Compositions and methods for controlling insect infestation of plants

Abstract

The present invention relates to a method of controlling or preventing infestation of a plant by lepidoptera or coleopteran insects, comprising applying a combination or composition to the plant, its locus or its propagation material in any desired sequence or simultaneously, the combination or composition comprises as component (A) a compound of formula (A-1) and as component (B) a compound of formula (B-1). Compositions suitable for use in the invention are also disclosed. (A-1) is greater than (B-1).

Description

[0001] This invention relates to compositions and methods for controlling or preventing plant infestations, such as those of corn or cotton, by insects, particularly the sea gray-winged moth (Spodoptera littoralis) and the cucumber leaf beetle (Diabrotica balteata).

[0002] The literature describes certain active ingredients and combinations of active ingredients used to control pest invasions.

[0003] There remains a need to provide combinations of pest control agents that offer, for example, improved biological properties such as synergistic properties, particularly for controlling insect, mites, and nematodes. These benefits may also include increased safety, improved physicochemical properties, or increased biodegradability.

[0004] It has been found that when specific combinations of active ingredients are applied to plants, their sites, or their propagation material, these combinations provide unexpected control or prevention of plant infestations. More specifically, these combinations have been found to be highly effective in controlling or preventing plant infestations by various insect pests of the orders Lepidoptera and Coleoptera, such as Spodoptera, especially the sea moth, and Diabrotica, especially the cucumber leaf beetle.

[0005] Accordingly, in one aspect, the present invention provides a composition comprising a compound having formula A-1 as component (A):

[0006]

[0007] (A-1; Cyclobutyral)

[0008] And compounds having formula B-1 as component (B):

[0009]

[0010] (B-1; λ-cyhalothrin),

[0011] The weight ratio of (A) to (B) is 500:1 to 1:500, 100:1 to 1:100, 50:1 to 1:50, or 20:1 to 1:20, or preferably 10:1 to 1:10 or 5:1 to 1:5; more preferably between 4:1 to 1:4, between 10:3 to 3:10, between 3:1 to 1:3, between 2.5:1 to 1:2.5, between 2:1 to 1:2, between 5:3 to 3:5, between 8:5 to 5:8, between 1.5:1 to 1:1.5, between 4:3 to 3:4, or between 5:4 to 4:5. Between 5, or approximately 1:1.

[0012] On the other hand, the present invention provides a method for controlling or preventing plant infestation by Lepidoptera or Coleoptera insects, the method comprising applying a combination or composition to the plant, its site, or its propagation material in any desired order or simultaneously, the combination or composition comprising a compound having formula A-1 as component (A):

[0013]

[0014] (A-1)

[0015] And compounds having formula B-1 as component (B):

[0016]

[0017] (B-1).

[0018] References to compounds having formula A-1 (cyclobutyral) and formula B-1 (λ-trifluorocypermethrin) also include their agrochemically acceptable ionic form, salts, solvates, isomers (including geometric and stereochemical isomers), tautomers, N-oxides, esters, prodrugs, isotopes, and protected forms. Preferably, references to compounds having formula A-1 and formula B-1 also include their salts or tautomers or isomers or N-oxides or solvates; and more preferably, their salts or tautomers or N-oxides or solvates, even more preferably their salts or tautomers or solvates.

[0019] Cyclobutyral contains 80%–100% N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide, as shown below for compounds having formula A-1a (hereinafter "(1S,2S) enantiomers"), and 20%–0% of the corresponding (1R,2R)-enantiomers, as shown below for compounds having formula A-1b (hereinafter "(1R,2R) enantiomers"). These enantiomers occur because the benzene ring on the left and the pyridyl-C(=O)-NH group on the right are cis-to-cis on the cyclobutyl ring. According to this application, the compound having formula A-1 may contain at least 85%, preferably at least 90%, and more preferably at least 95% of N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide.

[0020] (A-1a)

[0021] (A-1b)

[0022] In embodiments, the compositions and combinations of the present invention comprise compounds of formula A-1 in an enantiomer-enriched form. In other words, the compositions and combinations of the present invention may contain a mixture of enantiomer-enriched forms of two enantiomers of this compound (i.e., (1S,2S) enantiomers (A-1a) and (1R,2R) enantiomers (A-1b)), wherein the (1S,2S) enantiomer (A-1a) is in a larger proportion as defined herein.

[0023] In the embodiments, the compositions and combinations of the present invention comprise compounds of formula A-1 in an enantiomerically pure form or substantially enantiomerically pure form. For the purposes of the present invention, “compounds of formula A-1 that are substantially enantiomerically pure” should be understood as an enantiomerically pure form with an excess of at least 85% enantiomers (ee), preferably at least 90% ee, more preferably at least 95% ee, at least 96% ee, even more preferably at least 97% ee, and especially at least 98% ee, for example at least 99% or 99.9% ee, wherein the proportion of (1S, 2S) enantiomers is greater.

[0024] In the embodiments, compound A-1 is present in the compositions and combinations of the present invention as an enantiomer-enriched mixture containing, by weight, 80%-100% of compound (A-1a), N-((1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl)-2-(trifluoromethyl)nicotinamide.

[0025] Optionally, the combinations and compositions of the present invention may further comprise one or more adjuvants and / or diluents.

[0026] In another aspect, the present invention provides the use of a combination or composition in controlling or preventing plant infestation by Lepidoptera or Coleoptera insects, the combination or composition comprising, as component (A), a compound having formula (A-1):

[0027]

[0028] (A-1)

[0029] And compounds having formula B-1 as component (B):

[0030]

[0031] (B-1).

[0032] Certain weight ratios of component (A) to component (B) can produce synergistic activity. Therefore, according to another aspect of the invention, a composition is provided in which components (A) and (B) are present in the composition in amounts that produce a synergistic effect. This synergistic activity is evident from the fact that the activity of the composition comprising components (A) and (B) is greater than the sum of the respective activities of the individual components (A) and (B). This synergistic activity extends the range of action of components (A) and (B) in two ways. First, the application rates of components (A) and (B) are reduced while the effect remains equally good, meaning that even at such low application rate ranges, where the two individual components have become completely ineffective, the mixture of active ingredients still achieves a high degree of pest control. Second, there is a substantial expansion of the spectrum of pests that can be controlled.

[0033] The combinations or compositions of the present invention may comprise, by weight, a compound of formula (A-1) of component (A) and a compound of formula (B-1) of component (B), examples of which are between 2000:1 and 1:2000, between 1500:1 and 1:1500, between 1000:1 and 1:1000, between 750:1 and 1:750, between 500:1 and 1:500, between 400:1 and 1:400, between 300:1 and 1:300, between 250:1 and 1:250, between 200:1 and 1:200, between 150:1 and 1:150, and between 125:1 and 1:250. Between 1:125, between 100:1 and 1:100, between 80:1 and 1:80, between 75:1 and 1:75, between 70:1 and 1:70, between 125:2 and 2:125, between 60:1 and 1:60, between 50:1 and 1:50, between 40:1 and 1:40, between 30:1 and 1:30, between 25:1 and 1:25, between 20:1 and 1:20, between 16:1 and 1:16, between 15:1 and 1:15, between 12:1 and 1:12, between 10:1 and 1:1... Between 10, between 9:1 and 1:9, between 8:1 and 1:8, between 7.5:1 and 1:7.5, between 7:1 and 1:7, between 6:1 and 1:6, between 5:1 and 1:5, between 4:1 and 1:4, between 10:3 and 3:10, between 3:1 and 1:3, between 2.5:1 and 1:2.5, between 2:1 and 1:2, between 5:3 and 3:5, between 8:5 and 5:8, between 1.5:1 and 1:1.5, between 4:3 and 3:4, between 5:4 and 4:5, or approximately 1 : 1; Preferably, the combination or composition of the present invention comprises a compound of formula (A-1) of component (A) and a compound of formula (B) of component (B) in a ratio of 25:1 to 1:25, 20:1 to 1:20, 16:1 to 1:16, 10:1 to 1:10, 8:1 to 1:8 or 5:1 to 1:5, more preferably 3.2:1 to 1:3.2 or 3:1 to 1:3 by weight.In some instances, the ratio is in the range of 2:1 to 1:2, 1.25:1 to 1:1.25 by weight, or advantageously 1:1.

