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(11) EP 2 363 023 A1

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.: 07.09.2011 Bulletin 2011/36 A01N 37/24 (2006.01) A01N 43/40 (2006.01) A01N 43/56 (2006.01) A01N 43/78 (2006.01) (2006.01) (2006.01) (21) Application number: 10155513.4 A01N 47/12 A01N 47/22 A01N 47/24 (2006.01) A01N 47/38 (2006.01) (2006.01) (2006.01) (22) Date of filing: 04.03.2010 A01N 57/12 A01N 57/14 A01N 57/16 (2006.01) A01N 57/20 (2006.01) A01N 57/28 (2006.01)

(84) Designated Contracting States: (71) Applicant: BASF SE AT BE BG CH CY CZ DE DK EE ES FI FR GB GR 67056 Ludwigshafen (DE) HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR (72) Inventor: The designation of the inventor has not Designated Extension States: yet been filed AL BA ME RS

(54) Synergistic fungicidal and insecticidal mixtures

(57) The present invention relates to a mixture, com- the description in a synergistically effective amount, and prising a succinate dehydrogenase inhibitor as defined to compositions comprising these mixtures. in the description and at least one insecticidally active compound II selected from groups A) to E) as defined in EP 2 363 023 A1

Printed by Jouve, 75001 PARIS (FR) 1 EP 2 363 023 A1 2

Description milbemectin, lepimectin, , , , pymetrozine, , pyridaben, [0001] The present invention relates to mixtures com- tolfenpyrad, fenazaquin, fenpyroximate, pyrimidifen, prising, as active components flonicamid, , fenbutatin oxide, indox- 5 acarb, acequinocyl, fluacyprim, cyhexatin, diafenthiuron, 1) at least one compound I from the class of succi- propargite, benclothiaz, bifenazate, cartap, pyridalyl, thi- nate dehydrogenase inhibitors selected from ocyclam, cyenopyrafen, , flupyrazofos, cy- boscalid, mepronil, flutolanil, furametpyr and thiflu- flumetofen, amidoflumet, imicyafos, bistrifluron, iuquina- zamide; zon, pyrifluquinazon and 2,2-dimethyl-propionic acid-2- and 10 cyano-1-(2-methyl-4-trifluoromethyl- thiazol-5- yl)-2-(2- phenyl-thiazol-4-yl)-vinyl ester; 2) at least one insecticidally active compound II se- in a synergistically effective amount. lected from groups A) to E): [0003] Moreover, the invention relates also to a meth- od for controlling phytopathogenic harmful fungi, A) acetylcholinesterase inhibitors selected from 15 or other pests or for improving the health of the plants , , , , using mixtures of at least one compound I and at least alanycarb, , benfuracarb, , one active compound II and to the use of compounds I ethiofencarb, , furathiocarb, methio- and compounds II for preparing such mixtures, and to carb, , , , thiodicarb, compositions and seed comprising these mixtures. triazamate, , , , 20 [0004] Practical agricultural experience has shown , , , terbu- that the repeated and exclusive application of an individ- fos, , azinphos-methyl, cadusa- ual active compound in the control of harmful fungi or fos, , , , di- insects or other pests leads in many cases to a rapid crotophos, , , , fen- selection of those fungus strains or pest isolates which thion, , , methyl-par- 25 have developed natural or adapted resistance against athion, , , oxydeme- the active compound in question. Effective control of ton-methyl, , , , these fungi or pests with the active compound in question , , , , pir- is then no longer possible. imiphos-methyl, prothiofos, , tetra- [0005] To reduce the risk of the selection of resistant chlorvinphos, triazophos and trichlorfon; 30 fungus strains or isolates, mixtures of different ac- tive compounds are nowadays conventionally employed B) sodium channel modulators selected from for controlling harmful fungi or insects or other pests. By , , alpha-cypermethrin, combining active compounds having different mecha- zeta-cypermethrin, , esfen-valer- nisms of action, it is possible to ensure successful control ate, , lambda-, permeth- 35 over a relatively long period of time. rin, , , beta- cyfluthrin, [0006] It is an object of the present invention to provide, , allethrin, cycloprothrin, cyhalothrin, with a view to effective resistance management and ef- cyphenothrin, beta-cypermethrin, fenpropath- fective control of phytopathogenic harmful fungi, insects rin, , flucythrinate, , pral- or other pests, at application rates which are as low as lethrin, Iand II, , si- lafluofen, 40 possible, compositions which, at a reduced total amount tau-fluvalinate, , , trans- of active compounds applied, have improved activity fluthrin, profluthrin, dimefluthrin, gamma-cyha- against the harmful fungi or pests (synergistic mixtures) lothrin and theta-cypermethrin; and a broadenedactivty spectrum, in particular forcertain indications. C) insect growth regulators selected from 45 [0007] We have accordingly found that this object is , , novaluron, , achieved by the compositions, defined herein, compris- teflubenzuron, chlorfluazuron, cyramazin, dif- ing compound I and at least one compound II. lubenzuron, flucycloxuron, hexaflumuron, triflu- [0008] Moreover, we have found that simultaneous, muron, diofenolan, hexythiazox, etoxazole , that is joint or separate, application of compound I and clofentazine, methoxyfenozide, halofenozide, 50 at least one compound II or successive application of a and ; compound I and of a compound II allows better control of harmful fungi than is possible with the individual com- D) spinosyns selected from and spin- pounds alone (synergistic mixtures). Furthermore, syn- etoran ergistic effects in relation with the insecticidal and/or her- 55 bicidal action has been found with the inventive mixtures. E) other selected from [0009] Compound I and/or the compounds II of the in- ventive compositions can be present in different crystal [0002] March 04, 2010/JAB abamectin, emamectin, modifications, which may differ in biological activity.

2 3 EP 2 363 023 A1 4

[0010] The compounds I, their preparation and their are the following synergistic mixtures A1) to A47) com- activity against harmful fungi is known (cf.: http:prising boscalid (as compound I) and a specific com- //www.alanwood.net/pesticides/); these substances are pound II: commercially available and known, e.g. boscalid is de- scribed in EP 0 545 099 A1. Likewise, the compounds 5 A1) Synergistic mixture of boscalid and aldicarb. II, their preparation and their activity against insects is A2) Synergistic mixture of boscalid and carbofuran. known (cf.: http://www.alanwood. net/pesticides/); these A3) Synergistic mixture of boscalid and methomyl. substances are commercially available and known. A4) Synergistic mixture of boscalid and acephate. [0011] Mixtures of the GABA-gated chloride channel A5) Synergistic mixture of boscalid and chlorpyrifos. antagonist insecticides ethiprole and with with 10 A6) Synergistic mixture of boscalid and dimethoate. certain fungicide inter alia boscalid are mentioned in WO A7) Synergistic mixture of boscalid and malathion. 08/095913. A8) Synergistic mixture of boscalid and methamido- [0012] Mixtures of the nicotinic acetylcholine receptor phos. agonist with fungicides inter alia A9) Synergistic mixture of boscalid and profenofos. with boscalid are known from WO 06/23899. Mixtures of 15 A10) Synergistic mixture of boscalid and . insecticides with certain fungicides e.g. A11) Synergistic mixture of boscalid and thiodicarb. boscalid are known from WO 06/089876. A12) Synergistic mixture of boscalid and . [0013] In the inventive mixtures, compound I is prefer- A13) Synergistic mixture of boscalid and bifenthrin. ably selected from boscalid, mepronil and flutolanil, in A14) Synergistic mixture of boscalid and cypermeth- particular compound I is boscalid. 20 rin. [0014] According to another embodiment of the inven- A15) Synergistic mixture of boscalid and alpha-cy- tion, mixtures comprise as compound II a compound that . is selected from the group A), preferably selected from A16) Synergistic mixture of boscalid and zeta- cyper- aldicarb, carbofuran, carbosulfan, methomyl, acephate, methrin. chlorpyrifos, dimethoate, malathion, methamidophos, 25 A17) Synergistic mixture of boscalid and deltameth- profenofos, terbufos, thiodicarb and methiocarb, more rin. preferably from acephate, chlorpyrifos, dimethoate, A18) Synergistic mixture of boscalid and esfenvaler- methamidophos, terbufos, thiodicarb and methiocarb, in ate. particular chlorpyrifos. A19) Synergistic mixture of boscalid and etofenpox. [0015] According to a further embodiment, mixtures 30 A20) Synergistic mixture of boscalid and lambda- comprise as compound II a compound that is selected cyhalothrin. from the group B), preferably selected from bifenthrin, A21) Synergistic mixture of boscalid and permethrin. cypermethrin, alpha-cypermethrin, zeta-cypermethrin, A22) Synergistic mixture of boscalid and tefluthrin. deltamethrin, esfen-valerate, etofenprox, lambda-cyha- A23) Synergistic mixture of boscalid and beta-cy- lothrin, permethrin, tefluthrin and beta-cyfluthrin, more 35 fluthrin preferably from cypermethrin, alpha- cypermethrin, zeta- A24) Synergistic mixture of boscalid and flufenoxu- cypermethrin, esfen-valerate, permethrin, tefluthrin and ron. beta-cyfluthrin, in particular alpha-cypermethrin. A25) Synergistic mixture of boscalid and lufenuron. [0016] According to a further embodiment, mixtures A26) Synergistic mixture of boscalid and novaluron. comprise as compound II a compound of group C), pref- 40 A27) Synergistic mixture of boscalid and buprofezin. erably selected from selected from flufenoxuron, lufen- A28) Synergistic mixture of boscalid and tefluben- uron, novaluron, buprofezin and teflubenzuron, in partic- zuron. ular flufenoxuron. A29) Synergistic mixture of boscalid and spinosad. [0017] According to a further embodiment, mixtures A30) Synergistic mixture of boscalid and spinetoran. comprise as compound II a compound of group D), pref- 45 A31) Synergistic mixture of boscalid and abamectin. erably selected from spinosad and spinetoran, in partic- A32) Synergistic mixture of boscalid and emamectin. ular spinosad. A33) Synergistic mixture of boscalid and milbemec- [0018] According to a further embodiment, mixtures tin. comprise as compound II a compound of group E), pref- A34) Synergistic mixture of boscalid and lepimectin. erably selected from abamectin, emamectin, milbemec- 50 A35) Synergistic mixture of boscalid and chlo- tin, lepimectin, chlorfenapyr, metaflumizone, indoxacarb, rfenapyr. pymetrozine, tebufenpyrad, pyridaben, tolfenpyrad, A36) Synergistic mixture of boscalid and metaflumi- fenazaquin, fenbutatin oxide, hydramethylnon, flufeneri- zone. um, pyrifluquinazon and compound of formula (I), more A37) Synergistic mixture of boscalid and indoxacarb. preferably from abamectin, emamectin, chlorfenapyr,55 A38) Synergistic mixture of boscalid and pymetro- metaflumizone and tebufenpyrad, even more preferably zine. from chlorfenapyr, metaflumizone and tebufenpyrad. A39) Synergistic mixture of boscalid and tebufen- [0019] Specific embodiments of the inventive mixtures pyrad.

