GB2491594A - Pesticidal mixtures comprising enantiomerically enriched isoxazoline derivatives - Google Patents

Abstract

Pesticidal mixtures comprising a components A, B and C, wherein component A is an enantiomeric mixture of a compound of formula I that is enantiomerically enriched for the S enantiomers wherein the symbol * indicates the chiral centre; A1 and A2 are C-H, or one of A1 and A2 is C-H and the other is N; R1 is a carboxamide-linked group or 1,2,4-trizolyl; R2 is chlorodifluoromethyl or trifluoromethyl; R3 is 3,5-dibromo-phenyl, 3,5-dichloro-phenyl, 3,4-dichloro-phenyl, 3,5-dichloro-4- fluoro-phenyl or 3,4,5-trichloro-phenyl; R4 is hydrogen, methyl or cyano; R5 is hydrogen; or R4 and R5 together form a bridging 1,3-butadiene group; component B is a pesticide compound and component C is a compound selected from an insecticide, a fungicide and a nematicide, wherein components B and C are different. The mixture is useful in controlling phytopathogenic diseases and controlling insects, acarines, nematodes or molluscs on useful plants.

Description

PESTICIDAL M1>TIJRES The present invention relates to mixthres of pesticidally active ingredients and to methods

of using the mixtures in the field of agriculture.

EP1 731512 discloses that certain isoxazoline compounds have insecticidal activity. WO 2010/003877 and WO 2010/003923 disclose various pesticidal mixtures comprising certain isoxazoline compounds.

The present invention provides pesticidal mixtures comprising a component A, a component B, and a component C, wherein component A is an enantiomerie mixture of a compound of formula I that is enantiornerically enriched for the S enantiomer

RKJJR Ac

A n (1) wherein the symbol indicates the chiral centre; A' and A2 are C-H, or one of A' and A2 is C-H and the other is N; gt is a group selected from P1 to P11 10 CF LNQI rtc3 Qw' FM 1 P6

H SCF3

Plo P11 R2 is cbtorodilluoromethyl or trifluoromethyl; R3 is 3,5-dibromo-phenyl, 3,5-dichkro-phenyl, 3,4-dichtoro-pheny, 3,5-dichloro-4-fluoro-phenyl or 3,4,5-trichioro-phenyl; R4 is hydrogen, methyL or cyano; R5 is hydrogen; or R4 and R5 together form a bridging 1,3-butadiene group; component B is a compcund selected from Sedaxane, Fludioxonil, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenocona2ole, Thiabendazole, Fluopyram, Penflufen and Fuxapyroxad; and component C is a compound selected from an insecticide, a fungicide ard a nematicide, which insecticide is selected from neonicotinoids, carbarnates, diarnides, spinosyns, phenyipyrazoles. pyrethroids. Pyrifluquinazone, Pynetrozine, Suifoxaflor and Spirotetraniat; which fungicide is selected from Azoxystrobin, Tritloxystrobin, Fluoxastrobin, S Cyproconazole, Difenoconazole, Prothioconazole, Tebuconazole, Triticonazole, Fludioxoni!, Ipconazole, Cyprodinil, Myclobutanil, Metalaxyl, Mefenoxani, Sedaxane, Thiobendazole, Fluopyram, Penflufen, Fuxapyroxad and Penthiopyrad; which nematicide is selected from Avermectin (e.g, Abamectin), carbamate nematicides organophosphorus nematicides, Captan, Thiophanate-methyl and Thiabendazole a compound of formula X, wherein n is 0, 1 or 2 and the thi.azole ring may be optionally substituted, Bacillus firmus, Bacillus cereus, Bacillus subtilis, and Pasteuria penetrans; wherein components B and C are different.

Compounds of formula 1 are known to have insecticidal activity. Certain active ingredient mixtures of a compound of formula I and additional active ingredients can enhance the spectrum of action with respect to the pest to be controlled, eg. the animal pest and/or the fungal pest. For example, the combination of A, B and C may cause an increase in the expected insecticidal action and/or fungicidal action. This allows, on the one hand, a substantial broadening of the spectrum of pests that can be controlled and, on the other hand, increased safety in use through lower rates of application.