[0034] In some embodiments, the weight ratio of the compound of formula (A-1) of component (A) to the compound of formula (B-1) of component (B) is 25:1, 20:1, 16:1, 10:1, 8:1, 6:1, 5:1, 4:1, 3.2:1, 3:1, 2:1, 1.5:1, 1.25:1, 1:1, 1:1.25, 1:1.5, 1:2, 1:3, 1:3.2, 1:4, 1:5, 1:8, 1:10, 1:16, 1:20, or 1:25.

[0035] In another aspect, the present invention provides a method for controlling or preventing plant infestation by Lepidoptera or Coleoptera insects, the method comprising applying to seeds, in any desired order or simultaneously, a compound having formula A-1 as component (A):

[0036]

[0037] (A-1)

[0038] And compounds having formula B-1 as component (B):

[0039]

[0040] (B-1).

[0041] In these embodiments, the uses and methods described above do not include treating a human or animal body through surgical, therapeutic, or diagnostic procedures performed on the human or animal body. In these embodiments, the use is non-therapeutic. In these embodiments, the method is a non-therapeutic method.

[0042] In addition to any synergistic effects, combinations and compositions according to aspects of the invention may also possess other unexpectedly advantageous properties. Examples of such advantageous properties that may be mentioned are: more favorable biodegradability; improved toxicological and / or ecotoxicological behavior; or useful improved plant characteristics, including: seedling emergence, crop yield, more developed root system, increased tillering, increased plant height, larger leaves, less basal leaf mortality, stronger tillering, greener leaf color, less fertilizer required, less seed required, more tillering, earlier flowering, earlier grain maturity, less lodging, enhanced bud growth, improved plant vigor, and earlier germination.

[0043] The active ingredients in the combination of the present invention can be applied simultaneously (e.g., as a pre-formulated mixture or as a tank-mixed formulation) or sequentially within a suitable time frame to pests, plants, plant propagation materials or plant growing sites.

[0044] In this invention, the combined compounds (i.e., components (A) and (B)) and any other biocides may be used in pure form (i.e., as solid active ingredients, for example, at a specific particle size) or preferably in formulation form with at least one of the adjuvants (also known as supplements) conventional in formulation technology, such as a thickener, a solvent or solid carrier, or a surfactant compound. Generally, compounds (A) and (B) are each in the form of a formulation composition with one or more conventional formulation adjuvants.

[0045] Therefore, compounds (A) and (B) can be used as separate formulations. The compounds can be applied to the site where control is desired, simultaneously or sequentially at short intervals (e.g., within the same day), if desired, along with additional carriers, surfactants, or other adjuvants commonly used in formulation techniques to promote application. In a preferred embodiment, (A) and (B) are applied simultaneously. The co-application or simultaneous application of components (A) and (B) has the added benefit of minimizing the time farmers spend applying the product to crops. The combination may also include specific plant traits incorporated into the plant using any means, such as conventional breeding or genetic modification.

[0046] When the combined compounds (i.e., (A) and (B)) are applied simultaneously in this invention, they can be applied as a composition containing the combination, in which case (A) and (B) can each be obtained from separate formulation sources and mixed together (referred to as a tank mix, ready-to-use formulation, broth, or slurry), optionally mixed with other pest control agents; or (A) and (B) can be obtained as a single formulation mixture source (referred to as a premix, concentrate, or formulation product), optionally mixed with other pest control agents.

[0047] In one embodiment, the composition comprises an agriculturally acceptable formulation adjuvant. In another embodiment, a composition is provided that consists essentially of component (A), component (B), and an agriculturally acceptable adjuvant.

[0048] In another embodiment, a composition is provided comprising component (A), component (B), and an agriculturally acceptable adjuvant. The compositions of the present invention are typically formulated using formulation adjuvants such as carriers, solvents, and surfactants (SFAs).

[0049] The combinations and compositions of the present invention can be used to control pests, especially insects, improve crop plant tolerance to abiotic stress conditions, and / or increase crop plant yield. The present invention provides a method for controlling insect pests within or on crop plants, improving crop plant tolerance to abiotic stress conditions, and / or increasing crop plant yield, the method comprising treating pests, plants, plant parts, plant propagation material, or plant growing sites with the combinations or compositions described herein.

[0050] The combinations and compositions of the present invention can be used to prolong the duration of protection provided to plant material. In one embodiment, the combinations and compositions of the present invention can exhibit rapid therapeutic and preventative or protective effects.

[0051] The combinations and compositions of the present invention can be used to expand the range of crops to which these combinations and compositions are useful and / or the range of pests to which these combinations and compositions provide effective control.

[0052] Accordingly, the combinations and compositions of the present invention provide enhanced biological characteristics, which may include a more complete activity spectrum and / or complementary activity patterns. Advantageously, component (A) compound and component (B) compound can provide complementary mobility in plants. In some combinations, component (A) compound has greater acrotropic mobility in plants compared to component (B) compound, resulting in component (B) compound providing more localized protection.

[0053] In other combinations, compound (A) exhibits lower acrotropic migration in plants compared to compound (B), resulting in compound (A) providing more localized protection.

[0054] When used in this document, the indicator 'CAS' followed by a series of numbers refers to the Chemical Abstracts Service (CISA) number of the active ingredient. Where available or known, the active ingredient is also referred to by its common name as assigned in accordance with 'ISO 1750:1981 - Pesticides and other agrochemicals - Common names'.

[0055] Compounds having formula (A-1) (CAS 1460292-16-3) and compounds having formula B-1 (CAS 91465-08-6) are described in The Pesticide Manual, 19th edition, BCPC 2021.

[0056] Examples of the aforementioned harmful organisms are:

[0057] From Coleoptera, for example,

[0058] Species of the genera *Agriotes* spp., *Amphimallon majale*, *Anomala orientalis*, *Anthonomus* spp., *Aphodius* spp., *Astylus atromaculatus*, *Ataenius* spp., *Atomaria linearis*, *Chaetocnema tibialis*, *Cerotomas* spp., *Conoderus* spp., *Cosmopolites* spp., *Cotinis nitida*, *Curculio* spp., *Cyclocephalas* spp., *Dermestes* spp., and *Diabrotica*. spp.), Argentine rhinoceros beetle (Diloboderus abderus), species of ladybugs (Epilachna spp.), species of Eremnus, black cane beetle (Heteronychus arator), coffee berry beetle (Hypothenemus hampei), Lagria vilosa, potato beetle (Leptinotarsa ​​decemlineata), rice weevils (Lissorhoptrus spp.), species of Liogenys, species of Maecolaspis, chestnut velvet beetle (Maladera castanea), American leaf beetle (Megascelis spp.), rapeseed flower beetle (Melighetes aeneus), dwarf beetle (Melolontha spp.), Myochrousarmatus, sawmill beetle (Orycaephilus spp.), ear-beaked beetle (Otiorhynchus spp.), dwarf beetle (Phyllophaga) spp.), species of the genus *Phlyctinus*, species of the genus *Popillia*, species of the genus *Psylliodes*, species of the genus *Rhyssomatus aubtilis*, species of the genus *Rhizopertha*, species of the family Scarabidae, species of the genus *Sitophilus*, and species of the genus *Sitotroga*.), species of the genera *Somaticus*, *Sternechus subsignatus*, *Tenebrio*, *Tribolium*, and *Trogoderma*.

