WO2016146586A1 - Use of cyclaniliprole on cultivated plants - Google Patents

Use of cyclaniliprole on cultivated plants Download PDF

Info

Publication number
WO2016146586A1
WO2016146586A1 PCT/EP2016/055457 EP2016055457W WO2016146586A1 WO 2016146586 A1 WO2016146586 A1 WO 2016146586A1 EP 2016055457 W EP2016055457 W EP 2016055457W WO 2016146586 A1 WO2016146586 A1 WO 2016146586A1
Authority
WO
WIPO (PCT)
Prior art keywords
spp
plant
plants
soybean
resistance
Prior art date
Application number
PCT/EP2016/055457
Other languages
French (fr)
Inventor
Karsten Koerber
Matthias Pohlman
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2016146586A1 publication Critical patent/WO2016146586A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the present invention relates to a method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification (hereinafter abbreviated as "cultivated plant”) as compared to the respective non-modified control plant, comprising the application of a pesti- cidally active compound of formula I
  • plant health comprises various sorts of improvements of plants that are not connected to the control of pests and which do not embrace the reduction of negative consequences of harmful insects.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e.g.
  • plant vigor e.g. improved plant growth and/or greener leaves ("greening effect")
  • quality e.g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e.g. improved biomass and/or increased content of valuable ingredients
  • plant vigor e.g. improved plant growth and/or greener leaves ("greening effect")
  • quality e.g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e.g. improved content or composition of certain ingredients
  • cultivated plants are plants that have at least one insecticidal trait. It is a wide-spread problem that insects, that are combatted with insectides, develop resistance, i.e. they become less or not all anymore susceptible to the insecticidal effect. Surprisingly, it has now been found that the compound of formula (I) are useful in methods of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth, wherein the plant has at least one insecticidal trait, and wherein the harmful insects are resistant to an insecticidal trait of the plant.
  • cultivated plants are specific plants that have at least one herbicidal and at least one insecticidal trait, preferably soybeans, more preferably the soybeans known as"lntacta R 2 PRO" soybean (Monsanto).
  • soybeans more preferably the soybeans known as"lntacta R 2 PRO" soybean (Monsanto).
  • cultivated plants are plants that have at least one trait or trait combination which has not yet been described in connection with the use of the compound of formula (I) on cultivated plants, e.g. as listed in Table A1.
  • the compound of formula (I) are also useful in methods of controlling harmful insects by treating those mentioned cultivated plants, parts of such plants or their locus of growth.
  • the compound of formula (I) is described in WO2005/077934 and is known under the ISO name "cyclaniliprole”. It can be prepared according to standard methods of organic chemistry, or by the processes as described in WO2005/077934 or WO2008072743, without being limited to the routes given therein.
  • the preparation of the compound of formula I above may lead to isomer mixtures. If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.
  • Agronomically acceptable salts of the compound of formula (I) can be formed in a customary manner, e.g. by reaction with an acid of the anion in question.
  • the compound of formula (I) has been described in WO2014/128188 in methods and uses for controlling harmful pests on certain cultivated plants, there are further cultivated plants on which the compound of formula (I) is surprisingly effective.
  • the invention relates to certain mixtures of the com- pound of formula (I), and to the use of said mixture in the methods according to the invention as mentioned herein.
  • the mixtures of the present invention are those mixtures described in the following embodiments and Tables.
  • the mixtures comprise a compound of formula (I) and a further pesticide component II of Table B.
  • Table B
  • the mixtures comprise a compound of formula (I) and two further pesticide components II selected from the compounds listed in Table B.
  • each of the rows of Table T-1 corresponds to one mixture.
  • the mixtures comprise a compound of formula (I) and a further pesticide component II of Table C, which is of the type of biological pesticides.
  • Pesticide component II Compound Pesticide component II Compound abbreviation abbreviation
  • each of the rows of Table C-1 corresponds to one mixture.
  • the term "compound(s) of the present invention” or “compound(s) according to the invention” refers to the compound(s) of formula (I) as defined above, which are also referred to as “compound(s) of formula I” or “compound(s) I” or “formula I compound(s)”, and includes their salts, tautomers, stereoisomers, and N-oxides.
  • composition(s) according to the invention or “composition(s) of the present invention” encompasses composition(s) comprising at least one compound of formula (I) or mixtures of the the compound of formula (I) with other pesticidally active compound(s) II for being used and/or applied in methods according to the invention as defined above.
  • the compound of formula (I) has at least one center of chirality, therefore is present as mixtures of enantiomers or diastereomers, in any case as a pair of two enantiomers. Both enantiomers are said to contribute to the pesticidal effect.
  • the invention provides both the pure enantiomers or pure diastereomers of the the compound of formula (I), and its mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula (I) or its mixtures.
  • a suitable compound of the formula (I) also includes all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof.
  • Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond, nitrogen-sulfur double bond or amide group.
  • stereoisomer(s) encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
  • Salts of the compounds of the present invention are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.
  • suitable "agriculturally useful salts” or “agriculturally acceptable salts” are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH 4 + ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci- C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise me- thylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trime- thylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2- hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sul- fonium ions, preferably tri(Ci-C 4 -alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4- alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compound of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the compound of the formula (I) may be present in the form of its N-oxides.
  • N-oxide includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
  • N-oxides of compounds (I) can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides.
  • a suitable oxidizing agent such as peroxo carboxylic acids or other peroxides.
  • the preparation of the compound of formula I above may lead to them being obtained as isomer mixtures. If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.
  • Agronomically acceptable salts of the compounds I can be formed in a customary manner, e.g. by reaction with an acid of the anion in question.
  • the present invention also relates to a mixture of at least one compound of the present invention with at least one mixing partner as defined herein after.
  • Preferred weight ratios for such binary mixtures are from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, more preferably from 100:1 to 1 :100, particularly preferably from 10:1 to 1 :10.
  • components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the present invention or a mixture thereof.
  • An agrochemical composition comprises a pesticidally effective amount of a cormpound of the present invention or a mixture thereof.
  • the term "pesticidally effective amount” is defined below.
  • the compounds of the present invention or the mixtures thereof can be converted into customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • agro-chemical compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composi- tion types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
  • the compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo-'hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil frac- tions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydrona
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharide powders e.g. cellulose, starch
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • phosphates are phosphate esters.
  • Exam- pies of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth- oxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides.
  • polymeric surfactants are homo- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present invention on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxi- laries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the compositions cormprising them as premix or, if appropriate not until immedi- ately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • the user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired applica- tion concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the composition according to the in- vention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components e. g. components comprising compound I of the pre- sent invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.
  • the compounds of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the present invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are effective through both contact and ingestion. Furthermore, the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
  • the compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions comprising said mixtures as defined above.
  • the components of said mixture can be applied simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
  • the application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
  • Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application.
  • Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection.
  • Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting.
  • furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow.
  • Foliar application refers to the application of the pesticidally active compound to plant foliage, e.g. through spray equipment.
  • pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.
  • the term "contacting” includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habi- tat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
  • animal pest includes arthropods, gastropods, and nematodes.
  • Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.
  • Insects, which are of particular relevance for crops, are typically referred to as crop in- sect pests.
  • crop refers to both, growing and harvested crops.
  • plant includes in particular cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, fruit trees, citrus crop and nuts for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sug- arbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, tea, pepper, cucumbers, melons, Brassica species, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, apple, pear, peach, nectarine, oranges, mandarins, lemons, almonds, walnuts, pista- chios, petunias, geranium/pelarg
  • cultiva plant is to be understood as including plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.
  • Plants, which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugarbeet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice.
  • one or more genes have been mutagenized or integrated in the genetic material of the plant.
  • the one or more mutagenized or integrated genes are preferably selected from pat, epsps, cry1 Ab, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cry1 F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5.
  • the mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant. Such properties, also known as traits, include abiotic stress tolerance, altered
  • herbicide tolerance e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance
  • mutagenesis for example Clearfield® oilseed rape being tolerant to imidazolinones, e.g. imazamox.
  • genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available un- der the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • herbicides such as glyphosate and glufosinate, some of which are commercially available un- der the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • glyphosate and glufosinate some of which are commercially available un- der the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • herbicides such as glyphosate and glufosinate
  • RoundupReady® glyphosate
  • LibertyLink® glufosinate
  • insect resistance is of importance, in particular lepidopteran insect resistance and coleop-
  • Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance.
  • plant propagation material refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and dura- tion, weather, target species, locus, mode of application, and the like.
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 20 g per 100 m 2 .
  • the rate of application of the active in- gredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.
  • the compounds of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects.
  • the present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermina- tion with a compound of the present invention.
  • the protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes.
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods.
  • seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
  • the present invention also comprises seeds coated with or containing the active compound.
  • coated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the ac- tive ingredient.
  • Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Bras- sica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
  • the active compound may also be used for the treatment of seeds from genetically modified plants, which e.g. tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
  • genetically modified plants have been described in detail above.
  • Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.
  • the active substance concentrations in ready-to-use formulations are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • Especially preferred FS formulations of the compounds of the present invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g.
  • a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
  • a binder sticker /adhesion agent
  • a preservative such as a biocide, antioxidant or the like
  • the application rates of the compounds of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
  • the invention therefore also relates to seed comprising a compound of the present invention, or an agriculturally useful salt thereof, as defined herein.
  • the amount of the compound of the present invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
  • the compounds of the present invention may also be used for improving the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the present invention.
  • an effective and non-phytotoxic amount means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotox- ic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.
  • plant and “plant propagation material” are defined above.
  • Plant health is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting efficiency, processability).
  • yield for example increased biomass and/or increased content of valuable ingredients
  • quality for example improved content or composition of certain ingredients or shelf life
  • plant vigour for example improved plant growth and/or greener leaves ("greening effect")
  • tolerance to abiotic for example drought
  • biotic stress for example disease
  • production efficiency for example, harvesting efficiency, processability
  • the above identified indicators for the health condition of a plant may be interdependent and may result from each other.
  • Each indicator is defined in the art and can be determined by meth- ods known to a skilled person.
  • Pests are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
  • insects from the order of Lepidoptera for example Achroia grisella, Aden ' s spp. such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A.
  • Argyresthia conjugel- la Argyroploce spp., Argyrotaenia spp.
  • A. velutinana Athetis mindara, Austroasca vi- ridigrisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bon- agota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C.
  • Cactoblastis cactorum Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. Indi- cus, C. suppressalis, C partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C.
  • kuehniella kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Felt/a spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G.
  • H. armigera Heliothis armigera
  • H. zea Heliothis zea
  • Heliothis spp. such as H. assulta, H. subflexa, H. virescens
  • Hellula spp. such as H. undalis, H.
  • Mamestra spp. such as M. brassicae, M. configurata; Mamstra brassicae, Manduca spp. such as M. quin- quemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp. such as M. lapites, M.
  • operculella Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrods tripunctata, Plathy- pena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P.
  • stultana Platyptilia cardui- dadyla, Plebejus argus, Plodia interpundella, Pius/a spp, Plutella maculipennis, Plutella xy- lostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp. such as P. sequax, P.
  • Udea spp. such as U. rubigalis, U. rubi- galis
  • Virachola spp. Yponomeuta padella
  • Zeiraphera canadensis
  • insects from the order of Coleoptera for example Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimal- lus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala diveren- ta, Anomala rufocuprea, Anoplophora spp. such as A.
  • Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogo- nia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aula- cophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B.
  • vespertinus Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryp- torhynchus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D.
  • Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomaculata; Epitrix spp. such as E. hirtipennis, E.
  • hypomeces squamosus Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lath- ridius spp., Lema spp. such as L bilineata, L. melanopus; Leptinotarsa spp. such as L. decem- lineata; Leptispa pygmaea, Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Lu- perodes spp., Lyctus spp. such as L.
  • Saperda Candida Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Sternechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T.
  • Trogoderma spp. Tychius spp.
  • Xylotrechus spp. such as X. pyrrhoderus
  • Za- brus spp. such as Z. tenebrioides
  • insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bac- trocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capi- tata, Chrysomyia spp. such as C.
  • Aedes spp. such as A. aegypti, A. albopictus, A. vexans
  • Anastrepha ludens Anopheles spp.
  • A. albimanus such as A.
  • insects from the order of Thysanoptera for example, Basothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femora/is, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S.
  • insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A.
  • Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconoco- ris hewetti, Dora/is spp., Dreyfus/a nordmannianae, Dreyfus/a piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp.
  • E E solana Epidiaspis leperii, Eriosoma spp. such as E /#/7/i7- e/z//77, E pyricola; Erythroneura spp., Eurygaster spp. such as E integriceps; Euscelis bilobatus, Euschistus spp. such as E heros, E impictiventris, E servus; Fiorinia theae, Geococcus coffe- ae, Glycaspis brimblecombei, Halyomorpha spp. such as H.
  • Nasonovia ribis-nigri Nasonovia ribis-nigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. virescens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius button/, Oebalus spp. such as O.
  • P. devastatrix Piesma quadrata, Piezodorus spp. such as P. guildinii; Pinnaspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvi- naria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudo- coccus spp. such as P. comstocki; Psylla spp. such as P.
  • Pteromalus spp. Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada g/g ' as, Rastro- coccus spp., Reduvius senilis, Rhizoecus amer/canus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R.
  • T. accerra, T. perditor Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeurodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii, Insects from the order Hymenoptera for example Acanthomyops interjectus, Athalia rosae, At- ta spp. such as A. capiguara, A.
  • cephalotes such as C. florida- nus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocos- mus kuriphilus, Formica spp., Hoplocampa spp. such as H.
  • Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M.
  • Pests from the Class Arachnida for example Acari.e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Argas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. mi- croplus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I.
  • Amblyomma spp. e.g. A. americanum, A. variegatum, A. maculatum
  • Argas spp. such as A. persicu
  • Boophilus spp. such as B
  • rubicundus I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus everts/, Rhizoglyphus spp., Sarcoptes spp. such asS.
  • Acer/a spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pelekassr, Acu/us spp. such as A.
  • A. spp.
  • A. sheldoni such as A. anthocoptes, Acallitus spp.
  • A. lycopersici such as A. pelekassr, Acu/us spp.
  • A. spp.
  • Colomerus vitis Epitrimerus pyri, Phyllo- coptruta oleivora
  • Eriophytes ribis and Eriophyes spp.
  • T. cinnabarinus such as Eriophyes sheldoni, Family Tar- sonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinkr, Family Tenuipalpidae including Brevi- palpus spp. such as B. phoenicis, Family Tetranychidae including Eotetranychus spp., Eute- tranychus spp., Oligonychus s p., Petrobia latens, Tetranych us spp. such as T. cinnabarinus, T. evansi, T.
  • Halotydeus destructor Family Demodicidae with species such as Demodex spp.; Family Trombicidea including Trombicula spp.; Family Macro- nyssidae including Ornothonyssus spp. ; Family Pyemotidae including Pyemotes tritici, Tyropha- gus putrescentiae; Family Acaridae including Acarus siro; Family Araneida including Latrodec- tus mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa;
  • Pests from the Phylum Nematoda for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G rostochiensis; Heterodera spp. such as H. avenae, H. gly- cines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. such as A.
  • plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G rosto
  • Awl nematodes Dolichodorus spp.
  • Spiral nematodes Heliocotylenchus multicinctus
  • Sheath and sheathoid nematodes He/77- icycliophora spp. and Hemicriconemoides spp.
  • Hirshmanniella spp. Lance nematodes, loaimus spp.
  • False rootknot nematodes Nacobbus spp.
  • Needle nematodes Longidorus spp. such as Z.. elongatus
  • Lesion nematodes Pratylenchus spp. such as P.
  • brachyurus P. neglec- tus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as ?. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylench us spp. such as ?. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as 7 ⁇ obtusus, T. primitivus; Paratrichodorus spp. such as .
  • Stunt nematodes Tylencho- rhynchus spp. such as 7 ⁇ claytoni, T. dub/us
  • Citrus nematodes Tylenchulus spp. such as 7 ⁇ semipenetrans
  • Dagger nematodes Xiphinema spp.
  • other plant parasitic nematode species such as
  • Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longi- ceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp. such as /. /77//70 ⁇ , /. Snyder, Marginitermes hubbardi, Mastotermes spp. such as darwiniensis Neocapntermes spp.
  • Neotermes spp. such as ⁇ /. opacus, N. parvus
  • Neotermes spp. Procornitermes spp., Zootermopsis spp. S-/C 7 as Z angusticollis, Z. nevadensis, Reticulitermes spp. such as /?. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus
  • Termes natalensis Insects from the order Blattaria for example _?/a//a spp. such as fi orientalis, B. lateralis
  • Blat- tella spp. such as z?.
  • Thysanura for example Lepisma saccharina , Ctenolepisma urbana, and Thermobia domestica
  • Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera co/eoptrata;
  • Pests from the class Diplopoda for example Blaniulus guttulatus, Julus spp., Narceus spp.
  • Pests from the class Symphyla for example Scutigerella immaculata
  • Onychiurus spp. such as Onychiurus armatus, Pests from the order Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber, Insects from the order Phthiraptera, for example Damalinia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.,
  • Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, for example, Dreissena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Ga/ba spp., Lymnaea spp., Oncomelania spp., Pomacea canal/data, Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancy- lostoma spp., Ascaris lubricoides, Ascaris spp., Brugia ma lay i, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis s
  • Haemonchus contortus such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesoph- agostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonim us spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichi- nella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of a cultivated plant, in particular the yield of a cultivated plant, by treating plant propagation material, preferably seeds with the compound of formula I and its mixtures.
  • the present invention also comprises plant propagation material, preferably seed, of a cultivated plant treated with the compound of formula I and its mixtures.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of a cultivated plant, in particular the yield of a cultivated plant by treating the cultivated plant, part(s) of such plant or at its locus of growth with the compound of formula I and its mixtures.
  • cultivar plant(s) includes to "modified plant(s)" and "transgenic plant(s)".
  • the term “cultivated plants” refers to "modified plants”. In one embodiment of the invention, the term “cultivated plants” refers to "transgenic plants”. "Modified plants” are those which have been modified by conventional breeding techniques.
  • the term “modification” means in relation to modified plants a change in the genome, epigenome, tran- scriptome or proteome of the modified plant, as compared to the control, wild type, mother or parent plant whereby the modification confers a trait (or more than one trait) or confers the in- crease of a trait (or more than one trait) as listed below.
  • the modification may result in the modified plant to be a different, for example a new plant variety than the parental plant.
  • Transgenic plants are those, which genetic material has been modified by the use of recombi- nant DNA techniques that under natural circumstances can not readily be obtained by cross breeding, mutations or natural recombination, whereby the modification confers a trait (or more than one trait) or confers the increase of a trait (or more than one trait) as listed below as compared to the wild-type plant.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant, preferably increase a trait as listed below as compared to the wild-type plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), or to post- transcriptional modifications of oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated, phosphorylated or farnesylated moieties or PEG moieties.
  • modification when reffering to a transgenic plant or parts thereof is understood that the activity, expression level or amount of a gene product or the metabolite content is changed, e.g. increased or decreased, in a specific volume relative to a cor- responding volume of a control, reference or wild-type plant or plant cell, including the de novo creation of the activity or expression.
  • the activity of a polypeptide is increased or generated by expression or overexpresion of the gene coding for said polypeptide which confers a trait or confers the increase of a trait as listed below as compared to the control plant.
  • expression or “gene expression” means the transcription of a specific gene or specific genes or specific genetic construct.
  • expression or “gene expression” in particular means the transcription of a gene or genes or genetic construct into structural RNA (rRNA, tRNA), regulatory RNA (e.g. miRNA, RNAi, RNAa) or mRNA with or without subsequent translation of the latter into a protein.
  • expression in particular means the transcription of a gene or genes or genetic construct into structural RNA (rRNA, tRNA) or mRNA with or without subsequent translation of the latter into a protein. In yet another embodiment it means the transcription of a gene or genes or genetic construct into mRNA.
  • the process includes transcription of DNA and processing of the resulting mRNA product.
  • increased expression or “overexpression” as used herein means any form of expression that is additional to the original wild-type expression level.
  • polypeptide expression of a polypeptide is understood in one embodiment to mean the level of said protein or polypeptide, preferably in an active form, in a cell or organism.
  • the activity of a polypeptide is decreased by decreased expression of the gene coding for said polypeptide which confers a trait or confers the increase of a trait as listed below as compared to the control plant.
  • Reference herein to "decreased expression” or “reduction or substantial elimination” of expression is taken to mean a decrease in endogenous gene expression and/or polypeptide levels and/or polypeptide activity relative to control plants. It comprises further reducing, repressing, decreasing or deleting of an expression product of a nucleic acid molecule.
  • reduction relate to a corresponding change of a property in an organism, a part of an organism such as a tissue, seed, root, tuber, fruit, leave, flower etc. or in a cell.
  • change of a property it is understood that the activity, expression level or amount of a gene product or the metabolite content is changed in a specific volume or in a specific amount of protein relative to a corresponding volume or amount of protein of a control, reference or wild type.
  • the overall activity in the volume is reduced, decreased or deleted in cases if the reduction, decrease or deletion is related to the reduction, decrease or deletion of an activity of a gene product, independent whether the amount of gene product or the specific activity of the gene product or both is reduced, decreased or deleted or whether the amount, stability or translation efficacy of the nucleic acid sequence or gene encoding for the gene product is reduced, decreased or deleted.
  • the terms "reduction”, “repression”, “decrease” or “deletion” include the change of said property in only parts of the subject of the present invention, for example, the modification can be found in compartment of a cell, like an organelle, or in a part of a plant, like tissue, seed, root, leave, tuber, fruit, flower etc.
  • the "reduction”, “repression”, “decrease” or “deletion” is found cellular, thus the term “reduction, decrease or deletion of an activity” or “reduction, decrease or deletion of a metabolite content” relates to the cellular reduction, decrease or deletion compared to the wild type cell.
  • the terms “reduction”, “repression”, “decrease” or “deletion” include the change of said property only during different growth phases of the organism used in the inventive process, for example the reduction, repression, decrease or deletion takes place only during the seed growth or during blooming.
  • the terms include a transitional reduction, decrease or deletion for example because the used method, e.g. the antisense, RNAi, snRNA, dsRNA, siRNA, miRNA, ta-siRNA, cosuppression molecule, or ribozyme, is not stable integrated in the genome of the organism or the reduction, decrease, repression or deletion is under control of a regulatory or inducible element, e.g. a chemical or otherwise inducible pro- moter, and has therefore only a transient effect.
  • a regulatory or inducible element e.g. a chemical or otherwise inducible pro- moter
  • Reducing, repressing, decreasing or deleting of an expression product of a nucleic acid mole- cule in modified plants is known.
  • Examples are canola i.e. double nill oilseed rape with reduced amounts of erucic acid and sinapins.
  • Such a decrease can also be achieved for example by the use of recombinant DNA technology, such as antisense or regulatory RNA (e.g. miRNA, RNAi, RNAa) or siRNA approaches.
  • antisense or regulatory RNA e.g. miRNA, RNAi, RNAa
  • siRNA approaches e.g. RNAi, snRNA, dsRNA, siRNA, miRNA, ta-siRNA, cosuppression molecule, ribozyme, or antisense nucleic acid molecule
  • a nucleic acid molecule conferring the expression of a dominant-negative mutant of a protein or a nucleic acid construct capable to recombine with and silence, inactivate, repress or reduces the activity of an endogenous gene may be used to decrease the activity of a polypeptide in a transgenic plant or parts thereof or a plant cell thereof used in one embodiment of the methods of the invention.
  • transgenic plants with reduced, repressed, decreased or deleted expression product of a nucleic acid molecule are Carica papaya (Papaya plants) with the event name X17-2 of the University of Florida, Prunus domestica (Plum) with the event name C5 of the United States Department of Agriculture - Agri- cultural Research Service, or those listed in rows T9-48 and T9-49 of table 9 below. Also known are plants with increased resistance to nematodes for example by reducing, repressing, decreasing or deleting of an expression product of a nucleic acid molecule, e.g. from the PCT publication WO 2008/095886.
  • the reduction or substantial elimination is in increasing order of preference at least 10%, 20%, 30%, 40% or 50%, 60%, 70%, 80%, 85%, 90%, or 95%, 96%, 97%, 98%, 99% or more reduced compared to that of control plants.
  • Reference herein to an "endogenous" gene not only refers to the gene in question as found in a plant in its natural form (i.e., without there being any human intervention), but also refers to that same gene (or a substantially homologous nucleic ac- id/gene) in an isolated form subsequently (re) introduced into a plant (a transgene).
  • a transgenic plant containing such a transgene may encounter a substantial reduction of the transgene expression and/or substantial reduction of expression of the endogenous gene.
  • control or “reference” are exchangeable and can be a cell or a part of a plant such as an organelle like a chloroplast or a tissue, in particular a plant, which was not modified or treated according to the herein described process according to the invention. Accordingly, the plant used as control or reference corresponds to the plant as much as possible and is as identical to the subject matter of the invention as possible. Thus, the control or reference is treated identically or as identical as possible, saying that only conditions or properties might be different which do not influence the quality of the tested property other than the treatment of the present invention.
  • control or reference plants are wild-type plants.
  • control or reference plants may refer to plants carrying at least one genetic modification, when the plants employed in the process of the present invention carry at least one genetic modification more than said control or reference plants.
  • control or reference plants may be transgenic but differ from transgenic plants employed in the process of the present invention only by said modification contained in the transgenic plants employed in the process of the present invention.
  • wild type or wild-type plants refers to a plant without said genetic modification. These terms can refer to a cell or a part of a plant such as an organelle like a chloroplast or a tissue, in particular a plant, which lacks said genetic modification but is otherwise as identical as possible to the plants with at least one genetic modification employed in the present invention. In a particular embodiment the "wild-type" plant is not transgenic.
  • the wild type is identically treated according to the herein described process according to the invention.
  • the person skilled in the art will recognize if wild-type plants will not require certain treatments in advance to the process of the present invention, e.g. non-transgenic wild- type plants will not need selection for transgenic plants for example by treatment with a selecting agent such as a herbicide.
  • the control plant may also be a nullizygote of the plant to be assessed.
  • nullizygote refers to a plant that has undergone the same production process as a transgenic, yet has lost the once aquired genetic modification (e.g. due to mendelian segregation)as the corresponding transgenic. If the starting material of said production process is transgenic, then nullizygotes are also transgenic but lack the additional genetic modification introduced by the production process.
  • the purpose of wild-type and nullizygotes is the same as the one for control and reference or parts thereof. All of these serve as controls in any comparison to provide evidence of the advantageous effect of the present invention.
  • any comparison is carried out under analogous conditions.
  • analogous conditions means that all conditions such as, for example, culture or growing conditions, soil, nutrient, water content of the soil, temperature, humidity or surrounding air or soil, assay conditions (such as buffer composition, temperature, substrates, pathogen strain, concentrations and the like) are kept identical between the experiments to be compared.
  • assay conditions such as buffer composition, temperature, substrates, pathogen strain, concentrations and the like.
  • results can be normalized or standardized based on the control.
  • the "reference”, “control”, or “wild type” is preferably a plant, which was not modified or treated according to the herein described process of the invention and is in any other property as similar to a plant, employed in the process of the present invention of the invention as possible.
  • the reference, control or wild type is in its genome, transcriptome, proteome or metabolome as simi- lar as possible to a plant, employed in the process of the present invention of the present invention.
  • the term “reference-" "control-” or “wild-type-” plant relates to a plant, which is nearly genetically identical to the organelle, cell, tissue or organism, in particular plant, of the present invention or a part thereof preferably 90% or more, e.g.
  • the "reference”, “control”, or “wild type” is a plant, which is genetically identical to the plant, cell, a tissue or organelle used according to the process of the invention except that the responsible or activity conferring nucleic acid molecules or the gene product encoded by them have been amended, manipulated, exchanged or introduced in the organelle, cell, tissue, plant, employed in the process of the present invention.
  • the reference and the subject matter of the invention are compared after standardization and normalization, e.g. to the amount of total RNA, DNA, or protein or activity or expression of reference genes, like housekeeping genes, such as ubiquitin, actin or ribosomal proteins.
  • the genetic modification carried in the organelle, cell, tissue, in particular plant used in the pro- cess of the present invention is in one embodiment stable e.g. due to a stable transgenic integration or to a stable mutation in the corresponding endogenous gene or to a modulation of the expression or of the behaviour of a gene, or transient, e.g. due to an transient transformation or temporary addition of a modulator such as an agonist or antagonist or inducible, e.g. after transformation with a inducible construct carrying a nucleic acid molecule under control of a inducible promoter and adding the inducer, e.g. tetracycline.
  • the invention relates to methods and uses, wherein a compound of fomula IA as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T.
  • the invention relates to methods and uses, wherein a compound select- ed from the compounds of Table A, A' or A", is applied in an application type which corresponds in each case to one row of Table AP-T.
  • the application of the compounds and mixtures according to the invention especially the compounds as individualized herein, e.g. in Table A, A', or A", on specialty crops like fruits and vegetables.
  • the application is on fruiting vegetables, and especially on tomato, on pepper or on eggplant.
  • the application is on leafy vegetables, and especially on cabbage or on lettuce.
  • the application is on tubers (tuber vegetables), and especially on potato or on onion.
  • the following application types are used:

