WO2014086853A1 - Compositions comprising a quillay extract and a fungicidal compound - Google Patents

Compositions comprising a quillay extract and a fungicidal compound Download PDF

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Publication number
WO2014086853A1
WO2014086853A1 PCT/EP2013/075527 EP2013075527W WO2014086853A1 WO 2014086853 A1 WO2014086853 A1 WO 2014086853A1 EP 2013075527 W EP2013075527 W EP 2013075527W WO 2014086853 A1 WO2014086853 A1 WO 2014086853A1
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Prior art keywords
methyl
phenyl
chloro
inhibitors
acid
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PCT/EP2013/075527
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French (fr)
Inventor
Thorsten Jabs
Joao Paulo Vilela GUIMARAES
Jorge Pedro Nitsche
Fabrizio CARBONE ROMANO
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Basf Agro B.V., Arnhem (Nl)
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Publication of WO2014086853A1 publication Critical patent/WO2014086853A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • 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

  • compositions comprising a Quillay extract and a fungicidal compound
  • the present invention relates to mixtures comprising as active components a Quillay extract and a fungicidal compound as defined herein.
  • Quillaja saponaria, Molina, the soapbark tree is an evergreen tree in the family Quillajaceae, native to warm temperate central Chile.
  • Extracts of the barksoap tree are well-known (CAS-No. 68990-67-0) and safe cosmetic, food and pharmaceutical additives e.g. used as adjuvant in vaccine solutions.
  • Such soapbark tree also called China bark extract, Murillo bark extract, Panama bark extract, Quillai extract, Quillaia extract or Quillay extract, generally comprises the milled inner bark or small stems and branches of the soapbark tree and contains saponins, polyphenols and other ingredients.
  • Quillay extract-based products e.g. QL Agri 35, BASF SE
  • QL Agri 35 e.g. QL Agri 35
  • BASF SE acaricidal mixture comprising the Quillay extract QL Agri 35 and sulfur (Acoidal WG) is marketed by BASF SE.
  • Quillay extracts have antifungal activity against plant pathogenic fungal species such as Gaeumannomyces graminis (US 201 1/0190123 A1 ) and Botrytis cinerea (EP 2 106 698 A2).
  • Quillay extracts based on water extraction are commercially available e.g. under the trademark QL Agri 35 produced by Natural Response S.A., Quilpue, Chile, and marketed by Desert King Chile and BASF SE.
  • the extraction step takes place at temperatures between 5°C and 95°C, preferably at 20°C to 90°C, even more preferably at 40°C to 90°C.
  • It contains a minimum of 6 % of saponins, 15 % polyphenols and about 35 °Brix, and has a total solids content of 350 g/l (the total solids content, or dry mass content, containing in general a residual moisture content of at most 5% by weight, preferably at most 2% by weight, based on the total weight of the solids content).
  • the percentages are weight percentages and relative to the vol- ume of the extract.
  • One degree Brix is 1 gram of sucrose in 100 grams of solution and represents the strength of the solution as percentage by weight (% w/w) (strictly speaking, by mass). If the solution contains dissolved solids other than pure sucrose, then the °Brix is only approximate the dissolved solid content.
  • Further suitable Quillay extracts are commercially available (trademarks QL 1000, QP 1000, QL Ultra, QL 30B and Vax Sap, produced by Natural Re- sponse S.A. Quilpue, Chile).
  • fungicidal compounds II as defined herein, their preparation and biological activity against fungi are known (e.g.: http://www.alanwood.net/pesticides/); many of these substances are commercially available.
  • the present invention relates to mixtures comprising, as active components
  • DMI fungicides triazoles: azaconazole, bitertanol, bro- muconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxi- conazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutra- zole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1 -[rel-(2S;3R)-3-(2- chlorophenyl)-2-(
  • Delta14-reductase inhibitors aldimorph, dodemorph, dodemorph-acetate, fenpropi- morph, tridemorph, fenpropidin, piperalin, spiroxamine;
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hex- achlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro- 2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hex- achlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-
  • guanidines and others guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon and 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone.
  • the mixture according to the invention or to be used according to the invention is not re- stricted to a physical mixture of the Quillay extract and at least one compound II, but can be any combination of the Quillay extract and at least one compound II, it not being required for the Quillay extract and the at least one compound II to be present together in the same formulation.
  • the mixture of the invention is partly also termed "composition”.
  • combipack An example of a "mixture" (more correctly: a composition) according to the invention or to be used according to the invention in which the Quillay extract and the at least one compound II are not present together in the same formulation is a combipack.
  • a combipack two or more components of a combipack are packaged separately, i.e., not jointly pre-formulated.
  • combipacks include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical com- position.
  • One example is a two-component combipack.
  • the present invention also relates to a two-component combipack, comprising a first component which in turn comprises the Quillay extract, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary, and a second component which in turn comprises at least one compound II, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary. More details, e.g. as to suitable liquid and solid carriers, surfactants and customary auxiliaries are described below.
  • the mixture of the invention is a physical mixture.
  • the invention relates also to a method for controlling phytopathogenic harmful fungi, or for improving the health of the plants using mixtures of a Quillay extract and at least one compound II and to the use of the components 1 ) and 2) as defined herein for preparing such mixtures, and to compositions and seed comprising these mixtures.
  • the method of the invention does not include a treatment of a human or animal body.
  • the invention also relates to the use of a mixture of the invention as defined above or below or of an agricultural composition as defined below or of a Quillay extract in combination with at least one compound II as defined above or below and optionally also in combination with at least one active component 3) as defined below for controlling phytopathogenic fungi.
  • the use of the Quillay extract "in combination with" the at least one compound II on the one hand can be understood as using a physical mixture of Quillay extract and at least one compound II.
  • the combined use may also consist in using the Quillay extract and the at least one compound II separately, but locus- and time-related (i.e. both components are applied to the same "substrate" (plant, part thereof, seed, habitat of the fungus etc.) within a sufficiently short time of one another), so that the desired effect can take place. More detailed illustrations of the combined use can be found in the specifications below. Furthermore, synergistic effects in relation with the insecticidal and/or herbicidal action have been found with the inventive mixtures.
  • the mixtures comprise component 1 ) and component 2) in a synergistically effective amount.
  • Compounds II can be present in different crystal modifications, which may differ in biological activity.
  • the active component 1 ) of the mixture can be found on the basis of the soap bark tree (Quillaja saponaria), from wood, branches and the bark of the tree, which are milled. Quillaja can as well be used as an extract of flakes from branches and the bark from the soap bark tree.
  • the extract can be based on pure water extraction or a blend of water and alcohol as a means of extraction.
  • the extract can be used as a liquid product or it can be spray dried. The above- mentioned commercially available extracts are also suitable.
  • the mixtures comprise as component 1 ) a water-based Quillay extract.
  • water-based Quillay extract is to be understood that the extract of the material of the Quillay tree is obtained by solid-liquid extraction wherein the liquid is water or a water-based solution comprising water-soluble solvents (such as alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g.
  • auxiliaries such as liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, bactericides, anti-freezing agents, anti- foaming agents, tackifiers and binders).
  • the Quillay extract is obtained by extraction from the Quillay tree by employing water, alcohol or a water/alcohol solution.
  • the alcohol is ethanol or methanol.
  • the extraction is achieved by employing a water/alcohol solution.
  • the water/alcohol solution has a water/alcohol ratio of from 80:20 to 20:80. In further embodiments, the water/alcohol solution has a water/alcohol ratio of from 60:40 to 40:60. In further embodiments, the water/alcohol solution is 80:20 water/alcohol, 60:40 water/alcohol, 50:50 water/alcohol, 40:60 water/ alcohol ratio or 20:80 water/alcohol.
  • the water/alcohol ratios given are volume/volume. Specifically, the extractant is water.
  • the extraction time may vary without limitation from 1 to 8 hours, at or above room temperature (20°C-30°C), e.g., above 30°C, 40°C, 50°C or 60°C. In some embodiments, the extraction is carried out at a temperature between 30°C and 70°C.
  • the extraction process comprising: treating the Quillay material in a water or water/alcohol solution.
  • the so-extracted material may subsequently be purified by any means known in the art, including: filtration, centrifugation, re-crystallization, distillation, adsorption,
  • the Quillay material is first dried and ground before being treated in the water or water/alcohol solution.
  • the Quillay extract may be concentrated e.g. by evaporating or drying the extract- containing solution to obtain a concentrated liquid extract or a dried extract.
  • the Quillay extract contains a minimum of 2 % of saponins and 5 % polyphenols and at least 15 °Brix; more preferably a minimum of 4 % of saponins and 10 % polyphenols and at least 25 °Brix. The percentages are weight percentages and relative to the volume of the extract.
  • the Quillay extract contains a minimum of 5 % by weight of saponins and at least 10 % by weight of polyphenols, relative to the dry mass of the extract, and at least 15 °Brix; e.g.
  • the dry mass contains at most 5% by weight, preferably at most 2% by weight of residual liquid components, such as extractants (in general water, possibly also alcohol; mostly however residual moisture), based on the total weight of the dry mass.
  • the Quillay extract is obtained by a process as described for example in CL 2573-2002. Chipped or milled wood, branches and/or the bark or flakes from branches and/or the bark of Quillaja saponaria are submitted to a solid/liquid extraction process using water as extractant.
  • the extraction temperature may vary between 20 and 95°C (i.e. is of from 20 to 95°C), e.g. 40 to 90°C, but is specifically ca. 60°C (+/- 10°C, preferably +/- 5°C).
  • the extraction time is in inverse proportion to the extraction temperature and is in general of from 0.5 to 5 h. For an extraction temperature of ca. 60°C, it is specifically ca. 2 to 3 h.
  • the mixtures comprise a compound II from group B'), preferably from the subgroup of C14 demethylase inhibitors (DMI fungicides), even more preferably from triazoles selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, ox- poconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazo
  • the mixtures comprise as compound II bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, propiconazole, prothioconazole or tebuconazole.
  • the mixtures comprise as compound II cyproconazole, difenoconazole, epoxiconazole, metconazole, propiconazole, prothioconazole or tebuconazole; and in particular tebuconazole.
  • the mixtures comprise as compound II epoxiconazole or metconazole.
  • the mixtures comprise as compound II difenoconazole, or propiconazole.
  • the mixtures comprise as compound II at least one imidazole selected from imazalil, pefurazoate, prochloraz and triflumizol.
  • the mixtures comprise as compound II at least one Del- ta14-reductase inhibitor selected from aldimorph, dodemorph, dodemorph-acetate, fenpropi- morph, tridemorph, fenpropidin, piperalin and spiroxamine, more preferably selected from tridemorph and fenpropimorph.
  • the mixtures comprise a compound II from the group H') Inhibitors with Multi Site Action, preferably from thio- and dithiocarbamates selected from fer- bam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram; more preferably selected from mancozeb and metiram.
  • the mixtures comprise a compound II from the organo- chlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, cap- tafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlor- phenole and its salts, phthalide, tolylfluanid and N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide; more preferably from chlorothalonil, captafol, captan, folpet and di- chlofluanid, in particular chlorothalonil.
  • organo- chlorine compounds e.g. phthalimides, sulfamides, chloronitriles
  • mixtures and compositions thereof according to the invention can, in the use form as fungicides and/or insecticides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
  • other active substances e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
  • the mixtures comprise besides Mixing a water-based Quillay extract and a compound II and the compositions comprising them, respectively, in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development, as component 3) a further active compound, preferably in a synergisti- cally effective amount.
  • component 3) is an active compound III selected from groups A) to O):
  • Inhibitors of complex III at Q 0 site e.g. strobilurins: azoxystrobin, coumethoxystrobin,
  • coumoxystrobin dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino- N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
  • - inhibitors of complex II e. g. carboxamides: benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, 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,
  • complex II e. g. carboxamides: benodanil, benzovindiflupyr, bixafen,
  • respiration inhibitors e.g. complex I, uncouplers: diflumetorim, (5,8-difluoroquinazolin- 4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine; nitrophenyl deri- vates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthi- ofam;
  • complex I uncouplers
  • DMI fungicides triazoles: azaconazole, bitertanol, bromucona- zole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbu- conazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triti- conazole, uniconazole,
  • Delta14-reductase inhibitors aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
  • hymexazole hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl, carbendazim, fuber- idazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
  • cell division inhibitors diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
  • - methionine synthesis inhibitors anilino-pyrimidines: 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, isoprothiolane;
  • - lipid peroxidation dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
  • phospholipid biosynthesis and cell wall deposition dimethomorph, flumorph, mandipropa- mid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
  • oxathiapiprolin 2- ⁇ 3-[2-(1 - ⁇ [3,5-bis(di -, flu -, oromethyl-
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chloro- thalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pen- tachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4- methyl-benzenesulfonamide;
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles
  • guanidine dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl- 1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
  • glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors: pyroqui- lon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
  • Biopesticides Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus amyloliquefaciens, B. mojavensis, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C.
  • Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity chitosan (hydrolysate), harpin protein, laminarin, Menhaden fish oil, natamycin, Plum pox virus coat protein, potassium or sodium bicarbonate, Rey- noutria sachlinensis extract, salicylic acid, tea tree oil;
  • Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thurin- giensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B.
  • brongniartii Burkholderia sp., Chromobac- terium subtsugae, Cydia pomonella granulosis virus, Cryptophlebia leucotreta granulovirus (CrleGV), Isaria fumosorosea, Heterorhabditis bacteriophora, Lecanicil- lium longisporum, L. muscarium (formerly Verticillium lecanii), Metarhizium anisopli- ae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P.