3 5 EP 2 363 023 A1 6

A40) Synergistic mixture of boscalid and pyridaben. berries, raspberries, blackberries or gooseberries; legu- A41) Synergistic mixture of boscalid and tolfenpyrad. minous plants, such as lentils, peas, alfalfa or soybeans; A42) Synergistic mixture of boscalid and fenazaquin. oil plants, such as rape, mustard, olives, sunflowers, co- A43) Synergistic mixture of boscalid and fenbutatin conut, cocoa beans, castor oil plants, oil palms, ground oxide. 5 nuts or soybeans; cucurbits, such as squashes, cucum- A44) Synergistic mixture of boscalid and hydrame- ber or melons; fiber plants, such as cotton, flax, hemp or thylnon. jute; citrus fruit, such as oranges, lemons, grapefruits or A45) Synergistic mixture of boscalid and flufenerium. mandarins; vegetables, such as spinach, lettuce, aspar- A46) Synergistic mixture of boscalid and pyrfluquina- agus, cabbages, carrots, onions, tomatoes, potatoes, cu- zon. 10 curbits or paprika; lauraceous plants, such as avocados, A47) Synergistic mixture of boscalid and 2,2-dime- cinnamon or camphor; energy and raw material plants, thyl-propionic acid-2-cyano-1-(2-methyl-4-trifluor- such as corn, soybean, rape, sugar cane or oil palm; omethyl-thiazol-5-yl)-2-(2-phenyl-thiazol-4-yl)-vinyl corn; tobacco; nuts; coffee; tea; bananas; vines (table ester. grapes and grape juice grape vines); hop; turf; sweet leaf 15 (also called Stevia); natural rubber plants or ornamental [0020] Further specific embodiments of the inventive and forestry plants, such as flowers, shrubs, broad- mixtures are the synergistic mixtures B1) to B47), where- leaved trees or evergreens, e. g. conifers; and on the in the compound II is as described in each of the mixtures plant propagation material, such as seeds, and the crop A1) to A64) mentioned above and mepronil is compound material of these plants. I instead of boscalid. 20 [0027] Preferably, mixtures and compositions thereof, [0021] Further specific embodiments of the inventive respectively are used for controlling a multitude of fungi mixtures are the synergistic mixtures C1) to C47), where- on field crops, such as potatoes sugar beets, tobacco, in the compound II is as described in each of the mixtures wheat, rye, barley, oats, rice, corn, cotton, soybeans, A1) to A64) mentioned above and flutolanil is compound rape, legumes, sunflowers, coffee or sugar cane; fruits; I instead of boscalid. 25 vines; ornamentals; or vegetables, such as cucumbers, [0022] Further specific embodiments of the inventive tomatoes, beans or squashes. mixtures are the synergistic mixtures D1) to D47), where- [0028] The term "plant propagation material" is to be in the compound II is as described in each of the mixtures understood to denote all the generative parts of the plant A1) to A64) mentioned above and furametpyr is com- such as seeds and vegetative plant material such as cut- pound I instead of boscalid. 30 tings and tubers (e. g. potatoes), which can be used for [0023] Further specific embodiments of the inventive the multiplication of the plant. This includes seeds, roots, mixtures are the synergistic mixtures D1) to D47), where- fruits, tubers, bulbs, rhizomes, shoots, sprouts and other in the compound II is as described in each of the mixtures parts of plants, including seedlings and young plants, A1) to A64) mentioned above and thifluzamide is com- which are to be transplanted after germination or after pound I instead of boscalid. 35 emergence from soil. These young plants may also be [0024] Preference is also given to three-component protected before transplantation by a total or partial treat- mixtures of compound I with two of the active compounds ment by immersion or pouring. II mentioned above. [0029] Preferably, treatment of plant propagation ma- [0025] The mixtures and the compositions according terials with compounds I and compositions thereof, re- to the invention, respectively, are suitable as fungicides. 40 spectively, is used for controlling a multitude of fungi on They are distinguished by an outstanding effectiveness cereals, such as wheat, rye, barley and oats; rice, corn, against a broad spectrum of phytopathogenic fungi, in- cotton and soybeans. cluding soil-borne fungi, which derive especially from the [0030] The term "cultivated plants" is to be understood classes of the Plasmodiophoromycetes, Peronosporo- as including plants which have been modified by breed- mycetes (syn. Oomycetes), Chytridiomycetes, Zygo-45 ing, mutagenesis or genetic engineering including but mycetes, Ascomycetes, Basidiomycetes and Deutero- not limiting to agricultural biotech products on the market mycetes (syn. Fungi imperfecti). Some are systemically or in development (cf. http://www.bio.org/speeches/ effective and they can be used in crop protection as foliar pubs/er/agri_products.asp). Genetically modified plants fungicides, fungicides for seed dressing and soil fungi- are plants, which genetic material has been so modified cides. Moreover, they are suitable for controlling harmful 50 by the use of recombinant DNA techniques that under fungi, which inter alia occur in wood or roots of plants. natural circumstances cannot readily be obtained by [0026] The mixtures and the compositions according cross breeding, mutations or natural recombination. Typ- to the invention are particularly important in the control ically, one or more genes have been integrated into the of a multitude of phytopathogenic fungi on various culti- genetic material of a genetically modified plant in order vated plants, such as cereals, e. g. wheat, rye, barley, 55 to improve certain properties of the plant. Such genetic triticale, oats or rice; beet, e. g. sugar beet or fodder beet; modifications also include but are not limited to targeted fruits, such as pomes, stone fruits or soft fruits, e. g. ap- post-translational modification of protein(s), oligo- or ples, pears, plums, peaches, almonds, cherries, straw- polypeptides e. g. by glycosylation or polymer additions

4 7 EP 2 363 023 A1 8 such as prenylated, acetylated or farnesylated moieties patatin, cystatin or papain inhibitors; ribosome-inactivat- or PEG moieties. ing proteins (RIP), such as ricin, maize- RIP, abrin, luffin, [0031] Plants that have been modified by breeding, saporin or bryodin; steroid metabolism enzymes, such mutagenesis or genetic engineering, e. g. have been ren- as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl- dered tolerant to applications of specific classes of her- 5 transferase, cholesterol oxidases, ecdysone inhibitors or bicides, such as auxin herbicides such as dicamba or HMG-CoA-reductase; ion channel blockers, such as 2,4-D; bleacher herbicides such as hydroxylphenylpyru- blockers of sodium or calcium channels; juvenile hor- vate dioxygenase (HPPD) inhibitors or phytoene desat- mone esterase; diuretic hormone receptors (helicokinin urase (PDS) inhibittors; acetolactate synthase (ALS) in- receptors); stilben synthase, bibenzyl synthase, chitinas- hibitors such as sulfonyl ureas or imidazolinones;10 es or glucanases. In the context of the present invention enolpyruvylshikimate-3-phosphate synthase (EPSPS) these insecticidal proteins or toxins are to be understood inhibitors, such as glyphosate; glutamine synthetase expressly also as pre-toxins, hybrid proteins, truncated (GS) inhibitors such as glufosinate; protoporphyrinogen- or otherwise modified proteins. Hybrid proteins are char- IX oxidase inhibitors; lipid biosynthesis inhibitors such as acterized by a new combination of protein domains, (see, acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. 15 e. g. WO 02/015701). Further examples of such toxins e. bromoxynil or ioxynil) herbicides as a result of conven- or genetically modified plants capable of synthesizing tional methods of breeding or genetic engineering. Fur- such toxins are disclosed, e. g., in EP-A 374 753, WO thermore, plants have been made resistant to multiple 93/007278, WO 95/34656, EP- A 427 529, EP- A 451 878, classes of herbicides through multiple genetic modifica- WO 03/18810 und WO 03/52073. The methods for pro- tions, such as resistance to both glyphosate and glufosi- 20 ducing such genetically modified plants are generally nate or to both glyphosate and a herbicide from another known to the person skilled in the art and are described, class such as ALS inhibitors, HPPD inhibitors, auxin her- e. g. in the publications mentioned above. These insec- bicides, or ACCase inhibitors. These herbicide resist- ticidal proteins contained in the genetically modified ance technologies are e. g. described in Pest Managem. plants impart to the plants producing these proteins tol- Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 25 erance to harmful pests from all taxonomic groups of ath- 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; ropods, especially to beetles (Coeloptera), two-winged Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, insects (Diptera), and () and to nem- 2007, 708; Science 316, 2007, 1185; and references atodes (Nematoda). Genetically modified plants capable quoted therein. Several cultivated plants have been ren- to synthesize one or more insecticidal proteins are, e. g., dered tolerant to herbicides by conventional methods of 30 described in the publications mentioned above, and breeding (mutagenesis), e. g. Clearfield® summer rape some of which are commercially available such as (Canola, BASF SE, Germany) being tolerant to imida- YieldGard® (corn cultivars producing the Cry1Ab toxin), zolinones, e. g. imazamox, or ExpressSun® sunflowers YieldGard® Plus (corn cultivars producing Cry1Ab and (DuPont, USA) being tolerant to sulfonyl ureas, e. g. Cry3Bb1 toxins), Starlink® (corn cultivars producing the tribenuron. Genetic engineering methods have been35 Cry9c toxin), Herculex® RW (corn cultivars producing used to render cultivated plants such as soybean, cotton, Cry34Ab1, Cry35Ab1 and the enzyme Phosphinothricin- corn, beets and rape, tolerant to herbicides such as N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cul- glyphosate and glufosinate, some of which are commer- tivars producing the Cry1Ac toxin), Bollgard® I (cotton cially available under the trade names RoundupReady® cultivarsproducing the Cry1Ac toxin), Bollgard® II (cotton (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® 40 cultivars producing Cry1Ac and Cry2Ab2 toxins); VIP- (imidazolinone tolerant, BASF SE, Germany) and Liber- COT® (cotton cultivars producing a VIP-toxin); tyLink® (glufosinate-tolerant, Bayer CropScience, Ger- NewLeaf® (potato cultivars producing the Cry3A toxin); many). Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Pro- [0032] Furthermore, plants are also covered that are tecta®, Bt11 (e. g. Agrisure® CB) and Bt176 from Syn- by the use of recombinant DNA techniques capable to 45 genta Seeds SAS, France, (corn cultivars producing the synthesize one or more insecticidal proteins, especially Cry1Ab toxin and PAT enyzme), MIR604 from Syngenta those known from the bacterial Bacillus, particu- Seeds SAS, France (corn cultivars producing a modified larly from Bacillus thuringiensis, such as δ - endotoxins, version of the Cry3A toxin, c.f. WO 03/018810), MON e. g. CryIA (b), CryIA(c), CryIF, CryIF (a2), CryIIA(b), Cry- 863 from Monsanto Europe S.A., Belgium (corn cultivars IIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins 50 producing the Cry3Bb1 toxin), IPC 531 from Monsanto (VIP), e. g. VIP1, VIP2, VIP3 orVIP3A; insecticidal pro- Europe S.A., Belgium (cotton cultivars producing a mod- teins of bacteria colonizing nematodes, e. g. Photorhab- ified version of the Cry1Ac toxin) and 1507 from Pioneer dus spp. or Xenorhabdus spp.; toxins produced by ani- Overseas Corporation,Belgium (corn cultivarsproducing mals, such as scorpion toxins, arachnid toxins, wasp tox- the Cry1 F toxin and PAT enzyme). ins, or other insect- specific neurotoxins; toxins produced 55 [0033] Furthermore, plants are also covered that are by fungi, such Streptomycetes toxins, plant lectins, such by the use of recombinant DNA techniques capable to as pea or barleylectins; agglutinins;proteinase inhibitors, synthesize one or more proteins to increase the resist- such as trypsin inhibitors, serine protease inhibitors, ance or tolerance of those plants to bacterial, viral or