Abstract

The present invention relates to agricultural methods for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification, using cyclaniliprole or a mixture thereof. The present invention relates to agricultural methods for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification, using a compound of formula (I) or mixtures thereof. In particular, the invention relates to methods of controlling harmful insects, which are resistant to an insecticidal trait of the plant. Furthermore, the invention relates to certain mixtures of the compound of formula (I), and to their use in the methods for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification, and especially to methods of controlling harmful insects, which are resistant to an insecticidal trait of the plant.

Description

Use of cyclaniliprole on cultivated plants
The present invention relates to a method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification (hereinafter abbreviated as "cultivated plant") as compared to the respective non-modified control plant, comprising the application of a pesti- cidally active compound of formula I
or a stereoisomer, salt, tautomer or N-oxide thereof;
to a cultivated plant, parts of such plant, plant propagation material, or at its locus of growth.
One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavourable environmental or toxicological effects whilst still allowing effective pest control. Another problem underlying the invention is the desire for compositions that improve the health of a plant, a process which is commonly and hereinafter referred to as "plant health". The term plant health comprises various sorts of improvements of plants that are not connected to the control of pests and which do not embrace the reduction of negative consequences of harmful insects. The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e.g. increased biomass and/or increased content of valuable ingredients), plant vigor (e.g. improved plant growth and/or greener leaves ("greening effect"), quality (e.g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
It was therefore the object of the present invention to provide a method, which solves the problems as outlined above and which especially reduces the dosage rate and/or promotes the health of a plant.
Surprisingly, it has now been found that the use of a compound of formula (I) as defined above in cultivated plants displays a synergistic effect between the trait of the cultivated plant and the applied compound of formula (I).
In a first embodiment, cultivated plants are plants that have at least one insecticidal trait. It is a wide-spread problem that insects, that are combatted with insectides, develop resistance, i.e. they become less or not all anymore susceptible to the insecticidal effect. Surprisingly, it has now been found that the compound of formula (I) are useful in methods of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth, wherein the plant has at least one insecticidal trait, and wherein the harmful insects are resistant to an insecticidal trait of the plant.
In a second embodiment, cultivated plants are specific plants that have at least one herbicidal and at least one insecticidal trait, preferably soybeans, more preferably the soybeans known as"lntacta R 2 PRO" soybean (Monsanto). Surprisingly, it has now been found that the compound of formula (I) are also useful in methods of controlling harmful insects by treating those mentioned cultivated plants, parts of such plants or their locus of growth.
In a third embodiment, cultivated plants are plants that have at least one trait or trait combination which has not yet been described in connection with the use of the compound of formula (I) on cultivated plants, e.g. as listed in Table A1.
Surprisingly, it has now been found that the compound of formula (I) are also useful in methods of controlling harmful insects by treating those mentioned cultivated plants, parts of such plants or their locus of growth.
Compound of formula (I)
The compound of formula (I) is described in WO2005/077934 and is known under the ISO name "cyclaniliprole". It can be prepared according to standard methods of organic chemistry, or by the processes as described in WO2005/077934 or WO2008072743, without being limited to the routes given therein.
The preparation of the compound of formula I above may lead to isomer mixtures. If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers. Agronomically acceptable salts of the compound of formula (I) can be formed in a customary manner, e.g. by reaction with an acid of the anion in question. However, although the compound of formula (I) has been described in WO2014/128188 in methods and uses for controlling harmful pests on certain cultivated plants, there are further cultivated plants on which the compound of formula (I) is surprisingly effective.
In a further embodiment of the invention, the invention relates to certain mixtures of the com- pound of formula (I), and to the use of said mixture in the methods according to the invention as mentioned herein. The mixtures of the present invention are those mixtures described in the following embodiments and Tables.
Embodiment 1
In one embodiment (1), the mixtures comprise a compound of formula (I) and a further pesticide component II of Table B. Table B
Pesticide compoCompound
nent II abbreviation
Azoxystrobin ll-F-1
Trifloxistrobin ll-F-2
Picoxystrobin ll-F-3
Pyraclostrobin ll-F-4
Sedaxane ll-F-5
Penthiopyrad ll-F-6
Penflufen ll-F-7
Fluopyram ll-F-8
Fluxapyroxad ll-F-9
Boscalid ll-F- 0
Oxathiapiprolin ll-F-11
Metalaxyl ll-F- 2
Metalaxyl-M ll-F-13
Ethaboxam ll-F-14
Dimethomorph ll-F-15
Valifenalate ll-F-16
Cyproconazole ll-F-17
Difenoconazole ll-F-18
Prothioconazole ll-F-19
Flutriafol ll-F-20
Thiabendazole ll-F-21
Ipconazole ll-F-22
Tebuconazole ll-F-23
Triadimenol ll-F-24
Prochloraz ll-F-25
Fluquinconazole ll-F-26
Triticonazole ll-F-27
Fludioxinil ll-F-28
Carboxin ll-F-29
Figure imgf000004_0001
Silthiofam ll-F-30
Therefore, the mixtures in this embodiment are the mixtures listed in Table B-1 : Table B-1
Figure imgf000005_0001
Figure imgf000005_0002
Figure imgf000005_0003
Embodiment 2
In another embodiment (2), the mixtures comprise a compound of formula (I) and two further pesticide components II selected from the compounds listed in Table B.
In the context of the present invention, each of the rows of Table T-1 corresponds to one mixture.
Table T-1
Mixture I II III Mixture I II III
M.T1.1 ll-F-1 ll-F-5 M.T1.12 ll-F-1 ll-F-16
M.T1.2 ll-F-1 ll-F-6 M.T1.13 ll-F-1 ll-F-17
M.T1.3 ll-F-1 ll-F-7 M.T1.14 ll-F-1 ll-F-18
M.T1.4 ll-F-1 ll-F-8 M.T1.15 ll-F-1 ll-F-19
M.T1.5 ll-F-1 ll-F-9 M.T1.16 ll-F-1 ll-F-20
M.T1.6 ll-F-1 ll-F-10 M.T1.17 ll-F-1 ll-F-21
M.T1.7 ll-F-1 ll-F-11 M.T1.18 ll-F-1 ll-F-22
M.T1.8 ll-F-1 ll-F-12 M.T1.19 ll-F-1 ll-F-23
M.T1.9 ll-F-1 ll-F-13 M.T1.20 ll-F-1 ll-F-24
M.T1.10 ll-F-1 ll-F-14 M.T1.21 ll-F-1 ll-F-25
M.T1.1 1 ll-F-1 ll-F-15 M.T1.22 ll-F-1 ll-F-26 Mixture I II III Mixture I II III
M.T1.23 ll-F-1 ll-F-27 M.T1.64 ll-F-3 ll-F-8
M.T1.24 ll-F-1 ll-F-28 M.T1.65 ll-F-3 ll-F-9
M.T1.25 ll-F-1 ll-F-29 M.T1.66 ll-F-3 ll-F-10
M.T1.26 ll-F-1 ll-F-30 M.T1.67 ll-F-3 ll-F-11
M.T1.27 ll-F-1 ll-F-31 M.T1.68 ll-F-3 ll-F-12
M.T1.28 ll-F-1 ll-F-32 M.T1.69 ll-F-3 ll-F-13
M.T1.29 ll-F-1 ll-F-33 M.T1.70 ll-F-3 ll-F-14
M.T1.30 ll-F-1 ll-F-34 M.T1.71 ll-F-3 ll-F-15
M.T1.31 ll-F-2 ll-F-5 M.T1.72 ll-F-3 ll-F-16
M.T1.32 ll-F-2 ll-F-6 M.T1.73 ll-F-3 ll-F-17
M.T1.33 ll-F-2 ll-F-7 M.T1.74 ll-F-3 ll-F-18
M.T1.34 ll-F-2 ll-F-8 M.T1.75 ll-F-3 ll-F-19
M.T1.35 ll-F-2 ll-F-9 M.T1.76 ll-F-3 ll-F-20
M.T1.36 ll-F-2 ll-F-10 M.T1.77 ll-F-3 ll-F-21
M.T1.37 ll-F-2 ll-F-11 M.T1.78 ll-F-3 ll-F-22
M.T1.38 ll-F-2 ll-F-12 M.T1.79 ll-F-3 ll-F-23
M.T1.39 ll-F-2 ll-F-13 M.T1.80 ll-F-3 ll-F-24
M.T1.40 ll-F-2 ll-F-14 M.T1.81 ll-F-3 ll-F-25
M.T1.41 ll-F-2 ll-F-15 M.T1.82 ll-F-3 ll-F-26
M.T1.42 ll-F-2 ll-F-16 M.T1.83 ll-F-3 ll-F-27
M.T1.43 ll-F-2 ll-F-17 M.T1.84 ll-F-3 ll-F-28
M.T1.44 ll-F-2 ll-F-18 M.T1.85 ll-F-3 ll-F-29
M.T1.45 ll-F-2 ll-F-19 M.T1.86 ll-F-3 ll-F-30
M.T1.46 ll-F-2 ll-F-20 M.T1.87 ll-F-3 ll-F-31
M.T1.47 ll-F-2 ll-F-21 M.T1.88 ll-F-3 ll-F-32
M.T1.48 ll-F-2 ll-F-22 M.T1.89 ll-F-3 ll-F-33
M.T1.49 ll-F-2 ll-F-23 M.T1.90 ll-F-3 ll-F-34
M.T1.50 ll-F-2 ll-F-24 M.T1.91 ll-F-4 ll-F-5
M.T1.51 ll-F-2 ll-F-25 M.T1.92 ll-F-4 ll-F-6
M.T1.52 ll-F-2 ll-F-26 M.T1.93 ll-F-4 ll-F-7
M.T1.53 ll-F-2 ll-F-27 M.T1.94 ll-F-4 ll-F-8
M.T1.54 ll-F-2 ll-F-28 M.T1.95 ll-F-4 ll-F-9
M.T1.55 ll-F-2 ll-F-29 M.T1.96 ll-F-4 ll-F-10
M.T1.56 ll-F-2 ll-F-30 M.T1.97 ll-F-4 ll-F-11
M.T1.57 ll-F-2 ll-F-31 M.T1.98 ll-F-4 ll-F-12
M.T1.58 ll-F-2 ll-F-32 M.T1.99 ll-F-4 ll-F-13
M.T1.59 ll-F-2 ll-F-33 M.T1.100 ll-F-4 ll-F-14
M.T1.60 ll-F-2 ll-F-34 M.T1.101 ll-F-4 ll-F-15
M.T1.61 ll-F-3 ll-F-5 M.T1.102 ll-F-4 ll-F-16
M.T1.62 ll-F-3 ll-F-6 M.T1.103 ll-F-4 ll-F-17
M.T1.63 ll-F-3 ll-F-7 M.T1.104 ll-F-4 ll-F-18 Mixture I II III Mixture I II III
M.T1.105 ll-F-4 ll-F-19 M.T1.146 ll-F-6 ll-F-12
M.T1.106 ll-F-4 ll-F-20 M.T1.147 ll-F-6 ll-F-13
M.T1.107 ll-F-4 ll-F-21 M.T1.148 ll-F-6 ll-F-14
M.T1.108 ll-F-4 ll-F-22 M.T1.149 ll-F-6 ll-F-15
M.T1.109 ll-F-4 ll-F-23 M.T1.150 ll-F-6 ll-F-16
M.T1.1 10 ll-F-4 ll-F-24 M.T1.151 ll-F-6 ll-F-17
M.T1.1 11 ll-F-4 ll-F-25 M.T1.152 ll-F-6 ll-F-18
M.T1.1 12 ll-F-4 ll-F-26 M.T1.153 ll-F-6 ll-F-19
M.T1.1 13 ll-F-4 ll-F-27 M.T1.154 ll-F-6 ll-F-20
M.T1.1 14 ll-F-4 ll-F-28 M.T1.155 ll-F-6 ll-F-21
M.T1.1 15 ll-F-4 ll-F-29 M.T1.156 ll-F-6 ll-F-22
M.T1.1 16 ll-F-4 ll-F-30 M.T1.157 ll-F-6 ll-F-23
M.T1.1 17 ll-F-4 ll-F-31 M.T1.158 ll-F-6 ll-F-24
M.T1.1 18 ll-F-4 ll-F-32 M.T1.159 ll-F-6 ll-F-25
M.T1.1 19 ll-F-4 ll-F-33 M.T1.160 ll-F-6 ll-F-26
M.T1.120 ll-F-4 ll-F-34 M.T1.161 ll-F-6 ll-F-27
M.T1.121 ll-F-5 ll-F-11 M.T1.162 ll-F-6 ll-F-28
M.T1.122 ll-F-5 ll-F-12 M.T1.163 ll-F-6 ll-F-29
M.T1.123 ll-F-5 ll-F-13 M.T1.164 ll-F-6 ll-F-30
M.T1.124 ll-F-5 ll-F-14 M.T1.165 ll-F-6 ll-F-31
M.T1.125 ll-F-5 ll-F-15 M.T1.166 ll-F-6 ll-F-32
M.T1.126 ll-F-5 ll-F-16 M.T1.167 ll-F-6 ll-F-33
M.T1.127 ll-F-5 ll-F-17 M.T1.168 ll-F-6 ll-F-34
M.T1.128 ll-F-5 ll-F-18 M.T1.169 ll-F-6 ll-F-11
M.T1.129 ll-F-5 ll-F-19 M.T1.170 ll-F-6 ll-F-12
M.T1.130 ll-F-5 ll-F-20 M.T1.171 ll-F-6 ll-F-13
M.T1.131 ll-F-5 ll-F-21 M.T1.172 ll-F-6 ll-F-14
M.T1.132 ll-F-5 ll-F-22 M.T1.173 ll-F-6 ll-F-15
M.T1.133 ll-F-5 ll-F-23 M.T1.174 ll-F-6 ll-F-16
M.T1.134 ll-F-5 ll-F-24 M.T1.175 ll-F-6 ll-F-17
M.T1.135 ll-F-5 ll-F-25 M.T1.176 ll-F-6 ll-F-18
M.T1.136 ll-F-5 ll-F-26 M.T1.177 ll-F-6 ll-F-19
M.T1.137 ll-F-5 ll-F-27 M.T1.178 ll-F-6 ll-F-20
M.T1.138 ll-F-5 ll-F-28 M.T1.179 ll-F-6 ll-F-21
M.T1.139 ll-F-5 ll-F-29 M.T1.180 ll-F-6 ll-F-22
M.T1.140 ll-F-5 ll-F-30 M.T1.181 ll-F-6 ll-F-23
M.T1.141 ll-F-5 ll-F-31 M.T1.182 ll-F-6 ll-F-24
M.T1.142 ll-F-5 ll-F-32 M.T1.183 ll-F-6 ll-F-25
M.T1.143 ll-F-5 ll-F-33 M.T1.184 ll-F-6 ll-F-26
M.T1.144 ll-F-5 ll-F-34 M.T1.185 ll-F-6 ll-F-27
M.T1.145 ll-F-6 ll-F-11 M.T1.186 ll-F-6 ll-F-28 Mixture I II III Mixture I II III
M.T1.187 ll-F-6 ll-F-29 M.T1.228 ll-F-8 ll-F-22
M.T1.188 ll-F-6 ll-F-30 M.T1.229 ll-F-8 ll-F-23
M.T1.189 ll-F-6 ll-F-31 M.T1.230 ll-F-8 ll-F-24
M.T1.190 ll-F-6 ll-F-32 M.T1.231 ll-F-8 ll-F-25
M.T1.191 ll-F-6 ll-F-33 M.T1.232 ll-F-8 ll-F-26
M.T1.192 ll-F-6 ll-F-34 M.T1.233 ll-F-8 ll-F-27
M.T1.193 ll-F-7 ll-F-11 M.T1.234 ll-F-8 ll-F-28
M.T1.194 ll-F-7 ll-F-12 M.T1.235 ll-F-8 ll-F-29
M.T1.195 ll-F-7 ll-F-13 M.T1.236 ll-F-8 ll-F-30
M.T1.196 ll-F-7 ll-F-14 M.T1.237 ll-F-8 ll-F-31
M.T1.197 ll-F-7 ll-F-15 M.T1.238 ll-F-8 ll-F-32
M.T1.198 ll-F-7 ll-F-16 M.T1.239 ll-F-8 ll-F-33
M.T1.199 ll-F-7 ll-F-17 M.T1.240 ll-F-8 ll-F-34
M.T1.200 ll-F-7 ll-F-18 M.T1.241 ll-F-9 ll-F-11
M.T1.201 ll-F-7 ll-F-19 M.T1.242 ll-F-9 ll-F-12
M.T1.202 ll-F-7 ll-F-20 M.T1.243 ll-F-9 ll-F-13
M.T1.203 ll-F-7 ll-F-21 M.T1.244 ll-F-9 ll-F-14
M.T1.204 ll-F-7 ll-F-22 M.T1.245 ll-F-9 ll-F-15
M.T1.205 ll-F-7 ll-F-23 M.T1.246 ll-F-9 ll-F-16
M.T1.206 ll-F-7 ll-F-24 M.T1.247 ll-F-9 ll-F-17
M.T1.207 ll-F-7 ll-F-25 M.T1.248 ll-F-9 ll-F-18
M.T1.208 ll-F-7 ll-F-26 M.T1.249 ll-F-9 ll-F-19
M.T1.209 ll-F-7 ll-F-27 M.T1.250 ll-F-9 ll-F-20
M.T1.210 ll-F-7 ll-F-28 M.T1.251 ll-F-9 ll-F-21
M.T1.211 ll-F-7 ll-F-29 M.T1.252 ll-F-9 ll-F-22
M.T1.212 ll-F-7 ll-F-30 M.T1.253 ll-F-9 ll-F-23
M.T1.213 ll-F-7 ll-F-31 M.T1.254 ll-F-9 ll-F-24
M.T1.214 ll-F-7 ll-F-32 M.T1.255 ll-F-9 ll-F-25
M.T1.215 ll-F-7 ll-F-33 M.T1.256 ll-F-9 ll-F-26
M.T1.216 ll-F-7 ll-F-34 M.T1.257 ll-F-9 ll-F-27
M.T1.217 ll-F-8 ll-F-11 M.T1.258 ll-F-9 ll-F-28
M.T1.218 ll-F-8 ll-F-12 M.T1.259 ll-F-9 ll-F-29
M.T1.219 ll-F-8 ll-F-13 M.T1.260 ll-F-9 ll-F-30
M.T1.220 ll-F-8 ll-F-14 M.T1.261 ll-F-9 ll-F-31
M.T1.221 ll-F-8 ll-F-15 M.T1.262 ll-F-9 ll-F-32
M.T1.222 ll-F-8 ll-F-16 M.T1.263 ll-F-9 ll-F-33
M.T1.223 ll-F-8 ll-F-17 M.T1.264 ll-F-9 ll-F-34
M.T1.224 ll-F-8 ll-F-18 M.T1.265 ll-F-10 ll-F-11
M.T1.225 ll-F-8 ll-F-19 M.T1.266 ll-F-10 ll-F-12
M.T1.226 ll-F-8 ll-F-20 M.T1.267 ll-F-10 ll-F-13
M.T1.227 ll-F-8 ll-F-21 M.T1.268 ll-F-10 ll-F-14 Mixture I II III Mixture I II III
M.T1.269 ll-F-10 ll-F-15 M.T1.310 ll-F-12 ll-F-20
M.T1.270 ll-F-10 ll-F-16 M.T1.31 1 ll-F-12 ll-F-21
M.T1.271 ll-F-10 ll-F-17 M.T1.312 ll-F-12 ll-F-22
M.T1.272 ll-F-10 ll-F-18 M.T1.313 ll-F-12 ll-F-23
M.T1.273 ll-F-10 ll-F-19 M.T1.314 ll-F-12 ll-F-24
M.T1.274 ll-F-10 ll-F-20 M.T1.315 ll-F-12 ll-F-25
M.T1.275 ll-F-10 ll-F-21 M.T1.316 ll-F-12 ll-F-26
M.T1.276 ll-F-10 ll-F-22 M.T1.317 ll-F-12 ll-F-27
M.T1.277 ll-F-10 ll-F-23 M.T1.318 ll-F-12 ll-F-28
M.T1.278 ll-F-10 ll-F-24 M.T1.319 ll-F-12 ll-F-29
M.T1.279 ll-F-10 ll-F-25 M.T1.320 ll-F-12 ll-F-30
M.T1.280 ll-F-10 ll-F-26 M.T1.321 ll-F-12 ll-F-31
M.T1.281 ll-F-10 ll-F-27 M.T1.322 ll-F-12 ll-F-32
M.T1.282 ll-F-10 ll-F-28 M.T1.323 ll-F-12 ll-F-33
M.T1.283 ll-F-10 ll-F-29 M.T1.324 ll-F-12 ll-F-34
M.T1.284 ll-F-10 ll-F-30 M.T1.325 ll-F-13 ll-F-17
M.T1.285 ll-F-10 ll-F-31 M.T1.326 ll-F-13 ll-F-18
M.T1.286 ll-F-10 ll-F-32 M.T1.327 ll-F-13 ll-F-19
M.T1.287 ll-F-10 ll-F-33 M.T1.328 ll-F-13 ll-F-20
M.T1.288 ll-F-10 ll-F-34 M.T1.329 ll-F-13 ll-F-21
M.T1.289 ll-F-11 ll-F-17 M.T1.330 ll-F-13 ll-F-22
M.T1.290 ll-F-11 ll-F-18 M.T1.331 ll-F-13 ll-F-23
M.T1.291 ll-F-11 ll-F-19 M.T1.332 ll-F-13 ll-F-24
M.T1.292 ll-F-11 ll-F-20 M.T1.333 ll-F-13 ll-F-25
M.T1.293 ll-F-11 ll-F-21 M.T1.334 ll-F-13 ll-F-26
M.T1.294 ll-F-11 ll-F-22 M.T1.335 ll-F-13 ll-F-27
M.T1.295 ll-F-11 ll-F-23 M.T1.336 ll-F-13 ll-F-28
M.T1.296 ll-F-11 ll-F-24 M.T1.337 ll-F-13 ll-F-29
M.T1.297 ll-F-11 ll-F-25 M.T1.338 ll-F-13 ll-F-30
M.T1.298 ll-F-11 ll-F-26 M.T1.339 ll-F-13 ll-F-31
M.T1.299 ll-F-11 ll-F-27 M.T1.340 ll-F-13 ll-F-32
M.T1.300 ll-F-11 ll-F-28 M.T1.341 ll-F-13 ll-F-33
M.T1.301 ll-F-11 ll-F-29 M.T1.342 ll-F-13 ll-F-34
M.T1.302 ll-F-11 ll-F-30 M.T1.343 ll-F-14 ll-F-17
M.T1.303 ll-F-11 ll-F-31 M.T1.344 ll-F-14 ll-F-18
M.T1.304 ll-F-11 ll-F-32 M.T1.345 ll-F-14 ll-F-19
M.T1.305 ll-F-11 ll-F-33 M.T1.346 ll-F-14 ll-F-20
M.T1.306 ll-F-11 ll-F-34 M.T1.347 ll-F-14 ll-F-21
M.T1.307 ll-F-12 ll-F-17 M.T1.348 ll-F-14 ll-F-22
M.T1.308 ll-F-12 ll-F-18 M.T1.349 ll-F-14 ll-F-23
M.T1.309 ll-F-12 ll-F-19 M.T1.350 ll-F-14 ll-F-24 Mixture I II III Mixture I II III
M.T1.351 ll-F-14 ll-F-25 M.T1.392 ll-F-16 ll-F-30
M.T1.352 ll-F-14 ll-F-26 M.T1.393 ll-F-16 ll-F-31
M.T1.353 ll-F-14 ll-F-27 M.T1.394 ll-F-16 ll-F-32
M.T1.354 ll-F-14 ll-F-28 M.T1.395 ll-F-16 ll-F-33
M.T1.355 ll-F-14 ll-F-29 M.T1.396 ll-F-16 ll-F-34
M.T1.356 ll-F-14 ll-F-30 M.T1.397 ll-F-17 ll-F-28
M.T1.357 ll-F-14 ll-F-31 M.T1.398 ll-F-17 ll-F-29
M.T1.358 ll-F-14 ll-F-32 M.T1.399 ll-F-17 ll-F-30
M.T1.359 ll-F-14 ll-F-33 M.T1.400 ll-F-17 ll-F-31
M.T1.360 ll-F-14 ll-F-34 M.T1.401 ll-F-17 ll-F-32
M.T1.361 ll-F-15 ll-F-17 M.T1.402 ll-F-17 ll-F-33
M.T1.362 ll-F-15 ll-F-18 M.T1.403 ll-F-17 ll-F-34
M.T1.363 ll-F-15 ll-F-19 M.T1.404 ll-F-18 ll-F-28
M.T1.364 ll-F-15 ll-F-20 M.T1.405 ll-F-18 ll-F-29
M.T1.365 ll-F-15 ll-F-21 M.T1.406 ll-F-18 ll-F-30
M.T1.366 ll-F-15 ll-F-22 M.T1.407 ll-F-18 ll-F-31
M.T1.367 ll-F-15 ll-F-23 M.T1.408 ll-F-18 ll-F-32
M.T1.368 ll-F-15 ll-F-24 M.T1.409 ll-F-18 ll-F-33
M.T1.369 ll-F-15 ll-F-25 M.T1.410 ll-F-18 ll-F-34
M.T1.370 ll-F-15 ll-F-26 M.T1.41 1 ll-F-19 ll-F-28
M.T1.371 ll-F-15 ll-F-27 M.T1.412 ll-F-19 ll-F-29
M.T1.372 ll-F-15 ll-F-28 M.T1.413 ll-F-19 ll-F-30
M.T1.373 ll-F-15 ll-F-29 M.T1.414 ll-F-19 ll-F-31
M.T1.374 ll-F-15 ll-F-30 M.T1.415 ll-F-19 ll-F-32
M.T1.375 ll-F-15 ll-F-31 M.T1.416 ll-F-19 ll-F-33
M.T1.376 ll-F-15 ll-F-32 M.T1.417 ll-F-19 ll-F-34
M.T1.377 ll-F-15 ll-F-33 M.T1.418 ll-F-20 ll-F-28
M.T1.378 ll-F-15 ll-F-34 M.T1.419 ll-F-20 ll-F-29
M.T1.379 ll-F-16 ll-F-17 M.T1.420 ll-F-20 ll-F-30
M.T1.380 ll-F-16 ll-F-18 M.T1.421 ll-F-20 ll-F-31
M.T1.381 ll-F-16 ll-F-19 M.T1.422 ll-F-20 ll-F-32
M.T1.382 ll-F-16 ll-F-20 M.T1.423 ll-F-20 ll-F-33
M.T1.383 ll-F-16 ll-F-21 M.T1.424 ll-F-20 ll-F-34
M.T1.384 ll-F-16 ll-F-22 M.T1.425 ll-F-21 ll-F-28
M.T1.385 ll-F-16 ll-F-23 M.T1.426 ll-F-21 ll-F-29
M.T1.386 ll-F-16 ll-F-24 M.T1.427 ll-F-21 ll-F-30
M.T1.387 ll-F-16 ll-F-25 M.T1.428 ll-F-21 ll-F-31
M.T1.388 ll-F-16 ll-F-26 M.T1.429 ll-F-21 ll-F-32
M.T1.389 ll-F-16 ll-F-27 M.T1.430 ll-F-21 ll-F-33
M.T1.390 ll-F-16 ll-F-28 M.T1.431 ll-F-21 ll-F-34
M.T1.391 ll-F-16 ll-F-29 M.T1.432 ll-F-22 ll-F-28 Mixture I II III Mixture I II III
M.T1.433 ll-F-22 ll-F-29 M.T1.474 ll-F-28 ll-F-29
M.T1.434 ll-F-22 ll-F-30 M.T1.475 ll-F-28 ll-F-30
M.T1.435 ll-F-22 ll-F-31 M.T1.476 ll-F-28 ll-F-31
M.T1.436 ll-F-22 ll-F-32 M.T1.477 ll-F-28 ll-F-32
M.T1.437 ll-F-22 ll-F-33 M.T1.478 ll-F-28 ll-F-33
M.T1.438 ll-F-22 ll-F-34 M.T1.479 ll-F-28 ll-F-34
M.T1.439 ll-F-23 ll-F-28 M.T1.480 ll-F-30 ll-F-29
M.T1.440 ll-F-23 ll-F-29 M.T1.481 ll-F-30 ll-F-31
M.T1.441 ll-F-23 ll-F-30 M.T1.482 ll-F-30 ll-F-32
M.T1.442 ll-F-23 ll-F-31 M.T1.483 ll-F-30 ll-F-33
M.T1.443 ll-F-23 ll-F-32 M.T1.484 ll-F-30 ll-F-34
M.T1.444 ll-F-23 ll-F-33 M.T1.485 ll-F-29 ll-F-31
M.T1.445 ll-F-23 ll-F-34 M.T1.486 ll-F-29 ll-F-32
M.T1.446 ll-F-24 ll-F-28 M.T1.487 ll-F-29 ll-F-33
M.T1.447 ll-F-24 ll-F-29 M.T1.488 ll-F-29 ll-F-34
M.T1.448 ll-F-24 ll-F-30
M.T1.449 ll-F-24 ll-F-31 M.T1.489 11-1-1 ll-F-1
M.T1.450 ll-F-24 ll-F-32 M.T1.490 11-1-1 ll-F-2
M.T1.451 ll-F-24 ll-F-33 M.T1.491 11-1-1 ll-F-3
M.T1.452 ll-F-24 ll-F-34 M.T1.492 11-1-1 ll-F-4
M.T1.453 ll-F-25 ll-F-28 M.T1.493 11-1-1 ll-F-5
M.T1.454 ll-F-25 ll-F-29 M.T1.494 11-1-1 ll-F-6
M.T1.455 ll-F-25 ll-F-30 M.T1.495 11-1-1 ll-F-7
M.T1.456 ll-F-25 ll-F-31 M.T1.496 11-1-1 ll-F-8
M.T1.457 ll-F-25 ll-F-32 M.T1.497 11-1-1 ll-F-9
M.T1.458 ll-F-25 ll-F-33 M.T1.498 11-1-1 ll-F-10
M.T1.459 ll-F-25 ll-F-34 M.T1.499 11-1-1 ll-F-11
M.T1.460 ll-F-26 ll-F-28 M.T1.500 11-1-1 ll-F-12
M.T1.461 ll-F-26 ll-F-29 M.T1.501 11-1-1 ll-F-13
M.T1.462 ll-F-26 ll-F-30 M.T1.502 11-1-1 ll-F-14
M.T1.463 ll-F-26 ll-F-31 M.T1.503 11-1-1 ll-F-15
M.T1.464 ll-F-26 ll-F-32 M.T1.504 11-1-1 ll-F-16
M.T1.465 ll-F-26 ll-F-33 M.T1.505 11-1-1 ll-F-17
M.T1.466 ll-F-26 ll-F-34 M.T1.506 11-1-1 ll-F-18
M.T1.467 ll-F-27 ll-F-28 M.T1.507 11-1-1 ll-F-19
M.T1.468 ll-F-27 ll-F-29 M.T1.508 11-1-1 ll-F-20
M.T1.469 ll-F-27 ll-F-30 M.T1.509 11-1-1 ll-F-21
M.T1.470 ll-F-27 ll-F-31 M.T1.510 11-1-1 ll-F-22
M.T1.471 ll-F-27 ll-F-32 M.T1.511 11-1-1 ll-F-23
M.T1.472 ll-F-27 ll-F-33 M.T1.512 11-1-1 ll-F-24
M.T1.473 ll-F-27 ll-F-34 M.T1.513 11-1-1 ll-F-25 Mixture I II III Mixture I II III
M.T1.514 II- -1 ll-F-26 M.T1.555 II-I-2 ll-F-31
M.T1.515 II- -1 ll-F-27 M.T1.556 II-I-2 ll-F-32
M.T1.516 II- -1 ll-F-28 M.T1.557 II-I-2 ll-F-33
M.T1.517 II- -1 ll-F-29 M.T1.558 II-I-2 ll-F-34
M.T1.518 II- -1 ll-F-30 M.T1.559 II-I-2 II-I-22
M.T1.519 II- -1 ll-F-31 M.T1.560 II-I-2 II-I-23
M.T1.520 II- -1 ll-F-32 M.T1.561 II-I-3 ll-F-1
M.T1.521 II- -1 ll-F-33 M.T1.562 II-I-3 ll-F-2
M.T1.522 II- -1 ll-F-34 M.T1.563 II-I-3 ll-F-3
M.T1.523 II- -1 II-I-22 M.T1.564 II-I-3 ll-F-4
M.T1.524 II- -1 II-I-23 M.T1.565 II-I-3 ll-F-5
M.T1.525 II- -2 ll-F-1 M.T1.566 II-I-3 ll-F-6
M.T1.526 II- -2 ll-F-2 M.T1.567 II-I-3 ll-F-7
M.T1.527 II- -2 ll-F-3 M.T1.568 II-I-3 ll-F-8
M.T1.528 II- -2 ll-F-4 M.T1.569 II-I-3 ll-F-9
M.T1.529 II- -2 ll-F-5 M.T1.570 II-I-3 ll-F-10
M.T1.530 II- -2 ll-F-6 M.T1.571 II-I-3 ll-F-11
M.T1.531 II- -2 ll-F-7 M.T1.572 II-I-3 ll-F-12
M.T1.532 II- -2 ll-F-8 M.T1.573 II-I-3 ll-F-13
M.T1.533 II- -2 ll-F-9 M.T1.574 II-I-3 ll-F-14
M.T1.534 II- -2 ll-F-10 M.T1.575 II-I-3 ll-F-15
M.T1.535 II- -2 ll-F-11 M.T1.576 II-I-3 ll-F-16
M.T1.536 II- -2 ll-F-12 M.T1.577 II-I-3 ll-F-17
M.T1.537 II- -2 ll-F-13 M.T1.578 II-I-3 ll-F-18
M.T1.538 II- -2 ll-F-14 M.T1.579 II-I-3 ll-F-19
M.T1.539 II- -2 ll-F-15 M.T1.580 II-I-3 ll-F-20
M.T1.540 II- -2 ll-F-16 M.T1.581 II-I-3 ll-F-21
M.T1.541 II- -2 ll-F-17 M.T1.582 II-I-3 ll-F-22
M.T1.542 II- -2 ll-F-18 M.T1.583 II-I-3 ll-F-23
M.T1.543 II- -2 ll-F-19 M.T1.584 II-I-3 ll-F-24
M.T1.544 II- -2 ll-F-20 M.T1.585 II-I-3 ll-F-25
M.T1.545 II- -2 ll-F-21 M.T1.586 II-I-3 ll-F-26
M.T1.546 II- -2 ll-F-22 M.T1.587 II-I-3 ll-F-27
M.T1.547 II- -2 ll-F-23 M.T1.588 II-I-3 ll-F-28
M.T1.548 II- -2 ll-F-24 M.T1.589 II-I-3 ll-F-29
M.T1.549 II- -2 ll-F-25 M.T1.590 II-I-3 ll-F-30
M.T1.550 II- -2 ll-F-26 M.T1.591 II-I-3 ll-F-31
M.T1.551 II- -2 ll-F-27 M.T1.592 II-I-3 ll-F-32
M.T1.552 II- -2 ll-F-28 M.T1.593 II-I-3 ll-F-33
M.T1.553 II- -2 ll-F-29 M.T1.594 II-I-3 ll-F-34
M.T1.554 II- -2 ll-F-30 M.T1.595 II-I-3 II-I-22 Mixture I II III Mixture I II III
M.T1.596 II- -3 II-I-23 M.T1.637 II-I-5 ll-F-5
M.T1.597 II- -4 ll-F-1 M.T1.638 II-I-5 ll-F-6
M.T1.598 II- -4 ll-F-2 M.T1.639 II-I-5 ll-F-7
M.T1.599 II- -4 ll-F-3 M.T1.640 II-I-5 ll-F-8
M.T1.600 II- -4 ll-F-4 M.T1.641 II-I-5 ll-F-9
M.T1.601 II- -4 ll-F-5 M.T1.642 II-I-5 ll-F-10
M.T1.602 II- -4 ll-F-6 M.T1.643 II-I-5 ll-F-11
M.T1.603 II- -4 ll-F-7 M.T1.644 II-I-5 ll-F-12
M.T1.604 II- -4 ll-F-8 M.T1.645 II-I-5 ll-F-13
M.T1.605 II- -4 ll-F-9 M.T1.646 II-I-5 ll-F-14
M.T1.606 II- -4 ll-F-10 M.T1.647 II-I-5 ll-F-15
M.T1.607 II- -4 ll-F-11 M.T1.648 II-I-5 ll-F-16
M.T1.608 II- -4 ll-F-12 M.T1.649 II-I-5 ll-F-17
M.T1.609 II- -4 ll-F-13 M.T1.650 II-I-5 ll-F-18
M.T1.610 II- -4 ll-F-14 M.T1.651 II-I-5 ll-F-19
M.T1.611 II- -4 ll-F-15 M.T1.652 II-I-5 ll-F-20
M.T1.612 II- -4 ll-F-16 M.T1.653 II-I-5 ll-F-21
M.T1.613 II- -4 ll-F-17 M.T1.654 II-I-5 ll-F-22
M.T1.614 II- -4 ll-F-18 M.T1.655 II-I-5 ll-F-23
M.T1.615 II- -4 ll-F-19 M.T1.656 II-I-5 ll-F-24
M.T1.616 II- -4 ll-F-20 M.T1.657 II-I-5 ll-F-25
M.T1.617 II- -4 ll-F-21 M.T1.658 II-I-5 ll-F-26
M.T1.618 II- -4 ll-F-22 M.T1.659 II-I-5 ll-F-27
M.T1.619 II- -4 ll-F-23 M.T1.660 II-I-5 ll-F-28
M.T1.620 II- -4 ll-F-24 M.T1.661 II-I-5 ll-F-29
M.T1.621 II- -4 ll-F-25 M.T1.662 II-I-5 ll-F-30
M.T1.622 II- -4 ll-F-26 M.T1.663 II-I-5 ll-F-31
M.T1.623 II- -4 ll-F-27 M.T1.664 II-I-5 ll-F-32
M.T1.624 II- -4 ll-F-28 M.T1.665 II-I-5 ll-F-33
M.T1.625 II- -4 ll-F-29 M.T1.666 II-I-5 ll-F-34
M.T1.626 II- -4 ll-F-30 M.T1.667 II-I-5 II-I-22
M.T1.627 II- -4 ll-F-31 M.T1.668 II-I-5 II-I-23
M.T1.628 II- -4 ll-F-32 M.T1.669 II-I-6 ll-F-1
M.T1.629 II- -4 ll-F-33 M.T1.670 II-I-6 ll-F-2
M.T1.630 II- -4 ll-F-34 M.T1.671 II-I-6 ll-F-3
M.T1.631 II- -4 II-I-22 M.T1.672 II-I-6 ll-F-4
M.T1.632 II- -4 II-I-23 M.T1.673 II-I-6 ll-F-5
M.T1.633 II- -5 ll-F-1 M.T1.674 II-I-6 ll-F-6
M.T1.634 II- -5 ll-F-2 M.T1.675 II-I-6 ll-F-7
M.T1.635 II- -5 ll-F-3 M.T1.676 II-I-6 ll-F-8
M.T1.636 II- -5 ll-F-4 M.T1.677 II-I-6 ll-F-9 Mixture I II III Mixture I II III
M.T1.678 II- -6 ll-F-10 M.T1.719 II-I-7 ll-F-15
M.T1.679 II- -6 ll-F-11 M.T1J20 II-I-7 ll-F-16
M.T1.680 II- -6 ll-F-12 M.T1.721 II-I-7 ll-F-17
M.T1.681 II- -6 ll-F-13 M.T1.722 II-I-7 ll-F-18
M.T1.682 II- -6 ll-F-14 M.T1.723 II-I-7 ll-F-19
M.T1.683 II- -6 ll-F-15 M.T1J24 II-I-7 ll-F-20
M.T1.684 II- -6 ll-F-16 M.T1.725 II-I-7 ll-F-21
M.T1.685 II- -6 ll-F-17 M.T1.726 II-I-7 ll-F-22
M.T1.686 II- -6 ll-F-18 M.T1.727 II-I-7 ll-F-23
M.T1.687 II- -6 ll-F-19 M.T1.728 II-I-7 ll-F-24
M.T1.688 II- -6 ll-F-20 M.T1.729 II-I-7 ll-F-25
M.T1.689 II- -6 ll-F-21 M.T1.730 II-I-7 ll-F-26
M.T1.690 II- -6 ll-F-22 M.T1.731 II-I-7 ll-F-27
M.T1.691 II- -6 ll-F-23 M.T1.732 II-I-7 ll-F-28
M.T1.692 II- -6 ll-F-24 M.T1.733 II-I-7 ll-F-29
M.T1.693 II- -6 ll-F-25 M.T1.734 II-I-7 ll-F-30
M.T1.694 II- -6 ll-F-26 M.T1.735 II-I-7 ll-F-31
M.T1.695 II- -6 ll-F-27 M.T1.736 II-I-7 ll-F-32
M.T1.696 II- -6 ll-F-28 M.T1.737 II-I-7 ll-F-33
M.T1.697 II- -6 ll-F-29 M.T1.738 II-I-7 ll-F-34
M.T1.698 II- -6 ll-F-30 M.T1.739 II-I-7 II-I-22
M.T1.699 II- -6 ll-F-31 M.T1.740 II-I-7 II-I-23
M.T1.700 II- -6 ll-F-32 M.T1.741 II-I-8 ll-F-1
M.T1.701 II- -6 ll-F-33 M.T1.742 II-I-8 ll-F-2
M.T1.702 II- -6 ll-F-34 M.T1.743 II-I-8 ll-F-3
M.T1.703 II- -6 II-I-22 M.T1.744 II-I-8 ll-F-4
M.T1.704 II- -6 II-I-23 M.T1.745 II-I-8 ll-F-5
M.T1.705 II- -7 ll-F-1 M.T1.746 II-I-8 ll-F-6
M.T1.706 II- -7 ll-F-2 M.T1.747 II-I-8 ll-F-7
M.T1.707 II- -7 ll-F-3 M.T1.748 II-I-8 ll-F-8
M.T1.708 II- -7 ll-F-4 M.T1.749 II-I-8 ll-F-9
M.T1.709 II- -7 ll-F-5 M.T1.750 II-I-8 ll-F-10
M.T1.710 II- -7 ll-F-6 M.T1.751 II-I-8 ll-F-11
M.T1.711 II- -7 ll-F-7 M.T1.752 II-I-8 ll-F-12
M.T1.712 II- -7 ll-F-8 M.T1.753 II-I-8 ll-F-13
M.T1.713 II- -7 ll-F-9 M.T1.754 II-I-8 ll-F-14
M.T1.714 II- -7 ll-F-10 M.T1.755 II-I-8 ll-F-15
M.T1.715 II- -7 ll-F-11 M.T1.756 II-I-8 ll-F-16
M.T1.716 II- -7 ll-F-12 M.T1.757 II-I-8 ll-F-17
M.T1.717 II- -7 ll-F-13 M.T1.758 II-I-8 ll-F-18
M.T1.718 II- -7 ll-F-14 M.T1.759 II-I-8 ll-F-19 Mixture I II III Mixture I II III
M.T1.760 II- -8 ll-F-20 M.T1.801 II-I-9 ll-F-25
M.T1.761 II- -8 ll-F-21 M.T1.802 II-I-9 ll-F-26
M.T1.762 II- -8 ll-F-22 M.T1.803 II-I-9 ll-F-27
M.T1.763 II- -8 ll-F-23 M.T1.804 II-I-9 ll-F-28
M.T1.764 II- -8 ll-F-24 M.T1.805 II-I-9 ll-F-29
M.T1.765 II- -8 ll-F-25 M.T1.806 II-I-9 ll-F-30
