WO2014079766A1 - Mélanges pesticides - Google Patents

Mélanges pesticides Download PDF

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Publication number
WO2014079766A1
WO2014079766A1 PCT/EP2013/073809 EP2013073809W WO2014079766A1 WO 2014079766 A1 WO2014079766 A1 WO 2014079766A1 EP 2013073809 W EP2013073809 W EP 2013073809W WO 2014079766 A1 WO2014079766 A1 WO 2014079766A1
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WO
WIPO (PCT)
Prior art keywords
methyl
chloro
phenyl
inhibitors
compound
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PCT/EP2013/073809
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English (en)
Inventor
Lutz Brahm
Burghard Liebmann
Ronald Wilhelm
Markus Gewehr
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Basf Se
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Publication of WO2014079766A1 publication Critical patent/WO2014079766A1/fr

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    • 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
    • A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
    • A01N63/20—Bacteria; Substances produced thereby or obtained therefrom
    • A01N63/22—Bacillus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention relates to synergistic mixtures comprising as active components
  • Inhibitors of complex III at Qo site e.g. strobilurins: azoxystrobin, coumeth- oxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysa- strobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystro- bin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-me- thoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb
  • inhibitors of complex III at Qi site cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8- benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5- dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymeth- oxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
  • inhibitors of complex II e. g. carboxamides: benodanil, bixafen, boscalid, car- boxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepro- nil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-car- boxamide, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole- 4-carboxamide, N-[9-(dichloromethylene)-1 ,2,3,4-tetrahydro-1 ,4-methanonaphtha- len-5
  • respiration inhibitors e.g. complex I, uncouplers: diflumetorim, (5,8-di- fluoroquinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ - amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam; B) Sterol biosynthesis inhibitors (SBI fungicides)
  • SBI fungicides Sterol biosynthesis inhibitors
  • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, biterta- nol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutra- zole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole,
  • Delta14-reductase inhibitors aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, ofurace, oxadixyl;
  • hymexazole octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)- pyrimidin-4-amine;
  • tubulin inhibitors benomyl, carbendazim, fuberidazole, thiabendazole, thi- ophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1 -yl)- 6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine;
  • diethofencarb diethofencarb, ethaboxam, pencycuron, fluopico- lide, zoxamide, metrafenone, pyriofenone;
  • methionine synthesis inhibitors anilino-pyrimidines: cyprodinil, mepanipyrim, pyrimethanil;
  • blasticidin-S blasticidin-S, kasugamycin, kasugamycin hydro- chloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
  • - MAP / histidine kinase inhibitors fluoroimid, iprodione, procymidone, vinclo- zolin, fenpiclonil, fludioxonil;
  • G protein inhibitors quinoxyfen
  • Phospholipid biosynthesis inhibitors edifenphos, iprobenfos, pyrazophos, iso- prothiolane;
  • lipid peroxidation dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
  • phospholipid biosynthesis and cell wall deposition dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate, N-(1 -(1 -(4-cy- ano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
  • fatty acid amide hydrolase inhibitors 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihy- dro-3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyr- azol-1 -yl]ethanone;
  • inorganic active substances Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
  • thio- and dithiocarbamates ferbam, mancozeb, maneb, metam, metiram, pro- pineb, thiram, zineb, ziram;
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexa- chlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-
  • guanidines and others guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine- tris(albesilate), dithianon, 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole- 1 ,3,5,7(2H,6H)-tetraone;
  • inhibitors of glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
  • insecticidal compound IB selected from the group consisting of
  • aldicarb aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, car- baryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodi- carb, thiofanox, trimethacarb, XMC, xylylcarb, and triazamate;
  • O-(methoxyaminothio-phosphoryl) salicylate isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxy- demeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, teme- phos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;
  • fiproles phenylpyrazoles: ethiprole, fipronil, flufiprole, pyrafluprole, or pyriprole;
  • M-3 sodium channel modulators from the class of pyrethroids acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopen- tenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda- cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cyperme- thrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empen- thrin, esfenvalerate, etofenprox, fenpropathrin
  • M-4 nicotinic acteylcholine receptor agonists from the class of neonicotinoids: acet- amiprid, chlothianidin, cycloxaprid, dinotefuran, flupyradifurone, imidacloprid, niten- pyram, sulfoxaflor, thiacloprid, thiamethoxam or the compound 1 -[(6-chloro-3-pyri- dyl)methyl]-7-methyl-8-nitro-5-propoxy-3,5,6,7-tetrahydro-2H-imidazo[1 ,2-a]pyridine, 1 -[(6-chloro-3-pyridyl)methyl]-2-nitro-1 -[(E)-pentylideneamino]guanidine (known from WO2013/003977);
  • M-7 juvenile hormone mimics hydroprene, kinoprene, methoprene, fenoxycarb or pyriproxyfen;
  • M-8 non-specific multi-site inhibitors methyl bromide and other alkyl halides, chloro- picrin, sulfuryl fluoride, borax or tartar emetic;
  • M-9 selective homopteran feeding blockers pymetrozine, flonicamid, pyrifluquina- zon, 2-(5-fluoro-3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)thiazole hydrofluoride;
  • M-10 mite growth inhibitors clofentezine, hexythiazox, diflovidazin or etoxazole;
  • M-1 1 inhibitors of mitochondrial ATP synthase diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, or tetradifon;
  • M-12 uncouplers of oxidative phosphorylation chlorfenapyr, DNOC, or sulfluramid;
  • M-14 inhibitors of the chitin biosynthesis type 0 (benzoylurea class):
  • M-15 inhibitors of the chitin biosynthesis type 1 buprofezin;
  • M-16 moulting disruptors cyromazine
  • M-17 Ecdyson receptor agonists methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;
  • Mitochondrial complex III electron transport inhibitors hydramethylnon, acequinocyl, flometoquin, fluacrypyrim or pyriminostrobin;
  • fenazaquin fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim, or rotenone;
  • one compound IC having plant growth regulator activity selected from the group consisting of:
  • Antiauxins clofibric acid, 2,3,5-tri-iodobenzoic acid;
  • - Ethylene modulators aviglycine, 1 -methylcyclopropene (1 -MCP), prohexadione, prohexadione calcium, trinexapac, trinexapac-ethyl;
  • abscisic acid abscisic acid, ancymidol, butralin, carbaryl, chlorphonium, chlor- propham, dikegulac, flumetralin, fluoridamid, fosamine, glyphosine, isopyrimol, jasmonic acid, maleic hydrazide, mepiquat, mepiquat chloride, mepiquat pentabo- rate, piproctanyl, prohydrojasmon, propham, 2,3,5-tri-iodobenzoic acid;
  • chlormequat chlormequat chloride, daminozide, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, metconazole;
  • Unclassified plant growth regulators / classification unknown amidochlor, benzoflu- or, buminafos, carvone, choline chloride, ciobutide, clofencet, cloxyfonac, cyanamide, cyclanilide, cycloheximide, cyprosulfamide, epocholeone, ethychlozate, ethylene, fenridazon, fluprimidol, fluthiacet, heptopargil, holosulf, inabenfide, karetazan, lead arsenate, methasulfocarb, pydanon, sintofen, triapenthenol;
  • Bacillus subtilis MBI600 as compound ID having the accession number NRRL B-50595;
  • Bacillus subtilis MBI600 (defined herein as compound ID) having the accession number NRRL B-50595 is deposited with the United States Department of Agriculture on Nov. 10, 201 1 under the strain designation Bacillus subtilis 1430. It has also been deposited at The National Collec- tions of Industrial and Marine Bacteria Ltd. (NCIB), Torry Research Station, P.O. Box 31 , 135 Abbey Road, Aberdeen, AB9 8DG, Scotland under accession number 1237 on December 22, 1986. Bacillus subtilis MBI600 is known as plant growth-promoting rice seed treatment from Int. J. Microbiol. Res. ISSN 0975-5276, 3(2) (201 1 ), 120-130 and further described e.g. in US 2012/0149571 A1. This strain MBI600 is commercially available as liquid formulation product Integral® (Becker-Underwood Inc., USA).
  • Bacillus amyloliquefaciens Several plant-associated strains of the genus Bacillus have been described as belonging to the species Bacillus amyloliquefaciens or Bacillus subtilis are used commercially to promote the growth and improve the health of crop plants (Phytopathology 96, 145-154, 2006). Recently, the strain MBI 600 has been re-classified as Bacillus amyloliquefaciens subsp. plantarum based on polyphasic testing which combines classical microbiological methods relying on a mixture of traditional tools (such as culture-based methods) and molecular tools (such as genotyping and fatty acids analysis).