[0059] From the order Lepidoptera, for example,

[0060] Species of the genera *Longwinged Roller*, *Brown-banded Roller*, *Clearwing Moth*, *Noctuid Moth*, cotton leafhopper, *Amylois*, *Lysimachia*, *Yellow Roller*, *Argyresthia spp.*, *Betweenleaf Roller*, *Striped Roller*, cotton leafminer, corn leafminer, powdery leafminer, peach fruit borer, *Grass borer*, *Colored Roller*, *Chrysoteuchia topiaria*, grape fruit borer, *Leaf Roller*, *Cloud Roller*, *Striped Roller*, *Sheath Moth*, *Colias lesbia*, *Cosmophila* *Flava* species, including *Catharanthus*, *Catharanthus*, *Catharanthus*, *Catharanthus*, *Catharanthus*, *Catharanthus*, *Catharanthus*, *Catharanthus*, *Catharanthus*, *Catharanthus*, *Catharanthus*, *Elasmopalpus lignosellus*, *Catharanthus*, *Catharanthus*, *Epinotia* spp., *Estigmene acrea*, *Etiella zinckinella*, *Epinotia* ... spp.), American white moth, tomato codling moth, Lasmopalpus lignosellus, spiral leafminer, leafminer species, grape flower leaf roller, Loxostege bifidalis, tussock moth species, leafminer species, Malocosoma spp., cabbage moth, tobacco hawk moth, Mythimna spp., noctuid moth species, autumn geometrid moth species, Orniodes indica, European corn borer, small leafroller species, brown leafroller species, small-eyed noctuid moth, stem borer, red bollworm, coffee leafminer, armyworm, potato leafminer, cabbage white butterfly, cabbage white butterfly species, diamondback moth, small white nest moth species, geometrid moth species, mint gray noctuid moth (Rachiplusia nu), western bean pea shoot (Richia) (albicosta), species of the genera *Scirpophaga* spp., species of the genera *Steel borer*, species of the genera *Long-haired leafroller*, species of the genera *Grey-winged leafroller*, species of the genera *Cotton leafroller*, species of the genera *Clerodendrum*, species of the genera *Heterodendrum*, species of the genera *Tussilago fargesii ...Pteris vittata*, species of the genera *Tomato leafminer*, and species of the genera *Ophiopogon*.

[0061] The combinations and compositions of the present invention are particularly suitable for controlling pests from one or more of the following Lepidoptera species: sea gray-winged moth, fall armyworm (Spodoptera frugiperda), diamondback moth, rice leaf roller (Cnaphalocrocis medinalis), codling moth (Cydia pomonella), soybean looper (Chrysodeixis includens), rice stem borer (Chilo suppressalis), South American corn seedling borer, soybean looper (Pseudoplusia includens), and tomato leafminer; and from the Coleoptera species cucumber leaf beetle, western corn rootworm (Diabrotica virgifera virgifera), southern corn rootworm (Diabrotica undecimpunctatahowardi), South American leaf beetle (Diabrotica speciosa), thread-knot beetle, and potato beetle.

[0062] The combinations and compositions according to the invention can be used to prevent or control, i.e., to contain or destroy pests of the types described above, which are particularly found on plants, especially useful and ornamental plants in agriculture, horticulture and forestry, or on the organs of such plants (fruits, flowers, leaves, stems, tubers or roots), and in some cases, even plant organs formed at later points in time remain protected against these pests.

[0063] Suitable target crops include, for example, cereals such as wheat, barley, rye, oats, rice, corn, sorghum, millet, and triticale; beet crops such as sugar beets and forage beets; fruit trees such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries, blueberries, cranberries, nectarines, bananas, apricots, avocados, citrus fruits (oranges, lemons, grapefruits, tangerines), or grapes; legumes such as beans, lentils, peas, and soybeans; oilseed crops such as canola, mustard, poppies, olives, sunflowers, coconuts, castor beans, cocoa beans, peanuts, and nutmegs; cucurbit crops such as squash, cucumbers, and melons; fiber plants including cotton, flax, hemp, jute, and sisal; Lauraceae species such as avocados, cinnamon, and camphor; tobacco; and nuts. Examples of suitable target crops include almonds, cashews, peanuts, hazelnuts, pecans, pistachios, and walnuts; coffee; eggplants; sugarcane; tea; chili peppers; hops; bananas; latex plants; grasses such as Bermuda grass, bluegrass, benjamin grass, centipede grass, dandelion grass, ryegrass, St. Augustine grass, and zoysia grass; herbs such as basil, borage, chives, coriander, lavender, angelica, mint, oregano, parsley, rosemary, sage, and thyme; palm trees such as oil palms; ornamental plants, including flowers, shrubs, and trees; other trees such as cocoa trees, coconut palms, olive trees, and rubber trees; and various vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, bell peppers, broccoli, garlic, zucchini, okra, squash, and rhubarb. Additionally, vines such as grapevines are also suitable target crops.

[0064] Crops should be understood as those that exist naturally, are obtained through conventional breeding methods, or are obtained through genetic engineering. These include crops with so-called output traits, such as improved storage stability, higher nutritional value, and improved flavor.

[0065] Crops should be understood to also include those that have been conferred tolerance to herbicides (like bromonazine) or multiple classes of herbicides (such as ALS-, EPSPS-, GS-, HPPD-, and PPO- inhibitors). An example of a crop conferred tolerance to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods is Clearfield® Summer Canola. Examples of crops conferred herbicide tolerance through genetic engineering methods include, for example, glyphosate and glufosinate-resistant maize varieties, which are commercially available under the brand names RoundupReady®, Herculex I®, and LibertyLink®.

[0066] Crops should also be understood as those that are naturally or have been conferred resistance to harmful insects. This includes plants that, for example, are capable of synthesizing one or more selectively acting toxins through the use of recombinant DNA technology, such toxins as those known from toxin-producing bacteria. Examples of toxins that can be expressed include d-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of nematode-parasitic bacteria, and toxins produced by scorpions, arachnids, wasps, and fungi.

[0067] An example of a crop modified to express Bacillus thuringiensis toxin is Bt maize KnockOut (Syngenta Seeds). An example of a crop containing more than one gene encoding insecticidal resistance and thus expressing more than one toxin is VipCot® (Syngenta Seeds). Crops or their seed material can also be resistant to multiple types of pests (a so-called superimposed transgenic event when produced through genetic modification). For example, plants can express insecticidal proteins while also being resistant to herbicides, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0068] Typically, in crop management, growers will use one or more other agrochemicals or biological agents in addition to the compositions of this invention.

[0069] The term "crop" should be understood to also include crop plants that have been transformed using recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as those known to originate from toxin-producing bacteria, particularly those of the genus Bacillus.

[0070] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as those from Bacillus cereus or Bacillus thuringiensis; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins from nematode-parasitic bacteria, such as species of the genus *Photorhabdus* or species of the genus *Xenorhabdus*, such as *Photorhabdus luminescens* and *Xenorhabdus*. (nematophilus); toxins produced by animals, such as scorpion venom, spider venom, bee venom, and other insect-specific neurotoxins; toxins produced by fungi, such as streptotoxins; lectins, such as pea lectin, barley lectin, or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitors, serine inhibitors, potato glycoproteins, cystatin, and papain inhibitors; ribosome-inactivating proteins (RIPs), such as ricin, maize-RIP, absinthecin, loofah seed toxin, saponin toxin, or cassia root toxin; steroid metabolic enzymes, such as 3-hydroxysteroid oxidase, decidual steroid-UDP-glycosyltransferase, cholesterol oxidase, decidualin inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase, and glucanase.

[0071] In the context of this invention, δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, should be understood to obviously also include mixed toxins, truncated toxins, and modified toxins. Mixed toxins are generated through novel recombination of different combinations of domains of those proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are substituted. In such amino acid substitutions, it is preferable to insert a non-naturally occurring protease recognition sequence into the toxin, for example, as in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0072] Examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0073] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described in, for example, the disclosures mentioned above. CryI type deoxyribonucleic acid and its preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0074] Toxins contained in genetically modified plants confer tolerance to harmful insects. Such insects can exist in any insect taxonomy, but are particularly common in beetles (Coleoptera), dipterans (Diptera), and moths (Lepidoptera).