However, besides the actual synergistic action with respect to pest control, the pesticidal mixtures according to the invention can have further advantageous properties which can also be described, in a wider sense, as synergistic activity. Examples of such advantageous properties that may be mentioned are: a broadening of the spectrum of activity; a reduction in the rate of application of the active ingredients; adequate pest control with the aid of the mixtures according to the invention, sometimes even at a rate of application at which the individual compounds are totally ineffective; advantageous behaviour during formulation andiOr upon application, for example upon grinding, sieving, emulsifying, dissolving or dispensing; increased storage stability; improved stability to light; more advantageous degradability; improved toxicological and/or ecotoxicological behaviour; improved characteristics of the useful plants including: S emergence, crop yields, more developed root system, tiliering increase, increase in plant height, bigger leaf blade, less dead basal leaves., stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination; or any other advantages familiar to a person skilled in the art. to

Compounds of formula I as racemic mixtures are known. e.g. EPI 731512, WO 2010/003877 and WO 2010/003923. Methods of preparing enantio.mericaily enriched mixtures are described for example in WO 2009/063910. The components B are known, e.g. from "The Pesticide Manual", Fifteenth Edition, Edited by Clive Tomlin, British Crop Protection Council.

The mixtures of the invention may also comprise other active ingredients in addition to components A, B and C. In other embodiments the mixtures of invention may include only components A, B and C (or A, B, Ci and C2) as pesticidaily active ingredients.

Preferred substituents are, in any combination, as set out below.

It2 is preferably trifluoromethyl.

R3 is preferably 3,54ichloro-phenyl or 3,4,5-trichlorophenyL R4 is preferably methyl or -CN., more preferably It4 is methyl when R' is a group other than P3 and R4 is-CN when R4 is P3, It5 is preferably hydrogen.

Each substituent definition in each alternative preferred groups of compounds of formula I may be juxtaposed with any substituent definition in any other preferred group of compounds, in any combination.

Compounds of formula I include at least one chiral centre and may exist as compounds of formula J* or compounds of formula I'. (Ii

Generally compounds of formula J** (i.e. the S enantiomer) are more biologically active than compounds of formula 1* (i.e. the R enantiomer).

Component A according to the. invention is an enantiomeri.c mixture that is enantiomerically enriched for the compound of formula I. Enantiomericalty enriched means that the molar proportion of one enantiomer in the mixture compared to the total amount of both enantiomers is greater than 50%, eg. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or least 99°/ó, in one embodiment component A is a compound of formula I*t in substantially pure form, e.g. it is provided substantially in the absence of the alternative enantiorner.

Preferred compounds of formula 1 are shown in the Table below.

Tale 1: Compoimcis. of forniula, (hi) Cl (Ia) The symbol * indicates the location of the chiral centre [stereochemistryat* [RI rR2

--_________-

2 --S -HN'CF --i 4 Me S -Me H Me S Me N :8 S to a Me H Ii S Me H Bearing in mind the chiral centre referred to above, the present invention otherwise includes all isomers of compounds of formula (1) and salts thereof, including enantiorners, diastereomers and tautorners.

S

In one embodiment of the invention component C is an insecticide which is selected from neonicotinoids, carbamates, diamides, spinosyns, phenyipyrazoles, pyrethroids, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat. Examples of neonicotinoids are Thiarnethoxam, Ciothianidin, Imidacloprid, Acetamiprid, Dinotefuran., Nitenpyram, Nithiazine, Flonicaniid and Thiacloprid. Preferred neonieotinoids are Thianethoxam, Imidacioprid and Ciothianidin. Examples of carbamates include Thiodicarb, Aidicarb, Carbofuran, Furadan, Fenoxycarb, Carbaryl, Sevin, Ethienocarb, and Fenobucarb, Examples of diamides include Chiorantraniliprole, Cyantraniliprote, and Flubendiamide. Examples of spinosyns include Spinosad and Spinetoram. Examples of pyrethoids include Cyhalothrin, Lambdacyhalothrin, Farnmacyhalothrin, and Teflutbrin, An example of phenyipyrazole is Fipronil.

In another embodiment of the invention component C is a fungicide. The fungicide is preferably selected from Azoxyst.robin, Trifloxystrobin, Fluoxastrobin, Cyproconazole, Difenocona2oie, Prothioconazole, Tebuconazole, Triticonazote, Fludioxonil, lpconazoie, Cyprodinil, Myclobutanil, Metalaxyl, Mefenoxam (also known as Metalaxyl..M), Sedaxane, Thiobendazole, Fluopyram, Penflufen, Fuxapyroxad and Penthiopyrad.

