Polymorph

Abstract

To provide a compound, a composition thereof, and methods for preparing and using the same, for prevention or control of plant infection in agricultural or horticultural plants or propagation materials.SOLUTION: The present invention provides a solid form of diclobentiazox, a composition containing the solid form, and methods for using them as plant disease control agents.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to solid forms of dichlobenthiazox, compositions containing these solid forms, and methods of their use as agricultural and horticultural plant disease control agents. [Background technology]

[0002] Patent Document 1 discloses that certain 1,2-benzisothiazole derivatives exhibit remarkable effects against agricultural and horticultural plant diseases, including rice blast, wheat leaf spot, cucumber downy mildew, and cucumber anthracnose, without causing phytotoxicity to crops. In particular, the compound of formula I, [ka] That is, dichlorobenziazox is disclosed.

[0003] Mixtures of dichlobentiazox with other pest control agents are disclosed in US Pat. Nos. 2, 3, 499, 513 and 5,333, 499. The crystal structure of dichlobentiazox is disclosed in US Pat. No. 5, 499, 513. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2007 / 129454 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-155807 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-044791 [Non-patent literature]

[0005] [Non-Patent Document 1] Japan Institute of Invention and Innovation, Disclosure of Technical Information, No. 2017-502433 [Non-patent document 2] New Crystal Structures,2023,Vol.238,No.1,p.127-128 Summary of the Invention [Means for solving the problem]

[0006] Novel solid forms of isomers of this compound, their compositions, and methods for their preparation and use have now been discovered.

[0007] The present invention is characterized by the following gist. [1] A crystalline form of dichlorobenzizox, having a powder X-ray diffraction pattern comprising at least four 2θ angle values ​​selected from the group consisting of 12.5±0.2, 13.6±0.2, 16.0±0.2, 21.6±0.2, 24.8±0.2, 26.0±0.2 and 30.0±0.2. [2] The following lattice parameters: a = 12.78 Å ± 0.3 Å, b = 7.83 Å ± 0.3 Å, c = 14.15 Å ± 0.3 Å, α = 90° ± 2°, β = 109.8° ± 2°, γ = 90° ± 2° and volume = 1332 Å 3 ±30Å 3 2. The crystalline form according to claim 1, having the formula: [3] The crystalline form according to 1 above, having a melting point of 172.5 to 175°C. [4] The crystalline form described in 1 above, which is a monoclinic crystal. [5] An agricultural composition comprising the crystalline form described in any one of 1 to 4 above and at least one agriculturally acceptable carrier or excipient. [6] The composition according to item 5, which is enriched for the crystalline form according to any one of items 1 to 4. [7] The composition according to 5, further comprising at least one additional pest control agent. [8] A method for preventing or controlling disease infection in agricultural and horticultural plants or agricultural and horticultural plant propagation materials, comprising treating the agricultural and horticultural plants or agricultural and horticultural plant propagation materials with a disease-controlling effective amount of the agricultural composition described in 5 above. DETAILED DESCRIPTION OF THE INVENTION

[0008] Thus, the present invention relates to a novel crystalline form of dichlorobenzizox, crystalline form A. This crystalline form A can be characterized by its single crystal unit cell parameters, as shown in Table 1. The polymorph was obtained using the method described in Example 1.

[0009] [Table 1]

[0010] In the table, a, b, c are the edge lengths of the unit cell, α, β, γ are the angles of the unit cell, and Z = molecules per cell.

[0011] Thus, in one embodiment of the present invention, crystalline form A has the following lattice parameters: a=12.78 ű0.3 Å, b=7.83 ű0.3 Å, c=14.15 ű0.3 Å, α=90°±2°, β=109.8°±2°, γ=90°±2°, and volume=1332 Å. 3 ±30Å 3 .

[0012] Meanwhile, a known crystalline form of dichlorobenzizox, crystalline form B, has been reported in Non-Patent Document 2. This crystalline polymorph form B can be characterized by its single crystal unit cell parameters, as shown in Table 2. The polymorph was obtained using the method described in Comparative Example 1.

[0013] [Table 2]

[0014] Thus, crystalline form B, which is not according to the invention, has the following lattice parameters: a=6.71 ű0.3 Å, b=8.16 ű0.3 Å, c=12.19 ű0.3 Å, α=86.8°±2°, β=80.6°±2°, γ=87.7°±2° and volume=657 Å. 3 ±30Å 3 .

[0015] Crystalline Form A may also be characterized by an X-ray powder diffraction pattern expressed in terms of 2θ angles or d-spacings. Thus, in another embodiment of the present invention, the crystalline form has an X-ray powder diffraction pattern comprising at least four, at least five, at least six, or all 2θ angle values ​​selected from 12.5±0.2, 13.6±0.2, 16.0±0.2, 21.6±0.2, 24.8±0.2, 26.0±0.2, and 30.0±0.2. These peak values, along with the corresponding d-spacing values, are set forth in Table 3 below.

[0016] [Table 3]

[0017] These 2θ angle values ​​are derived from the powder X-ray diffraction pattern of the polymorph obtained using the method of Example 1. These values ​​are generated using a mean wavelength of 1.5418 Å with a 2θ step size of 0.01°.

[0018] In contrast, a non-inventive crystalline form of crystalline form B has an X-ray powder diffraction pattern that includes at least four, at least five, at least six, or all 2θ angle values ​​selected from 12.9±0.2, 16.4±0.2, 17.5±0.2, 21.8±0.2, 24.7±0.2, 26.0±0.2, and 26.8±0.2. These peak values, along with the corresponding d-spacing values, are shown in Table 4 below.

[0019] [Table 4]

[0020] In another embodiment, crystalline form A has a melting point of 172.5-175° C. This melting point is obtained using differential scanning calorimetry (DSC) with a heating rate of 10° C. / min.

[0021] In the context of the present invention, a polymorph is a specific crystalline form of a compound that can exist in more than one crystalline form in the solid state. A crystalline form of a compound contains constituent molecules arranged in an orderly, repeating pattern extending across all three spatial dimensions (in contrast, amorphous solids lack long-range order in the molecular positions). Different polymorphs of a compound have different arrangements of atoms and / or molecules in their crystalline structure. When the compound is a biologically active compound, including a plant disease control agent, differences in crystalline structure can result in different polymorphs with different chemical, physical, and biological properties. Properties that can be affected include crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. Therefore, a particular polymorph may have properties that make it more advantageous for a particular use than another polymorph of the same compound. In particular, the physical, chemical, and biological properties listed above can significantly impact the development of manufacturing methods and formulations that allow compounds to be easily combined with other active ingredients and formulation components in formulations, as well as the quality and effectiveness of plant treatments, including pest control agents. It is noted that it is not possible to predict whether the solid state of a compound may exist as more than one polymorph, nor is it possible to predict the properties of any of these crystalline forms.

[0022] In particular, the use of a specific polymorph may allow for the use of new formulations compared to existing polymorphic / amorphous forms of a compound. This may be advantageous for several reasons. For example, a suspension concentrate (SC) formulation may be preferable to an EC because the absence of a solvent in the SC often means that the formulation is likely to be less phytotoxic than an equivalent EC formulation. However, if the existing form of the compound is not stable in such an SC formulation, polymorphic conversion may occur, resulting in undesirable crystal growth. Such crystal growth may lead to, for example, thickening and potentially solidification of the formulation, which may be harmful because it may lead to clogging of the spray nozzle of application equipment, such as agricultural sprayers. The use of a stable polymorphic form would overcome these problems.

[0023] The assay of solid phase for the presence of crystals can be carried out by conventional methods known in the art.For example, it is convenient and common to use powder X-ray diffraction technique.Other techniques that can be used include differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Raman spectroscopy or infrared spectroscopy, NMR, gas chromatography or HPLC.Single crystal X-ray diffraction is particularly useful for identifying crystalline structure.

[0024] The polymorph of the present invention may be applied in its pure form, but more preferably may be incorporated into an agrochemical composition by conventional means. Thus, in a further aspect, the present invention provides an agrochemical composition comprising the polymorph of the present invention as defined above and at least one agriculturally acceptable carrier or diluent.

[0025] Furthermore, the compositions of the present invention may comprise more than one polymorph. In particular, they may be enriched for crystalline form A. "Enriched" means that the molar ratio of crystalline form A compared to the total amount of diclobentiazox is greater than 50%, for example at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or at least 99%.

[0026] Pesticide compositions containing one or more polymorphs of the present invention are preventatively and / or therapeutically beneficial active ingredients in the field of controlling agricultural and horticultural plant diseases and / or animal pests, even at low application rates, have favorable agricultural and horticultural plant disease control and biocidal spectra, and are well tolerated by warm-blooded animal species, fish, and plants. The compositions of the present invention can act not only against normally susceptible pathogens and animal pests of agricultural and horticultural plant diseases, including rice blast, wheat blight, cucumber downy mildew, cucumber anthracnose, and representative insects or Acarina, but also against all or only individual developmental stages of pathogens and animal pests of agricultural and horticultural plant diseases that are resistant to plant disease control agents. A good agricultural and horticultural plant disease control activity of a composition corresponds to a control value that reduces the incidence or extent of disease damage in agricultural and horticultural plants by at least 50-60% compared to controls not treated with the composition. The insecticidal or acaricidal activity of the composition may manifest itself directly, i.e., as destruction of the pest immediately or only after some time has passed, for example, during molting, or indirectly, for example, as reduced egg-laying and / or hatching rates, with good activity corresponding to a destruction rate (mortality) of at least 50-60%.

[0027] Thus, agrochemical compositions comprising one or more polymorphs of the present invention can be used to control plant diseases and plant-pathogenic insects in several agricultural and horticultural plant species. Accordingly, the present invention also provides a method for preventing or controlling disease and / or insect infestation in an agricultural or horticultural plant or plant propagation material, comprising treating the agricultural or horticultural plant or plant propagation material with a phytopathogenically and / or insecticidally effective amount of the agricultural composition of the present invention.

[0028] As used herein, the term "plant disease control agent" refers to a compound or composition that controls or regulates the infection of a plant disease. The term "phytolytically effective amount" refers to an amount of such a compound or composition, or a combination of such compounds or compositions, that is capable of killing, controlling, or preventing the infection of, slowing the growth or proliferation of, or reducing the population of, the causative agent of a plant disease, and / or reducing damage to the plant caused by the plant disease.

[0029] As used herein, the term "insecticide" refers to a compound or composition that controls or regulates the growth of insects. The term "pesticidally effective amount" refers to the amount of such a compound or composition, or a combination of such compounds or compositions, that is capable of killing, controlling, or infecting insects, slowing the growth or reproduction of insects, reducing insect populations, and / or reducing damage to plants caused by insects.

[0030] "Plant propagation material" means material including seeds of any kind (including fruits, tubers, bulbs and grains), cuttings and cutshoots.

[0031] Depending on the application form, the composition of the present invention can control plant diseases caused by fungi, bacteria, viruses, and viroids belonging to the phylum Oomycetes, Ascomycetes, Basidiomycetes, Zygomycetes, and Deuteromycetes.