M.T1.766 II- -8 ll-F-26 M.T1.807 II-I-9 ll-F-31
M.T1.767 II- -8 ll-F-27 M.T1.808 II-I-9 ll-F-32
M.T1.768 II- -8 ll-F-28 M.T1.809 II-I-9 ll-F-33
M.T1.769 II- -8 ll-F-29 M.T1.810 II-I-9 ll-F-34
M.T1.770 II- -8 ll-F-30 M.T1.811 II-I-9 II-I-22
M.T1.771 II- -8 ll-F-31 M.T1.812 II-I-9 II-I-23
M.T1.772 II- -8 ll-F-32 M.T1.813 11-1-10 ll-F-1
M.T1.773 II- -8 ll-F-33 M.T1.814 11-1-10 ll-F-2
M.T1.774 II- -8 ll-F-34 M.T1.815 11-1-10 ll-F-3
M.T1.775 II- -8 II-I-22 M.T1.816 11-1-10 ll-F-4
M.T1.776 II- -8 II-I-23 M.T1.817 11-1-10 ll-F-5
M.T1.777 II- -9 ll-F-1 M.T1.818 11-1-10 ll-F-6
M.T1.778 II- -9 ll-F-2 M.T1.819 11-1-10 ll-F-7
M.T1.779 II- -9 ll-F-3 M.T1.820 11-1-10 ll-F-8
M.T1.780 II- -9 ll-F-4 M.T1.821 11-1-10 ll-F-9
M.T1.781 II- -9 ll-F-5 M.T1.822 11-1-10 ll-F-10
M.T1.782 II- -9 ll-F-6 M.T1.823 11-1-10 ll-F-11
M.T1.783 II- -9 ll-F-7 M.T1.824 11-1-10 ll-F-12
M.T1.784 II- -9 ll-F-8 M.T1.825 11-1-10 ll-F-13
M.T1.785 II- -9 ll-F-9 M.T1.826 11-1-10 ll-F-14
M.T1.786 II- -9 ll-F-10 M.T1.827 11-1-10 ll-F-15
M.T1.787 II- -9 ll-F-11 M.T1.828 11-1-10 ll-F-16
M.T1.788 II- -9 ll-F-12 M.T1.829 11-1-10 ll-F-17
M.T1.789 II- -9 ll-F-13 M.T1.830 11-1-10 ll-F-18
M.T1.790 II- -9 ll-F-14 M.T1.831 11-1-10 ll-F-19
M.T1.791 II- -9 ll-F-15 M.T1.832 11-1-10 ll-F-20
M.T1.792 II- -9 ll-F-16 M.T1.833 11-1-10 ll-F-21
M.T1.793 II- -9 ll-F-17 M.T1.834 11-1-10 ll-F-22
M.T1.794 II- -9 ll-F-18 M.T1.835 11-1-10 ll-F-23
M.T1.795 II- -9 ll-F-19 M.T1.836 11-1-10 ll-F-24
M.T1.796 II- -9 ll-F-20 M.T1.837 11-1-10 ll-F-25
M.T1.797 II- -9 ll-F-21 M.T1.838 11-1-10 ll-F-26
M.T1.798 II- -9 ll-F-22 M.T1.839 11-1-10 ll-F-27
M.T1.799 II- -9 ll-F-23 M.T1.840 11-1-10 ll-F-28
M.T1.800 II- -9 ll-F-24 M.T1.841 11-1-10 ll-F-29 Mixture I II III Mixture I II III
M.T1.842 II- -10 ll-F-30 M.T1.883 11-1-11 II-I-22
M.T1.843 II- -10 ll-F-31 M.T1.884 11-1-11 II-I-23
M.T1.844 II- -10 ll-F-32 M.T1.885 11-1-12 ll-F-1
M.T1.845 II- -10 ll-F-33 M.T1.886 11-1-12 ll-F-2
M.T1.846 II- -10 ll-F-34 M.T1.887 11-1-12 ll-F-3
M.T1.847 II- -10 II-I-22 M.T1.888 11-1-12 ll-F-4
M.T1.848 II- -10 II-I-23 M.T1.889 11-1-12 ll-F-5
M.T1.849 II- -11 ll-F-1 M.T1.890 11-1-12 ll-F-6
M.T1.850 II- -11 ll-F-2 M.T1.891 11-1-12 ll-F-7
M.T1.851 II- -11 ll-F-3 M.T1.892 11-1-12 ll-F-8
M.T1.852 II- -11 ll-F-4 M.T1.893 11-1-12 ll-F-9
M.T1.853 II- -11 ll-F-5 M.T1.894 11-1-12 ll-F-10
M.T1.854 II- -11 ll-F-6 M.T1.895 11-1-12 ll-F-11
M.T1.855 II- -11 ll-F-7 M.T1.896 11-1-12 ll-F-12
M.T1.856 II- -11 ll-F-8 M.T1.897 11-1-12 ll-F-13
M.T1.857 II- -11 ll-F-9 M.T1.898 11-1-12 ll-F-14
M.T1.858 II- -11 ll-F-10 M.T1.899 11-1-12 ll-F-15
M.T1.859 II- -11 ll-F-11 M.T1.900 11-1-12 ll-F-16
M.T1.860 II- -11 ll-F-12 M.T1.901 11-1-12 ll-F-17
M.T1.861 II- -11 ll-F-13 M.T1.902 11-1-12 ll-F-18
M.T1.862 II- -11 ll-F-14 M.T1.903 11-1-12 ll-F-19
M.T1.863 II- -11 ll-F-15 M.T1.904 11-1-12 ll-F-20
M.T1.864 II- -11 ll-F-16 M.T1.905 11-1-12 ll-F-21
M.T1.865 II- -11 ll-F-17 M.T1.906 11-1-12 ll-F-22
M.T1.866 II- -11 ll-F-18 M.T1.907 11-1-12 ll-F-23
M.T1.867 II- -11 ll-F-19 M.T1.908 11-1-12 ll-F-24
M.T1.868 II- -11 ll-F-20 M.T1.909 11-1-12 ll-F-25
M.T1.869 II- -11 ll-F-21 M.T1.910 11-1-12 ll-F-26
M.T1.870 II- -11 ll-F-22 M.T1.911 11-1-12 ll-F-27
M.T1.871 II- -11 ll-F-23 M.T1.912 11-1-12 ll-F-28
M.T1.872 II- -11 ll-F-24 M.T1.913 11-1-12 ll-F-29
M.T1.873 II- -11 ll-F-25 M.T1.914 11-1-12 ll-F-30
M.T1.874 II- -11 ll-F-26 M.T1.915 11-1-12 ll-F-31
M.T1.875 II- -11 ll-F-27 M.T1.916 11-1-12 ll-F-32
M.T1.876 II- -11 ll-F-28 M.T1.917 11-1-12 ll-F-33
M.T1.877 II- -11 ll-F-29 M.T1.918 11-1-12 ll-F-34
M.T1.878 II- -11 ll-F-30 M.T1.919 11-1-12 II-I-22
M.T1.879 II- -11 ll-F-31 M.T1.920 11-1-12 II-I-23
M.T1.880 II- -11 ll-F-32 M.T1.921 11-1-13 ll-F-1
M.T1.881 II- -11 ll-F-33 M.T1.922 11-1-13 ll-F-2
M.T1.882 II- -11 ll-F-34 M.T1.923 11-1-13 ll-F-3 Mixture I II III Mixture I II III
M.T1.924 II- -13 ll-F-4 M.T1.965 11-1-14 ll-F-9
M.T1.925 II- -13 ll-F-5 M.T1.966 11-1-14 ll-F-10
M.T1.926 II- -13 ll-F-6 M.T1.967 11-1-14 ll-F-11
M.T1.927 II- -13 ll-F-7 M.T1.968 11-1-14 ll-F-12
M.T1.928 II- -13 ll-F-8 M.T1.969 11-1-14 ll-F-13
M.T1.929 II- -13 ll-F-9 M.T1.970 11-1-14 ll-F-14
M.T1.930 II- -13 ll-F-10 M.T1.971 11-1-14 ll-F-15
M.T1.931 II- -13 ll-F-11 M.T1.972 11-1-14 ll-F-16
M.T1.932 II- -13 ll-F-12 M.T1.973 11-1-14 ll-F-17
M.T1.933 II- -13 ll-F-13 M.T1.974 11-1-14 ll-F-18
M.T1.934 II- -13 ll-F-14 M.T1.975 11-1-14 ll-F-19
M.T1.935 II- -13 ll-F-15 M.T1.976 11-1-14 ll-F-20
M.T1.936 II- -13 ll-F-16 M.T1.977 11-1-14 ll-F-21
M.T1.937 II- -13 ll-F-17 M.T1.978 11-1-14 ll-F-22
M.T1.938 II- -13 ll-F-18 M.T1.979 11-1-14 ll-F-23
M.T1.939 II- -13 ll-F-19 M.T1.980 11-1-14 ll-F-24
M.T1.940 II- -13 ll-F-20 M.T1.981 11-1-14 ll-F-25
M.T1.941 II- -13 ll-F-21 M.T1.982 11-1-14 ll-F-26
M.T1.942 II- -13 ll-F-22 M.T1.983 11-1-14 ll-F-27
M.T1.943 II- -13 ll-F-23 M.T1.984 11-1-14 ll-F-28
M.T1.944 II- -13 ll-F-24 M.T1.985 11-1-14 ll-F-29
M.T1.945 II- -13 ll-F-25 M.T1.986 11-1-14 ll-F-30
M.T1.946 II- -13 ll-F-26 M.T1.987 11-1-14 ll-F-31
M.T1.947 II- -13 ll-F-27 M.T1.988 11-1-14 ll-F-32
M.T1.948 II- -13 ll-F-28 M.T1.989 11-1-14 ll-F-33
M.T1.949 II- -13 ll-F-29 M.T1.990 11-1-14 ll-F-34
M.T1.950 II- -13 ll-F-30 M.T1.991 11-1-14 II-I-22
M.T1.951 II- -13 ll-F-31 M.T1.992 11-1-14 II-I-23
M.T1.952 II- -13 ll-F-32 M.T1.993 11-1-15 ll-F-1
M.T1.953 II- -13 ll-F-33 M.T1.994 11-1-15 ll-F-2
M.T1.954 II- -13 ll-F-34 M.T1.995 11-1-15 ll-F-3
M.T1.955 II- -13 II-I-22 M.T1.996 11-1-15 ll-F-4
M.T1.956 II- -13 II-I-23 M.T1.997 11-1-15 ll-F-5
M.T1.957 II- -14 ll-F-1 M.T1.998 11-1-15 ll-F-6
M.T1.958 II- -14 ll-F-2 M.T1.999 11-1-15 ll-F-7
M.T1.959 II- -14 ll-F-3 M.T1.1000 11-1-15 ll-F-8
M.T1.960 II- -14 ll-F-4 M.T1.1001 11-1-15 ll-F-9
M.T1.961 II- -14 ll-F-5 M.T1.1002 11-1-15 ll-F-10
M.T1.962 II- -14 ll-F-6 M.T1.1003 11-1-15 ll-F-11
M.T1.963 II- -14 ll-F-7 M.T1.1004 11-1-15 ll-F-12
M.T1.964 II- -14 ll-F-8 M.T1.1005 11-1-15 ll-F-13 Mixture I II III Mixture I II III
M.T1.1006 II- -15 ll-F-14 M.T1.1047 11-1-16 ll-F-19
M.T1.1007 II- -15 ll-F-15 M.T1.1048 11-1-16 ll-F-20
M.T1.1008 II- -15 ll-F-16 M.T1.1049 11-1-16 ll-F-21
M.T1.1009 II- -15 ll-F-17 M.T1.1050 11-1-16 ll-F-22
M.T1.1010 II- -15 ll-F-18 M.T1.1051 11-1-16 ll-F-23
M.T1.1011 II- -15 ll-F-19 M.T1.1052 11-1-16 ll-F-24
M.T1.1012 II- -15 ll-F-20 M.T1.1053 11-1-16 ll-F-25
M.T1.1013 II- -15 ll-F-21 M.T1.1054 11-1-16 ll-F-26
M.T1.1014 II- -15 ll-F-22 M.T1.1055 11-1-16 ll-F-27
M.T1.1015 II- -15 ll-F-23 M.T1.1056 11-1-16 ll-F-28
M.T1.1016 II- -15 ll-F-24 M.T1.1057 11-1-16 ll-F-29
M.T1.1017 II- -15 ll-F-25 M.T1.1058 11-1-16 ll-F-30
M.T1.1018 II- -15 ll-F-26 M.T1.1059 11-1-16 ll-F-31
M.T1.1019 II- -15 ll-F-27 M.T1.1060 11-1-16 ll-F-32
M.T1.1020 II- -15 ll-F-28 M.T1.1061 11-1-16 ll-F-33
M.T1.1021 II- -15 ll-F-29 M.T1.1062 11-1-16 ll-F-34
M.T1.1022 II- -15 ll-F-30 M.T1.1063 11-1-16 II-I-22
M.T1.1023 II- -15 ll-F-31 M.T1.1064 11-1-16 II-I-23
M.T1.1024 II- -15 ll-F-32 M.T1.1065 11-1-17 ll-F-1
M.T1.1025 II- -15 ll-F-33 M.T1.1066 11-1-17 ll-F-2
M.T1.1026 II- -15 ll-F-34 M.T1.1067 11-1-17 ll-F-3
M.T1.1027 II- -15 II-I-22 M.T1.1068 11-1-17 ll-F-4
M.T1.1028 II- -15 II-I-23 M.T1.1069 11-1-17 ll-F-5
M.T1.1029 II- -16 ll-F-1 M.T1.1070 11-1-17 ll-F-6
M.T1.1030 II- -16 ll-F-2 M.T1.1071 11-1-17 ll-F-7
M.T1.1031 II- -16 ll-F-3 M.T1.1072 11-1-17 ll-F-8
M.T1.1032 II- -16 ll-F-4 M.T1.1073 11-1-17 ll-F-9
M.T1.1033 II- -16 ll-F-5 M.T1.1074 11-1-17 ll-F-10
M.T1.1034 II- -16 ll-F-6 M.T1.1075 11-1-17 ll-F-11
M.T1.1035 II- -16 ll-F-7 M.T1.1076 11-1-17 ll-F-12
M.T1.1036 II- -16 ll-F-8 M.T1.1077 11-1-17 ll-F-13
M.T1.1037 II- -16 ll-F-9 M.T1.1078 11-1-17 ll-F-14
M.T1.1038 II- -16 ll-F-10 M.T1.1079 11-1-17 ll-F-15
M.T1.1039 II- -16 ll-F-11 M.T1.1080 11-1-17 ll-F-16
M.T1.1040 II- -16 ll-F-12 M.T1.1081 11-1-17 ll-F-17
M.T1.1041 II- -16 ll-F-13 M.T1.1082 11-1-17 ll-F-18
M.T1.1042 II- -16 ll-F-14 M.T1.1083 11-1-17 ll-F-19
M.T1.1043 II- -16 ll-F-15 M.T1.1084 11-1-17 ll-F-20
M.T1.1044 II- -16 ll-F-16 M.T1.1085 11-1-17 ll-F-21
M.T1.1045 II- -16 ll-F-17 M.T1.1086 11-1-17 ll-F-22
M.T1.1046 II- -16 ll-F-18 M.T1.1087 11-1-17 ll-F-23 Mixture I II III Mixture I II III
M.T1.1088 II- -17 ll-F-24 M.T1.1129 11-1-18 ll-F-29
M.T1.1089 II- -17 ll-F-25 M.T1.1130 11-1-18 ll-F-30
M.T1.1090 II- -17 ll-F-26 M.T1.1131 11-1-18 ll-F-31
M.T1.1091 II- -17 ll-F-27 M.T1.1132 11-1-18 ll-F-32
M.T1.1092 II- -17 ll-F-28 M.T1.1133 11-1-18 ll-F-33
M.T1.1093 II- -17 ll-F-29 M.T1.1134 11-1-18 ll-F-34
M.T1.1094 II- -17 ll-F-30 M.T1.1135 11-1-18 II-I-22
M.T1.1095 II- -17 ll-F-31 M.T1.1136 11-1-18 II-I-23
M.T1.1096 II- -17 ll-F-32 M.T1.1137 11-1-19 ll-F-1
M.T1.1097 II- -17 ll-F-33 M.T1.1138 11-1-19 ll-F-2
M.T1.1098 II- -17 ll-F-34 M.T1.1139 11-1-19 ll-F-3
M.T1.1099 II- -17 II-I-22 M.T1.1140 11-1-19 ll-F-4
M.T1.1100 II- -17 II-I-23 M.T1.1141 11-1-19 ll-F-5
M.T1.1101 II- -18 ll-F-1 M.T1.1142 11-1-19 ll-F-6
M.T1.1102 II- -18 ll-F-2 M.T1.1143 11-1-19 ll-F-7
M.T1.1103 II- -18 ll-F-3 M.T1.1144 11-1-19 ll-F-8
M.T1.1104 II- -18 ll-F-4 M.T1.1145 11-1-19 ll-F-9
M.T1.1105 II- -18 ll-F-5 M.T1.1146 11-1-19 ll-F-10
M.T1.1106 II- -18 ll-F-6 M.T1.1147 11-1-19 ll-F-11
M.T1.1107 II- -18 ll-F-7 M.T1.1148 11-1-19 ll-F-12
M.T1.1108 II- -18 ll-F-8 M.T1.1149 11-1-19 ll-F-13
M.T1.1109 II- -18 ll-F-9 M.T1.1150 11-1-19 ll-F-14
M.T1.1110 II- -18 ll-F-10 M.T1.1151 11-1-19 ll-F-15
M.T1.1111 II- -18 ll-F-11 M.T1.1152 11-1-19 ll-F-16
M.T1.1112 II- -18 ll-F-12 M.T1.1153 11-1-19 ll-F-17
M.T1.1113 II- -18 ll-F-13 M.T1.1154 11-1-19 ll-F-18
M.T1.1114 II- -18 ll-F-14 M.T1.1155 11-1-19 ll-F-19
M.T1.1115 II- -18 ll-F-15 M.T1.1156 11-1-19 ll-F-20
M.T1.1116 II- -18 ll-F-16 M.T1.1157 11-1-19 ll-F-21
M.T1.1117 II- -18 ll-F-17 M.T1.1158 11-1-19 ll-F-22
M.T1.1118 II- -18 ll-F-18 M.T1.1159 11-1-19 ll-F-23
M.T1.1119 II- -18 ll-F-19 M.T1.1160 11-1-19 ll-F-24
M.T1.1120 II- -18 ll-F-20 M.T1.1161 11-1-19 ll-F-25
M.T1.1121 II- -18 ll-F-21 M.T1.1162 11-1-19 ll-F-26
M.T1.1122 II- -18 ll-F-22 M.T1.1163 11-1-19 ll-F-27
M.T1.1123 II- -18 ll-F-23 M.T1.1164 11-1-19 ll-F-28
M.T1.1124 II- -18 ll-F-24 M.T1.1165 11-1-19 ll-F-29
M.T1.1125 II- -18 ll-F-25 M.T1.1166 11-1-19 ll-F-30
M.T1.1126 II- -18 ll-F-26 M.T1.1167 11-1-19 ll-F-31
M.T1.1127 II- -18 ll-F-27 M.T1.1168 11-1-19 ll-F-32
M.T1.1128 II- -18 ll-F-28 M.T1.1169 11-1-19 ll-F-33 Mixture I II III Mixture I II III
M.T1.1170 II- -19 ll-F-34 M.T1.1211 11-1-21 ll-F-3
M.T1.1171 II- -19 II-I-22 M.T1.1212 11-1-21 ll-F-4
M.T1.1172 II- -19 II-I-23 M.T1.1213 11-1-21 ll-F-5
M.T1.1173 II- -20 ll-F-1 M.T1.1214 11-1-21 ll-F-6
M.T1.1174 II- -20 ll-F-2 M.T1.1215 11-1-21 ll-F-7
M.T1.1175 II- -20 ll-F-3 M.T1.1216 11-1-21 ll-F-8
M.T1.1176 II- -20 ll-F-4 M.T1.1217 11-1-21 ll-F-9
M.T1.1177 II- -20 ll-F-5 M.T1.1218 11-1-21 ll-F-10
M.T1.1178 II- -20 ll-F-6 M.T1.1219 11-1-21 ll-F-11
M.T1.1179 II- -20 ll-F-7 M.T1.1220 11-1-21 ll-F-12
M.T1.1180 II- -20 ll-F-8 M.T1.1221 11-1-21 ll-F-13
M.T1.1181 II- -20 ll-F-9 M.T1.1222 11-1-21 ll-F-14
M.T1.1182 II- -20 ll-F-10 M.T1.1223 11-1-21 ll-F-15
M.T1.1183 II- -20 ll-F-11 M.T1.1224 11-1-21 ll-F-16
M.T1.1184 II- -20 ll-F-12 M.T1.1225 11-1-21 ll-F-17
M.T1.1185 II- -20 ll-F-13 M.T1.1226 11-1-21 ll-F-18
M.T1.1186 II- -20 ll-F-14 M.T1.1227 11-1-21 ll-F-19
M.T1.1187 II- -20 ll-F-15 M.T1.1228 11-1-21 ll-F-20
M.T1.1188 II- -20 ll-F-16 M.T1.1229 11-1-21 ll-F-21
M.T1.1189 II- -20 ll-F-17 M.T1.1230 11-1-21 ll-F-22
M.T1.1190 II- -20 ll-F-18 M.T1.1231 11-1-21 ll-F-23
M.T1.1191 II- -20 ll-F-19 M.T1.1232 11-1-21 ll-F-24
M.T1.1192 II- -20 ll-F-20 M.T1.1233 11-1-21 ll-F-25
M.T1.1193 II- -20 ll-F-21 M.T1.1234 11-1-21 ll-F-26
M.T1.1194 II- -20 ll-F-22 M.T1.1235 11-1-21 ll-F-27
M.T1.1195 II- -20 ll-F-23 M.T1.1236 11-1-21 ll-F-28
M.T1.1196 II- -20 ll-F-24 M.T1.1237 11-1-21 ll-F-29
M.T1.1197 II- -20 ll-F-25 M.T1.1238 11-1-21 ll-F-30
M.T1.1198 II- -20 ll-F-26 M.T1.1239 11-1-21 ll-F-31
M.T1.1199 II- -20 ll-F-27 M.T1.1240 11-1-21 ll-F-32
M.T1.1200 II- -20 ll-F-28 M.T1.1241 11-1-21 ll-F-33
M.T1.1201 II- -20 ll-F-29 M.T1.1242 11-1-21 ll-F-34
M.T1.1202 II- -20 ll-F-30 M.T1.1243 11-1-21 II-I-22
M.T1.1203 II- -20 ll-F-31 M.T1.1244 11-1-21 II-I-23
M.T1.1204 II- -20 ll-F-32
M.T1.1205 II- -20 ll-F-33 M.T1.1245 11-1-1 II-I-2
M.T1.1206 II- -20 ll-F-34 M.T1.1246 11-1-1 II-I-3
M.T1.1207 II- -20 II-I-22 M.T1.1247 11-1-1 II-I-4
M.T1.1208 II- -20 II-I-23 M.T1.1248 11-1-1 II-I-5
M.T1.1209 II- -21 ll-F-1 M.T1.1249 11-1-1 II-I-6
M.T1.1210 II- -21 ll-F-2 M.T1.1250 11-1-1 II-I-7 Mixture I II III Mixture I II III
M.T1.1251 II- -1 II-I-8 M.T1.1292 11-1-12 11-1-15
M.T1.1252 II- -1 II-I-9 M.T1.1293 11-1-12 11-1-16
M.T1.1253 II- -1 11-1-10 M.T1.1294 11-1-12 11-1-17
M.T1.1254 II- -1 11-1-11 M.T1.1295 11-1-12 11-1-18
M.T1.1255 II- -1 11-1-12 M.T1.1296 11-1-12 11-1-19
M.T1.1256 II- -1 11-1-13 M.T1.1297 11-1-12 II-I-20
M.T1.1257 II- -1 11-1-14 M.T1.1298 11-1-12 11-1-21
M.T1.1258 II- -1 11-1-15 M.T1.1299 11-1-13 II-I-2
M.T1.1259 II- -1 11-1-16 M.T1.1300 11-1-13 II-I-3
M.T1.1260 II- -1 11-1-17 M.T1.1301 11-1-13 II-I-4
M.T1.1261 II- -1 11-1-18 M.T1.1302 11-1-13 II-I-5
M.T1.1262 II- -1 11-1-19 M.T1.1303 11-1-13 II-I-6
M.T1.1263 II- -1 II-I-20 M.T1.1304 11-1-13 II-I-7
M.T1.1264 II- -1 11-1-21 M.T1.1305 11-1-13 II-I-8
M.T1.1265 II- -12 II-I-2 M.T1.1306 11-1-13 II-I-9
M.T1.1266 II- -12 II-I-3 M.T1.1307 11-1-13 11-1-10
M.T1.1267 II- -12 II-I-4 M.T1.1308 11-1-13 11-1-14
M.T1.1268 II- -12 II-I-5 M.T1.1309 11-1-13 11-1-15
M.T1.1269 II- -12 II-I-6 M.T1.1310 11-1-13 11-1-16
M.T1.1270 II- -12 II-I-7 M.T1.1311 11-1-13 11-1-17
M.T1.1271 II- -12 II-I-8 M.T1.1312 11-1-13 11-1-18
M.T1.1272 II- -12 II-I-9 M.T1.1313 11-1-13 11-1-19
M.T1.1273 II- -12 11-1-10 M.T1.1314 11-1-13 II-I-20
M.T1.1274 II- -12 11-1-14 M.T1.1315 11-1-13 11-1-21
M.T1.1275 II- -12 11-1-15 M.T1.1316 II-I-2 II-I-8
M.T1.1276 II- -12 11-1-16 M.T1.1317 II-I-2 II-I-9
M.T1.1277 II- -12 11-1-17 M.T1.1318 II-I-2 11-1-10
M.T1.1278 II- -12 11-1-18 M.T1.1319 II-I-2 11-1-14
M.T1.1279 II- -12 11-1-19 M.T1.1320 II-I-2 11-1-15
M.T1.1280 II- -12 II-I-20 M.T1.1321 II-I-2 11-1-16
M.T1.1281 II- -12 11-1-21 M.T1.1322 II-I-2 11-1-17
M.T1.1282 II- -12 II-I-2 M.T1.1323 II-I-2 11-1-19
M.T1.1283 II- -12 II-I-3 M.T1.1324 II-I-2 II-I-20
M.T1.1284 II- -12 II-I-4 M.T1.1325 II-I-2 II-I-8
M.T1.1285 II- -12 II-I-5 M.T1.1326 II-I-2 II-I-9
M.T1.1286 II- -12 II-I-6 M.T1.1327 II-I-2 11-1-10
M.T1.1287 II- -12 II-I-7 M.T1.1328 II-I-2 11-1-14
M.T1.1288 II- -12 II-I-8 M.T1.1329 II-I-2 11-1-15
M.T1.1289 II- -12 II-I-9 M.T1.1330 II-I-2 11-1-16
M.T1.1290 II- -12 11-1-10 M.T1.1331 II-I-2 11-1-17
M.T1.1291 II- -12 11-1-14 M.T1.1332 II-I-2 11-1-19 Mixture I II III Mixture I II III
M.T1.1333 II- -2 II-I-20 M.T1.1374 II-I-6 11-1-15
M.T1.1334 II- -3 II-I-8 M.T1.1375 II-I-6 11-1-16
M.T1.1335 II- -3 II-I-9 M.T1.1376 II-I-6 11-1-17
M.T1.1336 II- -3 11-1-10 M.T1.1377 II-I-6 11-1-19
M.T1.1337 II- -3 11-1-14 M.T1.1378 II-I-6 II-I-20
M.T1.1338 II- -3 11-1-15 M.T1.1379 II-I-7 II-I-8
M.T1.1339 II- -3 11-1-16 M.T1.1380 II-I-7 II-I-9
M.T1.1340 II- -3 11-1-17 M.T1.1381 II-I-7 11-1-10
M.T1.1341 II- -3 11-1-19 M.T1.1382 II-I-7 11-1-14
M.T1.1342 II- -3 II-I-20 M.T1.1383 II-I-7 11-1-15
M.T1.1343 II- -4 II-I-8 M.T1.1384 II-I-7 11-1-16
M.T1.1344 II- -4 II-I-9 M.T1.1385 II-I-7 11-1-17
M.T1.1345 II- -4 11-1-10 M.T1.1386 II-I-7 11-1-19
M.T1.1346 II- -4 11-1-14 M.T1.1387 II-I-7 II-I-20
M.T1.1347 II- -4 11-1-15 M.T1.1388 11-1-21 II-I-8
M.T1.1348 II- -4 11-1-16 M.T1.1389 11-1-21 II-I-9
M.T1.1349 II- -4 11-1-17 M.T1.1390 11-1-21 11-1-10
M.T1.1350 II- -4 11-1-19 M.T1.1391 11-1-21 11-1-14
M.T1.1351 II- -4 II-I-20 M.T1.1392 11-1-21 11-1-15
M.T1.1352 II- -5 II-I-8 M.T1.1393 11-1-21 11-1-16
M.T1.1353 II- -5 II-I-9 M.T1.1394 11-1-21 11-1-17
M.T1.1354 II- -5 11-1-10 M.T1.1395 11-1-21 11-1-19
M.T1.1355 II- -5 11-1-14 M.T1.1396 11-1-21 II-I-20
M.T1.1356 II- -5 11-1-15 M.T1.1397 11-1-18 II-I-8
M.T1.1357 II- -5 11-1-16 M.T1.1398 11-1-18 II-I-9
M.T1.1358 II- -5 11-1-17 M.T1.1399 11-1-18 11-1-10
M.T1.1359 II- -5 11-1-19 M.T1.1400 11-1-18 11-1-14
M.T1.1360 II- -5 II-I-20 M.T1.1401 11-1-18 11-1-15
M.T1.1361 II- -5 II-I-8 M.T1.1402 11-1-18 11-1-16
M.T1.1362 II- -5 II-I-9 M.T1.1403 11-1-18 11-1-17
M.T1.1363 II- -5 11-1-10 M.T1.1404 11-1-18 11-1-19
M.T1.1364 II- -5 11-1-14 M.T1.1405 11-1-18 II-I-20
M.T1.1365 II- -5 11-1-15 M.T1.1406 11-1-16 II-I-8
M.T1.1366 II- -5 11-1-16 M.T1.1407 11-1-16 II-I-9
M.T1.1367 II- -5 11-1-17 M.T1.1408 11-1-16 11-1-10
M.T1.1368 II- -5 11-1-19 M.T1.1409 11-1-16 11-1-14
M.T1.1369 II- -5 II-I-20 M.T1.1410 11-1-16 11-1-15
M.T1.1370 II- -6 II-I-8 M.T1.1411 11-1-16 11-1-17
M.T1.1371 II- -6 II-I-9 M.T1.1412 11-1-16 11-1-19
M.T1.1372 II- -6 11-1-10 M.T1.1413 11-1-16 II-I-20
M.T1.1373 II- -6 11-1-14 M.T1.1414 11-1-15 II-I-8 Mixture I II III Mixture I II III
M.T1 .1415 II- -15 I I-I-9 M.T1 .1426 11-1-19 11-1-10
M.T1 .1416 II- -15 11-1-10 M.T1 .1427 11-1-19 11-1-14
M.T1 .1417 II- -15 11-1-14 M.T1 .1428 11-1-19 I I-I-20
M.T1 .1418 II- -15 11-1-17 M.T1 .1429 11-1-17 I I-I-9
M.T1 .1419 II- -15 11-1-19 M.T1 .1430 11-1-17 11-1-10
M.T1 .1420 II- -15 I I-I-20 M.T1 .1431 11-1-17 11-1-14
M.T1 .1421 II- -8 I I-I-9 M.T1 .1432 11-1-17 I I-I-20
M.T1 .1422 II- -8 11-1-10 M.T1 .1433 11-1-10 I I-I-9
M.T1 .1423 II- -8 11-1-14 M.T1 .1434 11-1-10 11-1-14
M.T1 .1424 II- -8 I I-I-20 M.T1 .1435 11-1-10 I I-I-20
M.T1 .1425 II- -19 I I-I-9
Embodiment 3
In another embodiment (3), the mixtures comprise a compound of formula (I) and a further pesticide component II of Table C, which is of the type of biological pesticides.
Table C
Pesticide component II Compound Pesticide component II Compound abbreviation abbreviation
Azospirillum amazonense II-B1-1 Rhizobium tropic/ II-B1-22
Azospirillum brasilense II-B1-2 Sinorhizobium meliloti II-B1-23
Azospirillum lipoferum II-B1-3 Bacillus altitudinis II-B2-1
Azospirillum irakense II-B1-4 Bacillus amyloliquefaciens II-B2-2
Azospirillum halopraeferens II-B1-5 Bacillus amyloliquefaciens
Bradyrhizobium spp. II-B1-6 ssp. plantarum II-B2-3
Bradyrhizobium sp. (Arachis) II-B1-7 Bacillus firmus II-B2-4
Bradyrhizobium sp. (Vigna) II-B1-8 Bacillus megaterium II-B2-5
Bradyrhizobium elkanii II-B1-9 Bacillus mojavensis II-B2-6
Bradyrhizobium japonicum II-B1-10 Bacillus mycoides II-B2-7
Bradyrhizobium liaoningense II-B1-11 Bacillus pumilus II-B2-8
Bradyrhizobium lupini II-B1-12 Bacillus simplex II-B2-9
Delftia acidovorans II-B1-13 Bacillus solisalsi II-B2-10
Glomus intraradices II-B1-14 Bacillus subtilis II-B2-11
Mesorhizobium spp. II-B1-15 Burkholderia sp. II-B2-12
Mesorhizobium ciceri II-B1-16 Coniothyrium minitans II-B2-13
Mesorhizobium huakii II-B1-17 Paecilomyces lilacinus II-B2-14
Mesorhizobium loti II-B1-18 Paenibacillus alvei II-B2-15
Rhizobium leguminosarum Paenibacillus polymyxa II-B2-16 bv. phaseoli II-B1-19 Paenibacillus popilliae II-B2-17
Rhizobium leguminosarum Pasteuria nishizawae II-B2-18 bv. trifolii II-B1-20 Pasteuria usgae II-B2-19
Rhizobium leguminosarum PenicHlium bilaiae II-B2-20 bv. viciae II-B1-21 Pseudomonas chloraphis II-B2-21 Pesticide component II Compound Pesticide component II Compound abbreviation abbreviation
Pseudomonas fluorescens II-B2-22 jasmonic acid or salts or de¬
Pseudomonas put/da II-B2-23 rivatives thereof II-B2-26 abscisic acid II-B2-24 cis-jasmone II-B2-27 harpin protein (alpha-beta) II-B2-25 methyl jasmonate II-B2-28
Therefore, in the context of the present invention, each of the rows of Table C-1 corresponds to one mixture.
Table C-1
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000024_0003
As used herein, the term "compound(s) of the present invention" or "compound(s) according to the invention" refers to the compound(s) of formula (I) as defined above, which are also referred to as "compound(s) of formula I" or "compound(s) I" or "formula I compound(s)", and includes their salts, tautomers, stereoisomers, and N-oxides.
The term "composition(s) according to the invention" or "composition(s) of the present invention" encompasses composition(s) comprising at least one compound of formula (I) or mixtures of the the compound of formula (I) with other pesticidally active compound(s) II for being used and/or applied in methods according to the invention as defined above.
The compound of formula (I) has at least one center of chirality, therefore is present as mixtures of enantiomers or diastereomers, in any case as a pair of two enantiomers. Both enantiomers are said to contribute to the pesticidal effect. The invention provides both the pure enantiomers or pure diastereomers of the the compound of formula (I), and its mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula (I) or its mixtures. A suitable compound of the formula (I) also includes all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond, nitrogen-sulfur double bond or amide group. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
Salts of the compounds of the present invention are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.
In general, suitable "agriculturally useful salts" or "agriculturally acceptable salts" are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4 +) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci- C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise me- thylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trime- thylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2- hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sul- fonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4- alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compound of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The compound of the formula (I) may be present in the form of its N-oxides. The term "N-oxide" includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides of compounds (I) can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides. The person skilled in the art knows if and in which positions the compound of the formula (I) of the present invention may form N-oxides.
The preparation of the compound of formula I above may lead to them being obtained as isomer mixtures. If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers. Agronomically acceptable salts of the compounds I can be formed in a customary manner, e.g. by reaction with an acid of the anion in question.
Mixtures
The present invention also relates to a mixture of at least one compound of the present invention with at least one mixing partner as defined herein after. Preferred are binary mixtures of one compound of the present invention as component I with one mixing partner as defined herein after as component II. Preferred weight ratios for such binary mixtures are from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, more preferably from 100:1 to 1 :100, particularly preferably from 10:1 to 1 :10. In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.
Especially, the following mixtures are preferred, in particular in the methods and uses according to the invention:
M1 : Compound of formula (I) [Cyclaniliprole] + fipronil
M2: Compound of formula (I) [Cyclaniliprole] + alpha cypermethrin,
M3: Compound of formula (I) [Cyclaniliprole] + dinotefuran
M4: Compound of formula (I) [Cyclaniliprole] + chlorfenapyr
M5: Compound of formula (I) [Cyclaniliprole] + teflubenzuron
M6: Compound of formula (I) [Cyclaniliprole] + sulfoxaflor
Formulations
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the present invention or a mixture thereof.
An agrochemical composition comprises a pesticidally effective amount of a cormpound of the present invention or a mixture thereof. The term "pesticidally effective amount" is defined below.
The compounds of the present invention or the mixtures thereof can be converted into customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composi- tion types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International. The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo-'hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Exam- pies of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth- oxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present invention on the target. Examples are surfactants, mineral or vegetable oils, and other auxi- laries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions cormprising them as premix or, if appropriate not until immedi- ately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired applica- tion concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area. According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the in- vention or partially premixed components, e. g. components comprising compound I of the present invention and/or mixing partners as defined above, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compound I of the pre- sent invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.
The compounds of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the present invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a compound of the present invention.
The compounds of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the present invention.
The compounds of the present invention are effective through both contact and ingestion. Furthermore, the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
The compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions comprising said mixtures as defined above. The components of said mixture can be applied simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures. The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow. Foliar application refers to the application of the pesticidally active compound to plant foliage, e.g. through spray equipment. For foliar applications, it can be advantageous to modify the behavior of the pests by use of pheromones in combination with the compounds of the present invention. Suitable pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.