  • Bacillus subtilis MBI600 (or MBI 600 or MBI-600) is identical to Bacil- lus amyloliquefaciens subsp. plantarum MBI600, formerly Bacillus subtilis MBI600.
  • Bacillus subitilis MBI 600 shall mean Bacillus amyloliquefaciens subsp. plantarum MBI600, formerly Bacillus subtilis MBI600.
  • Bacillus amyloliquefaciens and/or Bacillus subitlis are naturally occurring spore- forming bacteria found e.g. in soils or on plant surfaces all over the world.
  • the Bacillus subtilis strain MBI600 was isolated from a faba bean plant leaf surface growing at Nottingham University School of Agriculture, Sutton Bonington, United Kingdom.
  • Bacillus subtilis MBI 600 were cultivated using media and fermentation techniques known in the art, e.g. in Tryptic Soy Broth (TSB) at 27°C for 24-72 hrs.
  • the bacterial cells can be washed and concentrated (e.g. by centrifugation at room temperature for 15 min at 7000 x g).
  • bacterial cells preferably spores were suspended in a suitable dry carrier (e.g. clay).
  • a suitable liquid formulation cells, preferably spores, were re-suspended in a suitable liquid carrier (e.g. water-based) to the desired spore density.
  • the spore density number of spores per ml. was determined by identifying the number of heat- resistant colony-forming units (70°C for 10 min) on Trypticase Soy Agar after incubation for 18- 24 hrs at 37°C.
  • Bacillus subtilis MBI 600 is active in temperatures between 7°C and 52°C (Holtmann, G. & Bremer, E. (2004), J. Bacteriol. 186, 1683-1693).
  • Bacillus simplex strain ABU 288 (defined herein as compound II) having the accession number NRRL B-50340 is deposited with the United States Department of Agriculture on Jan. 19, 2010.
  • Bacillus simplex ABU 288 can be cultivated and prepared as described for Bacillus subtilis MBI 600.
  • the present invention relates to synergistic mixtures comprising Bacillus simplex strain ABU 288 as compound II having the accession number NRRL B-50340 and one compound IA.
  • the present invention furthermore relates to synergistic mixtures comprising Bacillus simplex strain ABU 288 as compound II having the accession number NRRL B-50340 and one compound IB.
  • the present invention furthermore relates to synergistic mixtures comprising Bacillus simplex strain ABU 288 as compound II having the accession number NRRL B-50340 and one com- pound IC.
  • the present invention furthermore relates to synergistic mixtures comprising Bacillus simplex strain ABU 288 as compound II having the accession number NRRL B-50340 and Bacillus sub- tilis MBI600 as compound ID having the accession number NRRL B-50595.
  • Bacillus simplex strain ABU 288 as compound II having the accession number NRRL B-50340
  • Bacillus sub- tilis MBI600 as compound ID having the accession number NRRL B-50595.
  • 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 or avoid unfavorable environmental or toxicolog- ical effects whilst still allowing effective pest control.
  • pests embrace animal pests, and harmful fungi.
  • compositions that improve plants a process which is commonly and hereinafter referred to as "plant health”.
  • insecticidal also denotes not only action against (or attac by) insects, but also against (by) arachnids and nematodes.
  • insecticidal also denotes not only action against (or attac by) insects, but also against (by) arachnids and nematodes.
  • simultaneous, that is joint or separate, application of the compound I and the compound II or successive application of the compound I and the compound II allows enhanced control of pests, that means harmful fungi or animal pests, compared to the control rates that are possible with the individual compounds (synergistic mixtures).
  • the present invention relates to the inventive mixtures having synergistically enhanced action of controlling harmful fungi.
  • the invention relates to a method for controlling pest, using the inventive mixtures having synergistically enhanced action for controlling pests and to the use of compound I and compound II for preparing such mixtures, and also to compositions comprising such mixtures, wherein such methods relate to foliar application.
  • the present invention relates to inventive mixtures having synergistically enhanced action of increasing the health of plants.
  • the invention relates to a method for improving the health of plants, using the in- ventive mixtures having synergistically enhanced action for improving the health of plants and to the use of compound I and compound II for preparing such mixtures, and also to compositions comprising such mixtures, wherein such methods relate to foliar application.
  • the present invention relates to a method for controlling pests and/or improving the health of plants, wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack are treated with an effective amount of an inventive mixture.
  • the present invention relates to a method for controlling pests, wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack are treated with an effective amount of an inventive mixture.
  • the present invention relates to a method for controlling harmful fungi, wherein the fungi, their habitat, breeding grounds, their locus or the plants to be protected against fungal attack are treated with an effective amount of an inventive mixture comprising compound IA and compound II.
  • the present invention relates to a method for controlling animal pests (insects, acarids or nematodes), wherein the animal pests (insects, acarids or nematodes), their habitat, breeding grounds, their locus or the plants to be protected against animal pest (insects, acarids or nematodes) attack are treated with an effective amount of an inventive mixture comprising compound IB and compound II.
  • the present invention relates to a method for improving the health of plants, wherein the plants are treated with an effective amount of an inventive mixture.
  • "pesticidally effective amount” means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or oth- erwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various mixtures / compositions used in the invention.
  • a pesticidally effective amount of the mixtures / compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • plant health effective amount denotes an amount of the inventive mixtures, which is sufficient for achieving plant health effects as defined herein below. More exemplary information about amounts, ways of application and suitable ratios to be used is given below. Again, the skilled artisan is well aware of the fact that such an amount can vary in a broad range and is dependent on various factors, e.g. the treated cultivated plant or material and the climatic conditions.
  • Healthier plants are desirable since they result among others in better yields and/or a better quality of the plants or crops, specifically better quality of the harvested plant parts. Healthier plants also better resist to biotic and/or abiotic stress. A high resistance against biotic stresses in turn allows the person skilled in the art to reduce the quantity of pesticides applied and consequently to slow down the development of resistances against the respective pesticides.
  • health of a plant or “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 increased yield, plant vigor, quality of harvested plant parts and tolerance to abiotic and/or biotic stress.
  • Each plant health indicator listed below which is selected from the groups consisting of yield, plant vigor, quality and tolerance of the plant to abiotic and/or biotic stress, is to be understood as a preferred embodiment of the present invention either each on its own or preferably in combination with each other.
  • "increased yield" of a plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the inventive mixture.
  • increased yield can be characterized, among others, by the following improved properties of the plant: increased plant weight; and/or increased plant height; and/or increased biomass such as higher overall fresh weight (FW); and/or increased number of flowers per plant; and/or higher grain and/or fruit yield ; and/or more tillers or side shoots (branches); and/or larger leaves; and/or increased shoot growth; and/or increased protein content; and/or increased oil content; and/or increased starch content; and/or increased pigment content; and/or increased chlorophyll content (chlorophyll content has a positive correlation with the plant's photosynthesis rate and accordingly, the higher the chlorophyll content the higher the yield of a plant) and/or increased quality of a plant.
  • Gram and “fruit” are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant.
  • the yield is increased by at least 4%.
  • the yield increase may even be higher, for example 5 to 10 %, more preferable by 10 to 20 %, or even 20 to 30 %
  • the yield - if measured in the absence of pest pressure - is increased by at least 2 %
  • the yield increase may even be higher, for example until 4%-5% or even more.
  • the plant vigor becomes manifest in several aspects such as the general visual appearance.
  • improved plant vigor can be characterized, among others, by the follow- ing improved properties of the plant: improved vitality of the plant; and/or improved plant growth; and/or improved plant development; and/or improved visual appearance; and/or improved plant stand (less plant verse/lodging-and/or bigger leaf blade; and/or bigger size; and/or increased plant height; and/or increased tiller number; and/or increased number of side shoots; and/or increased number of flowers per plant; and/or increased shoot growth; and/or enhanced photo- synthetic activity (e.g.
  • Another indicator for the condition of the plant is the "quality" of a plant and/or its products.
  • enhanced quality means that certain plant characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the mixtures of the present invention.
  • Enhanced quality can be characterized, among others, by following improved properties of the plant or its product: increased nutrient content; and/or increased protein content; and/or increased oil content; and/or increased starch content; and/or increased content of fatty acids; and/or increased metabolite content; and/or increased carotenoid content; and/or increased sugar content; and/or increased amount of essential amino acids; and/or improved nutrient composition; and/or improved protein composition; and/or improved composition of fatty acids; and/or improved metabolite composition; and/or improved carotenoid composition; and/or improved sugar composition; and/or improved amino acids composition ; and/or improved or optimal fruit color; and/or improved leaf color; and/or higher storage capacity; and/or better processability of the harvested products.