[0032] Specific diseases include, but are not limited to: Rice blast disease (Pyricularia oryzae), Southern leaf blight (Cochliobolus miyabeanus), Sheath blight (Rhizoctonia solani), Bakanae disease (Gibberella fujikuroi), Seedling damping-off (Fusarium spp., Pythium spp., Rhizopus spp., Trichoderma sp.), Bacterial seedling blight (Burkholderia plantarii), Bacterial leaf blight (Xanthomonas oryzae), Bacterial grain rot (Burkholderia glumae), Rice browning disease (Acidovorax avenae), Inner glume browning disease (Erwinia ananas), Rice stripe virus; Powdery mildew (Erysiphe graminis f.sp.hordei; f.sp.tritici) of wheat, leaf spot (Pyrenophora graminea), net blotch (Pyrenophora teres), and head blight (Gibberella zeae), rust (Puccinia striiformis; Puccinia. graminis; Puccinia. recondita; Puccinia. hordei), snow rot (Typhula incarnata; Typhula ishikariensis; Micronectriella nivalis; Microdochium nivale), naked smut (Ustilago tritici; U. nuda), Pseudocercosporella herpotrichoides, Rhynchosporium secalis, Septoria tritici, Septoria tritici nodorum; Leptosphaeria nodorum), brown snow rot caused by Pythium spp. (including Pythiumiwayamai), yellow mosaic virus; Grape downy mildew (Plasmopara viticola), powdery mildew (Uncinula necator), black rot (Elsinoe ampelina), late rot (Glomerella cingulata), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), fusarium wilt (Phomopsis viticola); apple powdery mildew (Podosphaera leucotricha), black spot (Venturia inaequalis), leaf spot (Alternaria alternata), red spot (Gymnosporangium yamadae), monilia (Sclerotinia mali), canker (Valsa ceratospema), ring spot (Physalospora piricola), apple scar skin viroid; Pear black spot (Alternaria kikuchiana), black scab (Venturia nashicola), red scab (Gymnosporangium haraeanum), and blight (Phomopsis fukushii); pear blight (Phytophthora cactorum); Peach brown rot (Monilinia fructicola), black spot (Cladosporium carpophilum), Phomopsis rot (Phomopsis sp.), late blight (Phytophthora sp.); Persimmon anthracnose (Colletotrichum gloeosporioides), leaf spot disease (Pseudocercospora kaki; Mycosphaerella nawae); Citrus black spot (Diaporthe citri), common scab (Elsinoe fawcetti); Cucurbit downy mildew (Pseudoperonospora cubensis), late blight (including Phytophthora parasitica; Phytophthora melonis; Phytophthora nicotianae; Phytophthora drechsleri; Phytophthora capsici), powdery mildew (Sphaerotheca fuliginea; Sphaerotheca cucurbitae), anthracnose (Colletotrichum lagenarium), vine wilt (Mycosphaerella melonis), vine wilt (Fusarium oxysporum), seedling damping-off (Pythium debaryanum), brown spot (Corynespora cassiicola), gray mold (Botrytis cinerea), bacterial spot (Pseudomonas syringae), cucumber mosaic virus (Cucumber mosaic virus), Cucumber green mottle mosaic virus, Tomato late blight (Phytophthora infestans), Seedling damping-off (Pythium vexans; Rhizoctonia solani), Ring blight (Alternaria solani), Root rot (Pythium myriotylum; Pythium dissotocum), Anthracnose (Colletotrichum phomoides), Leaf mold (Cladosporium fulvum), Canker (Corynebacterium michiganense), Tomato mosaic virus, Tomato spotted wilt virus; Eggplant powdery mildew (Sphaerotheca fuliginea), late blight (Phytophthora infestans), brown rot (Phytophthora capsici), bacterial wilt (Pseudomonas solanacearum); Sclerotinia rot of rapeseed (Sclerotinia scerotiorum), downy mildew (Peronospora brassicae); Black spot (Alternaria japonica), white spot (Pseudocercosporellacapsellae), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora brassicae) of cruciferous vegetables; White blight (Phytophthora porri) and rust (Puccinia allii) of leeks; Soft rot of Chinese cabbage (Erwinia carotovora); soybean stem rot (Phytophthora megasperma), downy mildew (Peronospora manshurica), purple spot (Cercospora kikuchii), black rot (Elsinoe glycines), black spot (Diaporthephaseololum); Anthracnose of beans (Colletotrichum lindemuthianum); Black spot of peanut (Mycosphaerella berkeleyii), brown spot (Mycosphaerella arachidis); Powdery mildew (Erysiphae pisi) and downy mildew (Peronospora pisi) on peas: Potato late blight (Phytophthora infestans), summer blight (Alternaria solani); Net blight (Exobasidium reticulatum) and white spot (Elsinoe leucospila) of tea; Tobacco red star (Alternaria alternata (tabacco pathotype)), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum); Brown spot of sugar beet (Cercospora beticola), downy mildew (Peronospora schachtii); Rose black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa); Brown spot of chrysanthemum (Septoria chrysanthemi-indici), white rust (Puccinia horiana); strawberry powdery mildew (Sphaerotheca macularis), late blight (Phytophthora nicotianae), fruit rot (Pythium ultimum), anthracnose (Colletotrichum fragariae); Gray mold (Botrytis cinerea) and stem rot (Sclerotinia sclerotiorum) on cucumbers, tomatoes, beans, strawberries, grapes, etc.; Turfgrass brown patch (Rhizoctonia solani), dollar spot (Sclerotinia homoeocarpa), curvularia leaf blight (Curvularia geniculata), rust (Puccinia zoysiae), helminthosporium leaf blight (Cochliobolus sp.), scald (Rhynchosporium secalis), damping-off (Gaeumannomyces graminis), anthracnose (Colletotrichum graminicola), brown snow blight (Typhula incarnata), black snow blight (Typhula ishikariensis), large snow blight (Sclerotinia borealis), fairy ring (including Marasmius oreades), Pythium wilt (including Pythium aphanidermatum).

[0033] Non-limiting examples of such animal pests are: From the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp. spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp.), Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; From the order of the Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; From the order Coleoptera, for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp. spp.), Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp.), Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabaeidae, Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;. From the order Diptera, for example, Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp. spp.), Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp. spp.), Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; From the order of Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigrella tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp., Thyanta spp., Triatoma spp.) and Vatiga illudens;. From the order Homoptera, for example, Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp. spp.), scale insects (Aonidiella auranti), aphids (Aphididae), cotton aphids (Aphis spp.), Aspidiotus spp., potato aphids (Aulacorthum solani), Bactericera cockerelli, Bemisia spp., Brachycaudus spp., radish aphids (Brevicoryne brassicae), Cacopsylla spp., carrot aphids (Cavariella aegopodii Scop.), Ceroplaster spp.), Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.), Neotoxoptera spp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Bayberry whitefly (Parabemisia myricae), Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Corn planthopper (Peregrinus maidis), Perkinsiella spp., Hop wart aphid (Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp. spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spisstilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera and Zyginidia scutellaris; From the order of Hymenoptera, for example, Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; From the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminate; From the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, peach fruit moth (Carposina nipponensis), Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, grapevine moth (Clysia ambiguella), Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, cotton moth (Cosmophila flava), Crambus spp., woolly moth (Crocidolomia binotalis), Cryptophlebia leucotreta leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp.), Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Grape moth (Eupoecilia ambiguella), Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp.), Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.), pine sawyer moth (Panolis flammea), Papaipema nebris, pink bollworm (Pectinophora gossypiela), coffee leafminer (Perileucoptera coffeella), Pseudaletia unipuncta, potato tuber moth (Phthorimaea operculella), cabbage white butterfly (Pieris rapae), Pieris spp., diamondback moth (Plutella xylostella), Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp.), Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta and Yponomeuta spp.;. From the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.; From the order of Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp. and Schistocerca spp.; From the order Psocoptera, for example, Liposcelis spp.; From the order of the Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; From the order of the Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.; and / or From the order Thysanura, for example, the silverfish (Lepisma saccharina).

[0034] Non-limiting examples of soil-dwelling pests that can damage crops at early stages of plant development include: From the order Lepidoptera, for example, Acleris spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Autographa spp., Busseola fusca, Cadra cautella, Chilo spp., Crocidolomia binotalis, Diatraea spp., Diparopsis castanea, Elasmopalpus spp., Heliothis spp., Mamestra brassicae), potato tuber moth (Phthorimaea operculella), diamondback moth (Plutella xylostella), Scirpophaga spp., Sesamia spp., Spodoptera spp. and Tortrix spp.; From the order Coleoptera, for example, Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Conotrachelus spp., Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Diloboderus spp., Epilachna spp., Eremnus spp., Heteronychus spp., Lissorhoptrus spp.), Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabaeidae, Sitotroga spp., Somaticus spp., Tanymecus spp., Tenebrio spp., Tribolium spp., Trogoderma spp.) and Zabrus spp.; From the order Orthoptera, for example, Gryllotalpa spp.; From the order Isoptera, for example, Reticulitermes spp.; From the order Psocoptera, for example, Liposcelis spp.; From the order of the Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; From the order Homoptera, for example, the apple aphid (Eriosoma larigerum); From the order of the Hymenoptera, for example, Acromyrmex, Atta spp., Cephus spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; From the order Diptera, for example, Tipula spp.; Crucifer flea beetles (Phyllotreta spp.), root maggots (Delia spp.), cabbage seedpod weevils (Ceutorhynchus spp.) and aphids on cruciferous plants.

[0035] The compositions of the present invention may also be useful for controlling nematodes. Thus, agrochemical compositions comprising the polymorphs of the present invention can be used to control plant pathogenic nematodes in many plant species. Thus, the present invention also provides a method for controlling damage to plants and plant parts caused by plant parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), comprising treating plants or plant propagation materials with a nematicidally effective amount of the agricultural composition of the present invention.

[0036] As used herein, the term "nematicide" refers to a compound or composition that controls or regulates the growth of nematodes. The term "nematicidally effective amount" refers to the amount of such a compound or composition, or a combination of such compounds or compositions, that is capable of killing, controlling, or infecting nematodes, slowing the growth or reproduction of nematodes, reducing nematode populations, and / or reducing damage to plants caused by nematodes.

[0037] Non-limiting examples of such plant parasitic nematodes are: Root-knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; Cyst-forming nematodes, such as the potato cyst nematode Globodera rostochiensis and other Globodera species; Wheat cyst nematode (Heterodera avenae), soybean cyst nematode (Heterodera glycines), sugar beet cyst nematode (Heterodera schachtii), clover cyst nematode (Heterodera trifolii) and other Heterodera species; Seed-knot nematodes, Anguina species; Stem and leaf nematodes, Aphelenchoides species; Sting nematode, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematode, Criconema species; Criconemella species; Criconemoides species; Mesocriconema species; Stem and lignematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematode, Dolichodorus species; Spiral nematode, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematode, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematode, Hoploaimus species; Root-knot nematode, Nacobbus species; Needle nematode, Longidorus elongatus and other Longidorus species; Pin nematode, Pratylenchus species; Lesion nematode, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematode, banana burrowing nematode (Radopholus similis) and other Radopholus species; Reniform nematode, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematode, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematode, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematode, Tylenchulus species; Dagger nematode, Xiphinema species; and Other plant-parasitic nematode species including Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp. and Quinisulcius spp.

[0038] In particular, nematode species of the genera Meloidogyne spp., Heterodera spp., Rotylenchus spp. and Pratylenchus spp. may be controlled by the compositions of the present invention.

[0039] The compositions according to the invention can be used to control, i.e. contain or destroy, pests of the above-mentioned types that occur in particular on plants, in particular on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of such plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even on plant organs that are formed at a later time and remain protected against these pests.

