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WO2014079772A1 - Pesticidal mixtures - Google Patents

Pesticidal mixtures Download PDF

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Publication number
WO2014079772A1
WO2014079772A1 PCT/EP2013/073909 EP2013073909W WO2014079772A1 WO 2014079772 A1 WO2014079772 A1 WO 2014079772A1 EP 2013073909 W EP2013073909 W EP 2013073909W WO 2014079772 A1 WO2014079772 A1 WO 2014079772A1
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WO
WIPO (PCT)
Prior art keywords
methyl
phenyl
chloro
inhibitors
compound
Prior art date
Application number
PCT/EP2013/073909
Other languages
French (fr)
Inventor
Lutz Brahm
Burghard Liebmann
Ronald Wilhelm
Markus Gewehr
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2014079772A1 publication Critical patent/WO2014079772A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
  • azoxystrobin coumethoxystrobin, coumoxystro- bin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyra- clostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phen- oxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichloro- phenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl- acetamide, pyribencarb, triclopyricarb/chlorodincarb, fam
  • inhibitors of complex II benodanil, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-
  • nitrophenyl derivates bina- pacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
  • - C14 demethylase inhibitors triazoles: azaconazole, bitertanol, bromuconazole, cy- proconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbu- conazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ip- conazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triad- imefon, triadimenol, triticonazole, uniconazole, 1 -[rel-(2S;3R)-3-(2-chlorophenyl)- 2-(2,4-di
  • Delta14-reductase inhibitors aldimorph, dodemorph, dodemorph-acetate, fenpropi- morph, tridemorph, fenpropidin, piperalin, spiroxamine;
  • - phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, met- alaxyl, ofurace, oxadixyl;
  • tubulin inhibitors benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate- methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluoro- phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine;
  • cell division inhibitors diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
  • - methionine synthesis inhibitors cyprodinil, mepanipyrim, pyrimethanil;
  • blasticidin-S blasticidin-S, kasugamycin, kasugamycin hydrochloride- hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
  • MAP / histidine kinase inhibitors fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
  • Phospholipid biosynthesis inhibitors edifenphos, iprobenfos, pyrazophos, isoprothi- olane;
  • lipid peroxidation dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
  • phospholipid biosynthesis and cell wall deposition dimethomorph, flumorph, mandi- propamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4-cy- ano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
  • inorganic active substances Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
  • thio- and dithiocarbamates ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
  • organochlorine compounds phthalimides, sulfamides, chloronitriles: anilazine, chlo- rothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)- N-ethyl-4-methyl-benzenesulfonamide;
  • guanidines and others guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithia- non, 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone; Cell wall synthesis inhibitors
  • inhibitors of glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
  • 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. BOTECTOR® from bio-ferm GmbH, Germany
  • Bacillus pumilus e.g. NRRL Accession No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA
  • Bacillus subtilis e.g. isolate NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA
  • amylolique-faciens FZB24 e.g. TAEGRO® from Novozyme Biologicals, Inc., USA
  • Candida oleophila 1-82 e.g. ASPIRE® from Ecogen Inc., USA
  • Candida sai- toana e.g. BIOCURE® (in mixture with lysozyme) and BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta
  • chitosan e.g. ARMOUR-ZEN from
  • Clonostachys rosea f. catenulata also named Gliocladium ca- tenulatum (e.g. isolate J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS® from Prophyta, Germany), 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. ROTSOP® from Verdera, Finland
  • Pseudozyma flocculosa e.g. SPORO- DEX® from Plant Products Co. Ltd., Canada
  • Pythium oligandrum DV74 e.g.
  • harzianum TH 35 e.g. ROOT PRO® from Mycontrol Ltd., Israel
  • T. harzianum T-39 e.g. TRICHO- DEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel
  • T. harzianum and T. viride e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ
  • T. harzianum ICC012 and T. 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
  • 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
  • BOTRY-ZEN® from Botry-Zen Ltd, NZ
  • 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;
  • M-2.B fiproles ethiprole, fipronil, flufiprole, pyrafluprole, or pyriprole;
  • M-3 sodium channel modulators from the class of pyrethroids M-3 sodium channel modulators from the class of pyrethroids:
  • 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-13 nicotinic acetylcholine receptor channel blockers bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;
  • 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;
  • M-24 Ryanodine receptor-modulators from the class of diamides flubendiamide, chlorantraniliprole (rynaxypyr), cyantraniliprole (cyazypyr), (R)-3-chloro-N1 - ⁇ 2-me- thyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluormethyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2-methyl- sulfonylethyl)phthalamide or (S)-3-chloro-N 1 - ⁇ 2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(tri- fluoromethyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2-methylsulfonylethyl)phthalamide (both known from WO 2007/101540), 3-bromo-N- ⁇ 2-bromo-4-chloro-6-[(1 -cyclopropyl- ethyl)car
  • M-26 Bacillus firmus (e.g. Bacillus firmus CNCM 1-1582; see WO 09/126473,
  • 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;
  • Ethylene releasers ACC, et messagingl, ethephon, glyoxime; - Gibberellins: gibberelline, gibberellic acid;
  • 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, cyana- mide, 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; and 5) Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 as compound II.
  • 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 pumilus INR-7 (defined herein as compound II) is also otherwise referred to as BUF-22 or as BU F-33 or similar codes and has been described e.g. in US 2012/0149571 A1 .
  • Bacillus pumilus INR-7 is deposited as BUF-22 having the accession number NRRL B-50153 with the United States Department of Agriculture on Jul. 23, 2008, and as BU-F-33, having the accession number NRRL B-50185 with the United States Department of Agriculture on Oct. 15, 2008.
  • Bacillus pumilus INR7 can be cultivated and prepared as described for Bacillus subtilis MBI 600.
  • the present invention relates to synergistic mixtures comprising Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 as compound II and one compound IA.
  • the present invention furthermore relates to synergistic mixtures comprising Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 as compound II and one compound IB.
  • the present invention furthermore relates to synergistic mixtures comprising Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 as compound II and one compound IC.
  • the remaining compounds IA, IB as well as their pesticidal action and methods for producing them are generally known. For instance, they may be found in the e-Pesticide Manual V5.2 (ISBN 978 1 901396 85 0) (2008-201 1 ) among other publications or in the references given above.
  • pests embrace animal pests, and harmful fungi.
  • Another difficulty in relation to the use of pesticides is that the repeated and exclusive applica- tion of an individual pesticidal compound leads in many cases to a rapid selection of pests, that means animal pests, and harmful fungi, which have developed natural or adapted resistance against the active compound in question. Therefore there is a need for pest control agents that help prevent or overcome resistance.
  • Another problem underlying the present invention is the desire for compositions that improve plants, a process which is commonly and hereinafter referred to as "plant health”.
  • the action of the inventive mixtures goes far beyond the fungicidal and/or insecticidal and/or plant health improving action of the active compounds I and II present in the mixture alone (synergism).
  • insecticidal or “insect attac” also denotes not only action against (or attac by) insects, but also against (by) arachnids and nematodes.
  • 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.
  • simultaneous, that is joint or separate, application of the compound I and the compound II or successive application of the compound I and compound II provides enhanced plant health effects compared to the plant health effects that are possible with the individual compounds (synergistic mixtures).
  • the present invention relates 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 inventive 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 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 lA 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, in- eluding the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various mixtures / compositions used in the invention.
  • a pesticidally effective amount of the mixtures / compositions will also vary according to the prevailing condi- tions 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.
  • the term "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. It has to be emphasized that the above mentioned effects of the inventive mixtures, i.e. enhanced health of the plant, are also present when the plant is not under biotic stress and in particular when the plant is not under pest pressure.
  • 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 con- tent; 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.
  • the yield is increased by at least 4%. In general, 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 following 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 in- creased 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 im- proved 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, especially over longer terms, 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. by its fungicidal or insecticidal action which directly destroys the microorganisms or pests, but rather by a stimulation of the plants' own defensive reactions against said stress factors.
  • 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 decreas- ing 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)
  • radiation for example by increased UV radiation due to the decreas- ing ozone layer
  • ozone levels ozone stress
  • the above identified indicators for the health condition of a plant may be interdependent and may result from each other.
  • an increased resistance to biotic and/or abiotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield.
  • a more developed root system may result in an increased resistance to biotic and/or abiotic stress.
  • these interdependencies and interactions are neither all known nor fully understood and therefore the different indicators are described separately.
  • the inventive mixtures effectuate an increased yield of a plant or its product.
  • inventive mixtures effectuate an increased vigor of a plant or its product. In another embodiment the 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 resistance of a plant or its product against abiotic stress.
  • the inventive mixtures effectuate an increase in the yield.
  • 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 physiologic state such as active or dormant.
  • Dormant compound II may be supplied for example frozen, dried, or lyophilized or partly desiccated (proceduers 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 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-hydrochloride
  • inorganic active substances Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
  • thio- and dithiocarbamates mancozeb, maneb, metiram, thiram;
  • organochlorine compounds chlorothalonil, captan, folpet,;
  • guanidines and others dodine, guazatine, guazatine-acetate, iminoctadine, iminoctadine- triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl-1 H,5H-[1 ,4]dithi- ino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
  • inhibitors of 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- T ECTOR® from bio-ferm GmbH, Germany
  • Bacillus pumilus e.g. NRRL B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA
  • Bacillus subtilis e.g. isolate NRRL B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA
  • Bacillus subtilis var Bacillus subtilis var.
  • amylolique-faciens FZB24 e.g. TAEGRO® from Novozyme Biologi- cals, Inc., USA
  • Candida oleophila I-82 e.g. ASPIRE® from Ecogen Inc., USA
  • Candida sai- toana e.g. BIOCURE® (in mixture with lysozyme) and BIO-COAT® from Micro Flo Company, USA (BASF SE) and Arysta
  • Chitosan e.g. ARMOUR-ZEN from BotriZen Ltd., NZ
  • Clonosta- chys rosea f. catenulata also named Gliocladium catenulatum (e.g.
  • isolate J 1446 PRESTOP® from Verdera, Finland
  • Coniothyrium minitans e.g. CONTANS® from Prophyta, Germany
  • 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
  • Microdochium dimerum e.g.
  • Phlebiopsis gigantea e.g. ROTSOP® from Verdera, Fin- land
  • Pseudozyma flocculosa e.g. SPORODEX® from Plant Products Co. Ltd., Canada
  • Pythium oligandrum DV74 e.g. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.
  • Reynoutria sachlinensis e.g. REGALIA® from Marrone Biolnnovations, USA
  • Talaromy- ces flavus V1 17b e.g.
  • Trichoderma asperellum SKT-1 e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan
  • T. atroviride 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
  • viride e.g. TRICHOPEL from Agrimm Tech- nologies Ltd, NZ
  • T. harzianum ICC012 and T. viride ICC080 e.g. REMEDIER® WP from Isa- gro 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.
  • 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 compound 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- cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenvalerate, flu- cythrinate, permethrin, tefluthrin;
  • acetamiprid for example acetamiprid, chlothianidin, cycloxaprid, dinotefuran, flupyradifurone, imidacloprid, nitenpyram, sulfoxaflor, thiacloprid, thiamethoxam, 1 -[(6-chloro-3-pyridyl)methyl]-7-methyl-8-ni- tro-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,
  • M-6 chloride channel activators from the class of mectins, 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
  • diflubenzuron for example diflubenzuron, flufenoxuron, lufenuron, novaluron, teflubenzuron;
  • M-15 inhibitors of the chitin biosynthesis type 1 for example buprofezin;
  • M-17 Ecdyson receptor agonists for example methoxyfenozide
  • M-22 Inhibitors of the lipid synthesis inhibitors of acetyl CoA carboxylase, for example spirodi- clofen, spirotetramat;
  • M-24 Ryanodine receptor-modulators from the class of diamides for example flubendiamide, chlorantraniliprole, cyantraniliprole, (R)-3-chloro-N1 - ⁇ 2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoro- methyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2-methylsulfonylethyl)phthalamide or (S)-3-Chlor-N1 - ⁇ 2-me- thyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2-methylsulfonylethyl)- phthalamide (both known from WO 2007/101540), 3-bromo-N- ⁇ 2-bromo-4-chloro-6-[(1 -cyclo- propylethyl)carbamoyl]phenyl ⁇ -1
  • M-26 Bacillus firmus (e.g. Bacillus firmus of strain CNCM 1-1582; see WO09126473 and WO 09/124707, commercially available as "Votivo").
  • Preferred inventive mixtures are those comprising compound II and fungicidal compound IA displayed in Table 1A:
  • Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185
  • Bacillus pumilus A Bacillus pumilus A
  • M-1 Pythium oligandrum A M-120. T. polysporum and A
  • Preferred inventive mixtures especially useful for foliar treatment are those comprising com- pound I I 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,
  • More preferred inventive mixtures especially useful for foliar treatment are those comprising compound II and insecticidal compound IB selected from momfluorothrin; 1 -[(6-chloro-3-py- ridyl)methyl]-2-nitro-1 -[(E)-pentylideneamino]guanidine; 1 -[(E)-[2-(4-cyanophenyl)-1 -[3-(triflu- oromethyl)phenyl]ethylidene]amino]-3-[4-(difluoromethoxy)phenyl]urea; N2-(1 -cyano-1 -methyl- ethyl)-N1 -(2,4-dimethylphenyl)-3-iodo-phthalamide, 3-chloro-N2-(1 -cyano-1 -methyl-ethyl)- N1 -(2,4-dimethylphenyl)phthalamide, 2-(3-chloro-2-pyridyl)-
  • 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- benzylaminopurine, 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- benzylaminopurine, chlormequat, chlormequat chloride, choline
  • inventive mixtures especially useful for foliar treatment are those compris- ing 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.
  • 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, pthidiazur
  • More preferred inventive mixtures are those comprising compound II and fungicidal compound IA displayed in Table 2A:
  • 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 I B 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 I B and I I in each case corresponds to a row of Table 2B.
  • the present invention also relates to ternary mixtures comprising compound IC, compound I I and compound I D, wherein the combination of compounds IC and I I in each case corresponds to a row of Table 1 C.
  • 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, coronafacoyl- L-serine, coronafacoyl-L-threonine, methyl esters of 1 -oxo-indanoyl-isoleucine, methyl esters of 1
  • 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 I I I and compound IV as set forth in Table 3 below:
  • 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.