[0075] Transgenic plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are known, and some of them are commercially available. An example of such a plant is YieldGard. (Corn variety, expressing Cry1Ab toxin); YieldGard Rootworm® (Corn variety, expressing Cry3Bb1 toxin); YieldGard Plus® (Corn variety, expressing Cry1Ab and Cry3Bb1 toxins); Starlink® (Corn variety, expressing Cry9C toxin); Herculex I® (Corn variety, expressing Cry1Fa2 toxin and the enzyme phosphatidylinin N-acetyltransferase (PAT) for acquiring tolerance to the herbicide glufosinate-ammonium); NuCOTN 33B® (Cotton variety, expressing Cry1Ac toxin); Bollgard I® (Cotton variety, expressing Cry1Ac toxin); Bollgard II® (Cotton variety, expressing Cry1Ac and Cry2Ab toxins); VipCot® (Cotton variety, expressing Vip3A and Cry1Ab toxins); NewLeaf® (Potato variety, expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate resistance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.

[0076] Another example of such genetically modified crops is:

[0077] 1. Bt11 corn, from Syngenta Seeds SAS, Cheminde l'Hobit 27, F-31 790 St. Sauveur, France, Registry No. C / FR / 96 / 05 / 10. A genetically modified corn variety that expresses a truncated Cry1Ab toxin to resist the European corn borer (corn borer and mealybug). Bt11 corn is also transgenic to express the PAT enzyme for tolerance to the herbicide glufosinate.

[0078] 2. Bt176 corn, from Syngenta Seed Company, 27 Hobbit Road, F-31 790 Saint-Soville, France, Registry No. C / FR / 96 / 05 / 10. A genetically modified corn variety that expresses the Cry1Ab toxin transgenic to resist the European corn borer (corn borer and mealybug). Bt176 corn is also transgenic to express the enzyme PAT for tolerance to the herbicide glufosinate.

[0079] 3. MIR604 corn, from Syngenta Seed Company, 27 Hobbit Road, F-31 790 Saint-Soville, France, Registry No. C / FR / 96 / 05 / 10. A transgenic corn variety resistant to insects by expressing a modified Cry3A toxin. This toxin is modified by inserting a cathepsin-G-protease recognition sequence, Cry3A055. The preparation of such transgenic corn plants is described in WO 03 / 018810.

[0080] 4. MON 863 corn, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses Cry3Bb1 toxin and is resistant to certain Coleoptera.

[0081] 5. IPC 531 cotton, from Monsanto Europe, 270-272 Tefallen Boulevard, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0082] 6.1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, Registry No. C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F to acquire resistance to certain lepidopteran insects and expressing the PAT protein to acquire tolerance to the herbicide glufosinate.

[0083] 7. NK603 × MON 810 corn, from Monsanto Europe, 270-272 Boulevard de Tverren, B-1150 Brussels, Belgium, Registry No. C / GB / 02 / M3 / 03. This hybrid corn variety was created by crossing the genetically modified cultivar NK603 with MON 810, using conventional breeding methods. NK603 × MON 810 transgenic corn expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, conferring resistance to the herbicide Roundup® (containing glyphosate), and also contains the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. Kurstak, conferring resistance to certain lepidopteran insects, including the European corn borer.

[0084] Transgenic crops of insect-resistant plants were also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, BATS Center, Clarastrasse 13, Basel 4058, Switzerland) report 2003. http: / / bats.ch )middle.

[0085] The term "crop" should be understood to also include crop plants that have been transformed using recombinant DNA technology to enable them to synthesize selectively active resistance substances, such as so-called "pathogenesis-associated proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such resistance substances and transgenic plants capable of synthesizing such resistance substances are known, for example, from EP-A-0 392 225, WO 95 / 33818, and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described in, for example, the disclosures mentioned above.

[0086] Crops can also be modified to enhance their resistance to pathogens such as fungi (e.g., Fusarium, Anthracnose, or Phytophthora), bacteria (e.g., Pseudomonas), or viruses (e.g., Potato Leaf Roll Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus).

[0087] Crops also include those that have enhanced resistance to nematodes such as the soybean heterodermal nematode.

[0088] Crops that are tolerant to abiotic stresses include those that, for example, have increased tolerance to drought, high salinity, high temperature, cold, frost, or light radiation by expressing NF-YB or other proteins known in the art.

[0089] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as sodium and calcium channel blockers, such as viral KP1, KP4 or KP6 toxins; stilbene synthase; bibenzyl synthase; chitinase; glucanase; so-called "pathogenesis-associated proteins" (PRP; see, for example, EP-A-0 392 225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0090] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0091] As used herein, the term "site" means the place in which or on which a plant grows, or the place where the seeds of a cultivated plant are sown, or the place where the seeds will be placed in the soil. It includes soil, seeds, and seedlings, along with the established vegetation.

[0092] The term "plant propagation material" refers to all reproductive parts of a plant, such as seeds or vegetative parts like cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and other parts of the plant. It may also refer to germinating plants and young plants that will be transplanted after germination or emergence. These young plants can be protected before transplanting by complete or partial treatment via maceration. Preferably, "plant propagation material" should be understood to mean seeds.

[0093] The term "regulating or improving crop growth" refers to improvements in plant vigor, plant quality, tolerance to stress factors, and / or input utilization efficiency.

[0094] In this embodiment, the insect is selected from the following species: sea tussock moth, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn leaf borer, soybean looper, and tomato leafminer. In this embodiment, the insect is the sea tussock moth.

[0095] In this embodiment, the insect is selected from the cucumber leaf beetle, the thread-knot beetle, and the potato beetle. In this embodiment, the insect is the cucumber leaf beetle.

[0096] In this embodiment, the plant is selected from soybeans, corn, cotton, rice, vegetables, grains, pome fruits, stone fruits, citrus fruits, and potatoes.

[0097] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control cotton plants infested by sea grebe moth, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn leaf borer, soybean looper moth, tomato leafminer, cucumber leaf beetle, western corn root borer (Diabrotica virgifera virgifera), southern corn root borer (Diabrotica undecimpunctata howardi), South American leaf beetle (Diabrotica speciosa), thread-knot beetle, or potato beetle.

[0098] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control maize plant infestations by sea gray-winged moth, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread-knot beetle, or potato beetle.

[0099] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control soybean plants infested by sea gray-winged armyworm, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread-knot beetle, or potato beetle.

[0100] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control rice plant infestations by sea gray-winged moth, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread-knot beetle, or potato beetle.

[0101] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control vegetable plants infested by sea gray-winged moth, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread-knot beetle, or potato beetle.

[0102] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control cereal plant infestations by sea gray-winged armyworm, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread-knot beetle, or potato beetle.

[0103] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control infestation of pome fruit plants by sea gray-winged armyworm, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread-knot beetle, or potato beetle.

[0104] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control infestation of stone fruit plants by sea gray-winged armyworm, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread-knot beetle, or potato beetle.

[0105] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control citrus plant infestations by sea gray-winged moth, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread-knot beetle, or potato beetle.

[0106] In the embodiments, the combinations and compositions disclosed herein are used to prevent or control potato plant infestations by sea grebe moth, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn leaf borer, soybean looper moth, tomato leafminer, cucumber leaf beetle, western corn rootworm, southern corn rootworm, South American leaf beetle, thread beetle, or potato beetle.

[0107] In this embodiment, the plant is cotton.

[0108] In this embodiment, the plant is corn.

[0109] In the embodiments, combinations and compositions as disclosed herein are used to prevent or control cotton plants from being infected by the sea moth.

[0110] In the embodiments, combinations and compositions as disclosed herein are used to prevent or control infection of maize plants by the cucumber leaf beetle.