In another embodiment of the invention component C is a nematicide, The nematicide can be any nematicide known in the art. Examples include an Avermectin (e.g., Abamectin), carbamate nematicides (e.g., Aldicarb, Thiodicarb, Carbofuran, Carbosulfan, Oxamyl, Aldoxycarb, Ethoprop, Methomyl, Benomyl, Aianyearb, Iprodione), organophosphorus nematicides (e.g, Phenamiphos (Fenamiphos), Fensulfothion, Terbufos, Fosthiazate, Dimethoate, Phosphocarb, Dichiofenthion, Isamidofos Fosthietan, Isazofos Ethoprophos, Cadusafos, Terbufos, Chiorpyrifos, Dichiofenthion, Heterophos, Isamidofos, Mecarphon, Phorate, Thionazin, Triazophos, Diamidafos, Fosthietan, Phosphamidon, Imicyafos), and certain fungicides, such as Captan, Thiophanatemethyl and Thiabendazole. Also included as a nematicide is a compound of formula X,

F

wherein n isO, I or 2 and the thiazole ring may be optionally substituted. Ahamectin, Aldicarb, Thiodicarb, Dimethoate, Ethomyl, a compound of formula X and Oxamyl are preferred nematicides for use in this invention.

In addition, nematieidally active biological agents can be included in the compositions of the invention. The nematicidally active biological agent refers to any biological agent that has nematicidal activity. The biological agent can be any type known in the art including bacteria and fungi. The wording "nematicidally active" refers to having an effect on, such as reduction in damage caused by, agricultural-related nematodes. The nematicidaily active biological agent can be a bacterium or a fungus. Preferably, the biological agent is a bacterium. Examples of nematicidaily active bacteria include Bacillus firmus, Bacillus cereus, Bacillus subtiiis, and Pasteuria penetrans. A suitable Bacillus firmus strain is strain C'JCM i1 582 which is commercially available as BioNemTM, A suitable Bacillus cereus strain is strain CNCM 1-1562. Of both Bacillus strains more details can be found in US 6,406,690.

In one embodiment component C is a compound selected from Thiarnethoxam, Ciothianidin, Nithiazine, Flonicamid, Imidacloprid, Acetamiprid, Dinotefuran, Nitenpyram, Thiacloprid, Thiodicarb, Aldicarb, Carbofuran, Furadan, Fenoxycarb, Carbaryl, Sevin, Ethienocarb, Fenobucarb, Chlorantraniliprole, Cyantraniliproic, Flubendiamide, Spinosad, Spinetoram, Cyhalothrin, Lambda-cyhalothrin, GammaS cyhalothrin, Tefluthrin, Fipronil, Azoxystrobin, Trifloxystrobin, Fluoxastrobin, Cyproconazole, Difenoconazole, Prothioeonazole, Tebuconazole, Tritieonazole, Fludioxonil, Thiabendazole, Ipeonazole, Cyprodinil, Myclobutanil, Metalaxyl, Mefenoxam, Sedaxane, Fluopyrarn, Penflufen, Fuxapyroxad, Abamectin, Aldicarb, Thiodicarb, Carboftir*m, Carbosuifan, Oxamyl, Atdoxycarb, Ethoprop, Methomyl,, Benotnyl, Alanycarb, Iprodione, Phenamiphos, Fensulfothion, Terbufos, Fosthiazat; Dimethoale, Phosphocarb, Dichiofenthion, Isamidofos, Fosthietan, Isazofos, Ethoprophos, Cadusafos, Terbufos, Chlorpyrifos, Dichiofenthion, Heterophos, Isamidofos, Mecarphon, Phorate, Thionazin, Triazophos, Diamidafos, Fosthietan, Phosphamidon, imicyafos, Captan, Thiophanate-methy!, Thiabendazole, a compound of formula X, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans. i0

In one embodiment component C is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetorain, Chlorpyrifos, Thiodiearb, Chlorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans.

In one embodiment component C is a compound selected from lmidacloprid, Thiacioprid, Acetamiprid, Nitenpyrarn, Dinotefuran, Thiamethoxam, Ciothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat.

In one embodiment component C is a compound selected from Sedaxane, Fludioxonil, Ivietalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenoconazole, Thiabendazole, Fluopyram, Penflufen and Fuxapyroxad, provided that components B and C arc different.

in a further embodiment the pesticidal mixture comprises, as component C, component Cl and component C2, wherein component Ci is a compound selected from Tefiuthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chlorpyrifos, Thiodicarb, Chiorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans; and component C2 is a compound selected from Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotethran, Thiamethoxam, Clothianidin, Nithiazinc, Flonicamid, Fipronil, Pyrifiuquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat.

Reference herein to component C includes reference to component Cl and component C2.

