl, alkenyl or alkynyl moiety that may be substituted with one or more heteroatoms, such as N, O, Si, or SO_n (n = 0, 1, 2) at any position , halo, alkyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkyl, cyclohaloalkyl, haloalkoxy, cyclohaloalkoxy, alkenyl, cycloalkenyl, alkynyl, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, ester, acetate, amide, amine, substituted amine group, unsubstituted aryloxy and substituted aryloxy aryloxy;

(j) an amino moiety substituted with any combination of hydrogen, alkyl, alkenyl, alkynyl moiety, wherein the alkyl, alkenyl, or alkynyl group is optionally substituted with at least one of heteroatom, halo, alkoxy, haloalkyl, and haloalkoxy.

8. The method of claim 7, wherein:

R4 is selected from the group consisting of hydrogen, halogen, C1-C8 alkyl substituted with at least two halogen atoms, C3-C8 cycloalkyl substituted with at least two halogen atoms, 0-(Cl -C8) alkyl that may be substituted with two halogen atoms, 0-(C3- C8) cycloalkyl that may be optionally substituted with at least one halogen atom, phenyl optionally substituted with at least one of halogen, haloalkyl, haloalkoxy, and heteroaryl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, and

R₆ may be selected from the group consisting of C1-C8 alkyl, C1-C8 alkyl substituted with at least two halogen atoms, C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with at least two halogen atoms, , 0-(Cl-C8) alkyl, 0-(Cl-C8) alkyl that may be substituted with two halogen atoms, 0-(C3-C8) cycloalkyl, 0-(C3-C8) cycloalkyl that may be substituted with at least one halogen atom, phenyl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, heteroaryl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, O-phenyl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, O-heteroaryl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, S-{C1-C8)alkyl, S-phenyl optionally substituted with at least one of halogen, haloalkyl and haloalkoxy, S-substituted with at least one of halogen, haloalkyl and haloalkoxy. 9. The method of claim 7, wherein reacting a substituted benzene- 1,2-diamine compound of forumula IV with an aldehyde compound of formula V comprises:

reacting the substituted benzene- 1 ,2-diamine compound of forumula IV with the aldehyde compound of formula V in a polar aprotic solvent at temperature from about 80 °C to 100 °C.

10. An pesticidal composition, comprising a benzimidazole compound of Claim 1.

1 1. An pesticidal composition, comprising a benzimidazole compound of Claim 4.

12. An pesticidal composition, comprising a benzimidazole compound of Claim 6.

13. A method of controlling insect, comprising applying an pesticidal composition near a population of insects, wherein the pesticidal composition comprises a benzimidazole compound of Claim 1.

14. A method of controlling insect, comprising applying an pesticidal composition near a population of insects, wherein the pesticidal composition comprises a benzimidazole compound of Claim 4.

15. A method of controlling insect, comprising applying an pesticidal composition near a population of insects, wherein the pesticidal composition comprises a benzimidazole compound of Claim 6.