  • Another indicator for the condition of the plant is the plant's tolerance or resistance to biotic and/or abiotic stress factors.
  • Biotic and abiotic stress can have harmful effects on plants. Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes.
  • "enhanced tolerance or resistance to biotic and/or abiotic stress factors” means (1 .) that certain negative factors caused by biotic and/or abiotic stress are diminished in a measurable or noticeable amount as compared to plants exposed to the same conditions, but without being treated with an inventive mixture and (2.) that the negative effects are not diminished by a direct action of the inventive mixture on the stress factors, e.g.
  • Negative factors caused by biotic stress such as pathogens and pests are widely known and are caused by living organisms, such as competing plants (for example weeds), microorganisms (such as phythopathogenic fungi and/or bacteria) and/or viruses.
  • Negative factors caused by abiotic stress are also well-known and can often be observed as reduced plant vigor (see above), for example:
  • Abiotic stress can be caused for example by: extremes in temperature such as heat or cold (heat stress / cold stress); and/or strong variations in temperature; and/or temperatures unusual for the specific season; and/or drought (drought stress); and/or extreme wetness; and/or high salinity (salt stress); and/or radiation (for example by increased UV radiation due to the decreasing ozone layer); and/or increased ozone levels (ozone stress); and/or organic pollution (for example by phythotoxic amounts of pesticides); and/or inorganic pollution (for example by heavy metal contaminants).
  • extremes in temperature such as heat or cold (heat stress / cold stress); and/or strong variations in temperature; and/or temperatures unusual for the specific season; and/or drought (drought stress); and/or extreme wetness; and/or high salinity (salt stress); and/or radiation (for example by increased UV radiation due to the decreasing ozone layer); and/or increased ozone levels (ozone stress); and/or organic pollution (for example by
  • inventive mixtures effectuate an increased yield of a plant or its product. In another embodiment the inventive mixtures effectuate an increased vigor of a plant or its product.
  • inventive mixtures effectuate in an increased quality of a plant or its product.
  • inventive mixtures effectuate an increased tolerance and/or resistance of a plant or its product against biotic stress.
  • inventive mixtures effectuate an increased tolerance and/or re- sistance of a plant or its product against abiotic stress.
  • the inventive mixtures effect an increase in the yield. In another preferred embodiment of the invention, the inventive mixtures effect an improvement of the plant vigor.
  • the plant health effects of the inventive mix- tures effect increased resistance of plant against biotic stress.
  • the plant health effects of the inventive mixtures effect increased resistance of plant against abiotic stress.
  • the inventive mixtures effect an increase in the yield.
  • the inventive mixtures effect an increase in the vigor.
  • the mass ratio of of any two ingredients in each combination is selected as to give the desired, for example, synergistic action. In general, the mass ratio would vary depending on the specific compound I. Generally, the ratio by weight between any two ingredients in any combination of the present invention (compound I: compound II / compound ll:lll) [in the ternary mixtures ratios between any of the compounds I, II and III or compounds I, II and IV, or comounds I, III and IV or in the quarternary mixtures the ratios between any of the compounds I, II, III and IV], independently of one another, is from 1000:1 to 1 :1000, preferably from 500:1 to 1 :500, more preferably the ratios from 100:1 to 1 :100 (for example ratios from 99:1 , 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91 :9, 90:10, 89:1 1 , 88:12, 87:13, 86:14,
  • preferred mass ratios are those between any two components of present invention are from 75:1 to 1 :75, more preferably, 50:1 to 1 .50, especially 25:1 to 1 :25, advantageously 10:1 to 1 :10, such as 5:1 to 1 :5. These ratios are suitable for inventive mixtures applied by foliar application.
  • compound II may be supplied in any physiological state such as active or dormant.
  • Dormant compound II may be supplied for example frozen, dried, or lyophilized or partly desiccated (procedures to produce these partly desiccated organisms are given in WO2008/002371 ) or in form of spores.
  • Organisms in an active state can be delivered in a growth medium without any additional additives or materials or in combination with suitable nutrient mixtures.
  • the compound II (ID) is preferably delivered and formulated in a dormant stage.
  • the microorganisms as used according to the invention can be cultivated continuously or dis- continuously in the batch process or in the fed batch or repeated fed batch process.
  • a review of known methods of cultivation will be found in the textbook by Chmiel (Bioreatechnik 1. Ein- bowung in die Biovonstechnik (Gustav Fischer Verlag, Stuttgart, 1991 )) or in the textbook by Storhas (Bioreaktoren und periphere bamboo (Vieweg Verlag, Braunschweig/Wiesbaden, 1994)).
  • the culture medium that is to be used must satisfy the require- ments of the particular strains in an appropriate manner.
  • culture media for various microorganisms are given in the handbook "Manual of Methods for General Bacteriology” of the American Society for Bacteriology (Washington D. C, USA, 1981 ).
  • These culture media that can be used according to the invention generally comprise one or more sources of carbon, sources of nitrogen, inorganic salts, vitamins and/or trace elements.
  • Preferred sources of car- bon are sugars, such as mono-, di- or polysaccharides.
  • Very good sources of carbon are for example glucose, fructose, mannose, galactose, ribose, sorbose, ribulose, lactose, maltose, sucrose, raffinose, starch or cellulose.
  • Sugars can also be added to the media via complex compounds, such as molasses, or other by-products from sugar refining. It may also be advantageous to add mixtures of various sources of carbon.
  • Other possible sources of carbon are oils and fats such as soybean oil, sunflower oil, peanut oil and coconut oil, fatty acids such as palmitic acid, stearic acid or linoleic acid, alcohols such as glycerol, methanol or ethanol and organic acids such as acetic acid or lactic acid.
  • Sources of nitrogen are usually organic or inorganic nitrogen compounds or materials containing these compounds.
  • sources of nitrogen include ammonia gas or ammonium salts, such as ammonium sulfate, ammonium chlo- ride, ammonium phosphate, ammonium carbonate or ammonium nitrate, nitrates, urea, amino acids or complex sources of nitrogen, such as corn-steep liquor, soybean flour, soybean protein, yeast extract, meat extract and others.
  • the sources of nitrogen can be used separately or as a mixture.
  • Inorganic salt compounds that may be present in the media comprise the chloride, phosphate or sulfate salts of calcium, magnesium, sodium, cobalt, molybdenum, potassium, manganese, zinc, copper and iron.
  • Inorganic sulfur-containing compounds for example sulfates, sulfites, dithionites, tetrathionates, thiosulfates, sulfides, but also organic sulfur compounds, such as mercaptans and thiols, can be used as sources of sulfur.
  • Phosphoric acid, potassium dihydrogenphosphate or dipotassium hydrogenphosphate or the corresponding sodium-containing salts can be used as sources of phosphorus.
  • Chelating agents can be added to the medium, in order to keep the metal ions in solution.
  • Especially suitable chelating agents comprise dihydroxyphenols, such as catechol or protocatechuate, or organic acids, such as citric acid.
  • the culture media used may also contain other growth factors, such as vitamins or growth promoters, which include for example biotin, riboflavin, thiamine, folic acid, nicotinic acid, pantothenate and pyridoxine. Growth factors and salts often come from complex components of the media, such as yeast extract, molasses, corn-steep liquor and the like. In addition, suitable precursors can be added to the culture medium. The precise composition of the compounds in the medium is strongly dependent on the particular experiment and must be decided individually for each specific case. Information on media optimization can be found in the textbook "Applied Microbiol. Physiology, A Practical Approach" (Publ. P.M. Rhodes, P.F. Stanbury, IRL Press (1997) p.
  • Growing media can also be obtained from commercial suppliers, such as Standard 1 (Merck) or BHI (Brain heart infusion, DIFCO) etc. All components of the medium are sterilized, either by heating (20 min at 2.0 bar and 121 °C) or by sterile filtration. The components can be sterilized either together, or if necessary separately. All the com- ponents of the medium can be present at the start of growing, or optionally can be added continuously or by batch feed.
  • the temperature of the culture of the respective microorganism is normally between 15°C and 45°C, preferably 25°C to 40°C and can be kept constant or can be varied during the experiment.
  • the pH value of the medium should be in the range from 5 to 8.5, preferably around 7.0.
  • the pH value for growing can be controlled during growing by adding basic compounds such as sodium hydroxide, potassium hydroxide, ammonia or ammonia water or acid compounds such as phosphoric acid or sulfuric acid.
  • Antifoaming agents e.g. fatty acid polyglycol esters, can be used for controlling foaming.
  • suitable substances with selective action e.g. antibiotics, can be added to the medium.