[0040] Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beets, for example sugar or fodder beets; fruits, for example pome fruits, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; legumes, for example beans, lentils, peas or soybeans; oil crops, for example rape, mustard, poppy, olives, sunflower, coconut, castor, cocoa or ground nuts; gourds plants from the Atractylodes family, such as pumpkin, cucumber or melon; fiber plants, such as cotton, flax, hemp or jute; citrus fruits, such as orange, lemon, grapefruit or tangerine; vegetables, such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato or bell pepper; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevine, hops, Plantaginaceae and latex plants.

[0041] The compositions and / or methods of the present invention may also be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees and evergreen trees.

[0042] For example, the present invention relates to the use of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g., B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp. spp.), Brassica spp. (ornamental plants), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp. spp.), bleeding hearts (Dicentra spectabilis), Dorotheantus spp., Lisianthus (Eustoma grandiflorum), Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Globetrotter (Gomphrena globosa), Heliotropium spp., Helianthus spp.), Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp. spp.), Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnations), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. zonale), Viola spp. (pansies), Petunia spp., Phlox spp. spp.), Plectranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (roses), Rudbeckia spp., Saintpaulia spp., Salvia spp.), Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp., as well as other bedding plants.

[0043] For example, the present invention relates to the production of vegetable crops from the following vegetable species: Allium spp. (A. sativum, A. cepa, A. oschaninii, A. porrum, A. ascalonicum, A. fistulosum), chervil (Anthriscus cerefolium), Asparagus officinalis, Beta vulgarus, Brassica spp. (B. oleracea, B. pekinensis, B. rapa), Capsicum annuum, chickpea (Cicer arietinum, endive (Cichorium endivia), Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. cardunculus), wild carrot (Daucus carota), fennel (Foeniculum vulgare, Hypericum spp., lettuce (Lactuca sativa), Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, parsley (Petroselinum crispum), Phaseolus spp. (P. vulgaris, P. cossinois),It may be used on any of the following plants: pea (Pisum sativum), radish (Raphanus sativus), rhubarb (Rheum rhaponticum), Rosemarinus spp., Salvia spp., Scorzonera hispanica, eggplant (Solanum melongena), Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa), and broad beans (Vicia faba).

[0044] Preferred ornamental species include African violets, begonias, dahlias, gerberas, hydrangeas, verbena, roses, kalanchoes, poinsettias, asters, centaurea, coreopsis, delphiniums, monardas, phloxes, rudbeckias, sedums, petunias, violas, impatiens, geraniums, chrysanthemums, ranunculus, fuchsias, salvias, hydrangeas, rosemary, sage, St. John's wort, mint, sweet peppers, tomatoes, and cucumbers.

[0045] The polymorphs according to the invention are particularly suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella, and Spodoptera littoralis in cotton, vegetable, corn, rice, and soybean crops. The polymorphs according to the invention are further particularly suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apple), Empoasca (preferably in vegetables, vineyards), Leptinotarsa ​​(preferably in potato), and Chilo supressalis (preferably in rice).

[0046] It should be understood that crops may be naturally occurring, obtained by conventional breeding methods, or obtained by genetic modification, and include crops that contain so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0047] It should be understood that crops also include those that have been made resistant to herbicides such as bromoxynil or classes of herbicides including ALS-, EPSPS-, GS-, HPPD-, and PPO-inhibitors. An example of a crop that has been made resistant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer canola. Examples of crops that have been made resistant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-resistant corn varieties sold under the trademarks RoundupReady®, Herculex I®, and LibertyLink®.

[0048] It should also be understood that crop plants may be naturally occurring or resistant to harmful insects. This includes plants that have been transformed, for example, by the use of recombinant DNA technology, to synthesize one or more selectively acting toxins, including those known to be derived from toxigenic fungi. Examples of toxins that may be expressed include delta-endotoxins, plant insecticidal proteins (Vips), insecticidal proteins of bacterial-colonizing nematodes, and toxins produced by scorpions, arachnids, wasps, and fungi.

[0049] An example of a crop modified to express a Bacillus thuringiensis toxin is Bt corn KnockOut® (Syngenta Seeds). An example of a crop containing two or more genes encoding insecticide resistance and therefore expressing two or more toxins is VipCot® (Syngenta Seeds). Crops or their seed material can also be resistant to multiple pests (so-called stacked transgenic events when formed by genetic modification). For example, a plant can be herbicide-resistant and simultaneously have the ability to express an insecticidal protein, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0050] Further areas of use of the compositions according to the invention are the protection of stored goods and storage rooms against pests of the types mentioned, as well as the protection of raw materials such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, in particular the protection of humans, livestock and productive livestock.

[0051] The present invention also provides a method for controlling pests (e.g., mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying the composition of the present invention to target pests, their habitats, or to a surface or substrate by brushing, rolling, spraying, dusting, or dipping. By way of example, IRS (indoor residual spray) application of surfaces, such as wall, ceiling, or floor surfaces, is contemplated by the method of the present invention. In another embodiment, it is contemplated to apply such compositions to substrates, such as nonwovens or textile materials, in the form of (or that can be used in the manufacture of) netting, clothing, bedding, curtains, and tents. Thus, another object of the present invention is a substrate selected from nonwovens and textile materials comprising a composition containing a compound of formula (I).

[0052] In one embodiment, a method for controlling such pests comprises applying a pesticidally effective amount of a composition of the present invention to target pests, their habitat, or to a surface or substrate to achieve effective residual pesticidal activity on the surface or substrate. Such application may be by brushing, rolling, spraying, dusting, or dipping the pesticidal composition of the present invention. By way of example, IRS application of a surface, such as a wall, ceiling, or floor surface, is contemplated by the method of the present invention to achieve effective residual pesticidal activity on the surface. In another embodiment, application of such a composition for residual control of pests on substrates, such as fabric materials in the form of (or that can be used in the manufacture of) netting, clothing, bedding, curtains, and tents, is contemplated.

[0053] The substrates to be treated, including nonwovens, fabrics, or netting, may be made of natural fibers such as cotton, raffia, jute, flax, sisal, burlap, or wool, or synthetic fibers such as polyamide, polyester, polypropylene, or polyacrylonitrile. Polyester is particularly suitable. Methods for treating textiles are known, for example, see WO 2008 / 151984, WO 2003 / 034823, U.S. Pat. No. 5,631,072, WO 2005 / 64072, WO 2006 / 128870, EP 1,724,392, WO 2005,113,886, or WO 2007 / 090739.

[0054] A further area of ​​use of the compositions according to the invention is in the field of trunk injection / trunk treatment for all ornamental trees and all fruit and nut trees.

[0055] In the field of trunk injection / trunk treatment, the polymorph according to the invention is particularly suitable against wood-boring insects from the orders Lepidoptera and Coleoptera, as mentioned above, in particular against the wood-boring organisms listed below: From the family Buprestidae, Agrilus planipennis, Agrilus anxius, Agrilus politus, Agrilus sayi, Agrilus vittaticollis, Chrysobothris femorata, and Texania campestris; From the family Cerambycidae: Anoplura glabripennis, Goes pulverulentus, Goes tigrinus, Neoclytus acuminatus, Neoptychodes trilineatus, Oberea ocellata, Oberea tripunctata, Oncideres cingulata, Saperda calcarata, Strophiona nitens; From the Scolytidae family, Xylosandrus crassiusculus, X. mutilatus, Tomicus piniperda, Corthylus columbianus, Dendroctorus frontalis, Dryocoetes betulae, Monarthrum fasciatum, Phloeotribus liminaris, and Pseudopityophthrus pruinosus; From the family Sesiidae: Paranthrene simulans, Sannina uroceriformis, Synanthedon exitiosa, Synanthedon pictipes, Synanthedon rubrofascia, Synanthedon scitula, and Vitacea polistiformis.

[0056] The present invention may also be used to control any pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, woodlice, mites, mole crickets, scale insects, mealybugs, mites, boxworms, long-legged bugs, and grubs. The present invention may be used to control pests at various stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0057] In particular, the present invention may be used to control grubs (e.g., Cyclocephala spp. (e.g., masked chafer, C. lurida), Rhizotrogus spp. (e.g., European chafer, R. majalis), Cotinus spp. (e.g., blue cockroach, C. nitida), Popillia spp. (e.g., Japanese beetle, P. japonica), Phyllophaga spp. (e.g., May / June beetle), Ataenius spp. spp.) (e.g., Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., red-veined scarab beetles, M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.), mole crickets (tan, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana), and crane fly larvae (European crane fly, Tipula spp.).

[0058] The present invention may also be used to control straw-dwelling turfgrass pests, including cutworms (e.g., the armyworm Spodoptera frugiperda and the common cutworm Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., e.g., S. venatus verstitus and S. parvulus), and sod webworms (e.g., Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).

[0059] The present invention may also be used to control turfgrass pests that live above ground and feed on turfgrass leaves, including stink bugs (e.g., the Japanese longhorn bug, Blissus insularis), the horse chestnut mite (Eriophyes cynodoniensis), the oak leafbug (Antonina graminis), the two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae), and greenbugs.

[0060] The present invention may also be used to control other pests of turfgrass, such as the red fire ant (Solenopsis invicta), which causes ant mounds in turf.

[0061] In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard mites, scorpion mites, scabies mites, chiggers, flies (stable flies and dentaries), parasitic fly larvae, lice, head lice, biting lice and fleas.

[0062] Examples of such parasites are: In the order Anoplurida, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp.; from the order Mallophagida, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.; From the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp. spp.), Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp. spp.), Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.; In the order Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.; In the Heteropterida order, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.; From the order Blattaria, for example, the Asian cockroach, the American cockroach, Blattela germanica and Supella spp.; From the subclass Acaria (Acarida) and the orders Mesostigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermacentor spp., spp.), Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.; From the suborder Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp. spp.), Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

[0063] The compositions according to the invention are also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings against insect infestations.

[0064] The compositions according to the invention are effective against, for example, the following pests: beetles, such as, for example, Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, pine wood beetles, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicolis, planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus species, Tryptodendron species, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon species) and Dinoderus minutus, and also insects of the order Hymenoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, It can be used against insects such as lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, and Coptotermes formosanus, and against silverfish such as Lepisma saccharina.

[0065] The amount of the pesticide composition of the present invention to be applied depends on the specific type of disease or insect to be controlled, the degree of control required, and the timing and method of application, and can be easily determined by one skilled in the art. Generally, the composition of the present invention can be applied at a rate of 0.005 kilograms per hectare (kg / ha) to about 5.0 kg / ha, based on the total amount of active ingredient (wherein "active ingredient" refers to one or more polymorphs of the present invention) in the composition. A rate of about 0.1 kg / ha to about 1.5 kg / ha is preferred, with a rate of about 0.3 kg / ha to 0.8 kg / ha being particularly preferred.

[0066] In practice, the pesticide compositions comprising one or more polymorphs of the present invention are applied as formulations containing various adjuvants and carriers known or used in the art.

[0067] These formulations may be in various physical forms, such as dusts, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, aqueous dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or a water-miscible organic solvent as a carrier), impregnated polymer films, or other forms known, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations may be used directly or diluted before use. Dilution may be carried out, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0068] The formulations may be prepared, for example, by mixing one or more polymorphs ("active ingredient") with formulation adjuvants to obtain a formulation in the form of a finely divided solid, granules, solution, dispersion, or emulsion. The active ingredient may also be formulated with other adjuvants, such as finely divided solids, mineral oil, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants, or combinations thereof.