  • 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 furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derivative thereof 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 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 derivative 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 derivative 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 derivative 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.
  • 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.
  • compositions can be converted jointly with formulation auxil- iaries 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 in- vention 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. chemcial pesticidal agents) and of the further auxiliaries should not influence the viability of the microbial pesticides in the composition mixed by the user.
  • compatibility with the respective microbial pesticide has to be taken into account.
  • one embodiment of the invention is a kit for preparing a usable pesticidal com- position, the kit compring a) a composition comprising component 1 ) as defined herein and at least one auxiliary; or b) a composition comprising component 2) as defined herein and at least one auxiliary; or c) a composition comprising component 3) as defined herein and at least one auxiliary; or d) a composition comprising component 4) as defined herein and at least one auxil- iary; and e) a composition comprising component 5) as defined herein and at least one auxiliary.
  • 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 de- fined above. This applies also to combinations of compound II and III.
  • 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.
  • 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.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
  • 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 fractions 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 fractions 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, tetrahydronaphthalene, alkylated
  • 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.
  • fertilizers e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas
  • products of vegetable origin e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • 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 tar- get.
  • 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.
  • the 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 protectants.
  • 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.
  • 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 alcohol 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 alcohol 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 sub- stance.
  • 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 formation 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. aromatic hydrocarbon), and an isocyanate monomer (e.g.
  • diphenylmethene-4,4'-diisocyanatae are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol).
  • 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.
  • 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 knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired 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 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 pre- mixed 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 consecutively.
  • 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 I, type of plant propagation material (if appropriate), 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 or- dinary skill in the art.
  • the amounts of active substances applied 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.
  • 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) gram- inis (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, bana- nas, 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 (teleo- morph: 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, veg- etables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • 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.
  • yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
  • 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 pa Imi 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
  • 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
  • Triggerpidae spp. such as Brevipalpus phoenicis
  • Tetra- nychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g.
  • Narceus spp. 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 rostochien
  • 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.
  • Most preferred 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.
  • auxin herbicides
  • 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 anoth- er class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are 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 bacte- rial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ -endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, 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 pro- prised 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
  • 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 generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. Furthermore, 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 Scienc- es, 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 components 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.
  • 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 concentra- tions 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 together 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 (wet- ting 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/em ulsifier/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. Simul- taneously 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 inoculation, the trial plants were immediately transferred to a humid chamber. After 6 days at 18 to 200C and a relative humidity close to 100%, the extent of fungal attack on the leaves was visu- ally assessed as % diseased leaf area.
  • 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 concentration 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.
  • 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.
  • Pyraclostrobin was applied as commercial seed treatment formulation STAMINA (200 g/L a.i., BASF SE, Ludwigshafen, Germany).
  • 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 amount 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 B. pumilus INR7 were grown in shake flasks and used as fermentation broth with of at least 1 x 10 12 CFU 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.
  • rye kernels inoculated with Sclerotinia sclerotiorum were used. The trial was sown in 8 cm pots and as a substrate a mix of peat substrate and sand in the ratio 1 : 4 was used. The pots were filled with the substrate and the rye kernels inoculated with Sclerotinia sclerotiorum were placed directly adjacent to the seeds. In each pot 5 soy bean seeds (cv. Go- riziana) were sown at a sowing depth of 2 cm, then covered with substrate. For each treatment 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.
  • rye kernels inoculated with Gaeumannomyces graminis were used. The trial was sown in 8 cm pots and a mix of peat substrate and sand (ratio 1 : 4) was used as a sub- strate. The pots were filled with the substrate and the rye kernels inoculated with Gaeumannomyces graminis were placed directly adjacent to the wheat seeds. In each pot 5 wheat seeds (cv. JB Asano) were sown at a sowing depth of 1.5 cm and then covered with substrate. For each treatment 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 green- house cabin (16 h light, relative humidity ⁇ 95 %) for 14 days at 20°C. When necessary, they were irrigated with fertilized water.
  • 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 water 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. In both methods, 4 replicates are used and the plates are cultured at 28 °C and 80% rel. humidity for 24 to 48 h. Compatibility is determined after 1 , 24 h and optionally 48 h as follwos: 1 ) by counting germinated vs.
  • non-germinated spores/conidia counted ⁇ 100 in the mixture using a microscope and hemacytometer to establish the germination rate in %, or number of germinated spores/conidia; or 2) by determining colony diameter in mm, speed of growth in mm/day, shape of the colony and/or color of the colony on the plates. All parameters are compared to a suspension of spores/conidia in absence of chemical pesticide (negative control).
  • 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).
  • 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)
  • Lima bean leaves were cut and dipped into the respective treatments and placed in Petri dishes on wet filter paper to keep humidity. Once the surface of the leaves dried, 5 first/second instar larvae were infested per petri dish. Efficacy was evaluated at 3, 7 and 10 days after treatment.
  • 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.
  • the plant health improving action of the mixtures according to the invention can be shown by the tests described below.
  • 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).
  • 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

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Abstract

The present invention relates to pesticidal mixtures comprising one biological com- pound and at least one fungicidal, insecticidal or plant growth regulating compound and respective agricultural uses thereof as defined herein.

Description

Pesticidal mixtures
Description The present invention relates to synergistic mixtures comprising as active components,
1 ) one fungicidal compound IA selected from the group consisting of
A) Respiration inhibitors
- Inhibitors of complex III at Qo site: azoxystrobin, coumethoxystrobin, coumoxystro- bin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyra- clostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phen- oxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichloro- phenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl- acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
- inhibitors of complex III at Qi site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8-benz- yl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-di- oxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)- 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-isobutoxycarbonyloxy-4-meth- oxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl- 4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate;
- inhibitors of complex II: benodanil, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-
2- yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl- butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, benzovindiflupyr,
3- (difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide,
3- (trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide,
1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluorometh- yl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoro- methyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-tri- methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide;
- other respiration inhibitors: diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-
4- (4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivates: bina- pacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
B) Sterol biosynthesis inhibitors
- C14 demethylase inhibitors: triazoles: azaconazole, bitertanol, bromuconazole, cy- proconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbu- conazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ip- conazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triad- imefon, triadimenol, triticonazole, uniconazole, 1 -[rel-(2S;3R)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazole,
2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]tri- azole-3-thiol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
- Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropi- morph, tridemorph, fenpropidin, piperalin, spiroxamine;
- Inhibitors of 3-keto reductase: fenhexamid;
C) Nucleic acid synthesis inhibitors
- phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, met- alaxyl, ofurace, oxadixyl;
- others: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-
2- (p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin- 4-amine;
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate- methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluoro- phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine;
- other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil;
- protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride- hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F) Signal transduction inhibitors
- MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
- G protein inhibitors: quinoxyfen;
G) Lipid and membrane synthesis inhibitors
- Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothi- olane;
- lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
- phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph, mandi- propamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4-cy- ano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
- compounds affecting cell membrane permeability and fatty acides: propamocarb, propamocarb-hydrochloride;
- fatty acid amide hydrolase inhibitors: 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-
3- isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol- 1 -yl]ethanone; Inhibitors with Multi Site Action
inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
organochlorine compounds (phthalimides, sulfamides, chloronitriles): anilazine, chlo- rothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)- N-ethyl-4-methyl-benzenesulfonamide;
guanidines and others: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithia- non, 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone; Cell wall synthesis inhibitors
inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
Plant defence inducers
acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; 4-cy- clopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide; phosphonates:
fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
Unknown mode of action
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclome- zine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumet- over, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxine- copper, picarbutrazox, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy- 6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy- 2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-tri- fluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine,
N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-me- thyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine, 2-methoxy-acetic acid 6-tert-butyl-8-fluoro- 2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyris- oxazole), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro- 1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, 4,4-difluoro- 3,3-dimethyl-1 -(3-quinolyl)isoquinoline;
Antifungal biological Control Agents:
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. BOTECTOR® from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL Accession No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA), 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 1-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida sai- toana (e.g. BIOCURE® (in mixture with lysozyme) and BIOCOAT® 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 ca- tenulatum (e.g. isolate J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS® from Prophyta, Germany), 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- dochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Phlebiopsis gigantea (e.g. ROTSOP® from Verdera, Finland), Pseudozyma flocculosa (e.g. SPORO- DEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis (e.g. REGALIA® from Marrone Biolnnovations, USA), Talaromyces fla- vus V1 17b (e.g. PROTUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. 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. TRICHO- DEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ICC012 and T. 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);
or
one insecticidal compound IB selected from the group consisting of
M-1 .A acetylcholine esterase inhibitors from the class of carbamates:
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;
M-1 .B acetylcholine esterase inhibitors from the class of organophosphates:
acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethox- yfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimetho- ate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl 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; M-2 GABA-gated chloride channel antagonists:
M-2.A cyclodiene organochlorine compounds: endosulfan; or
M-2.B fiproles: ethiprole, fipronil, flufiprole, pyrafluprole, or pyriprole;
M-2. Others: 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4H-isoxazol-
3- yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene-1 -carboxamide,
4- [5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo- 2-(2,2,2-trifluoroethylamino)ethyl]benzamide;
M-3 sodium channel modulators from the class of pyrethroids:
acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bi- oallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cyper- methrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flu- cythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, meperfluthrin, meto- fluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (py- rethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralome- thrin, transfluthrin, DDT and methoxychlor;
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-5 allosteric nicotinic acteylcholine receptor activators from the class of spinosyns: spinosad, spinetoram;
M-6 chloride channel activators from the class of mectins: abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
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-13 nicotinic acetylcholine receptor channel blockers: bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;
M-14 inhibitors of the chitin biosynthesis type 0:
bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
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;
M-18 Octopamin receptor agonists: amitraz;
M-19 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, flometoquin, fluacrypyrim or pyriminostrobin;
M-20 Mitochondrial complex I electron transport inhibitors:
fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim, or rotenone;
M-21 Voltage-dependent sodium channel blockers:
indoxacarb, metaflumizone or 1 -[(E)-[2-(4-cyanophenyl)-1 -[3-(trifluoromethyl)phen- yl]ethylidene]amino]-3-[4-(difluoromethoxy)phenyl]urea (known from CN101715774);
M-22 Inhibitors of the lipid synthesis, inhibitors of acetyl CoA carboxylase:
spirodiclofen, spiromesifen or spirotetramat;
M-23 Mitochondrial complex II electron transport inhibitors:
cyenopyrafen, cyflumetofen or pyflubumide;
M-24 Ryanodine receptor-modulators from the class of diamides: flubendiamide, chlorantraniliprole (rynaxypyr), cyantraniliprole (cyazypyr), (R)-3-chloro-N1 -{2-me- thyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2-methyl- sulfonylethyl)phthalamide or (S)-3-chloro-N 1 -{2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(tri- fluoromethyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamide (both known from WO 2007/101540), 3-bromo-N-{2-bromo-4-chloro-6-[(1 -cyclopropyl- ethyl)carbamoyl]phenyl}-1 -(3-chloropyridin-2-yl)-1 H-pyrazole-5-carboxamide (known from WO 2005/077934), the compound methyl-2-[3,5-dibromo-2-({[3-bromo-1 - (3-chloropyridin-2-yl)-1 H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydra- zinecarboxylate (known from WO 2007/043677), N2-[2-(3-chloro-2-pyridyl)-5-[(5-me- thyltetrazol-2-yl)methyl]pyrazol-3-yl]-5-cyano-N1 ,3-dimethyl-phthalamide (known from WO 2007/144100), N2-(1 -cyano-1 -methyl-ethyl)-N1 -(2,4-dimethylphenyl)-3-io- do-phthalamide (known from CN102613183), 3-chloro-N2-(1 -cyano-1 -methyl-ethyl)- N1 -(2,4-dimethylphenyl)phthalamide (known from CN102613183), 2-(3-chloro- 2-pyridyl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-5-[[5-(trifluoromethyl)- tetrazol-2-yl]methyl]pyrazole-3-carboxamide (known from WO 2007/144100), N-[2-(tert-butylcarbamoyl)-4-chloro-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(flu- oromethoxy)pyrazole-3-carboxamide (known from WO2012/034403), 5-bromo- N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-2-(3,5-dichloro-2-pyridyl)pyrazole-3-car- boxamide (known from US201 1/046186), 5-chloro-2-(3-chloro-2-pyridyl)-N-[2,4-di- chloro-6-[(1 -cyano-1 -methyl-ethyl)carbamoyl]phenyl]pyrazole-3-carboxamide (known from WO2008/134969), N-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-me- thyl-phenyl]-5-bromo-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from M-25 Others: afidopyropen, 2-(5-ethylsulfinyl-2-fluoro-4-methyl-phenyl)-5-methyl- 1 ,2,4-triazol-3-amine (known from WO 06/043635), 1 -(5-ethylsulfinyl-2,4-dimethyl- phenyl)-3-methyl-1 ,2,4-triazole (known from WO 06/043635), triflumezopyrim, 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)-imidazo[1 ,2-a]py- ridine-2-carboxamide (known from WO 2013/055584), 5-[3-[2,6-dichloro-4-(3,3-di- chloroallyloxy)phenoxy]propoxy]-1 H-pyrazole (known from WO2010/060379), N-[1 - [(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide, N-[1 -[(6-chloro- 3-pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro-propanamide, N-[1 -[(6-bromo- 3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide, N-[1 -[(2-chloropyrimidin- 5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide, N-[1 -[(6-chloro-5-fluoro-3-pyri- dyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide, 2,2,2-trifluoro-N-[1 -[(6-fluoro- 3-pyridyl)methyl]-2-pyridylidene]acetamide, 2-chloro-N-[1 -[(6-chloro-3-pyridyl)meth- yl]-2-pyridylidene]-2,2-difluoro-acetamide, N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridyl- idene]-2,2,2-trifluoro-acetamide, N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]- 2,2-difluoro-acetamide (all known from WO2012/029672); 1 1 -(4-chloro-2,6-dimethyl- phenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-1 1 -en-10-one (known from WO 2006/089633), 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-
1 - azaspiro[4.5]dec-3-en-2-one (known from WO 2008/06791 1 ), 2-(5-fluoro-3-pyri- dyl)-5-(6-pyrimidin-2-yl-2-pyridyl)thiazole hydrofluoride, 2-(3-pyridyl)-5-(6-pyrimidin-
2- yl-2-pyridyl)thiazole, 5-[6-(1 ,3-dioxan-2-yl)-2-pyridyl]-2-(3-pyridyl)thiazole (all known from WO 2010/006713), 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoro- methyl)-4H-isoxazol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene- 1 -carboxamide (known from WO 2009/002809), 4-[5-(3,5-dichlorophenyl)-5-(triflu- oromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]- benzamide (known from WO 05/085216), 4-[5-(3,5-dichlorophenyl)-5-(trifluoro- methyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 -oxothietan-3-yl)benzamide (known from WO 2013/050317);
M-26: Bacillus firmus (e.g. Bacillus firmus CNCM 1-1582; see WO 09/126473,
WO 09/124707, commercially available as "Votivo");
or
compound IC having plant growth regulator activity selected from the group consisting
- Antiauxins: clofibric acid, 2,3,5-tri-iodobenzoic acid;
- Auxins: 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, dichlorprop, fenoprop, IAA (indole-3-acetic acid), IBA, naphthaleneacetamide, onaphthaleneacetic acid, 1 -naphthol, naphthox- yacetic acid, potassium naphthenate, sodium naphthenate, 2,4,5-T;
- Cytokinins: 2iP, 6-benzylaminopurine (6-BA) (= N-6-benzyladenine), 2,6- N-Oxide- 2,6-lutidine, 2,6-dimethylpyridine, kinetin, zeatin;
- Defoliants: calcium cyanamide, dimethipin, endothal, merphos, metoxuron, penta- chlorophenol, thidiazuron, tribufos, tributyl phosphorotrithioate;
- Ethylene modulators: aviglycine, 1 -methylcyclopropene (1 -MCP), prohexadione, prohexadione calcium, trinexapac, trinexapac-ethyl;
- Ethylene releasers: ACC, etacelasil, ethephon, glyoxime; - Gibberellins: gibberelline, gibberellic acid;
- Growth inhibitors : 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;
- Morphactins: chlorfluren, chlorflurenol, dichlorflurenol, flurenol;
- Growth retardants: chlormequat, chlormequat chloride, daminozide, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, metconazole;
- Growth stimulators: brassinolide, forchlorfenuron, hymexazol;
- Unclassified plant growth regulators / classification unknown: amidochlor, benzoflu- or, buminafos, carvone, choline chloride, ciobutide, clofencet, cloxyfonac, cyana- mide, cyclanilide, cycloheximide, cyprosulfamide, epocholeone, ethychlozate, ethylene, fenridazon, fluprimidol, fluthiacet, heptopargil, holosulf, inabenfide, karetazan, lead arsenate, methasulfocarb, pydanon, sintofen, triapenthenol;
or
4) Bacillus subtilis MBI600 as compound ID having the accession number NRRL B-50595; and 5) Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 as compound II.