  • Oxygen or oxygen-containing gas mixtures e.g. the ambient air, are fed into the culture in order to main- tain aerobic conditions.
  • the temperature of the culture is normally from 20°C to 45°C.
  • the methodology of the present invention can further include a step of recovering individual compositions such as cell-free extracts, supernatants, metabolites or alike.
  • the term "recovering” includes extracting, harvesting, isolating or purifying of an extract, supernatant or metabolite e.g. from whole culture broth.
  • Recovering can be performed according to any conventional isolation or purification methodology known in the art in- eluding, but not limited to, treatment with a conventional resin (e.g., anion or cation exchange resin, non-ionic adsorption resin, etc.), treatment with a conventional adsorbent (e.g., activated charcoal, silicic acid, silica gel, cellulose, alumina, etc.), alteration of pH, solvent extraction (e.g., with a conventional solvent such as an alcohol, ethyl acetate, hexane and the like), distillation, dialysis, filtration, concentration, crystallization, recrystallization, pH adjustment, lyophilization and the like.
  • a conventional resin e.g., anion or cation exchange resin, non-ionic adsorption resin, etc.
  • a conventional adsorbent e.g., activated charcoal, silicic acid, silica gel, cellulose, alumina, etc.
  • the agent can be recovered from culture media by first removing the microorganisms. The remaining broth is then passed through or over a cation exchange resin to remove unwanted cations and then through or over an anion exchange resin to remove unwanted inorganic anions and organic acids.
  • Preferred inventive mixtures are those comprising compound II and fungicidal compound IA selected from the group consisting of
  • Inhibitors of complex III at Qo site e.g. strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy-strobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-
  • inhibitors of complex II e. g. carboxamides: bixafen, boscalid, carboxin, fluopyram, fluxa- pyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane, N-(4'-trifluoromethylthiobiphenyl-2-yl)-
  • C14 demethylase inhibitors (DMI fungicides): triazoles: bitertanol, difenoconazole, cypro- conazole, diniconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, myclobutanil, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimenol, triticonazole, 1 -[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-di- fluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazole, 2-[rel-(2S;3R)-3-(2-chlorophenyl)-
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, oxadixyl;
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl, carbendazim, thiabendazole, thiophanate-methyl;
  • Phospholipid biosynthesis inhibitors iprobenfos
  • lipid peroxidation quintozene, tolclofos-methyl, etridiazole;
  • phospholipid biosynthesis and cell wall deposition dimethomorph, flumorph, mandipro- pamid, N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester; compounds affecting cell membrane permeability and fatty acides: propamocarb, pro- pamocarb-hydrochlorid
  • inorganic active substances Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
  • thio- and dithiocarbamates mancozeb, maneb, metiram, thiram;
  • guanidines and others dodine, guazatine, guazatine-acetate, iminoctadine, iminoctadine- triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6- c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
  • glucan synthesis validamycin
  • melanin synthesis inhibitors pyroquilon, tricy- clazole
  • Ampelomyces quisqualis e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany
  • Aspergillus flavus e.g. AFLAGUARD® from Syngenta, CH
  • Aureobasidium pullulans e.g. BO- TECTOR® from bio-ferm GmbH, Germany
  • Bacillus pumilus e.g. NRRL Accession No.
  • Bacillus subtilis e.g. isolate NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA
  • Bacillus subtilis var. amylolique-faciens FZB24 e.g. TAEGRO® from Novozyme Biologicals, Inc., USA
  • Candida oleophila I-82 e.g. ASPIRE® from Ecogen Inc., USA
  • Candida saitoana e.g.
  • BIOCURE® in mixture with lysozyme
  • BIO-COAT® from Micro Flo Company, USA (BASF SE) and Arysta
  • Chitosan e.g. ARMOUR-ZEN from BotriZen Ltd., NZ
  • Clonostachys rosea f. catenulata also named Gliocladium catenulatum (e.g. isolate J 1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS® from
  • Cryphonectria parasitica e.g. Endothia parasitica from CNICM, France
  • Cryptococcus albidus e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa
  • Fusarium oxysporum e.g. BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from Natural Plant Protection, France
  • Metschnikowia fructicola e.g. SHEMER® from Agrogreen, Israel
  • Micro-dicium dimerum e.g. ANTIBOT® from Agrauxine, France
  • Phlebiopsis gigantea e.g.
  • ROT- SOP® from Verdera, Finland
  • Pseudozyma flocculosa e.g. SPORODEX® from Plant Products Co. Ltd., Canada
  • Pythium oligandrum DV74 e.g. POLYVERSUM® from Remeslo SSRO, Bio- preparaty, Czech Rep.
  • Reynoutria sachlinensis e.g. REGALIA® from Marrone Biolnnovations, USA
  • Talaromyces flavus V1 17b e.g. PROTUS® from Prophyta, Germany
  • Trichoderma asperellum SKT-1 e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan
  • Atro- viride LC52 e.g. SENTINEL® from Agrimm Technologies Ltd, NZ
  • T. harzianum T-22 e.g. PLANTSHIELD® der Firma BioWorks Inc., USA
  • T. harzianum TH 35 e.g. ROOT PRO® from Mycontrol Ltd., Israel
  • T. harzianum T-39 e.g. TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel
  • T. harzianum and T. viride e.g. TRI- CHOPEL from Agrimm Technologies Ltd, NZ
  • viride ICC080 (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB® from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g. TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (e.g. SOILGARD® from Certis LLC, USA), T. viride (e.g. TRIECO® from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T. Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g. BOTRY-ZEN® from Botry-Zen Ltd, NZ).
  • Equally preferred inventive mixtures are those comprising compound II and insecticidal com- pound IB selected from the group consisting of
  • aldicarb for example aldicarb, benfuracarb, carbofuran, carbosulfan, isoprocarb, methomyl, thiodicarb, triazamate;
  • acephate for example acephate, cadusafos, chlorethoxyfos, chlorfenvinphos, chlorpyrifos, chlorpyrifos- methyl, diazinon, dichlorvos/ DDVP, dimethoate, disulfoton, ethoprophos, fenamiphos, fenitro- thion, imicyafos, isofenphos, methamidophos, phoxim, profenofos, tebupirimfos, terbufos;
  • ethiprole for example ethiprole, fipronil, flufiprole, pyrafluprole, or pyriprole;
  • bifenthrin for example bifenthrin, cyfluthrin, beta-cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cyper- methrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenvalerate, flucythrinate, permethrin, tefluthrin;
  • acetamiprid for example acetamiprid, chlothianidin, cycloxaprid, dinotefuran, flupyradifurone, imidacloprid, nitenpyram, sulfoxaflor, thiacloprid, thiamethoxam, 1 -[(6-chloro-3-pyridyl)methyl]-7-methyl- 8-nitro-5-propoxy-3,5,6,7-tetrahydro-2H-imidazo[1 ,2-a]pyridine (known from WO 2007/101369); M-5 allosteric nicotinic acteylcholine receptor activators from the class of spinosyns,
  • spinosad spinetoram
  • M-6 chloride channel activators from the class of mectins for example spinosad, spinetoram; M-6 chloride channel activators from the class of mectins,
  • abamectin for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
  • M-12 uncouplers of oxidative phosphorylation for example chlorfenapyr
  • M-13 nicotinic acetylcholine receptor channel blockers for example cartap hydrochloride; M-14 inhibitors of the chitin biosynthesis type 0 (benzoylurea class),
  • diflubenzuron for example diflubenzuron, flufenoxuron, lufenuron, novaluron, teflubenzuron;
  • buprofezin for example buprofezin
  • spirodiclofen for example spirodiclofen, spirotetramat
  • flubendiamide for example flubendiamide, chlorantraniliprole, cyantraniliprole, (R)-3-chloro-N1 - ⁇ 2-methyl- 4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2-methylsulfonylethyl)- phthalamide, (S)-3-chloro-N 1 - ⁇ 2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl ⁇ - N2-(1 -methyl-2-methylsulfonylethyl)phthalamide, 3-bromo-N- ⁇ 2-bromo-4-chloro-6-[(1 -cyclopro- pylethyl)carbamoyl]phenyl ⁇ -1 -(3-chloropyridin-2-yl)-1 H-pyrazole-5-carboxamide
  • M-25 Others for example afidopyropen, 2-(5-ethylsulfinyl-2-fluoro-4-methyl-phenyl)-5-methyl- 1 ,2,4-triazol-3-amine, 1 -(5-ethylsulfinyl-2,4-dimethyl-phenyl)-3-methyl-1 ,2,4-triazole;
  • M-26 Bacillus firmus (e.g. Bacillus firmus CNCM 1-1582).