[0069] The active ingredient can also be contained in fine microcapsules. Microcapsules contain the active ingredient in a porous carrier, allowing the active ingredient to be released into the environment in controlled amounts (e.g., sustained release). Microcapsules typically have a diameter of 0.1 to 500 μm. They contain the active ingredient in an amount of about 25 to 95% by weight of the capsule. The active ingredient can be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulating membrane can comprise, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers, and starch xanthate, or other polymers known to those skilled in the art. Alternatively, fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the substrate, but the microcapsule itself is not encapsulated.

[0070] Suitable formulation adjuvants for preparing the formulations according to the present invention are known per se. The following may be used as liquid carriers: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0071] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials.

[0072] A large number of surface-active substances can be used advantageously in both solid and liquid formulations, especially in formulations that can be diluted with a carrier before use. The surface-active substances can be anionic, cationic, nonionic or polymeric and they can be used as emulsifying agents, wetting agents or suspending agents, or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide adducts, such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphate esters; and further, for example, McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New York, NY Further substances are mentioned in Jersey (1981).

[0073] Further adjuvants that may be used in the pesticide formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, antifoaming agents, complexing agents, neutralizing or pH adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, uptake promoters, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.

[0074] The formulations of the present invention may contain additives including vegetable or animal-derived oils, mineral oils, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the formulations of the present invention is generally 0.01 to 10% based on the mixture to be applied. For example, the oil additive can be added to a spray tank at the desired concentration after the spray mixture is prepared. Preferred oil additives include mineral oil or vegetable-derived oils, such as rapeseed oil, olive oil, or sunflower oil, emulsified vegetable oils, alkyl esters of vegetable-derived oils, such as methyl derivatives, or animal-derived oils, such as fish oil or beef tallow. Preferred oil additives include alkyl esters of C8 to C22 fatty acids, particularly methyl derivatives of C12 to C18 fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010.

[0075] Formulations of the invention generally contain 0.1 to 99 wt. %, in particular 0.1 to 95 wt. % of the polymorph of the invention and 1 to 99.9 wt. % of formulation adjuvants, which preferably contain 0 to 25 wt. % of a surfactant. Commercial products may preferably be formulated as concentrates, although end users will typically use diluted formulations.

[0076] The application rate varies within wide limits and depends on the nature of the soil, the application method, the crop, the pests to be controlled, the current climatic conditions and other factors which depend on the application method, time of application and target crop. As a general guideline, the polymorphs of the invention may be applied in amounts of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0077] A preferred formulation may have the following composition (% by weight): Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1 to 30%, preferably 5 to 20% Liquid carrier: 1 to 80%, preferably 1 to 35%

[0078] Powder: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0079] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1 to 40%, preferably 2 to 30%

[0080] Wettable powder: Active ingredient: 0.5 to 90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0081] Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0082] The following formulation examples further illustrate, but do not limit, the present invention.

[0083] Wettable powder example 1: Active ingredient: 25% Sodium lignosulfonate: 5% Sodium lauryl sulfate: 3% Highly dispersed silicic acid: 5% Kaolin: 62% The combination is thoroughly mixed with the adjuvant, the mixture is thoroughly ground in a suitable mill, and the wettable powder is This can be diluted with water to obtain a suspension of the desired concentration.

[0084] Wettable powder example 2: Active ingredient: 50% Sodium lignosulfonate: 5% Sodium dibutylnaphthalene sulfonate: 6% Phenol polyethylene glycol ether (7-8 mol ethylene oxide): 2% Highly dispersed silicic acid: 10% Kaolin: 27% The combination is thoroughly mixed with the adjuvant, the mixture is thoroughly ground in a suitable mill, and the wettable powder is This can be diluted with water to obtain a suspension of the desired concentration.

[0085] Wettable powder example 3: Active ingredient: 75% Sodium lauryl sulfate: 5% Sodium dibutylnaphthalene sulfonate: 10% Highly dispersed silicic acid: 10% The combination is thoroughly mixed with the adjuvant, the mixture is thoroughly ground in a suitable mill, and the wettable powder is This can be diluted with water to obtain a suspension of the desired concentration.

[0086] Dust for dry seed treatment Example 1: Active ingredient: 25% Diesel: 5% Highly dispersed silicic acid: 5% Kaolin: 65% The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0087] Dust for dry seed treatment Example 2: Active ingredient: 50% Diesel: 5% Highly dispersed silicic acid: 5% Kaolin: 40% The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0088] Dust for dry seed treatment Example 3: Active ingredient: 75% Diesel: 5% Kaolin: 20% The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0089] Examples of emulsifiable concentrates: Active ingredient: 10% Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide): 3% Calcium dodecylbenzenesulfonate: 3% Castor oil polyglycol ether (35 mol ethylene oxide): 4% Cyclohexanone: 30% Xylene mixture: 50% Emulsions of any required dilution that can be used in plant protection can be obtained from this concentrate by dilution with water.

[0090] Powder Example 1: Active ingredient: 5% Talcum: 95% Ready-to-use dusts can be obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressing of seeds.

[0091] Powder Example 2: Active ingredient: 6% Kaolin: 94% Ready-to-use dusts can be obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressing of seeds.

[0092] Powder Example 3: Active ingredient: 4% Inorganic filler: 96% Ready-to-use dusts can be obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressing of seeds.

[0093] Extruded granules example: Active ingredient: 15% Sodium lignosulfonate: 2% Carboxymethylcellulose: 1% Kaolin: 82% The combination is mixed and ground with the adjuvants, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0094] Coated granules example: Active ingredient: 8% Polyethylene glycol (molecular weight 200): 3% Kaolin: 89% The pulverized combination is mixed in a mixer with kaolin moistened with polyethylene glycol. Apply evenly to the area. Dust-free coated granules are thus obtained.

[0095] Suspension concentrate examples: Active ingredient: 40% Propylene glycol: 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide): 6% Sodium lignosulfonate: 10% Carboxymethylcellulose: 1% Silicone oil (in the form of a 75% emulsion in water): 1% Water: 32% The pulverized combination is thoroughly mixed with adjuvants to obtain a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring, or immersion.

[0096] Examples of flowable concentrates for seed treatment: Active ingredient: 40% Propylene glycol: 5% Copolymer butanol PO / EO: 2% Tristyrenephenol containing 10-20 mol EO: 2% 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water): 0.5% Monoazo pigment calcium salt: 5% Silicone oil (in the form of a 75% emulsion in water): 0.2% Water: 45.3% The micronized combination is homogeneously mixed with an adjuvant to obtain a suspension concentrate, and the suspension concentrate A suspension of any desired dilution can be obtained from the solution by dilution with water. Living plants and plant propagation materials are treated by spraying, pouring or immersion to kill microorganisms. can be protected from harm by

[0097] Sustained-release capsule suspension examples: 28 parts of the active ingredient are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenylisocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size is obtained. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of the active ingredient. The median capsule diameter is 8-15 μm. The resulting formulation is applied to seeds as an aqueous suspension in equipment suitable for the purpose.

[0098] Each of the above formulations may be prepared as a package containing one or more polymorphs of the present invention along with other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.) The formulations may also be prepared by the tank mix method, in which the ingredients are obtained separately and combined at the grower's location.

[0099] These formulations can be applied to the area where control is required by conventional methods. For example, dust and liquid formulations can be applied by using a power duster, brush, and hand atomizer and spray duster. The formulations can also be applied from an airplane as a dust or spray, or by rope wick application. Both solid and liquid formulations can be applied to the soil of the habitat of the plants to be treated, allowing the active ingredients to penetrate the plants through the roots.

[0100] The polymorphs of the present invention and compositions thereof are also suitable for protecting plant propagation material, such as seeds, e.g., fruits, tubers, or grains, or seedlings, against the above-mentioned types of pests. The propagation material can be treated with the polymorphs before planting, e.g., seeds can be treated before sowing. Alternatively, the polymorphs can be applied (coated) to seed kernels by immersing the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the composition when the propagation material is planted at the application site, e.g., in the seed furrow during planting. These treatment methods for plant propagation material, and the plant propagation material thus treated, are further objects of the present invention. Typical application rates depend on the plant and pest / fungus to be controlled and are generally 1 to 200 grams per 100 kg of seed, preferably 5 to 150 grams per 100 kg of seed, e.g., 10 to 100 grams per 100 kg of seed.

[0101] The term seed encompasses all types of seeds and plant propagules, including but not limited to true seeds, seed fragments, underground stolons, grains, bulbs, fruits, tubers, flour, rhizomes, cuttings, cuttings, etc., and in a preferred embodiment refers to true seeds.

[0102] The present invention also includes seeds coated, treated, or containing the polymorph of the present invention. The term "coated, treated, and / or containing" generally indicates that the active ingredient is mostly on the surface of the seed upon application, although depending on the method of application, a greater or lesser portion of the ingredient may penetrate into the seed material. When the seed product is (re)planted, the seed product may absorb the active ingredient. In one embodiment, the present invention provides a plant propagation material to which a compound of formula (I) is adhered. This further provides a composition comprising plant propagation material treated with a compound of formula (I).

[0103] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed spraying, seed soaking and seed pelleting. The seed treatment application of the compound of formula (I) can be carried out by any known method, such as spraying or dusting the seeds before sowing or during sowing / planting of the seeds.

[0104] Suitably, the agrochemical compositions and formulations of the present invention are applied prior to disease infestation, with the rate and frequency of application of the formulation being those conventionally used in the art and dependent on the risk of infestation by the insect pathogen.

[0105] The activity of compositions containing the compounds and polymorphs according to the present invention can be significantly broadened and adapted to a wide range of commonly occurring conditions by including other active substances. Active substances can be chemical or biological in type, and if biological, can be further modified from naturally occurring biological species. Active substances generally include substances that control, repel, or attract pests that damage or harm useful plants, as well as substances that improve the growth of useful plants, such as plant growth disruptors, and substances that improve the performance of active substances, such as synergists. Examples include insecticides, acaricides, nematicides, molluscicides, algaecides, viruicides, rodenticides, bactericides, fungicides, chemosterilants, and anthelmintics. Examples of biologically active substances include baculoviruses, plant extracts, and bacteria.

[0106] Thus, the present invention provides for the use of a composition of the present invention together with one or more pesticides, plant nutrients or plant fertilizers, which combination may include specific plant traits that are incorporated into the plant by any means, such as traditional breeding or genetic modification.

[0107] Mixtures of the polymorphs of the invention with other active substances may also have additional unexpected advantages, sometimes more broadly described as synergistic activity, such as better tolerance by plants, reduced phytotoxicity, insects being controlled at different stages of their development, or better behavior in relation to production, e.g., grinding or mixing, storage, or use.

[0108] An individual active substance may occur in more than one group or class, and in more than one location within a group or class: information about active substances, their spectrum, source and classification can be found in the Compendium of Pesticide Common Names (see http: / / www.alanwood.net / pesticides / index.html) or in the Pesticide Manual produced by the British Crop Production Council (see http: / / bcpcdata.com / pesticide-manual.html).

[0109] Preferred polymorph(s) are shown below, where the polymorph of diclobentiazox according to the present invention is designated as "I".

[0110] Non-limiting examples of compositions that include adjuvants include compounds selected from the group of substances consisting of I+ petroleum.