The above-referred mixtures and all further embodiments of mixtures described hereinbelow are for the purpose of this application also referred to as "inventive mixtures".
Synergistic mixtures comprising certain fungicidal compounds and inter alia the Bacillus pumilis strain NRRL B-30087 (QST2808) (active ingredient of commercial products SONATA® and BALLAD® Pluis from AgraQuest, Inc. USA) have been disclosed in WO 2009/037242 and WO 2010/139656. However, no mixtures comprising the specific B. pumilis strain INR7 as defined herein are mentioned therein.
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).
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). Thus, Bacillus subtilis MBI600 (or MBI 600 or MBI-600) is identical to Bacil- lus amyloliquefaciens subsp. plantarum MBI600, formerly Bacillus subtilis MBI600. For the purpose of this invention, Bacillus subitilis MBI 600 shall mean Bacillus amyloliquefaciens subsp. plantarum MBI600, formerly Bacillus subtilis MBI600.
The bacteria 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 (vegatitive cells and spores) can be washed and concentrated (e.g. by centrifugation at room temperature for 15 min at 7000 x g). To produce a dry formulation, bacterial cells, preferably spores were suspended in a suitable dry carrier (e.g. clay). To produce a 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 pumilus INR-7 (defined herein as compound II) is also otherwise referred to as BUF-22 or as BU F-33 or similar codes and has been described e.g. in US 2012/0149571 A1 .
Bacillus pumilus INR-7 is deposited as BUF-22 having the accession number NRRL B-50153 with the United States Department of Agriculture on Jul. 23, 2008, and as BU-F-33, having the accession number NRRL B-50185 with the United States Department of Agriculture on Oct. 15, 2008.
Bacillus pumilus INR7 can be cultivated and prepared as described for Bacillus subtilis MBI 600. Thus, the present invention relates to synergistic mixtures comprising Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 as compound II and one compound IA.
The present invention furthermore relates to synergistic mixtures comprising Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 as compound II and one compound IB.
The present invention furthermore relates to synergistic mixtures comprising Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 as compound II and one compound IC. The remaining compounds IA, IB as well as their pesticidal action and methods for producing them are generally known. For instance, they may be found in the e-Pesticide Manual V5.2 (ISBN 978 1 901396 85 0) (2008-201 1 ) among other publications or in the references given above.
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.
In regard to the instant invention the term pests embrace animal pests, and harmful fungi.
Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests, e.g. both animal pests and harmful fungi.
There also exists the need for pest control agents that combine knock-down activity with prolonged control, that is, fast action with long lasting action.
Another difficulty in relation to the use of pesticides is that the repeated and exclusive applica- tion of an individual pesticidal compound leads in many cases to a rapid selection of pests, that means animal pests, and harmful fungi, which have developed natural or adapted resistance against the active compound in question. Therefore there is a need for pest control agents that help prevent or overcome resistance. Another problem underlying the present invention is the desire for compositions that improve plants, a process which is commonly and hereinafter referred to as "plant health".
It was therefore an object of the present invention to provide pesticidal mixtures which solve the problems of reducing the dosage rate and / or enhancing the spectrum of activity and / or com- bining knock-down activity with prolonged control and / or to resistance management and/or promoting (increasing) the health of plants.
We have found that this object is in part or in whole achieved by the mixtures comprising the active compounds defined in the outset.
In particular, it has been found that the action of the inventive mixtures goes far beyond the fungicidal and/or insecticidal and/or plant health improving action of the active compounds I and II present in the mixture alone (synergism). As used herein, the term "insecticidal" (or "insect attac") also denotes not only action against (or attac by) insects, but also against (by) arachnids and nematodes.
Herein, we have found that 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).
Thus, the present invention relates to the inventive mixtures having synergistically enhanced action of controlling harmful fungi.
Moreover, 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. Herein, we have found that simultaneous, that is joint or separate, application of the compound I and the compound II or successive application of the compound I and compound II provides enhanced plant health effects compared to the plant health effects that are possible with the individual compounds (synergistic mixtures).
Thus, the present invention relates inventive mixtures having synergistically enhanced action of increasing the health of plants.
Moreover, the invention relates to a method for improving the health of plants, using the inventive 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 to foliar application.
In particular, 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. In a preferred embodiment, 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.
In an equally preferred embodiment, 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 lA and compound II.
In an equally preferred embodiment, 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. In an equally preferred embodiment, 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.
In general, "pesticidally effective amount" means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, in- eluding the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures / compositions used in the invention. A pesticidally effective amount of the mixtures / compositions will also vary according to the prevailing condi- tions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
The term "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. Anyway, 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.
It was therefore an object of the present invention to provide a pesticidal composition which solves the problems outlined above, and which should, in particular, improve the health of plants, in particular the yield of plants. The term "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. It has to be emphasized that the above mentioned effects of the inventive mixtures, i.e. enhanced health of the plant, are also present when the plant is not under biotic stress and in particular when the plant is not under pest pressure.
For example, for foliar applications, it is evident that a plant suffering from fungal or insecticidal attack produces a smaller biomass and leads to a reduced yield as compared to a plant which has been subjected to curative or preventive treatment against the pathogenic fungus or any other relevant pest and which can grow without the damage caused by the biotic stress factor. However, the methods according to the invention lead to an enhanced plant health even in the absence of any biotic stress. This means that the positive effects of the mixtures of the invention cannot be explained just by the pesticidal activities of the compounds (I) and (II), but are based on further activity profiles. Accordingly, the application of the inventive mixtures can also be carried out in the absence of pest pressure.
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. According to the present invention, "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. For foliar appalication forms, 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 con- tent; 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. "Grain" 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. According to the present invention, the yield is increased by at least 4%. In general, the yield increase may even be higher, for example 5 to 10 %, more preferable by 10 to 20 %, or even 20 to 30 %
According to the present invention, the yield - if measured in the absence of pest pressure - is increased by at least 2 % In general, the yield increase may even be higher, for example until 4%-5% or even more.
Another indicator for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects such as the general visual appearance.
For foliar applications, improved plant vigor can be characterized, among others, by the following 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. based on increased stomatal conductance and/or increased CO2 assimilation rate)); and/or earlier flowering; and/or earlier fruiting;; and/or earlier grain maturity; and/or less non-productive tillers; and/or less dead basal leaves; and/or less input needed (such as fertilizers or water); and/or greener leaves; and/or complete maturation under shortened vegetation periods; and/or easier harvesting; and/or faster and more uniform ripening; and/or longer shelf-life; and/or longer panicles; and/or delay of senescence ; and/or stronger and/or more productive tillers; and/or better extractability of ingredients; and/or improved quality of seeds (for being seeded in the following seasons for seed production); and/or reduced production of ethylene and/or the inhibition of its reception by the plant.
Another indicator for the condition of the plant is the "quality" of a plant and/or its products. According to the present invention, 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 in- creased 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 im- proved 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, especially over longer terms, can have harmful effects on plants.
Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes. According to the present invention, "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. by its fungicidal or insecticidal action which directly destroys the microorganisms or pests, but rather by a stimulation of the plants' own defensive reactions against said stress factors.
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:
less yield and/or less vigor, for both effects examples can be burned leaves, less flowers, premature ripening, later crop maturity, reduced nutritional value amongst others. 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 decreas- ing 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).
As a result of biotic and/or abiotic stress factors, the quantity and the quality of the stressed plants decrease. As far as quality (as defined above) is concerned, reproductive development is usually severely affected with consequences on the crops which are important for fruits or seeds. Synthesis, accumulation and storage of proteins are mostly affected by temperature; growth is slowed by almost all types of stress; polysaccharide synthesis, both structural and storage is reduced or modified: these effects result in a decrease in biomass (yield) and in changes in the nutritional value of the product.
As pointed out above, the above identified indicators for the health condition of a plant may be interdependent and may result from each other. For example, an increased resistance to biotic and/or abiotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield. Inversely, a more developed root system may result in an increased resistance to biotic and/or abiotic stress. However, these interdependencies and interactions are neither all known nor fully understood and therefore the different indicators are described separately. In one embodiment the 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. In another embodiment the inventive mixtures effectuate in an increased quality of a plant or its product.
In yet another embodiment the inventive mixtures effectuate an increased tolerance and/or resistance of a plant or its product against biotic stress.
In yet another embodiment the inventive mixtures effectuate an increased tolerance and/or resistance of a plant or its product against abiotic stress.
In a preferred embodiment of the invention, the inventive mixtures effectuate an increase in the yield.
In a preferred embodiment of the invention, 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.
In another preferred embodiment of the invention, the plant health effects of the inventive mix- tures effect increased resistance of plant against biotic stress.
In another preferred embodiment of the invention, the plant health effects of the inventive mixtures effect increased resistance of plant against abiotic stress. In a more preferred embodiment of the invention, the inventive mixtures effect an increase in the yield.
In a more preferred embodiment of the invention, 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, 85:15, 84:16, 83:17, 82:18, 81 :19, 80:20, 79:21 , 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71 :29, 70:30, 69:31 , 68:32, 67:33, 66:34, 65:45, 64:46, 63:47, 62:48, 61 :49, 60:40, 59:41 , 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51 :49, 50:50, 49:51 , 48:52, 47:53, 46:54, 45:55, 44:56, 43:57, 42:58, 41 :59, 40:60, 39:61 , 38:62, 37:63, 36:64, 35:65, 34:66, 33:67, 32:68, 31 :69, 30:70, 29:71 , 28:72, 27:73, 26:74, 25:75, 24:76, 23:77, 22:78, 21 :79, 20:80, 19:81 , 18:82, 17:83, 16:84, 15:85, 14:86, 13:87, 12:88, 1 1 :89, 10:90, 9:91 , 8:92, 7:93, 6:94, 5:95, 4:96, 3:97, 2:98, to 1 :99). Herein, 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.
For compound II (and, if present compound ID), all of these ratios refer to a preparation with at least 106 CFU ("colony foming units per gram")/g.
Herein, compound II (ID) may be supplied in any physiologic state such as active or dormant. Dormant compound II may be supplied for example frozen, dried, or lyophilized or partly desiccated (proceduers 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. However, the compound II (ID) is preferably delivered and formulated in a dormant stage.