As used herein, the term "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habi- tat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
The term "animal pest" includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop in- sect pests.
The term "crop" refers to both, growing and harvested crops.
The term "plant" includes in particular cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, fruit trees, citrus crop and nuts for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sug- arbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, tea, pepper, cucumbers, melons, Brassica species, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, apple, pear, peach, nectarine, oranges, mandarins, lemons, almonds, walnuts, pista- chios, petunias, geranium/pelargoniums, pansies and impatiens, and grasses for animal feed or ornamental uses.
The term "cultivated plant" is to be understood as including plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof. Plants, which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance, include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugarbeet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice.
In plants, which have been modified by mutagenesis or genetic engineering, one or more genes have been mutagenized or integrated in the genetic material of the plant. The one or more mutagenized or integrated genes are preferably selected from pat, epsps, cry1 Ab, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cry1 F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5. The mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant. Such properties, also known as traits, include abiotic stress tolerance, altered
growth/yield, disease resistance, herbicide tolerance, insect resistance, modified product quality, and pollination control. Of these properties, herbicide tolerance, e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance, is of particular importance. Several plants have been rendered tolerant to herbicides by mutagenesis, for example Clearfield® oilseed rape being tolerant to imidazolinones, e.g. imazamox. Alternatively, genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available un- der the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate). Furthermore, insect resistance is of importance, in particular lepidopteran insect resistance and coleop- teran insect resistance. Insect resistance is typically achieved by modifying plants by integrating cry and/or vip genes, which were isolated from Bacillus thuringiensis (Bt), and code for the respective Bt toxins. Genetically modified plants with insect resistance are commercially available under trade names including WideStrike®, Bollgard®, Agrisure®, Herculex®, YieldGard®, Genuity®, and Intacta®. Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance. In general, all relevant modified plants in connection with singular or stacked traits as well as detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations "International Service for the Acquisition of Agri-biotech Applications (ISAAA)" (http://www.isaaa.org/gmapprovaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http://cera-gmc.org/GMCropDatabase). The term "plant propagation material" refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
The term "seed" embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and dura- tion, weather, target species, locus, mode of application, and the like.
In the case of soil treatment, in furrow application or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.
For use in treating crop plants, e.g. by foliar application, the rate of application of the active in- gredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare. The compounds of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects. The present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermina- tion with a compound of the present invention. The protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes.
The term "seed treatment" comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
The present invention also comprises seeds coated with or containing the active compound. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the ac- tive ingredient.
Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Bras- sica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
In addition, the active compound may also be used for the treatment of seeds from genetically modified plants, which e.g. tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods. Such genetically modified plants have been described in detail above.
Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.
The active substance concentrations in ready-to-use formulations, which may be obtained after two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.
In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of the compounds of the present invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
In the treatment of seed, the application rates of the compounds of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the present invention, or an agriculturally useful salt thereof, as defined herein. The amount of the compound of the present invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
The compounds of the present invention may also be used for improving the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the present invention.
As used herein "an effective and non-phytotoxic amount" means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotox- ic symptom on the treated plant or on the plant grown from the treated propagule or treated soil. The terms "plant" and "plant propagation material" are defined above.
"Plant health" is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting efficiency, processability).
The above identified indicators for the health condition of a plant may be interdependent and may result from each other. Each indicator is defined in the art and can be determined by meth- ods known to a skilled person.
Pests The compounds of the the present invention are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
insects from the order of Lepidoptera, for example Achroia grisella, Aden's spp. such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sarcitella, Anagasta kuehniella, Anarsia lineatella, Anisota senator/a, Antheraea pernyi, Anticar- sia (=Thermesia) spp. such as A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp. such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugel- la, Argyroploce spp., Argyrotaenia spp. such as A. velutinana; Athetis mindara, Austroasca vi- ridigrisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bon- agota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. Indi- cus, C. suppressalis, C partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Colias eurytheme, Conopomorpha spp., Conotrachelus spp., Cop/tarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp. such as C. pomonella, C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp. such as D. pini, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp. such as D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera festiva, Earias spp. such as E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curia/is, E/asmopa/pus ligno- sellus, Eldana saccharina, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Felt/a spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseu- dospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leu- coma salicis, Leucoptera spp. such as L. coffee/la, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobes/a botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp. such as L. sticticalis, L. cereralis; Lymantria spp. such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malaco- soma spp. such as M. americanum, M. californicum, M. constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mamstra brassicae, Manduca spp. such as M. quin- quemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp. such as M. lapites, M. repanda; Mods latipes, Mon- ochroa fragariae, Mythimna separata, Nemapogon doacella, Neoleudnodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Oper- ophtera brumata, Orgyia pseudotsugata, Oria spp., Orthaga thyrisalis, Ostrinia spp. such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene regalis, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma sauda, Perileucoptera spp., such as P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp. such as P. operculella; Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrods tripunctata, Plathy- pena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P. stultana; Platyptilia cardui- dadyla, Plebejus argus, Plodia interpundella, Pius/a spp, Plutella maculipennis, Plutella xy- lostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp. such as P. sequax, P. unipunda; Pyrausta nubilalis, Rachiplusia nu, Rich/a albicosta, Rhizobius ven- tralis, Rhyadonia frustrana, Sabulodes aegrotata, Schizura condnna, Schoenobius spp., Schreckensteinia festaliella, Sdrpophaga spp. such as S. incertulas, S. innotata; Scotia segetum, Sesamia spp. such as S. inferens, Seudyra subflava, Sitotroga cerealella, Spargan- othis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. eridania, S. exigua, S. frugiperda, S. latisfascia, S. Iittoralis, S. Iitura, S. omithogalli; Stigmelia spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. such as S. exitiosa, Tec/a solanivora, Telehin Ileus, Thaumatopoea pityocampa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, Thecla spp., Theresimima am- pelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. such as T. doacella, T. pel- lionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga tapetzella, Trichoplu- sia spp. such as T. ni; Tuta (=Scrobipalpula) absolute, Udea spp. such as U. rubigalis, U. rubi- galis; Virachola spp., Yponomeuta padella, and Zeiraphera canadensis;
insects from the order of Coleoptera, for example Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimal- lus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulen- ta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis; Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogo- nia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aula- cophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B. ruf/'manus; Bydiscus betulae, Callidiellum rufipenne, Cal- lopistria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Ceroto- ma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as C. vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryp- torhynchus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomaculata; Epitrix spp. such as E. hirtipennis, E. similaris; Eutheola humilis, Eu- tinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Cnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hy- pera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lath- ridius spp., Lema spp. such as L bilineata, L. melanopus; Leptinotarsa spp. such as L. decem- lineata; Leptispa pygmaea, Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Lu- perodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus spp. such as M. subspinosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus com- munis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M. hippocastani, M. melol- ontha; Metamasius hemipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monocha- mus spp. such as M. alternatus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhyn- chus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema ory- zae, Oxycetonia jucunda, Phaedon spp. such as P. brassicae, P. cochleariae; Phoracantha re- curva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Pop- illia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R. vulneratus; Saperda Candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Sternechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T. castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp. such as X. pyrrhoderus; and, Za- brus spp. such as Z. tenebrioides;
insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bac- trocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capi- tata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pip/ens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inor- nata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp. such as D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicularis; Gastraphilus spp. such as G. intestinalis; Geomyza tipunctata, Glossina spp. such as G. fusel- pes, G. morsitans, G. palpalis, G tachinoides; Haematobia irritans, Haplodiplosis equestns, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppo- bosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifo- lii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as M. destructor; Musca spp. such as M. autumnalis, M. domestica; Musci- na stabulans, Oestrus spp. such as O. ovis; Opomyza florum, Oscinella spp. such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as P. antique, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp. such as R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. such as S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. such as S. calci- trans; Tabanus spp. such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodi- plosis japonensis, Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp;
insects from the order of Thysanoptera for example, Baliothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femora/is, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae; Stenchae- tothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. ima- gines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;
insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolo- bus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pom/, A. sambuci, A. schneideri, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cockerelli (Paratrioza cockerelli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horn/, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis te- galensis, Chlorita onuk/i, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Ci- mex spp. such as C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp. such as C. hesperidum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbulus spp., Dasynus piperis, Dialeurodes spp. such as D. citrifolii; Dalbulus maidis, Di- aphorina spp. such as D. citri; Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconoco- ris hewetti, Dora/is spp., Dreyfus/a nordmannianae, Dreyfus/a piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp. such as E E solana; Epidiaspis leperii, Eriosoma spp. such as E /#/7/i7- e/z//77, E pyricola; Erythroneura spp., Eurygaster spp. such as E integriceps; Euscelis bilobatus, Euschistus spp. such as E heros, E impictiventris, E servus; Fiorinia theae, Geococcus coffe- ae, Glycaspis brimblecombei, Halyomorpha spp. such as H. 73/ys/ Heliopeltis spp., Homalodis- ca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, lcerya spp. such as /. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecani- um spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L i///77/; Leptocorisa spp., Z.e 7- toglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L hesperus, L. lineolaris, L. praten- s/s; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp. such as M rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriola- ta, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocal- l/s (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Mo- nelliopsis pecanis, Myzocallis cory/i, Murgantia spp., Myzus spp. such as M. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia ribis-nigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. virescens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius button/, Oebalus spp. such as O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Para- bemisia myricae, Parlatoria spp., Parthenolecanium spp. such as P. corn/, P. persicae; Pemphi- gus spp. such as P. bursarius, P. popuiivenae; Peregrinus maidis, Perkinsiella saccharicida, Phenacoccus spp. such as P. aceris, P. gossypii; Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp. such as P. devastatrix, Piesma quadrata, Piezodorus spp. such as P. guildinii; Pinnaspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvi- naria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudo- coccus spp. such as P. comstocki; Psylla spp. such as P. mall; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada g/g' as, Rastro- coccus spp., Reduvius senilis, Rhizoecus amer/canus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R. pad/;' Saga- todes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scapto- coris spp., Scaphoides titan us, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insu- laris, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeurodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii, Insects from the order Hymenoptera for example Acanthomyops interjectus, Athalia rosae, At- ta spp. such as A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. florida- nus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocos- mus kuriphilus, Formica spp., Hoplocampa spp. such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. such as L niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. such as M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinen- sis, Paratrechina longicomis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenopsis spp. such as S. geminata, S.invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp. such as T. melanocephalum, T. sessile; Tetramorium spp. such as T. caespitum, T. bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V. squamosal; Wasmannia auropunctata, Xylocopa sp;
Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris sep- temfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. america- na, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus;
Pests from the Class Arachnida for example Acari.e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Argas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. mi- croplus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus everts/, Rhizoglyphus spp., Sarcoptes spp. such asS. Scabier, and Family Eriophyidae including Acer/a spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pelekassr, Acu/us spp. such as A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllo- coptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldoni, Family Tar- sonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinkr, Family Tenuipalpidae including Brevi- palpus spp. such as B. phoenicis, Family Tetranychidae including Eotetranychus spp., Eute- tranychus spp., Oligonychus s p., Petrobia latens, Tetranych us spp. such as T. cinnabarinus, T. evansi, T. kanzawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp. such as P. ulmi, P. citrr, Metatetranychus spp. and Oligonychus spp. such as O. pratensis, O. perseae, Vasates lycopersici, Raoiella indica, Fa/ro/y Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp. such as Halotydeus destructor, Family Demodicidae with species such as Demodex spp.; Family Trombicidea including Trombicula spp.; Family Macro- nyssidae including Ornothonyssus spp. ; Family Pyemotidae including Pyemotes tritici, Tyropha- gus putrescentiae; Family Acaridae including Acarus siro; Family Araneida including Latrodec- tus mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa;
Pests from the Phylum Nematoda, for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G rostochiensis; Heterodera spp. such as H. avenae, H. gly- cines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. such as A. besseyi; Sting nematodes, Belonolaim us spp. such as £. /cv?- gicaudatus; Pine nematodes, Bursaphelenchus spp. such as lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Criconemoides spp. such as Criconemoides informis; Mesocriconema spp.; Stem and bulb nematodes, Ditylenchus spp. such as £>. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, He/77- icycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; Lance nematodes, loaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. such as Z.. elongatus; Lesion nematodes, Pratylenchus spp. such as P. brachyurus, P. neglec- tus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as ?. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylench us spp. such as ?. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as 7^ obtusus, T. primitivus; Paratrichodorus spp. such as . minor; Stunt nematodes, Tylencho- rhynchus spp. such as 7^ claytoni, T. dub/us; Citrus nematodes, Tylenchulus spp. such as 7^ semipenetrans; Dagger nematodes, Xiphinema spp.; and other plant parasitic nematode species;
Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longi- ceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp. such as /. /77//70Γ, /. Snyder, Marginitermes hubbardi, Mastotermes spp. such as darwiniensis Neocapntermes spp. such as Λ/. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis spp. S-/C 7 as Z angusticollis, Z. nevadensis, Reticulitermes spp. such as /?. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis, Insects from the order Blattaria for example _?/a//a spp. such as fi orientalis, B. lateralis; Blat- tella spp. such as z?. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Peri- planeta spp. such as . americana, P. australasiae, P. brunnea, P. fuligginosa, P. japonica; Su- pella long/pa/pa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis, Insects from the order Siphonoptera for example Cediopsylla simples, Ceratophyllus spp., Ctenocephalides spp. such as C. fells, C. canis, Xenopsylla cheopis, Pulex irritans, Tricho- dectes canis, Tunga penetrans, and Nosopsyllus fasciatus,
Insects from the order Thysanura for example Lepisma saccharina , Ctenolepisma urbana, and Thermobia domestica,
Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera co/eoptrata;
Pests from the class Diplopoda for example Blaniulus guttulatus, Julus spp., Narceus spp., Pests from the class Symphyla for example Scutigerella immaculata,
Insects from the order Dermaptera. for example Forf/cu/a auricular/a,
Insects from the order Collembola, for example Onychiurus spp., such as Onychiurus armatus, Pests from the order Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber, Insects from the order Phthiraptera, for example Damalinia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.,
Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, for example, Dreissena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Ga/ba spp., Lymnaea spp., Oncomelania spp., Pomacea canal/data, Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancy- lostoma spp., Ascaris lubricoides, Ascaris spp., Brugia ma lay i, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooper/a spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyl- lobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocu- laris, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesoph- agostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonim us spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichi- nella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
In a preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of a cultivated plant, in particular the yield of a cultivated plant, by treating plant propagation material, preferably seeds with the compound of formula I and its mixtures.
The present invention also comprises plant propagation material, preferably seed, of a cultivated plant treated with the compound of formula I and its mixtures.
In another preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of a cultivated plant, in particular the yield of a cultivated plant by treating the cultivated plant, part(s) of such plant or at its locus of growth with the compound of formula I and its mixtures.
The term cultivated plant(s) includes to "modified plant(s)" and "transgenic plant(s)".
In one embodiment of the invention, the term "cultivated plants" refers to "modified plants". In one embodiment of the invention, the term "cultivated plants" refers to "transgenic plants". "Modified plants" are those which have been modified by conventional breeding techniques. The term "modification" means in relation to modified plants a change in the genome, epigenome, tran- scriptome or proteome of the modified plant, as compared to the control, wild type, mother or parent plant whereby the modification confers a trait (or more than one trait) or confers the in- crease of a trait (or more than one trait) as listed below.
The modification may result in the modified plant to be a different, for example a new plant variety than the parental plant.
"Transgenic plants" are those, which genetic material has been modified by the use of recombi- nant DNA techniques that under natural circumstances can not readily be obtained by cross breeding, mutations or natural recombination, whereby the modification confers a trait (or more than one trait) or confers the increase of a trait (or more than one trait) as listed below as compared to the wild-type plant.