[0111] Non-limiting examples of compositions comprising a fungicide include I+acibenzolar, I+aldimorph, I+ampropylphos, I+andoprim, I+azaconazole, I+azoxystrobin, I+benalaxyl, I+benomyl, I+bialaphos, I+blasticidin-S, I+Bordeaux mixture, I+bromuconazole, I+bupirimate, I+carpropamid, I+captafol, I+captan, I+carbendazim, I+chlorphenazole, I+chloroneb, I+chloropicrin, I+chlorothalonil, I+chlozolinate, I+copper oxychloride, I+copper salts, I+citric acid ... Flufenamid, I + Cymoxanil, I + Cyproconazole, I + Cyprodinil, I + Cyproflam, I + RH-7281, I + Diclocymet, I + Diclobutrazol, I + Diclomedine, I + Dicloran, I + Difenoconazole, I + RP-407213, I + Dimethomorph, I + Domoxystrobin, I + Diniconazole, I + Diniconazole-M, I + Dodine, I + Edifenphos, I + Epoxiconazole, I + Famoxadone, I + Fenamidone, I + Fenarimol, I + Fenbuconazole, I + Fen I+Fencalamide, I+Fenpiclonil, I+Fenpropidin, I+Fenpropimorph, I+Fentin acetate, I+Fluazinam, I+Fludioxonil, I+Flumetober, I+Flumorph / Flumorin, I+Fentin hydroxide, I+Fluoxastrobin, I+Fluquinconazole, I+Flusilazole, I+Flutanil, I+Flutriafol, I+Folpet, I+Fosetylaluminum, I+Furalaxyl, I+Furametapyr, I+Hexaconazole, I+Ipconazole, I+Iprobenfos, Iprodione, Isoprothiolane, Kasugamycin, Kresoxim-methyl, Mancozeb, Maneb, Mefenoxam, Mepronil, Metalaxyl, Metconazole, Metominostrobin / Fenominostrobin, Metrafenone, Myclobutanil, Neoasozin, Nicobifen, Orysastrobin, Oxadixyl, Penconazole, Pencycuron, Probenazole, Prochloraz, Propamocarb, PropioconazoleI + proquinazid, I + prothioconazole, I + pyrifenox, I + pyraclostrobin, I + pyrimethanil, I + pyroquilon, I + quinoxyfen, I + spiroxamine, I + sulfur, I + tebuconazole, I + tetoronazole, I + thiabendazole, I + thifluzamide, I + thiophanate-methyl, I + thiram, I + tiadinil, I + triadimefon, I + triadimenol, I + tricyclazole, I + trifloxystrobin, I + triticonazole, I + validamycin, I + vinclozine.

[0112] Non-limiting examples of compositions comprising acaricides include I + 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, I + 2,4-dichlorophenylbenzenesulfonate, I + 2-fluoro-N-methyl-N-1-naphthylacetamide, I + 4-chlorophenylphenylsulfone, I + abamectin, I + acequinocyl, I + acetoprole, I + acrinathrin, I + aldicarb, I + aldoxicarb, I + α-cypermethrin, I + amidithione, I + amidoflumet, I + amidothioate, I + amiton, I + amiton hydrogen oxalate, I + amitraz, I + alamite, I + diarsenic trioxide, I + AVI 382, ​​I + AZ 60541, I+Azinphos-ethyl, I+Azinphos-methyl, I+Azobenzene, I+Azocyclotine, I+Azotoate, I+Benomyl, I+Benoxafos, I+Benzoximate, I+Benzyl Benzoate, I+Bifenazate, I+Bifenthrin, I+Binapacryl, I+Bromofenvalerate, I+Bromocyclen, I+Bromophos, I+Bromophos-ethyl, I+Bromopropylate, I+Buprofezin, I+Butocarboxim, I+Butoxycarboxim, I+Butylpyridaben, I+Calcium Polysulfide, I+Camphechlor, I+Carbanolate, I+Carbaryl, I+Carbofuran, I+Carbophenothion, I+CGA 50'439, I+Chinomethionate, I+Chlorbeside, I+Chlordimeform, I+Chlordimeform Hydrochloride, I+Chlorfenapyr, I+Chlorphenetole, I+Chlorfenson, I+Chlorphenesulfide, I+Chlorfenvinphos, I+Chlorobenzilate, I+Chlormebuform, I+Chloromethionate, I+Chloropropylate, I+Chlorpyrifos, I+Chlorpyrifos-methyl, I+Chlorthiophos, I+Cineline, I+Cineline Ion II, I+cinerine, I+clofentezine, I+closantel, I+coumaphos, I+crotamiton, I+crotoxyphos, I+kufuraneb, I+cyantoate, I+cyflumetofen, I+cyhalothrin, I+cyhexatin, I+cypermethrin, I+DCPM, I+DDT, I+Demefion, I+Demefion-O, I+Demefion-S, I+Demeton, I+Demeton-methyl, I+Demeton-O, I+Demeton-O-methyl, I+Demeton-S,Demeton-S-methyl, Demeton-S-methyl sulfone, Diafenthiuron, Dialifos, Diazinon, Dichlofluanid, Dichlorvos, Dicrifos, Dicofol, Dicrotophos, Dienochlor, Dimefox, Dimethoate, Dinactin, Zinex, Zinex-diclexin, Zinobuton, Dinocap, Dinocap-4, Dinocap-6, Dinocton, Dinopenton, Dinosulfone, Dinotervone, Dioxathion, Diphenyl sulfone, Disulfiram, Disulfoton, DNOC, Dofenapine, Doramectin, Endosulfan, I+Endothion, I+EPN, I+Eprinomectin, I+Ethion, I+Ethoate-methyl, I+Etoxazole, I+Etrimphos, I+Fenazaflor, I+Fenazaquin, I+Fenbutatin oxide, I+Fenothiocarb, I+Fenpropathrin, I+Fenpyrad, I+Fenpyroximate, I+Fenthone, I+Fentrifanil, I+Fenvalerate, I+Fipronil, I+Fluacrypyrim, I+Fluazuron, I+Flubenzimine, I+Flucycloxuron, I+Flucythrinate, I+Flueneethyl, I+Flufenoxuron, I+Flumethrin, I+Fluorbenside, I+Fluvalinate, I+FMC 1137, I + Formetanate, I + Formetanate Hydrochloride, I + Formothion, I + Formoparanate, I + γ-HCH, I + Gliodin, I + Halfenprox, I + Heptenophos, I + Hexadecylcyclopropanecarboxylate, I + Hexythiazox, I + Iodomethane, I + Isocarbophos, I + Isopropyl O-(methoxyaminothiophosphoryl) salicylate, I + Ivermectin, I + Jasmolin I, I + Jasmolin I I, I + Iodofenphos, I + Lindane, I + Lufenuron, I + Malathion, I + Malonoben, I + Mecarbam, I + Mephosphoran, I + Mesulfen, I + Methacrifos, I + Methamidophos, I + Methidathion, I + Methiocarb, I + Methomyl, I + Methyl bromide, I + Metolcarb, I + Mevinphos, I + Mexacarbate, I + Milbemectin, I + Milbemycin oxime, I + Mipafox, I + Monocrotophos, I + Morphothion,Moxidectin, Naled, NC-184, NC-512, Nifluridide, Nikkomycin, Nitrilacarb, Nitrilacarb 1:1 Zinc Chloride Complex, NNI-0101, NNI-0250, Omethoate, Oxamyl, Oxydeprophos, Oxydisulfoton, pp'-DDT, Parathion, Permethrin, Petroleum, Fencapton, Phenthoate, Phorate, Phosalone, I+phospholane, I+phosmet, I+phosphamidon, I+phoxim, I+pirimiphos-methyl, I+polychloroterpene, I+polynactin, I+proclonol, I+profenofos, I+promacil, I+propargite, I+propetamphos, I+propoxar, I+protidathion, I+protoate, I+pyrethrin I, I+pyrethrin II, I+pyrethrin, I+pyridaben, I+pyridafenthion, I+pyrimidifen, I+Pirimitate, I+Quinalphos, I+Quintiox, I+R-1492, I+RA-17, I+Rotenone, I+Schradan, I+Cebufos, I+Selamectin, I+SI-0009, I+Sofamide, I+Spirodiclofen, I+Spiromesifen, I+SSI-121, I+Sulfiram, I+Sulfuramide, I+Sulfotep, I+Sulfur, I+SZI-121, I+τ-Fulvalinate, I+Tebufenpyrad, I+TEPP, I+Terba Examples of such antibacterial agents include I+tetrachlorvinphos, I+tetradifon, I+tetranactin, I+tetrasul, I+thiafenox, I+thiocarboxim, I+thiofanox, I+thiometon, I+thioquinox, I+thuringiensin, I+triamiphos, I+triatene, I+triazophos, I+triazuron, I+trichlorfon, I+tripenophos, I+triactin, I+vamidothion, I+vaniliprole, and I+YI-5302.

[0113] Non-limiting examples of compositions comprising biological control agents include I+ Adoxophyes orana GV, I+ Agrobacterium radiobacter, I+ Amblyseius spp., I+ Anagrapha falcifera NPV, I+ Anagrus atomus, I+ Aphelinus abdominalis, I+ Aphidius colemani, I+ Aphidoletes aphidimyza, I+ Autographa californica NPV, I+ Bacillus firmus, I+ Bacillus sphaericus neide, I+ Bacillus sphaericus Neide), I+ Bacillus thuringiensis Berliner, I+ Bacillus thuringiensis subsp. aizawai, I+ Bacillus thuringiensis subsp. israelensis, I+ Bacillus thuringiensis subsp. japonensis, I+ Bacillus thuringiensis subsp. kurstaki, I+ Bacillus thuringiensis subsp. tenebrionistenebrionis, I+Beauveria bassiana, I+Beauveria brongniartii, I+Chrysoperla carnea, I+Cryptolaemus montrouzieri, I+Cydia pomonella GV, I+Dacnusa sibirica, I+Diglyphus isaea, I+Encarsia formosa, I+Eretmocerus eremicus, I+Helicoverpa zea NPV, I+Heterorhabditis bacteriophora and H. megidis, I+ Hippodamia convergens, I+ Leptomastix dactylopii, I+ Macrolophus caliginosus, I+ Mamestra brassicae NPV, I+ Metaphycus helvolus, I+ Metarhizium anisopliae var. acridum, I+ Metarhizium anisopliae var. anisopliae, I+ Neodiprion sertifer NPV and N. lecontei NPV, I+ Orius spp.), I+ Paecilomyces fumosoroseus, I+ Phytoseiulus persimilis, I+ Spodoptera exigua multicapsid nuclear polyhedrosis virus, I+ Steinernema bibionis, I+ Steinernema carpocapsae, I+ Steinernema feltiae, I+ Steinernema glaseri, I+ Steinernema riobrave, I+ Steinernema riobravis, I+ Steinernema scapterisi scapterisci, I+ Steinernema spp., I+ Trichogramma spp., I+ Typhlodromus occidentalis, and I+ Verticillium lecanii.

[0114] Non-limiting examples of compositions that include soil sterilants include I+ iodomethane and methyl bromide.

[0115] Non-limiting examples of compositions comprising sterilizing agents include I+Afolate, I+Visadyl, I+Busulfan, I+Diflubenzuron, I+Zimatif, I+Hemel, I+Hempa, I+Metepa, I+Methiotepa, I+Methylafolate, I+Moldid, I+Penfluron, I+Tepa, I+Thiohempa, I+Thiotepa, I+Tretamine, and I+Uredep.