The microorganisms as used according to the invention (e.g. compound ID, compound II or a compound lA from antifungal biocontrol agent class L), t 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 (Bioprozesstechnik 1. Ein- fuhrung in die Bioverfahrenstechnik (Gustav Fischer Verlag, Stuttgart, 1991 )) or in the textbook by Storhas (Bioreaktoren und periphere Einrichtungen (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. Descriptions of 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. Examples of 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. 53-73, ISBN 0 19 963577 3). 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. To maintain the stability of plasmids, 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. Culture is continued until a maximum of the desired product has formed. This is normally achieved within 10 hours to 160 hours. To obtain cell-free extracts, the cells can be disrupted optionally by high- frequency ultrasound, by high pressure, e.g. in a French pressure cell, by osmolysis, by the action of detergents, lytic enzymes or organic solvents, by means of homogenizers or by a combi- nation of several of the methods listed. 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. For example 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
A) Respiration inhibitors
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]-
3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-di-chlorophenyl)-1 -methyl-allylideneamino- oxymethyl)-phenyl)-2-methoxyimino-N methyl-acetamide, pyribencarb, triclopyricarb/chloro- dincarb, famoxadone, fenamidone; 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-(acetoxymethoxy)-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-isobutoxycarbonyloxy-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-(1 ,3-benzodioxol-5-yl- methoxy)-4-methoxy-pyridine-2-car-bonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2- methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6- methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate;
- inhibitors of complex II (e. g. carboxamides): bixafen, boscalid, carboxin, fluopyram, fluxa- pyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane, N-(4'-trifluoromethylthiobiphenyl-2-yl)-
3- difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, 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- methanonaphthalen-5-yl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide, 3-(diflu- oromethyl)-1 -methyl-N-(1 , 1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-
1 - methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethyl- indan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-
4- yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyr- azole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide - other respiration inhibitors: (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethyl- pyridin-2-yloxy)-phenyl]-ethyl}-amine, fluazinam, ametoctradin, and silthiofam;
B) Sterol biosynthesis inhibitors (SBI fungicides)
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)-
2- (2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol; imidazoles: imazalil, prochloraz, triflumizol;
- Delta14-reductase inhibitors: fenpropimorph, spiroxamine;
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, oxadixyl;
others: hymexazole, oxolinic acid, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro- 2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
D) Inhibitors of cell division and cytoskeleton
tubulin inhibitors: benomyl, carbendazim, thiabendazole, thiophanate-methyl;
other cell division inhibitors: ethaboxam, pencycuron, metrafenone;
E) Inhibitors of amino acid and protein synthesis
- cyprodinil, pyrimethanil;
F) Signal transduction inhibitors: iprodione, fludioxonil;
G) Lipid and membrane synthesis inhibitors
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-hydrochloride,
H) Inhibitors with Multi Site Action
inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
thio- and dithiocarbamates: mancozeb, maneb, metiram, thiram;
organochlorine compounds: chlorothalonil, captan, folpet,;
- guanidines and others: dodine, guazatine, guazatine-acetate, iminoctadine, iminoctadine- triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl-1 H,5H-[1 ,4]dithi- ino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
I) Cell wall synthesis inhibitors
inhibitors of glucan synthesis: validamycin; melanin synthesis inhibitors: pyroquilon, tricy- clazole;
J) Plant defence inducers
acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; 4-cyclopropyl- N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide; phosphonates: fosetyl, fosetyl-aluminum; K) Unknown mode of action
- cymoxanil, oxine-copper, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetam- ide, 2-methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-meth- ylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazo- lidin-3-yl]-pyridine (pyrisoxazole), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid am- ide, 5-chloro-1 -(4,6-di-methoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phen- yl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide 4,4-difluoro-3,3-di- methyl-1 -(3-quinolyl)isoquinoline;
L) Antifungal biological Control Agents:
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- T ECTOR® from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA), Bacillus subtilis (e.g. isolate NRRL B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA), Bacillus subtilis var. amylolique-faciens FZB24 (e.g. TAEGRO® from Novozyme Biologi- cals, Inc., USA), Candida oleophila I-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida sai- toana (e.g. BIOCURE® (in mixture with lysozyme) and BIO-COAT® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), Clonosta- chys rosea f. catenulata, also named Gliocladium catenulatum (e.g. isolate J 1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS® from Prophyta, Germany), 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), Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Phlebiopsis gigantea (e.g. ROTSOP® from Verdera, Fin- land), Pseudozyma flocculosa (e.g. SPORODEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis (e.g. REGALIA® from Marrone Biolnnovations, USA), Talaromy- ces flavus V1 17b (e.g. PROTUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride 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. TRICHOPEL from Agrimm Tech- nologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isa- gro 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 compound IB selected from the group consisting of
M-1 .A acetylcholine esterase inhibitors from the class of carbamates,
for example aldicarb, benfuracarb, carbofuran, carbosulfan, isoprocarb, methomyl, thiodicarb, triazamate;
M-1 .B acetylcholine esterase inhibitors from the class of organophosphates,
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;
M-2 GABA-gated chloride channel antagonists:
M-2.B fiproles (phenylpyrazoles),
for example ethiprole, fipronil, flufiprole, pyrafluprole, or pyriprole;
M-2. Others, for example 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4H-isoxa- zol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene-1 -carboxamide (known from
WO 2007/079162), 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-
N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide (known from WO 05/085216);
M-3 sodium channel modulators from the class of pyrethroids,
for example bifenthrin, cyfluthrin, beta-cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha- cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenvalerate, flu- cythrinate, permethrin, tefluthrin;
M-4 nicotinic acteylcholine receptor agonists from the class of neonicotinoids;
for example acetamiprid, chlothianidin, cycloxaprid, dinotefuran, flupyradifurone, imidacloprid, nitenpyram, sulfoxaflor, thiacloprid, thiamethoxam, 1 -[(6-chloro-3-pyridyl)methyl]-7-methyl-8-ni- tro-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,
for example spinosad, spinetoram;
M-6 chloride channel activators from the class of mectins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
M-9 selective homopteran feeding blockers,
for example pymetrozine, pyrifluquinazon, 2-(5-fluoro-3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)- thiazole hydrofluoride;
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),
for example diflubenzuron, flufenoxuron, lufenuron, novaluron, teflubenzuron;
M-15 inhibitors of the chitin biosynthesis type 1 , for example buprofezin;
M-17 Ecdyson receptor agonists, for example methoxyfenozide;
M-20 Mitochondrial complex I electron transport inhibitors, for example tebufenpyrad,;
M-21 Voltage-dependent sodium channel blockers,
for example indoxacarb or metaflumizone;
M-22 Inhibitors of the lipid synthesis, inhibitors of acetyl CoA carboxylase, for example spirodi- clofen, spirotetramat;
M-24 Ryanodine receptor-modulators from the class of diamides, for example flubendiamide, chlorantraniliprole, cyantraniliprole, (R)-3-chloro-N1 -{2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoro- methyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamide or (S)-3-Chlor-N1 -{2-me- thyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)- phthalamide (both known from WO 2007/101540), 3-bromo-N-{2-bromo-4-chloro-6-[(1 -cyclo- propylethyl)carbamoyl]phenyl}-1 -(3-chloropyridin-2-yl)-1 H-pyrazole-5-carboxamide (known from WO 2005/077934), methyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3-chloropyridin-2-yl)-1 H-pyrazol-5-yl]- carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate (known from WO 2007/043677), N2-[2-(3-chloro-2-pyridyl)-5-[(5-methyltetrazol-2-yl)methyl]pyrazol-3-yl]-5-cyano-N1 ,3-dimethyl- phthalamide (known from WO 2007/144100);
M-25 Others, for example afidopyropen, 2-(5-ethylsulfinyl-2-fluoro-4-methyl-phenyl)-5-methyl- 1 ,2,4-triazol-3-amine (known from WO 06/043635), 1 -(5-ethylsulfinyl-2,4-dimethyl-phenyl)- 3-methyl-1 ,2,4-triazole (known from WO 06/043635.)
M-26: Bacillus firmus (e.g. Bacillus firmus of strain CNCM 1-1582; see WO09126473 and WO 09/124707, commercially available as "Votivo").
Preferred inventive mixtures are those comprising compound II and fungicidal compound IA displayed in Table 1A:
In Table 1A, the following abbreviations are used:
Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185
IA = Compound IA II = Compound II
No IA II No IA II
M-1 . azoxystrobin A M-7. pyraclostrobin A
M-2. dimoxystrobin A M-8. trifloxystrobin A
M-3. fluoxastrobin A M-9. pyribencarb A
M-4. kresoxim-methyl A M-10. cyazofamid A
M-5. orysastrobin A M-1 1 . amisulbrom A
M-6. picoxystrobin A M-12. [(3S,6S,7R,8R)-8- A No IA II No IA II benzyl-3-[(3- M-19. fluopyram A acetoxy-4-methoxy- M-20. fluxapyroxad A pyridine-2- M-21 . isopyrazam A carbonyl)amino]-6- M-22. penflufen A methyl-4,9-dioxo- M-23. penthiopyrad A
1 ,5-dioxonan-7-yl] M-24. sedaxane A
2-methylpropanoate M-25. N-(4'- A
M-13. [(3S,6S,7R,8R)-8- A trifluoromethylthiobi- benzyl-3-[[3-(acet- phenyl-2-yl)- oxymethoxy)-4- 3- difluoromethyl-1 - methoxy-pyridine- methyl-1 H-pyrazole-
2-carbonyl]amino]-6- 4- carboxamide methyl-4,9-dioxo- M-26. N-(2-(1 ,3,3-trimethyl- A
1 ,5-dioxonan-7-yl] butyl)-phenyl)-1 ,3-
2-methylpropanoate dimethyl-5-fluoro-
M-14. [(3S,6S,7R,8R)-8- A 1 H-pyrazole- benzyl-3-[(3-isobut- 4-carboxamide oxycarbonyloxy-4- (benzovindiflupyr) methoxy-pyridine- M-27. N-[9- A
2-carbonyl)amino]-6- (dichloromethylene)- methyl-4,9-dioxo- 1 ,2,3,4-tetrahydro-
1 ,5-dioxonan-7-yl] 2- 1 ,4-me- methylpropanoate thanonaphthalen-5-
M-15. [(3S,6S,7R,8R)-8- A yl]-3- benzyl-3-[[3-(1 ,3- (difluoromethyl)-l - benzodioxol-5- methyl-1 H-pyrazole- ylmethoxy)-4- 4-carboxamide methoxy-pyridine-2- M-28. 3-(difluoromethyl)-1 - A carbonyl]amino]-6- methyl-N-(1 ,1 ,3- methyl-4,9-dioxo- trimethylindan-4-
1 ,5-dioxonan-7-yl] 2- yl)pyrazole-4- methylpropanoate; carboxamide
M-16. (3S,6S,7R,8R)-3- A M-29. 3-(trifluoromethyl)-1 - A
[[(3-hydroxy-4- methyl-N-(1 ,1 ,3- methoxy-2- trimethylindan-4- pyridi- yl)pyrazole-4- nyl)carbonyl]amino]- carboxamide
6-methyl-4,9-dioxo- M-30. 1 ,3-dimethyl-N- A 8-(phenylmethyl)- (1 ,1 ,3- 1 ,5-dioxonan-7-yl 2- trimethylindan-4- methylpropanoate yl)pyrazole-4-
M-17. bixafen A carboxamide
M-18. boscalid A M-31 . 3-(trifluoromethyl)- A No IA II No IA II
1 ,5-dimethyl-N- thiol
(1 ,1 ,3- M-47. prochloraz A trimethylindan-4- M-48. fenpropimorph A yl)pyrazole-4- M-49. benalaxyl A carboxamide M-50. benalaxyl-M A
M-32. 3-(difluoromethyl)- A M-51 . kiralaxyl A
1 ,5-dimethyl-N- M-52. metalaxyl A
(1 ,1 ,3- M-53. 5-fluoro-2-(p- A trimethylindan-4- tol- yl)pyrazole-4- ylmethoxy)pynmidin- carboxamide 4-amine
M-33. 1 ,3,5-trimethyl-N- A M-54. 5-fluoro-2-(4- A
(1 ,1 ,3- fluorophenyl- trimethylindan-4- methoxy)pynmidin- yl)pyrazole-4- 4-amine
carboxamide M-55. carbendazim A
M-34. (5,8-difluoro- A M-56. thiophanate-methyl A quinazolin-4-yl)-{2- M-57. ethaboxam A
[2-fluoro-4-(4-
M-58. metrafenone A trifluoromethylpyri-
M-59. cyprodinil A din-2-yloxy)-phenyl]-
M-60. pyrimethanil A ethyl}-amine
M-61 . fludioxonil A
M-35. ametoctradin A
M-62. iprodione A
M-36. cyproconazole A
M-63. dimethomorph A
M-37. difenoconazole A
M-64. flumorph A
M-38. epoxiconazole A
M-65. mandipropamid A
M-39. fluquinconazole A
M-66. N-(1 -(1 -(4-cyano- A
M-40. metconazole A
phenyl)-
M-41 . propiconazole A ethanesulfonyl)-but-
M-42. prothioconazole A 2-yl) carbamic acid-
M-43. tebuconazole A (4-fluorophenyl) es¬
M-44. triadimenol A ter
M-45. 1 -[re/-(2S;3R)-3-(2- A M-67. mancozeb A chlorophenyl)-2-(2,4- M-68. maneb A difluorophenyl)-
M-69. metiram A oxiranylmethyl]-
M-70. thiram A
5-thiocyanato-1 H-
M-71 . chlorothalonil A
[1 ,2,4]triazole
M-72. captan A
M-46. 2-[re/-(2S;3R)-3-(2- A
M-73. dithianon A chlorophenyl)-2-(2,4-
M-74. 2,6-dimethyl-1 H,5H- A difluorophenyl)-
[1 ,4]dithiino[2,3- oxiranylmethyl]- c:5,6-c']dipyrrole-
2H-[1 ,2,4]triazole-3- No IA II No IA II
1 ,3,5,7(2H,6H)- M-86. 2-(4-chloro-phenyl)- A tetraone N-[4-(3,4-dimethoxy-
M-75. isotianil A phenyl)-isoxazol-5-
M-76. tiadinil A yl]-2-prop-2-ynyloxy-
M-77. prohexadione- A acetamide 4,4- calcium; 4- difluoro-3,3- cyclopropyl-N-(2,4- dimethyl-1 -(3- dimethoxy- quinolyl)isoquinoline phenyl)thiadiazole-5- M-87. Ampelomyces A carboxamide quisqualis
M-78. triazoxide A M-88. Aspergillus flavus A
M-79. 2- butoxy-6-iodo- A M-89. Aureobasidium pul- A
3- propylchromen-4- lulans
one M-90. Bacillus pumilus A
M-80. N-(cyclo- A M-91 . Bacillus pumilus A propylmethoxyimino- NRRL Accession
(6-difluoro-methoxy- No. B-30087
2,3-difluoro-phenyl)- M-92. Bacillus subtilis A methyl)-2-phenyl M-93. Bacillus subtilis A acetamide NRRL-Nr. B-21661
M-81 . 2-methoxy-acetic A M-94. Bacillus subtilis var. A acid 6-tert-butyl-8- amylolique-faciens fluoro-2,3-dimethyl- FZB24
quinolin-4-yl ester M-95. Candida oleophila I- A
M-82. 3-[5-(4- A 82
methylphenyl)-2,3- M-96. Candida saitoana A dimethyl- M-97. chitosan A isoxazolidin-3-yl]- M-98. Clonostachys rosea A pyridine f. catenulate
M-83. 3-[5-(4-chloro- A M-99. Clonostachys rosea A phenyl)-2,3- f. catenulate J 1446 dimethyl- M-100. Coniothyrium mini- A isoxazolidin-3-yl]- tans
pyridine (pyrisoxa- M-101 . Cryphonectria paraA zole) sitica
M-84. N-(6-methoxy- A M-102. Endothia parasitica A pyridin-3-yl) cyclo- M-103. Cryptococcus albi- A propanecarboxylic dus
acid amide M-104. Fusarium ox- A
M-85. 5-chloro-1 -(4,6-di- A ysporum
methoxy-pyrimidin- M-105. FUSACLEAN® A 2-yl)-2-methyl-1 H-
M-106. Metschnikowia fruc- A benzoimidazole ticola No IA II No IA II
M-107. Microdochium A M-1 18. T. harzianum and T. A
dimerum viride
M-108. Phlebiopsis gigantea A M-1 19. T. harzianum A
M-109. Pseudozyma floccu- A ICC012 and T. viride
losa ICC080
M-1 10. Pythium oligandrum A M-120. T. polysporum and A
DV74 T. harzianum
M-1 1 1 . Reynoutria sach- A M-121 . T. stromaticum A
linensis M-122. T. virens GL-21 A
M-1 12. Talaromyces flavus A M-123. T. viride A
V1 17b M-124. T. viride TV1 A
M-1 13. Trichoderma A M-125. Ulocladium A
asperellum SKT-1 oudemansii HRU3
M-1 14. T. atroviride LC52 A
M-1 15. T. harzianum T-22 A
M-1 16. T. harzianum TH 35 A
M-1 17. T. harzianum T-39 A
Preferred inventive mixtures especially useful for foliar treatment are those comprising com- pound I I 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, Flu- quinconazole, Triticonazole, Fenpropimorph and Iprodione; more preferably selected from Dimoxystrobin, Pyraclostrobin, Azoxystrobin, Trifloxystrobin, Picoxystrobin, Cyazofamid, Boscalid, Fluoxapyroxad, Fluopyram, Bixafen, Isopyrazam, Benzovindiflupyr, Penthiopyrad, Ame- toctradin, Difenoconazole, Metconazole, Prothioconazole, Tebuconazole, Cyproconazole, Penconazole, Myclobutanil, Tetraconazole, Hexaconazole, Metrafenone, Zoxamid, Pyrimethanil, Cyprodinil, Metalaxyl, Fludioxonil, Dimethomorph, Mandipropamid, Copper, Metiram, Chlorothalonil, Dithianon, Fluazinam, Folpet, Fosetyl-AI, Captan, Cymoxanil and Mancozeb.