5 9 EP 2 363 023 A1 10 fungal pathogens. Examples of such proteins are the so- es), rape, flowers, vines, forestry plants and wheat; called " pathogenesis-related proteins" (PR proteins, Bremia lactucae (downy mildew) on lettuce; Cerato- see, e. g. EP- A 392 225), plant disease resistance genes cystis (syn. Ophiostoma) spp. (rot or wilt) on broad- (e. g. potato cultivars, which express resistance genes leaved trees and evergreens, e. g. C. ulmi (Dutch acting against Phytophthora infestans derived from the 5 elm disease) on elms; Cercospora spp. (Cercospora mexican wild potato Solanum bulbocastanum) or T4- lys- leaf spots) on corn (e.g. Gray leaf spot: C. zeae- ozym (e. g. potato cultivars capable of synthesizing these maydis), rice, sugar beets (e. g. C. beticola), sugar proteins with increased resistance against bacteria such cane, vegetables, coffee, soybeans (e. g. C. sojina as Erwinia amylvora). The methods for producing such or C. kikuchii) and rice; Cladosporium spp. on toma- genetically modified plants are generally known to the 10 toes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. person skilled in the art and are described, e. g. in the herbarum (black ear) on wheat; Claviceps purpurea publications mentioned above. (ergot) on cereals; Cochliobolus (anamorph: [0034] Furthermore, plants are also covered that are Helminthosporium of Bipolaris) spp. (leaf spots) on by the use of recombinant DNA techniques capable to corn (C. carbonum), cereals (e. g. C. sativus, an- synthesize one or more proteins to increase the produc- 15 amorph: B. sorokiniana) and rice (e. g. C. miyabea- tivity (e. g. bio mass production, grain yield, starch con- nus, anamorph: H. oryzae); Colletotrichum (teleo- tent, oil content or protein content), tolerance to drought, morph: Glomerella) spp. (anthracnose) on cotton (e. salinity or other growth-limiting environmental factors or g. C. gossypii), corn (e. g. C. graminicola: Anthrac- tolerance to pests and fungal, bacterial or viral pathogens nose stalk rot), soft fruits, potatoes (e. g. C. coc- of those plants. 20 codes: black dot), beans (e. g. C. lindemuthianum) [0035] Furthermore, plants are also covered that con- and soybeans (e. g. C. truncatum or C. gloeospori- tain by the use of recombinant DNA techniques a modi- oides); Corticium spp., e. g. C. sasakii (sheath blight) fied amount of substances of content or new substances on rice; Corynespora cassiicola (leaf spots) on soy- of content, specifically to improve human or nu- beans and ornamentals; Cycloconium spp., e. g. C. trition, e. g. oil crops that produce health-promoting long- 25 oleaginum on olive trees; Cylindrocarpon spp. (e. g. chain omega-3 fatty acids or unsaturated omega-9 fatty fruit tree canker or young vine decline, teleomorph: acids (e. g. Nexera® rape, DOW Agro Sciences, Cana- Nectria or Neonectria spp.) on fruit trees, vines (e. da). g. C. liriodendri, teleomorph: Neonectria liriodendri: [0036] Furthermore, plants are also covered that con- Black Foot Disease) and ornamentals; Dematopho- tain by the use of recombinant DNA techniques a modi- 30 ra (teleomorph: Rosellinia) necatrix (root and stem fied amount of substances of content or new substances rot) on soybeans; Diaporthe spp., e. g. D. phaseolo- of content, specifically to improve raw material produc- rum (damping off) on soybeans; Drechslera (syn. tion, e. g. potatoes that produce increased amounts of Helminthosporium, teleomorph: Pyrenophora) spp. amylopectin (e. g. Amflora® potato, BASF SE, Germa- on corn, cereals, such as barley (e. g. D. teres, net ny). 35 blotch) and wheat (e. g. D. tritici-repentis: tan spot), [0037] The mixtures and compositions thereof, re- rice and turf; Esca (dieback, apoplexy) on vines, spectively, are particularly suitable for controlling the fol- caused by Formitiporia (syn. Phellinus) punctata, F. lowing plant diseases: mediterranea, Phaeomoniella chlamydospora (ear- lier Phaeoacremonium chlamydosporum), Phaeoa- Albugo spp. (white rust) on ornamentals, vegetables 40 cremonium aleophilum and/or Botryosphaeria obtu- (e. g. A. candida) and sunflowers (e. g. A. tragopo- sa; Elsinoe spp. on pome fruits (E. pyri), soft fruits gonis); Alternaria spp. (Alternaria leaf spot) on veg- (E. veneta: anthracnose) and vines (E. ampelina: an- etables, rape (A. brassicola or brassicae), sugar thracnose); Entyloma oryzae (leaf smut) on rice; Ep- beets (A. tenuis), fruits, rice, soybeans, potatoes (e. icoccum spp. (black mold) on wheat; Erysiphe spp. g. A. solani or A. alternata), tomatoes (e. g. A. solani 45 (powdery mildew) on sugar beets (E. betae), vege- or A. alternata) and wheat; Aphanomyces spp. on tables (e. g. E. pisi), such as cucurbits (e. g. E. ci- sugar beets and vegetables; Ascochyta spp. on ce- choracearum), cabbages, rape (e. g. E. cruciferar- reals and vegetables, e. g. A. tritici (anthracnose) on um); Eutypa lata (Eutypa canker or dieback, an- wheat and A. hordei on barley; Bipolaris and amorph: Cytosporina lata, syn. Libertella blepharis) Drechslera spp. (teleomorph: Cochliobolus spp.), e. 50 on fruit trees, vines and ornamental woods; Exsero- g. Southern leaf blight (D. maydis) or Northern leaf hilum (syn. Helminthosporium) spp. on corn (e. g. E. blight (B. zeicola) on corn, e. g. spot blotch (B. so- turcicum); Fusarium (teleomorph: Gibberella) spp. rokiniana) on cereals and e.g. B. oryzae on rice and (wilt, root or stem rot) on various plants, such as F. turfs; Blumeria (formerly Erysiphe) graminis (pow- graminearum or F. culmorum (root rot, scab or head dery mildew) on cereals (e. g. on wheat or barley); 55 blight) on cereals (e. g. wheat or barley), F. oxyspo- Botrytis cinerea (teleomorph: Botryotinia fuckeliana: rum on tomatoes, F. solani on soybeans and F. ver- grey mold) on fruits and berries (e. g. strawberries), ticillioides on corn; Gaeumannomyces graminis vegetables (e. g. lettuce, carrots, celery and cabbag- (take-all) on cereals (e. g. wheat or barley) and corn;

6 11 EP 2 363 023 A1 12

Gibberella spp. on cereals (e. g. G. zeae) and rice dei (dwarf rust), P. graminis (stem or black rust) or (e. g. G. fujikuroi: Bakanae disease); Glomerella cin- P. recondita (brown or leaf rust) on cereals, such as gulata on vines, pome fruits and other plants and G. e. g. wheat, barley or rye, P. kuehnii (orange rust) gossypii on cotton; Grainstaining complex on rice; on sugar cane and P. asparagi on asparagus; Pyren- Guignardia bidwellii (black rot) on vines; Gymnospo- 5 ophora (anamorph: Drechslera) tritici-repentis (tan rangium spp. on rosaceous plants and junipers, e. spot) on wheat or P. teres (net blotch) on barley; g.G. sabinae (rust) on pears; Helminthosporium spp. Pyricularia spp., e. g. P. oryzae (teleomorph: Mag- (syn. Drechslera, teleomorph: Cochliobolus) on naporthe grisea, rice blast) on rice and P. grisea on corn, cereals and rice; Hemileia spp., e. g. H. vasta- turf and cereals; Pythium spp. (damping-off) on turf, trix (coffee leaf rust) on coffee; Isariopsis clavispora 10 rice, corn, wheat, cotton, rape, sunflowers, soy- (syn. Cladosporium vitis) on vines; Macrophomina beans, sugar beets, vegetables and various other phaseolina (syn. phaseoli) (root and stem rot) on plants (e. g. P. ultimum or P. aphanidermatum); Ra- soybeansand cotton;Microdochium (syn. Fusarium) mularia spp., e. g. R. collo-cygni (Ramularia leaf nivale (pink snow mold) on cereals (e. g. wheat or spots, Physiological leaf spots) on barley and R. beti- barley); Microsphaera diffusa (powdery mildew) on 15 cola on sugar beets; Rhizoctonia spp. on cotton, rice, soybeans; Monilinia spp., e. g. M. laxa, M. fructicola potatoes, turf, corn, rape, potatoes, sugar beets, and M. fructigena (bloom and twig blight, brown rot) vegetables and various other plants, e. g. R. solani on stone fruits and other rosaceous plants; My- (root and stem rot) on soybeans, R. solani (sheath cosphaerella spp. on cereals, bananas, soft fruits blight) on rice or R. cerealis (Rhizoctonia spring and ground nuts, such as e. g. M. graminicola (an- 20 blight) on wheat or barley; Rhizopus stolonifer (black amorph: Septoria tritici, Septoria blotch) on wheat or mold, soft rot) on strawberries, carrots, cabbage, M. fijiensis (black Sigatoka disease) on bananas; vines and tomatoes; Rhynchosporium secalis Peronospora spp. (downy mildew) on cabbage (e. (scald) on barley, rye and triticale; Sarocladium g. P. brassicae), rape (e. g. P. parasitica), onions (e. oryzae and S. attenuatum (sheath rot) on rice; Scle- g. P. destructor), tobacco (P. tabacina) and soy-25 rotinia spp. (stem rot or white mold) on vegetables beans (e. g. P. manshurica); Phakopsora pachyrhizi and field crops, such as rape, sunflowers (e. g. S. and P. meibomiae (soybean rust) on soybeans; Phi- sclerotiorum) and soybeans (e. g. S. rolfsii or S. scle- alophora spp. e. g. on vines (e. g. P. tracheiphila and rotiorum); Septoria spp. on various plants, e. g. S. P. tetraspora) and soybeans (e. g. P. gregata: stem glycines (brown spot) on soybeans, S. tritici (Septo- rot); Phoma lingam (root and stem rot) on rape and 30 ria blotch) on wheat and S. (syn. Stagonospora) no- cabbage and P. betae (root rot, leaf spot and damp- dorum (Stagonospora blotch) on cereals; Uncinula ing-off) on sugar beets; Phomopsis spp. on sunflow- (syn. Erysiphe) necator (powdery mildew, an- ers, vines (e. g. P. viticola: can and leaf spot) and amorph: Oidium tuckeri) on vines; Setospaeria spp. soybeans (e. g. stem rot: P. phaseoli, teleomorph: (leaf blight) on corn (e. g. S. turcicum, syn. Diaporthe phaseolorum); Physoderma maydis35 Helminthosporium turcicum) and turf; Sphacelothe- (brown spots) on corn; Phytophthora spp. (wilt, root, ca spp. (smut) on corn, (e. g. S. reiliana: head smut), leaf, fruit and stem root) on various plants, such as sorghum und sugar cane; Sphaerotheca fuliginea paprika and cucurbits (e. g. P. capsici), soybeans (e. (powdery mildew) on cucurbits; Spongospora sub- g. P. megasperma, syn. P. sojae), potatoes and to- terranea (powdery scab) on potatoes and thereby matoes (e. g. P. infestans: late blight) and broad- 40 transmitted viral diseases; Stagonospora spp. on ce- leaved trees (e. g. P. ramorum: sudden oak death); reals, e. g. S. nodorum (Stagonospora blotch, tele- Plasmodiophora brassicae (club root) on cabbage, omorph: Leptosphaeria [syn. Phaeosphaeria] nodo- rape, radish and other plants; Plasmopara spp., e. rum) on wheat; Synchytrium endobioticum on pota- g. P. viticola (grapevine downy mildew) on vines and toes (potato wart disease); Taphrina spp., e. g. T. P. halstedii on sunflowers; Podosphaera spp. (pow- 45 deformans (leaf curl disease) on peaches and T. pru- dery mildew) on rosaceous plants, hop, pome and ni (plum pocket) on plums; Thielaviopsis spp. (black soft fruits, e. g. P. leucotricha on apples; Polymyxa root rot) on tobacco, pome fruits, vegetables, soy- spp., e. g. on cereals, such as barley and wheat (P. beans and cotton, e. g. T. basicola (syn. Chalara graminis) and sugar beets (P. betae) and thereby elegans); Tilletia spp. (common bunt or stinking transmitted viral diseases; Pseudocercosporella50 smut) on cereals, such as e. g. T. tritici (syn. T. caries, herpotrichoides (eyespot, teleomorph: Tapesia yal- wheat bunt) and T. controversa (dwarf bunt) on lundae) on cereals, e. g. wheat or barley; Pseudoper- wheat;Typhula incarnata (grey snow mold) on barley onospora (downy mildew) on various plants, e. g. P. or wheat; Urocystis spp., e. g. U. occulta (stem smut) cubensis on cucurbits or P. humili on hop; Pseudo- on rye; Uromyces spp. (rust) on vegetables, such as pezicula tracheiphila (red fire disease or, rotbrenner’, 55 beans (e. g. U. appendiculatus, syn. U. phaseoli) and anamorph: Phialophora) on vines; Puccinia spp. sugar beets (e. g. U. betae); Ustilago spp. (loose (rusts) on various plants, e. g. P. triticina (brown or smut) on cereals (e. g. U. nuda and U. avaenae), leaf rust), P. striiformis (stripe or yellow rust), P. hor- corn (e. g. U. maydis: corn smut) and sugar cane;