[0116] Non-limiting examples of compositions containing insect pheromones include I(E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, I(E)-tridec-4-en-1-yl acetate, I(E)-6-methylhept-2-en-4-ol, I(E,Z)-tetradec-4,10-dien-1-yl acetate, I(Z)-dodec-7-en-1-yl acetate, I(Z)-hexadec-11-enal, I(Z)-hexadec-11-en-1-yl acetate ... I+(Z)-hexadec-13-en-11-yn-1-yl acetate, I+(Z)-icosa-13-en-10-one, I+(Z)-tetradec-7-en-1-al, I+(Z)-tetradec-9-en-1-ol, I+(Z)-tetradec-9-en-1-yl acetate, I+(7E,9Z)-dodeca-7,9-dien-1-yl acetate, I+(9Z,11E)-tetradec-9,11-dien-1-yl acetate, I+(9Z,12E)-tetradec-7,9-dien-1-yl acetate, I+(9Z,11E)-tetradec-9,11-dien-1-yl acetate, I+(9Z,12E)-tetradec-9,11-dien-1-yl acetate Deca-9,12-dien-1-yl acetate, I + 14-methyloctadec-1-ene, I + 4-methylnonan-5-ol and 4-methylnonan-5-one, I + α-multistriatin, I + Brevicomin, I + Codrelure, I + Codlemone, I + Curure, I + Disparle, I + Dodec-8-en-1-yl acetate, I + Dodec-9-en-1-yl acetate, I + Dodec-8, I + 10-dien-1-yl acetate, I + Dominicalure, I + 4-methyloctadecane Ethyl phosphate, I+eugenol, I+frontalin, I+gossiplua, I+grandlua, I+grandlua I, I+grandlua II, I+grandlua III, I+grandlua IV, I+hexalure, I+ipsdienol, I+ipsenol, I+japonilure, I+lineatin, I+litalure, I+lupula, I+medula, I+megatomoic acid, I+methyleugenol, I+muscalure, I+octadeca-2,13-dien-1-yl acetate, I+octadeca-3,13-dien-1-yl acetate, Iolfural, Iorictal, Iostramon, Iciglua, Isoldidin, Isulcatol, Itetradec-11-en-1-yl acetate, Itrimedula, Itrimedula A, Itrimedula B1, Itrimedula B2, Itrimedula C, and Itrunc-call.

[0117] Non-limiting examples of compositions comprising insect repellents include I+2-(octylthio)ethanol, I+butopyronoxyl, I+butoxy(polypropylene glycol), I+dibutyl adipate, I+dibutyl phthalate, I+dibutyl succinate, I+diethyltoluamide, I+dimethylcarbate, I+dimethyl phthalate, I+ethylhexanediol, I+hexamide, I+methoquin-butyl, I+methylneodecanamide, I+oxamate, and I+picaridin.

[0118] Non-limiting examples of compositions containing insecticides include I + 1-dichloro-1-nitroethane, I + 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, I + 1,2-dichloropropane, I + 1,2-dichloropropane and 1,3-dichloropropene, I + 1-bromo-2-chloroethane, I + 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, I + 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate. , I + 2-(1,3-dithiolan-2-yl)phenyl dimethyl carbamate, I + 2-(2-butoxyethoxy)ethyl thiocyanate, I + 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate, I + 2-(4-chloro-3,5-xylyloxy)ethanol, I + 2-chlorovinyl diethyl phosphate, I + 2-imidazolidone, I + 2-isovalerylindan-1,3-dione, I + 2-methyl(prop-2-ynyl) ) Aminophenylmethylcarbamate, I + 2-thiocyanatoethyl laurate, I + 3-bromo-1-chloroprop-1-ene, I + 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate, I + 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate, I + 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate, I + abamectin, I + acephate, I + acetamiprid, I + acetione, I + Acetoprole, I + Acrinathrin, I + Acrylonitrile, I + Alanycarb, I + Aldicarb, I + Aldoxycarb, I + Aldrin, I + Allethrin, I + Allosamidin, I + Alixycarb, I + α-Cypermethrin, I + α-Ecdysone, I + Aluminum phosphide, I + Amidithione, I + Amidothioate, I + Aminocarb, I + Amiton, I + Amiton hydrogen oxalate, I + Amitraz, I + Anabasine, I + Atidathion, I + AVI 382, I+AZ 60541, I+Azadirachtin, I+Azamethiphos, I+Azinphos-ethyl, I+Azinphos-methyl, I+Azotoate, I+Bacillus thuringiensis delta-endotoxin, I+Barium hexafluorosilicate, I+Barium polysulfide, I+Bartholin,I+Bayer 22 / 190, I+Bayer 22408, I+Bendiocarb, I+Benfuracarb, I+Bensultap, I+β-Cyfluthrin, I+β-Cypermethrin, I+Bifenthrin, I+Bioallethrin, I+Bioallethrin S-Cyclopentenyl Isomer, I+Bioethanomethrin, I+Biopermethrin, I+Bioresmethrin, I+Bis(2-chloroethyl)ether, I+Bistrifluron, I+Borax, I+Brofenvalerate, I+Bromfenvinphos, I+Bromocyphen Clen, I+bromo-DDT, I+bromophos, I+bromophos-ethyl, I+bufencarb, I+buprofezin, I+butacarb, I+butathiophos, I+butocarboxim, I+butonate, I+butoxycarboxim, I+butylpyridaben, I+cadusafos, I+calcium arsenate, I+calcium cyanide, I+calcium polysulfide, I+camphechlor, I+carbanolate, I+carbaryl, I+carbofuran, I+carbon disulfide, I+tetrachloride Carbon, I+Carbophenothione, I+Carbosulfan, I+Cartap, I+Cartap Hydrochloride, I+Cevadine, I+Chlorbicyclen, I+Chlordane, I+Chlordecone, I+Chlordimeform, I+Chlordimeform Hydrochloride, I+Chlorethoxyphos, I+Chlorfenapyr, I+Chlorfenvinphos, I+Chlorfluazuron, I+Chlormephos, I+Chloroform, I+Chloropicrin, I+Chlorphoxim, I+Chlorprazophos, I+ Chlorpyrifos, I+chlorpyrifos-methyl, I+chlorthiophos, I+chromafenozide, I+cinerin I, I+cinerin II, I+cinerin, I+cis-resmethrin, I+cismethrin, I+clocitrin, I+cloetocarb, I+closantel, I+clothianidin, I+copper acetoarsenite, I+copper arsenate, I+copper oleate, I+coumaphos, I+coumitoate, I+crotamiton, I+crotoxyphos, I+crufomate, I+cryolite, I+CS 708, I+cyanofenphos, I+cyanophos, I+cyantoate, I+cyclethrin, I+cycloprothrin, I+cyfluthrin, I+cyhalothrin, I+cypermethrin, I+cyphenothrin, I+cyromazine, I+cythioate, I+d-limonene, I+d-tetramethrin, I+DAEP, I+dazomet, I+DDT,Decarbofuran, Deltamethrin, Demefion, Demefion-O, Demefion-S, Demeton, Demeton-methyl, Demeton-O, Demeton-O-methyl, Demeton-S, Demeton-S-methyl, Demeton-S-methyl sulfone, Diafenthiuron, Dialifos, Diamidaphos, Diazinon, Dikapton, Diclofenthion, Dichlorvos, Dicrifos, Dicresyl, Dicrotophos, Dicyclanil, Dieldrin, Diethyl 5- Methylpyrazol-3-yl phosphate, I+Diflubenzuron, I+Dilol, I+Dimefluthrin, I+Dimefox, I+Dimethane, I+Dimethoate, I+Dimethrine, I+Dimethylvinphos, I+Dimethiran, I+Zinex, I+Zinex-Diclexin, I+Dinoprop, I+Dinosam, I+Dinoseb, I+Dinotefuran, I+Diofenolan, I+Dioxabenzophos, I+Dioxacarb, I+Dioxathion, I+Disulfoton, I+Dicyclophos, I+DNOC, I+Dramectin, I+DSP, I+Ecdysterone, I+EI 1642, I+Emamectin, I+Emamectin Benzoate, I+EMPC, I+Empenthrin, I+Endosulfan, I+Endothion, I+Endrin, I+EPBP, I+EPN, I+Epofenonane, I+Eprinomectin, I+Esfenvalerate, I+Etaphos, I+Ethiofencarb, I+Ethion, I+Ethiprole, I+Ethoate-Methyl, I+Ethoprophos, I+Ethyl Formate, I+Ethyl-DDD, I+Ethylene Dibromide, I+Ethylene Dichloride, I+Ethylene Oxide, I+Etofenprox, I+Etrimphos, I+EX D, I+Fanfar, I+Fenamiphos, I+Fenazaflor, I+Fenchlorphos, I+Fenetacarb, I+Fenfluthrin, I+Fenitrothion, I+Fenobucarb, I+Fenoxacrim, I+Fenoxycarb, I+Fenpyritrin, I+Fenpropathrin, I+Fenpyrad, I+Fensulfothion, I+Fenthion, I+Fenthion-ethyl, I+Fenvalerate, I+Fipronil, I+Flonicamid, I+Flubendiamide, I+Flucofuron, I+Flucycloxuron, I+Flucythrinate, I+Flueneethyl,Flufenerim, Flufenoxuron, Flufenprox, Flumethrin, Fluvalinate, FMC 1137, Fonofos, Formetanate, Formetanate Hydrochloride, Formothion, Formparanate, Fosmetilan, Fospirate, Fosthiazate, Fostietan, Furathiocarb, Frethrin, γ-Cyhalothrin, γ-HCH, Guazatine, Guazatine Acetate, GY-81, Halfenprox, Halofenozide, HCH, HEOD, Heptachlor, Heptenofos, Heterofos, Hexaflumuron, HHDN, +Hydramethylnon, I+Hydrogen cyanide, I+Hydroprene, I+Hikincarb, I+Imidacloprid, I+Imiprothrin, I+Indoxacarb, I+Iodomethane, I+IPSP, I+Isazophos, I+Isobenzan, I+Isocarbophos, I+Isodrin, I+Isofenphos, I+Isolane, I+Isoprocarb, I+Isopropyl O-(methoxyaminothiophosphoryl) salicylate, I+Isoprothiolane, I+Isothioate, I+Isoxathion, I+Ivermectin, I+Jasmolin, I+Di Jasmolin II, I+Iodofenphos, I+Juvenile hormone I, I+Juvenile hormone II, I+Juvenile hormone III, I+Kelevan, I+Kinoprene, I+λ-Cyhalothrin, I+Lead arsenate, I+Lepimectin, I+Leptophos, I+Lindan, I+Lilimphos, I+Lufenuron, I+Ritidathion, I+m-Cumenylmethylcarbamate, I+Magnesium phosphide, I+Malthion, I+Malonoben, I+Majidox, I+Mecarbam, I+Mecarfone, I+Menasone, I+Mefolan, I+Mercurous chloride, I+Meth Rufenphos, I + metaflumizone, I + metam, I + metam-potassium, I + metam-sodium, I + methacrifos, I + methamidophos, I + methanesulfonyl fluoride, I + methidathion, I + methiocarb, I + metoclothos, I + methomyl, I + methoprene, I + methoquin-butyl, I + metotrin, I + methoxychlor, I + methoxyfenozide, I + methyl bromide, I + methyl isothiocyanate, I + methyl chloroform, I + methylene chloride, I + metofluthrin, I + metolcarb, I + metoxadiazone,I+Mevinphos, I+Mexacarbate, I+Milbemectin, I+Milbemycin oxime, I+Mipafox, I+Mirex, I+Moncrotophos, I+Morphothion, I+Moxidectin, I+Naphthalophos, I+Naled, I+Naphthalene, I+NC-170, I+NC-184, I+Nicotine, I+Nicotine sulfate, I+Nifluridide, I+Nitenpyram, I+Nithiazine, I+Nitrilacarb, I+Nitrilacarb 1:1 Zinc Chloride Complex, I+NNI-0101, I+NNI-0250, I+Nornicotine, I+Novaluron, I+Noviflumuron, I+O-5-Dichloro-4-iodophenyl O-ethyl ethylphosphonothioate , I+O,O-Diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, I+O,O-Diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, I+O,O,O',O'-Tetrapropyldithiopyrophosphate, I+Oleic acid, I+Omethoate, I+Oxamyl, I+Oxydemeton-methyl, I+Oxydeprophos, I+Oxydisulfoton, I+pp'-DDT, I+para-dichlorobenzene, I+Parathion, I+Parathion-methyl, I+Penfluron, I+Pentachlorophenol, I+Pentachlorophenyl laurate, I+Permethrin, I+Petroleum, I+PH 60-38, I+Fencaptone, I+Fenothrin, I+Phenthoate, I+Phorate+TX, I+Phosalone, I+Phosphorane, I+Phosmet, I+Phosniclor, I+Phosphamidon, I+Phosphine, I+Phoxim, I+Phoxim-methyl, I+Pirimetaphos, I+Pirimicarb, I+Pirimiphos-ethyl, I+Pirimiphos-methyl, I+Polychlorodicyclopentadiene isomers, I+Polychloroterpenes, I+Potassium arsenite, I+Potassium thiocyanate I+prallethrin, I+precocene I, I+precocene II, I+precocene III, I+primidophos, I+profenofos, I+profluthrin, I+promacyl, I+promecarb, I+propafos, I+propetamphos, I+propoxar, I+protidathion, I+prothiofos, I+protoate, I+protrifenbute, I+pymetrozine, I+pyraclofos, I+pyrazophos, I+pyresmethrin, I+pyrethrin I, I+pyrethrin II,I + Pyrethrins, I + Pyridaben, I + Pyridalyl, I + Pyridaphenthion, I + Pyrimidifen, I + Pirimitate, I + Pyriproxyfen, I + Quassia, I + Quinalphos, I + Quinalphos-methyl, I + Quinothione, I + Quinthiox, I + R-1492, I + Rafoxanide, I + Resmethrin, I, +Rotenone, I+RU 15525, I+RU 25475, I+Ryania, I+Ryanodine, I+Sabadila, I+Schradan, I+Cebufos, I+Selamectin, I+SI-0009, I+SI-0205, I+SI-0404, I+SI-0405, I+Silafluofen, I+SN 72129, I+Sodium arsenite, I+Sodium cyanide, I+Sodium fluoride, I+Sodium hexafluorosilicate, I+Sodium pentachlorophenoxide, I+Sodium selenate, I+Sodium thiocyanate, I+Sofamide, I+Spinosad, I+Spiromesifen, I+Spirotetramat, I+Sulcofuron, I+Sulcofuron-sodium, I+Sulfuramide, I+Sulfotep, I+Sulfuryl fluoride, I+ Sulprofos, I+Tar oil, I+τ-fluvalinate, I+Thazimcarb, I+TDE, I+Tebufenozide, I+Tebufenpyrad, I+Tebupirimfos, I+Teflubenzuron, I+Tefluthrin, I+Temephos, I+TEPP, I+Teralethrin, I+Terbam, I+Terbufos, I+Tetrachloroethane, I+Tetrachlorvinphos, I+Tetramethrin, I+θ-cypermethrin, I+Thiacloprid, I+Thiafenox, I+ Thiamethoxam, I+cyclofos, I+thiocarboxim, I+thiocyclam, I+thiocyclam hydrogen oxalate, I+thiodicarb, I+thiofanox, I+thiometon, I+thionazine, I+thiosultap, I+thiosultap-sodium, I+thuringiensin, I+tolfenpyrad, I+tralomethrin, I+transfluthrin, I+transpermethrin, I+triamiphos, I+triazamate, I+triazophos, I+Triazuron, I+Trichlorfon, I+Trichlormethaphos-3, I+Trichloronate, I+Trifenofos, I+Triflumuron, I+Trimethacarb, I+Triplene, I+Vamidothion, I+Vaniliprole, I+Veratridine, I+Veratrine, I+XMC, I+Xylylcarb, I+YI-5302, I+ζ-Cypermethrin, I+Zetamethrin, I+Zinc phosphide, I+Zolaprophos and ZXI8901, I+cyantraniliprole, I+chlorantraniliprole, I+cyenopyrafen, I+cyflumetofen, I+pyrifluquinazone, I+spinetoram, I+spirotetramat, I+sulfoxaflor, I+flufiprole, I+meperfluthrin, I+tetramethylfluthrin, and I+triflumezopyrim.