In one embodiment, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant, preferably increase a trait as listed below as compared to the wild-type plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), or to post- transcriptional modifications of oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated, phosphorylated or farnesylated moieties or PEG moieties.
In one embodiment under the term "modification" when reffering to a transgenic plant or parts thereof is understood that the activity, expression level or amount of a gene product or the metabolite content is changed, e.g. increased or decreased, in a specific volume relative to a cor- responding volume of a control, reference or wild-type plant or plant cell, including the de novo creation of the activity or expression.
In one embodiment the activity of a polypeptide is increased or generated by expression or overexpresion of the gene coding for said polypeptide which confers a trait or confers the increase of a trait as listed below as compared to the control plant. The term "expression" or "gene expression" means the transcription of a specific gene or specific genes or specific genetic construct. The term "expression" or "gene expression" in particular means the transcription of a gene or genes or genetic construct into structural RNA (rRNA, tRNA), regulatory RNA (e.g. miRNA, RNAi, RNAa) or mRNA with or without subsequent translation of the latter into a protein. In another embodiment the term "expression" or "gene expression" in particular means the transcription of a gene or genes or genetic construct into structural RNA (rRNA, tRNA) or mRNA with or without subsequent translation of the latter into a protein. In yet another embodiment it means the transcription of a gene or genes or genetic construct into mRNA.
The process includes transcription of DNA and processing of the resulting mRNA product. The term "increased expression" or "overexpression" as used herein means any form of expression that is additional to the original wild-type expression level.
The term "expression of a polypeptide" is understood in one embodiment to mean the level of said protein or polypeptide, preferably in an active form, in a cell or organism.
In one embodiment the activity of a polypeptide is decreased by decreased expression of the gene coding for said polypeptide which confers a trait or confers the increase of a trait as listed below as compared to the control plant. Reference herein to "decreased expression" or "reduction or substantial elimination" of expression is taken to mean a decrease in endogenous gene expression and/or polypeptide levels and/or polypeptide activity relative to control plants. It comprises further reducing, repressing, decreasing or deleting of an expression product of a nucleic acid molecule.
The terms "reduction", "repression", "decrease" or "deletion" relate to a corresponding change of a property in an organism, a part of an organism such as a tissue, seed, root, tuber, fruit, leave, flower etc. or in a cell. Under "change of a property" it is understood that the activity, expression level or amount of a gene product or the metabolite content is changed in a specific volume or in a specific amount of protein relative to a corresponding volume or amount of protein of a control, reference or wild type. Preferably, the overall activity in the volume is reduced, decreased or deleted in cases if the reduction, decrease or deletion is related to the reduction, decrease or deletion of an activity of a gene product, independent whether the amount of gene product or the specific activity of the gene product or both is reduced, decreased or deleted or whether the amount, stability or translation efficacy of the nucleic acid sequence or gene encoding for the gene product is reduced, decreased or deleted. The terms "reduction", "repression", "decrease" or "deletion" include the change of said property in only parts of the subject of the present invention, for example, the modification can be found in compartment of a cell, like an organelle, or in a part of a plant, like tissue, seed, root, leave, tuber, fruit, flower etc. but is not detectable if the overall subject, i.e. complete cell or plant, is tested. Preferably, the "reduction", "repression", "decrease" or "deletion" is found cellular, thus the term "reduction, decrease or deletion of an activity" or "reduction, decrease or deletion of a metabolite content" relates to the cellular reduction, decrease or deletion compared to the wild type cell. In addition the terms "reduction", "repression", "decrease" or "deletion" include the change of said property only during different growth phases of the organism used in the inventive process, for example the reduction, repression, decrease or deletion takes place only during the seed growth or during blooming. Furthermore the terms include a transitional reduction, decrease or deletion for example because the used method, e.g. the antisense, RNAi, snRNA, dsRNA, siRNA, miRNA, ta-siRNA, cosuppression molecule, or ribozyme, is not stable integrated in the genome of the organism or the reduction, decrease, repression or deletion is under control of a regulatory or inducible element, e.g. a chemical or otherwise inducible pro- moter, and has therefore only a transient effect.
Methods to achieve said reduction, decrease or deletion in an expression product are known in the art, for example from the international patent application WO 2008/034648, particularly in paragraphs [0020.1.1.1], [0040.1.1.1], [0040.2.1.1] and [0041.1.1.1].
Reducing, repressing, decreasing or deleting of an expression product of a nucleic acid mole- cule in modified plants is known. Examples are canola i.e. double nill oilseed rape with reduced amounts of erucic acid and sinapins.
Such a decrease can also be achieved for example by the use of recombinant DNA technology, such as antisense or regulatory RNA (e.g. miRNA, RNAi, RNAa) or siRNA approaches. In particular RNAi, snRNA, dsRNA, siRNA, miRNA, ta-siRNA, cosuppression molecule, ribozyme, or antisense nucleic acid molecule, a nucleic acid molecule conferring the expression of a dominant-negative mutant of a protein or a nucleic acid construct capable to recombine with and silence, inactivate, repress or reduces the activity of an endogenous gene may be used to decrease the activity of a polypeptide in a transgenic plant or parts thereof or a plant cell thereof used in one embodiment of the methods of the invention. Examples of transgenic plants with reduced, repressed, decreased or deleted expression product of a nucleic acid molecule are Carica papaya (Papaya plants) with the event name X17-2 of the University of Florida, Prunus domestica (Plum) with the event name C5 of the United States Department of Agriculture - Agri- cultural Research Service, or those listed in rows T9-48 and T9-49 of table 9 below. Also known are plants with increased resistance to nematodes for example by reducing, repressing, decreasing or deleting of an expression product of a nucleic acid molecule, e.g. from the PCT publication WO 2008/095886. The reduction or substantial elimination is in increasing order of preference at least 10%, 20%, 30%, 40% or 50%, 60%, 70%, 80%, 85%, 90%, or 95%, 96%, 97%, 98%, 99% or more reduced compared to that of control plants. Reference herein to an "endogenous" gene not only refers to the gene in question as found in a plant in its natural form (i.e., without there being any human intervention), but also refers to that same gene (or a substantially homologous nucleic ac- id/gene) in an isolated form subsequently (re) introduced into a plant (a transgene). For example, a transgenic plant containing such a transgene may encounter a substantial reduction of the transgene expression and/or substantial reduction of expression of the endogenous gene.
The terms "control" or "reference" are exchangeable and can be a cell or a part of a plant such as an organelle like a chloroplast or a tissue, in particular a plant, which was not modified or treated according to the herein described process according to the invention. Accordingly, the plant used as control or reference corresponds to the plant as much as possible and is as identical to the subject matter of the invention as possible. Thus, the control or reference is treated identically or as identical as possible, saying that only conditions or properties might be different which do not influence the quality of the tested property other than the treatment of the present invention.
It is possible that control or reference plants are wild-type plants. However, "control" or "reference" may refer to plants carrying at least one genetic modification, when the plants employed in the process of the present invention carry at least one genetic modification more than said control or reference plants. In one embodiment control or reference plants may be transgenic but differ from transgenic plants employed in the process of the present invention only by said modification contained in the transgenic plants employed in the process of the present invention.
The term "wild type" or "wild-type plants" refers to a plant without said genetic modification. These terms can refer to a cell or a part of a plant such as an organelle like a chloroplast or a tissue, in particular a plant, which lacks said genetic modification but is otherwise as identical as possible to the plants with at least one genetic modification employed in the present invention. In a particular embodiment the "wild-type" plant is not transgenic.
Preferably, the wild type is identically treated according to the herein described process according to the invention. The person skilled in the art will recognize if wild-type plants will not require certain treatments in advance to the process of the present invention, e.g. non-transgenic wild- type plants will not need selection for transgenic plants for example by treatment with a selecting agent such as a herbicide.
The control plant may also be a nullizygote of the plant to be assessed. The term "nullizygotes" refers to a plant that has undergone the same production process as a transgenic, yet has lost the once aquired genetic modification (e.g. due to mendelian segregation)as the corresponding transgenic. If the starting material of said production process is transgenic, then nullizygotes are also transgenic but lack the additional genetic modification introduced by the production process. In the process of the present invention the purpose of wild-type and nullizygotes is the same as the one for control and reference or parts thereof. All of these serve as controls in any comparison to provide evidence of the advantageous effect of the present invention.
Preferably, any comparison is carried out under analogous conditions. The term "analogous conditions" means that all conditions such as, for example, culture or growing conditions, soil, nutrient, water content of the soil, temperature, humidity or surrounding air or soil, assay conditions (such as buffer composition, temperature, substrates, pathogen strain, concentrations and the like) are kept identical between the experiments to be compared. The person skilled in the art will recognize if wild-type, control or reference plants will not require certain treatments in advance to the process of the present invention, e.g. non-transgenic wild-type plants will not need selection for transgenic plants for example by treatment with herbicide.
In case that the conditions are not analogous the results can be normalized or standardized based on the control.
The "reference", "control", or "wild type" is preferably a plant, which was not modified or treated according to the herein described process of the invention and is in any other property as similar to a plant, employed in the process of the present invention of the invention as possible. The reference, control or wild type is in its genome, transcriptome, proteome or metabolome as simi- lar as possible to a plant, employed in the process of the present invention of the present invention. Preferably, the term "reference-" "control-" or "wild-type-" plant, relates to a plant, which is nearly genetically identical to the organelle, cell, tissue or organism, in particular plant, of the present invention or a part thereof preferably 90% or more, e.g. 95%, more preferred are 98%, even more preferred are 99,00%, in particular 99,10%, 99,30%, 99,50%, 99,70%, 99,90%, 99,99%, 99,999%) or more. Most preferable the "reference", "control", or "wild type" is a plant, which is genetically identical to the plant, cell, a tissue or organelle used according to the process of the invention except that the responsible or activity conferring nucleic acid molecules or the gene product encoded by them have been amended, manipulated, exchanged or introduced in the organelle, cell, tissue, plant, employed in the process of the present invention.
Preferably, the reference and the subject matter of the invention are compared after standardization and normalization, e.g. to the amount of total RNA, DNA, or protein or activity or expression of reference genes, like housekeeping genes, such as ubiquitin, actin or ribosomal proteins.
The genetic modification carried in the organelle, cell, tissue, in particular plant used in the pro- cess of the present invention is in one embodiment stable e.g. due to a stable transgenic integration or to a stable mutation in the corresponding endogenous gene or to a modulation of the expression or of the behaviour of a gene, or transient, e.g. due to an transient transformation or temporary addition of a modulator such as an agonist or antagonist or inducible, e.g. after transformation with a inducible construct carrying a nucleic acid molecule under control of a inducible promoter and adding the inducer, e.g. tetracycline. In some embodiments, the invention relates to methods and uses, wherein a compound of fomula IA as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T.
In some embodiments, the invention relates to methods and uses, wherein a compound select- ed from the compounds of Table A, A' or A", is applied in an application type which corresponds in each case to one row of Table AP-T.
Also preferred is the application of the compounds and mixtures according to the invention, especially the compounds as individualized herein, e.g. in Table A, A', or A", on specialty crops like fruits and vegetables. In one embodiment thereof, the application is on fruiting vegetables, and especially on tomato, on pepper or on eggplant. In another embodiment thereof, the application is on leafy vegetables, and especially on cabbage or on lettuce. In still another embodiment thereof, the application is on tubers (tuber vegetables), and especially on potato or on onion. In one embodiment, in the methods and uses according to the invention, the following application types are used:
(Abbreviations: SPC = specialty crops; SPC-FV = fruiting vegetable; SPC-LV = leafy vegetable; SPC-T: tubers; ST = seed treatment) Table AP-T
Appl. Crop Pest
type
AP-T-1 Soybeans Spodoptera littoralis
AP-T-2 Soybeans Anticarsia gemmatalis
AP-T-3 Soybeans Spodoptera exigua
AP-T-4 Soybeans Stinkbug
AP-T-5 Soybeans Helicoverpa sp.
AP-T-6 Soybeans Spodoptera eridania
AP-T-7 Corn Spodoptera Frugiper- ta
AP-T-8 Corn Spodoptera exigua
AP-T-9 Rice Sesamia inferens
AP-T-10 Rice Cnaphalocerus medi- nalis
AP-T-11 Rice Chilo suppressalis
AP-T- 12 Rice Leptocorisa oratorius
AP-T-13 Rice Brown plant hopper
AP-T- 14 Cotton Spodoptera littoralis
AP-T-15 Cotton Thrips spp.
AP-T-16 Cotton Spodoptera eridania
AP-T-17 Cotton Helicoverpa sp. The cultivated plants are plants, which comprise at least one trait. The term "trait" refers to a property, which is present in the plant either by genetic engineering or by conventional breeding techniques. Each trait has to be assessed in relation to its respective control. Examples of traits are:
· herbicide tolerance,
• insect resistance by expression of bacterial toxins,
• fungal resistance or viral resistance or bacterial resistance,
• antibiotic resistance,
• stress tolerance,
· maturation alteration,
• content modification of chemicals present in the cultivated plant, preferably increasing the content of fine chemicals advantageous for applications in the field of the food and/or feed industry, the cosmetics industry and/or the pharmaceutical industry,
• modified nutrient uptake, preferably an increased nutrient use efficiency and/or resistance to conditions of nutrient deficiency,
• improved fiber quality,
• plant vigor,
• modified colour,
• fertility restoration,
and male sterility.
Principally, cultivated plants may also comprise combinations of the aforementioned traits, e.g. they may be tolerant to the action of herbicides and express bacterial toxins.
Principally, all cultivated plants may also provide combinations of the aforementioned proper- ties, e.g. they may be tolerant to the action of herbicides and express bacterial toxins.
In the detailed description below, the term "plant" refers to a cultivated plant.
Tolerance to herbicides can be obtained by creating insensitivity at the site of action of the herbicide by expression of a target enzyme which is resistant to herbicide; rapid metabolism (conju- gation or degradation) of the herbicide by expression of enzymes which inactivate herbicide; or poor uptake and translocation of the herbicide. Examples are the expression of enzymes which are tolerant to the herbicide in comparison to wild type enzymes, such as the expression of 5- enolpyruvylshikimate-3-phosphate synthase (EPSPS), which is tolerant to glyphosate (see e.g. Heck et.al, Crop Sci. 45, 2005, 329-339; Funke et.al, PNAS 103, 2006, 13010-13015; US 5188642, US 4940835, US 5633435, US 5804425, US 5627061), the expression of glutamine synthase which is tolerant to glufosinate and bialaphos (see e.g. US 5646024, US 5561236) and DNA constructs coding for dicamba-degrading enzymes (see e.g. US 7105724). Gene constructs can be obtained, for example, from micro-organism or plants, which are tolerant to said herbicides, such as the Agrobacterium strain CP4 EPSPS which is resistant to glyphosate; Streptomyces bacteria which are resistance to glufosinate; Arabidopsis, Daucus carota, Pseu- domonoas spp. or Zea mais with chimeric gene sequences coding for HDDP (see e.g. WO 1996/38567, WO 2004/55191 ); Arabidopsis thaliana which is resistant to protox inhibitors (see e.g. US 2002/0073443). Tolerance to glyphosate can also be achieved by any one of the genes 2mepsps, epsps, gat4601 , goxv247 or mepsps.
Tolerance to glufosinate can be achieved by any one of the genes bar, pat or pat(syn). Preferaby, the herbicide tolerant plant can be selected from cereals such as wheat, barley, rye, oat; canola, sorghum, soybean, rice, oil seed rape, sugar beet, sugarcane, grapes, lentils, sunflowers, alfalfa, pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vegetables, such as tomatoes, potatoes, cucurbits and lettuce, more preferably, the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape in particular canola, tomatoes, potatoes, sug- arcane, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat. More preferably, the cultivated plant is selected from the group consisting of Gossypium hirsutum L (cotton), Zea mays L (maize), Glycine max L. (soybean), Triticum aestivum (wheat), and Oryza sativa L (rice), preferably from the group consisting of Gossypium hirsutum L. (cotton), Zea mays L. (maize) and Glycine max L. (soybean). Particularly preferably, the cultivated plant is Glycine max L. (soybean).
Examples of commercial available transgenic plants with tolerance to herbicides, are the corn varieties "Roundup Ready Corn", "Roundup Ready 2" (Monsanto), "Agrisure GT", "Agrisure GT/CB/LL", "Agrisure GT/RW",„Agrisure 3000GT" (Syngenta), "YieldGard VT Rootworm/RR2" and "YieldGard VT Triple" (Monsanto) with tolerance to glyphosate; the corn varieties "Liberty Link" (Bayer), "Herculex I", "Herculex RW", "Herculex Xtra"(Dow, Pioneer), "Agrisure GT/CB/LL" and "Agrisure CB/LL/RW" (Syngenta) with tolerance to glufosinate; the soybean varieties "Roundup Ready Soybean" (Monsanto) and "Optimum GAT" (DuPont, Pioneer) with tolerance to glyphosate; the cotton varieties "Roundup Ready Cotton" and "Roundup Ready Flex" (Mon- santo) with tolerance to glyphosate; the cotton variety "FiberMax Liberty Link" (Bayer) with tolerance to glufosinate; the cotton variety "BXN" (Calgene) with tolerance to bromoxynil; the canola varieties ..Navigator" und ..Compass" (Rhone-Poulenc) with bromoxynil tolerance; the canola varierty"Roundup Ready Canola" (Monsanto) with glyphosate tolerance; the canola variety "InVigor" (Bayer) with glufosinate tolerance; the rice variety "Liberty Link Rice" (Bayer) with glulfosinate tolerance and the alfalfa variety "Roundup Ready Alfalfa" with glyphosate tolerance. Further transgenic plants with herbicide tolerance are commonly known, for instance alfalfa, apple, eucalyptus, flax, grape, lentils, oil seed rape, peas, potato, rice, sugar beet, sunflower, tobacco, tomatom turf grass and wheat with tolerance to glyphosate (see e.g. US 5188642, US 4940835, US 5633435, US 5804425, US 5627061); beans, soybean, cotton, peas, potato, sun- flower, tomato, tobacco, corn, sorghum and sugarcane with tolerance to dicamba (see e.g. US 7105724 and US 5670454); pepper, apple, tomato, millet, sunflower, tobacco, potato, corn, cucumber, wheat and sorghum with tolerance to 2,4-D (see e.g. US 6153401 , US 6100446, WO 2005107437, US 5608147 and US 5670454); sugarbeet, potato, tomato and tobacco with tolerance to glufosinate (see e.g. US 5646024, US 5561236); canola, barley, cotton, lettuce, melon, millet, oats, potato, rice, rye, sorghum, soybean, sugarbeet, sunflower, tobacco, tomato and wheat with tolerance to acetolactate synthase (ALS) inhibiting herbicides, such as triazolopyrim- idine sulfonamides, sulfonylureas and imidazolinones (see e.g. US 5013659, WO 2006060634, US 4761373, US 5304732, US 6211438, US 6211439 and US 6222100); cereals, sugar cane, rice, corn, tobacco, soybean, cotton, rapeseed, sugar beet and potato with tolerance to HPPD inhibitor herbicides (see e.g. WO 2004/055191 , WO 199638567, WO 1997049816 and US 6791014); wheat, soybean, cotton, sugar beet, rape, rice, sorghum and sugar cane with tolerance to protoporphyrinogen oxidase (PPO) inhibitor herbicides (see e.g. US 2002/0073443, US 20080052798, Pest Management Science, 61 , 2005, 277-285). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Plants, which are capable of synthesising one or more selectively acting bacterial toxins, comprise for example at least one toxin from toxin-producing bacteria, especially those of the genus Bacillus, in particular plants capable of synthesising one or more insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as del- ta.-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdy- sone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In one embodiment a plant is capable of producing a toxin, lectin or inhibitor if it contains at least one cell comprising a nucleic acid sequence encoding said toxin, lectin, inhibitor or inhibitor producing enzyme, and said nucleic acid sequence is transcribed and translated and if ap- propriate the resulting protein processed and/or secreted in a constitutive manner or subject to developmental, inducible or tissue-specific regulation.
In the context of the present invention there are to be understood delta. -endotoxins, for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c, or vegetative in- secticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). An example for a truncated toxin is a truncated CrylA(b), which is expressed in the Bt11 maize from Syngen- ta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non- naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D-recognition sequence is inserted into a CrylllA toxin (see WO 2003/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 2003/052073. Examples of genes conferring resistance to coleopteran insects include cry34Ab1 , cry35 Ab1 , cry3A, cry3Bb1 , dvsnf7, and mcry3A.
Examples of genes conferring resistance to lepidopteran insects include crylA, cry1A.105, crylAb, cry1Ab-Ac, crylAc, cry1 C, cryl F, cry1 Fa2, cry2Ab2, cry2Ae, cry9c, mocryl F, pinll, vip3A(a), and vip3Aa20.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A- 0 367 474, EP-A-0 401 979 and WO 1990/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera). Preferably, the plant capable of expression of bacterial toxins is selected from cereals such as wheat, barley, rye, oat; canola, cotton, eggplant, lettuce, sorghum, soybean, rice, oil seed rape, sugar beet, sugarcane, grapes, lentils, sunflowers, alfalfa, pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vegetables, such as tomatoes, potatoes, cucurbits and lettuce, more preferably, the plant is selected from cotton, soybean, maize (corn), rice, tomatoes, pota- toes, oilseed rape and cereals such as wheat, barley, rye and oat, most preferably from cotton, soybean, maize, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat. More preferably, the cultivated plant is selected from the group consisting of Gossypium hirsutum L. (cotton), Zea mays L (maize), Glycine max L. (soybean), Triticum aestivum (wheat), and Oryza sativa L. (rice), preferably from the group consisting of Gossypium hirsutum L (cot- ton), Zea mays L. (maize) and Glycine max L. (soybean). Particularly preferably, the cultivated plant is Glycine max L. (soybean).