  • Preferred inventive mixtures are those comprising compound II and fungicidal compound IA displayed in Table 1A:
  • Bacillus pumilus A Bacillus pumilus A
  • Preferred inventive mixtures especially useful for foliar treatment are those comprising compound II and fungicidal compound IA selected from Dimoxystrobin, Pyraclostrobin,
  • Azoxystrobin Trifloxystrobin, Picoxystrobin, Cyazofamid, Boscalid, Fluoxapyroxad, Fluopyram, Bixafen, Isopyrazam, Benzovindiflupyr, Penthiopyrad, Ametoctradin, Difenoconazole, Metcona- zole, Prothioconazole, Tebuconazole, Cyproconazole, Penconazole, Myclobutanil, Tetracona- zole, Hexaconazole, Metrafenone, Zoxamid, Pyrimethanil, Cyprodinil, Metalaxyl, Fludioxonil, Dimethomorph, Mandipropamid, Copper, Metiram, Chlorothalonil, Dithianon, Fluazinam, Folpet, Fosetyl-AI, Captan, Cymoxanil, Mancozeb, Kresoxim-methyl, Oryzastrobin, Epoxiconazole,
  • Bacillus simplex strain ABU 288 having the accession number N RRL B-503405 having the accession number N RRL B-503405
  • More preferred inventive mixtures especially useful for foliar treatment are those comprising compound I I and insecticidal compound I B selected from momfluorothrin; 1 -[(6-chloro-3-py- ridyl)methyl]-2-nitro-1 -[(E)-pentylideneamino]guanidine; 1 -[(E)-[2-(4-cyanophenyl)-1 -[3-(tri- fluoromethyl)phenyl]ethylidene]amino]-3-[4-(difluoromethoxy)phenyl]urea; N2-(1 -cyano-
  • 2- pyridyl)thiazole hydrofluoride 2-(3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)thiazole, 5-[6-(1 ,3-di- oxan-2-yl)-2-pyridyl]-2-(3-pyridyl)thiazole, 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoro- methyl)-4H-isoxazol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethyta
  • Equally preferred inventive mixtures are those comprising compound II and compound IC having plant growth regulating activity displayed in Table 1 C:
  • More preferred inventive mixtures especially useful for foliar treatment are those comprising compound II and compound IC having plant growth regulating activity selected from 6-benzyl- aminopurine, chlormequat, chlormequat chloride, choline chloride, cyclanilide, dikegulac, diflufenzopyr, dimethipin, ethephon, flumetralin, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, maleic hydrazide, mepiquat, mepiquat chloride, 1 -MCP, paclobutrazol, prohexadione, prohexadione calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, trinexapac-ethyl and uniconazole.
  • plant growth regulating activity selected from 6-benzyl- aminopurine, chlormequat, chlormequat chloride, choline chloride
  • inventive mixtures especially useful for foliar treatment are those comprising compound II and compound IC having plant growth regulating activity selected from chlormequat (chlormequat chloride), choline chloride, cyclanilide, dimethipin, ethephon, forchlorfenuron, gibberellic acid, maleic hydrazide, mepiquat, mepiquat chloride, 1 -MCP, pro- hexadione, prohexadione calcium, pthidiazuron and trinexapac-ethyl.
  • chlormequat chlormequat chloride
  • choline chloride choline chloride
  • cyclanilide dimethipin
  • ethephon dimethipin
  • forchlorfenuron gibberellic acid
  • maleic hydrazide mepiquat, mepiquat chloride
  • 1 -MCP pro- hexadione
  • prohexadione calcium prohexa
  • More preferred inventive mixtures are those comprising compound II and fungicidal compound IA displayed in Table 2A:
  • Bacillus simplex strain ABU 288 having the number NRRL B-50340 A
  • Bacillus pumilus A Bacillus pumilus A
  • Bacillus pumilus A Bacillus pumilus A
  • Bacillus subtilis A Bacillus subtilis A
  • Bacillus subtilis A Bacillus subtilis A
  • Equally preferred and more preferred inventive mixtures are those comprising compound I I and compound I D.
  • the present invention also relates to ternary mixtures comprising compound IA, compound I I and compound I D, wherein the combination of compounds IA and I I in each case corresponds to a row of Table 1A.
  • the present invention also relates to ternary mixtures comprising compound IA, compound I I and compound I D, wherein the combination of compounds IA and I I in each case corresponds to a row of Table 2A.
  • the present invention also relates to ternary mixtures comprising compound I B, compound I I and compound I D, wherein the combination of compounds IA and I I in each case corresponds to a row of Table 1 B.
  • the present invention also relates to ternary mixtures comprising compound I B, compound I I and compound I D, wherein the combination of compounds lA and I I in each case corresponds to a row of Table 2B.
  • Salts of jasmonic acid or derivatives include without limitation the jasmonate salts potassium jasmonate, sodium jasmonate, lithium jasmonate, ammonium jasmonate, dimethylammonium jasmonate, isopropylammonium jasmonate, diolammonium jasmonate, diethtriethanolammoni- um jasmonate, jasmonic acid methyl ester, jasmonic acid amide, jasmonic acid methylamide, jasmonic acid-L-amino acid (amide-linked) conjugates (e.g., conjugates with L- isoleucine, L-valine, L-leucine, or L-phenylalanine), 12-oxo-phytodienoic acid, coronatine, coronafaco
  • jasmonic acid Preferred amongst the group of salts of jasmonic acid or derivatives are jasmonic acid, methyl jasmonate, sodium jasmonate, potassium jasmonate, lithium jasmonate and ammonium jasmonate. More preferred is jasmonic acid methyl ester.
  • the present invention also relates to mixtures comprising compound II and comprising compound III as set forth in Table 3 below:
  • Bacillus simplex ABU 288 as compound II having the accession number NRRL B-50340 A
  • the jasmonate salt sodium jasmonate, potassium jasmonate, lithium jasmonate or ammonium jasmonate - No.3
  • the present invention also relates to ternary mixtures comprising compound III as third component, wherein compopund III is selected from jasmonates or salts or derivatives thereof.
  • compopund III is selected from jasmonates or salts or derivatives thereof.
  • Preferred amongst the group of salts of jasmonic acid or derivatives are jasmonic acid, methyl jasmonate, sodium jasmonate, potassium jasmonate, lithium jasmonate and ammonium jasmonate. More preferred is jasmonic acid methyl ester.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derlllatllle thereof and the combination of compounds I and II in each case corresponds to a row of Table 1 A.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid and the combination of compounds I and II in each case corresponds to a row of Table 1A.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is methyl jasmonate and the combination of compounds I and II in each case corresponds to a row of Table 1A.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is a jasmonate salt (e.g. potassium, lithium or ammonium) and the combination of compounds I and II in each case corresponds to a row of Table 1 A.
  • a jasmonate salt e.g. potassium, lithium or ammonium
  • the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derlllatllle thereof and the combination of compounds I and II in each case corresponds to a row of Table 1 B.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid and the combination of compounds I and II in each case corresponds to a row of Table 1 B.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is methyl jasmonate and the combination of compounds I and II in each case corresponds to a row of Table 1 B.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is a jasmonate salt (e.g. potassium, lithium or ammonium) and the combination of compounds I and II in each case corresponds to a row of Table 1 B.
  • a jasmonate salt e.g. potassium, lithium or ammonium
  • the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derlllatllle thereof and the combination of compounds I and II in each case corresponds to a row of Table 2A.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid and the combination of compounds I and II in each case corresponds to a row of Table 2A.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is methyl jasmonate and the combination of compounds I and II in each case corresponds to a row of Table 2A.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is a jasmonate salt (e.g. potassium, lithium or ammonium) and the combination of compounds I and II in each case corresponds to a row of Table 2A.
  • a jasmonate salt e.g. potassium, lithium or ammonium
  • the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derlllatllle thereof and the combination of compounds I and II in each case corresponds to a row of Table 2B.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid and the combination of compounds I and II in each case corresponds to a row of Table 2B.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is methyl jasmonate and the combination of compounds I and II in each case corresponds to a row of Table 2B.
  • the present invention furthermore relates to ternary mixtures, wherein compound III is a jasmonate salt (e.g. potassium, lithium or ammonium) and the combination of compounds I and II in each case corresponds to a row of Table 2B..
  • a jasmonate salt e.g. potassium, lithium or ammonium
  • the inventive mixtures can further contain one or more insecticides, fungicides, plant growth regulators and/or herbicides. As stated above, the compounds of the inventive mixtures can be applied simultaneously, that is jointly or separately, or in succession. The inventive mixtures can further contain one or more insecticides, fungicides, herbicides.
  • the compounds of the inventive mixtures can be applied simultaneously, that is jointly or separately, or in succession.