[0119] Non-limiting examples of compositions comprising a molluscicide include I+bis(tributyltin)oxide, I+bromoacetamide, I+calcium arsenate, I+cloetocarb, I+copper acetoarsenite, I+copper sulfate, I+fentin, I+ferric phosphate, I+metaldehyde, I+methiocarb, I+niclosamide, I+niclosamide-olamine, I+pentachlorophenol, I+sodium pentachlorophenoxide, I+thazimcarb, I+thiodicarb, I+tributyltin oxide, I+trifenmorph, I+trimethacarb, I+triphenyltin acetate and triphenyltin hydroxide, I+pyriprole.

[0120] Non-limiting examples of compositions comprising nematicides include I + AKD-3088, I + 1,2-dibromo-3-chloropropane, I + 1,2-dichloropropane, I + 1,2-dichloropropane and 1,3-dichloropropene, I + 1,3-dichloropropene, I + 3,4-dichlorotetrahydrothiophene 1,1-dioxide, I + 3-(4-chlorophenyl)-5-methylrhodanine, I + 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, I + 6-isopentenylaminopurine, I + abamectin, I + acetoprole, I + alanycarb, I + aldicarb, I + aldoxicarb, I + AZ 60541, I+Benclotiaz, I+Benomyl, I+Butylpyridaben, I+Cadusafos, I+Carbofuran, I+Carbon disulfide, I+Carbosulfan, I+Chloropicrin, I+Chlorpyrifos, I+Chloetocarb, I+Cytokinin, I+Dazomet, I+DBCP, I+DCIP, I+Diamidaphos, I+Diclofenthion, I+Dicrifos, I+Dimethoate, I+Doramectin, I+Emamectin, I+Emamectin benzoate, I+Eprinomectin, I+Ethoprophos, I+Dibrominated Ethylene, I+Fenamiphos, I+Fenpyrad, I+Fensulfothion, I+Fosthiazate, I+Fosthietan, I+Furfural, I+GY-81, I+Heterophos, I+Iodomethane, I+Isamidophos, I+Isazophos, I+Ivermectin, I+Kinetin, I+Mecarfone, I+Metam, I+Metam-potassium, I+Metam-sodium, I+Methyl bromide, I+Methyl isothiocyanate, I+Milbemycin oxime, I+Moxidectin, I+Mulberry dark spot fungus (Myrothecium verrucaria) composition, I+NC-184, I+oxamyl, I+phorate, I+phosphamidon, I+phosphocarb, I+cebufos, I+selamectin, I+spinosad, I+terbam, I+terbufos, I+tetrachlorothiophene, I+thiafenox, I+thionazine, I+triazophos, I+triazuron, I+xylenol, I+YI-5302, and zeatin, I+fluensulfone.

[0121] Non-limiting examples of compositions containing synergists include I + 2-(2-butoxyethoxy)ethyl piperonylate, I + 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, I + farnesol and nerolidol, I + MB-599, I + MGK 264, I + piperonyl butoxide, I + piperotal, I + propyl isomer, I + S421, I + sesamex, I + sesamolin, and I + sulfoxide.

[0122] Non-limiting examples of compositions comprising animal repellents include I+anthraquinone, I+chloralose, I+copper naphthenate, I+copper oxychloride, I+diazinon, I+dicyclopentadiene, I+guazatine, I+guazatine acetate, I+methiocarb, I+pyridin-4-amine, I+thiram, I+trimethacarb, I+zinc naphthenate, and I+ziram.

[0123] Non-limiting examples of additional compositions include I+broflutrinate, I+cycloxapride, I+diflvidadin, I+flometoquin, I+fluhexafon, I+guadipyr, I+Plutella xylostella granulosis virus, I+Cydia pomonella granulosis virus, I+harpin, I+imisiaphos, I+Heliothis virescens nucleopolyhedrovirus, I+Heliothis punctigera nucleopolyhedrovirus, I+Helicoverpa armigera nucleopolyhedrovirus, I+Helicoverpa zea nucleopolyhedrovirus, I+Spodoptera frugiperda nucleopolyhedrovirus, I+Plutella I+ (Ironyx xylostella) nuclear polyhedrosis virus, I+ Pasteuria nishizawae, I+ p-cymene, I+ piflubumid, I+ pyrafluprole, I+ pyrethrum, I+ QRD 420, I+ QRD 452, I+ QRD 460, I+ terpenoid blend, I+ terpenoid, I+ tetraniliprole, and I+ α-terpinene.

[0124] The composition is I+ code AE ​​1887196 (BSC-BX60309), I+ code NNI-0745 GR, I+Code IKI-3106, I+Code JT-L001, I+Code ZNQ-08056, I+Code IPPA152201, I+Code HNPC-A9908 (CAS: [660411-21-2]), I+Code HNPC-A2005 (CAS: [860028-12-2]), I+Code JS118, I+Code ZJ0967, I+Code ZJ2242, I+Code JS7119 (CAS: [929545-74-4]), I+Code SN-1172, I+Code HNPC-A9835, I+Code HNPC-A9955, I+Code HNPC-A3061, I+Code Chuanhua 89-1, I+ Code IPP-10, I+ Code ZJ3265, I+ Code JS9117, I+ Code SYP-9080, I+ Code ZJ3757, I+ Code ZJ4042, I+ Code ZJ4014, I+ Code ITM-121, I+ Code DPX-RAB55 (DKI-2301), I+ Code Me5382, I+ Code NC-515, I+ Code NA-89, I+ Code MIE-1209, I+ Code MCI-8007, I+ Code BCS-CL73507, I+ Code S-1871, I+ Code DPX-RDS63 and I+ Code AKD-1193.

[0125] While compositions comprising one or more polymorphs of the present invention and another plant disease control agent and / or insecticide, etc., are explicitly disclosed above, those skilled in the art will appreciate that the present invention extends to additional combinations, including ternary and binary mixtures as described above.

[0126] The weight ratio of the polymorph of the present invention to another plant disease control agent and / or insecticide is generally from 1000:1 to 1:100, more preferably from 500:1 to 1:100, for example, from 250:1 to 1:66, 125:1 to 1:33, 100:1 to 1:25, 66:1 to 1:10, 33:1 to 1:5, and 8:1 to 1:3.

[0127] The polymorphs of the present invention may be used alone or in combination with one or more other bioactive ingredients.

[0128] In one aspect, the present invention provides a combination product comprising a disease controlling effective amount of component A and a pesticidally effective amount of component B, wherein component A is a polymorph of the present invention and component B is a compound as follows:

[0129] The polymorphs of the present invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth disruptors, for example, lufenuron; ecdysone agonists, for example, tebufenozide; neonicotinoids, for example, imidacloprid;

[0130] The polymorphs of the present invention may be used in combination with terpene alkaloids such as those described in WO 95 / 19363 or WO 04 / 72086, particularly the compounds disclosed therein.