Examples of commercial available transgenic plants capable of expression of bacterial toxins are the corn varieties "YieldGard corn rootworm" (Monsanto), "YieldGard VT" (Monsanto), "Her- culex RW" (Dow, Pioneer), "Herculex Rootworm" (Dow, Pioneer) and "Agrisure CRW" (Syngen- ta) with resistance against corn rootworm; the corn varieties "YieldGard corn borer" (Monsanto), „YieldGard VT Pro" (Monsanto), "Agrisure CB/LL" (Syngenta), "Agrisure 3000GT" (Syngenta), "Hercules I", "Hercules II" (Dow, Pioneer), "KnockOut" (Novartis),„NatureGard" (Mycogen) and „Starl_ink" (Aventis) with resistance against corn borer, the corn varieties„Herculex I" (Dow, Pioneer) and„Herculex Xtra" (Dow, Pioneer) with resistance against western bean cutworm, corn borer, black cutworm and fall armyworm; the corn variety "YieldGard Plus" (Monsanto) with resistance against corn borer and corn rootworm; the cotton variety "Bollgard I"" (Monsanto) with resistance against tobacco budworm; the cotton varieties "Bollgard II" (Monsanto),„WideStrike" (Dow) and„VipCot" (Syngenta) with resistance against tobacco budworm, cotton bollworm, fall armyworm, beet armyworm, cabbage looper, soybean lopper and pink bollworm; the potato varieties "NewLeaf", "NewLeaf Y" and "NewLeaf Plus" (Monsanto) with tobacco hornworm resistance and the eggplant varieties "Bt brinjal", "Dumaguete Long Purple", "Mara" with resistance against brinjal fruit and shoot borer, bruit borer and cotton bollworm (see e.g.
US5128130). Further transgenic plants with insect resistance are commonly known, such as yellow stemborer resistant rice (see e.g. Molecular Breeding, Volume 18, 2006, Number 1 ), lep- idopteran resistant lettuce (see e.g. US 5349124), resistant soybean (see e.g. US 7432421 ) and rice with resistance against Lepidopterans, such as rice stemborer, rice skipper, rice cutworm, rice caseworm, rice leaffolder and rice armyworm (see e.g. WO 2001021821). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Preferably, plants, which are capable of synthesising antipathogenic substances are selected from soybean, maize (corn), rice, tomatoes, potato, banana, papaya, tobacco, grape, plum and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, tomatoes, potato, banana, papaya, oil seed rape, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
Plants, which are capable of synthesising antipathogenic substances having a selective action are for example plants expressing the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225) or so-called "antifungal proteins" (AFPs, see e.g. US 6864068). A wide range of antifungal proteins with activity against plant pathogenic fungi have been isolated from certain plant species and are common knowledge. Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for ex- ample, from EP-A-0 392 225, WO 93/05153, WO 95/33818, and EP-A-0 353 191. Transgenic plants which are resistant against fungal, viral and bacterial pathogens are produced by introducing plant resistance genes. Numerous resistant genes have been identified, isolated and were used to improve plant resistant, such as the N gene which was introduced into tobacco lines that are susceptible to Tobacco Mosaic Virus (TMV) in order to produce TMV-resistant tobacco plants (see e.g. US 5571706), the Prf gene, which was introduced into plants to obtain enhanced pathogen resistance (see e.g. WO 199802545) and the Rps2 gene from Arabidopsis thaliana, which was used to create resistance to bacterial pathogens including Pseudomonas syringae (see e.g. WO 199528423). Plants exhibiting systemic acquired resistance response were obtained by introducing a nucleic acid molecule encoding the TIR domain of the N gene (see e.g. US 6630618). Further examples of known resistance genes are the Xa21 gene, which has been introduced into a number of rice cultivars (see e.g. US 5952485, US 5977434, WO 1999/09151 , WO 1996/22375), the Rcg1 gene for colletotrichum resistance (see e.g. US 2006/225152), the prpl gene (see e.g. US 5859332, WO 2008/017706), the ppv-cp gene to introduce resistance against plum pox virus (see e.g. US PP15,154Ps), the P1 gene (see e.g. US5968828), genes such as Blb1 , Blb2, Blb3 and RB2 to introduce resistance against Phy- tophthora infestans 'm potato (see e.g. US 7148397), the LRPKml gene (see e.g.
W01999064600), the P1 gene for potato virus Y resistance (see e.g. US 5968828), the HA5-1 gene (see e.g. US5877403 and US6046384), the PIP gene to indroduce a broad resistant to viruses, such as potato virus X (PVX), potato virus Y (PVY), potato leafroll virus (PL V) (see e.g. EP 0707069) and genes such as Arabidopsis NI 16, ScaM4 and ScaM5 genes to obtain fungal resistance (see e.g. US 6706952 and EP 1018553). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for ex- ample, in the publications mentioned above.
Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glu- canases; the so-called "pathogenesis-related proteins"" (PRPs; see e.g. EP-A-0 392 225); anti- pathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 1995/33818) or protein or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO
2003/000906).
Antipathogenic substances produced by the plants are able to protect the plants against a variety of pathogens, such as fungi, viruses and bacteria. Useful plants of elevated interest in connection with present invention are cereals, such as wheat, barley, rye and oat; soybean; maize; rice; alfalfa, cotton, sugar beet, sugarcane, tobacco , potato, banana, oil seed rape; pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes, potatoes, cucurbits, papaya, melon, lenses and lettuce, more preferably selected from soybean, maize (corn), alfalfa, cotton, potato, banana, papaya, rice, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, potato, tomato, oilseed rape, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
Transgenic plants with resistance against fungal pathogens, are, for examples, soybeans with resistance against Asian soybean rust (see e.g. WO 2008/017706); plants such as alfalfa, corn, cotton, sugar beet, oileed, rape, tomato, soybean, wheat, potato and tobacco with resistance against Phytophtora infestans (see e.g. US5859332, US 7148397, EP 1334979); corn with re- sistance against leaf blights, ear rots and stalk rots (such as anthracnose leaf bligh, anthrac- nose stalk rot, diplodia ear rot, Fusarium verticilioides, Gibberella zeae and top dieback, see e.g. US 2006/225152); apples with resistance against apple scab ( Venturia inaequalis, see e.g. WO 1999064600); plants such as rice, wheat, barley, rye, corn, oats, potato, melon, soybean and sorghum with resistance against fusarium diseases, such as Fusarium graminearum, Fusarium sporotrichioides, Fusarium lateritium, Fusarium pseudograminearum Fusarium sam- bucinum, Fusarium culmorum, Fusarium poae, Fusarium acuminatum, Fusarium equiseti (see e.g. US 6646184, EP 1477557); plants, such as corn, soybean, cereals (in particular wheat, rye, barley, oats, rye, rice), tobacco, sorghum, sugarcane and potatoes with broad fungal resistance (see e.g. US 5689046, US 6706952, EP 1018553 and US 6020129).
Transgenic plants with resistance against bacterial pathogens and which are covered by the present invention, are, for examples, rice with resistance against Xylella fastidiosa (see e.g. US 6232528); plants, such as rice, cotton, soybean, potato, sorghum, corn, wheat, balrey, sugarcane, tomato and pepper, with resistance against bacterial blight (see e.g. WO 2006/42145, US 5952485, US 5977434, WO 1999/09151 , WO 1996/22375); tomato with resistance against Pseudomonas syringae (see e.g. Can. J. Plant Path., 1983, 5: 251-255).
Transgenic plants with resistance against viral pathogens, are, for examples, stone fruits, such as plum, almond, apricot, cherry, peach, nectarine, with resistance against plum pox virus (PPV, see e.g. US PP15,154Ps, EP 0626449); potatoes with resistance against potato virus Y (see e.g. US 5968828); plants such as potato, tomato, cucumber and leguminosaes which are resistant against tomato spotted wilt virus (TSWV, see e.g. EP 0626449, US 5973135); corn with resistance against maize streak virus (see e.g. US 6040496); papaya with resistance against papaya ring spot virus (PRSV, see e.g. US 5877403, US 6046384); cucurbitaceae, such as cucumber, melon, watermelon and pumpkin, and solanaceae, such as potato, tobacco, tomato, eggplant, paprika and pepper, with resistance against cucumber mosaic virus (CMV, see e.g. US 6849780); cucurbitaceae, such as cucumber, melon, watermelon and pumkin, with resistance against watermelon mosaic virus and zucchini yellow mosaic virus (see e.g. US 6015942); potatoes with resistance against potato leafroll virus (PLRV, see e.g. US 5576202); potatoes with a broad resistance to viruses, such as potato virus X (PVX), potato virus Y (PVY), potato leafroll virus (PLRV) (see e.g. EP 0707069).
Further examples of deregulated orcommercially available transgenic plants with modified ge- netic material capable of expression of antipathogenic substances are the following plants: Carica papaya (papaya), Event: 55-1/63-1 ; Cornell University, Carica papaya (Papaya); Event: (X17-2); University of Florida, Cucurbita pepo (Squash); Event: (CZW-3); Asgrow (USA); Semi- nis Vegetable Inc. (Canada), Cucurbita pepo (Squash); Event: (ZW20); Upjohn (USA); Seminis Vegetable Inc. (Canada), Prunus domestica (Plum); Event: (C5); United States Department of Agriculture - Agricultural Research Service, Solanum tuberosum L. (Potato); Event: (RBMT15- 101 , SEMT15-02, SEMT15-15); Monsanto Company and Solanum tuberosum L. (Potato); Event: (RBMT21-129, RBMT21-350, RBMT22-082); Monsanto Company.
Transgenic plants with resistance against nematodes and which may be used in the methods of the present invention are, for examples, soybean plants with resistance to soybean cyst nema- todes.
Methods have been proposed for the genetic transformation of plants in order to confer increased resistance to plant parasitic nematodes. U.S. Patent Nos. 5,589,622 and 5,824,876 are directed to the identification of plant genes expressed specifically in or adjacent to the feeding site of the plant after attachment by the nematode.
Also known in the art are transgenic plants with reduced feeding structures for parasitic nematodes, e.g. plants resistant to herbicides except of those parts or those cells that are nematode feeding sites and treating such plant with a herbicide to prevent, reduce or limit nematode feeding by damaging or destroying feeding sites (e.g. US 5866777).
Use of RNAi to target essential nematode genes has been proposed, for example, in PCT Pub- lication WO 2001/96584, WO 2001/17654, US 2004/0098761 , US 2005/0091713, US
2005/0188438, US 2006/0037101 , US 2006/0080749, US 2007/0199100, and US
2007/0250947. Transgenic nematode resistant plants have been disclosed, for example in the PCT publications WO 2008/095886 and WO 2008/095889.
Plants wich are resistant to antibiotics, such as kanamycin, neomycin and ampicillin. The natu- rally occurring bacterial nptll gene expresses the enzyme that blocks the effects of the antibiotics kanamycin and neomycin. The ampicillin resistance gene ampR (also known as blaTEMI ) is derived from the bacterium Salmonella paratyphi 'and is used as a marker gene in the transformation of micro-organisms and plants. It is responsible for the synthesis of the enzyme beta- lactamase, which neutralises antibiotics in the penicillin group, including ampicillin. Transgenic plants with resistance against antibiotics, are, for examples potato, tomato, flax, canola, oilseed rape and corn (see e.g. Plant Cell Reports, 20, 2001 , 610-615. Trends in Plant Science, 1 1 , 2006, 317-319. Plant Molecular Biology, 37, 1998, 287-296. Mol Gen Genet., 257, 1998, 606- 13.). Plant Cell Reports, 6, 1987, 333-336. Federal Register (USA), Vol.60, No.1 13, 1995, page 31 139. Federal Register (USA), Vol.67, No.226, 2002, page 70392. Federal Register (USA), Vol.63, No.88, 1998, page 25194. Federal Register (USA), Vol.60, No.141 , 1995, page 37870. Canadian Food Inspection Agency, FD/OFB-095-264-A, October 1999, FD/OFB-099-127-A, October 1999. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape, potato, sugarcane, alfalfa, tomatoes and cereals, such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
Plants which are tolerant to stress conditions (see e.g. WO 2000/04173, WO 2007/131699, CA 2521729 and US 2008/0229448) are plants, which show increased tolerance to abiotic stress conditions such as drought, high salinity, high light intensities, high UV irradiation, chemical pol- lution (such as high heavy metal concentration), low or high temperatures, limitied supply of nutrients (i.e. nitrogen, phosphorous) and population stress. Preferably, transgenic plants with resistance to stress conditions, are selected from rice, corn, soybean, sugarcane, alfalfa, wheat, tomato, potato, barley, rapeseed, beans, oats, sorghum and cotton with tolerance to drought (see e.g. WO 2005/048693, WO 2008/002480 and WO 2007/030001); corn, soybean, wheat, cotton, rice, rapeseed and alfalfa with tolerance to low temperatures (see e.g. US 4731499 and WO 2007/1 12122); rice, cotton, potato, soybean, wheat, barley, rye, sorghum, alfalfa, grape, tomato, sunflower and tobacco with tolerance to high salinity (see e.g. US 7256326, US
7034139, WO 2001/030990). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications men- tioned above. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, sugar beet, potato, oilseed rape, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, sugarcane, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat. Altered maturation properties, are for example delayed ripening, delayed softening and early maturity. Preferably, transgenic plants with modified maturation properties, are, selected from tomato, melon, raspberry, strawberry, muskmelon, pepper and papaya with delayed ripening (see e.g. US 5767376, US 7084321 , US 6107548, US 5981831 , WO 1995035387, US 5952546, US 5512466, WO 1997001952, WO 1992/008798, Plant Cell. 1989, 53-63. Plant Molecular Biology, 50, 2002). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Preferably, the plant is selected from fruits, such as tomato, vine, melon, papaya, banana, pepper, raspberry and strawberry; stone fruits, such as cherry, apricot and peach; pome fruits, such as apple and pear; and citrus fruits, such as citron, lime, orange, pomelo, grapefruit, and mandarinT more preferably from tomato, vine, apple, banana, orange and strawberry, most preferably tomatoes.
Content modification is synthesis of modified chemical compounds (if compared to the corre- sponding control plant) or synthesis of enhanced amounts of chemical (if compounds compared to the corresponding control plant) and corresponds to an increased or reduced amount of vitamins, amino acids, proteins and starch, different oils and a reduced amount of nicotine.
Commercial examples are the soybean varieties "Vistive II" and "Visitive III" with low- linolenic/medium oleic content; the corn variety "Mavera high-value corn" with increased lysine content; and the soybean variety "Mavera high value soybean" with yielding 5% more protein compared to conventional varieties when processed into soybean meal. Further transgenic plants with altered content are, for example, potato and corn with modified amylopectin content (see e.g. US 6784338, US 20070261136); canola, corn, cotton, grape, catalpa, cattail, rice, soybean, wheat, sunflower, balsam pear and vernonia with a modified oil content (see e.g. US 7294759, US7157621 , US 5850026, US 6441278, US 6380462, US 6365802, US 6974898, WO 2001/079499, US 2006/0075515 and US 7294759); sunflower with increased fatty acid content (see e.g. US 6084164); soybeans with modified allergens content (so called "hypoaller- genic soybean, see e.g. US 6864362); tobacco with reduced nicotine content (see e.g. US 20060185684, WO 2005000352 and WO 2007064636); canola and soybean with increased lysine content (see e.g. Bio/Technology 13, 1995, 577 - 582); corn and soybean with altered composition of methionine, leucine, isoleucine and valine (see e.g. US 6946589, US 6905877); soybean with enhanced sulfur amino acid content (see e.g. EP 0929685, WO 1997041239); tomato with increased free amino acid contents, such as asparagine, aspartic acid, serine, threonine, alanine, histidine and glutamic acid (see e.g. US 672741 1 ); corn with enhanced amino acid content (see e.g. WO 050771 17); potato, corn and rice with modified starch content (see e.g. WO 1997044471 and US 7317146); tomato,corn, grape, alfalfa, apple, beans and peas with modified flavonoid content (see e.g. WO 2000/04175); corn, rice, sorghum, cotton, soybeans with altered content of phenolic compounds (see e.g. US 20080235829). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, potato, tomato, oilseed rape, flax and cereals such as wheat, barley, rye and oat, most preferably soybean, maize (corn), rice, oilseed rape, potato, tomato, cotton, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
Enhanced nutrient utilization is e.g. assimilation or metabolism of nitrogen or phosphorous. Preferably, transgenic plants with enhanced nitrogen assimilatory and utilization capacities are selected from for example, canola, corn, wheat, sunflower, rice, tobacco, soybean, cotton, alfalfa, tomato, wheat, potato, sugar beet, sugar cane and rapeseed (see e.g. WO 1995/009911 , WO 1997/030163, US 6084153, US 5955651 and US 6864405). Plants with improved phosphorous uptake are, for example, tomato and potato (see e.g. US 7417181). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, potato, oilseed rape and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley.
Transgenic plants with male steriliy are preferably selected from canola, corn, tomato, rice, Indian mustard, wheat, soybean and sunflower (see e.g. US 6720481 , US 6281348, US 5659124, US 6399856, US 7345222, US 7230168, US 6072102, EP1 135982, WO 2001/092544 and WO 1996/040949). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley.
Further examples of deregulated or commercially available transgenic plants with modified genetic material being male sterile are
Brassica napus (Argentine Canola:(Event: MS1 , RF1 =>PGS1 ; Bayer CropScience (formerly Plant Genetic Systems); Brassica napus (Event: MS1 , RF2 =>PGS2 ; Bayer CropScience (formerly Plant Genetic Systems); Brassica napus (Event: MS8xRF3 ; Bayer CropScience (Aventis CropScience(AgrEvo)); Brassica napus (Event: PHY14, PHY35 ; Bayer CropScience (formerly Plant Genetic Systems); Brassica napus (Event: PHY36 ; Bayer CropScience (formerly Plant Genetic Systems); Cichorium intybus (Chicory:(Event: RM3-3, RM3-4, RM3-6 ; Bejo Zaden BV; Zea mays L. (Maize:(Event: 676, 678, 680 ; Pioneer Hi-Bred International Inc.; Zea mays L. (Event: MS3 ; Bayer CropScience (Aventis CropScience(AgrEvo)) and Zea mays L. (Event: MS6 ; Bayer CropScience (Aventis CropScience(AgrEvo)).
Plants, which produce higher quality fiber are e.g. transgenic cotton plants. The such improved quality of the fiber is related to improved micronaire of the fiber, increased strength, improved staple length, improved length unifomity and color of the fibers (see e.g. WO 1996/26639, US 7329802, US 6472588 and WO 2001/17333). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. As set forth above, cultivated plants may comprise one or more traits, e.g. selected from the group consisting of herbicide tolerance, insect resistance, fungal resistance, viral resistance, bacterial resistance, stress tolerance, maturation alteration, content modification, modified nutrient uptake and male sterility (see e.g. WO 2005033319 and US 6376754). Examples of commercial available transgenic plants with two combined properties are the corn varieties "YieldGard Roundup Ready" and YieldGard Roundup Ready 2" (Monsanto) with glyphosate tolerance and resistance to corn borer; the corn variety "Agrisure CB/LL" (Syntenta) with glufosinate tolerance and corn borer resistance; the corn variety "Yield Gard VT Root- worm/RR2" with glyphosate tolerance and corn rootworm resistance; the corn variety "Yield Gard VT Triple" with glyphosate tolerance and resistance against corn rootworm and corn borer; the corn variety "Herculex I" with glufosinate tolerance and lepidopteran resistance (Cryl F), i.e. against western bean cutworm, corn borer, black cutworm and fall armyworm; the corn variety "YieldGard Corn Rootworm/Roundup Ready 2" (Monsanto) with glyphosate tolerance and corn rootworm resistance; the corn variety "Agrisure GT/RW" (Syngenta) with gluphosinate tolerance and lepidopteran resistance (Cry3A), i.e. against western corn rootworm, northern corn root- worm and Mexican corn rootworm; the corn variety "Herculex RW" (Dow, Pioneer) with glufosinate tolerance and lepidopteran resistance (Cry34/35Ab1 ), i.e. against western corn rootworm, northern corn rootworm and Mexican corn rootworm; the corn variety "Yield Gard VT Rootworm/RR2" with glyphosate tolerance and corn rootworm resistance; the soybean variety "Optimum GAT" (DuPont, Pioneer) with glyphosate tolerance and ALS herbicide tolerance; the corn variety "Mavera high-value corn" with glyphosate tolerance, resistance to corn rootworm and European corn borer and high lysine trait.
Examples of commercial available transgenic plants with three traits are the corn variety "Herculex I / Roundup Ready 2" with glyphosate tolerance, gluphosinate tolerance and lepidopteran resistance (Cry1 F), i.e. against western bean cutworm, corn borer, black cutworm and fall armyworm; the corn variety "YieldGard Plus / Roundup Ready 2" (Monsanto) with glyphosate tolerance, corn rootworm resistance and corn borer resistance; the corn variety "Agrisure GT/CB/LL" (Syngenta) with tolerance to glyphosate tolerance, tolerance to gluphosinate and corn borer resistance; the corn variety "Herculex Xtra" (Dow, Pioneer) with glufosinate tolerance and lepidopteran resistance (Cry1 F + Cry34/35Ab1), i.e. against western corn rootworm, northern corn rootworm, Mecxican corn rootworm, western bean cutworm, corn borer, black cutworm and fall armyworm; the corn varieties "Agrisure CB/LL/RW" (Syngenta) with glufosinate tolerance, corn borer resistance (Cry1 Ab) and lepidopteran resistance (Cry3A), i.e. against western corn rootworm, northern corn rootworm and Mexican corn rootworm; the corn variety "Agrisure 3000GT" (Syngenta) with glyphosate tolerance + corn borer resistance (CrylAb) and lepidopteran resistance (Cry3A), i.e. against western corn rootworm, northern corn rootworm and Mexi- can corn rootworm. The methods of producing such transgenic plants are generally known to the person skilled in the art.
An example of a commercial available transgenic plant with four traits is„Hercules Quad-Stack" with glyphosate tolerance, glufosinate tolerance, corn borer resistance and corn rootworm resistance.
Second embodiment of the invention
In one embodiment of the invention, the commercial transgenic plant is a soybean variety with glyphosate tolerance and lepidopteran resistance, preferably with one trait of glyphosate tolerance and two traits of lepidopteran resistance. Preferably, the glyphosate tolerance is through expression of the EPSPS encoding gene from A. tumefaciens strain CP4, more preferably it is based on the transgenic event MON89788 (see A1 -14, T1-100). Also preferably, the lepidopteran resistance is a resistance to lepidopteran pests of soybean, preferably through express- sion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpil- lar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably it is based on the transgenic event MON87701.
More preferably, the glyphosate tolerance is based on the transgenic event MON89788 and the trait of lepidopteran resistance is achieved through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably based on the transgenic event
MON87701. Pseudoplusia includens is a synonym for Chrysodeixis includens.
Most preferably, the commercial transgenic plant is "Intacta R2 PRO" soybean (Monsanto) which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soybean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential. It is understood that "Intacta RR2 Pro" is used as a synonym for "Intacta™ Roundup Ready™ 2 Pro" soybean variety. Therefore, in one embodiment, the invention relates to methods according to the invention wherein the cultivated plant is a soybean variety with glyphosate tolerance and lepidopteran resistance.
In a further embodiment, the invention relates to methods according to the invention, wherein the glyphosate tolerance is through the expression of the cp4epsps gene, or wherein the lepi- dopteran resistance is through expresssion of the CrylAC encoding gene from B. thuringiensis, or wherein both the glyphosate tolerance is through the expression of the cp4epsps gene and the lepidopteran resistance is through expresssion of the CrylAC encoding gene from B. thuringiensis.