[0111] Another area of ​​use for the compositions according to the invention is the protection of stored articles and storage rooms, as well as the protection of raw materials such as timber, textiles, flooring, or buildings, and also in the field of hygiene, particularly the protection of humans, livestock, and productive animals from pests of the types mentioned.

[0112] The present invention provides a method for improving the tolerance of plants to abiotic stresses, wherein the method comprises applying a composition as described herein to the plant, plant parts, plant propagation material, or plant growing site.

[0113] This invention provides a method for regulating or improving plant growth, wherein the method includes applying a composition as described herein to a plant, plant parts, plant propagation material, or plant growth site. In one embodiment, plant growth is regulated or improved when the plant is subjected to abiotic stress conditions.

[0114] This document discloses a range of numbers (e.g., 1 to 10), which is intended to include all numbers and intermediate values ​​within that range (e.g., 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9, and 10) as well as numbers and intermediate values ​​within any subrange of that range (e.g., 2 to 8, 1.5 to 5.5, and 3.1 to 4.7). Furthermore, both upper and lower limits are intended to be included within the range.

[0115] Where the term “about” precedes a range or value used herein, this term is intended to support the precise number preceding it, as well as numbers that are close to or approximate to the preceding number. In determining whether a number is close to or approximate to a specifically cited number, the close or approximate number can be a number that will be rounded to or substantially equivalent to the specifically cited number. For example, the term “about 5” includes 5.0, 4.5, 5.4, 4.92, 5.01, etc.

[0116] The composition may be in the form of a concentrate, which is diluted before use, although it may also be made into a ready-to-use composition. Final dilution is usually done with water, but it may be done in place of water or with other substances such as liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0117] The compositions according to the invention are typically formulated in a variety of ways using adjuvants such as carriers, solvents, and surfactants. These formulations can be in various physical forms, for example, as powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspensions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as a carrier), impregnated polymer films, or in other known forms, for example, as known from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. They can be diluted with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0118] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant to obtain a composition in the form of a finely dispersed solid, granules, solution, dispersion, or emulsion. These active ingredients can also be formulated with other adjuvants, such as finely dispersed solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surfactants, or combinations thereof.

[0119] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredient within a porous carrier. This allows the active ingredient to be released into the environment in a controlled amount (e.g., slow release). Microcapsules typically have a diameter of 0.1 to 500 micrometers. They contain an amount of active ingredient that is approximately 25% to 95% by weight of the capsule. These active ingredients can be in the form of a monolithic solid, fine particles in a solid or liquid dispersion, or in a solution-suitable form. The encapsulating membrane can contain, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, or chemically modified polymers, as well as starch xanthates, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely dispersed particles within a solid matrix of the base material, but these microcapsules themselves are not encapsulated.

[0120] Suitable adjuvants for preparing formulations of these compositions according to the invention are known in themselves. As liquid carriers, the following can be used: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butenyl carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-di... Methylformamide, 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, glyceryl acetate, glyceryl diacetate, triethyl... Glyceryl esters, hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, isopropylidene acetone, methoxypropanol, methyl isopentyl ketone, methyl isobutyl ketone, methyl lauryl ester, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleyleneamine, o-xylene, phenol, polyethylene glycol, propionic acid, emulsion Propylene acetate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols with higher molecular weights, such as pentanol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0121] Suitable solid carriers include, 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 substances.

[0122] Many surfactants can be advantageously used in both solid and liquid formulations, particularly those that can be diluted with a carrier before use. Surfactants can be anionic, cationic, nonionic, or polymeric, and they can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include, for example, salts of alkyl sulfates, such as diethanolamine dodecyl sulfate.

[0123] Salts of alkyl aryl sulfonates, such as calcium dodecylbenzenesulfonate.

[0124] Alkylphenol / olefin oxide addition products, such as ethoxylated nonylphenol

[0125] Alcohol / olefin addition products, such as ethoxylated tridecyl alcohol

[0126] Soap, such as sodium stearate

[0127] Salts of alkyl naphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate.

[0128] Salts of dialkyl sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate.

[0129] Sorbitol esters, such as sorbitol oleate

[0130] Quaternary ammonium compounds, such as dodecyltrimethylammonium chloride, and polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate.

[0131] Block copolymers of ethylene oxide and propylene oxide

[0132] And salts of monoalkyl and dialkyl phosphates

[0133] And there are other substances, such as those described in: McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey (1981).

[0134] Other adjuvants that can be used in formulations for killing harmful organisms include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances that neutralize or alter pH and buffer solutions, corrosion inhibitors, fragrances, humectants, absorption enhancers, micronutrients, plasticizers, flow aids, lubricants, dispersants, thickeners, antifreeze agents, microbial agents, and liquid and solid fertilizers.

[0135] The compositions according to the invention may include additives comprising oils of plant or animal origin, mineral oils, alkyl esters of such oils, or mixtures of such oils with oil derivatives. The amount of oil additive in the compositions according to the invention is typically 0.01% to 10% of the mixture to be applied. For example, the oil additive may be added to the spray can at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or plant-derived oils, such as rapeseed oil, olive oil, or sunflower oil; emulsified vegetable oils; alkyl esters of plant-derived oils, such as methyl derivatives; or animal-derived oils, such as fish oil or tallow. Preferred oil additives include C8-C... 22 Alkyl esters of fatty acids, especially C12 -C 18 Methyl derivatives of fatty acids, such as methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known in the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0136] The compositions of the present invention generally comprise 0.1% to 99%, particularly 0.1% to 95% by weight, of an active ingredient and 1% to 99.9% by weight of a formulation adjuvant, which preferably comprises 0 to 25% by weight of a surfactant. Commercial products may preferably be formulated as concentrates, while end users will typically use diluted formulations.

[0137] Examples of leaf formulations used in premixed compositions are:

[0138] GR: Granules

[0139] WP: Wettable powder

[0140] WG: Water-dispersible granules (powders)

[0141] SG: Water-soluble granules

[0142] SL: Soluble Concentrate

[0143] EC: Emulsifiable concentrate

[0144] EW: Oil-in-water emulsion

[0145] ME: Microemulsion

[0146] SC: Aqueous suspension concentrate

[0147] CS: Aqueous Capsule Suspension

[0148] OD: Oil-based suspension concentrate, and

[0149] SE: Aqueous suspension emulsion.

[0150] Examples of seed-treated formulations used in premixed compositions are:

[0151] WS wettable powder for seed treatment slurry

[0152] LS: Solution for seed treatment

[0153] ES emulsion for seed treatment

[0154] FS suspension concentrate for seed treatment

[0155] WG: Water-dispersible granules, and

[0156] CS: Aqueous capsule suspension.

[0157] Examples of formulation types suitable for tank-mixed compositions include solutions, diluted emulsions, suspensions or mixtures thereof, and dusts. Depending on the properties of the formulation, the application method (e.g., foliar application, drenching, spraying, atomizing, dusting, broadcasting, coating, or dumping) can be selected based on the intended purpose and the prevailing environment.

[0158] Tank-mix compositions are typically prepared by diluting one or more premixed compositions containing different pesticides and optionally additional adjuvants with a solvent (e.g., water). Suitable carriers and adjuvants can be solid or liquid and are substances commonly used in formulation technology, such as natural or recycled minerals, solvents, dispersions, wetting agents, thickeners, binders, or fertilizers. Typically, tank-mix formulations for foliar or soil application contain 0.1% to 20%, particularly 0.1% to 1%, of the desired ingredient and 99.9% to 80%, particularly 99.9% to 85%, of solid or liquid adjuvants (including, for example, solvents such as water), wherein these adjuvants may be surfactants, in amounts based on 0% to 20%, particularly 0.1% to 15%, of the tank-mix formulation.

[0159] Typically, premixed formulations for foliar application contain 0.1% to 99.9%, especially 1% to 95% of the desired ingredient and 99.9% to 0.1%, especially 99% to 5% of a solid or liquid adjuvant (including, for example, a solvent, such as water), wherein the adjuvant may be a surfactant, in an amount based on 0% to 50%, especially 0.5% to 40% of the premixed formulation.