  • PrleGV Cryptophlebia leucotreta granulovirus
  • Isaria fumosorosea Heterorhabditis bacteriophora
  • Lecanicil- lium longisporum L. muscarium (formerly Verticillium lecanii)
  • Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 - butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1 -ol, (E,Z)- 2,13-octadecadien-1 -ol acetate, (E,Z)-3,13
  • Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity Azospirillum amazonense A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. ja- ponicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Meso- rhizobium sp., Paenibacillus alvei, Penicillium bilaiae, Rhizobium leguminosarum bv. phaseoli, R. I. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti;
  • Biochemical pesticides with plant stress reducing, plant growth regulator and/or plant yield enhancing activity abscisic acid, aluminium silicate (kaolin), 3-decen-2- one, formononetin, genistein, hesperetin, homobrassinlide, humates, jasmonic acid or salts or derivatives thereof, lysophosphatidyl ethanolamine, naringenin, polymeric polyhydroxy acid, Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract and Ecklonia maxima (kelp) extract;
  • abscisic acid amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, di- methipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadi- one (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phos- phorotrithioate, 2,3,
  • acetochlor alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefe- nacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
  • EPTC esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thio- bencarb, triallate;
  • acifluorfen acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, ox- yfluorfen;
  • - phenoxy acetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlor- prop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
  • - pyrazines chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
  • - pyridines aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
  • - sulfonyl ureas amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfu- ron, triflusulfuron, trito
  • - triazines ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
  • ureas chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
  • acetolactate synthase inhibitors bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrim- isulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
  • organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyri- fos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethi- on, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phentho- ate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
  • - carbamates alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosul- fan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodi- carb, triazamate;
  • - pyrethroids allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, pralle
  • - insect growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cy- ramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juve- noids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
  • - nicotinic receptor agonists/antagonists compounds clothianidin, dinotefuran, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -2-chloro-thiazol-5- ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
  • - GABA antagonist compounds endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole,
  • - macrocyclic lactone insecticides abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
  • - oxidative phosphorylation inhibitors cyhexatin, diafenthiuron, fenbutatin oxide, propargite; - moulting disruptor compounds: cryomazine;
  • biopesticides from group L) of pesticides III, their preparation and their pesticidal activity e.g. against harmful fungi or insects are known (e-Pesticide Manual V 5.2 (ISBN 978 1 901396 85 0) (2008-201 1 ); http://www.epa.gov/opp00001/biopesticides/, see product lists therein; http://www.omri.org/omri-lists, see lists therein; Bio-Pesticides Database BPDB
  • the biopesticides from group L1 ) and/or L2) may also have insecticidal, acaricidal, mollus- cidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L5) and/or L6) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
  • biopesticides are registered and/or are commercially available: aluminium sili- cate (ScreenTM Duo from Certis LLC, USA), Agrobacterium radio->bacter K1026 (e.g. NoGall® from Becker Underwood Pty Ltd., Australia), A. radiobacter K84 (Nature 280, 697-699, 1979; e.g. GallTroll® from AG Biochem, Inc., C, USA), Ampelomyces quisqualis M-10 (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract or filtrate (e.g.
  • A. brasilense AZ39 (Eur. J. Soil Biol 45(1 ), 28-35, 2009), A. brasilense XOH (e.g. AZOS from Xtreme Gardening, USA or RTI Reforestation Technologies International; USA), A. brasilense BR 1 1002 (Proc. 9th Int. and 1 st Latin American PGPR meeting, Quimara, Medellin, Colombia 2012, p. 60, ISBN 978-958-46-0908-3), A. brasilense BR 1 1005 (SP245; e.g. in GELFIX Gramineas from BASF Agricultural Specialties Ltd., Brazil), A.
  • SP245 e.g. in GELFIX Gramineas from BASF Agricultural Specialties Ltd., Brazil
  • lipoferum BR 1 1646 (Sp31 ) (Proc. 9th Int. and 1 st Latin American PGPR meeting, Quimara, Medellin, Colombia 2012, p. 60), B. amyloliquefaciens IN937a (J. Microbiol. Bio- technol. 17(2), 280-286, 2007; e.g. in BioYield® from Gustafson LLC, TX, USA), B. amyloliquefaciens IT-45 (CNCM I 3800) (e.g. Rhizocell C from ITHEC, France), B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595, deposited at United States Department of Agriculture) (e.g.
  • B. subtilis GB03 e.g. Kodiak® or BioYield® from Gustafson, Inc., USA; or Companion® from Growth Products, Ltd., White Plains, NY 10603, USA
  • B. subtilis GB07 Epic® from Gustafson, Inc., USA
  • B. subtilis QST-713 NRRL B 21661 in Rhapsody®, Serenade® MAX and Serenade® ASO from AgraQuest Inc., USA
  • B. subtilis var. amylolique-'faciens FZB24 e.g. Taegro® from Novozyme Biologicals, Inc., USA
  • B. subtilis GB03 e.g. Kodiak® or BioYield® from Gustafson, Inc., USA; or Companion® from Growth Products, Ltd., White Plains, NY 10603, USA
  • B. subtilis GB07 Epic® from Gustafson, Inc., USA
  • subtilis var. amyloliquefaciens D747 e.g. Double Nickel 55 from Certis LLC, USA
  • B. thuringiensis ssp. aizawai ABTS-1857 e.g. in XenTari® from BioFa AG, Munsingen, Germany
  • Bacillus t. ssp. israelensis AM65-52 e.g. in VectoBac® from Valent Biosciences, IL, USA
  • Bacillus thuringiensis ssp. kurstaki SB4 NRRL B-50753; e.g.
  • Beta Pro® from Becker Underwood, South Africa B. t. ssp. kurstaki ABTS-351 identical to HD-1 (ATCC SD-1275; e.g. in Dipel® DF from Valent Biosciences, IL, USA), B. t. ssp. kurstaki EG 2348 (e.g. in Lepinox® or Rapax® from CBC (Europe) S.r.l., Italy), B. t. ssp. tenebrionis DSM 2803 (EP 0 585 215 B1 ; identical to NRRL B-15939; Mycogen Corp.), B. t. ssp.
  • tenebrionis NB-125 (DSM 5526; EP 0 585 215 B1 ; also referred to as SAN 418 I or ABG-6479; former production strain of Novo-Nordisk), B. t. ssp. tenebrionis NB-176 (or NB- 176-1 ) a gamma-irridated, induced high-yielding mutant of strain NB-125 (DSM 5480; EP 585 215 B1 ; Novodor® from Valent Biosciences, Switzerland), Beauveria bassiana ATCC 74040 (e.g. in Naturalis® from CBC (Europe) S.r.l., Italy), B.
  • DSM 5526 EP 0 585 215 B1 ; also referred to as SAN 418 I or ABG-6479; former production strain of Novo-Nordisk
  • B. t. ssp. tenebrionis NB-176 (or NB- 176-1 ) a
  • bassiana DSM 12256 (US 200020031495; e.g. BioExpert® SC from Live Sytems Technology S.A., Colombia), B. bassiana GHA (Botani- Gard® 22WGP from Laverlam Int. Corp., USA), B. bassiana PPRI 5339 (ARSEF number 5339 in the USDA ARS collection of entomopathogenic fungal cultures; NRRL 50757) (e.g. Broad- Band® from Becker Underwood, South Africa), B. brongniartii (e.g. in Melocont® from Agrifutur, Agrianello, Italy, for control of cockchafer; J. Appl. Microbiol.
  • Bradyrhi- zobium sp. e.g. Vault® from Becker Underwood, USA
  • B. japonicum e.g. VAULT® from Becker Underwood, USA
  • Candida oleophila 1-182 NRRL Y-18846; e.g. Aspire® from Ecogen Inc., USA, Phytoparasitica 23(3), 231 -234, 1995
  • C. oleophila strain O NRRL Y-2317; Biological Control 51 , 403-408, 2009
  • Candida saitoana 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 J 1446: Prestop® from Verdera Oy, Finland), Chromobacterium subtsu- gae PRAA4-1 isolated from soil under an eastern hemlock (Tsuga canadensis) in the Catoctin Mountain region of central Maryland (e.g. in GRANDEVO from Marrone Bio Innovations, USA), Coniothyrium minitans CON/M/91 -08 (e.g. Contans® WG from Prophyta, Germany),
  • Gliocladium ca- tenulatum e.g. isolate J 1446: Prestop® from Verdera Oy, Finland
  • Cryphonectria parasitica e.g. Endothia parasitica from CNICM, France
  • Cryptococcus albidus e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa
  • Cryptophlebia leucotreta granulovirus e.g. in CRYPTEX from Adermatt Biocontrol, Switzerland
  • Cydia pomo- nella granulovirus CpGV) V03
  • DSM GV-0006 e.g. in MADEX Max from Andermatt Biocontrol, Switzerland
  • CpGV V22 DSM GV-0014; e.g.
  • Delftia acidovorans RAY209 (ATCC PTA-4249; WO 2003/57861 ; e.g. in BIOBOOST from Brett Young, Winnipeg, Canada), Dilophosphora alopecuri (Twist Fungus from Becker Underwood, Australia), Ecklonia maxima (kelp) extract (e.g. KELPAK SL from Kelp Products Ltd, South Africa), formononetin (e.g. in MYCONATE from Plant Health Care pic, U.K.), Fusarium oxysporum (e.g.
  • Nemasys® G from Becker Underwood Ltd., UK
  • Isaria fumosorosea Apopka-97 (ATCC 20874)
  • PFR-97TM from Certis LLC, USA
  • cis- jasmone US 8,221 ,736
  • laminarin e.g. in VACCI PLANT from Laboratoires Goemar, St. Malo, France or Stahler SA, Switzerland
  • Lecanicillium longisporum KV42 and KV71 e.g. VERTAL- EC® from Koppert BV, Netherlands
  • L. muscarium KV01 (formerly Verticillium lecanii) (e.g.
  • acridum FI-985 e.g. GREEN GUARD® SC from Becker Underwood Pty Ltd, Australia
  • M. anisopliae FI-1045 e.g. BIOCANE® from Becker Underwood Pty Ltd, Australia
  • M. anisopliae F52 DSM 3884, ATCC 90448; e.g. MET52® Novozymes Biologicals BioAg Group, Canada
  • M. anisopliae ICIPE 69 e.g. METATHRI POL from ICIPE, Nairobe, Kenya
  • Metschnikowia fructicola NRRL Y-30752; e.g.
  • NEMATA® SC from Live Systems Technology S.A., Colombia
  • Iilacinus BCP2 (NRRL 50756; e.g. PL GOLD from Becker Underwood BioAg SA Ltd, South Africa), mixture of Paenibacillus alvei NAS6G6 (NRRL B-50755), Pantoea vagans (formerly agglomerans) C9-1 (originally isolated in 1994 from apple stem tissue; Blight- Ban C9-1® from NuFrams America Inc., USA, for control of fire blight in apple; J. Bacteriol. 192(24) 6486-6487, 2010), Pasteuria spp. ATCC PTA-9643 (WO 2010/085795), Pasteuria spp. ATCC SD-5832 (WO 2012/064527), P. nishizawae (WO 2010/80169), P. penetrans (US 5,248,500), P. ramose (WO 2010/80619), P. thornea (WO 2010/80169), P. usgae (WO
  • Penicillium bilaiae e.g. Jump Start® from Novozymes Biologicals BioAg Group, Canada, originally isolated from soil in southern Alberta; Fertilizer Res. 39, 97-103, 1994
  • Phle- biopsis gigantea e.g. RotStop® from Verdera Oy, Finland
  • Pichia anomala WRL-076 NRRL Y- 30842; US 8,206,972
  • potassium bicarbonate e.g. Amicarb® fromm Stahler SA, Switzerland
  • potassium silicate e.g. Sil-MATRIXTM from Certis LLC, USA
  • Pseudozyma flocculosa PF-A22 UL e.g.
  • Pseudomonas sp. DSM 13134 WO 2001/40441 , e.g. in PRORADIX from Sourcon Padena GmbH & Co. KG, Hechinger Str. 262, 72072 Tubingen, Germany
  • P. chloraphis MA 342 e.g. in CERALL or CEDEMON from BioAgri AB, Uppsala, Sweden
  • P. fluorescens CL 145A e.g. in ZEQUANOX from Marrone Bio- Innovations, Davis, CA, USA; J. Invertebr. Pathol.
  • R. I. bv. viciae P1 NP3Cst also referred to as 1435; New Phytol 179(1 ), 224-235, 2008; e.g. in NODULATOR PL Peat Granule from Becker Underwood, USA; or in NODULATOR XL PL bfrom Becker Underwood, Canada
  • R. I. bv. viciae SU303 e.g. NODULAID Group E from Becker Underwood, Australia
  • R. I. bv. viciae WSM1455 e.g. NODULAID Group F from Becker Underwood, Australia
  • SEMIA 4080 (identical to PRF 81 ; Soil Biology & Biochemistry 39, 867-876, 2007), Sinorhizobi- um meliloti MSDJ0848 (INRA, France) also referred to as strain 201 1 or RCR201 1 (Mol Gen Genomics (2004) 272: 1-17; e.g. DORMAL ALFALFA from Becker Underwood, USA; Nl- TRAGIN® Gold from Novozymes Biologicals BioAg Group, Canada), Sphaerodes mycoparasiti- ca IDAC 301008-01 (WO 201 1/022809), Steinernema carpocapsae (e.g. MILLENIUM® from Becker Underwood Ltd., UK), S. feltiae (NEMASHIELD® from BioWorks, Inc., USA;
  • T. asperellum SKT-1 e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan
  • T. asperellum ICC 012 e.g. in TENET WP, REMDIER WP, BIOTEN WP from Isagro NC, USA, BIO-TAM from AgraQuest, USA
  • T. atroviride LC52 e.g. SENTI- NEL® from Agrimm Technologies Ltd, NZ
  • T. atroviride CNCM 1-1237 e.g. in Esquive WG from Agrauxine S.A., France, e.g. against pruning wound diseases on vine and plant root pathogens
  • T. atroviride LC52 e.g. SENTI- NEL® from Agrimm Technologies Ltd, NZ
  • T. atroviride CNCM 1-1237 e.g. in Esquive WG from Agrauxine S.A., France, e.g. against pruning wound
  • 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.