In a further embodiment, the invention relates to methods according to the invention, wherein the glyphosate tolerance is based on the transgenic event MON89788, or wherein the lepidopteran resistance is based on the transgenic event MON87701 , or wherein both the glyphosate tolerance is based on the transgenic event MON89788 and the lepidopteran resistance is based on the transgenic event MON87701.
In a further embodiment, the invention relates to methods according to the invention, wherein the lepidopteran resistance is against a species selected from the group of velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens).
In a further embodiment, the invention relates to methods according to the invention, wherein the cultivated plant is "Intacta RR2 PRO" soybean (Monsanto), which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soy- bean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential.
In a further embodiment, the invention relates to such methods according to the invention, wherein the pest is selected from the group of stinkbug species (preferably Euschistus heros), Spodoptera frugiperda and Helicoverpa.
In another embodiment, the commercial transgenic plant is a soybean variety selected from "Roundup Ready 2 Yield", "Intacta RR2 Pro" and "Vistive Gold" (all Monsanto), or "Stearidonic Acid (SDA) Omega-3" (higher content of SDA in soybean, Monsanto). In another embodiment, the trait is Bacillus thuringiensis Cry1A.105 and cry2Ab2 and Vector PV-GMIR13196, for Mon87751 soybean (Monsanto).
In a further embodiment, the commercial transgenic plant is a soybean variety with herbicide tolerance and lepidopteran resistance, wherein the control of Lepidopteran pest is based on Bt Cry1 Ac and Cry1 F toxins. Preferably, the insect-resistant and herbicide-tolerant soybean is DAS81419 (see Table A1 , entry A1 -334).
preferably with one trait of glyphosate tolerance and two traits of lepidopteran resistance. Preferably, the glyphosate tolerance is through expression of the EPSPS encoding gene from A. tumefaciens strain CP4, more preferably it is based on the transgenic event MON89788 (see A1-14, T1-100). Also preferably, the lepidopteran resistance is a resistance to lepidopteran pests of soybean, preferably through expresssion of the Cry1 AC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably it is based on the transgenic event MON87701. More preferably, the glyphosate tolerance is based on the transgenic event MON89788 and the trait of lepidopteran resistance is achieved through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably based on the transgenic event
MON87701. Pseudoplusia includens is a synonym for Chrysodeixis includens.
Most preferably, the commercial transgenic plant is "Intacta RR2 PRO" soybean (Monsanto) which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soybean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential.
In a further embodiment, the commercial transgenic plant is a corn variety which has above- ground insect protection from "Genuity VT Triple PRO" or "Herculex Xtra" or both of them, and herbicide tolerance from "Roundup Ready 2" and Liberty Link, preferably corn varieties selected from "Genuity SmartStax", "Genuity VT Triple PRO" and "Genuity VT Double PRO" (all Monsan- to), optionally as RIB (refuge-in-bag) solution. In a further embodiment, the commercial transgenic corn plant variety has a drought tolerance trait, preferably "Genuity DroughtGard". In another embodiment, the trait is double-stranded ribonucleic acid (dsRNA), Bacillus thuringiensis Cry3Bb1 protein and vector PV-ZMIR10871 for MON87411 corn. In a further embodiment, the commercial transgenic plant is a cotton variety selected from "Boll- gard II" (insect protection), "Roundup Ready Flex" (herbicide tolerance) and "Bollgard II with Roundup Ready Flex" (both), all Monsanto.
Preferably, the cultivated plants are plants, which comprise at least one trait of insect resistance (preferably by expression of bacterial toxins) and at least one trait selected from
herbicide tolerance,
fungal resistance or viral resistance or bacterial resistance by expression of antipathogenic substances stress tolerance,
content modification of chemicals present in the cultivated plant compared to the corresponding control plant.
Most preferably, the cultivated plants are plants, which are tolerant to the action of herbicides and plants, which express bacterial toxins, which provides resistance against animal pests (such as insects or arachnids or nematodes), wherein the bacterial toxin is preferably a toxin from Bacillus thuriginensis. Herein, the plant is preferably selected from cotton, rice, maize, wheat, barley, rye, oat, soybean, potato, vine, apple, pear, citron and orange.
In one embodiment, the plant is soybean.
In one embodiment, the invention relates to a method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification as compared to the respective non-modified control plant, wherein the plant is soybean, which method comprises applying a compound of formula I.
In an utmost preferred embodiment, the cultivated plants are plants, which are tolerant to the action of herbicides. Further guidance for specific combinations within this utmost preferred embodiment can be found in Table 1.
If such plants are used in the methods according to the present invention, the compound of formula I and its mixtures may additionally comprise a herbicide III, to which the plant is tolerant. For example, if the cultivated plant is a cultivated plant tolerant to glyphosate, the compound of formula I and its mixtures may additionally comprise glyphosate.
For example, if the cultivated plant is a cultivated plant tolerant to glufosinate, the compound of formula I and its mixtures may additionally comprise glufosinate.
For example, if the cultivated plant is a cultivated plant tolerant to a imidazolione herbicide, the compound of formula I and its mixtures may additionally comprise at least one imidazolione- herbicide. Herein, the imidazolionone-herbicide is selected from imazamox, imazethapyr, , ima- zapic, imazapyr, imazamethabenz or imazaquin.
For example, if the cultivated plant is a cultivated plant tolerant to dicamba, the compound of formula I and its mixtures may additionally comprise dicamba.
For example, if the cultivated plant is a cultivated plant tolerant to sethoxidim, the compound of formula I and its mixtures may additionally comprise sethoxidim.
For example, if the cultivated plant is a cultivated plant tolerant to cycloxidim, the compound of formula I and its mixtures may additionally comprise cyloxidim. Thus, the present invention also relates to ternary mixtures, comprising a compound of formula I, an insecticide II and a herbicide III. In particular, the present invention also relates to ternary mixtures comprising two insecticides and a fungicide.
In another particular embodiment, the present invention also relates to ternary mixtures comprising two fungicides and one insecticide.
In another particular embodiment, the present invention also relates to ternary mixtures comprising an insectide, a fungicide and a herbicide. In one embodiment of the invention the cultivated plant is selected from the group of plants as mentioned in the paragraphs and tables of this disclosure, preferably as mentioned above. Preferably, the cultivated plants are plants, which comprise at least one trait selected from herbicide tolerance, insect resistance for example by expression of one or more bacterial toxins, fungal resistance or viral resistance or bacterial resistance by expression of one or more anti- pathogenic substances, stress tolerance, nutrient uptake, nutrient use efficiency, content modification of chemicals present in the cultivated plant compared to the corresponding control plant.
More preferably, the cultivated plants are plants, which comprise at least one trait selected from herbicide tolerance, insect resistance by expression of one or more bacterial toxins, fungal resistance or viral resistance or bacterial resistance by expression of one or more antipathogenic substances, stress tolerance, content modification of one or more chemicals present in the cultivated plant compared to the corresponding control plant. Most preferably, the cultivated plants are plants, which are tolerant to the action of herbicides and plants, which express one or more bacterial toxins, which provides resistance against one or more animal pests (such as insects or arachnids or nematodes), wherein the bacterial toxin is preferably a toxin from Bacillus thuriginensis. Herein, the cultivated plant is preferably selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, potato, oilseed rape, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), cotton, rice and cereals such as wheat, barley, rye and oat.
In another utmost preference, the cultivated plants are plants, which are given in table 1.
Sources: AgBios database and GMO-compass database (AG BIOS, P.O. Box 475, 106 St. John St. Merrickville, Ontario KOG1 NO, Canada, access: http://cera-gmc.org/, also see Bio- Techniques, Volume 35, No. 3, Sept. 2008, p. 213, and http://www.gmo- compass.org/eng/gmo/db/).
Thus, in one preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with the compound of formula I and its mixtures, wherein the plant is a plant, which is rendered tolerant to herbicides, more preferably to herbicides such as glutamine synthetase inhibitors, 5-enol-pyrovyl- shikimate-3-phosphate-synthase inhibitors, acetolactate synthase (ALS) inhibitors, protoporphy- rinogen oxidase (PPO) inhibitors, auxine type herbicides, most preferably to herbicides such as glyphosate, glufosinate, imazapyr, imazapic, imazamox, imazethapyr, imazaquin, imaza- methabenz methyl, dicamba and 2,4-D.
In a more preferred embodiment, the present invention relates to a method of controlling harm- ful pests, especially insects, by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with the compound of formula I, wherein the plant corresponds to a row of table A1. Furthermore, the invention relates to a method for increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with the compound of formula I, wherein the plant corresponds to a row of table A1.
Table A1
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
In a special embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with the compound of formula I and its mixtures, wherein the plant is a plant, which express at least one insecticidal toxin, pref- erably a toxin from Bacillus speicies, more preferably from Bacillus thuringiensis.
In one embodiment, these are the insecticidal traits, against which the insects to be controlled are resistant in the methods of the first embodiment of the present invention.
In another embodiment, these are the traits, which have not yet been described in a trait combination for the the compound of formula (I) and its mixtures, accordingt to the second or third embodiment of the invention.
In a more preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating plant propagation materials, preferably seeds with the compound of formula I or its mixtures as defined above, prefera- bly wherein the plant corresponds to a row of table A2 or table 3.
In another more preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I and its mixtures wherein the plant corresponds to a row of table A2 or table 3.
In a most preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I and its mixtures, wherein the plant corresponds to a row of table A2 or table 3.
In a most preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation materials, preferably seeds of cultivated plants of cultivated crops with the compound of formula I and its mixtures, wherein the plant corresponds to a row of table A2 or table 3.
Table A2
No description transgenic plant literature / commercial
event plants
Lepidoptera re281 -24-236 Gossypium hirsu- available, DOW Agro-
A2-1 sistance (DAS- tum L. (cotton) Sciences LLC
24236-5)
Lepidoptera re281 -24-236 Gossypium hirsu- available, Dow Agro-
A2-2 sistance x 3006-210- tum L. (cotton) Sciences
23
Lepidoptera re3006-210- Gossypium hirsu- available, DOW Agro-
A2-3
sistance 23 (DAS- tum L. (cotton) Sciences LLC
Lepidoptera reCOT102 Gossypium hirsu- available, Syngenta
A2-4
sistance (SYN- tum L (cotton) Seeds, Inc.
Figure imgf000106_0001
Figure imgf000107_0001
dopteran pests tum L. (Cotton) Seeds
Table 3
Literature / commer¬
No detailed description [Event] plant
cial plants
T3-1 corn rootworm resistance maize B*
T3-2 corn borer resistance maize C*
T3-3 western bean cutworm resistance maize D*
T3-4 black cutworm resistance maize E*
„Herculex I" (Dow,
T3-5 fall armyworm resistance maize Pioneer),„Herculex
Xtra" (Dow, Pioneer)
"Bollgard I" (Monsan¬
T3-6 tobacco budworm resistance cotton
to), E*
T3-7 cotton bollworm resistance cotton E*
T3-8 fall armyworm resistance cotton E*
T3-9 beet armyworm resistance cotton E*
T3-10 cabbage looper resistance cotton E*
T3-1 1 soybean lopper resistance cotton E*
T3-12 pink bollworm resistance cotton E*
T3-13 rice stemborer resistance rice A*
T3-14 striped rice borer resistance rice A* Literature / commer¬
No detailed description [Event] plant
cial plants
T3-15 rice leaf roller resistance rice A*
T3-16 yellow stemborer resistance rice A*
T3-17 rice skipper resistance rice A*
T3-18 rice caseworm resistance rice A*
T3-19 rice cutworm resistance rice A*
T3-20 rice armyworm resistance rice A*
brinjal fruit and shoot borer re¬
T3-21 eggplant F*
sistance
T3-22 cotton bollworm resistance eggplant F*"
T3-23 tobacco hornworm resistance potato D*
US 5349124
T3-24 lepidopteran resistance lettuce
T3-25 lepidopteran resistance soybean US 7432421
A* refers to„Zhuxian B", WO2001021821 , Molecular Breeding, Volume 18, Number 1 / August 2006.
B* "YieldGard corn rootworm" (Monsanto), "YieldGard Plus" (Monsanto), "YieldGard VT" (Monsanto), "Herculex RW" (Dow, Pioneer), "Herculex Rootworm" (Dow, Pioneer), "Agrisure OCRW" (Syngenta)
C* "YieldGard corn borer" (Monsanto),„YieldGard Plus" (Monsanto),„YieldGard VT Pro" (Monsanto), "Agrisure CB/LL" (Syngenta), "Agrisure 3000GT" (Syngenta), "Hercules I", "Hercules II" (Dow, Pioneer), "KnockOut" (Novartis),„NatureGard" (Mycogen),„StarLink" (Aventis)
D*"NewLeaf" (Monsanto), "NewLeaf Y" (Monsanto), "NewLeaf Plus" (Monsanto), US6100456 E* "Bollgard II" (Monsanto),„WideStrike" (Dow),„VipCot" (Syngenta)
F* US 5128130, "Bt brinjal", "Dumaguete Long Purple", "Mara"
First embodiment of the invention
In the cases, where the cultivated plant has an arthropodicidal, preferably insecticidal, trait, it often occurs that the pest that should be combatted becomes resistant to that trait.
Resistance may be defined as 'a heritable change in the sensitivity of a pest population that is reflected in the repeated failure of a product to achieve the expected level of control when used according to the label recommendation for that pest species'. (IRAC) Resistance therefore means that the original activitiy of a pesticide against the target organisms (arthropods, insects) decreases or is even lost, due to genetic or metabolic adaptation of the target organism.
"Resistant" to an insecticide is understood to mean resistant to at least one insecticide or insecticidal trait, i.e. the insect may be resistant to only one, but also to several insecticides or insecticidal traits.
In the present context of cultivated plants with at least one insecticidal trait, the resistance is against an insecticidal effect which is due to a genetic modification of a plant (modified or transgenic plant), which caused a resistance of the plant or crop to certain pests, especially insect pests, in susceptible insects. This is to be understood to include plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those mentioned herein, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., and so on.
Therefore, in a most preferred embodiment, the present invention relates to a method of control- ling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant has at least one insecticidal trait, and wherein the harmful insects are resistant to that at least one insecticidal trait of the plant.
Preferably, the present invention relates to a method of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant has at least one lepidopteran or coleopteran trait, and wherein the harmful insects are resistant to that lepidopteran or coleopteran insecticidal trait of the plant.
In particular, the present invention relates to a method of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant having the insecticidal trait corresponds to a row of table A2 or Table 3 or Table A1 , and wherein the harmful insects are resistant to an insecticidal trait of the plant.
In a further embodiment, the invention relates to such methods according to the invention, wherein the pest is selected from the group of stinkbug species (preferably Euschistus heros), Spodoptera frugiperda and Helicoverpa.
It is to be understood, that also in the mentioned methods of controlling resistant insects, the compound of formula (I) may optionally be mixed with one or more further pesticides.
Methods and uses of the invention as described herein may also involve a step of assessing whether insects are resistant to certain insecticides. This step will in general involve collecting a sample of insects from the area (e.g. crop, field, habitat) to be treated, before actually applying a compound of formula (I), and testing (for example using any suitable phenotypic, biochemical or molecular biological technique applicable) for resistance/sensitivity.
Apart from the traits and events that the plants have in the methods according to the invention, the plants may have more traits and/or events, e.g. those described in Table A1.
In a particularly preferred embodiment, the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with c the compound of formula (I) and its mixtures, wherein the plant is a lepidopteran insect resistant soybean, which has been modified by introducing at least one gene or at least one gene combination, which corresponds to a row of table C. Table C
Figure imgf000110_0001
The present invention also relates to a method for controlling pests and/or increasing the plant health of a cultivated plant as compared to the respective non-modified control plant, comprising the application of the compound of formula (I) and its mixtures, to a plant with at least one modi- fication, parts of such plant, plant propagation material, or at its locus of growth, wherein the cultivated plant is
(i) Gossypium hirsutum L. (cotton) or Zea mays L. (maize) and comprises at least one gene selected from the group consisting of dvsnf7, cry1A, cry1Ab-Ac, cryl C, cry2Ab2, cry2Ae, mocryl F; or
(ii) Glycine max L. (soybean), Triticum aestivum (wheat) or Oryza sativa L. (rice) and comprises at least one gene selected from the group consisting of cry34Ab1 , cry35 Ab1 , cry3A, cry3Bb1 , dvsnf7, mcry3A, crylA, cry1A.105, crylAb, cry1Ab-Ac, crylAc, crylC, cryl F, cry1 Fa2, cry2Ab2, cry2Ae, cry9c, mocryl F, pinll, vip3A(a), vip3Aa20.
Table D2
No. crop gene No. crop gene
D2-1 cotton dvsnf7 D2-5 cotton cry2Ab2
D2-2 cotton crylA D2-6 cotton cry2Ae
D2-3 cotton cry1Ab-Ac D2-7 cotton mocryl F
D2-4 cotton cryl C D2-8 maize dvsnf7 No. crop gene No. crop gene
D2-9 maize crylA D2-44 wheat crylAb
D2-10 maize cry1Ab-Ac D2-45 wheat cry1Ab-Ac
D2-11 maize cry1 C D2-46 wheat cry 1 Ac
D2-12 maize cry2Ab2 D2-47 wheat cryl C
D2-13 maize cry2Ae D2-48 wheat cryl F
D2-14 maize mocryl F D2-49 wheat cry1 Fa2
D2-15 soybean cry34Ab1 D2-50 wheat cry2Ab2
D2-16 soybean cry35 Ab1 D2-51 wheat cry2Ae
D2-17 soybean cry3A D2-52 wheat cry9c
D2-18 soybean cry3Bb1 D2-53 wheat mocryl F
D2-19 soybean dvsnf7 D2-54 wheat pinll
D2-20 soybean mcry3A D2-55 wheat vip3A(a)
D2-21 soybean crylA D2-56 wheat vip3Aa20
D2-22 soybean cry1A.105 D2-57 rice cry34Ab1
D2-23 soybean crylAb D2-58 rice cry35 Ab1
D2-24 soybean cry1Ab-Ac D2-59 rice cry3A
D2-25 soybean crylAc D2-60 rice cry3Bb1
D2-26 soybean cry1 C D2-61 rice dvsnf7
D2-27 soybean cryl F D2-62 rice mcry3A
D2-28 soybean cryl Fa2 D2-63 rice crylA
D2-29 soybean cry2Ab2 D2-64 rice cry1A.105
D2-30 soybean cry2Ae D2-65 rice crylAb
D2-31 soybean cry9c D2-66 rice cry1Ab-Ac
D2-32 soybean mocryl F D2-67 rice cry 1 Ac
D2-33 soybean pinll D2-68 rice cryl C
D2-34 soybean vip3A(a) D2-69 rice cryl F
D2-35 soybean vip3Aa20 D2-70 rice cry1 Fa2
D2-36 wheat cry34Ab1 D2-71 rice cry2Ab2
D2-37 wheat cry35 Ab1 D2-72 rice cry2Ae
D2-38 wheat cry3A D2-73 rice cry9c
D2-39 wheat cry3Bb1 D2-74 rice mocryl F
D2-40 wheat dvsnf7 D2-75 rice pinll
D2-41 wheat mcry3A D2-76 rice vip3A(a)
D2-42 wheat crylA D2-77 rice vip3Aa20
D2-43 wheat cry1A.105
Further preferred embodiments of the invention are those methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I or its mixtures, wherein the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1.
In a more preferred embodiment, the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I or its mixtures, wherein the mixing partner of the compound of formula I is fipronil and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1.
In a more preferred embodiment, the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I or its mixtures, wherein the mixing partner of the compound of formula I is ethiprole and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1.
In a more preferred embodiment, the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I or its mixtures, wherein the mixing partner of the compound of formula lcompound is chlorfenapyr and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1.
Therefore, further embodiments of the invention are those methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with a compound of formula (I) or a mixture thereof according to the in- vention, wherein the plant expresses one or more genes selected from aad, ACCase, ALS, AMY797E, APH4, bar, barnase, barstar, bla, bxn, cDHDPS, CP, cmv-cp, CrylAb, CrylAc, Cry1A.105, Cryl F, Cry1 Fa2, Cry2Ab, Cry34Ab1 , Cry35Ab1 , Cry3A, Cry3Bb1 , Cry9C, dam, DHFR, fad2, fanl , FH, flcrylAb, GAT4601 , GAT4602, gmFAD2-1 , GM-HRA, goxv247, gus, hel, mCry3A, nos, NPTII, pat, PG, pinll, PMI, prsv-cp, QTPASE, rep, SAMase, spc, TE, vip3A, vip3A(a), wmv2-cp and zymv-cp.
Examples
The present invention is now illustrated in further detail by the following examples.
As stated above, the the compound of formula (I) can be prepared according to standard methods of organic chemistry, or by the processes as described in WO 2007/006670,
WO2013/024007, WO2013/024008, WO2013/076092, and the unpublished applications PCT/EP2014/056164, EP13173044.2, PCT/EP2014/060082, and EP14166089.4 d, without be- ing limited to the routes given therein.
The characterization can be done by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points. B. Biology
Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The pres- ence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. ., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):
When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.
The following tests can demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific pests. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to the species described. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests. The analysis of synergism or antagonism between the mixtures or compositions is determined using Colby's equation.
B1 : Test on GMO soybeans
Trial is carried out under greenhouse conditions on soybean (GMO plant variety, e.g. roundup, growth stage 109). 12 treatments are compared in a complete randomized blocks (4 replications) with plot size of 1 m x 3 meters. Only selected plants are considered for artificial infestation and evaluations.
Due to glyphosate timing for application on GMO-soybeans, all treatments are applied in older plants (GS 109) otherwise a significant phytotoxicity is expected. Application is done, using 400 l/ha. All treatments are applied using a C02 backpack (nozzle type TXVK-10). Temperature at the time of applications is around 25 to 30 °C and air humidity is between 30 and 100%. Soil condition is e.g. R4 (when <75% of surface is dried up) and the moisture is moist (normal). Roundup Original ® (Glyfosate-sal isopropilamina @360g/L) is used in the rate of 867 g a.i./ha. Artificial infestation is done one day after the application. The species used is Anticarsia gem- matalis (Hubner) [ Thermesia elegantula (Herrich-Schaffer, 1869)], Noctuidae. 5 plants/plot are infested with 3 larvae (stage L2) using a entomological metallic tweezers, totaling 15 larvae per repetition. Larvae used in this trial are e.g. provided by BASF rearing laboratory, Campinas, Brazil.
A second infestation is held seven days after application in the same plants and using the same larval numbers. A third infestation might be done if necessary in order to observe residual activity- The mortality (number) and eating damage (%) are evaluated with 01 , 02, 05, 07, 14 and 21 DAA (days after application), comparing to untreated control plants.
Increased mortalities in combination with the application of roundup can be observed when compared to the untreated control plants:
Additionally, after 5 days after application at 12.5 g a.i./ha a reduction of feeding damage compared to the untreated controls can be observed. In another test, a non-GM soybean variety is treated with 12.5 g a.i./ha and showed less reduction in feeding damage compared to the untreated controls.