[0160] Typically, tank-mixed products for seed treatment application contain 0.25% to 80%, especially 1% to 75% of the desired ingredient and 99.75% to 20%, especially 99% to 25% of solid or liquid adjuvants (including, for example, solvents such as water), wherein the adjuvants may be surfactants, in amounts based on 0% to 40%, especially 0.5% to 30% of the tank-mixed product.

[0161] Typically, premixed formulations for seed treatment application contain 0.5% to 99.9%, especially 1% to 95% of the desired ingredient and 99.5% to 0.1%, especially 99% to 5% of a solid or liquid adjuvant (including, for example, a solvent, such as water), wherein the adjuvant may be a surfactant, in an amount based on 0% to 50%, especially 0.5% to 40% of the premixed formulation.

[0162] Commercial products will preferably be formulated as concentrates (e.g., premixed compositions (formulations)), while end users will typically use diluted formulations (e.g., tank-mixed compositions). Preferred seed treatment premixed formulations are aqueous suspension concentrates. The formulations can be applied to seeds using conventional processing techniques and machinery, such as fluidized bed technology, roller milling methods, rotostatic seed processors, and roller coating machines. Other methods (such as spray beds) may also be useful. Seeds can be pre-sized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art. The compounds of the present invention are particularly suitable for soil and seed treatment applications.

[0163] Typically, the premixed compositions of the present invention contain 0.5% to 99.9%, especially 1% to 95%, advantageously 1% to 50% by weight of the desired ingredient and 99.5% to 0.1%, especially 99% to 5% by weight of a solid or liquid adjuvant (including, for example, a solvent, such as water), wherein the adjuvant (or auxiliary agent) may be a surfactant, the amount of which is 0% to 50%, especially 0.5% to 40% by weight based on the mass of the premixed formulation.

[0164] The application rate of the combinations and compositions of the present invention can vary widely and depends on soil properties, application method (pre- or post-emergence, seed dressing, application to seed furrows, no-till application, etc.), crop species, major climatic conditions, and other factors governed by the application method, application time, and target crop.

[0165] When used for foliar or wet application, the application rate of the combinations and compositions of the present invention is typically from 1 g / ha to 2000 g / ha, especially from 10 g / ha to 1000 g / ha.

[0166] In some instances, the application rate of component (A) is from 20 g / ha to 200 g / ha. In some instances, the application rate of component (A) is from 50 g / ha to 100 g / ha, optionally from 60 g / ha to 75 g / ha or about 100 g / ha.

[0167] In some instances, the application rate of component (B) is from 20 g / ha to 200 g / ha. In some instances, the application rate of component (A) is from 50 g / ha to 100 g / ha, optionally from 60 g / ha to 75 g / ha or about 100 g / ha.

[0168] For seed treatment, the application rate is typically between 0.0005 and 150 g of component (A) / kg seed and between 0.0005 and 150 g of component (B) / kg seed.

[0169] In some instances, the application rate was between 0.002 and 0.03 mg of component (A) / seed and between 0.002 and 0.03 mg of component (B) / seed.

[0170] In some instances, seed treatment includes applying 0.001-50 g of component (A) per kg of seed; preferably 0.01-10 g per kg of seed; more preferably 0.05-1.25 g per kg of seed; and most preferably 0.25-0.6 g per kg of seed.

[0171] In some instances, seed treatment includes applying 0.001-50 g of component (B) per kg of seed; preferably 0.01-10 g per kg of seed; more preferably 0.05-1 g per kg of seed; and most preferably 0.1-0.8 g per kg of seed.

[0172] Preferred formulations may have the following composition (by weight%):

[0173] Emulsifiable concentrate :

[0174]

[0175] Dust powder :

[0176]

[0177] Suspension concentrate:

[0178]

[0179] wettable powder :

[0180]

[0181] Granules:

[0182]

[0183] The following examples further illustrate (but do not limit) the invention.

[0184]

[0185] The combination was thoroughly mixed with these adjuvants and the mixture was thoroughly ground in a suitable grinder to obtain a wettable powder that could be diluted with water to give a suspension of the desired concentration.

[0186]

[0187] The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to obtain a powder that can be used directly for seed treatment.

[0188]

[0189] Emulsions with any required dilution that can be used in plant protection can be obtained by diluting such concentrates with water.

[0190]

[0191] A ready-to-use dust powder is obtained by mixing the mixture with a carrier and grinding the mixture in a suitable grinder. Such a powder can also be used for dry seed dressing.

[0192]

[0193] The mixture is combined with these adjuvants and ground, and the mixture is moistened with water. The mixture is then extruded and dried in an air stream.

[0194]

[0195] The finely ground mixture is then uniformly applied in a mixer to kaolin moistened with polyethylene glycol. This process yields dust-free coated particles.

[0196] suspension concentrate

[0197]

[0198] The finely ground mixture is tightly mixed with an adjuvant to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension of any desired dilution. Using such a dilution, living plants along with their propagation material can be treated and protected against microbial infection by spraying, watering, or immersion.

[0199] Flowable concentrate for seed treatment

[0200]

[0201] The finely ground mixture is tightly mixed with an adjuvant to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension of any desired dilution. Using such a dilution, living plants along with their propagation material can be treated and protected against microbial infection by spraying, watering, or immersion.

[0202] Sustained-release capsule suspension

[0203] 28 parts of the mixture were combined with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was 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 was achieved. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water were added to this emulsion. The mixture was stirred until polymerization was complete. The resulting capsule suspension was stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation contained 28% of the active ingredient. The diameter of the medium capsules was 8-15 micrometers. The resulting formulation was applied to seeds as an aqueous suspension suitable for this purpose.

[0204] The combinations or compositions of the present invention can be applied to plants, parts of plants, plant organs, plant propagation materials, or plant growing sites.

[0205] Application is typically made by spraying (A) and (B) separately (i.e., the combination) or together (i.e., the composition), usually via a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping, or wetting can also be used. Alternatively, the combination or composition can be applied in furrows or directly to the seeds before or at planting.

[0206] The combinations or compositions of the present invention can be applied before or after emergence. When used to regulate crop growth or enhance its tolerance to abiotic stresses, they can be applied after crop emergence. When used to inhibit or delay seed germination, they can be applied before emergence. When used to control pests, they can be used as a preventative (before pest colonization) or a therapeutic (after pest colonization) treatment.

[0207] The present invention envisions applying the combinations and compositions of the present invention, or any combination thereof, to plant propagation material before, during, or after planting.

[0208] While active ingredients can be applied to plant propagation material in any physiological state, the usual approach is to use seeds in a sufficiently robust state to avoid damage during treatment. Typically, seeds will have been harvested from the field, removed from the plant, and separated from any rachis, stem, husk, and surrounding pulp or other non-seed plant material. Seeds are also preferably biologically stable to the extent that the treatment will not cause biological damage to them. It is believed that seeds can be treated at any time between seed harvesting and sowing (including during the sowing process).

[0209] Methods of applying or treating the active ingredient on plant propagation material or in the planting site are known in the art and include coating, granulation, and impregnation, as well as application in rice pots, furrow application, soil wetting, soil injection, drip irrigation, application via a sprayer or central pivot, or incorporation into the soil (band application). Alternatively or additionally, the active ingredient may be applied to a suitable substrate sown together with the plant propagation material.

[0210] The combinations and compositions according to the invention can be used in combination with other pest control agents, including insecticides, acaricides, nematicides, fungicides, or agents that enhance the activity of the compositions according to the invention, in, for example, chemical treatments or pest control procedures. The combination may have additional unexpected advantages, which can be described as synergistic effects.

[0211] Other suitable pest control agents are those with active ingredients such as organophosphates, nitrophenol derivatives, thiourea, juvenile hormones, formamidin, benzophenone derivatives, urea, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylurea, pyridylmethylene amino derivatives, macrolides, benzoylurea, neonicotinoids, and biological agents such as Bacillus thuringiensis strains or bacterial-derived pest control agents such as spinosad, abamectin, and Cry protein.