  • T. harzianum and T. viride e.g. TRICHOPEL from Ag- rimm 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. stromaticum e.g. TRICOVAB® from C.E.P.L.A.C., Brazil
  • virens GL-21 also named Gliocladium virens
  • Gliocladium virens 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. in BOTRY-ZEN® from Botry-Zen Ltd, NZ.
  • Strains can be sourced from genetic resource and deposition centers: American Type Culture Collection, 10801 University Boulevard., Manassas, VA 201 10-2209, USA (strains with ATCC prefic); CABI Europe - International Mycological Institute, Bakeham Lane, Egham, Surrey, TW20 9TYNRRL, UK (strains with prefices CABI and I Ml); Centraalbureau voor Schimmelcul- tures, Fungal Biodiversity Centre, Uppsalaan 8, PO Box 85167, 3508 AD Utrecht, Netherlands (strains with prefic CBS); Division of Plant Industry, CSIRO, Canberra, Australia (strains with prefix CC); Collection Nationale de Cultures de Microorganismes, Institut Pasteur, 25 rue du Do Sheffield Roux, F-75724 PARIS Cedex 15 (strains with prefix CNCM); Leibniz-lnstitut DSMZ- Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Inhoffenst ⁇ e 7 B,
  • Bacillus amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595) is deposited under accession number NRRL B-50595 with the strain designation Bacillus subtilis 1430 (and identical to NCIMB 1237).
  • MBI 600 has been re-classified as Bacillus amyloliquefaciens subsp. plantarum based on polyphasic testing which combines classical microbiological meth- ods 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 Bacillus amyloliquefaciens subsp.
  • Bacillus amyloliquefaciens MBI600 is known as plant growth-promoting rice seed treatment from Int. J. Microbiol. Res. 3(2) (201 1 ), 120-130 and further described e.g. in US 2012/0149571 A1.
  • This strain MBI600 is e.g. commercially available as liquid formulation product INTEGRAL® (Becker-Underwood Inc., USA).
  • Bacillus subtilis strain FB17 was originally isolated from red beet roots in North America (System Appl. Microbiol 27 (2004) 372-379). This B. subtilis strain promotes plant health (US 2010/0260735 A1 ; WO 201 1/109395 A2). B. subtilis FB17 has also been deposited at ATCC under number PTA-1 1857 on April 26, 201 1 . Bacillus subtilis strain FB17 may be referred elsewhere to as UD1022 or UD10-22.
  • Bacillus amyloliquefaciens AP-136 (NRRL B-50614), B. amyloliquefaciens AP-188 (NRRL B- 50615), B. amyloliquefaciens AP-218 (NRRL B-50618), B. amyloliquefaciens AP-219 (NRRL B- 50619), B. amyloliquefaciens AP-295 (NRRL B-50620), B. japonicum SEMIA 5079 (e.g. Gelfix 5 or Adhere 60 from Nitral Urbana Laoboratories, Brazil, a BASF Company), B. japonicum SEMIA 5080 (e.g.
  • B. mojavensis AP-209 NRRL B-50616
  • B. solisalsi AP-217 NRRL B-50617
  • B. pumilus strain INR-7 otherwise referred to as BU-F22 (NRRL B-50153) and BU-F33 (NRRL B-50185)
  • B. simplex ABU 288 NRRL B-50340
  • B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595) have been mentioned i.a. in US patent appl. 20120149571 , US 8,445,255, WO 2012/079073. Bradyrhizobium japonicum USDA 3 is known from US patent 7,262,151.
  • Jasmonic acid or salts (jasmonates) or derivatives include without limitation potassi-um jasmonate, sodium jasmonate, lithium jasmonate, ammonium jasmonate, dimethyl-ammonium 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
  • Humates are humic and fulvic acids extracted from a form of lignite coal and clay, known as leonardite.
  • Humic acids are organic acids that occur in humus and other organically derived materials such as peat and certain soft coal. They have been shown to increase fertilizer efficiency in phosphate and micro-nutrient uptake by plants as well as aiding in the development of plant root systems.
  • the mixtures comprise as compounds III fungicidal compounds that are independently of each other selected from the groups A), B), C), D), E), F), G), H), I), J), K) and L), more preferably in combination with an organic acid such as citric acid, lactic acid or ascorbic acid.
  • mixtures comprise as compound III a herbicidal compound that is selected from the group N).
  • mixtures comprise as compound III (component 3) at least one active substance selected from group A) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, tri- floxystrobin; famoxadone, fenamidone; benzovindiflupyr, bixafen, boscalid, fluopyram, fluxapy- roxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such as fentin acetate.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group B) and particularly selected from cyproconazole, difeno- conazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetracon- azole, triticonazole, prochloraz, fenarimol, triforine; dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine; fenhexamid.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group C) and particularly selected from metalaxyl, (metalaxyl-M) mefenoxam, ofurace.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group D) and particularly selected from benomyl, carbendazim, thiophanate-methyl, ethaboxam, fluopicolide, zoxamide, metrafenone, pyriofenone.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group E) and particularly selected from cyprodinil, mepanipyrim, pyrimethanil.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group F) and particularly selected from iprodione, fludioxonil, vinclozolin, quinoxyfen.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group G) and particularly selected from dimethomorph, flumorph, iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group H) and particularly selected from copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb, metiram, propineb, thiram, captafol, folpet, chlorothalonil, dichlofluanid, dithianon.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group I) and particularly selected from carpropamid and fenoxanil.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group J) and particularly selected from acibenzolar-S-methyl, probenazole, tiadinil, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group K) and particularly selected from cymoxanil, proquinazid and A/-methyl-2- ⁇ 1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl ⁇ -A/-[(1 R)- 1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide.
  • mixtures comprise as compound III (component 3) at least one active substance selected from group L) and particularly selected from Bacillus subtilis strain NRRL No. B-21661 , Bacillus pumilus strain NRRL No. B-30087 and Ulocladium oudemansii .
  • mixtures comprise as compound Ili a further insecticidal compound that is selected from the group O).
  • component 3 is an extract of Acacia negra (see WO 2006/0210264), more preferably a water-based extract of Acacia negra.
  • the mixtures and compositions according to the invention are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiopho- romycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomy- cetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the mixtures and compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on 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.
  • 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.
  • inventive mixtures and compositions are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • treatment of plant propagation materials with the inventive combination of the Quillay extract and compounds II and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is 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://www.bio.org/speeches/pubs/er/agri_products.asp).
  • 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-transtional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • inventive mixtures and compositions are particularly suitable for controlling the following 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 brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alterna- ta), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A.
  • tritici anthracnose
  • Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.) on corn (e. g. D. maydis), cereals (e. g. B. sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley);
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g.
  • strawberries strawberries
  • vegetables e. g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Bremia lactucae downy mildew
  • 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, 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
  • Claviceps purpurea ergot
  • Cochliobolus ana- morph: Helminthosporium of Bipolaris
  • spp. leaf spots
  • corn C. carbonum
  • cereals e. g. C. sativus, anamorph: B. sorokiniana
  • rice e. g. C. miyabeanus, anamorph: H. oryzae
  • Colle- totrichum teleomorph: Glomerella
  • spp. anthracnose
  • cotton e. g. C. gossypii
  • corn e. g. C. graminicola
  • soft fruits potatoes
  • C. coccodes black dot
  • beans e. g. C. lindemuthi- anum
  • soybeans e. g. C. truncatum or C. gloeosporioides
  • Corticium spp. e. g. C. sasakii (sheath blight) on rice
  • Corynespora cassiicola leaf spots
  • Cy- cloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g.
  • teleomorph Nectria or Neonectria spp.
  • fruit trees canker or young vine decline
  • teleomorph Nectria or Neonectria spp.
  • fruit trees canker or young vine decline
  • teleomorph Nectria or Neonectria spp.
  • vines e. g. C. lirio- dendri
  • teleomorph Neonectria liriodendri: Black Foot Disease
  • 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 cu- curbits (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.
  • cu- curbits e. g. E. cichoracearum
  • cabbages rape (e. g. E. cruciferarum)
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella
  • phaseoli root and stem rot
  • soybeans and cotton
  • Microdochium syn. Fusarium
  • nivale pink snow mold
  • Microsphaera diffusa prowdery mildew
  • Monilinia spp. e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M.
  • soybeans e. g. P. gregata: stem rot
  • Phoma lingam root and stem rot
  • P. betae root rot, leaf spot and damping-off
  • sugar beets e. g. P. viticola: can and leaf spot
  • soybeans e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolo- rum
  • Physoderma maydis brown spots
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P. megasperma, syn. P. sojae
  • potatoes and tomatoes e. g. P. infestans: late blight
  • broad- leaved trees e. g. P. ramorum: sudden oak death
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • 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, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph:
  • Drechslera tritici-repentis (tan spot) on wheat or P. feres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R.
  • collo-cygni (Ram ularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • S. reiliana head smut
  • S. reiliana head smut
  • Sphaerotheca fuliginea powdery mildew
  • Spongospora subterra- nea powdery scab
  • Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeo- sphaeria] nodorum) on wheat
  • Synchytrium endobioticum on potatoes potato wart disease
  • Taphrina spp. e. g. T.
  • deformans leaf curl disease
  • T. pruni plum pocket
  • plums Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U.
  • occulta stem smut
  • Uromyces spp. rust
  • vegetables such as beans (e. g. U. appendicula- tus, 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
  • apples e. g. V. inaequalis
  • pears 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.
  • mixtures and compositions of the present invention are effective against plant pathogens in speciality crops such as vine, fruits, hop, vegetables and tabacco.
  • Plant propagation materials may be treated with the mixtures and compositions of the invention prophylactically either at or before planting or transplanting.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least a water-based Quillay extract and a compound II according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a Quillay extract and a compound II.
  • the term "effective amount” denotes an amount of the composition or of the Quillay extract and of the compound II, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material and the climatic conditions.
  • the inventive mixtures and compositions are also suitable for controlling the following plant parasitic nematodes such as Meloidogyne, Globodera, Heterodera, Radopholus, Rotylenchulus, Pratylenchus and other genera.
  • the Quillay extract and a compound II can be converted into customary types of agrochemi- cal compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g.
  • EW, EO, ES, ME cap- sules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
  • These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, disper- sants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibil- izers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil frac- tions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalen
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.g. cellulose, starch
  • fertilizers
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox- ylated 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 active ingredient on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkyliso- thiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, pro- pylene 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
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g.
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
  • the solid material (total dry matter) of the Quillay extract is considered as active component (e.g. to be obtained after drying or evaporation of the extraction medium).
  • the (weight) ratios used herein for the Quillay extract are based on the total weight of the dry content (solid material) of the extract.
  • the 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 components.
  • Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), pow- ders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the compositions in question give, after two-to-tenfold dilution, active components concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying or treating with the Quillay extract and compound II and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the Quillay extract and compound II or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active components applied are, depending on the kind of effect desired, from 0.001 to 10 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • amounts of active components of from 0.1 to 10000 g, preferably from 1 to 2000 g, more preferably from 1 to 500 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of active components applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active components per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • a polyether polymethylsiloxane copolymer may be added to the composition accoding to the invention, preferably in a weight ratio of 1 :100 to 100:1 , more preferably in a weight ratio of 1 :10 to 10:1 , in particular in a weight ratio of 1 :5 to 5:1 based on the total weight of the dry content of Quillay extract and the amount of respective compound II together.
  • a mineral oil or a vegetable oil may be added to the composition according to the invention, preferably in a weight ratio of 1 :100 to 100:1 , more preferably in a weight ratio of 1 :10 to 10:1 , in particular in a weight ratio of 1 :5 to 5:1 based on the total weight of the dry content of Quillay extract and the amount of respective compound II together.
  • an organic acid such as citric acid, lactic acid or ascorbic acid may be added to the composition according to the invention, preferably in a weight ratio of 1 :100 to 100:1 , more preferably in a weight ratio of 1 :10 to 10:1 , in particular in a weight ratio of 1 :5 to 5:1 based on the total weight of the dry content of Quillay extract and the amount of respective compound II together.
  • the user applies the composition according to the invention usually from a predosage de- vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the ag- rochemical 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.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • 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 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 :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 Quillay extract is used in excess as compared to the compound II, i.e. the weight ratio of the Quillay extract versus compound II usually is in the range of from 100:1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , particularly in the range of from 20:1 to 1 :1 , more particularly in the range of from 10:1 to 1 :1 , specifically in the range of from 4:1 to 1 :1 , e.g. of from 3:1 to 1 :1 , and in particular in the range of from 2:1 to 1 :1.
  • the amount of Quillay extract is based on the amount of the solid material (dry matter).
  • the solid material may contain at most 5% by weight, preferably at most 2% by weight, based on the total weight of the solid material, of residual liquid components, such as extractants (in general water, possibly also alcohol; mostly however residual moisture).
  • 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 compound ratios are advantageously chosen so as to produce a synergistic effect.
  • the relative amount i.e. the weight ratio of the Quillay extract and the at least one compound II in the mixture or composition provides for an increased fungicidal effica- cy on at least one harmful fungus which exceeds the additive fungicidal efficacy of the components of the mixture or composition as calculated from the fungicidal efficacy of the individual components at a given application rate.