  • the mixtures according to the present invention can be converted jointly with formulation auxiliaries into individual formulations (compositions) or can be converted jointly with formulation auxiliaries into customary formulations (co-formulation).
  • compound I and compound II are naturally be formulated separately.
  • the compounds of the inventive mixtures can be present in a kit of parts comprising as part one formulated compound I as defined above; and as second component one formulated compound II as defined above.
  • 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 or any other kind of vessel used for applications (e.g seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • a spray tank or any other kind of vessel used for applications e.g seed treater drums, seed pelleting machinery, knapsack sprayer
  • further auxiliaries may be added, if appropriate.
  • living microorganisms, such as compound II, form part of such kit it must be taken care that choice and amounts of the other parts of the kit (e.g.
  • one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit compring a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
  • the present invention therefore also relates to a kit of parts comprising as part one formulated compound I as defined above; and as second component one formulated compound II as defined above. This applies also to combinations of compound II and III.
  • the kit of part may also optionally additionally comprise additional components III (and/ or IV) as outlined above, which can be also be provided separately packed, or, alternatively be present in combination with compound I or compound II.
  • inventive mixtures can be converted individually or jointly into customary types of agro- chemical compositions, e. g. solutions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types for compound I and/or compound II are suspensions (e.g. SC, OD, FS), emulsifiable concentrates, 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 (e.g. GF).
  • suspensions e.g. SC, OD, FS
  • emulsifiable concentrates e.g. CS, ZC
  • pastes e.g. WP, SP, WS, DP, DS
  • pressings e.g. BR, TB, DT
  • granules e.g. WG, SG, GR, FG,
  • 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.
  • Preferred examples of foliar formulation types for pre-mix compositions are :
  • WP wettable powders
  • WG water dispersable granules (powders)
  • OD oil-based suspension concentrate
  • SE aqueous suspo-emulsion
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, 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, stabilizers or nutrients, UV protectants, tackifiers and binders.
  • suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, 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, stabilizers or nutrients, UV protectants, tackifiers
  • 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, cyclohexanol; 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, tetrahydronaphthalen
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • 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; polysaccharides, 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
  • polysaccharides e.g. cellulose, starch
  • fertilizers
  • 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 & Detergents, 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 alkylarylsulfonates, 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 alkylnaphthalenes, 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.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • 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 home- 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 inventive mixtures on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. 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 alkylisothiazolinones 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, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
  • compositions When living microorganisms, such as compound II, form part of the compositions, such compositions can be prepared as compositions comprising besides the active ingredients at least one auxiliary (inert ingredient) by usual means (see e.g. H.D. Burges: Formulation of Micobial Bi- opestcides, Springer, 1998).
  • auxiliary inert ingredient
  • Suitable customary types of such compositions are suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g.
  • WP 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
  • gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
  • Suitable formulations are e.g. mentioned in WO 2008/002371 , US 6955,912, US 5,422,107.
  • auxiliaries examples are those mentioned earlier herein, wherein it must be taken care that choice and amounts of such auxiliaries should not influence the viability of the microbial pesticides in the composition.
  • auxiliaries Especially for bactericides and solvents, compatibility with the respective microorganism of the respective microbial pesticide has to be taken into account.
  • compositions with microbial pesticides may further contain stabilizers or nutrients and UV protectants.
  • Suitable stabilzers or nutrients are e.g. alpha-tocopherol, trehalose, glutamate, potassium sorbate, various sugars like glucose, sucrose, lactose, maltodextrine.
  • Suitable UV protectants are e.g. inorganic compouns like titan dioxide, zinc oxide and iron oxide pigments or organic compounds like benzophenones, benzotriazoles, phenyltriazines.
  • compositions may in addition to auxiliaries mentioned for compositions comprising compounds I herein optionally comprise 0.1 - 80% stabilizers or nutrients and 0.1 -10% UV protect- ants.
  • composition types and their preparation are given below. It has to be noted that each compound present in the mixture of the present invention can be formulated separately and then, for preparation of the mixture, combined, e.g. in any spray device by consecutive or simultaneaous application as outlined in more detail below.
  • CS formulations are particularly useful for compound I, less for compound II and compound III.
  • granules, powders or suspensions are preferred formulation type.
  • agitated vessel 1 -60 wt% of compound I or II or an inventive mixture are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alco- hoi ethoxylate), 0.1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water or an suitable oil to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alco- hoi ethoxylate
  • 0.1 -2 wt% thickener e.g. xanthan gum
  • up to 100 wt% water or an suitable oil to give a fine active substance suspension.
  • Dilution with water gives a stable suspension of the active substance.
  • binder e.g. polyvinylalcohol
  • 1 -80 wt% of compound I or II or an inventive mixture are are mixed to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray- drying, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • 1 -80 wt% of a of compound I or II or an inventive mixture are are mixed with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -3 wt% wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • compound I or II or an inventive mixture are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxy- methylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -5 wt% thickener e.g. carboxy- methylcellulose
  • An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, meth- acrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the for- mation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g.
  • an isocyanate monomer e.g. diphenylmethene-4,4'-diisocyanatae
  • a protective colloid e.g. polyvinyl alcohol
  • the addition of a polyamine results in the formation of polyurea microcapsules.
  • the monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
  • 1 -10 wt% of compound I or II or an inventive mixture are mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
  • 0.5-30 wt% of of compound I or II or an inventive mixture is mixed and associated with up to 100 wt% solid carrier (e.g. silicate).
  • Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • compositions types i) to vii) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, 0.1 - 80% stabilizers or nutrients, 0.1 -10% UV protectants and 0,1 -1 wt% colorants.
  • auxiliaries such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, 0.1 - 80% stabilizers or nutrients, 0.1 -10% UV protectants and 0,1 -1 wt% colorants.
  • compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% col- orants.
  • auxiliaries such as 0.1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% col- orants.
  • the resulting agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • a tank-mix formulation for foliar comprises 0.1 to 20 percent, especially 0.1 to 15 percent, of the desired ingredients, and 99.9 to 80 percent, especially 99.9 to 85 percent, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 20 percent, especially 0.1 to 15 percent, based on the tank-mix formulation.
  • auxiliaries including, for example, a solvent such as water
  • a pre-mix formulation for foliar application comprises 0.1 to 99.9 percent, especially 1 to 95 percent, of the desired ingredients, and 99.9 to 0.1 percent, especially 99 to 5 percent, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation.
  • a solid or liquid adjuvant including, for example, a solvent such as water
  • the inventive mixture is applied usually from a predosage device, a knap- sack 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 application 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.
  • either individual compounds of the inventive mixtures formulated as composition or partially premixed components, e. g. components set forth in the inventive mixtures may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).
  • either individual components of the inventive mixture or partially premixed components e. g. components comprising the compound I and II (or the compounds inventive ternary and quarternary mixtures), can be applied jointly (e. g. after tankmix) or consec- utively.
  • the time between both applications may vary e.g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1 .5 hours to 5 days, even more preferred from 2 hours to 1 day.
  • compound II is applied as last treatment.
  • the rates of application (use) of a combination vary, for example, according to type of use, type of crop, the compound (I) in the combination with II, but is such that the active ingredients in the combination is an effective amount to provide the desired synergistically enhanced action (such as disease or pest control and plant heath effects) and can be determined by trials and routine experimentation known to one of ordinary skill in the art.
  • the amounts of active substances ap- plied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.01 to 1 .0 kg per ha, and in particular from 0.05 to 0.75 kg per ha.
  • the application rates preferably range from about 1 x 10 6 to 5 x 10 15 (or more) CFU/ha.
  • the spore concentration is about 1 x 10 7 to about 1 x 10 11 CFU/ha.
  • inventive mixtures are suitable for controlling the following fungal plant diseases:
  • Albugo spp. white rust on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Altemaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A.retemata), tomatoes (e. g. A. solani or A.retemata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A.
  • Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botry- otinia fuckeliana: grey mold) on fruits and berries (e.
  • strawberries vegetables
  • vegetables e. g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Bremia lactucae downy mildew
  • Ceratocystis syn. Ophiostoma
  • Cercospora spp. rot or wilt
  • corn e.g. Gray leaf spot: C. zeae-maydis
  • sugar beets e. g. C.
  • sa- sakii sheath blight
  • Corynespora cassiicola leaf spots
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
  • lirio- dendri teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D.
  • phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyr- enophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formiti- poria (syn. Phellinus) punctata, F.
  • Phaeomoniella chlamydospora (earlier Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa
  • Elsinoe spp. on pome fruits £. pyri
  • soft fruits £. veneta: anthracnose
  • vines £. ampelina: anthracnose
  • Entyloma oryzae leaf smut
  • E. pisi such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F.