7 13 EP 2 363 023 A1 14

Venturia spp. (scab) on apples (e. g. V. inaequalis) ralis, Spodoptera litura, Thaumatopoea pityocampa, Tor- and pears; and Verticillium spp. (wilt) on various trix viridana, Trichoplusia ni and Zeiraphera canadensis, plants, such as fruits and ornamentals, vines, soft beetles (Coleoptera), for example Agrilus sinuatus, Agri- fruits, vegetables and field crops, e. g. V. dahliae on otes lineatus, Agriotes obscurus, Amphimallus solstitia- strawberries, rape, potatoes and tomatoes. 5 lis, Anisandrus dispar, Anthonomus grandis, An- thonomus pomorum, Atomaria linearis, Blastophagus [0038] The compounds I and compositions thereof, re- piniperda, Blitophaga undata, Bruchus rufimanus, Bru- spectively, are also suitable for controlling harmful fungi chus pisorum, Bruchus lentis, Byctiscus betulae, Cassi- in the protection of stored products or harvest and in the da nebulosa, Cerotoma trifurcata, Ceuthorrhynchus as- protection of materials. The term "protection of materials" 10 similis, Ceuthorrhynchus napi, Chaetocnema tibialis, is to be understood to denote the protection of technical Conoderus vespertinus, Crioceris asparagi, Diabrotica and non-living materials, such as adhesives, glues, longicornis, Diabrotica speciosa, Diabrotica 12- punctata, wood, paper and paperboard, textiles, leather, paint dis- Diabrotica virgifera, Diloboderus abderus, Epilachna var- persions, plastics, colling lubricants, fiber or fabrics, ivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hy- against the infestation and destruction by harmful micro- 15 lobius abietis, Hypera brunneipennis, Hypera postica, lps organisms, such as fungi and bacteria. As to the protec- typographus, Lema bilineata, Lema melanopus, Leptino- tion of wood and other materials, the particular attention tarsa decemlineata, Limonius californicus, Lissorhoptrus is paid to the following harmful fungi: Ascomycetes such oryzophilus, Melanotus communis, Meligethes aeneus, as Ophiostoma spp., Ceratocystis spp., Aureobasidium Melolontha hippocastani, Melolontha melolontha, Oule- pullulans, Sclerophoma spp., Chaetomium spp., Humi- 20 ma oryzae, Ortiorrhynchus sulcatus, Oryazophagus cola spp., Petriella spp., Trichurus spp.; Basidiomycetes oryzae, Otiorrhynchus ovatus, Phaedon cochleariae, such as Coniophora spp., Coriolus spp., Gloeophyllum Phyllotreta chrysocephala, Phyllophaga sp., Phyllo- spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula phaga cuyabana, Phyllophaga triticophaga, Phylloper- spp. and Tyromyces spp., Deuteromycetes such as As- tha horticola, Phyllotreta nemorum, Phyllotreta striolata, pergillus spp., Cladosporium spp., Penicillium spp., Tri- 25 Popillia japonica, Sitona lineatus and Sitophilus granaria, chorma spp., Alternaria spp., Paecilomyces spp. and Zy- dipterans (Diptera), for example Aedes aegypti, Aedes gomycetes such as Mucor spp., and in addition in the vexans, Anastrepha ludens, Anopheles maculipennis, protection of stored products and harvest the following Ceratitis capitata, Chrysomya bezziana, Chrysomya ho- yeast fungi are worthy of note: Candida spp. and Sac- minivorax, Chrysomya macellaria, Contarinia sorghicola, charomyces cerevisae. 30 Cordylobia anthropophaga, Culex pipiens, Dacus cucur- [0039] The mixtures and compositions thereof, re- bitae, Dacus oleae, Dasineura brassicae, Fannia canic- spectively, are also particularly suitable for controlling ularis, Gasterophilus intestinalis, Glossina morsitans, the following harmful insects from the order of the Haematobia irritans, Haplodiplosis equestris, Hylemyia lepidopterans (Lepidoptera), for example Agrotis ypsilon, platura, Hypoderma lineata, Liriomyza sativae, Liriomyza Agrotis segetum, Alabama argillacea, Anticarsia gem- 35 trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, matalis, Argyresthia conjugella, Autographa gamma, Lycoria pectoralis, Mayetiola destructor, Musca domes- Bupalus piniarius, Cacoecia murinana, Capua reticula- tica, Muscina stabulans, Oestrus ovis, Oscinella frit, na, Cheimatobia brumata, Choristoneura fumiferana, Pegomya hysocyami, Phorbia antiqua, Phorbia brassi- Choristoneura occidentalis, Cirphis unipuncta, Cydia cae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Dendrolimus pini, Diaphania nitidalis, Diat- 40 pomonella, Tabanus bovinus, Tipula oleracea and Tipula raea grandiosella, Earias insulana, Elasmopalpus paludosa, lignosellus, Eupoecilia ambiguella, Evetria bouliana, thrips (Thysanoptera), e.g. Frankliniella fusca, Franklin- Feltia subterranea, Galleria mellonella, Grapholitha fu- iella occidentalis, Frankliniella tritici, Scirtothrips citri, nebrana, Grapholitha molesta, Heliothis armigera, Heli- Thrips oryzae, Thrips palmi and Thrips tabaci, othis virescens, Heliothis zea, Hellula undalis, Hibernia 45 hymenopterans (Hymenoptera), e.g. Acromyrmex am- defoliaria, Hyphantria cunea, Hyponomeuta malinellus, buguus, Acromyrmex crassispinus, Acromyrmex heiery, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma Acromyrmex landolti, Acromyrmex subterraneus, Athalia exigua, Leucoptera coffeella, Leucoptera scitella, Lithoc- rosae, Atta capiguara, Atta cephalotes, Atta laevigata, olletis blancardella, Lobesia botrana, Loxostege stictica- Atta robusta, Atta sexdens, Atta texana, Hoplocampa lis, Lymantria dispar, Lymantria monacha, Lyonetia cler- 50 minuta, Hoplocampa testudinea, Monomorium kella, Malacosoma neustria, Mamestra brassicae, Or- pharaonis, Solenopsis geminata and Solenopsis invicta, gyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, heteropterans (Heteroptera), e.g. Acrosternum hilare, Pectinophora gossypiella, Peridroma saucia, Phalera Blissus leucopterus, Cyrtopeltis notatus, Dichelops fur- bucephala, Phthorimaea operculella, Phyllocnistis citrel- catus, Dysdercus cingulatus, Dysdercus intermedius, la, Pieris brassicae, Plathypena scabra, Plutella xylos- 55 Euchistos heros, Eurygaster integriceps, Euschistus im- tella, Pseudoplusia includens, Rhyacionia frustrana, pictiventris, Leptoglossus phyllopus, Lygus lineolaris, Scrobipalpula absoluta, Sitotroga cerealella, Spargano- Lygus pratensis, Nezara viridula, Piesma quadrata, Pie- this pilleriana, Spodoptera frugiperda, Spodoptera litto- zodorus guildini, Solubea insularis and Thyanta perditor,

8 15 EP 2 363 023 A1 16

Hemiptera and Homoptera, e.g. Acrosternum hilare, Blis- ychus kanzawai, Tetranychus pacificus, Tetranychus te- sus leucopterus, Cyrtopeltis notatus, Diaphorina citri, larius and Tetranychus urticae, Panonychus ulmi, Pan- Dysdercus cingulatus, Dysdercus intermedius, Euryg- onychus citri, and oligonychus pratensis. In particular, aster integriceps, Euschistus impictiventris, Leptoglos- the inventive mixtures are suitable for combating pests sus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara 5 of the orders Coleoptera, Lepidoptera, Thysanoptera, viridula, Piesma quadrata, Solubea insularis, Thyanta Homoptera, Isoptera, and Orthoptera. perditor, Acyrthosiphon onobrychis, Adelges laricis, [0040] They are also suitable for controlling the follow- Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis po- ing plant parasitic nematodes such as Meloidogyne, Glo- mi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, bodera,Heterodera, Radopholus, Rotylenchulus, Praty- Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, 10 lenchus and other genera. Aulacorthum solani, Brachycaudus cardui, Brachy- [0041] The mixtures and compositions thereof, re- caudus helichrysi, Brachycaudus persicae, Brachy- sepectively, may be used for improving the health of a caudus prunicola, Brevicoryne brassicae, Capitophorus plant. The invention also relates to a method for improv- horni, Cerosipha gossypii, Chaetosiphon fragaefolii, ing plant health by treating a plant, its propagation ma- Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia 15 terial and/or the locus where the plant is growing or is to piceae, Dysaphis radicola, Dysaulacorthum pseu- grow with an effective amount of mixtures comprising dosolani, Dysaphis plantaginea, Dysaphis pyri, Em- compounds I and compounds II and compositions there- poasca fabae, Hyalopterus pruni, Hyperomyzus lactu- of, respectively. cae, Macrosiphum avenae, Macrosiphum euphorbiae, [0042] The term "plant health" is to be understood to Macrosiphon rosae, Megoura viciae, Melanaphis pyrar- 20 denote a condition of the plant and/or its products which ius, Metopolophium dirhodum, Myzodes persicae, is determined by several indicators alone or in combina- Myzus ascalonicus, Myzus cerasi, Myzus varians, Na- tion with each other such as yield (e. g. increased bio- sonovia ribis-nigri, Nilaparvata lugens, Pemphigus bur- mass and/or increased content of valuable ingredients), sarius, Perkinsiella saccharicida, Phorodon humuli, Psyl- plant vigor (e. g. improved plant growth and/or greener la mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopal- 25 leaves (" greening effect" )), quality (e. g. improved con- osiphum maidis, Rhopalosiphum padi, Rhopalosiphum tent or composition of certain ingredients) and tolerance insertum, Sappaphis mala, Sappaphis mali, Schizaphis to abiotic and/or biotic stress.The above identified indi- graminum, Schizoneura lanuginosa, Sitobion avenae, cators for the health condition of a plant may be interde- Trialeurodes vaporariorum, Toxoptera aurantiiand, Vi- pendent or may result from each other. teus vitifolii, Cimex lectularius, Cimex hemipterus, Redu- 30 [0043] The compounds I and/or compounds II can be vius senilis, Triatoma spp., and Arilus critatus, present in different crystal modifications whose biological termites (Isoptera), e.g. Calotermes flavicollis, Corni- activity may differ. They are likewise subject matter of termes cumulans, Heterotermes tenuis, Leucotermes the present invention. flavipes, Neocapritemes opacus, Procornitermes triacif- [0044] The mixtures are employed as such or in form er; Reticulitermes lucifugus, Syntermes molestus, and 35 of compositions by treating the fungi or the plants, plant Termes natalensis, propagation materials, such as seeds, soil, surfaces, ma- orthopterans (Orthoptera), e.g. Acheta domestica, Blatta terials or rooms to be protected from fungal attack with orientalis, Blattella germanica, Forficula auricularia, Gryl- a fungicidally effective amount of the active substances. lotalpa gryllotalpa, Locusta migratoria, Melanoplus bivit- The application can be carried out both before and after tatus, Melanoplus femur-rubrum, Melanoplus mexica- 40 the infection of the plants, plant propagation materials, nus, Melanoplus sanguinipes, Melanoplus spretus, No- such as seeds, soil, surfaces, materials or rooms by the madacris septemfasciata, Periplaneta americana, Schis- fungi. tocerca americana, Schistocerca peregrina, Stauronotus [0045] Plant propagation materials may be treated with maroccanus and Tachycines asynamorus, mixtures as such or a composition comprising at least Arachnoidea, such as arachnids, e.g. of the families Ar- 45 one compound I and one compound II prophylactically gasidae, Ixodidaeand Sarcoptidae, such as Amblyomma either at or before planting or transplanting. americanum, Amblyomma variegatum, Argas persicus, [0046] Suitable targets for seed treatment are various Boophilus annulatus, Boophilus decoloratus, Boophilus crop seeds, fruit species, vegetables, spices and orna- microplus, Dermacentor silvarum, Hyalomma truncatum, mental seed, for example corn/maize (sweet and field), Ixodes ricinus, Ixodes rubicundus, Ornithodorus mouba- 50 durum wheat, soybean, wheat, barley, oats, rye, triticale, ta, Otobius megnini, Dermanyssus gallinae, Psoroptes bananas, rice, cotton, sunflower, potatoes, pasture, al- ovis, Rhipicephalus appendiculatus, Rhipicephalus falfa, grasses, turf, sorghum, rapeseed, Brassica spp., evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as sugar beet, eggplants, tomato, lettuce, iceberg lettuce, Aculus schlechtendali, Phyllocoptrata oleivora and Erio- pepper, cucumber, squash, melon, bean, dry-beans, phyes sheldoni; Tarsonemidae spp. such as Phytone- 55 peas, leek, garlic, onion, cabbage, carrot, tuber such as mus pallidus and Polyphagotarsonemus latus; Tenui- sugar cane, tobacco, coffee, turf and forage, cruciferous, palpidae spp. such as Brevipalpus phoenicis; Tetrany- cucurbits, grapevines, pepper, fodder beet, oil seed rape, chidae spp. such as Tetranychus cinnabarinus, Tetran- pansy, impatiens, petunia and geranium.