  • the components can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used as combination such as a kit of parts.
  • a conidia suspension of Botrytis cinerea (isolate obtained from Thompson Seedless grape) was prepared at a concentration of 10 6 conidia / ml.
  • culture medium a potato dextrose broth was used.
  • a Quillay extract alone used in form of the commercial product QL Agri® 35 from BASF; a soluble concentrate containing 35% by weight of solid matter, relative to the total weight of the concentrate; diluted with water to a concentration of 5000 ppm); or chlorothalonil alone (used in form of the commercial product Bravo® from Bayer; a suspension concentrate with 720 g a.i.
  • X percent activity using active compound A at an application rate a

Abstract

The present invention relates to mixtures comprising a Quillay extract and at least one fungicidal compound as defined in the description, and to compositions comprising these mixtures.

Description

Compositions comprising a Quillay extract and a fungicidal compound Description The present invention relates to mixtures comprising as active components a Quillay extract and a fungicidal compound as defined herein.
Quillaja saponaria, Molina, the soapbark tree, is an evergreen tree in the family Quillajaceae, native to warm temperate central Chile.
Extracts of the barksoap tree (Quillaja saponaria Mol.) are well-known (CAS-No. 68990-67-0) and safe cosmetic, food and pharmaceutical additives e.g. used as adjuvant in vaccine solutions. Such soapbark tree, also called China bark extract, Murillo bark extract, Panama bark extract, Quillai extract, Quillaia extract or Quillay extract, generally comprises the milled inner bark or small stems and branches of the soapbark tree and contains saponins, polyphenols and other ingredients.
Quillay extract-based products (e.g. QL Agri 35, BASF SE) have been also applied as ne- maticides especially indicated for the control of nematodes in vineyards and citric trees. Further, an acaricidal mixture comprising the Quillay extract QL Agri 35 and sulfur (Acoidal WG) is marketed by BASF SE.
Quillay's biocide activity has been previously described for instance in Apablaza et al (Fitopatologia 39, 2004, 144-149), where experiments are described about the control of cucur- bitaceae oidium [Erysiphe cichoracearum DC. ex Merat and Sphaerotheca fuliginea (Schlecht ex Fr.) Poll] with the saponin-containing Quillay extracts QL 1000 and QL 30B; said experiments provided satisfactory results in cucumber and pumpkins.
It was further known that Quillay extracts have antifungal activity against plant pathogenic fungal species such as Gaeumannomyces graminis (US 201 1/0190123 A1 ) and Botrytis cinerea (EP 2 106 698 A2).
Quillay extracts based on water extraction are commercially available e.g. under the trademark QL Agri 35 produced by Natural Response S.A., Quilpue, Chile, and marketed by Desert King Chile and BASF SE. Usually the extraction step takes place at temperatures between 5°C and 95°C, preferably at 20°C to 90°C, even more preferably at 40°C to 90°C. It contains a minimum of 6 % of saponins, 15 % polyphenols and about 35 °Brix, and has a total solids content of 350 g/l (the total solids content, or dry mass content, containing in general a residual moisture content of at most 5% by weight, preferably at most 2% by weight, based on the total weight of the solids content). The percentages are weight percentages and relative to the vol- ume of the extract. One degree Brix is 1 gram of sucrose in 100 grams of solution and represents the strength of the solution as percentage by weight (% w/w) (strictly speaking, by mass). If the solution contains dissolved solids other than pure sucrose, then the °Brix is only approximate the dissolved solid content. Further suitable Quillay extracts are commercially available (trademarks QL 1000, QP 1000, QL Ultra, QL 30B and Vax Sap, produced by Natural Re- sponse S.A. Quilpue, Chile).
The fungicidal compounds II as defined herein, their preparation and biological activity against fungi are known (e.g.: http://www.alanwood.net/pesticides/); many of these substances are commercially available.
Practical agricultural experience has shown that the repeated and exclusive application of an individual active compound in the control of harmful fungi leads in many cases to a rapid selection of those fungus strains which have developed natural or adapted resistance against the active compound in question. Effective control of these fungi with the active compound in question is then no longer possible.
To reduce the risk of the selection of resistant fungus strains, mixtures of different active compounds are nowadays conventionally employed for controlling harmful fungi. By combining active compounds or active biological extracts having different mechanisms of action, it is possible to ensure successful control over a relatively long period of time.
It is an object of the present invention to provide, with a view to effective resistance management and effective control of phytopathogenic harmful fungi, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful fungi (synergistic mixtures) and a broadened activity spectrum, in particular for certain indications.
We have accordingly found that this object is achieved by the mixtures and compostions defined herein, comprising a Quillay extract and a fungicidal compound as defined herein.
Thus, the present invention relates to mixtures comprising, as active components
1 ) a Quillay extract;
and
2) at least one fungicidal compound II selected from the groups B') and H'):
B') Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bro- muconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxi- conazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutra- zole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, 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]triazole-3-thiol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; py- rimidines, 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;
H') Inhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate;
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
- organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hex- achlorobenzene, 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), dithianon and 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone.
The mixture according to the invention or to be used according to the invention is not re- stricted to a physical mixture of the Quillay extract and at least one compound II, but can be any combination of the Quillay extract and at least one compound II, it not being required for the Quillay extract and the at least one compound II to be present together in the same formulation. In the following, the mixture of the invention is partly also termed "composition".
An example of a "mixture" (more correctly: a composition) according to the invention or to be used according to the invention in which the Quillay extract and the at least one compound II are not present together in the same formulation is a combipack. In a combipack, two or more components of a combipack are packaged separately, i.e., not jointly pre-formulated. As such, combipacks include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical com- position. One example is a two-component combipack. Accordingly the present invention also relates to a two-component combipack, comprising a first component which in turn comprises the Quillay extract, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary, and a second component which in turn comprises at least one compound II, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary. More details, e.g. as to suitable liquid and solid carriers, surfactants and customary auxiliaries are described below.
In a specific embodiment, the mixture of the invention is a physical mixture.
Moreover, the invention relates also to a method for controlling phytopathogenic harmful fungi, or for improving the health of the plants using mixtures of a Quillay extract and at least one compound II and to the use of the components 1 ) and 2) as defined herein for preparing such mixtures, and to compositions and seed comprising these mixtures.
In a specific embodiment of the invention, the method of the invention does not include a treatment of a human or animal body.
Moreover, we have found that simultaneous, that is joint or separate, application of a Quillay extract and at least one compound II or successive application of a Quillay extract and of a compound II allows better control of harmful fungi than is possible with the individual compounds alone (synergistic mixtures). Thus, the invention also relates to the use of a mixture of the invention as defined above or below or of an agricultural composition as defined below or of a Quillay extract in combination with at least one compound II as defined above or below and optionally also in combination with at least one active component 3) as defined below for controlling phytopathogenic fungi.
The use of the Quillay extract "in combination with" the at least one compound II on the one hand can be understood as using a physical mixture of Quillay extract and at least one compound II. On the other hand, the combined use may also consist in using the Quillay extract and the at least one compound II separately, but locus- and time-related (i.e. both components are applied to the same "substrate" (plant, part thereof, seed, habitat of the fungus etc.) within a sufficiently short time of one another), so that the desired effect can take place. More detailed illustrations of the combined use can be found in the specifications below. Furthermore, synergistic effects in relation with the insecticidal and/or herbicidal action have been found with the inventive mixtures.
According to one embodiment, the mixtures comprise component 1 ) and component 2) in a synergistically effective amount.
Compounds II can be present in different crystal modifications, which may differ in biological activity.
The active component 1 ) of the mixture can be found on the basis of the soap bark tree (Quillaja saponaria), from wood, branches and the bark of the tree, which are milled. Quillaja can as well be used as an extract of flakes from branches and the bark from the soap bark tree. The extract can be based on pure water extraction or a blend of water and alcohol as a means of extraction. The extract can be used as a liquid product or it can be spray dried. The above- mentioned commercially available extracts are also suitable.
According to one embodiment, the mixtures comprise as component 1 ) a water-based Quillay extract. The term "water-based Quillay extract" is to be understood that the extract of the material of the Quillay tree is obtained by solid-liquid extraction wherein the liquid is water or a water-based solution comprising water-soluble solvents (such as alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters) and/or other auxiliaries (such as liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, bactericides, anti-freezing agents, anti- foaming agents, tackifiers and binders).
In some embodiments of the invention, the Quillay extract is obtained by extraction from the Quillay tree by employing water, alcohol or a water/alcohol solution. In some embodiments, the alcohol is ethanol or methanol.
In some embodiments, the extraction is achieved by employing a water/alcohol solution. In some embodiments, the water/alcohol solution has a water/alcohol ratio of from 80:20 to 20:80. In further embodiments, the water/alcohol solution has a water/alcohol ratio of from 60:40 to 40:60. In further embodiments, the water/alcohol solution is 80:20 water/alcohol, 60:40 water/alcohol, 50:50 water/alcohol, 40:60 water/ alcohol ratio or 20:80 water/alcohol. The water/alcohol ratios given are volume/volume. Specifically, the extractant is water.
The extraction time may vary without limitation from 1 to 8 hours, at or above room temperature (20°C-30°C), e.g., above 30°C, 40°C, 50°C or 60°C. In some embodiments, the extraction is carried out at a temperature between 30°C and 70°C.
In some embodiments, the extraction process comprising: treating the Quillay material in a water or water/alcohol solution.
Optionally, the so-extracted material may subsequently be purified by any means known in the art, including: filtration, centrifugation, re-crystallization, distillation, adsorption,
chromatographic methods, fractionation, etc.
In some embodiments, the Quillay material is first dried and ground before being treated in the water or water/alcohol solution.
Optionally, the Quillay extract may be concentrated e.g. by evaporating or drying the extract- containing solution to obtain a concentrated liquid extract or a dried extract.
According to a further embodiment, the Quillay extract contains a minimum of 2 % of saponins and 5 % polyphenols and at least 15 °Brix; more preferably a minimum of 4 % of saponins and 10 % polyphenols and at least 25 °Brix. The percentages are weight percentages and relative to the volume of the extract. In an alternative embodiment, the Quillay extract contains a minimum of 5 % by weight of saponins and at least 10 % by weight of polyphenols, relative to the dry mass of the extract, and at least 15 °Brix; e.g. at least 9 % by weight of saponins and at least 20 % by weight of polyphenols, relative to the dry mass of the extract, and at least 15 °Brix; more preferably a minimum of 4 % by weight of saponins and at least 10 % by weight of polyphenols, relative to the dry mass of the extract, and at least 25 °Brix; e.g. at least 10 % by weight of saponins and at least 25 % by weight of polyphenols, relative to the dry mass of the extract, and at least 25 °Brix. The dry mass contains at most 5% by weight, preferably at most 2% by weight of residual liquid components, such as extractants (in general water, possibly also alcohol; mostly however residual moisture), based on the total weight of the dry mass.
In a specific embodiment, the Quillay extract is obtained by a process as described for example in CL 2573-2002. Chipped or milled wood, branches and/or the bark or flakes from branches and/or the bark of Quillaja saponaria are submitted to a solid/liquid extraction process using water as extractant. The extraction temperature may vary between 20 and 95°C (i.e. is of from 20 to 95°C), e.g. 40 to 90°C, but is specifically ca. 60°C (+/- 10°C, preferably +/- 5°C). The extraction time is in inverse proportion to the extraction temperature and is in general of from 0.5 to 5 h. For an extraction temperature of ca. 60°C, it is specifically ca. 2 to 3 h. After extraction, undesired products are generally removed. To this purpose, clarifying (precipitation- inducing) additives, such as albumen, bovine or fish gelatin, polyvinyl pyrrolidone (OVP), polyvinyl polypyrrolidone (PVPP), silica or, in particular, bentonite are added. Filtration of the mixture over suitable means, e.g. over diatomaceous earth or silica pads, is followed by concentration and pasteurization. For preservation purposes, the concentrate is brought to a pH of 3-4, especially 3.5 to 4.5, very especially ca. 3.9 (+/- 0.2). Very specifically, the Quillay extract used is QL Agri® 35. Further details of this product are given above and in the examples (minimum of 6 % of saponins, ca. 15 % polyphenols, about 35 °Brix, ca. 350 g/l of solids content).
According to a further embodiment, the mixtures comprise a compound II from group B'), preferably from the subgroup of C14 demethylase inhibitors (DMI fungicides), even more preferably from triazoles selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, ox- poconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1 -[rel-(2S;3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazolo and 2-[rel- (2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol.
According to a further embodiment, the mixtures comprise as compound II bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, propiconazole, prothioconazole or tebuconazole.
According to a further embodiment, the mixtures comprise as compound II cyproconazole, difenoconazole, epoxiconazole, metconazole, propiconazole, prothioconazole or tebuconazole; and in particular tebuconazole. According to a further embodiment, the mixtures comprise as compound II epoxiconazole or metconazole.
According to a further embodiment, the mixtures comprise as compound II difenoconazole, or propiconazole.
According to a further embodiment, the mixtures comprise as compound II at least one imidazole selected from imazalil, pefurazoate, prochloraz and triflumizol.
According to a further embodiment, the mixtures comprise as compound II at least one Del- ta14-reductase inhibitor selected from aldimorph, dodemorph, dodemorph-acetate, fenpropi- morph, tridemorph, fenpropidin, piperalin and spiroxamine, more preferably selected from tridemorph and fenpropimorph.
According to a further embodiment, the mixtures comprise a compound II from the group H') Inhibitors with Multi Site Action, preferably from thio- and dithiocarbamates selected from fer- bam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram; more preferably selected from mancozeb and metiram.