Equally preferred inventive mixtures are those comprising compound I I and insecticidal pound I B displayed in Table 1 B:
In Table 1 B, the following abbreviations are used:
Bacillus pumilus I NR7 having the accession number NRRL B-50153 or NRRL B-50185
I B
Figure imgf000027_0001
No IB II No IB II
M'-5. acephate A M'-34. thiacloprid A
M'-6. chlorpyrifos A M'-35. thiamethoxam A
M'-7. chlorpyrifos-methyl A M'-36. 1 -[(6-chloro-3-pyri- A
M'-8. dimethoate A dyl)methyl]-7-meth-
M'-9. methamidophos A yl-8-nitro-5-propoxy-
M'-10. ethiprole A 3,5,6,7-tetrahydro-
M'-1 1 . fipronil A 2H-imidazo[1 ,2-a]py-
M'-12. 4-[5-[3-chloro-5-(tri- A ridine
fluoromethyl)phen- M'-37. spinosad A yl]-5-(trifluorometh- M'-38. spinetoram A yl)-4H-isoxazol-3-yl]- M'-39. abamectin A
N-[2-oxo-2-(2,2,2- M'-40. emamectin benzoate A trifluoroethylamino)- M'-41 . 2-(5-fluoro-3-pyri- A ethyl]naphthalene- dyl)-5-(6-pyrimidin-2-
1 -carboxamide yl-2-pyridyl)thiazole
M'-13. 4-[5-(3,5-dichloro- A hydrofluoride
phenyl)-5-(trifluoro- M'-42. chlorfenapyr A methyl)-4H-isoxazol- M'-43. diflubenzuron A
3-yl]-2-methyl-N-[2- M'-44. flufenoxuron A oxo-2-(2,2,2-triflu- M'-45. novaluron A oroethylmino)ethyl]- M'-46. teflubenzuron A benzamide M'-47. tebufenpyrad A
M'-14. bifenthrin A M'-48. indoxacarb A
M'-15. cyfluthrin A M'-49. metaflumizone A
M'-16. beta-cyfluthrin A M'-50. flubendiamide A
M'-17. lambda-cyhalothrin A M'-51 . chlorantraniliprole A
M'-18. cypermethrin A M'-52. cyantraniliprole A
M'-19. alpha-cypermethrin A M'-53. (R)-3-chloro-N 1 -{2- A
M'-20. zeta-cypermethrin A methyl-4-[1 ,2,2,2-te-
M'-21 . deltamethrin A trafluoro-1 -(trifluoro-
M'-22. fenvalerate A methyl)ethyl]phenyl}-
M'-23. flucythrinate A N2-(1 -methyl-2-me-
M'-24. permethrin A thylsulfonylethyl)-
M'-25. tefluthrin A phthalamide or (S)-
M'-26. acetamiprid A 3-chloro-N1 -{2-me-
M'-27. chlothianidin A thyl-4-[1 ,2,2,2-te-
M'-28. cycloxaprid A trafluoro-1 -(trifluoro-
M'-29. dinotefuran A methyl)ethyl]phenyl}-
M'-30. flupyradifurone A N2-(1 -methyl-2-
M'-31 . imidacloprid A methylsulfonyl-
M'-32. nitenpyram A ethyl)phthalamide
M'-33. sulfoxaflor A M'-54. 3-bromo-N-{2-bro- A mo-4-chloro-6-[(1 - No IB II No IB II cyclopropylethyl)- phthalamide
carbamoyl]phenyl}- M'-57. 2-(5-ethylsulfinyl-2- A
1 -(3-chloropyridin-2- fluoro-4-methyl- yl)-1 H-pyrazole-5- phenyl)-5-methyl- carboxamide 1 ,2,4-triazol-3-amine
M'-55. methyl-2-[3,5-di- A M'-58. 1 -(5-ethylsulfinyl- A bromo-2-({[3-bromo- 2,4-dimethyl- 1 -(3-chloropyridin-2- phenyl)-3-methyl- yl)-1 H-pyrazol-5-yl]- 1 ,2,4-triazole
carbonyl}amino)- M'-59. afidopyropen A benzoyl]-1 ,2-dimeth- M'-60. Bacillus firmus A ylhydrazine- M'-61 . Bacillus firmus A carboxylate CNCM 1-1582
M'-56. N2-[2-(3-chloro-2- A
pyridyl)-5-[(5-methyl- tetrazol-2-yl)methyl]- pyrazol-3-yl]-5-cya- no-N1 ,3-dimethyl-
More preferred inventive mixtures especially useful for foliar treatment are those comprising compound II and insecticidal compound IB selected from momfluorothrin; 1 -[(6-chloro-3-py- ridyl)methyl]-2-nitro-1 -[(E)-pentylideneamino]guanidine; 1 -[(E)-[2-(4-cyanophenyl)-1 -[3-(triflu- oromethyl)phenyl]ethylidene]amino]-3-[4-(difluoromethoxy)phenyl]urea; N2-(1 -cyano-1 -methyl- ethyl)-N1 -(2,4-dimethylphenyl)-3-iodo-phthalamide, 3-chloro-N2-(1 -cyano-1 -methyl-ethyl)- N1 -(2,4-dimethylphenyl)phthalamide, 2-(3-chloro-2-pyridyl)-N-[4-cyano-2-methyl-6-(methylcar- bamoyl)phenyl]-5-[[5-(trifluoromethyl)tetrazol-2-yl]methyl]pyrazole-3-carboxamide, N-[2-(tert- butylcarbamoyl)-4-chloro-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(fluoromethoxy)pyrazole- 3-carboxamide, 5-bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-2-(3,5-dichloro-2-pyridyl)- pyrazole-3-carboxamide, 5-chloro-2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(1 -cyano-1 -methyl- ethyl)carbamoyl]phenyl]pyrazole-3-carboxamide, N-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro- 6-methyl-phenyl]-5-bromo-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide; triflumezopyrim, 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)-imidazo[1 ,2-a]pyridine-2-car- boxamide, 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole,
N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide, N-[1 -[(6-chloro-3-py- ridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro-propanamide, N-[1 -[(6-bromo-3-pyridyl)- methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide, N-[1 -[(2-chloropyrimidin-5-yl)methyl]-2-pyridyl- idene]-2,2,2-trifluoro-acetamide, N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide, 2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acet- amide, 2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide, N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide, N-[1 -[(6-chloro-3-py- ridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydro- xy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-1 1 -en-10-one, 3-(4'-fluoro-2,4-dimethylbiphenyl- 3-yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en-2-one, 2-(5-fluoro-3-pyridyl)-5-(6-pyrimidin-2-yl- 2-pyridyl)thiazole hydrofluoride, 2-(3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyndyl)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-trifluoroethylamino)ethyl]naphthalene
amide, 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo- 2-(2,2,2-trifluoroethylamino)ethyl]benzamide and 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)- 4H-isoxazol-3-yl]-2-methyl-N-(1 -oxothietan-3-yl)benzamide.
Equally preferred inventive mixtures are those comprising compound II and compound IC having plant growth regulating activity displayed in Table 1 C:
In Table 1 C, the following abbreviations are used:
Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 = A IC = Compound IC II = Compound II
Figure imgf000030_0001
Figure imgf000030_0002
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- benzylaminopurine, 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.
Even more preferred inventive mixtures especially useful for foliar treatment are those compris- ing 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.
More preferred inventive mixtures are those comprising compound II and fungicidal compound IA displayed in Table 2A:
In Table 2A, the following abbreviations are used:
Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B-50185 IA = Compound IA II = Compound II
No IA II No IA II
C-1 . azoxystrobin A 1 ,5-dioxonan-7-yl] 2-
C-2. dimoxystrobin A methylpropanoate
C-3. fluoxastrobin A C-14. [(3S,6S,7R,8R)-8- A
C-4. kresoxim-methyl A benzyl-3-[[3-(1 ,3-
C-5. orysastrobin A benzodioxol-5-
C-6. picoxystrobin A ylmethoxy)-4-
C-1. pyraclostrobin A methoxy-pyridine-2-
C-8. trifloxystrobin A carbonyl]amino]-6-
C-9. pyribencarb A methyl-4,9-dioxo-
C-10. amisulbrom A 1 ,5-dioxonan-7-yl] 2-
C-1 1 . [(3S,6S,7R,8R)-8- A methylpropanoate;
benzyl-3-[(3- C-15. (3S,6S,7R,8R)-3- A acetoxy-4-methoxy- [[(3-hydroxy-4- pyridine-2- methoxy-2- carbonyl)amino]-6- pyridi- methyl-4,9-dioxo- nyl)carbonyl]amino]-
1 ,5-dioxonan-7-yl] 6-methyl-4,9-dioxo-
2-methylpropanoate 8-(phenylmethyl)-
C-12. [(3S,6S,7R,8R)-8- A 1 ,5-dioxonan-7-yl 2- benzyl-3-[[3-(acet- methylpropanoate oxymethoxy)-4- C-16. bixafen A methoxy-pyridine- C-17. boscalid A
2-carbonyl]amino]-6- C-18. fluopyram A methyl-4,9-dioxo- C-19. fluxapyroxad A
1 ,5-dioxonan-7-yl] C-20. isopyrazam A
2-methylpropanoate C-21 . penthiopyrad A
C-13. [(3S,6S,7R,8R)-8- A C-22. N-[9- A benzyl-3-[(3-isobut- (dichloromethylene)- oxycarbonyloxy-4- 1 ,2,3,4-tetrahydro- methoxy-pyridine- 1 ,4-me-
2-carbonyl)amino]-6- thanonaphthalen-5- methyl-4,9-dioxo- yl]-3- No IA II No IA II
(difluoromethyl)-l - C-32. epoxiconazole A methyl-1 H-pyrazole- C-33. fluquinconazole A 4-carboxamide C-34. metconazole A
C-23. 3-(difluoromethyl)-1 - A C-35. prothioconazole A methyl-N-(1 ,1 ,3- C-36. tebuconazole A trimethylindan-4- C-37. 1 -[re/-(2S;3R)-3-(2- A yl)pyrazole-4- chlorophenyl)-2-(2,4- carboxamide difluorophenyl)-
C-24. 3-(trifluoromethyl)-1 - A oxiranylmethyl]- methyl-N-(1 ,1 ,3- 5-thiocyanato-1 H- trimethylindan-4- [1 ,2,4]triazole yl)pyrazole-4- C-38. 2-[re/-(2S;3R)-3-(2- A carboxamide chlorophenyl)-2-(2,4-
C-25. 1 ,3-dimethyl-N- A difluorophenyl)- (1 ,1 ,3- oxiranylmethyl]- trimethylindan-4- 2H-[1 ,2,4]triazole-3- yl)pyrazole-4- thiol
carboxamide C-39. prochloraz A
C-26. 3-(trifluoromethyl)- A C-40. fenpropimorph A
1 ,5-dimethyl-N- C-41 . metalaxyl A (1 ,1 ,3- C-42. carbendazim A trimethylindan-4- C-43. thiophanate-methyl A yl)pyrazole-4- C-44. metrafenone A carboxamide C-45. pyrimethanil A
C-27. 3-(difluoromethyl)- A C-46. fludioxonil A
1 ,5-dimethyl-N- C-47. dimethomorph A (1 ,1 ,3-
C-48. N-(1 -(1 -(4-cyano- A trimethylindan-4- phenyl)- yl)pyrazole-4- ethanesulfonyl)-but- carboxamide
2-yl) carbamic acid-
C-28. 1 ,3,5-trimethyl-N- A (4-fluorophenyl) es(1 ,1 ,3- ter
trimethylindan-4-
C-49. mancozeb A yl)pyrazole-4-
C-50. metiram A carboxamide
C-51 . dithianon A
C-29. (5,8-difluoro- A
C-52. 2,6-dimethyl-1 H,5H- A quinazolin-4-yl)-{2-
[1 ,4]dithiino[2,3-
[2-fluoro-4-(4- c:5,6-c']dipyrrole- trifluoromethylpyri-
1 ,3,5,7(2H,6H)- din-2-yloxy)-phenyl]- tetraone
ethyl}-amine
C-53. isotianil A
C-30. ametoctradin A
C-54. prohexadione- A
C-31 . difenoconazole A No IA II No IA II calcium; 4- C-65. Aureobasidium pul- A cyclopropyl-N-(2,4- lulans
dimethoxy- C-66. Bacillus pumilus A phenyl)thiadiazole-5- C-67. Bacillus pumilus A carboxamide NRRL Accession
C-55. 2- butoxy-6-iodo- A No. B-30087
3- propylchromen-4- C-68. Bacillus subtilis A one C-69. Bacillus subtilis A
C-56. N-(cyclo- A NRRL-Nr. B-21661
propylmethoxyimino- C-70. Bacillus subtilis var. A
(6-difluoro-methoxy- amylolique-faciens
2,3-difluoro-phenyl)- FZB24
methyl)-2-phenyl C-71 . Candida oleophila I- A acetamide 82
C-57. 2-methoxy-acetic A C-72. Candida saitoana A acid 6-tert-butyl-8- C-73. Chitosan A fluoro-2,3-dimethyl- C-74. Clonostachys rosea A quinolin-4-yl ester f. catenulate
C-58. 3-[5-(4- A C-75. Clonostachys rosea A methylphenyl)-2,3- f. catenulate isolate dimethyl- J 1446
isoxazolidin-3-yl]- C-76. Coniothyrium mini- A pyridine tans
C-59. 3-[5-(4-chloro- A C-77. Cryphonectria paraA phenyl)-2,3- sitica
dimethyl- C-78. Endothia parasitica A isoxazolidin-3-yl]- C-79. Cryptococcus albi- A pyridine (pyrisoxa- dus
zole)
C-80. Fusarium ox- A
C-60. N-(6-methoxy- A ysporum
pyridin-3-yl) cyclo-
C-81 . FUSACLEAN® A propanecarboxylic
C-82. Metschnikowia fruc- A acid amide
ticola
C-61 . 5-chloro-1 -(4,6-di- A
C-83. Microdochium A methoxy-pyrimidin- dimerum
2-yl)-2-methyl-1 H-
C-84. Phlebiopsis gigantea A benzoimidazole
C-85. Pseudozyma floccu- A
C-62. 4,4-difluoro-3,3- A
losa
dimethyl-1 -(3-
C-86. Pythium oligandrum A quinolyl)isoquinoline
DV74
C-63. Ampelomyces A
C-87. Reynoutria sach- A quisqualis
linensis
C-64. Aspergillus flavus A No IA I I No IA I I
C-88. Talaromyces flavus A ICC080
V1 17b C-96. T. polysporum and A
C-89. Trichoderma A T. harzianum
asperellum SKT-1 C-97. T. stromaticum A
C-90. T. atroviride LC52 A C-98. T. virens GL-21 A
C-91 . T. harzianum T-22 A C-99. T. viride A
C-92. T. harzianum TH 35 A C-100. T. viride TV1 A
C-93. T. harzianum T-39 A C-101 . Ulocladium A
C-94. T. harzianum and T. A oudemansii HRU3
viride
C-95. T. harzianum A
ICC012 and T. viride
Equally preferred inventive mixtures are those comprising compound I I and insecticidal pound I B displayed in Table 2B:
In Table 2B, the following abbreviations are
Bacillus pumilus I NR7 having the accession NRRL B-50153 or NRRL B-50185 = A I B = Comopund I B I I = Compoound I I
No IB II
C-1 . thiodicarb, A
C-2. ethiprole A
C-3. fipronil A
C-4. 4-[5-[3-chloro-5- A
(trifluorome- thyl)phenyl]-5-
(trifluoromethyl)-4H- isoxazol-3-yl]-N-[2- oxo-2-(2,2,2- trifluoroethyla- mino)ethyl]naphthale