9 17 EP 2 363 023 A1 18

[0047] The term seed treatment comprises all suitable 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701, seed treatment techniques known in the art, such as, but US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: not limited to, seed dressing, seed coating, seed dusting, Weed Control as a Science (J. Wiley & Sons, New York, seed soaking, seed film coating, seed multilayer coating, 1961), Hance et al.: Weed Control Handbook (8th Ed., seed encrusting, seed dripping, and seed pelleting. 5 Blackwell Scientific, Oxford, 1989) and Mollet, H. and [0048] The active ingredient mixtures according to the Grubemann, A.: Formulation technology (Wiley VCH invention are especially advantageous for seed treat- Verlag, Weinheim, 2001). ment of oil seed rape, wheat, corn, rye, barley, oats, sor- [0057] The agrochemical compositions may also com- ghum, sunflowers, rice, maize, turf and forage, sugar prise auxiliaries which are customary in agrochemical beet, beans, peas, soybeans, ornamentals, and vegeta- 10 compositions. The auxiliaries used depend on the par- bles such as cucurbits, tomatoes, eggplant, potatoes, ticular application form and active substance, respective- pepper, lettuce, cabbage, carrots, cruciferous. ly. [0049] Especially preferred is the seed treatment of oil [0058] Examples for suitable auxiliaries are solvents, seed rape, wheat, beans, corn, soybeans, sugar beet, solid carriers, dispersants or emulsifiers (such as further rice, vegetables, and ornamentals. 15 solubilizers, protective colloids, surfactants and adhe- [0050] The mixtures according to the invention are sion agents), organic and anorganic thickeners, bacteri- most preferably used for the seed treatment of oil seed cides, anti-freezing agents, anti-foaming agents, if ap- rape. propriate colorants and tackifiers or binders (e. g. for seed [0051] The invention also relates to agrochemical treatment formulations). compositions comprising a solvent or solid carrier and at 20 [0059] Suitable solvents are water, organic solvents least one compound I and one compound II and to the such as mineral oil fractions of medium to high boiling use for controlling harmful fungi. point, such as kerosene or diesel oil, furthermore coal [0052] An agrochemical composition comprises a fun- tar oils and oils of vegetable or animal origin, aliphatic, gicidally effective amount of a compound I and a of a cyclic and aromatic hydrocarbons, e. g. toluene, xylene, compound II. The term "effective amount" denotes an 25 paraffin, tetrahydronaphthalene, alkylated naphthalenes amount of the composition or of the compounds I and or their derivatives, alcohols such as methanol, ethanol, compounds II, which is sufficient for controlling harmful propanol, butanol and cyclohexanol, glycols, ketones fungi on cultivated plants or in the protection of materials such as cyclohexanone and gamma- butyrolactone, fatty and which does not result in a substantial damage to the acid dimethylamides, fatty acids and fatty acid esters and treated plants. Such an amount can vary in a broad range 30 strongly polar solvents, e. g. amines such as N-methyl- and is dependent on various factors, such as the fungal pyrrolidone. species to be controlled, the treated cultivated plant or [0060] Solid carriers are mineral earths such as sili- material, the climatic conditions and the specific mixture cates, silica gels, talc, kaolins, limestone, lime, chalk, used. bole, loess, clays, dolomite, diatomaceous earth, calcium [0053] The mixtures can be converted into customary 35 sulfate, magnesium sulfate, magnesium oxide, ground types of agrochemical compositions, e. g. solutions, synthetic materials, fertilizers, such as, e. g., ammonium emulsions, suspensions, dusts, powders, pastes and sulfate, ammonium phosphate, ammonium nitrate, ure- granules. The composition type depends on the particu- as, and products of vegetable origin, such as cereal meal, lar intended purpose; in each case, it should ensure a tree bark meal, wood meal and nutshell meal, cellulose fine and uniform distribution of the compound according 40 powders and other solid carriers. to the invention. [0061] Suitable surfactants (adjuvants, wtters, tackifi- [0054] Examples for composition types are suspen- ers, dispersants or emulsifiers) are alkali metal, alkaline sions (SC, OD, FS), emulsifiable concentrates (EC), earth metal and ammonium salts of aromatic sulfonic ac- emulsions (EW, EO, ES), pastes, pastilles, wettable pow- ids, such as ligninsoulfonic acid (Borresperse® types, ders or dusts (WP, SP, SS, WS, DP, DS) or granules 45 Borregard, Norway) phenolsulfonic acid, naphthale- (GR, FG, GG, MG), which can be water-soluble or wet- nesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), table, as well as gel formulations for the treatment of plant dibutylnaphthalenesulfonic acid (Nekal® types, BASF, propagation materials such as seeds (GF). Germany),and fatty acids, alkylsulfonates, alkylarylsul- [0055] Usually the composition types (e. g. SC, OD, fonates, alkyl sulfates, laurylether sulfates, fatty alcohol FS, EC, WG, SG, WP, SP, SS, WS, GF) are employed 50 sulfates, and sulfated hexa-, hepta- and octadecan- diluted. Composition types such as DP, DS, GR, FG, GG olates, sulfated fatty alcohol glycol ethers, furthermore and MG are usually used undiluted. condensates of naphthalene or of naphthalenesulfonic [0056] The compositions are prepared in a known acid with phenol and formaldehyde, polyoxy-ethylene oc- manner (cf. US 3,060,084, EP- A 707 445 (for liquid con- tylphenyl ether, ethoxylated isooctylphenol, octylphenol, centrates), Browning: " Agglomeration" , Chemical Engi- 55 nonylphenol, alkylphenyl polyglycol ethers, tributylphe- neering, Dec. 4, 1967, 147-48, Perry’ s Chemical Engi- nyl polyglycol ether, tristearylphenyl polyglycol ether, neer’ s Handbook, 4th Ed., McGraw- Hill, New York, 1963, alkylaryl polyether alcohols, alcohol and fatty alcohol/ eth- S. 8-57 und ff. WO 91/13546, US 4,172,714, US ylene oxide condensates, ethoxylated castor oil, polyox-

10 19 EP 2 363 023 A1 20 yethylene alkyl ethers, ethoxylated polyoxypropylene, ground synthetic materials, fertilizers, such as, e. g., am- lauryl alcohol polyglycol ether acetal, sorbitol esters, monium sulfate, ammonium phosphate, ammonium ni- lignin-sulfite waste liquors and proteins, denatured pro- trate, ureas, and products of vegetable origin, such as teins, polysaccharides (e. g. methylcellulose), hydropho- cereal meal, tree bark meal, wood meal and nutshell bically modified starches, polyvinyl alcohols (Mowiol® 5 meal, cellulose powders and other solid carriers. types, Clariant, Switzerland), polycarboxylates (Soko- Examples for composition types are: lan® types, BASF, Germany), polyalkoxylates, polyvi- nylamines (Lupasol® types, BASF, Germany), polyvi- 1. Composition types for dilution with water nylpyrrolidone and the copolymers therof. [0062] Examples for thickeners (i. e. compounds that 10 i) Water-soluble concentrates (SL, LS) impart a modified flowability to compositions, i. e. high 10 parts by weight of a mixture according to the viscosity under static conditions and low viscosity during invention are dissolved in 90 parts by weight of agitation) are polysaccharides and organic and anorgan- water or in a water-soluble solvent. As an alter- ic clays such as Xanthan gum (Kelzan®, CP Kelco, native, wetting agents or other auxiliaries are U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum®15 added. The active substances dissolve upon di- (R.T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., lution with water. In this way, a composition hav- NJ, USA). ing a content of 10% by weight of active sub- [0063] Bactericides may be added for preservation stance is obtained. and stabilization of the composition. Examples for suita- ii) Dispersible concentrates (DC) ble bactericides are those based on dichlorophene and 20 20 parts by weight of a mixture according to the benzylalcohol hemi formal (Proxel® from ICI or Acticide® invention are dissolved in 70 parts by weight of RS from Thor Chemie and Kathon® MK from Rohm & cyclohexanone with addition of 10 parts by Haas) and isothiazolinone derivatives such as alkyliso- weight of a dispersant, e. g. polyvinylpyrro- thiazolinones and benzisothiazolinones (Acticide® MBS lidone. Dilution with water gives a dispersion. from Thor Chemie). 25 The active substances content is 20% by weight. [0064] Examples for suitable anti-freezing agents are iii) Emulsifiable concentrates (EC) ethylene glycol, propylene glycol, urea and glycerin. 15 parts by weight of a mixture according to the [0065] Examples for anti-foaming agents are silicone invention are dissolved in 75 parts by weight of emulsions (such as e. g. Silikon® SRE, Wacker, Germa- xylene with addition of calcium dodecylbenze- ny or Rhodorsil®, Rhodia, France), long chain alcohols, 30 nesulfonate and castor oil ethoxylate (in each fatty acids, salts of fatty acids, fluoroorganic compounds case 5 parts by weight). Dilution with water gives and mixtures thereof. an emulsion. The composition has an active [0066] Suitable colorants are pigments of low water substance content of 15% by weight. solubility and water-soluble dyes. Examples to be men- iv)Emulsions (EW, EO, ES) tioned und the designations rhodamin B, C. I. pigment 35 25 parts by weight of a mixture according to the red 112, C. I. solvent red 1, pigment blue 15:4, pigment invention are dissolved in 35 parts by weight of blue 15:3, pigment blue 15: 2, pigment blue 15:1, pigment xylene with addition of calcium dodecylbenze- blue 80, pigment yellow 1, pigment yellow 13, pigment nesulfonate and castor oil ethoxylate (in each red 112, pigment red 48:2, pigment red 48:1, pigment case 5 parts by weight). This mixture is intro- red 57:1, pigment red 53: 1, pigment orange 43, pigment 40 duced into 30 parts by weight of water by means orange 34, pigment orange 5, pigment green 36, pigment of an emulsifying machine (Ultraturrax) and green 7, pigment white 6, pigment brown 25, basic violet made into a homogeneous emulsion. Dilution 10, basic violet 49, acid red 51, acid red 52, acid red 14, with water gives an emulsion. The composition acid blue 9, acid yellow 23, basic red 10, basic red 108. has an active substance content of 25% by [0067] Examples for tackifiers or binders are polyvi- 45 weight. nylpyrrolidons, polyvinylacetates, polyvinyl alcohols and v) Suspensions (SC, OD, FS) cellulose ethers (Tylose®, Shin-Etsu, Japan). In an agitated ball mill, 20 parts by weight of a [0068] Powders, materials for spreading and dusts can mixture according to the invention are commi- be prepared by mixing or concomitantly grinding the com- nuted with addition of 10 parts by weight of dis- pounds I and, if appropriate, further active substances, 50 persants and wetting agents and 70 parts by with at least one solid carrier. weight of water or an organic solvent to give a [0069] Granules, e. g. coated granules, impregnated fine active substance suspension. Dilution with granules and homogeneous granules, can be prepared water gives a stable suspension of the active by binding the active substances to solid carriers. Exam- substance. The active substance content in the ples of solid carriers are mineral earths such as silica 55 composition is 20% by weight. gels, silicates, talc, kaolin, attaclay, limestone, lime, vi)Water-dispersible granules and water-solu- chalk, bole, loess, clay, dolomite, diatomaceous earth, ble granules (WG, SG) calcium sulfate, magnesium sulfate, magnesium oxide, 50 parts by weight of a mixture according to the

11 21 EP 2 363 023 A1 22

invention are ground finely with addition of 50 100% (according to NMR spectrum). parts by weight of dispersants and wetting [0071] Water-soluble concentrates (LS), flowable con- agents and prepared as water- dispersibleor wa- centrates (FS), powders for dry treatment (DS), water- ter-soluble granules by means of technical ap- dispersible powders for slurry treatment (WS), water- sol- pliances (e. g. extrusion, spray tower, fluidized 5 uble powders (SS), emulsions (ES) emulsifiable concen- bed). Dilution with water gives a stable disper- trates (EC) and gels (GF) are usually employed for the sion or solution of the active substance. The purposes of treatment of plant propagation materials, composition has an active substance content of particularly seeds. These compositions can be applied 50% by weight. to plant propagation materials, particularly seeds, diluted vii) Water-dispersible powders and water-solu- 10 or undiluted. The compositions in question give, after ble powders (WP, SP, SS, WS) two-to-tenfold dilution, active substance concentrations 75 parts by weight of a mixture according to the of from 0.01 to 60% by weight, preferably from 0.1 to 40% invention are ground in a rotor-stator mill with by weight, in the ready-to-use preparations. Application addition of 25 parts by weight of dispersants, can be carried out before or during sowing. Methods for wetting agents and silica gel. Dilution with water 15 applying or treating agrochemical compounds and com- gives a stable dispersion or solution of the active positions thereof, respectively, on to plant propagation substance. The active substance content of the material, especially seeds, are known in the art, and in- composition is 75% by weight. clude dressing, coating, pelleting, dusting, soaking and viii) Gel (GF) in-furrow application methods of the propagation mate- In an agitated ball mill, 20 parts by weight of a 20 rial. In a preferred embodiment, the compounds or the mixture according to the invention are commi- compositions thereof, respectively, are applied on to the nuted with addition of 10 parts by weight of dis- plant propagation material by a method such that germi- persants, 1 part by weight of a gelling agent wet- nation is not induced, e. g. by seed dressing, pelleting, ters and 70 parts by weight of water or of an coating and dusting. organic solvent to give a fine suspension of the 25 [0072] In a preferred embodiment, a suspension- type active substance. Dilution with water gives a sta- (FS) composition is used for seed treatment. Typcially, ble suspension of the active substance, where- a FS composition may comprise 1-800 g/I of active sub- by a composition with 20% (w/w) of active sub- stances, 1-200 g/I surfactant, 0 to 200 g/I antifreezing stance is obtained. agent, 0 to 400 g/I of binder, 0 to 200 g/I of a pigment 30 and up to 1 liter of a solvent, preferably water. 2. Composition types to be applied undiluted [0073] The active substances can be used as such or in the form of their compositions, e. g. in the form of di- ix)Dustable powders (DP, DS) rectly sprayable solutions, powders, suspensions, dis- 5 parts by weight of a mixture according to the persions, emulsions, oil dispersions, pastes, dustable invention are ground finely and mixed intimately 35 products, materials for spreading, or granules, by means with 95 parts by weight of finely divided kaolin. of spraying, atomizing, dusting, spreading, brushing, im- This gives a dustable composition having an ac- mersing or pouring. The application forms depend en- tive substance content of 5% by weight. tirely on the intended purposes; it is intended to ensure x) Granules (GR, FG, GG, MG) in each case the finest possible distribution of the active 0.5 parts by weight of a mixture according to the 40 substances according to the invention. invention is ground finely and associated with [0074] Aqueous application forms can be prepared 99.5 parts by weight of carriers. Current meth- from emulsion concentrates, pastes or wettable powders ods are extrusion, spray-drying or the fluidized (sprayable powders, oil dispersions) by adding water. To bed. This gives granules to be applied undiluted prepare emulsions, pastes or oil dispersions, the sub- having an active substance content of 0.5% by 45 stances, as such or dissolved in an oil or solvent, can be weight. homogenized in water by means of a wetter, tackifier, xi)ULV solutions (UL) dispersant or emulsifier. Alternatively, it is possible to pre- 10 parts by weight of a mixture according to the pare concentrates composed of active substance, wet- invention are dissolved in 90 parts by weight of ter, tackifier, dispersant or emulsifier and, if appropriate, an organic solvent, e. g. xylene. This gives a 50 solvent or oil, and such concentrates are suitable for di- composition to be applied undiluted having an lution with water. active substance content of 10% by weight. [0075] The active substance concentrations in the ready-to-use preparations can be varied within relatively [0070] The agrochemical compositions generally com- wide ranges. In general, they are from 0.0001 to 10%, prise between 0.01 and 95%, preferably between 0.1 and 55 preferably from 0.001 to 1 % by weight of active sub- 90%, most preferably between 0.5 and 90%, by weight stance. ofactive substance. The active substances are employed [0076] The active substances may also be used suc- in a purity of from 90% to 100%, preferably from 95% to cessfully in the ultra-low-volume process (ULV), it being