According to a further embodiment, the mixtures comprise a compound II from the organo- chlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, cap- tafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlor- phenole and its salts, phthalide, tolylfluanid and N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide; more preferably from chlorothalonil, captafol, captan, folpet and di- chlofluanid, in particular chlorothalonil.
The mixtures and compositions thereof according to the invention can, in the use form as fungicides and/or insecticides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
Mixing a water-based Quillay extract and a compound II and the compositions comprising them, respectively, in the use form as fungicide with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.
According to the present invention, it may be preferred that the mixtures comprise besides Mixing a water-based Quillay extract and a compound II and the compositions comprising them, respectively, in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development, as component 3) a further active compound, preferably in a synergisti- cally effective amount. Another embodiment relates to mixtures wherein the component 3) is an active compound III selected from groups A) to O):
The following list of active substances, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors
- Inhibitors of complex III at Q0 site (e.g. strobilurins): azoxystrobin, coumethoxystrobin,
coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino- N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
- inhibitors of complex III at Q, 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-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 (e. g. carboxamides): benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, 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,
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-(trifluoromethyl)-1 ,5- dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide, N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3- dimethyl-pyrazole-4-carboxamide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3- (difluoromethyl)-1 -methyl-pyrazole-4-carboxamide;
- other respiration inhibitors (e.g. complex I, uncouplers): diflumetorim, (5,8-difluoroquinazolin- 4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl deri- vates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthi- ofam;
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bromucona- zole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbu- conazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triti- conazole, 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]triazole-3-thiol; 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 (1 ,2,4-triazol-1 -yl)pentan-
2- ol, 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 cyclopropyl-2-(1 ,2,4-triazol-1 - yl)ethanol, 2-[4-(4-chlorophenoxy)-2-(trifluorometh-"yl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)-"phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol, 2-[2-chloro-4-(4- chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)^phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol, 2-[4-(4-fluorophenoxy)-2- (trifluoromethyl)-phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3- pyridyl)methanol;
- Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, 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, metalaxyl, metalaxyl-M (mefenoxam), 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, such as benzimidazoles, thiophanates: benomyl, carbendazim, fuber- idazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[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 (anilino-pyrimidines): 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, isoprothiolane; - lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
- phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph, mandipropa- mid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
- compounds affecting cell membrane permeability and fatty acides: propamocarb, propamo- carb-hydrochlorid
- fatty acid amide hydrolase inhibitors: oxathiapiprolin, 2-{3-[2-(1 -{[3,5-bis(di-,flu-,oromethyl-
1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2 oxazol-5-yl}phenyl me- thanesulfonate, 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl) 1 ,3- thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5 yl}-3-chlorophenyl methanesulfonate
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 (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chloro- thalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pen- tachlorphenole 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), dithianon, 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: pyroqui- lon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defence inducers
- acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Unknown mode of action
- bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difen- zoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, picarbutrazox, tolpro- carb, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-(prop-2-yn-1 -yloxy)phenyl]-4,5- dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, 2-[3,5-bis(difluoromethyl)- 1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yhoxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3- yl}-1 ,3-th azol-2-yl)piperidin-1 -yl]ethanone, 2 [3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4- (4-{5-[2-chloro-6-(prop-2-yn-1 -yhoxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2 yl)piperidin-1 -yl]ethanone, oxin-copper, 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-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl- 4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl- 2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, 2methoxy- 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 (pyrisoxazole),
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, ethyl (Z) 3 amino-2- cyano-3-phenyl-prop-2-enoate, pentyl N-[6-[[(Z)-[(1 -methyltetra-"zol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate, 2-[2-[(7,8-di-,fluoro-2-methyl-3- quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, 2-[2-fluoro-6-[(8-flu-Oro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol, 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroiso-"quinolin-1 - yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydro-,isoquinolin-1 -yl)-"quinoline, 3-(4,4,5- trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline;
L) Biopesticides Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus amyloliquefaciens, B. mojavensis, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibac- ter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonosta- chys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Micro- dochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus pol- ymyxa, Pantoea vagans, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum,
Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. vio- laceusniger, Talaromyces flavus, Trichoderma asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum; mixture of T. harzia^num and T. viride; mixture of T. polysporum and T. harzianum; T. stromaticum, T. virens (also named Gliocladium virens), T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: chitosan (hydrolysate), harpin protein, laminarin, Menhaden fish oil, natamycin, Plum pox virus coat protein, potassium or sodium bicarbonate, Rey- noutria sachlinensis extract, salicylic acid, tea tree oil;
Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thurin- giensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B. brongniartii , Burkholderia sp., Chromobac- terium subtsugae, Cydia pomonella granulosis virus, Cryptophlebia leucotreta granulovirus (CrleGV), Isaria fumosorosea, Heterorhabditis bacteriophora, Lecanicil- lium longisporum, L. muscarium (formerly Verticillium lecanii), Metarhizium anisopli- ae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. li- lacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramose, P. reneformis, P. thornea, P. usgae, Pseudomonas fluorescens, Steinernema carpocapsae, S. feltiae, S. kraussei;
Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 - butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1 -ol, (E,Z)- 2,13-octadecadien-1 -ol acetate, (E,Z)-3,13-octadecadien-1 -ol, R-1 -octen-3-ol, pen- tatermanone, potassium silicate, sorbitol actanoate, (E,Z,Z)-3,8,1 1 -tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1 -yl acetate, Z-7-tetradecen-2-one, Z-9- tetradecen-1 -yl acetate, Z-1 1 -tetradecenal, Z-1 1 -tetradecen-1 -ol, Acacia negra ex- tract, extract of grapefruit seeds and pulp, extract of Chenopodium ambrosiodae, Catnip oil, Neem oil, Quillay extract, Tagetes oil;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. ja- ponicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Meso- rhizobium sp., Paenibacillus alvei, Penicillium bilaiae, Rhizobium leguminosarum bv. phaseoli, R. I. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti;
L6) Biochemical pesticides with plant stress reducing, plant growth regulator and/or plant yield enhancing activity: abscisic acid, aluminium silicate (kaolin), 3-decen-2- one, formononetin, genistein, hesperetin, homobrassinlide, humates, jasmonic acid or salts or derivatives thereof, lysophosphatidyl ethanolamine, naringenin, polymeric polyhydroxy acid, Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract and Ecklonia maxima (kelp) extract;
M) Growth regulators
abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, di- methipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadi- one (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phos- phorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;
N) Herbicides
- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefe- nacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionat.es: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- Bipyridyls: diquat, paraquat;
- (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam
(EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thio- bencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepralox- ydim, tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, ox- yfluorfen;
- hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;
- imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlor- prop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
- pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; - pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfu- ron, triflusulfuron, tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3- (4,6-dimethoxy-pyrimidin-2-yl)urea;
- triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
- ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrim- isulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromo- butide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinme- thylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr,
Drechslera monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl ar- sonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, py- raclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H- pyrimidin-1 -yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2- cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl- phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2- carboxylic acid methyl ester.
O) Insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyri- fos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethi- on, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phentho- ate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosul- fan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodi- carb, triazamate; - pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;
- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cy- ramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juve- noids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
- nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -2-chloro-thiazol-5- ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
- GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole,
pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1 H-pyrazole-3-carbothioic acid amide;
- macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben,
tebufenpyrad, tolfenpyrad, flufenerim;
- METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;
- Uncouplers: chlorfenapyr;
- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; - moulting disruptor compounds: cryomazine;
- mixed function oxidase inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizone;
- ryanodine receptor inhibitors: chlorantraniliprole, cyantraniliprole, flubendiamide, N [4,6- dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2 pyridyl)-5- (trifluoromethyl)pynazole-3-carboxamide; N-[4-chloro-2-[(diethyl-lambda-4- sulfanylidene)carbamoyl]-6 methyl-phenyl]-2-(3-chloro-2-pyridyl)-5- (triflu-Oromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(di-2-propyl-lambda-4- sulfanyl dene)carbamoyl]-6-methyl-phenyl]-2 (3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-dichloro-2 [(di-2-propyl-lambda-4- sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5 (trifluoromethyl)pyrazole-3- carboxamide; N-[4,6-d chloro-2-[(diethyl-lambda-4 sulfanylidene)carbamoyl]-phenyl]-2-(3- chloro-2-pyridyl)-5-(difluoromethyl)pyr-azole-3-carboxamide; N-[4,6-dibromo-2-[(di-2-propyl- lambda-4 sulfanylidene)carba-,moyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyr- azole-3-carboxamide; N [4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carba-moyl]-6- cyano-phenyl]-2 (S-chloro^-pyridy -S-itrifluoromethy pyrazole-S-carbox-'amide; N-[4,6- dibromo-2 [(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2 (3 chloro-2-pyridyl)-5 (tr fluoromethyl)pyrazole-3-carboxamide;
- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocydam, cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, pyrifluquina- zon, and l .l'-pS^R^aR.eS.eaS.^R.^aS.^bSH-I^-cyclopropylacety oxylmethyl]- 1 , 3,4,4a, 5,6,6a, 12, 12a, 12b-decahydro-12-hydroxy-4, 6a, 12b-trimethyl-1 1 -oxo- 9-(3-pyridinyl)-2H,1 1 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester.
The compounds III of chemical nature described by common names, their preparation and their biological activity e.g. against harmful fungi, pests or weed is known (e.g.:
http://www.alanwood.net/pesticides/); many of these substances are commercially available.
The compounds III described by lUPAC nomenclature, their preparation and their pesticidal activity is also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP A 141 317; EP-A 152 031 ; EP-A 226 917; EP A 243 970; EP A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP A 1 201 648; EP A 1 122 244, JP 2002316902; DE 19650197; DE
10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657, WO2012/168188, WO 2007/006670, WO 1 1/77514; WO13/047749, WO
10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009 and WO 13/024010).
The biopesticides from group L) of pesticides III, their preparation and their pesticidal activity e.g. against harmful fungi or insects are known (e-Pesticide Manual V 5.2 (ISBN 978 1 901396 85 0) (2008-201 1 ); http://www.epa.gov/opp00001/biopesticides/, see product lists therein; http://www.omri.org/omri-lists, see lists therein; Bio-Pesticides Database BPDB
http://sitem.herts.ac.uk/aeru/bpdb/, see A to Z link therein).