ne-1 -carboxamide
C-5. 4-[5-(3,5-dichloro- A
phenyl)-5-(trifluoro- methyl)-4H-isoxazol-
3-yl]-2-methyl-N-[2- oxo-2-(2,2,2-triflu- oroethylamino)eth- yl]benzamide
C-6. lambda-cyhalothrin A
C-7. alpha-cypermethrin A
C-8. fenvalerate A
Figure imgf000034_0001
C-9. permethrin A No IB II No IB II pyrimidin-2-yl-2- 1 -(3-chlorpyridin-2- pyridyl)thiazole hy- yl)-1 H-pyrazole-5- drofluoride carboxamide
C-25. chlorfenapyr A C-35. methyl-2-[3,5-dibro- A
C-26. flufenoxuron A mo-2-({[3-bromo-1 -
C-27. teflubenzuron A (3-chlorpyridin-2-yl)-
C-28. metaflumizone A 1 H-pyrazol-5-yl]car-
C-29. flubendiamide A bonyl}amino)benzo-
C-30. chlorantraniliprole A yl]-1 ,2-dimethylhy-
C-31 . cyantraniliprole A d razi necarboxylate
C-32. (R)-3-chloro-N 1 -{2- A C-36. N2-[2-(3-chloro-2- A methyl-4-[1 ,2,2,2-te- pyridyl)-5-[(5-meth- trafluoro-1 -(trifluoro- yltetrazol-2-yl)meth- methyl)ethyl]phenyl}- yl]pyrazol-3-yl]-5-cy-
N2-(1 -methyl-2-me- ano-N 1 ,3-dimethyl- thylsulfonylethyl)- phthalamide
phthalamide C-37. 2-(5-ethylsulfinyl-2- A
C-33. (S)-3-chloro-N 1 -{2- A fluoro-4-methyl- methyl-4-[1 ,2,2,2-te- phenyl)-5-methyl- trafluoro-1 -(trifluoro- 1 ,2,4-triazol-3-amine methyl)ethyl]phenyl}- C-38. 1 -(5-ethylsulfinyl- A
N2-(1 -methyl-2-me- 2,4-dimethyl- thylsulfonylethyl)- phenyl)-3-methyl- phthalamide 1 ,2,4-triazole
C-34. 3-bromo-N-{2-bro- A C-39. afidopyropen A mo-4-chloro-6-[(1 - C-40. Bacillus firmus A cyclopropylethyl)- C-41 . Bacillus firmus A carbamoyl]phenyl}- CNCM 1-1582
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 I B 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 I B and I I in each case corresponds to a row of Table 2B.
The present invention also relates to ternary mixtures comprising compound IC, compound I I and compound I D, wherein the combination of compounds IC and I I in each case corresponds to a row of Table 1 C.
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, coronafacoyl- L-serine, coronafacoyl-L-threonine, methyl esters of 1 -oxo-indanoyl-isoleucine, methyl esters of 1 -oxo-indanoyl-leucine, coronalon (2-[(6-ethyl-1 -oxo-indane-4-carbonyl)-amino]-3-methyl-pen- tanoic acid methyl ester), linoleic acid or derivatives thereof, or combinations of any of the above.
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.
Thus, the present invention also relates to mixtures comprising compound II and comprising compound I I I and compound IV as set forth in Table 3 below:
In Table 3, the following abbreviations are used:
Bacillus pumilus I NR7 having the accession number NRRL B-50153 or NRRL B-50185 = A I I = Compound I I I I I = Compound I I I
jasmonic acid - No.1 methyl jasmonate - No.2
the jasmonate salt sodium jasmonate, potassium jasmonate, lithium jasmonate or ammonium jasmonate - No.3
No. II III No. II III
3M-1 . A - 3M-13. A No.2
3M-2. A - 3M-14. A No.2
3M-3. A - 3M-15. A No.2
3M-4. A - 3M-16. A No.2
3M-5. A - 3M-17. A No.2
3M-6. A - 3M-18. A No.2
3M-7. A No.1 3M-19. A No.3
3M-8. A No.1 3M-20. A No.3
3M-9. A No.1 3M-21 . A No.3
3M-10. A No.1 3M-22. A No.3
3M-1 1 . A No.1 3M-23. A No.3
3M-12. A No.1 3M-24. A 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.
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.
In particular, the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derivative thereof and the combination of compounds I and II in each case corresponds to a row of Table 1A.
In particular, 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.
In particular, 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.
In particular, 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.
In particular, the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derivative thereof and the combination of compounds I and II in each case corresponds to a row of Table 1 B.
In particular, 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.
In particular, 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.
In particular, 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.
In particular, the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derivative thereof and the combination of compounds I and II in each case corresponds to a row of Table 2A.
In particular, 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.
In particular, 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.
In particular, 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.
In particular, the present invention furthermore relates to ternary mixtures, wherein compound III is jasmonic acid or a salt or derivative thereof and the combination of compounds I and II in each case corresponds to a row of Table 2B.
In particular, 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.
In particular, 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.
In particular, 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.
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.
As stated above, 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 auxil- iaries into individual formulations (compositions) or can be converted jointly with formulation auxiliaries into customary formulations (co-formulation).
If applied separately or in succession, compound I and compound II are naturally be formulated separately.
Thus, in one embodiment, 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.
According to one embodiment, individual components of the composition according to the in- vention 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. When 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. chemcial pesticidal agents) and of the further auxiliaries should not influence the viability of the microbial pesticides in the composition mixed by the user. Especially for bactericides and solvents, compatibility with the respective microbial pesticide has to be taken into account.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal com- position, the kit compring a) a composition comprising component 1 ) as defined herein and at least one auxiliary; or b) a composition comprising component 2) as defined herein and at least one auxiliary; or c) a composition comprising component 3) as defined herein and at least one auxiliary; or d) a composition comprising component 4) as defined herein and at least one auxil- iary; and e) a composition comprising component 5) as defined herein and at least one auxiliary.
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 de- fined 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.
The 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. General examples for 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). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Preferred examples of foliar formulation types for pre-mix compositions are:
GR: Granules
WP: wettable powders
WG: water dispersable granules (powders)
SG: water soluble granules
SL: soluble concentrates
ME: micro-emulsion
SC: aqueous suspension concentrate
CS: aqueous capsule suspension
OD: oil-based suspension concentrate, and SE: aqueous suspo-emulsion.
Examples for 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 and binders.
Especially for bactericides, choice and amounts of this auxiliary should not influence the viability of compound II or III (also if present in formulations comprising compound I).
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions 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. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. However, if such solvents are used, compatibility with compound II needs to be taken into account. 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.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are 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. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are 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 tar- get. 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 (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
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). Suitable customary types of such compositions are suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). Herein, it has to be taken into account that each formulation type or choice of auxiliary should not influence the viability of the microorganism during storage of the composition and when finally applied to the plant propagation material. Suitable formulations are e.g. mentioned in WO 2008/002371 , US 6955,912, US 5,422,107. Examples for suitable auxiliaries 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. Especially for bactericides and solvents, compatibility with the respective microorganism of the respective microbial pesticide has to be taken into account. In addition, compositions with microbial pesticides may further contain stabilizers or nutrients and UV protectants.
Suitable stabilzers or nutrients (H.D. Burges Formulaztion of Micobial Biopestcides) 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. The 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 protectants.
General examples of suitable ratios for multiple formulation types referenced above are given in Agrow Reports DS243, T&F Informa, London, 2005.
Examples for 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. In particular for compound II, granules, powders or suspensions (suspension concentrates) are preferred formulation type.
Herein, it has to be taken into account that each formulation type or choice of auxiliary should not influence the viability of the microorganism, if finally applied by foliar application. As referenced above, a suitable formulation of compound II is referenced in WO 2008/002371. i) Suspensions (SC, OD)
In an 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 alcohol 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. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
ii) Water-dispersible granules and water-soluble granules (WG)
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 sub- stance.
iii) Water-dispersible powders and water-soluble powders (WP)
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.
iv) Gel (GW, GF)
In an mixer, 5-25 wt% of 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.
v) Microcapsules (CS)
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 formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
vi) Dustable powders (DP)
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.
vii) Granules (GR)
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.
The 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.
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).
Generally, 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. Typically, 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.
For foliar application the inventive mixture is applied usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready- to-use spray liquor are applied per hectare of agricultural useful area.
In a further embodiment, 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).
In a further embodiment, either individual components of the inventive mixture or partially pre- mixed 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 consecutively.
When applying Compound IA, IB or IC and a pesticide II sequentially 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. Preferably, 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 I, type of plant propagation material (if appropriate), 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 or- dinary skill in the art.
When employed in plant protection by foliar application, the amounts of active substances applied 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.