The invention also relates to the following combinations: I 0 A B -C-Au C _19_ Sedaxane --tefiuthnn IF Sedaxane Lambda-F -..-. -. -. -. _. -...-...-. _______ TI Fludioxonil Tefluthnn TI Fludrnxonil Lambda --._-._-....-. - . . TI Metalaxyl Tefiuthrin TI Metaiaxyl Larnbda --,...-..,-...-.--fl.- ....--.... -... -________ TI Mefenoxarn Tefluthrin TI Mefenoxam Lambda- -., -. ---....---_________ TI Cyprodinil Tefluthrin Ti Cyprodinil Lambda- -______________ -_------_--cyhalothrin TI Azoxystrobin Tefluthrin Ti Azoxystrobin Lambda- -... cS!n TI Tebuconazole Tefluthrm TI Tebuconazole Lambda- ----- ---_!9tttr_- TI Difenoconazole Tefluthrin TI Difenoconazole lambda- ---cyhaloihrin Ti Thiabendazole Tefluthrin Ti Thiabendazole Lambda- -,.-cyh9k!ri1! Ti Fiuopyrarn Telluthrin TI Fluopyram Lambda- - . ________ __ Ti Penflufen Tefluthrin TI Penflufen Lambda- --... -, _______ __ _______ ________ TI Fuxapyroxad Tetluthrin Ti Fuxapyroxad Lambda- ------------- --yaIotMn _Ij__ Sedaxane Abarnectin Ti Sedaxane Spinosad IL Fludioxonil Abamectm Ti Fludioxomi Spinosad IL Metalaxyl Abamectin TI Mthdaxyi °!4 i[i Mefenoxam Abamectm TI Mefemxam pposad _Ij__ Cyprodinil Abamectm TI Cyprodmil S p IPOSacI IL Azo,çystrobin Abamectm TI Azoxystrobin Spinosad TI Tebuconazole Abamectin Ti Tebuconazole Spmosad TI Difenoconazole Abamectrn -TI Difenoconazole Spmosad IL Tht*ndazole Abamecim -TI Thiabendazole Spmosad TI Fluopyrarn -Abarnectin TI Fluopyram Spinosad -TI Penflufrn Abamectm --TI Penflulèn Spinosad TI Fuxapyroxad -Abamecirn -TI Fuxapyroxad -Sjinosad TI Sedaxane Spetoram -TI Sedaxane -Chiorpynfos IL top!LSJ?yet0raIP IL Th!1!2'E9E1 --ChIffflnfos TI Metalaxyl Spinetoram --TI Metalaxyl Chiorpynfos - TI Mefenoxam -!p1netoram_ TI Mefenoxarn Chioxpynlos -TI Cyprodimi Spinetoram IL Chiorpynfos TI Azoxystrobin Spmetorarn Ti Azoxystrobrn Chiorpyrifos -TI Tebuconazole Spinetoram Ti Tebuconazole Chlorpyrifos TI Difenoconazole -!p!netoram Ti Difenoconazole Chlorpyps Ti Thiabendazole h!netoram TI gbend Chiorpynfos - 1L * Syinetoram Ti Fluqpyram h1orpyrifos iL Penflufen Spinetoram TI Penflufen hkwpynfos ilL!wapy!o xa ii * Spinqtomm TI &!2rf 1L Sedaxane Thiodicarb:j1_ Sedaxane _ __ Chiorantraniliprole iL Fluchoxorni T!!i9c!w!rP -. _ij___ Fludioxonti ChIorantrarn1ipoIe iL Metalaxyl Thiodicarb TI Metalaxyl Chlorantrarnhprole iL Mefenoxam Ihis.rk TI Mefenoxam ChJoutrnniJiproIe iL fyprodini1 _ -Thiodicarb TI Cyproclinil ChiorantranihErole LL Azoxystrobm Thiodicarb TI Ayçrobn Chiorantraniliprole TI Tebuconazole Thiodicarb T Tebuconazole Chlorantranihp,role iL Difenoconazole Thiodicarb TI Lhfenoeonazole Chiorantraniliprole IL Thiabendazole Thic4icrb TI Thiabendazole Chlorantrarnhprole IL!!?nram Thtodicarb TI Fiuqpyram Chlorantranthpyo!e ilL Penflufen Thiodicarb 11 Penflufen Chlorantranihprole iiL Fuxapyroxad Thiodicarb TI Fuxapyroxad ChSorantranittpr&e :ti: Sedaxane!9±P!9k ii: Sedaxane Bacillus firmus IL Fludioxonil Cyantranitiprole TI Fludioxorni Bacillus firmus IL M!!SYL cy!n!cnthxa9i IL Metalaxyt Bacillus firmus IL ±h2!!L_ »=S1'IPI9I! IL iic!a1iL liacillusflrmus IL Cyprodinil Cyantranztip!ole TI ci°'qL N. c4I firmus iL Azoxtmbm Cyntrani1qroIe TI Azoxystrobin Bacillus firmus TI Tebuconazole Cyantrani1pro1e TI Tebuconazole Bacillus fu'mus TI Dtfenoconazole CyantraniLpje TI Difenoconazole Bacillus firmus TI Thiabendazole Cyantranittprote TI Thiabendazote Bacillus firmus iL Fluopyram Cyantrarn1m1e TI Fluopyram!acillus firmus iL Penflufen CyintraniIproIe TI Penflufen Bacillus firmus _ii__ Fuxapyroxad Cyantrarnhprole Ti Fuxapyroxad Bacfllus flrmus ii: a!c Bacillus subtilis Sedaxane 1!iaiinths iL!Iuto?on Bacillussubtths TI Fludioxorni Pasteunpenetrans _Ij_ Metalaxyl Bacillus subtilis TI Metalax4 Pasteunajenetrans IL Mefenoxam Baciflussubtilis TI Mefenoxarn ______________ IL Cyprodmil Bacillus subtilis TI 9'podinil Pasteunay!netrans _I_!__ Azoxystrobin Bacillus subtilis TI Azoxystrobrn Pasteuna P!'!!!LL a_ JeuconazoIe Bacillus subtilis TI Tebuconazole Pasteuria penetrans TI Difenoconazoic Bacillus subtilis TI Difenoconazole Pasteuna penetrans Ti Thiabendazole Bacillus subtilis TI Thiabendazolc Pasteuria penetrans - TI Fluopyram Bacillus subtilis TI Fluopyram --?asc9ua penetrans -IL eflufen -Bacillus subtilis TI Penflufcn Pasteuna penetrans Ti Fuxapyroxad -Bacillus subtilis TI Fuxapyroxad Pasteuna penetrans