[0212] The term "seed treatment" generally refers to the application of a material to seeds before or during planting in the soil to improve their treatment properties, protect them before germination, support germination, and / or support the growth of the resulting plants. Some seed treatments are used solely to improve the treatment properties or other physical properties of seeds and do not include agriculturally active ingredients. Other seed treatments incorporate one or more active ingredients into the seeds for various beneficial purposes. For example, seed treatments including one or more active ingredients are commonly used to ensure uniform stand establishment by preventing soil-borne diseases and insects. Typical examples include the application of pest control agents such as fungicides, insecticides, and plant growth regulators. Systematic seed treatments can eliminate or at least reduce the need for traditional broadcast spraying of foliar fungicides or insecticides against certain early-season airborne diseases and insects.

[0213] Seed treatment mixtures may also contain additional active compounds or may be applied together with and / or sequentially with additional active compounds. These additional compounds may be fertilizers or micronutrient donors or other plant growth-influencing agents such as inoculants.

[0214] Component (A) is present in the formulation in an insecticidal amount, for example, in an amount of 1% to about 60% by weight based on the total weight of the seed-treated mixture. The compound of component (B) is present in an insecticidal amount of about 1% to about 60% by weight based on the total weight of the seed-treated mixture.

[0215] Components (A) and (B) can be applied to the seeds sequentially or simultaneously.

[0216] Seed treatment agents may include additional components, such as additional fungicides, insecticides, acaricides, and / or nematicides. In yet another embodiment, the active ingredient further includes other active ingredients.

[0217] Seed treatment mixtures may additionally contain a certain amount of inactive ingredients. For example, the mixture may include surfactants, solvents (such as water and / or other solvents), thickeners, preservatives (including bactericides and other biocides), humectants, antifreeze ingredients, defoaming ingredients, and (if appropriate) colorants or other additives.

[0218] Seed treatment mixtures can be applied to seeds in a variety of conventional methods in the field of seed treatment, including but not limited to mixing in containers (e.g., bottles, bags, or drums), mechanical application, tumbling, spraying, and soaking, followed by drying. Examples of seed coating technologies and machines that can be employed include fluidized bed technology, roller milling, rotary seed processors, rotary drum coating machines, side-dispensing trays, drum mixers, and sputtering beds. Seeds can be pre-sizing before coating. In one embodiment, the seed treatment mixture is applied to seeds in a Hege seed processor, which rotates as the formulation is added to the seeds. Mixing is preferably continued until the seed treatment mixture is uniformly distributed on the seeds (i.e., uniformly coating all the seeds to be treated and uniformly coating each individual seed). Seed treatment mixtures can be applied to seeds in a batch processing process or a continuous processing process. In a representative batch processing process, the seeds to be treated are introduced into a batch processing tank, and then the seed treatment mixture is added and mixed with the seeds. Alternatively, a continuous processing method can be used to apply the seed treatment mixture to the seeds, wherein the seed stream is introduced into a container containing the seed treatment slurry, and after contact with the formulation, it is recovered from the container for drying. The seed treatment mixture stream can also be continuously fed into the container to replenish the amount of mixture removed along with the treated seeds.

[0219] After applying the seed treatment mixture (whether in a batch or continuous process), allow the seeds to dry for a period of time. For example, the seeds can be swirl in a bowl for a period of time, such as at least 15 seconds, to allow for drying. Different time periods may be required to allow for variations in drying conditions, depending on weather or different seed sizes. Additionally, if necessary, heat can be provided to increase the drying time, for example, in the form of a heated airflow. After drying, the coated seeds can undergo size separation or sorting processes.

[0220] As used herein, the term "seed" refers to any dormant stage of a plant that is physically separated from the plant's vegetative stage and / or can be stored for a considerable period of time and / or used to re-cultivate another individual of the same species. In this text, the term "dormancy" refers to a state in which a plant remains viable to reasonable limits despite the lack of light, water, and / or nutrients necessary for a vegetative (i.e., non-seed) state. Specifically, the term refers to true seeds but does not include plant propagules such as suckers, bulbs, corms, fruits, tubers, grains, cuttings, and pruning cuttings.

[0221] In one embodiment, the seeds treated as described herein include corn (maize), cereals (such as wheat, barley, oats, rye, and spelt wheat), soybeans, rapeseed, rice, sugar beets, cotton, millet varieties (such as sorghum), sunflowers, kidney beans, peas, oilseed plants (such as canola and rapeseed), soybeans, cabbage, tomatoes, eggplants (or aubergines), peppers, and other plants and spices, as well as seeds of ornamental shrubs and flowers. Suitable target crops also include genetically modified crops of the aforementioned types. In one embodiment, the seeds are derived from maize, cotton, wheat, barley, soybeans, or canola, preferably maize or cotton.

[0222] While the seed treatment methods described herein can be applied to seeds in any physiological state, it is preferred that the seeds be in a sufficiently durable state that does not cause significant damage during the treatment process. Typically, seeds are those that have been harvested from the field; removed from the plant; and / or separated from the fruit and any corn cob, pod, stem, husk, and surrounding pulp or other non-seed plant material. The seeds are also preferably biologically stable to the extent that the treatment does not cause biological damage to them. For example, in one embodiment, the treatment may be applied to harvested, cleaned, and dried seeds to a moisture content of less than about 15% by weight. In alternative embodiments, the seeds may be those that have been dried, then sprayed with water and / or another material, and then re-dried before or during treatment with the seed treatment mixture described herein. In one embodiment, the seeds to be treated are therefore substantially dry. As used herein, “substantially dry” means seeds that have a certain moisture content if allowed to equilibrate in an air atmosphere at 20°C to 30°C and 30%–90% relative humidity (e.g., 25°C and 50% relative humidity).

[0223] Seed treatment mixtures can be applied to seeds at any stage between seed harvesting and sowing in the soil, for the purpose of plant germination and growth. For example, treatment can be carried out weeks or months before planting, such as up to 12 months, for example, in the form of seed dressing, without a significant decrease in efficacy observed. For example, seeds can be treated in a central location and then dispersed for planting. This allows those planting the seeds to avoid treatment and the use of active ingredients, and instead treat and plant the treated seeds in a manner conventional to ordinary untreated seeds, thus reducing human exposure.

[0224] Using the composition and diluent according to the invention, the seed dressing is applied to seeds in a suitable seed dressing form, such as an aqueous suspension or a dry powder having good adhesion to seeds, in a manner known to the art. Such seed dressings are known in the art. The seed dressing may contain a single active ingredient or a combination of active ingredients in an encapsulated form, such as as a sustained-release capsule or microcapsule.

[0225] In another aspect, this application also relates to plant propagation materials coated with compositions according to the invention.

[0226] A synergistic effect exists as long as the combined effect of the active ingredients is greater than the sum of the effects of the individual components. For a given combination of active ingredients, the expected effect E follows the so-called Colby formula and can be calculated as follows (COLBY, SR, "Calculating synergistic and antagonistic responses of herbicide combination," Weeds, Vol. 15, pp. 20-22, 1967):

[0227] ppm = milligrams of active ingredient (AI) per liter

[0228] X = % effect of active ingredient (based on the first active ingredient) using p ppm.

[0229] Y = % effect of the active ingredient in q ppm as the second active ingredient.

[0230] According to Colby, using p + q ppm of active ingredients, the expected effect of the (additive) active ingredients A + B is...

[0231] If the observed effect of O is greater than the expected effect E, then the combined effect is superadditive, meaning a synergistic effect exists. Mathematically, synergy corresponds to a positive value of the difference (OE). In the case of purely complementary addition of the active ingredient (expected activity), the difference (OE) is zero. A negative value of the difference (OE) indicates a loss of activity compared to the expected activity.