In the case of compound II (or compound ID), the application rates preferably range from about 1 x 106 to 5 x 1015 (or more) CFU/ha. Preferably, the spore concentration is about 1 x 107 to about 1 x 1011 CFU/ha. The methods according to the invention for controlling pests or increasing the health of plants of the abovementioned type is carried out in a manner known per se to those skilled in the art, depending on the intended aims and prevailing circumstances. Advantageously, the 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. altemata), tomatoes (e. g. A. solani or A. altemata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; 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) gram- inis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botry- otinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. soro- kiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemu- thianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sa- sakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; 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.) on fruit trees, vines (e. g. C. 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. mediterranea, Phaeomoniella chlamydospora (earlier Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (£. pyri), soft fruits (£. veneta: anthracnose) and vines (£. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (£. betae), vegetables (e. g. 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. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticillioides on corn; Gaeumanno- myces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Gui- gnardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochli- obolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn.
phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; 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, bana- nas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septo- ria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and 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. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plas- mopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; 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. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; 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) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. feres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleo- morph: 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. aphanidermatum); 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, veg- etables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhyn- chosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Un- cinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Se- tospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. miliaria: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; 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) on peaches and T. pruni (plum pocket) on 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) on rye; Uro- myces spp. (rust) on 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.
avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and 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. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: 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. and 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 har- vest 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 funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibemia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Ly- onetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xy- lostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cere- alella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis, beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Am- phimallus solstitialis, Anisandrus dispar, Anthonomus grand is, Anthonomus pomorum, Aphtho- na euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebu- losa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotre- fa chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria, flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gam- biae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadri- maculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia pla- tura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophi- lus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cu- prina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca do- mestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhago- letis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips pa Imi 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. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nastur- tii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifo- lii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus pru- nicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefo- lii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaula- corthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lug ens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rhopalomy- zus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sap- paphis mala, Sappaphis mail, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex he- mipterus, Reduvius senilis, Triatoma spp., and Arilus critatus. ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogono- myrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Doli- chovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and
Linepithema humile, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Lo- custa migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Me- lanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca america- na, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus se- negalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Callip- tarn us italicus, Chortoicetes termini fera, and Locustana pardalina,
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 gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus palli- dus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetra- nychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa, fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata, millipedes (Diplopoda), e.g. Narceus spp., 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 pallida, Globodera tabacum and other Globodera species, Heterodera avenae, Heterodera gly- cines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; seed gall nematodes, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, Aphelenchoides fragariae, Aphelenchoides ritzemabosi and other Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, Criconema species, Criconemella species, Criconemoides species, and Mesocri- conema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, Dity- lenchus myceliophagus and other Ditylenchus species; awl nematodes, Dolichodorus species; spiral nematodes, Helicotylenchus dihystera, Helicotylenchus multicinctus and other Helicoty- lenchus species, Rotylenchus robustus and other Rotylenchus species; sheath nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; lance nematodes, Hoplolaimus columbus, Hoplolaimus galeatus and other Hoplolaimus species; false root-knot nematodes, Nacobbus aberrans and other Nacobbus species; needle nematodes, Longidorus elongates and other Longidorus species; pin nematodes, Paratylenchus species; lesion nematodes, Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus, Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans, Pratylenchus scribneri, Pratylenchus vulnus, Pratylenchus zeae and other Pratylenchus species; Radinaphelenchus cocophilus and other Radinaphelenchus species; burrowing nematodes, Radopholus similis and other Radopholus species; reniform nematodes, Rotylenchulus reniformis and other Rotylen- chulus species; Scutellonema species; stubby root nematodes, Trichodorus primitivus and other Trichodorus species; Paratrichodorus minor and other Paratrichodorus species; stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species and Merlinius species; citrus nematodes, Tylenchulus semipenetrans and other Tylen- chulus species; dagger nematodes, Xiphinema americanum, Xiphinema index, Xiphinema di- versicaudatum and other Xiphinema species; and other plant parasitic nematode species.
The term "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. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as oilseed rape, canola, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn (maize), soybean, oilseed rape, canola, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
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.
Most preferred plants are fruits (temperate and tropical), grapes and vegetables.
The term " 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. Typically, 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. have been rendered tolerant to applications of specific classes of herbicides, such as 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; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. 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 anoth- er class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several 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. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially availa- ble under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cul- tivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, 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 bacte- rial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins pro- duced 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 sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention 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. in the publications mentioned above. These 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. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphinothri- cin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the CrylAc toxin), Bollgard® I (cotton cultivars producing the CrylAc toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Pro- tecta®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. 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).
Furthermore, 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. Examples of such 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). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. Furthermore, 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.
Furthermore, 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 Scienc- es, Canada).
Furthermore, 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).
In the mixtures and compositions, the compound ratios are advantageously chosen so as to produce a synergistic effect.
The term "synergstic effect" is understood to refer in particular to that defined by Colby's formula (Colby, S. R., "Calculating synergistic and antagonistic responses of herbicide combina- tions", Weeds, 15, pp. 20-22, 1967).
The term "synergistic effect" is also understood to refer to that defined by application of the Tammes method, (Tammes, P. M. L, "Isoboles, a graphic representation of synergism in pesticides", Netherl. J. Plant Pathol. 70, 1964).
According to the invention, 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 109 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. In addition, here "CFU" may also be understood as the number of (juvenile) individual nematodes in case of (entomopathogenic) nematode biopesticides, such as
Steinernema feltiae.
In the binary mixtures and compositions according to the invention the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active components 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.
According to a further embodiments of the binary mixtures and compositions, 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.
According to a further embodiments of the binary mixtures and compositions, 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.
In the ternary mixtures, i.e. compositions according to the invention comprising the component 1 ) and component 2) and a compound III (component 3), 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 ).
These ratios are also suitable for inventive mixtures applied by foliar treatment.
The fungicidal action of the mixtures according to the invention can be shown by the tests described below.
Microtiter plate tests
The chemical pesticides (e.g. compounds IA, IB or IC) 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.) in e.g. 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 combina- tions, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.
Colby's formula: E = x + y - x »y/100
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 concentra- tions a and b
x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a
y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b.
Use example FM-1 : Activity against Septoria tritici, the causal agent of leaf blotch on wheat
A spore suspension of Septoria tritici in an aqueous biomalt solution was used. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. B) Greenhouse tests
The chemical pesticides (e.g. compounds IA, IB or IC) were formulated separately or together 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 (wet- ting 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/em ulsifier/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.
Use example FG-1 : Activity against early blight on tomatoes caused by Phytophthora infestans with protective application
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. Simul- taneously 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 inoculation, the trial plants were immediately transferred to a humid chamber. After 6 days at 18 to 200C and a relative humidity close to 100%, the extent of fungal attack on the leaves was visu- ally assessed as % diseased leaf area.
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 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 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.
Use example FG-3: Protective action against Puccinia recondita on wheat (brown rust 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 pesticide 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 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 test plants were returned into the greenhouse and cultivated at temperatures be- tween 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.
Use example FG-5: Protective action against Sphaerotheca fuliginea on cucumber (mildew of cucumber)
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. 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 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. Use example FG-6: Action against Sclerotinia sclerotiorum in soybean using pot trials
Pyraclostrobin was applied as commercial seed treatment formulation STAMINA (200 g/L a.i., BASF SE, Ludwigshafen, Germany).
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 amount of seeds was placed in the bowl of the treater and the slurry was dosed on the spinning disk.
The B. pumilus INR7 were grown in shake flasks and used as fermentation broth with of at least 1 x 1012 CFU 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.
For the infection, rye kernels inoculated with Sclerotinia sclerotiorum were used. The trial was sown in 8 cm pots and as a substrate a mix of peat substrate and sand in the ratio 1 : 4 was used. The pots were filled with the substrate and the rye kernels inoculated with Sclerotinia sclerotiorum were placed directly adjacent to the seeds. In each pot 5 soy bean seeds (cv. Go- riziana) were sown at a sowing depth of 2 cm, then covered with substrate. For each treatment 5 replications were made. After sowing, 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.
For the assessment, the plants were evaluated according to a 2 class evaluation (healthy, diseased). Those figures were converted into efficacies in % of the untreated control and the efficacy (E) was calculated as follows using Abbot's formula.
The results are shown in the following Table.
Figure imgf000058_0001
Use example FG-7: Action against Gaeumannomyces graminis in wheat using pot trials
Experimental setup was identical to Use example FG-6 unless described below.
For the infection, rye kernels inoculated with Gaeumannomyces graminis were used. The trial was sown in 8 cm pots and a mix of peat substrate and sand (ratio 1 : 4) was used as a sub- strate. The pots were filled with the substrate and the rye kernels inoculated with Gaeumannomyces graminis were placed directly adjacent to the wheat seeds. In each pot 5 wheat seeds (cv. JB Asano) were sown at a sowing depth of 1.5 cm and then covered with substrate. For each treatment 5 replications were made. After the sowing, the pots were irrigated with fertilized water (0,3 % Kamasol Blau 8+8+6) and placed according the randomization plan in a green- house cabin (16 h light, relative humidity < 95 %) for 14 days at 20°C. When necessary, they were irrigated with fertilized water.
The results are shown in the following Table. Product/Mix Product rate Observed efficacy Calculated efficacy acc. to Colby untreated check - 0 (infection level:
96%)
Pyraclostrobin 2.5 g ai/100 kg seeds 5.0
B. pumilus INR7 10 ml broth per seed 42.5
Pyraclostrobin + 2.5 g a.i./100 kg + 78.8 45.4
B. pumilus INR7 10 ml broth per seed
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).
I. Compatibility of chemical pesticides (e.g. compound IA, IB or IC) with microbial pesticides (e.g. compound II)
Materials:
- autoclaved medium adapted to the microbial pesticide to cultivate: potato dextrose agar (PDA), malt dextrose agar (MEA), potato carrot agar (PCA) or sabouraud dextrose agar (SDA)
- sterile plates (e.g. Petri dishes), vessels (e.g. bottles) and sterile water.
For dilution of oil formulations it may be recommended to use kerosene or add Tween® 80 at
0.05% v/v to the sterile water.
A) Liquid mixture in a bottle
Chemical pesticide formulations are prepared from stock solutions (see above) in sterile water 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.
B) Solid plate assay
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. In both methods, 4 replicates are used and the plates are cultured at 28 °C and 80% rel. humidity for 24 to 48 h. Compatibility is determined after 1 , 24 h and optionally 48 h as follwos: 1 ) by counting germinated vs. non-germinated spores/conidia (counted≥ 100) in the mixture using a microscope and hemacytometer to establish the germination rate in %, or number of germinated spores/conidia; or 2) by determining colony diameter in mm, speed of growth in mm/day, shape of the colony and/or color of the colony on the plates. All parameters are compared to a suspension of spores/conidia in absence of chemical pesticide (negative control). II. Determination of sub-lethal rates of the chemical pesticide (e.g. compound IA, IB or IC) and microbial pesticide (e.g. compound II)
These studies can be conducted in the growth chamber, greenhouse and/or in the field. 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:
a) chemical pesticide at the sub-lethal rate a
b) microbial pesticide alone at the sub-lethal rate b
c) mixture of the chemical pesticide at rate a and the microbial pesticide at rate b
d) Untreated control.
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.
Use example 1-1 : Curative action against stink bugs (Nezara viridula) in the field
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.
Use example I-2: Curative action against whiteflies (Bemisia tabaci) in the field
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)
Lima bean leaves were cut and dipped into the respective treatments and placed in Petri dishes on wet filter paper to keep humidity. Once the surface of the leaves dried, 5 first/second instar larvae were infested per petri dish. Efficacy was evaluated at 3, 7 and 10 days after treatment.
Use example I-5: Protective action against Colorado potato beetle (Leptinotarsa decemlineata) in the field
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.
The plant health improving action of the mixtures according to the invention can be shown by the tests described below.
Use example H-1 : Action against drought stress
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).
In pot trials in Limburgerhof greenhouses, Bacillus pumilis INR7 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 amount of seeds was placed in the bowl of the treater and the slurry was dosed on the spinning disk.
The bacterials were grown in shake flasks and used as fermentation broth with a CFU of at least 1 x 1012 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. For each treatment 5 replications were made. After the sowing, 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.
For the assessment, the plant height from all plants was measured in cm. Those figures were converted into the relative plant height in % compared to the untreated control, which is 100 %.
The expected relative plant height 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.
Colby's formula: ECoiby = PA + PB - PA * PB/100
Ecoiby expected relative plant height, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b
PA relative plant height, expressed in % of the untreated control, when using the active
compound A at the concentration a
PB relative plant height, expressed in % of the untreated control, when using the active
compound B at the concentration b.
The results are shown in the following Table.
Figure imgf000062_0001
The combined treatment with Pyraclostrobin and B. pumilus INR7 showed an improvement of plant height, whereas the solo treatments had no or a negative effect compared to the untreated check.