The biopesticides from group L1 ) and/or L2) may also have insecticidal, acaricidal, mollus- cidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L5) and/or L6) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
Many of these biopesticides are registered and/or are commercially available: aluminium sili- cate (Screen™ Duo from Certis LLC, USA), Agrobacterium radio->bacter K1026 (e.g. NoGall® from Becker Underwood Pty Ltd., Australia), A. radiobacter K84 (Nature 280, 697-699, 1979; e.g. GallTroll® from AG Biochem, Inc., C, USA), Ampelomyces quisqualis M-10 (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract or filtrate (e.g. ORKA GOLD from Becker Underwood, South Africa; or Goemar® from Laboratoires Goemar, France), Aspergillus flavus NRRL 21882 isolated from a peanut in Georgia in 1991 by the USDA, National Peanut Research Laboratory (e.g. in Afla- Guard® from Syngenta, CH), mixtures of Aureobasidium pullulans DSM14940 and DSM 14941 (e.g. blastospores in Blossom Protect® from bio-ferm GmbH, Germany), Azospirillum ama- zonense BR 1 1 140 (SpY2T) (Proc. 9th Int. and 1 st Latin American PGPR meeting, Quimara, Medellin, Colombia 2012, p. 60, ISBN 978-958-46-0908-3), A. brasilense AZ39 (Eur. J. Soil Biol 45(1 ), 28-35, 2009), A. brasilense XOH (e.g. AZOS from Xtreme Gardening, USA or RTI Reforestation Technologies International; USA), A. brasilense BR 1 1002 (Proc. 9th Int. and 1 st Latin American PGPR meeting, Quimara, Medellin, Colombia 2012, p. 60, ISBN 978-958-46-0908-3), A. brasilense BR 1 1005 (SP245; e.g. in GELFIX Gramineas from BASF Agricultural Specialties Ltd., Brazil), A. lipoferum BR 1 1646 (Sp31 ) (Proc. 9th Int. and 1 st Latin American PGPR meeting, Quimara, Medellin, Colombia 2012, p. 60), B. amyloliquefaciens IN937a (J. Microbiol. Bio- technol. 17(2), 280-286, 2007; e.g. in BioYield® from Gustafson LLC, TX, USA), B. amyloliquefaciens IT-45 (CNCM I 3800) (e.g. Rhizocell C from ITHEC, France), B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595, deposited at United States Department of Agriculture) (e.g. Integral®, Subtilex® NG from Becker Underwood, USA), B. cereus CNCM 1-1562 (US 6,406,690), B. firmus CNCM 1-1582 (WO 2009/126473, WO 2009/124707, US 6,406,690; Voti- vo® from Bayer Crop Science LP, USA), B. pumilus GB34 (ATCC 700814; e.g. in YieldShield® from Gustafson LLC, TX, USA), and Bacillus pumilus KFP9F (NRRL B-50754) (e.g. in BAC-UP or FUSION-P from Becker Underwood South Africa), B. pumilus QST 2808 (NRRL B 30087) (e.g. Sonata® and Ballad® Plus from AgraQuest Inc., USA), B. subtilis GB03 (e.g. Kodiak® or BioYield® from Gustafson, Inc., USA; or Companion® from Growth Products, Ltd., White Plains, NY 10603, USA), B. subtilis GB07 (Epic® from Gustafson, Inc., USA), B. subtilis QST-713 (NRRL B 21661 in Rhapsody®, Serenade® MAX and Serenade® ASO from AgraQuest Inc., USA), B. subtilis var. amylolique-'faciens FZB24 (e.g. Taegro® from Novozyme Biologicals, Inc., USA), B. subtilis var. amyloliquefaciens D747 (e.g. Double Nickel 55 from Certis LLC, USA), B. thuringiensis ssp. aizawai ABTS-1857 (e.g. in XenTari® from BioFa AG, Munsingen, Germany), B. t. ssp. aizawai SAN 401 I, ABG-6305 and ABG-6346, Bacillus t. ssp. israelensis AM65-52 (e.g. in VectoBac® from Valent Biosciences, IL, USA), Bacillus thuringiensis ssp. kurstaki SB4 (NRRL B-50753; e.g. Beta Pro® from Becker Underwood, South Africa), B. t. ssp. kurstaki ABTS-351 identical to HD-1 (ATCC SD-1275; e.g. in Dipel® DF from Valent Biosciences, IL, USA), B. t. ssp. kurstaki EG 2348 (e.g. in Lepinox® or Rapax® from CBC (Europe) S.r.l., Italy), B. t. ssp. tenebrionis DSM 2803 (EP 0 585 215 B1 ; identical to NRRL B-15939; Mycogen Corp.), B. t. ssp. tenebrionis NB-125 (DSM 5526; EP 0 585 215 B1 ; also referred to as SAN 418 I or ABG-6479; former production strain of Novo-Nordisk), B. t. ssp. tenebrionis NB-176 (or NB- 176-1 ) a gamma-irridated, induced high-yielding mutant of strain NB-125 (DSM 5480; EP 585 215 B1 ; Novodor® from Valent Biosciences, Switzerland), Beauveria bassiana ATCC 74040 (e.g. in Naturalis® from CBC (Europe) S.r.l., Italy), B. bassiana DSM 12256 (US 200020031495; e.g. BioExpert® SC from Live Sytems Technology S.A., Colombia), B. bassiana GHA (Botani- Gard® 22WGP from Laverlam Int. Corp., USA), B. bassiana PPRI 5339 (ARSEF number 5339 in the USDA ARS collection of entomopathogenic fungal cultures; NRRL 50757) (e.g. Broad- Band® from Becker Underwood, South Africa), B. brongniartii (e.g. in Melocont® from Agrifutur, Agrianello, Italy, for control of cockchafer; J. Appl. Microbiol. 100(5), 1063-72, 2006), Bradyrhi- zobium sp. (e.g. Vault® from Becker Underwood, USA), B. japonicum (e.g. VAULT® from Becker Underwood, USA), Candida oleophila 1-182 (NRRL Y-18846; e.g. Aspire® from Ecogen Inc., USA, Phytoparasitica 23(3), 231 -234, 1995), C. oleophila strain O (NRRL Y-2317; Biological Control 51 , 403-408, 2009),, Candida saitoana (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 J 1446: Prestop® from Verdera Oy, Finland), Chromobacterium subtsu- gae PRAA4-1 isolated from soil under an eastern hemlock (Tsuga canadensis) in the Catoctin Mountain region of central Maryland (e.g. in GRANDEVO from Marrone Bio Innovations, USA), Coniothyrium minitans CON/M/91 -08 (e.g. Contans® WG from Prophyta, Germany),
Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa), Cryptophlebia leucotreta granulovirus (CrleGV) (e.g. in CRYPTEX from Adermatt Biocontrol, Switzerland), Cydia pomo- nella granulovirus (CpGV) V03 (DSM GV-0006; e.g. in MADEX Max from Andermatt Biocontrol, Switzerland), CpGV V22 (DSM GV-0014; e.g. in MADEX Twin from Adermatt Biocontrol, Swit- zerland), Delftia acidovorans RAY209 (ATCC PTA-4249; WO 2003/57861 ; e.g. in BIOBOOST from Brett Young, Winnipeg, Canada), Dilophosphora alopecuri (Twist Fungus from Becker Underwood, Australia), Ecklonia maxima (kelp) extract (e.g. KELPAK SL from Kelp Products Ltd, South Africa), formononetin (e.g. in MYCONATE from Plant Health Care pic, U.K.), Fusarium oxysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from Natural Plant Protection, France), Glomus intraradices (e.g. MYC 4000 from ITHEC, France), Glomus intraradices RTI- 801 (e.g. MYKOS from Xtreme Gardening, USA or RTI Reforestation Technologies International; USA), grapefruit seeds and pulp extract (e.g. BC-1000 from Chemie S.A., Chile), harpin (alpha-beta) protein (e.g. MESSENGER or HARP-N-Tek from Plant Health Care pic, U.K.; Science 257, 1-132, 1992), Heterorhabditis bacteriophaga (e.g. Nemasys® G from Becker Underwood Ltd., UK), Isaria fumosorosea Apopka-97 (ATCC 20874) (PFR-97™ from Certis LLC, USA), cis- jasmone (US 8,221 ,736), laminarin (e.g. in VACCI PLANT from Laboratoires Goemar, St. Malo, France or Stahler SA, Switzerland), Lecanicillium longisporum KV42 and KV71 (e.g. VERTAL- EC® from Koppert BV, Netherlands), L. muscarium KV01 (formerly Verticillium lecanii) (e.g. MYCOTAL from Koppert BV, Netherlands), Lysobacter antibioticus 13-1 (Biological Control 45, 288-296, 2008), L. antibioticus HS124 (Curr. Microbiol. 59(6), 608-615, 2009), L. enzymogenes 3.1 T8 (Microbiol. Res. 158, 107-1 15; Biological Control 31 (2), 145-154, 2004), Metarhizium an- isopliae var. acridum IMI 330189 (isolated from Ornithacris cavroisi in Niger; also NRRL 50758) (e.g. GREEN MUSCLE® from Becker Underwood, South Africa), M. a. var. acridum FI-985 (e.g. GREEN GUARD® SC from Becker Underwood Pty Ltd, Australia), M. anisopliae FI-1045 (e.g. BIOCANE® from Becker Underwood Pty Ltd, Australia), M. anisopliae F52 (DSM 3884, ATCC 90448; e.g. MET52® Novozymes Biologicals BioAg Group, Canada), M. anisopliae ICIPE 69 (e.g. METATHRI POL from ICIPE, Nairobe, Kenya), Metschnikowia fructicola (NRRL Y-30752; e.g. SHEMER® from Agrogreen, Israel, now distributed by Bayer CropSciences, Germany; US 6,994,849), Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Micro- sphaeropsis ochracea P130A (ATCC 74412 isolated from apple leaves from an abandoned orchard, St-Joseph-du-Lac, Quebec, Canada in 1993; Mycologia 94(2), 297-301 , 2002), Mus- codor albus QST 20799 originally isolated from the bark of a cinnamon tree in Honduras (e.g. in development products Muscudor™ or QRD300 from AgraQuest, USA), Neem oil (e.g. TRILOGY®, TRIACT® 70 EC from Certis LLC, USA), Nomuraea rileyi strains SA86101 , GU87401 , SR86151 , CG128 and VA9101 , Paecilomyces fumosoroseus FE 9901 (e.g. NO FLY™ from Natural Industries, Inc., USA), P. Iilacinus 251 (e.g. in BioAct®/MeloCon® from Prophyta, Germany; Crop Protection 27, 352-361 , 2008; originally isolated from infected nematode eggs in the Philippines), P. Iilacinus DSM 15169 (e.g. NEMATA® SC from Live Systems Technology S.A., Colombia), P. Iilacinus BCP2 (NRRL 50756; e.g. PL GOLD from Becker Underwood BioAg SA Ltd, South Africa), mixture of Paenibacillus alvei NAS6G6 (NRRL B-50755), Pantoea vagans (formerly agglomerans) C9-1 (originally isolated in 1994 from apple stem tissue; Blight- Ban C9-1® from NuFrams America Inc., USA, for control of fire blight in apple; J. Bacteriol. 192(24) 6486-6487, 2010), Pasteuria spp. ATCC PTA-9643 (WO 2010/085795), Pasteuria spp. ATCC SD-5832 (WO 2012/064527), P. nishizawae (WO 2010/80169), P. penetrans (US 5,248,500), P. ramose (WO 2010/80619), P. thornea (WO 2010/80169), P. usgae (WO
2010/80169), Penicillium bilaiae (e.g. Jump Start® from Novozymes Biologicals BioAg Group, Canada, originally isolated from soil in southern Alberta; Fertilizer Res. 39, 97-103, 1994), Phle- biopsis gigantea (e.g. RotStop® from Verdera Oy, Finland), Pichia anomala WRL-076 (NRRL Y- 30842; US 8,206,972), potassium bicarbonate (e.g. Amicarb® fromm Stahler SA, Switzerland), potassium silicate (e.g. Sil-MATRIX™ from Certis LLC, USA), Pseudozyma flocculosa PF-A22 UL (e.g. Sporodex® from Plant Products Co. Ltd., Canada), Pseudomonas sp. DSM 13134 (WO 2001/40441 , e.g. in PRORADIX from Sourcon Padena GmbH & Co. KG, Hechinger Str. 262, 72072 Tubingen, Germany), P. chloraphis MA 342 (e.g. in CERALL or CEDEMON from BioAgri AB, Uppsala, Sweden), P. fluorescens CL 145A (e.g. in ZEQUANOX from Marrone Bio- Innovations, Davis, CA, USA; J. Invertebr. Pathol. 1 13(1 ):104-14, 2013), Pythium oligandrum DV 74 (ATCC 38472; e.g. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep. and GOWAN, USA; US 2013/0035230), Reynoutria sachlinensis extract (e.g. REGALIA® SC from Marrone Biolnnovations, Davis, CA, USA), Rhizobium leguminosarum bv. phaseoli (e.g. RHIZO-STICK from Becker Underwood, USA), R. I. trifolii RP1 13-7 (e.g. DORMAL from Becker Underwood, USA; Appl. Environ. Microbiol. 44(5), 1096-1 101 ), R. I. bv. viciae P1 NP3Cst (also referred to as 1435; New Phytol 179(1 ), 224-235, 2008; e.g. in NODULATOR PL Peat Granule from Becker Underwood, USA; or in NODULATOR XL PL bfrom Becker Underwood, Canada), R. I. bv. viciae SU303 (e.g. NODULAID Group E from Becker Underwood, Australia), R. I. bv. viciae WSM1455 (e.g. NODULAID Group F from Becker Underwood, Australia), R. tropici
SEMIA 4080 (identical to PRF 81 ; Soil Biology & Biochemistry 39, 867-876, 2007), Sinorhizobi- um meliloti MSDJ0848 (INRA, France) also referred to as strain 201 1 or RCR201 1 (Mol Gen Genomics (2004) 272: 1-17; e.g. DORMAL ALFALFA from Becker Underwood, USA; Nl- TRAGIN® Gold from Novozymes Biologicals BioAg Group, Canada), Sphaerodes mycoparasiti- ca IDAC 301008-01 (WO 201 1/022809), Steinernema carpocapsae (e.g. MILLENIUM® from Becker Underwood Ltd., UK), S. feltiae (NEMASHIELD® from BioWorks, Inc., USA;
NEMASYS® from Becker Underwood Ltd., UK), S. kraussei L137 (NEMASYS® L from Becker Underwood Ltd., UK), Streptomyces griseoviridis K61 (e.g. MYCOSTOP® from Verdera Oy, Espoo, Finland; Crop Protection 25, 468-475, 2006), S. lydicus WYEC 108 (e.g. Actinovate® from Natural Industries, Inc., USA, US 5,403,584), S. violaceusniger YCED-9 (e.g. DT-9® from Natural Industries, Inc., USA, US 5,968,503), Talaromyces flavus V1 17b (e.g. PROTUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. asperellum ICC 012 (e.g. in TENET WP, REMDIER WP, BIOTEN WP from Isagro NC, USA, BIO-TAM from AgraQuest, USA), T. atroviride LC52 (e.g. SENTI- NEL® from Agrimm Technologies Ltd, NZ), T. atroviride CNCM 1-1237 (e.g. in Esquive WG from Agrauxine S.A., France, e.g. against pruning wound diseases on vine and plant root pathogens), T. fertile JM41 R (NRRL 50759; e.g. RICHPLUS™ from Becker Underwood Bio Ag SA Ltd, South Africa), T. gamsii ICC 080 (e.g. in TENET WP, REMDIER WP, BIOTEN WP from Isagro NC, USA, BIO-TAM from AgraQuest, USA), 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 Ag- rimm 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 (also named Gliocladium virens) (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) and Ulocladium oudemansii HRU3 (e.g. in BOTRY-ZEN® from Botry-Zen Ltd, NZ).