  • cucurbits e. g. E. cichoracearum
  • cabbages rape (e. g. E. cruciferarum)
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella
  • phaseoli root and stem rot
  • soybeans and cotton
  • Microdochium syn. Fusarium
  • nivale pink snow mold
  • Microsphaera diffusa prowdery mildew
  • Monilinia spp. e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M.
  • soybeans e. g. P. gregata: stem rot; Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Pho- mopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp.
  • Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpo- trichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseu- doperonospora (downy mildew) on various plants, e.
  • Puccinia spp. rusts on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P.
  • kuehnii orange rust
  • Pyrenophora anamorph: Drechslera
  • tritici-repentis tan spot
  • P. feres net blotch
  • Pyricularia spp. e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals
  • Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P.
  • Ramularia spp. e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • R. solani root and stem rot
  • S. reiliana head smut
  • Sphaerotheca fuliginea mofetil
  • Spongospora subterranea mofetil
  • Spongospora subterranea mofetil
  • Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat
  • Synchytrium endobioticum on potatoes potato wart disease
  • Taphrina spp. e. g. T.
  • deformans leaf curl disease
  • T. pruni plum pocket
  • plums Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U.
  • occulta stem smut
  • Uro- myces spp. rust
  • vegetables such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae);
  • Ustilago spp. loose smut) on cereals (e. g. U. nuda and U.
  • corn e. g. U. maydis: corn smut
  • sugar cane e. g. V. inaequalis
  • Venturia spp. scab
  • apples e. g. V. inaequalis
  • pears e. g. Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
  • the mixtures according to the present inventino and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • the term "protection of materials” is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and pa- perboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomy- cetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
  • the inventive mixtures exhibit also outstanding action against animal pests from the following orders: insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choris- toneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendroli- mus pini, Diaphania nitidalis, Diatraea grand iosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha
  • Dichromothrips corbetti Dichromothrips ssp, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Re- ticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus, cockroaches (Blattaria - Blattodea), e.g.
  • Blattella germanica Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta aus- tralasiae, and Blatta orientalis, true bugs (Hemiptera), e.g.
  • Hoplocampa minuta Hoplocampa testudinea
  • Monomorium pharaonis Solenopsis geminata
  • Solenopsis invicta
  • Vespula squamosa Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Doli- chovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and
  • Orthoptera e.g. Acheta domestica, Gryllotalpa gryl
  • Arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sar- coptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus mou- bata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Der- manyssus
  • Tarsonemidae spp. such as Phytonemus palli- dus and Polyphagotarsonemus latus
  • Tenuipalpidae spp. such as Brevipalpus phoenicis
  • Tetranychus cinnabarinus Tetranychus kanzawai, Tetranychus pacifi- cus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis
  • Araneida e.g. Latrodectus mactans, and Loxosceles reclusa, fleas (Siphonaptera), e.g.
  • Earwigs (DermapteraJ, e.g. forficula auricularia, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurystemus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne java- nica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pal
  • plant denotes various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • Preferred plants are cotton, alfalfa, sugarcane, sugarbeet, sunflower, mustard, sorghum, potato, ornamentals, corn, soybean, OSR/canola, cereals, rice, legumes/pulses, coffee, fruits (temperate and tropical), grapes and vegetables.
  • More preferred plants are corn, soybean, OSR/canola, cereals, rice, legumes/pulses, coffee, fruits (temperate and tropical), grapes and vegetables.
  • plants are fruits (temperate and tropical), grapes and vegetables.
  • plants is also to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • 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.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g.
  • auxin herbicides such as dicamba or 2,4-D
  • bleacher herbicides such as hydroxylphenylpyruvate dioxy- genase (HPPD) inhibitors or phytoene desaturase (PDS) inhibittors
  • acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones
  • glutamine synthetase (GS) inhibitors such as glufosinate
  • protoporphyrinogen-IX oxidase inhibitors lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i.
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors.
  • ALS inhibitors e.g. described in Pest Managem. Sci.
  • cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, 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 nema- todes, e. g. Photorhabdus spp.
  • VIP1 , VIP2, VIP3 or VIP3A vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coelop- tera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called "path- ogenesis-related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora).
  • PR proteins path- ogenesis-related proteins
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lysozym e
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • a modified amount of substances of content or new substances of content specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • the compound ratios are advantageously chosen so as to produce a synergistic effect.
  • the solid material (dry matter) of the microorganisms such as compound II, compound III or antifungal biocontrol agents (with the exception of oils) are considered as active components (e.g. to be obtained after drying or evaporation of the extraction medium or the suspension medium in case of liquid formulations of the microbial pesticides).
  • the total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms can be determined using the amount of CFU of the respective microorganism to calclulate the total weight of the respective active component with the following equation that 1 x 10 9 CFU equals one gram of total weight of the respective active component.
  • Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells.
  • CFU may also be understood as the number of (juvenile) individual nematodes in case of (entomopathogenic) nematode biopesticides, such as
  • the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active com- ponents used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1.
  • the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100: 1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1.
  • the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
  • the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4: 1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1.
  • any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1 ).
  • the chemical pesticides e.g. compounds IA, IB or IC
  • the chemical pesticides were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions of the chemical pesticides were mixed according to the ratio, diluted to the stated concentrations and pipetted onto a filter micro titer plate (MTP).
  • a spore suspension of the pathogen e.g. Botrytis cinerea, Septoria tritici, etc.
  • aqueous biomalt solution was added as well as different concentrations of spores or cells of the microbial pesticide (e.g. compound II).
  • the plates were incubated at optimal temperature depending on the pathogen and further processed 1 -7 days after incubation. The supernatant was removed using CaptiVac Vacuum Collar and a vacuum filter pump. The remaining cell pellet was resolved in water and DNA was extracted.
  • the growth of the pathogen was quantified via quantitative Real Time PCR using species- or strain-specific primers. To assess synergistic effects growth of the fungal pathogens was calculated in comparison to the different controls containing either the chemical pesticide or the microbial pesticide alone.
  • the measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.
  • the expected efficacies of active compound combinations were determined using Colby's formula (Colby, S.R., Calculating synergistic and antagonistic responses of herbicide combinations, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.
  • E expected efficacy expressed in % of the untreated control, when using the mixture of the active compounds A (e.g. compound IA, IB, IC or ID) and B (e.g. compound II) at the concentrations a and b
  • y efficacy expressed in % of the untreated control, when using the active compound B at the concentration b.
  • FM-1 Activity against Septoria tritici, the causal agent of leaf blotch on wheat
  • the chemical pesticides (e.g. compounds IA, IB or IC) were formulated separately or togeth- er as a stock solution comprising 25 mg of active substance which was made up to 10 ml using a mixture of acetone and/or dimethyl sulfoxide (DMSO) and the emulsifier Wettol EM 31 (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent/emulsifier of 99 to 1. This solution was then made up to 100 ml using water. This stock solution was diluted with the solvent/emulsifier/water mixture described to the active substance concentration given below.
  • the microbial pesticide (e.g. compound II) was cultivated as described herein and was diluted with water to the concentration given below.
  • Young seedlings of tomato plants were grown in pots. The plants were sprayed to runoff with an aqueous suspension containing the concentration of chemical pesticide stated below. Simultaneously or up to 6 hours later, the plants were sprayed with an aquous suspension containg the concentration of the microbial pesticide stated below. The next day, the treated plants were inoculated with an aqueous suspension of sporangia of Phytophthora infestans. After inocula- tion, the trial plants were immediately transferred to a humid chamber. After 6 days at 18 to
  • Use example FG-2 Curative action against Puccinia recondita on wheat (brown rust of wheat) Leaves of potted wheat seedlings of the cultivar "Kanzler” were dusted with a suspension of spores of brown rust of wheat (Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%), at 20-22°C, for 24 hours. During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The next day, the infected plants were sprayed to runoff point with an aqueous suspension having the concentra- tion of chemical pesticide stated below.
  • the plants were sprayed with an aquous suspension containg the concentration of microbial pesticide stated below. After drying of the sprayed suspension, the test plants were returned into the greenhouse and cultivated at temperatures between 20 and 22°C and at 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust development on the leaves was then determined visually.
  • test plants were returned into the greenhouse and cultivated at temperatures between 20 and 22°C and at 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust development on the leaves was then determined visually.