Claims

Claims
Synergistic mixtures comprising, as active components,
1 ) one fungicidal compound IA selected from the group consisting of
A) Respiration inhibitors
- Inhibitors of complex III at Qo site: azoxystrobin, coumethoxystrobin, coumoxy- strobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyra- clostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phen- oxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichloro- phenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl- acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
- inhibitors of complex III at Qi site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8-benz- yl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-di- oxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)- 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-isobutoxycarbonyloxy-4-meth- oxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl- 4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate;
- inhibitors of complex II: benodanil, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-
2- yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl- butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, benzovindiflupyr,
3- (difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide,
3- (trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide,
1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluorometh- yl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoro- methyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-tri- methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide;
- other respiration inhibitors: diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-
4- (4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivates: bina- pacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
B) Sterol biosynthesis inhibitors
- C14 demethylase inhibitors: triazoles: azaconazole, bitertanol, bromuconazole, cy- proconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbu- conazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ip- conazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triad- imefon, triadimenol, triticonazole, uniconazole, 1 -[rel-(2S;3R)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazole,
2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]tri- azole-3-thiol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
- Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropi- morph, tridemorph, fenpropidin, piperalin, spiroxamine;
- Inhibitors of 3-keto reductase: fenhexamid;
C) Nucleic acid synthesis inhibitors
- phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, met- alaxyl, ofurace, oxadixyl;
- others: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-
2- (p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin- 4-amine;
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate- methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluoro- phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine;
- other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil;
- protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride- hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F) Signal transduction inhibitors
- MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
- G protein inhibitors: quinoxyfen;
G) Lipid and membrane synthesis inhibitors
- Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothi- olane;
- lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
- phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph, mandi- propamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4-cy- ano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
- compounds affecting cell membrane permeability and fatty acides: propamocarb, propamocarb-hydrochlorid
- fatty acid amide hydrolase inhibitors: 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-
3- isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol- 1 -yl]ethanone;
H) Inhibitors with Multi Site Action - inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
- organochlorine compounds: anilazine, chlorothalonil, captafol, captan, folpet, dichlo- fluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthal- ide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
- guanidines and others: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithia- non, 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
I) Cell wall synthesis inhibitors
- inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defence inducers
- acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium;
4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Unknown mode of action
- bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclome- zine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumet- over, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxine- copper, picarbutrazox, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy- 6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy- 2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-tri- fluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine,
N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-me- thyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine, 2-methoxy-acetic acid 6-tert-butyl-8-fluoro- 2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-
3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyris- oxazole), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro- 1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, 4,4-difluoro- 3,3-dimethyl-1 -(3-quinolyl)isoquinoline;
L) Antifungal biological Control Agents:
- Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus pu- milus, Bacillus pumilus NRRL B-30087, Bacillus subtilis, Bacillus subtilis NRRL B-21661 , Bacillus subtilis var. amylolique-faciens FZB24, Candida oleophila I-82, Candida saitoana, chitosan, Clonostachys rosea f. catenulate, Clonostachys rosea f. catenulate J 1446, Coniothyrium minitans, Cryphonectria parasitica, Endothia parasitica, Cryptococcus albidus, Fusarium oxysporum, Metschnikowia fructicola, Micro- dochium dimerum, Phlebiopsis gigantea, Pseudozyma flocculosa, Pythium oli- gandrum DV74, Reynoutria sachlinensis, Talaromyces flavus \/^ ^ 7b, Trichoderma asperellum SKT-1 , 7 a tro viride LC 52, Γ. harzianum T '-22, Γ. harzianum TH 35, Γ. harzianum T-39, 7. harzianum and 7. v/r/c/e, 7. harzianum ICC012 and 7 v/r/c/e ICC080, 7 polysporum and 7 harzianum, T. stromaticum, T. virens GL-21 , 7 v/r/c/e, 7 v/r/c/e TV1 , Ulocladium oudemansii HRU3;
or
one insecticidal compound IB selected from the group consisting of
M-1 .A acetylcholine esterase inhibitors from the class of carbamates:
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;
M-1 .B acetylcholine esterase inhibitors from the class of organophosphates:
acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethox- yfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimetho- ate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl
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;
M-2 GABA-gated chloride channel antagonists:
M-2.A cyclodiene organochlorine compounds: endosulfan; or
M-2.B fiproles: ethiprole, fipronil, flufiprole, pyrafluprole, or pyriprole;
M-2. Others: 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4H-isoxazol-
3- yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene-1 -carboxamide,
4- [5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo- 2-(2,2,2-trifluoroethylamino)ethyl]benzamide;
M-3 sodium channel modulators from the class of pyrethroids:
acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bi- oallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cyper- methrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flu- cythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, meperfluthrin, meto- fluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (py- rethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralome- thrin, transfluthrin, DDT and methoxychlor;
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;
M-5 allosteric nicotinic acteylcholine receptor activators from the class of spinosyns: spinosad, spinetoram;
M-6 chloride channel activators from the class of mectins:
abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
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-13 nicotinic acetylcholine receptor channel blockers:
bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;
M-14 inhibitors of the chitin biosynthesis type 0 (benzoylurea class):
bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
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;
M-18 Octopamin receptor agonists: amitraz;
M-19 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, flometoquin, fluacrypyrim or pyriminostrobin;
M-20 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroxi- mate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim, or rotenone;
M-21 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone or
1 -[(E)-[2-(4-cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylidene]amino]-3-[4-(di- fluoromethoxy)phenyl]urea;
M-22 Inhibitors of the lipid synthesis, inhibitors of acetyl CoA carboxylase:
spirodiclofen, spiromesifen or spirotetramat;
M-23 Mitochondrial complex II electron transport inhibitors:
cyenopyrafen, cyflumetofen or pyflubumide;
M-24 Ryanodine receptor-modulators from the class of diamides: 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 -cyclopropylethyl)carbamoyl]phenyl}-1 -(3-chloropyridin-2-yl)-1 H-pyrazole-
5- carboxamide, methyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3-chloropyridin-2-yl)-1 H-py- razol-5-yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate, N2-[2-(3-chlo- ro-2-pyridyl)-5-[(5-methyltetrazol-2-yl)methyl]pyrazol-3-yl]-5-cyano-N1 ,3-dimethyl- phthalamide, N2-(1 -cyano-1 -methyl-ethyl)-N1 -(2,4-dimethylphenyl)-3-iodo-phthal- amide, 3-chloro-N2-(1 -cyano-1 -methyl-ethyl)-N1 -(2,4-dimethylphenyl)phthalamide, 2-(3-chloro-2-pyridyl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-5-[[5-(tri- fluoromethyl)tetrazol-2-yl]methyl]pyrazole-3-carboxamide, N-[2-(tert-butylcarbamo- yl)-4-chloro-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(fluoromethoxy)pyrazole-3-car- boxamide, 5-bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-2-(3,5-dichloro- 2-pyridyl)pyrazole-3-carboxamide, 5-chloro-2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-
6- [(1 -cyano-1 -methyl-ethyl)carbamoyl]phenyl]pyrazole-3-carboxamide,
N-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methyl-phenyl]-5-bromo-2-(3-chloro- 2-pyridyl)pyrazole-3-carboxamide;
M-25 Others: 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, triflumezopyrim, 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)- imidazo[1 ,2-a]pyridine-2-carboxamide, 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)- phenoxy]propoxy]-1 H-pyrazole, N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide, N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,3,3,3-pentafluoro-propanamide, N-[1 -[(6-bromo-3-pyndyl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide, N-[1 -[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide, N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyndylidene]- 2,2,2-trifluoro-acetamide, 2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyndyl)methyl]-2-pyndyl- idene]acetamide, 2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-di- fluoro-acetamide, N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide, N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetra- dec-1 1 -en-10-one, 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1 -aza- spiro[4.5]dec-3-en-2-one, 2-(5-fluoro-3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)thiazole hydrofluoride, 2-(3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)thiazole, 5-[6-(1 ,3-dioxan- 2-yl)-2-pyridyl]-2-(3-pyridyl)thiazole, 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(tri- fluoromethyl)-4H-isoxazol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphtha- lene-1 -carboxamide, 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]- 2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide, 4-[5-(3,5-dichloro- phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 -oxothietan-3-yl)benz- amide;
M-26 Bacillus firmus, Bacillus firmus CNCM 1-1582;
or
3) one compound IC having plant growth regulator activity selected from the group consisting of:
- Antiauxins: clofibric acid, 2,3,5-tri-iodobenzoic acid;
- Auxins: 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, dichlorprop, fenoprop, IAA, IBA, naphtha- leneacetamide, α-naphthaleneacetic acid, 1 -naphthol, naphthoxyacetic acid, potassium naphthenate, sodium naphthenate, 2,4,5-T;
- Cytokinins: 2iP, 6-benzylaminopurine, N-Oxide-2,6-lutidine, 2,6-dimethylpyridine, kinetin, zeatin;
- Defoliants: calcium cyanamide, dimethipin, endothal, merphos, metoxuron,
pentachlorophenol, thidiazuron, tribufos, tributyl phosphorotrithioate;
- Ethylene modulators: aviglycine, 1 -MCP, prohexadione, prohexadione calcium, trinexapac, trinexapac-ethyl;
- Ethylene releasers: ACC, etacelasil, ethephon, glyoxime;
- Gibberellins: gibberelline, gibberellic acid;
- Growth inhibitors : abscisic acid, ancymidol, butralin, carbaryl, chlorphonium, chlorpropham, dikegulac, flumetralin, fluoridamid, fosamine, glyphosine, isopyrimol, jasmonic acid, maleic hydrazide, mepiquat, mepiquat chloride, mepiquat
pentaborate, piproctanyl, prohydrojasmon, propham, 2,3,5-tri-iodobenzoic acid;
- Morphactins: chlorfluren, chlorflurenol, dichlorflurenol, flurenol;
- Growth retardants: chlormequat, chlormequat chloride, daminozide, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, metconazole;
- Growth stimulators: brassinolide, forchlorfenuron, hymexazol;
- 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;
or
4) Bacillus subtilis MBI600 as compound ID having the accession number NRRL B- 50595; and
5) Bacillus pumilus INR7 having the accession number NRRL B-50153 or NRRL B- 50185 as compound II.
The mixture according to claim 1 comprising compound IA and compound II.
The mixture according to claim 1 comprising compound IB and compound II.
The mixture according to claim 2 comprising as compound IA one fungicidal compound selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim- methyl, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, pyribencarb, amisul- brom, [(3S,6S,7R,8R)-8-beftnzyl-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-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-di- oxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy- 4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-me- thylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; (3S,6S R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyndinyl)carbonyl]amino]-6-methyl-4,9-dioxo- 8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate, bixafen, boscalid, fluopyram, flu- xapyroxad, isopyrazam, penthiopyrad, N-[9-(dichloromethylene)-1 ,2,3,4-tetrahydro-1 ,4-me- thanonaphthalen-5-yl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide, 3-(difluoro- methyl)-1 -methyl-N-(1 , 1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-
1 - methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-tri- methylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-tri- methylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-tri- methylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)- pyrazole-4-carboxamide, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethyl- pyridin-2-yloxy)-phenyl]-ethyl}-amine, ametoctradin, difenoconazole, epoxiconazole, flu- quinconazole, metconazole, prothioconazole, tebuconazole, 1 -[rel-(2S;3R)-3-(2-chloro- phenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thio-cyanato-1 H-[1 ,2,4]triazole,
2- [rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl-methyl]-2H-[1 ,2,4]triazole-
3- thiol, prochloraz, fenpropimorph, metalaxyl, carbendazim, thiophanate-methyl, met- rafenone, pyrimethanil, fludioxonil, dimethomorph, N-(1 -(1 -(4-cyano-phenyl)ethanesul- fonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester, mancozeb, metiram, dithianon, 2,6-di- methyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone, isotianil, prohex- adione-calcium; 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide, 2-but- oxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy- 2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, 2-methoxy-acetic acid 6-tert-butyl-8-flu- oro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1 -(4,6-dimethoxy- pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 4,4-difluoro-3,3-dimethyl-1 -(3-quinolyl)iso- quinoline, Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus pumilus, Bacillus pumilus NRRL B-30087, Bacillus subtilis, Bacillus subtilis NRRL B-21661 , Bacillus subtilis var. amylolique-faciens FZB24, Candida oleophila I -82, Candida saitoana, chitosan, Clonostachys rosea f. catenulate, Clonostachys rosea f. catenulate J 1446, Coni- othyrium minitans, Cryphonectria parasitica, Endothia parasitica, Cryptococcus albidus, Fusarium oxysporum, Metschnikowia fructicola, Microdochium dimerum, Phlebiopsis gi- gantea, Pseudozyma flocculosa, Pythium oligandrum DV74, Reynoutria sachlinensis, Tala- romyces flavus V1 17b, Trichoderma asperellum SKT-1 , T. atroviride LC52, T. harzianum T-22, T. harzianum JH 35, T. harzianum T-39, T. harzianum and T. viride, T. harzianum ICC012 and T. viride ICC080, T. polysporum and T. harzianum, T. stromaticum, T. virens GL-21 , T. viride, T. viride TV1 and Ulocladium oudemansii HRU3.
The mixture according to claim 4 wherein compound IA is selected from dimoxystrobin, pyraclostrobin, azoxystrobin, trifloxystrobin, picoxystrobin, cyazofamid, boscalid, fluoxapy- roxad, fluopyram, bixafen, isopyrazam, benzovindiflupyr, penthiopyrad, ametoctradin, dife- noconazole, metconazole, prothioconazole, tebuconazole, cyproconazole, penconazole, myclobutanil, tetraconazole, hexaconazole, metrafenone, zoxamid, pyrimethanil, cyprodi- nil, metalaxyl, fludioxonil, dimethomorph, mandipropamid, copper, metiram, chlorothalonil, dithianon, fluazinam, folpet, fosetyl-AI, captan, cymoxanil and mancozeb.
The mixture according to claim 3 comprising as compound IB one insecticidal compound selected from carbofuran, methomyl, thiodicarb, triazamate, acephate, chlorpyrifos, chlor- pyrifos-methyl, dimethoate, methamidophos, ethiprole, fipronil, 4-[5-[3-chloro-5-(trifluoro- methyl)phenyl]-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)- ethyl]naphthalene-1 -carboxamide, 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isox- azol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide, bifenthrin, cyflu- thrin, beta-cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cyper- methrin, deltamethrin, fenvalerate, flucythrinate, permethrin, tefluthrin, acteamiprid, chlo- thianidin, 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, spinosad, spinetoram, abamectin, emamec- tin benzoate, 2-(5-fluoro-3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)thiazole hydrofluoride, chlorfenapyr, diflubenzuron, flufenoxuron, novaluron, teflubenzuron, tebufenpyrad, indoxa- carb, metaflumizone, flubendiamide, chlorantraniliprole, cyantraniliprole, (R)-3-chloro- N 1 -{2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl}-N2-(1 -methyl-2-methyl- sulfonylethyl)phthalamide, (S)-3-chloro-N 1 -{2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluorometh- yl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamide, 3-bromo-N-{2-bromo-
4- chloro-6-[(1 -cyclopropylethyl)carbamoyl]phenyl}-1 -(3-chloropyridin-2-yl)-1 H-pyrazole-
5- carboxamide, methyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3-chloropyridin-2-yl)-1 H-pyrazol- 5-yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate, N2-[2-(3-chloro-2-pyridyl)- 5-[(5-methyltetrazol-2-yl)methyl]pyrazol-3-yl]-5-cyano-N1 ,3-dimethyl-phthalamide, 2-(5-eth- ylsulfinyl-2-fluoro-4-methyl-phenyl)-5-methyl-1 ,2,4-triazol-3-amine, 1 -(5-ethylsulfinyl-2,4-di- methyl-phenyl)-3-methyl-1 ,2,4-triazole, afidopyropen, Bacillus firmus and Bacillus firmus CNCM 1-1582.
The mixture according to claim 1 comprising compound ID and compound II.
The mixture according to any of claims 2 to 7 comprising compound IA or IB and compound ID and compound II.
The mixture according to any of claims 1 to 8, wherein the ratio by weight from compound I to compound II is from 1 :500 to 500:1 .
0. The mixture according to claim 8 comprising compound IA or IB and compound ID and compound II, in which each combination of two ingredients in the mixture of three ingredients ranges from 500:1 to 1 :500.
1 . A kit for preparing a usable pesticidal composition, the kit comprising: a) a composition comprising component 1 ) as defined in any of the abovementioned claims and at least one auxiliary; or
b) a composition comprising component 2) as defined as defined in any of the abovementioned claims and at least one auxiliary; or
c) a composition comprising component 3) as defined as defined in any of the abovementioned claims and at least one auxiliary; or
d) a composition comprising component 4) as defined as defined in any of the abovementioned claims and at least one auxiliary; and
e) a composition comprising component 5) as defined as defined in any of the abovemen- tioned claims and at least one auxiliary.
12. A pesticidal composition, comprising a liquid or solid carrier and a mixture as defined in any of claims 1 to 10. 13. 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 a effective amount of a mixture as defined in any of claims 1 to 10 or with an effective amount of a composition as defined in claim 12.
The method as claimed in claims 1 to 9, wherein the compounds as defined in any of claims 1 to 10 are applied simultaneously, that is jointly or separately, or in succession.
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