[0232] Table 1 lists some preferred combinations for controlling or preventing plant infections. Table 1 also lists exemplary application rates and key pests for which the combinations are particularly effective, as well as key crops for which the combinations of the present invention are particularly advantageous.

[0233] Table 1A

[0234]

[0235] Table 1B

[0236]

[0237] Table 1C

[0238]

[0239] Table 1D

[0240]

[0241] Table 1E

[0242]

[0243] Table 2 lists some combinations for seed treatment and identifies key pests for which these combinations are particularly effective, as well as key seed species for which the combinations of the present invention are particularly advantageous as seed treatment.

[0244] Table 2A

[0245]

[0246] Table 2B

[0247]

[0248] Table 2C

[0249]

[0250] Biological examples

[0251] method

[0252] Feeding / contact activity of the sea gray-winged noctuid moth (Egyptian cotton leafworm)

[0253] The synergistic bioactivity of the combination of components (A) and (B) as disclosed herein was assessed using a feeding / contact activity assay for the sea grizzly-winged moth (Egyptian cotton leafworm). Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with a test aqueous solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infected with L1-stage larvae. The mortality rate of these samples was assessed 3 days post-infection.

[0254] result

[0255]

[0256] Cucumber Leaf Beetle (Striped Cucumber Beetle) Feeding / Contact Activity

[0257] The synergistic bioactivity of the combination of components (A) and (B) as disclosed herein was assessed using a feeding / contact activity assay for the cucumber leaf beetle (Striped cucumber beetle). Corn sprouts placed on an agar layer in 24-well microtiter plates were treated by spraying with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infected with L2 stage larvae (6 to 8 larvae / well). Mortality was assessed in these samples 4 days post-infection.

[0258] result

[0259] 。

Claims

1. A composition comprising a compound having formula A-1 as component (A): (A-1; Cyclobutyral) And compounds having formula B-1 as component (B): (B-1; λ-cyhalothrin), The weight ratio of (A) to (B) is 500:1 to 1:500, 100:1 to 1:100, 50:1 to 1:50, or 20:1 to 1:20, or preferably 10:1 to 1:10 or 5:1 to 1:5; more preferably between 4:1 to 1:4, between 10:3 to 3:10, between 3:1 to 1:3, between 2.5:1 to 1:2.5, between 2:1 to 1:2, between 5:3 to 3:5, between 8:5 to 5:8, between 1.5:1 to 1:1.5, between 4:3 to 3:4, or between 5:4 to 4:

5. Between 5, or approximately 1:

1.

2. The composition according to claim 1, wherein, The weight ratio of the compound of formula (A-1) in component (A) to the compound of formula (B-1) in component (B) is 25:1, 20:1, 16:1, 10:1, 8:1, 6:1, 5:1, 4:1, 3.2:1, 3:1, 2:1, 1.5:1, 1.25:1, 1:1, 1:1.25, 1:1.5, 1:2, 1:3, 1:3.2, 1:4, 1:5, 1:8, 1:10, 1:16, 1:20, or 1:

25.

3. A method for controlling or preventing plant infestation by Lepidoptera or Coleoptera insects, said method comprising applying a combination or composition to the plant, its location, or its propagation material in any desired order or simultaneously, said combination or composition comprising a compound having formula A-1 as component (A): (A-1) And compounds having formula B-1 as component (B): (B-1)。 4. The method according to claim 3, wherein, The insects are selected from sea tadpole moth, fall armyworm, diamondback moth, rice leaf roller, codling moth, soybean looper, rice stem borer, South American corn seedling borer, soybean looper, and tomato leafminer, with sea tadpole moth being the preferred species.

5. The method according to claim 3, wherein, The insects are selected from cucumber leaf beetle, thread-knot beetle, and potato beetle, with cucumber leaf beetle being the preferred choice.

6. The method according to any one of claims 3 to 5, wherein, The plants are selected from soybeans, corn, cotton, rice, vegetables, grains, pome fruits, stone fruits, citrus fruits, and potatoes.

7. The method according to any one of claims 3 to 6, wherein, The application rate of component (A) is 1 to 2000 g / ha, preferably 10 to 1000 g / ha, more preferably 20 to 200 g / ha or 50 to 100 g / ha, and most preferably 60 to 75 g / ha; and the application rate of component (B) is 1 to 2000 g / ha, preferably 10 to 1000 g / ha, more preferably 20 to 200 g / ha or 50 to 100 g / ha, and most preferably 60 to 75 g / ha.

8. A seed treatment composition comprising a compound having formula A-1 as component (A): (A-1) And compounds having formula B-1 as component (B): (B-1)。 9. A method for controlling or preventing plant infestation by Lepidoptera or Coleoptera insects, said method comprising applying to seeds, in any desired order or simultaneously, a compound having formula A-1 as component (A): (A-1) And compounds having formula B-1 as component (B): (B-1)。 10. The method according to claim 9, wherein the method comprises applying 0.001-50 g component (A) / kg seed to the seed; preferably 0.01-10 g / kg seed; more preferably 0.05-1.25 g / kg seed; most preferably 0.25-0.6 g / kg seed, and / or 0.001-50 g component (B) / kg seed; preferably 0.01-10 g / kg seed; more preferably 0.05-1 g / kg seed; most preferably 0.1-0.8 g / kg seed.

11. The method according to any one of claims 3 to 7 or 9 to 10, or the composition according to claim 8, wherein, The weight ratio of (A) to (B) is between 2000:1 and 1:2000, between 1500:1 and 1:1500, between 1000:1 and 1:1000, between 750:1 and 1:750, between 500:1 and 1:500, between 400:1 and 1:400, between 300:1 and 1:300, between 250:1 and 1:250, between 200:1 and 1:200, between 150:1 and 1:150, between 125:1 and 1:125, between 100:1 and 1:100, and between 80:1 and 1:1:

100. Between 80, between 75:1 and 1:75, between 70:1 and 1:70, between 125:2 and 2:125, between 60:1 and 1:60, between 50:1 and 1:50, between 40:1 and 1:40, between 30:1 and 1:30, between 25:1 and 1:25, between 20:1 and 1:20, between 16:1 and 1:16, between 15:1 and 1:15, between 12:1 and 1:12, between 10:1 and 1:10, between 9:1 and 1:9, between 8:1 and 1:8, between 7.5 The ranges are: 1 to 1:7.5, 7:1 to 1:7, 6:1 to 1:6, 5:1 to 1:5, 4:1 to 1:4, 10:3 to 3:10, 3:1 to 1:3, 2.5:1 to 1:2.5, 2:1 to 1:2, 5:3 to 3:5, 8:5 to 5:8, 1.5:1 to 1:1.5, 4:3 to 3:4, 5:4 to 4:5, or approximately 1:

1.

12. The method according to any one of claims 3 to 7 or 9 to 11, or the composition according to claim 8 or 11, wherein, The weight ratio of the compound of formula (A-1) in component (A) to the compound of formula (B-1) in component (B) is 25:1, 20:1, 16:1, 10:1, 8:1, 6:1, 5:1, 4:1, 3.2:1, 3:1, 2:1, 1.5:1, 1.25:1, 1:1, 1:1.25, 1:1.5, 1:2, 1:3, 1:3.2, 1:4, 1:5, 1:8, 1:10, 1:16, 1:20, or 1:

25.

13. The composition according to any one of claims 1-2, 8, or 11-12, or the method according to any one of claims 3-7 or 9-12, wherein, Component A comprises at least 90%, and preferably at least 95%, of an S-enantiomer having formula (A-1a): (A-1a)。 14. A coated plant propagation material, wherein the coating comprises a composition comprising a compound having formula A-1 as component (A): (A-1) And compounds having formula B-1 as component (B): (B-1)。 15. Use of a composition for controlling or preventing infection of plants, more particularly cotton or maize plants, by lepidopteran or coleopteran insects, said composition comprising, as component (A), a compound having formula A-1: (A-1) And compounds having formula B-1 as component (B): (B-1)。

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