[0131] Other examples of such biologically active compounds with which the polymorphs of the present invention may be used in combination include, but are not limited to:

[0132] Organic phosphates: Acephate, Azamethiphos, Azinphos-ethyl, Azinophos-methyl, Bromophos, Brumophos-ethyl, Cadusafos, Chlorethoxyphos, Chlorpyrifos, Chlorfenvinphos, Chlormephos, Demeton, Demeton-S-methyl, Demeton-S-methylsulfone, Dialifos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Ethoprophos, Etrimphos, Fanfur, Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazophos, Fonofos, Formothion, Fosthiazate, Heptenophos, Isazophos, Isothioate, Isoxathion, Malathion, Meta Crifos, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phospholane, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos-methyl, profenofos, propafos, proethamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulprofos, temephos, terbufos, tebupirimiphos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.

[0133] Carbamates: alanycarb, aldicarb, 2-sec-butylphenylmethylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenothiocarb, furatiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazameate, UC-51717.

[0134] Pyrethroids: acrinathrin, allethrin, alphamethrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cicithrin ithrin), cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, fenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, zeta-cypermethrin.

[0135] Arthropod growth disruptors: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.

[0136] Other antiparasitic drugs: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis thuringiensis), bensultap, bifenazate, binapropacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloride, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfa, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzin, flufenprox, fluproxifen, halofenprox, hydramethylnon, IKI-220, kanemite, NC-196, neem guard, nidinolterfuran, nitenpyram, SD-35651, WL-108477, pyridaryl, propargite, protrifenbut, pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, cyromazine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazameate, triethoxyspinosyn, trinactin, berubutin, vertalec, YI-5301.

[0137] Fungicides: acibenzolar, aldimorph, ampropylphos, andoprim, azaconazole, azoxystrobin, benalaxyl, benomyl, bialaphos, blasticidin-S, Bordeaux mixture, bromuconazole, bupirimate, carpropamid, captafol, captan, carbendazim, chlorphenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, copper oxychloride, copper salts, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, cyproflam, RH-7281, diclocymet, diclobutrazo ol, diclomedine, dicloran, difenoconazole, RP-407213, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencalamide, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fluazinam, fludioxonil, flumetobir, flumorph / flumorin, fentin hydroxide, fluoxastrobin , fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetylaluminum, furalaxyl, furametapyr, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, krsoxim-methyl, mancozeb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metominostrobin / fenominostrobin, metrafenone, myclobutanil, neoasozin, nicobifen, orisa Strobin, oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propamocarb, propioconazole, proquinazid, prothioconazole, pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quinoxyfen, spiroxamine, sulfur, tebuconazole, tetoronazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, triadimefon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin, vinclozin.

[0138] Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta-endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.

[0139] When used in combination with other active ingredients, the polymorphs of the present invention are preferably used in combination with chlorantraniliprole, triflumezopyrim, cyantraniliprole, tetraniliprole, penflufen, oxazosulfil, tetraniliprole, benfuracarb and / or spinetoram.

[0140] Particularly noteworthy is the combination in which the additional active ingredient has a different site of action from the polymorph of the present invention.In some cases, the combination with at least one other parasitic invertebrate pest control active ingredient with the same control spectrum but different site of action is particularly advantageous for resistance management.In this way, the combination product of the present invention can comprise a pesticidal amount of the polymorph of the present invention and a pesticidal amount of at least one other parasitic invertebrate pest control active ingredient with the same control spectrum but different site of action.

[0141] Those skilled in the art will recognize that salts of compounds are in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions, and therefore, salts share the biological utility of the non-salt forms.

[0142] Thus, a wide variety of salts of the polymorphs of the present invention (and active ingredients used in combination with the active ingredients of the present invention) can be useful for controlling invertebrate pests. Salts include acid addition salts with inorganic or organic acids, such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. The polymorphs of the present invention also include N-oxides. Thus, the present invention includes combinations of the polymorphs of the present invention, including their N-oxides and salts, as well as additional active ingredients, including their N-oxides and salts.

[0143] Although the polymorphs of the present invention can be applied without other adjuvants, in most cases, application is in the form of a formulation containing one or more active ingredients, optionally in combination with food, along with suitable carriers, excipients, and surfactants, depending on the intended end use. One method of application involves spraying an aqueous dispersion or refined oil solution of the combination product. Compositions with spray oils, spray oil concentrates, spreading agents, adjuvants, other solvents, and synergists, such as piperonyl butoxide, often enhance the effectiveness of the compound. Such sprays can be applied from a spray container, such as a can, bottle, or other container, using a pump or by releasing it from a pressurized container, such as a pressurized aerosol spray can. Such spray compositions can take various forms, such as sprays, mist, foam, fog, or mist. Thus, such spray compositions can optionally further include propellants, foaming agents, etc. Of note are spray compositions comprising a pesticidally effective amount of the compound of the present invention and a carrier. One embodiment of such a spray composition comprises a pesticidally effective amount of a compound of the present invention and a propellant. Representative propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures thereof. Of note is the spray composition (and method of utilizing such a spray composition dispensed from a spray container) used to control at least one parasitic invertebrate pest, individually or in combination, selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, hornets, hornets, ticks, spiders, ants, black flies, etc.

[0144] The invention will now be illustrated by the following non-limiting examples and figures. [Brief explanation of the drawings]

[0145] [Figure 1] 1 shows the powder X-ray diffraction pattern of crystalline form A of dichlorobenzizox. [Figure 2]1 shows a DSC trace of crystalline form A of dichlorobenzizox. [Figure 3] 1 shows the powder X-ray diffraction pattern of crystalline form B of dichlorobenzizox (not the present invention). [Figure 4] 1 shows a DSC trace of crystalline form B of dichlorobenzizox (not of the present invention). [Example]

[0146] Example 1: Preparation of Form A A compound of formula II, [ka] 3,4-dichloro-5-isothiazolemethanol (73.0 g), the compound of formula III, [ka] Specifically, 3-chloro-1,2-benzisothiazole-1,1-dioxide (80.0 g) and acetonitrile (626.9 g) were added to a 1 L four-neck flask. The flask was cooled, and triethylamine (80.3 g) was added dropwise while controlling the temperature at 0 to 10°C. The mixture was further stirred (200 rpm) for 30 minutes while maintaining the temperature at 0 to 10°C, and water (468.1 g) and 35% aqueous hydrochloric acid (44.0 g) were added. The reaction mixture was then filtered, and the resulting cake was washed with isopropanol (239.8 g) and 50% aqueous acetonitrile (400 g). The mixture was then dried under reduced pressure (40°C, less than 10 mmHg) in an evaporator to obtain dichlorobenthiazox (129.4 g), which is crystalline form A of the present invention.

[0147] Comparative Example 1: Preparation of Form B Dichlorobenthiazox (129.44 g) and acetonitrile (1200 mL) were added to a 2 L four-neck flask. The flask was heated to 70°C to completely dissolve the dichlorobenthiazox. After visually confirming dissolution, the mixture was cooled to 25°C. The reaction solution was then filtered, and the resulting cake was washed with isopropanol (240 g). The mixture was then dried under reduced pressure (40°C, less than 10 mmHg) in an evaporator to obtain dichlorobenthiazox (80.0 g), which is crystalline form B and not of the present invention.

[0148] Polymorphism analysis: After preparation, the samples were subjected to analysis by powder X-ray diffraction and / or single crystal X-ray diffraction and / or differential scanning calorimetry (DSC), as detailed above. The methods used for these analytical techniques are detailed below.

[0149] Powder X-ray diffraction analysis of solid materials was performed at room temperature using a SmartLab (Rigaku) ​​powder diffractometer. The Cu-Kα radiation was used as the light source, and measurements were performed using the transmission method.

[0150] Single-crystal intensity data were collected on an XtaLAB Synergy R / DW (Rigaku) ​​diffractometer using Cu-Kα radiation, and the data were solved using the CrysAlisPro software package.

[0151] DSC was performed using a Thermo plus EV02 DSCvesta (Rigaku) ​​using a sample load of approximately 2 mg, which was heated from approximately 25°C to approximately 250°C at a rate of 10°C / min.

[0152] Example 2: Preparation of formulations using Form A The dichlorobenthiazox of crystalline form A obtained in Example 1 was mixed with clay and impact-pulverized to obtain a premix containing 30% by mass of dichlorobenthiazox. 6.83 parts by mass of the premix, 0.35 parts by mass of linear C12-C14 alkylbenzenesulfonic acid sodium salt, 3 parts by mass of pregelatinized starch, and 89.82 parts by mass of clay were mixed, and 20 parts by mass of water was added and kneaded. The resulting kneaded mixture was extrusion-granulated using a screen with many 1.2 mm diameter holes and dried to obtain granules that are the agricultural composition of the present invention.

[0153] Comparative Example 2: Preparation of a formulation using Form B The dichlorobenthiazox of crystalline form B obtained in Comparative Example 1 was mixed with clay and impact-pulverized to obtain a premix containing 30% by mass of dichlorobenthiazox. 6.83 parts by mass of the premix, 0.35 parts by mass of linear C12-C14 alkylbenzenesulfonic acid sodium salt, 3 parts by mass of pregelatinized starch, and 89.82 parts by mass of clay were mixed, and 20 parts by mass of water was added and kneaded. The resulting kneaded mixture was extrusion-granulated using a screen with many 1.2 mm diameter holes and dried to obtain a granule (not the present invention) that is an agricultural composition.

[0154] Formulation Performance - Dissolution Testing: Approximately 300 mg of the formulation was added to 30 mL of tap water, and the water samples were collected over time. The amounts of diclobentiazox and its hydrolyzate, 3,4-dichloro-5-isothiazolemethanol, dissolved in the water were quantified using high-performance liquid chromatography. The latter was calculated as equivalent to the diclobentiazox, and the dissolution rate of diclobentiazox was calculated. The results are shown in Table 5.

[0155] [Table 5]

[0156] While the present invention has been described with reference to its preferred embodiments and examples, the scope of the present invention is not limited to only the described embodiments. As will be apparent to those skilled in the art, changes and modifications to the invention described above can be made without departing from the spirit and scope of the invention, which is defined and limited by the appended claims. All publications cited herein are incorporated by reference in their entirety for all purposes to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference.

Claims

1. A compound of formula I, 【Chemistry 1】 That is, a crystalline polymorph of dichlorobenzizox having a powder X-ray diffraction pattern including at least three 2θ angle values ​​selected from the group consisting of 12.5±0.2, 13.6±0.2, 16.0±0.2, 21.6±0.2, 24.8±0.2, 26.0±0.2 and 30.0±0.

2.

2. The following lattice parameters: a=12.78 ű0.3 Å, b=7.83 ű0.3 Å, c=14.15 ű0.3 Å, α=90°±2°, β=109.8°±2°, γ=90°±2° and volume=1332 Å ３ ±30 Å ３ 2. The crystalline form of claim 1, having the formula:

3. 2. The crystalline form of claim 1 having a melting point of 172.5 to 175°C.

4. The crystalline form of claim 1, which is a monoclinic crystal.

5. 5. An agricultural composition comprising the crystalline form of any one of claims 1 to 4 and at least one agriculturally acceptable carrier or excipient.

6. 6. The composition of claim 5, enriched for the crystalline form of any one of claims 1 to 4.

7. 6. The composition of claim 5, comprising at least one additional pest control agent.

8. 10. A method for preventing or controlling disease infection in agricultural and horticultural plants or agricultural and horticultural plant propagation materials, comprising treating the agricultural and horticultural plants or agricultural and horticultural plant propagation materials with a disease-controlling effective amount of the agricultural composition of claim 5.

Images