12 23 EP 2 363 023 A1 24 possible to apply compositions comprising over 95% by [0083] In the binary mixtures, i.e. compositions accord- weight of active substance, or even to apply the active ing to the invention comprising one compound I (compo- substance without additives. nent 1) and one compound II (component 2), the weight [0077] When employed in plant protection, the ratio of component 1 and component 2 generally de- amounts of active substances applied are, depending on 5 pends from the properties of the active substances used, the kind of effect desired, from 0.001 to 2 kg per ha, pref- generally it is in the range of from 1:500 to 500:1, usually erably from 0.005 to 2 kg per ha, more preferably from it is in the range of from 1:100 to 100:1, regularly in the 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per range of from 1: 50 to 50:1, preferably in the range of from ha. 1:20 to 20:1, more preferably in the range of from 1:10 [0078] In treatment of plant propagation materials such 10 to 10:1 and in particular in the range of from 1:3 to 3:1. as seeds, e. g. by dusting, coating or drenching seed, [0084] The compositions according to the invention amounts of active substance of from 0.1 to 1000 g, pref- can, in the use form as fungicides or insecticides, also erably from 1 to 1000 g, more preferably from 1 to 100 g be present together with further active substances (ter- and most preferably from 5 to 100 g, per 100 kilogram of nary mixtures), e. g. with herbicides, insecticides, growth plant propagation material (preferably seed) are gener- 15 regulators, fungicides or else with fertilizers, as pre-mix ally required. or, if appropriate, not until immeadiately prior to use (tank [0079] When used in the protection of materials or mix). stored products, the amount of active substance applied [0085] Mixing the binary mixtures according to the in- depends on the kind of application area and on the de- vention or the compositions comprising them in the use sired effect. Amounts customarily applied in the protec- 20 form as fungicides with other fungicides results in many tion of materials are, e. g., 0.001 g to 2 kg, preferably cases in an expansion of the fungicidal spectrum of ac- 0.005 g to 1 kg, of active substance per cubic meter of tivity being obtained or in a prevention of fungicide re- treated material. sistance development. Furthermore, in many cases, syn- [0080] Various types of oils, wetters, adjuvants, herbi- ergistic effects are obtained. cides, bactericides, other fungicides and/or pesticides 25 [0086] The following list of active substances, in con- may be added to the active substances or the composi- junction with which the binary mixtures according to the tions comprising them, if appropriate not until immediate- invention can be used, is intended to illustrate the pos- ly prior to use (tank mix). These agents can be admixed sible combinations but does not limit them: with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1. 30 A) strobilurins [0081] Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S - azoxystrobin, coumethoxystrobin, coumoxys- 240®; alcohol alkoxylates such as Atplus 245®, Atplus trobin, dimoxystrobin, enestroburin, fluoxas- MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; trobin, kresoxim-methyl, metominostrobin, EO/PO block polymers, e. g. Pluronic RPE 2035® and 35 orysastrobin, picoxystrobin, pyraclostrobin, Genapol B®; alcohol ethoxylates such as Lutensol XP pyrametostrobin, pyraoxystrobin, pyribencarb, 80®; and dioctyl sulfosuccinate sodium such as Leophen trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxyme- RA®. thyl)-phenyl]-3-methoxy-acrylic acid methyl es- [0082] According to this invention, applying the com- ter and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl- pounds I together with at least one compound II is to be 40 allylideneaminooxymethyl)-phenyl)-2-methox- understood to denote, that at least one compound I and yimino-N-methyl-acetamide; at least one compound II occur simultaneously at the site of action (i.e. the harmful fungi, insects or other pests to B) carboxamides be controlled or their habitats such as infected plants, plant propagation materials, particularly seeds, surfaces, 45 - carboxanilides: benalaxyl, benalaxyl-M, beno- materials or the soil as well as plants, plant propagation danil, bixafen, boscalid, carboxin, fenfuram, fen- materials, particularly seeds, soil, surfaces, materials or hexamid, flutolanil, fluxapyroxad, furametpyr, rooms to be protected from fungal attack) in a fungicidally isopyrazam, isotianil, kiralaxyl, mepronil, meta- and/or insecticidally effective amount. This can be ob- laxyl, metalaxyl-M (mefenoxam), ofurace, oxa- tained by applying the compounds I and at least one com- 50 dixyl, oxycarboxin, penflufen, penthiopyrad, poundnd II simultaneously, either jointly (e. g. as tank- sedaxane, tecloftalam, thifluzamide, tiadinil, 2- mix) or sperately, or in succession, wherein the time in- amino-4-methyl-thiazole-5-carboxanilide, terval between the individual applications is selected to N-(4’-trifluoromethylthiobiphenyl-2-yl)-3-dif- ensure that the active substance applied first still occurs luoromethyl-1-methyl-1H-pyrazole-4-carboxa- at the site of action in a sufficient amount at the time of 55 mide and N-(2-(1,3,3-trimethylbutyl)-phenyl)- application of the further active substance(s). The order 1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxa- of application is not essential for working of the present mide; invention. - carboxylic morpholides: dimethomorph, flumor-

13 25 EP 2 363 023 A1 26

ph, pyrimorph; yl)-2-methyl-1H-benzoimidazole and 5-chloro- - benzoic acid amides: flumetover, fluopicolide, 7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophe- fluopyram, zoxamide; nyl)-[1,2,4]triazolo-[1,5-a]pyrimidine; - other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthiofarm and 5 E) N-(6-methoxy-pyridin-3-yl) cyclopropanecar- boxylic acid amide; - thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, C) azoles propineb, thiram, zineb, ziram; 10 - carbamates: benthiavalicarb, diethofencarb, - triazoles: azaconazole, bitertanol, bromucona- iprovalicarb, propamocarb, propamocarb hy- zole, cyproconazole, difenoconazole, dinicona- drochlorid, valifenalate and N-(1-(1-(4-cyano- zole, diniconazole-M, epoxiconazole, fenbuco- phenyl)ethanesulfonyl)-but-2-yl) carbamic ac- nazole, fluquinconazole, flusilazole, flutriafol, id-(4-fluorophenyl) ester; hexaconazole, imibenconazole, ipconazole,15 metconazole, myclobutanil, oxpoconazole, pa- F) other active substances clobutrazole, penconazole, propiconazole, pro- thioconazole, simeconazole, tebuconazole, tet- - guanidines: guanidine, dodine, dodine free raconazole, triadimefon, triadimenol, triticona- base, guazatine, guazatine-acetate, iminocta- zole, uniconazole; 20 dine, iminoctadine-triacetate, iminoctadine-tris - imidazoles: cyazofamid, imazalil, pefurazoate, (albesilate); prochloraz, triflumizol; - antibiotics: kasugamycin, kasugamycin hydro- - benzimidazoles: benomyl, carbendazim, fuberi- chloride-hydrate, streptomycin, polyoxine, vali- dazole, thiabendazole; damycin A; - others: ethaboxam, etridiazole, hymexazole25 - nitrophenyl derivates: binapacryl, dinobuton, di- and 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy- nocap, nitrthal-isopropyl, tecnazen, organomet- phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-aceta- al compounds: fentin salts, such as fentin-ace- mide; tate, fentin chloride or fentin hydroxide; - sulfur-containing heterocyclyl compounds: dithi- D) heterocyclic compounds 30 anon, isoprothiolane; - organophosphorus compounds: edifenphos, fo- - pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro- setyl, fosetyl-aluminum, iprobenfos, phospho- phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyrid- rous acid and its salts, pyrazophos, tolclofos- ine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxa- methyl; zolidin-3-yl]-pyridine; 35 - organochlorine compounds: chlorothalonil, - pyrimidines: bupirimate, cyprodinil, diflume- dichlofluanid, dichlorophen, flusulfamide, hex- torim, fenarimol, ferimzone, mepanipyrim, ni- achlorobenzene, pencycuron, pentachlorphe- trapyrin, nuarimol, pyrimethanil; nole and its salts, phthalide, quintozene, thi- - piperazines: triforine; ophanate-methyl, tolylfluanid, N-(4-chloro-2-ni- - pyrroles: fenpiclonil, fludioxonil; 40 tro-phenyl)-N-ethyl-4-methylbenzenesulfona- - morpholines: aldimorph, dodemorph, dode- mide; morph-acetate, fenpropimorph, tridemorph; - inorganic active substances: Bordeaux mixture, - piperidines: fenpropidin; copper acetate, copper hydroxide, copper oxy- - dicarboximides: fluoroimid, iprodione, procymi- chloride, basic copper sulfate, sulfur; done, vinclozolin; 45 - antifungal biocontrol agents, plant bioactivators: - non-aromatic 5-membered heterocycles: fa- Ampelomyces quisqualis (e.g. AQ 10® from In- moxadone, fenamidone, flutianil, octhilinone, trachem Bio GmbH & Co. KG, Germany), As- probenazole, 5-amino-2-isopropyl-3-oxo-4-or- pergillus flavus (e.g. AFLA- GUARD® from Syn- tho-tolyl-2,3-dihydro-pyrazole-1-carbothioic ac- genta, CH), Aureobasidium pullulans (e.g. BO- id S-allyl ester; 50 TECTOR® from bioferm GmbH, Germany), Ba- - others: acibenzolar-S-methyl, ametoctradin, cillus pumilius (e.g. isolate NRRL-Nr. B-21661 amisulbrom, anilazin, blasticidin-S, captafol, in RHAP-SODY®, SERENADE® MAX and captan, chinomethionat, dazomet, debacarb, di- SERENADE® ASO from Fa. AgraQuest Inc., clomezine, difenzoquat, difenzoquat- methylsul- USA), Bacillus subtilis var. amyloliquefaciens fate, fenoxanil, Folpet, oxolinic acid, piperalin, 55 FZB24 (e.g. TAEGRO® from Novozyme Biolog- proquinazid, pyroquilon, quinoxyfen, triazoxide, icals, Inc., USA), Candida oleophila 1-82 (e.g. tricyclazole, 2-butoxy-6-iodo-3-propylchromen- ASPIRE® from Ecogen Inc., USA), Candida sai- 4-one, 5-chloro-1-(4,6-dimethoxy-pyrimidin-2- toana (e.g. BIOCURE® (in mixture with lys-