  • Use example FG-4 Protective action against Blumeria graminis tritici on wheat (mildew of wheat)
  • Leaves of potted wheat seedlings of the cultivar "Kanzler" were sprayed to runoff point with an aqueous suspension having the concentration of chemical persticide stated below. Simultaneously or up to 6 hours later, the plants were sprayed with an aquous suspension containg the concentration of microbial pesticide stated below. The next day, the treated plants were dusted with a suspension of spores of mildew of wheat (Blumeria graminis tritici). The plants were then returned into the greenhouse and cultivated at temperatures between 20 and 24°C and at 60 to 90% relative atmospheric humidity for a further 7 days. The extent of the mildew development on the leaves was then determined visually.
  • Leaves of potted cucumber seedlings (in the germ layer stage) were sprayed to runoff point with an aqueous suspension having the concentration of chemical pesticide stated below. Sim- ultaneously or up to 6 hours later, the plants were sprayed with an aquous suspension containg the concentration of microbial pesticide stated below. The next day, the treated plants were dusted with a suspension of spores of mildew of cucumber (Sphaerotheca fuliginea). The plants were then returned into the greenhouse and cultivated at temperatures between 20 and 24°C and at 60 to 80% relative atmospheric humidity for a further 7 days. The extent of the mildew development on the seed leaves was then determined visually.
  • the insecticidal action of the mixtures according to the invention can be shown by the tests as described below using the respective microbial pesticide (e.g. compound II) as formulated product or conidia/spores suspensions in sterile water with 0.05% v/v adjuvant (e.g. Tween® 80).
  • microbial pesticide e.g. compound II
  • conidia/spores suspensions in sterile water with 0.05% v/v adjuvant
  • PDA potato dextrose agar
  • MEA malt dextrose agar
  • PCA potato carrot agar
  • SDA sabouraud dextrose agar
  • sterile plates e.g. Petri dishes
  • vessels e.g. bottles
  • sterile water e.g. water
  • Chemical pesticide formulations are prepared from stock solutions (see above) in sterile wa- ter or water with 0.05% v/v Tween® 80 using a logarithmic range of concentrations expressed in ppm.
  • the spore/conidia solution of the microbial pesticide at the concentration stated below is pipetted into each vessel containing the chemical pesticide. The vessels are shaken to ensure the complete suspension of the microbial pesticide and kept at room temperature (24-26 °C) during the experiment.
  • the mixture is then diluted to a concentration of 1 x 106 spores/conidia per ml.
  • a fixed volume (i.e. 1 ml.) of each treatment is pipetted at different time intervals and distributed aseptical- ly onto a plate containing the autoclaved medium for culture.
  • Chemical pesticide at various test concentrations is added to a series of vessels containing warm autoclaved medium before it gets solid, and then poured into separate pates using 4 replicates per treatment. After the medium solidified, the spore/conidia solution (i.e. 1 x 106 spores/conidia per ml.) is pipetted into each plate.
  • Test plants are either dipped or sprayed with spore/conidia suspensions of the microbial pesticide at various concentrations or with formulations of the chemical pesticide at various concentrations and subsequently left to dry. Then, the plants are artificially or naturally infested with the respective target insect species. Assessments are carried out at different timings after treatment. The parameters evaluated are: efficacy (counting dead insects vs. alive), feeding damage, and/or plant vigor. All parameters are determined in comparison to the untreated insect-infested plants (free of microbialpesticide and chemical pesticide, respectively). III. Synergism trials
  • a synergism trial will contain at least the following treatments:
  • the microbial pesticide suspensions and chemical pesticide formulations can be prepared as described above.
  • the expected efficacies of the mixtures are determined using Colby's formula as described above and compared with the observed efficacies. Efficacy is determined as insect mortality (number of dead insects vs. number of insects tested in the experiment) and/or % feeding damage.
  • Soybean plants are grown in the field allowing natural infestation with stinkbugs. Plants were sprayed with the respective treatments. Efficacy was determined at 3, 7 and 14 days after treatment.
  • Tomato plants were grown in the field allowing natural infestation with whiteflies. Plants were sprayed with the respective treatments. Efficacy on adults was determined at 3, 7, 14 and 21 days after treatment, on larvae at 21 days after treatment.
  • Use example I-3 Protective action against thrips (Frankiniella occidentalis) in the growth chamber
  • Lima bean plants were grown in small pots. Plants were dipped into the respective treatments. Plants were put into plastic cups and left to dry. Once dried, plants were infested with 15 adult thrips and cups were closed. Efficacy was evaluated at 3, 7 and 10 days after treatment.
  • Use example I-4 Protective action against Southern armyworm (Spodoptera eridiana)
  • Potato plants were grown in the field allowing natural infestation with Colorado potato beetles. Plants were sprayed with the respective treatments. Efficacy was determined at 3, 7 and 14 days after treatment.
  • Drought stress tolerance can be tested e.g. on duckweed plants grown in 24-well microplates according to the method disclosed J. Plant Growth Regul. 30, 504-51 1 (201 1 ).
  • the measured parameters were compared to the growth of the active compound-free control variant under drought stress (e.g. PEG treatment) (0%) and the active compound-free blank value without drought stress (e.g. PEG-fee) (100%) to determine the relative growth in % in the respective active compounds.
  • the expected efficacies of active compound combinations were determined using Colby's formula as described above.
  • Use example H-2 Improvement of plant height in wheat Pyraclostrobin was applied as commercial seed treatment formulation STAMINA (200 g/L a.i., BASF SE, Ludwigshafen, Germany).
  • Bacillus simplex ABU 288 was tested in wheat and maize as solo products and in combination with pyraclostrobin to show effects on plant height.
  • the application of the pyraclostrobin was done as seed treatment and the seeds were treated in the BASF Seed Solutions Technology Center (SSTC) Limburgerhof using a batch lab treater. The respective amounts of seeds was placed in the bowl of the treater and the slurry was dosed on the spinning disk.
  • SSTC BASF Seed Solutions Technology Center
  • the bacterials were grown in shake flasks and used as fermentation broth with a CFU of at least 1 x 10 12 per ml. This broth was added as a drench solution directly adjacent to the seeds with 10 ml for each seed kernel which makes 50 ml per pot.
  • the trial was sown in 8 cm pots and a mix of peat substrate and sand (ratio 1 : 4) was used as a substrate.
  • the pots were filled with the substrate and in each pot 5 wheat seeds (cv. JB Asano) were sown at a sowing depth of 1 ,5 cm and then covered with substrate.
  • 5 replications were made.
  • the pots were irrigated with fertilized water (0,3 % Kamasol Blau 8+8+6) and placed according the randomization plan in a greenhouse cabin (16 h light, relative humidity ⁇ 95 %) for 14 days at 20°C. When necessary, they were irrigated with fertilized water.
  • PA relative plant height expressed in % of the untreated control, when using the active

Abstract

La présente invention concerne des mélanges pesticides comprenant un composé biologique et au moins un fongicide, un insecticide ou un composé régulateur de croissance des plantes, tels que définis dans la description, ainsi que des utilisations respectives de ceux-ci en agriculture.
PCT/EP2013/073809 2012-11-22 2013-11-14 Mélanges pesticides WO2014079766A1 (fr)

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EP12193734 2012-11-22
EP12193734.6 2012-11-22
EP13186998 2013-10-02
EP13186998.4 2013-10-02

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CN105181870A (zh) * 2015-09-24 2015-12-23 通标标准技术服务(上海)有限公司 一种测定蔬菜水果中噁霉灵残留物的方法
CN105454231A (zh) * 2015-12-24 2016-04-06 河北博嘉农业有限公司 一种含有甲氧虫酰肼的杀虫杀菌组合物
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CN105695376A (zh) * 2016-04-25 2016-06-22 北京市农林科学院 一株毒杀植物根结线虫的简单芽孢杆菌及其应用
CN105929060A (zh) * 2016-04-25 2016-09-07 山东省农业科学院农业质量标准与检测技术研究所 一种蔬菜水果中乙基多杀菌素残留量的lc-ms-ms检测方法
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US10512267B2 (en) 2013-07-08 2019-12-24 BASF Agro, B.V. Compositions comprising a triazole compound and a biopesticide
US10519122B2 (en) 2013-01-09 2019-12-31 BASF Agro B.V. Process for the preparation of substituted oxiranes and triazoles
US10537110B2 (en) 2012-11-22 2020-01-21 Basf Corporation Pesticidal mixtures
US10743535B2 (en) 2017-08-18 2020-08-18 H&K Solutions Llc Insecticide for flight-capable pests
US10759767B2 (en) 2012-12-20 2020-09-01 BASF Agro B.V. Compositions comprising a triazole compound
US10779536B2 (en) 2014-11-07 2020-09-22 Basf Se Pesticidal mixtures
US10905122B2 (en) 2016-03-16 2021-02-02 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on cereals
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