Strains can be sourced from genetic resource and deposition centers: American Type Culture Collection, 10801 University Blvd., Manassas, VA 201 10-2209, USA (strains with ATCC prefic); CABI Europe - International Mycological Institute, Bakeham Lane, Egham, Surrey, TW20 9TYNRRL, UK (strains with prefices CABI and I Ml); Centraalbureau voor Schimmelcul- tures, Fungal Biodiversity Centre, Uppsalaan 8, PO Box 85167, 3508 AD Utrecht, Netherlands (strains with prefic CBS); Division of Plant Industry, CSIRO, Canberra, Australia (strains with prefix CC); Collection Nationale de Cultures de Microorganismes, Institut Pasteur, 25 rue du Docteur Roux, F-75724 PARIS Cedex 15 (strains with prefix CNCM); Leibniz-lnstitut DSMZ- Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Inhoffenst^e 7 B, 38124 Braunschweig, Germany (strains with prefix DSM); International Depositary Authority of Canada Collection, Canada (strains with prefix IDAC); Interntional Collection of Micro-orgniasms from Plants, Landcare Research, Private Bag 92170, Auckland Mail Centre, Auckland 1 142, New Zealand (strans with prefix ICMP); IITA, PMB 5320, Ibadan, Nigeria (straisn with prefix IITA); The National Collections of Industrial and Marine Bacteria Ltd., Torry Research Station, P.O. Box 31 , 135 Abbey Road, Aberdeen, AB9 8DG, Scotland (strains with prefix NCIMB); ARS Culture Collection of the National Center for Agricultural Utilization Research, Agricultural Research Service, U.S. Department of Agriculture, 1815 North University Street, Peoria, Illinois 61604, USA (strains with prefix NRRL); Department of Scientific and Industrial Research Culture Collection, Applied Biochemistry Division, Palmerston North, New Zealand (strains with prefix NZP); FEPAGRO-Fundagao Estadual de Pesquisa Agropecuaria, Rua Gongalves Dias, 570, Bairro Menino Deus, Porto Alegre/RS, Brazil (strains with prefix SEMIA); SARDI, Adelaide, South Australia (strains with prefix SRDI); U.S. Department of Agriculture, Agricultural Research Service, Soybean and Alfalfa Research Laboratory, BARC-West, 10300 Baltimore Boulevard, Building 01 1 , Room 19-9, Beltsville, MD 20705, USA (strains with prefix USDA: Beltsville Rhi- zobium Culture Collection Catalog March 1987 USDA-ARS ARS-30:
http://pdf.usaid.gov/pdf_docs/PNAAW891.pdf); and Murdoch University, Perth, Western Australia (strains with prefix WSM). Further strains may be found at the Global catalogue of Microorganisms: http://gcm.wfcc.info/ and
http://www.landcareresearch.co.nz/resources/collections/icmp and further references to strain collections and their prefixes at http://refs.wdcm.org/collections.htm.
Bacillus amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595) is deposited under accession number NRRL B-50595 with the strain designation Bacillus subtilis 1430 (and identical to NCIMB 1237). Recently, MBI 600 has been re-classified as Bacillus amyloliquefaciens subsp. plantarum based on polyphasic testing which combines classical microbiological meth- ods 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 Bacillus amyloliquefaciens subsp. plantarum MBI600, formerly Bacillus subtilis MBI600. Bacillus amyloliquefaciens MBI600 is known as plant growth-promoting rice seed treatment from Int. J. Microbiol. Res. 3(2) (201 1 ), 120-130 and further described e.g. in US 2012/0149571 A1. This strain MBI600 is e.g. commercially available as liquid formulation product INTEGRAL® (Becker-Underwood Inc., USA).
Bacillus subtilis strain FB17 was originally isolated from red beet roots in North America (System Appl. Microbiol 27 (2004) 372-379). This B. subtilis strain promotes plant health (US 2010/0260735 A1 ; WO 201 1/109395 A2). B. subtilis FB17 has also been deposited at ATCC under number PTA-1 1857 on April 26, 201 1 . Bacillus subtilis strain FB17 may be referred elsewhere to as UD1022 or UD10-22.
Bacillus amyloliquefaciens AP-136 (NRRL B-50614), B. amyloliquefaciens AP-188 (NRRL B- 50615), B. amyloliquefaciens AP-218 (NRRL B-50618), B. amyloliquefaciens AP-219 (NRRL B- 50619), B. amyloliquefaciens AP-295 (NRRL B-50620), B. japonicum SEMIA 5079 (e.g. Gelfix 5 or Adhere 60 from Nitral Urbana Laoboratories, Brazil, a BASF Company), B. japonicum SEMIA 5080 (e.g. GELFIX 5 or ADHERE 60 from Nitral Urbana Laoboratories, Brazil, a BASF Company), B. mojavensis AP-209 (NRRL B-50616), B. solisalsi AP-217 (NRRL B-50617), B. pumilus strain INR-7 (otherwise referred to as BU-F22 (NRRL B-50153) and BU-F33 (NRRL B-50185)), B. simplex ABU 288 (NRRL B-50340) and B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595) have been mentioned i.a. in US patent appl. 20120149571 , US 8,445,255, WO 2012/079073. Bradyrhizobium japonicum USDA 3 is known from US patent 7,262,151.
Jasmonic acid or salts (jasmonates) or derivatives include without limitation potassi-um jasmonate, sodium jasmonate, lithium jasmonate, ammonium jasmonate, dimethyl-ammonium 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-l-oxo-indane-4-carbonyl) -amino]-3-methyl - pentanoic acid methyl ester), linoleic acid or derivatives thereof and cis-jasmone, or combinations of any of the above.
Humates are humic and fulvic acids extracted from a form of lignite coal and clay, known as leonardite. Humic acids are organic acids that occur in humus and other organically derived materials such as peat and certain soft coal. They have been shown to increase fertilizer efficiency in phosphate and micro-nutrient uptake by plants as well as aiding in the development of plant root systems.
It is preferred that the mixtures comprise as compounds III fungicidal compounds that are independently of each other selected from the groups A), B), C), D), E), F), G), H), I), J), K) and L), more preferably in combination with an organic acid such as citric acid, lactic acid or ascorbic acid.
According to another embodiment of the invention, mixtures comprise as compound III a herbicidal compound that is selected from the group N).
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group A) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, tri- floxystrobin; famoxadone, fenamidone; benzovindiflupyr, bixafen, boscalid, fluopyram, fluxapy- roxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such as fentin acetate.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group B) and particularly selected from cyproconazole, difeno- conazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetracon- azole, triticonazole, prochloraz, fenarimol, triforine; dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine; fenhexamid.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group C) and particularly selected from metalaxyl, (metalaxyl-M) mefenoxam, ofurace.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group D) and particularly selected from benomyl, carbendazim, thiophanate-methyl, ethaboxam, fluopicolide, zoxamide, metrafenone, pyriofenone.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group E) and particularly selected from cyprodinil, mepanipyrim, pyrimethanil.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group F) and particularly selected from iprodione, fludioxonil, vinclozolin, quinoxyfen.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group G) and particularly selected from dimethomorph, flumorph, iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group H) and particularly selected from copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb, metiram, propineb, thiram, captafol, folpet, chlorothalonil, dichlofluanid, dithianon.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group I) and particularly selected from carpropamid and fenoxanil.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group J) and particularly selected from acibenzolar-S-methyl, probenazole, tiadinil, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group K) and particularly selected from cymoxanil, proquinazid and A/-methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-A/-[(1 R)- 1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide.
Preference is also given to mixtures comprise as compound III (component 3) at least one active substance selected from group L) and particularly selected from Bacillus subtilis strain NRRL No. B-21661 , Bacillus pumilus strain NRRL No. B-30087 and Ulocladium oudemansii .
According to a further embodiment, mixtures comprise as compound Ili a further insecticidal compound that is selected from the group O).
According to a further embodiment of ternary mixtures, component 3) is an extract of Acacia negra (see WO 2006/0210264), more preferably a water-based extract of Acacia negra.
The mixtures and compositions according to the invention are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiopho- romycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomy- cetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The mixtures and compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on 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 rape, 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, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; 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.
Preferably the inventive mixtures and compositions are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, treatment of plant propagation materials with the inventive combination of the Quillay extract and compounds II and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is 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://www.bio.org/speeches/pubs/er/agri_products.asp). 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-transtional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
The inventive mixtures and compositions are particularly suitable for controlling the following 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 brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alterna- ta), tomatoes (e. g. A. solani or A. alternata) 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.) on corn (e. g. D. maydis), cereals (e. g. B. sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia 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, 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 (ana- morph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colle- totrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthi- anum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cy- cloconium 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 cu- curbits (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; Gaeumannomy- ces 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, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septo- ria blotch) on wheat; 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; Phialopho- ra 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; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolo- rum); 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; Plasmopara 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 herpotrichoides (eyespot, teleomorph: Tapesia yal- lundae) on cereals, e. g. wheat or barley; Pseudoperonospora (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, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph:
Drechslera) tritici-repentis (tan spot) on wheat or P. feres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ram ularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium 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 soy- beans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuck- eri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterra- nea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeo- sphaeria] 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; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendicula- tus, 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.
In particular, the mixtures and compositions of the present invention are effective against plant pathogens in speciality crops such as vine, fruits, hop, vegetables and tabacco.
Plant propagation materials may be treated with the mixtures and compositions of the invention prophylactically either at or before planting or transplanting.
The invention also relates to agrochemical compositions comprising an auxiliary and at least a water-based Quillay extract and a compound II according to the invention.
An agrochemical composition comprises a fungicidally effective amount of a Quillay extract and a compound II. The term "effective amount" denotes an amount of the composition or of the Quillay extract and of the compound II, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material and the climatic conditions.
The inventive mixtures and compositions are also suitable for controlling the following plant parasitic nematodes such as Meloidogyne, Globodera, Heterodera, Radopholus, Rotylenchulus, Pratylenchus and other genera. The Quillay extract and a compound II can be converted into customary types of agrochemi- cal compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), cap- sules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, disper- sants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibil- izers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, 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.
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 alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox- ylated 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 active ingredient on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkyliso- thiazolinones and benzisothiazolinones. Suitable anti-freezing agents are ethylene glycol, pro- pylene 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 hexacyanoferrate) 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.
According to the invention, the solid material (total dry matter) of the Quillay extract is considered as active component (e.g. to be obtained after drying or evaporation of the extraction medium).
In accordance with the present invention, the (weight) ratios used herein for the Quillay extract are based on the total weight of the dry content (solid material) of the extract.
The 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 components.
Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), pow- ders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active components concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating with the Quillay extract and compound II and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, the Quillay extract and compound II or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active components applied are, depending on the kind of effect desired, from 0.001 to 10 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active components of from 0.1 to 10000 g, preferably from 1 to 2000 g, more preferably from 1 to 500 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
When used in the protection of materials or stored products, the amount of active components applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active components per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
According to one embodiment, a polyether polymethylsiloxane copolymer may be added to the composition accoding to the invention, preferably in a weight ratio of 1 :100 to 100:1 , more preferably in a weight ratio of 1 :10 to 10:1 , in particular in a weight ratio of 1 :5 to 5:1 based on the total weight of the dry content of Quillay extract and the amount of respective compound II together.
According to a further embodiment, a mineral oil or a vegetable oil may be added to the composition according to the invention, preferably in a weight ratio of 1 :100 to 100:1 , more preferably in a weight ratio of 1 :10 to 10:1 , in particular in a weight ratio of 1 :5 to 5:1 based on the total weight of the dry content of Quillay extract and the amount of respective compound II together.
According to a further embodiment, an organic acid such as citric acid, lactic acid or ascorbic acid may be added to the composition according to the invention, preferably in a weight ratio of 1 :100 to 100:1 , more preferably in a weight ratio of 1 :10 to 10:1 , in particular in a weight ratio of 1 :5 to 5:1 based on the total weight of the dry content of Quillay extract and the amount of respective compound II together.
The user applies the composition according to the invention usually from a predosage de- vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the ag- rochemical 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.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In 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 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 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 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 :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.
Preferably, however, the Quillay extract is used in excess as compared to the compound II, i.e. the weight ratio of the Quillay extract versus compound II usually is in the range of from 100:1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , particularly in the range of from 20:1 to 1 :1 , more particularly in the range of from 10:1 to 1 :1 , specifically in the range of from 4:1 to 1 :1 , e.g. of from 3:1 to 1 :1 , and in particular in the range of from 2:1 to 1 :1.
In the above weight ratios, the amount of Quillay extract is based on the amount of the solid material (dry matter). The solid material may contain at most 5% by weight, preferably at most 2% by weight, based on the total weight of the solid material, of residual liquid components, such as extractants (in general water, possibly also alcohol; mostly however residual moisture).
In the ternary mixtures, i.e. compositions according to the invention comprising the compo- nent 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 ). In the mixtures and compositions, uses and methods of the present invention, the compound ratios are advantageously chosen so as to produce a synergistic effect.
This means that the relative amount, i.e. the weight ratio of the Quillay extract and the at least one compound II in the mixture or composition provides for an increased fungicidal effica- cy on at least one harmful fungus which exceeds the additive fungicidal efficacy of the components of the mixture or composition as calculated from the fungicidal efficacy of the individual components at a given application rate.
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).
The components can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used as combination such as a kit of parts.
Examples 1 . Activity of Quillay extract in combination with chlorothalonil or with tebuconazole against Bo- trytis cinerea
To determine the effect of different treatments of fungicides and Quillay extract on the inhibition of the germination (conidia / Botrytis cinerea), a conidia suspension of Botrytis cinerea (isolate obtained from Thompson Seedless grape) was prepared at a concentration of 106 conidia / ml. As culture medium a potato dextrose broth was used. In each case, first a Quillay extract alone (used in form of the commercial product QL Agri® 35 from BASF; a soluble concentrate containing 35% by weight of solid matter, relative to the total weight of the concentrate; diluted with water to a concentration of 5000 ppm); or chlorothalonil alone (used in form of the commercial product Bravo® from Bayer; a suspension concentrate with 720 g a.i. per I; diluted with water to a concentration of 100 ppm) or both the Quillay extract and chlorothalonil (5000 + 100 ppm) or tebuconazole alone (used in form of the commercial product Horizon® from Bayer; a wettable powder with 250 g/kg; diluted with water to a concentration of 0.24 ppm), or both the Quillay extract and tebuconazole (5000 + 0.24 ppm) and then 10 ml of conidial suspension of Botrytis cinerea were added to 100 ml of culture medium, respectively. The design was randomized completely with three replications by treatment.