14 27 EP 2 363 023 A1 28

ozyme) and BIOCOAT® from Micro Flo Com- omethylphenoxy)-2,5-dimethyl-phenyl)-N- pany, USA (BASF SE) and Arysta), Chitosan ethyl-N-methyl formamidine, N’-(2-methyl-5-tri- (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), fluoromethyl-4-(3-trimethylsilanyl-pro- Clonostachys rosea f. catenulata, also named poxy)-phenyl)-N-ethyl-N-methyl formamidine, Gliocladium catenulatum (e.g. isolate J1446: 5 N’-(5-difluoromethyl-2-methyl-4-(3-trimethylsi- PRESTOP® from Verdera, Finland), Coniothy- lanyl-propoxy)-phenyl)-N-ethyl-N-methyl form- rium minitans (e.g. CONTANS® from Prophyta, amidine, Germany), Cryphonectria parasitica (e.g. Endo- 2 -{1-[2 -(5-methyl-3-trifluoromethyl-pyrazole-1- thia parasitica from CNICM, France), Crypto- yl)-acetyl]-piperidin-4-yl}-thiazole-4-carboxylic coccus albidus (e.g. YIELD PLUS® from Anchor 10 acid methyl-(1,2,3,4-tetrahydro-naphthalen-1- Bio-Technologies, South Africa), Fusarium ox- yl)-amide, 2-{1-[2-(5-methyl-3-trifluoromethyl- ysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole- FUSACLEAN® from Natural Plant Protection, 4-carboxylic acid methyl-(R)-1,2,3,4-tetrahy- France), Metschnikowia fructicola (e.g. SHEM- dro-naphthalen-1-yl-amide, methoxy-acetic ac- ER® from Agrogreen, Israel), Microdochium15 id 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4- dimerum (e.g. ANTIBOT® from Agrauxine, yl ester and N-Methyl-2-{1-[(5-methyl-3-trifluor- France), Phlebiopsis gigantea (e.g. ROTSOP® omethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4- from Verdera, Finland), Pseudozyma flocculosa yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]- (e.g. SPORODEX® from Plant Products Co. 4-thiazolecarboxamide. Ltd., Canada), Pythium oligandrum DV74 (e.g. 20 POLYVERSUM® from Remeslo SSRO, Biopre- G) growth regulators paraty, Czech Rep.), Reynoutria sachlinensis abscisic acid, amidochlor, ancymidol, 6-benzylami- (e.g. REGALIA® from Marrone Biolnnovations, nopurine, brassinolide, butralin, chlormequat (chlo- USA), Talaromyces flavus V117b (e.g. PRO- rmequat chloride), choline chloride, cyclanilide, TUS® from Prophyta, Germany), Trichoderma 25 daminozide, dikegulac, dimethipin, 2,6-dimethylpu- asperellum SKT-1 (e.g. ECO-HOPE® from Ku- ridine, ethephon, flumetralin, flurprimidol, fluthiacet, miai Chemical Industry Co., Ltd., Japan), T. atro- forchlorfenuron, gibberellic acid, inabenfide, indole- viride LC52 (e.g. SENTINEL® from Agrimm 3-acetic acid , maleic hydrazide, mefluidide, mepi- Technologies Ltd, NZ), T. harzianum T-22 (e.g. quat (mepiquat chloride), naphthaleneacetic acid, N- PLANTSHIELD® der Firma BioWorks Inc.,30 6-benzyladenine, paclobutrazol, prohexadione (pro- USA), T. harzianum TH 35 (e.g. ROOT PRO® hexadione-calcium), prohydrojasmon, thidiazuron, from Mycontrol Ltd., Israel), T. harzianum T-39 triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri- (e.g. TRICHODEX® and TRICHODERMA iodobenzoic acid , trinexapac-ethyl and unicona- 2000® from Mycontrol Ltd., Israel and Ma- zole; khteshim Ltd., Israel), T. harzianum and T. viride 35 H) herbicides (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ICC012 and T. viride - acetamides: acetochlor, alachlor, butachlor, ICC080 (e.g. REMEDIER® WP from Isagro dimethachlor, dimethenamid, flufenacet, Ricerca, Italy), T. polysporum and T. harzianum mefenacet, metolachlor, metazachlor, napropa- (e.g. BINAB® from BINAB Bio-Innovation AB, 40 mide, naproanilide, pethoxamid, pretilachlor, Sweden), T. stromaticum (e.g. TRICOVAB® propachlor, thenylchlor; from C.E.P.L.A.C., Brazil), T. virens GL- 21 (e.g. - amino acid derivatives: bilanafos, glyphosate, SOILGARD® from Certis LLC, USA), T. viride glufosinate, sulfosate; (e.g. TRIECO® from Ecosense Labs. (India) - aryloxyphenoxypropionates: clodinafop, cy- Pvt. Ltd., Indien, BIO-CURE® F from T. Stanes 45 halofop-butyl, fenoxaprop, fluazifop, haloxyfop, & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride metamifop, propaquizafop, quizalofop, quizalo- TV1 from Agribiotec srl, Italy), Ulocladium oude- fop-P-tefuryl; mansii HRU3 (e.g. BOTRY-ZEN® from Botry- - Bipyridyls: diquat, paraquat; Zen Ltd, NZ); - (thio)carbamates: asulam, butylate, carbeta- - others: biphenyl, bronopol, cyflufenamid, cy-50 mide, desmedipham, dimepiperate, eptam moxanil, diphenylamin, metrafenone, pyri- (EPTC), esprocarb, molinate, orbencarb, phen- ofenone, mildiomycin, oxin-copper, prohexadi- medipham, prosulfocarb, pyributicarb, thioben- one-calcium, spiroxamine, tebufloquin, tolylflu- carb, triallate; anid, N-(cyclopropylmethoxyimino-(6-difluoro- - cyclohexanediones: butroxydim, clethodim, cy- methoxy-2,3-difluorophenyl)-methyl)-2-phenyl 55 cloxydim, profoxydim, sethoxydim, tepraloxy- acetamide, N’-(4-(4-chloro-3-trifluoromethyl- dim, tralkoxydim; phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-me- - dinitroanilines: benfluralin, ethalfluralin, oryzal- thyl formamidine, N’-(4-(4-fluoro-3-trifluor- in, pendimethalin, prodiamine, trifluralin;

15 29 EP 2 363 023 A1 30

- diphenyl ethers: acifluorfen, aclonifen, bifenox, pentoxazone, pinoxaden, pyraclonil, pyraflufen- diclofop, ethoxyfen, fomesafen, lactofen, oxy- ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, fluorfen; quinoclamine, saflufenacil, sulcotrione, sulfen- - hydroxybenzonitriles: bomoxynil, dichlobenil, trazone, terbacil, tefuryltrione, tembotrione, ioxynil; 5 thiencarbazone, topramezone, (3-[2-chloro-4- - imidazolinones: imazamethabenz, imazamox, fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl- imazapic, imazapyr, imazaquin, imazethapyr; 3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyrid- - phenoxy acetic acids: clomeprop, 2,4-dichlo- in-2-yloxy)-acetic acid ethyl ester, 6-amino-5- rophenoxyacetic acid (2,4-D), 2,4-DB, dichlor- chloro-2-cyclopropyl-pyrimidine-4-carboxylic prop, MCPA, MCPA-thioethyl, MCPB, Meco- 10 acid methyl ester, 6-chloro-3-(2-cyclopropyl-6- prop; methyl-phenoxy)-pyridazin-4-ol, 4-amino-3- - pyrazines: chloridazon, flufenpyr-ethyl, fluthiac- chloro-6-(4-chloro-phenyl)-5-fluoropyridine-2- et, norflurazon, pyridate; carboxylic acid, 4-amino-3-chloro-6-(4-chloro- - pyridines: aminopyralid, clopyralid, diflufenican, 2-fluoro-3-methoxyphenyl)-pyridine-2-carboxy- dithiopyr, fluridone, fluroxypyr, picloram, picol- 15 lic acid methyl ester, and 4- amino-3-chloro-6-(4- inafen, thiazopyr; chloro-3-dimethylamino-2-fluoro-phenyl)-pyrid- - sulfonyl ureas: amidosulfuron, azimsulfuron, ine-2-carboxylic acid methyl ester. bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, I) insecticides flazasulfuron, flucetosulfuron, flupyrsulfuron, fo- 20 ramsulfuron, halosulfuron, imazosulfuron, iodo- - organo(thio)phosphates: acephate, azame- sulfuron, mesosulfuron, metazosulfuron, met- thiphos, azinphos-methyl, chlorpyrifos, chlorpy- sulfuron-methyl, nicosulfuron, oxasulfuron, rifos-methyl, chlorfenvinphos, diazinon, dichlo- primisulfuron, prosulfuron, pyrazosulfuron, rim- rvos, , dimethoate, disulfoton, sulfuron, sulfometuron, sulfosulfuron, thifensul- 25 ethion, fenitrothion, , isoxathion, furon, triasulfuron, tribenuron, trifloxysulfuron, malathion, methamidophos, methidathion, me- triflusulfuron, tritosulfuron, 1-((2-chloro-6-pro- thyl-parathion, mevinphos, monocrotophos, ox- pyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)- ydemeton-methyl, , parathion, ph- 3-(4,6-dimethoxy-pyrimidin-2-yl)urea; enthoate, phosalone, phosmet, phosphamidon, - triazines: ametryn, atrazine, cyanazine, dimeth- 30 phorate, phoxim, pirimiphos-methyl, profeno- ametryn, ethiozin, hexazinone, metamitron, fos, prothiofos, sulprophos, , metribuzin, prometryn, simazine, terbuthyla- terbufos, triazophos, trichlorfon; zine, terbutryn, triaziflam; - carbamates: alanycarb, aldicarb, bendiocarb, - ureas: chlorotoluron, daimuron, diuron, benfuracarb, carbaryl, carbofuran, carbosulfan, fluometuron, isoproturon, linuron, methabenz- 35 fenoxycarb, furathiocarb, methiocarb, meth- thiazuron,tebuthiuron; omyl, oxamyl, pirimicarb, propoxur, thiodicarb, - other acetolactate synthase inhibitors: bispyrib- triazamate; ac-sodium, cloransulam-methyl, diclosulam, flo- - : allethrin, bifenthrin, cyfluthrin, cy- rasulam, flucarbazone, flumetsulam, metosu- halothrin, cyphenothrin, cypermethrin, alpha- lam, ortho-sulfamuron, penoxsulam, propoxy- 40 cypermethrin, beta-cypermethrin, zeta-cyper- carbazone, pyribambenz-propyl, pyribenzoxim, methrin, deltamethrin, , etofen- pyriftalid, pyriminobac-methyl, pyrimisulfan, py- prox, , fenvalerate, imiprothrin, rithiobac, pyroxasulfone, pyroxsulam; lambda-cyhalothrin, permethrin, , py- - others: amicarbazone, aminotriazole, anilofos, rethrin I and II, resmethrin, , tau-flu- beflubutamid, benazolin, bencarbazone,ben- 45 valinate, tefluthrin, tetramethrin, tralomethrin, fluresate, benzofenap, bentazone, benzobicy- , profluthrin, dimefluthrin; clon, bicyclopyrone, bromacil, bromobutide, - insect growth regulators: a) chitin synthesis in- butafenacil, butamifos, cafenstrole, carfentra- hibitors: : chlorfluazuron, zone, cinidon-ethlyl, chlorthal, cinmethylin, clo- cyramazin, , flucycloxuron, mazone, cumyluron, cyprosulfamide, dicamba, 50 flufenoxuron, hexaflumuron, lufenuron, no- difenzoquat, diflufenzopyr, Drechslera valuron, teflubenzuron, triflumuron; buprofezin, monoceras, endothal, ethofumesate, etobenza- diofenolan, hexythiazox, etoxazole, clofen- nid, fenoxasulfone, fentrazamide, flumiclorac- tazine; b) ecdysone antagonists: halofenozide, pentyl, flumioxazin, flupoxam, flurochloridone, methoxyfenozide, tebufenozide, azadirachtin; flurtamone, indanofan, isoxaben, isoxaflutole, 55 c) juvenoids: , , fenox- lenacil, propanil, propyzamide, quinclorac, quin- ycarb; d) lipid biosynthesis inhibitors: spirodi- merac, mesotrione, methyl arsonic acid, napta- clofen, spiromesifen, spirotetramat; lam, oxadiargyl, oxadiazon, oxaziclomefone, - nicotinic receptor agonists/antagonists com-