Claims

Claims
1. A method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification as compared to the respective non-modified control plant, comprising the application of at least one pesticide to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, wherein the pesticide is a pesticide compound of formula (I):
Figure imgf000115_0001
or a stereoisomer, salt, tautomer or N-oxide, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof, or a mixture of the compound of formula I.
Method according to claim 1 , wherein the cultivated plant is a soybean variety with glyphosate tolerance and lepidopteran resistance.
Method according to any of claims 1 or 2, wherein the glyphosate tolerance is through the expression of the cp4epsps gene, or wherein the lepidopteran resistance is through ex- presssion of the CrylAC encoding gene from B. thuringiensis, or wherein both the glyphosate tolerance is through the expression of the cp4epsps gene and the lepidopteran resistance is through expresssion of the CrylAC encoding gene from B. thuringiensis.
Method according to any of claims 1 to 3, wherein the glyphosate tolerance is based on the transgenic event MON89788, or wherein the lepidopteran resistance is based on the transgenic event MON87701 , or wherein both the glyphosate tolerance is based on the transgenic event MON89788 and the lepidopteran resistance is based on the transgenic event MON87701.
Method according to any of claims 1 to 4, wherein the lepidopteran resistance is against a species selected from the group of velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens, Chrvsodeixis includens ).
The method according to any of claims 1 to 5, wherein the cultivated plant is "Intacta RR2 PRO" soybean (Monsanto), which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soybean looper, soybean budborer, bean shoot borer, bollworm, com stalk borer, Helicoverpa, e.g. Helicoverpa ar- migera), along with increased yield potential.
7. Method according to any of claims 1 to 6, wherein the plant has at least one insecticidal trait, and wherein the pests are harmful insects which are resistant to that at least one insecticidal trait of the plant.
8. The method according to any of claims 1 to 7, wherein the pest is selected from the group of stinkbug species (preferably Euschistus heros), Spodoptera frugiperda and Helicoverpa.
9. The method according to any of claims 1 to 8, wherein the yield of a cultivated plant is increased.
10. The method according to any of claims 1 to 9, comprising the application of a mixture of a pesticide of formula I and at least one pesticide II to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth.
11. The method according to claim 10, wherein the pesticide II is selected from the group of fipronil, alpha-cypermethrin, dinotefuran, chlorfenapyr, teflubenzuron and sulfoxaflor.
12. The method according to any of claims 1 to 10, additionally comprising the application of a herbicide, to which the plant is tolerant.
13. The method according to any of claims 1 to 1 1 , wherein the at least one pesticide is applied to the plant propagation material of the cultivated plant.
14. The method according to any of claims 1 to 1 1 , wherein the treatment(s) are carried out by applying at least one pesticide to the cultivated plant, parts of the cultivated plant or to their habitat.
15. Seed of a cultivated plant as defined in any one of claims 1 to7 treated with at least one pesticide as defined in claim 1 .
PCT/EP2016/055457 2015-03-16 2016-03-14 Use of cyclaniliprole on cultivated plants WO2016146586A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15159229.2 2015-03-16
EP15159229 2015-03-16

Publications (1)

Publication Number Publication Date
WO2016146586A1 true WO2016146586A1 (en) 2016-09-22

Family

ID=52684098

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/055457 WO2016146586A1 (en) 2015-03-16 2016-03-14 Use of cyclaniliprole on cultivated plants

Country Status (1)

Country Link
WO (1) WO2016146586A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107089989A (en) * 2017-05-25 2017-08-25 海南大学 A kind of new and effective insecticide and preparation method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006040113A2 (en) * 2004-10-11 2006-04-20 Syngenta Participations Ag Heterocyclic diamide insecticidal agents
WO2014128188A1 (en) * 2013-02-20 2014-08-28 Basf Se Anthranilamide compounds, their mixtures and the use thereof as pesticides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006040113A2 (en) * 2004-10-11 2006-04-20 Syngenta Participations Ag Heterocyclic diamide insecticidal agents
WO2014128188A1 (en) * 2013-02-20 2014-08-28 Basf Se Anthranilamide compounds, their mixtures and the use thereof as pesticides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107089989A (en) * 2017-05-25 2017-08-25 海南大学 A kind of new and effective insecticide and preparation method

Similar Documents

Publication Publication Date Title
EP3255990B1 (en) Pesticidal mixture comprising a pyrazole compound, an insecticide and a fungicide
CA2989253C (en) Pesticidal compositions comprising a triazole compound
AU2017295593B2 (en) Pesticidally active mixtures
WO2016038067A1 (en) Use of afidopyropene in genetically modified plants
US10440953B2 (en) Control of pests in maize by ginkgolides and bilobalide
US20190008162A1 (en) Control of pests in cotton by ginkgolides and bilobalides
WO2016162371A1 (en) Use of an insecticidal carboxamide compound against pests on cultivated plants
EP3329777A1 (en) Pesticidal mixtures
WO2016091674A1 (en) Use of cyclaniliprole on cultivated plants
US10959431B2 (en) Pesticidal mixtures
EP3628157A1 (en) Method of controlling insecticide resistant insects and virus transmission to plants
US11297837B2 (en) Pesticidally activi mixtures comprising anthranilamide compounds
US20190307127A1 (en) Pesticidal Mixtures
EP3522709A1 (en) Pesticidal mixture
EP3908584B1 (en) Crystalline forms of 1-(1,2-dimethylpropyl)-n-ethyl-5-methyl-n-pyridazin-4-yl-pyrazole-4-carboxamide
EP3269246A1 (en) Pesticidal mixtures
WO2016146586A1 (en) Use of cyclaniliprole on cultivated plants
US20200383333A1 (en) New agrochemical formulations
WO2018015843A1 (en) Pesticidally active mixtures comprising afidoypropen
WO2016030108A1 (en) Use of chlorfenapyr and teflubenzuron on genetically modified plants
BR112017021450B1 (en) PEST CONTROL METHODS, PLANT HEALTH IMPROVEMENT METHOD AND COATED SEED

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16711191

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16711191

Country of ref document: EP

Kind code of ref document: A1