The different treatments were incubated at 15°C for 14 h. The next day the number of germinated and not germinated spores was counted in 10 visual fields of a hemacytometer in each treatment and replication. Data were expressed as percentage of spores germinated and not germinated. The results were analyzed statistically and means separated by LSD test with significance of P≤ 0.05, and are compiled in table 1 below. Table 1
Figure imgf000031_0001
1 QL: Quillay extract QL Agri® 35
2 Percentage of not germinated conidia
3 Calc. eff. = efficacy calculated according to the Colby formula (S. R. Colby (1967) "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, p. 22ff., the value E, which is expected if the activity of the individual active compounds is only additive, is calculated as follows:
E = X + Y - (X Y/100)
where
X = percent activity using active compound A at an application rate a;
Y = percent activity using active compound B at an application rate b;
E = expected activity (in %) by A + B at application rates a + b.)

Claims

We claim:
A mixture comprising, as active components:
1 ) a Quillay extract and
2) at least one fungicidal compound II selected from the groups B') and H'):
B') Sterol biosynthesis inhibitors (SBI fungicides) selected from
- C14 demethylase inhibitors (DMI fungicides) in turn selected from: triazoles: azacon- azole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, dini- conazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, ox- poconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simecon- azole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, unicona- zole, 1 -[rel-(2S;3R)-3-(2-chlorophenyl)-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)- oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol; imidazoles: imazalil, pefurazoate, prochlo- raz, triflumizol; and pyrimidines, pyridines and piperazines selected from fenarimol, nuarimol, pyrifenox, and triforine;
- Delta14-reductase inhibitors in turn selected from: aldimorph, dodemorph, do- demorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, and spirox- amine; and
- The inhibitor of 3-keto reductase fenhexamid;
H') Inhibitors with Multi Site Action selected from
- inorganic active substances in turn selected from: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, and basic copper sulfate;
- thio- and dithiocarbamates in turn selected from: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, and ziram;
- organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles) in turn selected from: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichloro- phen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, and N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide; and
- guanidines and others in turn selected from: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine- tris(albesilate), dithianon and 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-
1 ,3,5,7(2H,6H)-tetraone.
2. The mixture according to claim 1 , wherein component 1 ) and component 2) are present in a synergistically effective amount.
3. The mixture according to any of the claims 1 to 2, wherein component 1 ) and component 2) are present in a total weight ratio of from 100:1 to 1 :100 wherein the total weight of component 1 ) is based on the amount of the solid material (dry matter) of component 1 ).
4. The mixture according to any of the claims 1 to 3, wherein component 1 ) is a water-based Quillay extract.
5. The mixture according to any of the claims 1 to 4, wherein the Quillay extract is obtainable by subjecting chipped or milled wood, branches and/or the bark or flakes from branches and/or the bark of Quillaja saponaria to a solid/liquid extraction process using water as ex- tractant at an extraction temperature of from 20 to 95°C, preferably of from 40 to 90°C, specifically ca. 60°C, for an extraction time of from 0.5 to 5 h, preferably of from 2 to 3 h, and optionally removing undesired products.
6. The mixture according to any of the claims 1 to 5, wherein component 2) is selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebucona- zole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole 1 -[rel-(2S;3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazolo and
2- [rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-
3- thiol.
7. The mixture according to claim 6, wherein component 2) is selected from cyproconazole, difenoconazole, epoxiconazole, metconazole, propiconazole, prothioconazole or tebucon- azole, and is in particular tebuconazole.
8. The mixture according to any of the claims 1 to 5, wherein component 2) is selected from fenpropimorph and tridemorph.
9. The mixture according to any of the claims 1 to 5, wherein component 2) is metiram, man- cozeb or chlorothalonil, and is in particular chlorothalonil.
10. An agrochemical composition, comprising an auxiliary and a mixture as defined in any one of claims 1 to 9.
1 1 . The agrochemical composition according to claim 10, wherein the auxiliary is an organic acid.
12. The agrochemical composition according to any of the claims 10 to 1 1 , further comprising as active component 3) a further active compound.
3. The agrochemical composition according to claim 12, wherein the further active compound is a compound III selected from groups A) to O):
A) Respiration inhibitors
- Inhibitors of complex III at Q0 site (e.g. strobilurins): azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metomino- strobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)- phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodin- carb, famoxadone, fenamidone;
- inhibitors of complex III at Q, 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-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 (e. g. carboxamides): benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetam- id, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyr- azole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H- pyrazole-4-carboxamide, 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-car- boxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-car- boxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, N-(7- fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carboxamide, N-[2-(2,4- dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4- carboxamide;
- other respiration inhibitors (e.g. complex I, uncouplers): diflumetorim, (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organo- metal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bro- muconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxicon- azole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imiben- conazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, pen- conazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1 -[re/-(2S;3R)-3-(2-chlorophenyl)-
2- (2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazole, 2-[re/-(2S;3R)-
3- (2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol; 2- [2-chloro-4-(4-chlorophenoxy)phenyl]-1 (1 ,2,4-triazol-1 -yl)pentan-2-ol, 1 -[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol, 2- [4-(4-chlorophenoxy)-2-(trifluorometh-"yl)phenyl]-1-(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[2- chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2- [4-(4-chlorophenoxy)-2-(trifluoromethyl)-"phenyl]-1-(1 ,2,4-triazol-1 -yl)propan-2-ol, 2-[2- chloro-4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)-'phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol, 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)-phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, [3-(4-chloro-2-fluoro-phenyl)-5-(2,4- difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol;
- 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, metalaxyl-M (mefenoxam), 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, such as benzimidazoles, thiophanates: benomyl, carbendazim,
fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro- 7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine - other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zox- amide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim, pyrime- thanil;
- 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, fen- piclonil, 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-cyano- phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
- compounds affecting cell membrane permeability and fatty acides: propamocarb, pro- pamocarb-hydrochlorid
- fatty acid amide hydrolase inhibitors: oxathiapiprolin, 2-{3-[2-(1 -{[3,5- bisid flLnoromethyl-l H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2 oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5 yl}-3- chlorophenyl methanesulfonate
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 (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachloroben- zene, 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), dithianon, 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; phospho- nates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Unknown mode of action
- bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, pi- carbutrazox, tolprocarb, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-(prop- 2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 - yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2- yn-1 -yhoxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-th azol-2-yl)piperidin-1 - yl]ethanone, 2 [3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2- yn-1 -yhoxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2 yl)piperidin-1 - yl]ethanone, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6- iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-di- fluoro-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-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5- trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, 2methoxy-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 (pyrisoxazole), 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, ethyl (Z) 3 amino-2-cyano-3-phenyl-prop-2-enoate, pentyl N-[6-[[(Z)-[(1 -methyltetra-,zol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate, 2-[2-[(7,8-di-"fluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-
2-ol, 2-[2-fluoro-6-[(8-flu-"oro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, 3-(5-fluoro- 3,3,4,4-tetramethyl-3,4-dihydroiso^quinolin-1 -yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl- S^-dihydrcnisoquinolin-l -yl^quinoline, 3-(4,4,5-trifluoro-3,3-dimethyl-3,4- dihydroisoquinolin-1 -yl)quinoline;
L) Biopesticides
L1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus amyloliquefaciens, B. mojavensis, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibac- ter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonosta- chys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Micro- dochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus pol- ymyxa, Pantoea vagans, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum,
Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. vio- laceusniger, Talaromyces flavus, Trichoderma asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum; mixture of T. harzia^num and T. viride; mixture of T. polysporum and T. harzianum; T. stromaticum, T. virens (also named Gliocladium virens), T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: chitosan (hydrolysate), harpin protein, laminarin, Menhaden fish oil, natamycin, Plum pox virus coat protein, potassium or sodium bicarbonate, Rey- noutria sachlinensis extract, salicylic acid, tea tree oil;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thurin- giensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B. brongniartii , Burkholderia sp., Chromobac- terium subtsugae, Cydia pomonella granulosis virus, Cryptophlebia leucotreta granulovirus (CrleGV), Isaria fumosorosea, Heterorhabditis bacteriophora, Lecanicil- lium longisporum, L. muscarium (formerly Verticillium lecanii), Metarhizium anisopli- ae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. li- lacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramose, P. reneformis, P. thornea, P. usgae, Pseudomonas fluorescens, Steinernema carpocapsae, S. feltiae, S. kraussei;
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 - butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1 -ol, (E,Z)- 2,13-octadecadien-1 -ol acetate, (E,Z)-3,13-octadecadien-1 -ol, R-1 -octen-3-ol, pen- tatermanone, potassium silicate, sorbitol actanoate, (E,Z,Z)-3,8,1 1 -tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1 -yl acetate, Z-7-tetradecen-2-one, Z-9- tetradecen-1 -yl acetate, Z-1 1 -tetradecenal, Z-1 1 -tetradecen-1 -ol, Acacia negra extract, extract of grapefruit seeds and pulp, extract of Chenopodium ambrosiodae, Catnip oil, Neem oil, Quillay extract, Tagetes oil;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. ja- ponicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Meso- rhizobium sp., Paenibacillus alvei, Penicillium bilaiae, Rhizobium leguminosarum bv. phaseoli, R. I. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti;
L6) Biochemical pesticides with plant stress reducing, plant growth regulator and/or plant yield enhancing activity: abscisic acid, aluminium silicate (kaolin), 3-decen-2- one, formononetin, genistein, hesperetin, homobrassinlide, humates, jasmonic acid or salts or derivatives thereof, lysophosphatidyl ethanolamine, naringenin, polymeric polyhydroxy acid, Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract and Ecklonia maxima (kelp) extract;
M) Growth regulators
abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dike- gulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, tri- apenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;
N) Herbicides
- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, preti- lachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, halox- yfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl; Bipyridyls: diquat, paraquat;
(thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;
dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lac- tofen, oxyfluorfen;
hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;
imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, ima- zethapyr;
phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, di- chlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, piclo- ram, picolinafen, thiazopyr;
sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfu- ron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfu- ron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfu- ron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1 -((2-chloro-6-propyl- imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;
triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metam- itron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosu- lam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsu- lam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac- methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlor- thal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fenox- asulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quin- clorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, ter- bacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, (3-[2-chloro-4-fluoro-5- (3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1 -yl)-phenoxy]-pyridin- 2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4- amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3- chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2- carboxylic acid methyl ester.
O) Insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, di- sulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methi- dathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimi- phos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazo- phos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, car- bosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;
- pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, al- pha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetrame- thrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;
- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, no- valuron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clo- fentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
- nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, flupyradi- furone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -2-chloro- thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
- GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1 H-pyrazole-3- carbothioic acid amide;
- macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spi- nosad, spinetoram;
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
- METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;
- Uncouplers: chlorfenapyr;
- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, pro- pargite;
- moulting disruptor compounds: cryomazine;
- mixed function oxidase inhibitors: piperonyl butoxide; - sodium channel blockers: indoxacarb, metaflumizone;
- ryanodine receptor inhibitors: chlorantraniliprole, cyantraniliprole, flubendiamide, N
[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2 pyridyl)-5-(trifluoromethyl)pynazole-3-carboxamide; N-[4-chloro-2-[(diethyl-lambda-4- sulfanylidene)carbamoyl]-6 methyl-phenyl]-2-(3-chloro-2-pyridyl)-5- (triflu-Oromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(di-2-propyl-lambda-4- sulfanyl dene)carbamoyl]-6-methyl-phenyl]-2 (3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-dichloro-2 [(di-2-propyl-lambda-4- sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5 (trifluoromethyl)pyrazole-3- carboxamide; N-[4,6-d chloro-2-[(diethyl-lambda-4 sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(difluoromethyl)pyr-azole-3-carboxamide; N-[4,6-dibromo-2- [(di-2-propyl-lambda-4 sulfanylidene)carba-,moyl]-phenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyr-azole-3-carboxamide; N [4-chloro-2-[(di-2-propyl-lambda-4- sulfanylidene)carba-moyl]-6-cyano-phenyl]-2 (3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carbox^amide; N-[4,6-dibromo-2 [(diethyl-lambda-4- sulfanylidene)carbamoyl]-phenyl]-2 (3 chloro-2-pyridyl)-5 (tr fluoromethyl)pyrazole-3- carboxamide;
- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thio- cyclam, cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, pyrifluquinazon, and 1 , 1 '-[(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-4-[[(2-cyclopropyl- acetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b- trimethyl-1 1 -oxo-9-(3-pyridinyl)-2H,1 1 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl] cy- clopropaneacetic acid ester.
A method for controlling phytopathogenic harmful fungi, comprising treating the fungi, their habitat or the seed, the soil or the plants to be protected against fungal attack with an effective amount of the mixture as defined in any one of claims 1 to 9 or of the composition as defined in any of the claims 10 to 13, or with a Quillay extract in combination with at least one compound II as defined in any of claims 1 to 9 and optionally also with at least one active component 3) as defined in any of claims 12 or 13.
The use of a mixture as defined in any one of claims 1 to 9 or of a composition as defined in any of the claims 10 to 13 or of a Quillay extract in combination with at least one compound II as defined in any of claims 1 to 9 and optionally also in combination with at least one active component 3) as defined in any of claims 12 or 13 for controlling phytopathogenic harmful fungi.
6. A plant propagation material, comprising the mixture as defined in any one of claims 1 to 9 or the composition as defined in any of the claims 10 to 13 in an amount of from 0.01 g to 10000 g per 100 kg of plant propagation material.
PCT/EP2013/075527 2012-12-04 2013-12-04 Compositions comprising a quillay extract and a fungicidal compound WO2014086853A1 (en)

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