16 31 EP 2 363 023 A1 32

pounds: , , imidacloprid, vided in a kit, the components may already be combined , , , thia- together and as such are packaged in a single container cloprid, 1-(2-chloro-thiazol-5-ylmethyl)-2-nitrim- such as a vial, bottle, can, pouch, bag or canister. In other ino-3,5-dimethyl-[1,3,5]triazinane; embodiments, two or more components of a kit may be - GABA antagonist compounds: ,5 packaged separately, i. e., not preformulated. As such, ethiprole, fipronil, vaniliprole, pyrafluprole, py- kits may include one or more separate containers such riprole, 5-amino-1-(2,6-dichloro-4-methyl-phe- as vials, cans, bottles, pouches, bags or canisters, each nyl)-4-sulfinamoyl-1H-pyrazole-3-carbothioic container containing a separate component for an agro- acid amide; chemical composition. In both forms, a component of the - macrocyclic lactone insecticides: abamectin, 10 kit may be applied separately from or together with the emamectin, milbemectin, lepimectin, spinosad, further components or as a component of a combination spinetoram; composition according to the invention for preparing the - mitochondrial electron transport inhibitor (METI) composition according to the invention. I acaricides: fenazaquin, pyridaben, tebufen- [0090] The user applies the composition according to pyrad, tolfenpyrad, flufenerim; 15 the invention usually from a predosage device, a knap- - METI II and III compounds: acequinocyl, flua- sack sprayer, a spray tank or a spray plane. Here, the cyprim, hydramethylnon; agrochemical composition is made up with water and/or - Uncouplers: chlorfenapyr; buffer to the desired application concentration, it being - oxidative phosphorylation inhibitors: cyhexatin, possible, if appropriate, to add further auxiliaries, and the diafenthiuron, fenbutatin oxide, propargite; 20 ready-to-use spray liquor or the agrochemical composi- - moulting disruptor compounds: cryomazine; tion according to the invention is thus obtained. Usually, - mixed function oxidase inhibitors: piperonyl bu- 50 to 500 liters of the ready-to-use spray liquor are ap- toxide; plied per hectare of agricultural useful area, preferably - sodium channel blockers: indoxacarb, metaflu- 100 to 400 liters. mizone; 25 [0091] According to one embodiment, individual com- - others: benclothiaz, bifenazate, cartap, flonica- ponents of the composition according to the invention mid, pyridalyl, pymetrozine, sulfur, thiocyclam, such as parts of a kit or parts of a binary or ternary mixture , , cyazypyr may be mixed by the user himself in a spray tank and (HGW86), cyenopyrafen, flupyrazofos, cy- further auxiliaries may be added, if appropriate (tank flumetofen, amidoflumet, imicyafos, bistrifluron, 30 mix). and pyrifluquinazon. [0092] The fungicidal action of the mixtures according to the invention can be shown by the tests described [0087] In ternary mixtures, i.e. compositions according below. to the invention comprising one compound I (component [0093] The active compounds I and compoundsII, sep- 1) and a first further active substance (component 2) and 35 arately or jointly, are prepared as a stock solution com- a second further active substance (component 3), e. g. prising 25 mg of active compound which is made up to two active substances from groups A) to I), the weight 10 ml using a mixture of acetone and/or DMSO and the ratio of component 1 and component 2 depends from the emulsifier Uniperol® EL (wetting agent having an emul- properties of the active substances used, preferably it is sifying and dispersing action based on ethoxylated alkyl- in the range of from 1:50 to 50:1 and particularly in the 40 phenols) in a ratio by volume of solvent/ emulsifier of 99: range of from 1:10 to 10:1, and the weight ratio of com- 1. The mixture is then made up to 100 ml with water. This ponent 1 and component 3 preferably is in the range of stock solution is diluted with the solvent/ emulsifier/water from 1:50 to 50:1 and particularly in the range of from 1: mixture described to give the concentration of active 10 to 10:1. compound stated below. [0088] The components can be used individually or al- 45 [0094] The visually determined percentages of infect- ready partially or completely mixed with one another to ed leaf areas are converted into efficacies in % of the prepare the composition according to the invention. It is untreated control. also possible for them to be packaged and used further The efficacy (E) is calculated as follows using Abbot’s as combination composition such as a kit of parts. formula: [0089] In one embodiment of the invention, the kits 50 may include one or more, including all, components that may be used to prepare a subject agrochemical compo- sition. E. g., kits may include one or more fungicide com- ponent(s) and/or an adjuvant component and/or a insec- ticide component and/or a growth regulator component 55 α corresponds to the fungicidal infection of the treated and/or a herbicde. One or more of the components may plants in % and already be combined together or preformulated. In those β corresponds to the fungicidal infection of the un- embodiments where more than two components are pro- treated (control) plants in %

17 33 EP 2 363 023 A1 34

[0095] An efficacy of 0 means that the infection level from of the treated plants corresponds to that of the untreated bifenthrin, cypermethrin, alpha-cypermeth- control plants; an efficacy of 100 means that the treated rin, zeta- cypermethrin, deltamethrin, esfen- plants were not infected. valerate, etofenprox, lambda-cyhalothrin, [0096] The expected efficacies of active compound 5 permethrin, tefluthrin, beta-cyfluthrin, cy- combinations were determined using Colby’s formula fluthrin, acrinathrin, allethrin, cycloprothrin, (Colby, S.R. "Calculating synergistic and antagonistic re- cyhalothrin, cyphenothrin, beta-cypermeth- sponses of herbicide combinations", Weeds, 15, pp. rin, fenpropathrin, fenvalerate, flucythri- 20-22, 1967) and compared with the observed efficacies. nate, imiprothrin, prallethrin, and 10 II, resmethrin, si-lafluofen, tau-fluvalinate, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin, gamma-cyha- lothrin and theta-cypermethrin; C) insect growth regulators selected from E expected efficacy, expressed in % of the untreated 15 flufenoxuron, lufenuron, novaluron, bupro- control, when using the mixture of the active com- fezin, teflubenzuron, chlorfluazuron, pounds A and B at the concentrations a and b cyramazin, diflubenzuron, flucycloxuron, x efficacy, expressed in % of the untreated control, hexaflumuron, triflumuron, diofenolan, hex- when using the active compound A at the concen- ythiazox, etoxazole, clofentazine, methox- tration a 20 yfenozide, halofenozide, tebufenozide and y efficacy, expressed in % of the untreated control, azadirachtin; when using the active compound B at the concen- D) spinosyns selected from spinosad and tration b. spinetoran E) other insecticides selected from 25 abamectin, emamectin, milbemectin, lep- Claims imectin, chlorfenapyr, metaflumizone, in- doxacarb, pymetrozine, tebufenpyrad, pyri- 1. A mixture, comprising as active compounds daben, tolfenpyrad, fenazaquin, fenpyroxi- mate, pyrimidifen, flonicamid, hydramethyl- 1) at least one active compound I from the class 30 non, fenbutatin oxide, indoxacarb, acequi- of succinate dehydrogenase inhibitors selected nocyl, fluacyprim, cyhexatin, diafenthiuron, from propargite, benclothiaz, bifenazate, cartap, boscalid, mepronil, flutolanil, furametpyr and thi- pyridalyl, thiocyclam, cyenopyrafen, dico- fluzamide; fol, flupyrazofos, cyflumetofen, amid- and 35 oflumet, imicyafos, bistrifluron, iuquinazon, 2) at least one insecticidally active compound II pyrifluquinazon and 2,2-dimethyl-propionic selected from groups A) to E): acid- 2- cyano- 1-(2- methyl- 4- trifluorome- thyl- thiazol- 5- yl)- 2-(2- phenyl- thiazol- 4- A) acetylcholinesterase inhibitors selected yl)-vinyl ester; from 40 aldicarb, carbofuran, carbosulfan, meth- in a synergistically effective amount. omyl, alanycarb, bendiocarb, benfuracarb, carbaryl, ethiofencarb, fenoxycarb, furathi- 2. A mixture according to any of claims 1, comprising ocarb, methiocarb, oxamyl, pirimicarb, pro- a compound I and a compound II in a weight ratio of poxur, thiodicarb, triazamate, acephate,45 from 500:1 to 1:500. chlorpyrifos, dimethoate, malathion, meth- amidophos, profenofos, terbufos, azame- 3. A mixture according to claim 1 or 2, wherein com- thiphos, azinphos-methyl, cadusafos, chlo- pound I is boscalid. rfenvinphos, diazinon, dichlorvos, dicroto- phos, disulfoton, ethion, fenitrothion, fen- 50 4. A mixture according to any of claims 1 to 3, wherein thion, isoxathion, methidathion, methyl- par- compound II is selected from acephate, chlorpyrifos, athion, mevinphos, monocrotophos, oxy- dimethoate, methamidophos, terbufos, thiodicarb demeton-methyl, parathion, phenthoate, and methiocarb. phosalone, phorate, phosmet, phosphami- don, phoxim, pirimiphos- methyl, prothiofos, 55 5. A mixture according to any of claims 1 to 3, wherein tebupirimfos, tetrachlorvinphos, triazophos compound II is a compound of group B) selected and trichlorfon; from bifenthrin, cypermethrin, alpha-cypermethrin, B) sodium channel modulators selected zeta-cypermethrin, deltamethrin, esfen-valerate,

18 35 EP 2 363 023 A1 36

etofenprox, lambda-cyhalothrin, permethrin, te- fluthrin and beta-cyfluthrin.

6. A mixture according to claim 5, wherein compound II is selected from cypermethrin, alpha-cypermeth- 5 rin, zeta-cypermethrin, esfen-valerate, permethrin, tefluthrin and beta-cyfluthrin.

7. A mixture according to any of claims 1 to 3, wherein compound II is flufenoxuron. 10

8. A mixture according to any of claims 1 to 3, wherein compound II is a compound of group D) selected from spinosad and spinetoran. 15 9. A mixture according to any of claims 1 to 3, wherein compound II is a compound of group E) selected from abamectin, emamectin, milbemectin, lepimec- tin, chlorfenapyr, metaflumizone, indoxacarb, pymetrozine, tebufenpyrad, pyridaben, tolfenpyrad, 20 fenazaquin, fenbutatin oxide, hydramethylnon, flufenerium, pyrifluquinazon and compound of for- mula (I).

10. A mixture according to claim 9, wherein compound 25 II is selected from abamectin, emamectin, chlo- rfenapyr, metaflumizone and tebufenpyrad.

11. A mixture according to any of claims 1 to 10, com- prising at least two compounds II. 30

12. An agrochemical composition, comprising a solvent or solid carrier and a mixture according to any of claims 1 to 11. 35 13. Seed comprising the mixture according to any one of claims 1 to 11 or the composition according to claim 12 in an amount of from 1 g to 1000 g per 100 kg of seed. 40 14. 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 com- pound I and the compound II as defined in any one 45 of claims 1 to 11 or of the composition as defined in claim 12.

15. A method for improving plant health, comprising treating a plant, its propagation material, the locus 50 where the plant is growing or is to grow with an ef- fective amount of the compound I and the compound II as defined in any one of claims 1 to 11 or of the composition as defined in claim 12. 55

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• EP 0545099 A1 [0010] • EP 392225 A [0033] • WO 08095913 A [0011] • US 3060084 A [0056] • WO 0623899 A [0012] • EP 707445 A [0056] • WO 06089876 A [0012] • WO 9113546 A [0056] • WO 02015701 A [0032] • US 4172714 A [0056] • EP 374753 A [0032] • US 4144050 A [0056] • WO 93007278 A [0032] • US 3920442 A [0056] • WO 9534656 A [0032] • US 5180587 A [0056] • EP 427529 A [0032] • US 5232701 A [0056] • EP 451878 A [0032] • US 5208030 A [0056] • WO 0318810 A [0032] • GB 2095558 A [0056] • WO 0352073 A [0032] • US 3299566 A [0056] • WO 03018810 A [0032]

Non-patent literature cited in the description

• Pest Managem. Sci., 2005, vol. 61, 246 [0031] • Perry’ s Chemical Engineer’ s Handbook. Mc- • PEST MANAGEM. SCI., 2005, vol. 61, 258 [0031] Graw-Hill, 1963, 8-57 [0056] • PEST MANAGEM. SCI., 2005, vol. 61, 277 [0031] • KLINGMAN. Weed Control as a Science. J. Wiley & • PEST MANAGEM. SCI., 2005, vol. 61, 269 [0031] Sons, 1961 [0056] • PEST MANAGEM. SCI., 2005, vol. 61, 286 [0031] • HANCE et al. Weed Control Handbook. Blackwell • PEST MANAGEM. SCI., 2008, vol. 64, 326 [0031] Scientific, 1989 [0056] • PEST MANAGEM. SCI., 2008, vol. 64, 332 [0031] • MOLLET, H. ; GRUBEMANN, A. Formulation tech- • Weed Sci., 2009, vol. 57, 108 [0031] nology. Wiley VCH Verlag, 2001 [0056] • Austral. J. Agricult. Res., 2007, vol. 58, 708 [0031] • COLBY, S.R. Calculating synergistic and antagonis- • Science, 2007, vol. 316, 1185 [0031] tic responses of herbicide combinations.Weeds, •BROWNING. Agglomeration. Chemical Engineer- 1967, vol. 15, 20-22 [0096] ing, 04 December 1967, 147-48 [0056]

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