A B C A B ______

Ti Sedaxane Imd!c!w!Ick -11 Sedaxane Thiaelopnd IL TI Fludioxonil -Thiacloprid TI Metalaxyl Irnidaclopnd -TI Metalaxyl -Thiacpd TI Mefenoxam -imidacloprid IL ic!xan Thiacloprid -ii__ çro&'if -Imidadprid TI Cyprodinil Thiaclop4çd _ii_ Azoxystrobrn Imidacloprid TI Azoxystrobrn Thiaclopnd _ii_ Tebuconazole Jmidaclopnd TI Tebuconazole hiac1opng iL Difenoconazole Inudacloprid TI Difenoconazcde Tknaclopnd iL Thiabendazole IrnidacIprid TI Thiabendazole Thiaclopnd iiL Fluopyrarn Jnudacloprid TI F1uopam Jhiadopnd IL ?cpflifer Jmidaclopnd TI Pentlufen Thiactopnd IL Imida1oprid TI Fuxpyroxad Thiac!opri� -19--Sedaxane Acetampnd TI Sedaxane Nitenpyram _ii_ Fludioxorni Acetamiprid TI Fludioxonil Nitenpyram IL Metalaxyl Acetamipnd TI Metalaxyl Niteqpyram IL Mefenoxam Acetamiprid TI Mefenoxam Nitenpyrarn L!_ Cyprodinil Acetamipnd TI Cyprodinil Nitenpyram ilL Azoxystrobin Acetamiprtd TI Azoxystrobin Nitenpyram :p__ Tebuçonazole Acetamipnd TI Tebuconazole Nitenpyram ij___ Difenoconazole Acetarnipnd TI Difènoconazole Nitenpyram _Ii_ Thiabendazole Acetamiprid TI Thiabendazole Nitenpyram iL!i92PYaLP Acetamiprid TI Fluopyram Nitenpyram IL ?eafly!en Acetarnipr!d TI Penflufen Nnepyrarn :L!___ Fuxapyroxad Acetamiprid 11 Fuxajyroxad Nitepyram TI Sedaxane Dinotefuran TI Sedaxane Thiametboxam TI Fiudioxonil Dinotefuran TI Fludioxonil Thiametboxam ij_ Met&ay -Dmotefuran 11 Mettilaxyi Thiamethoxam TI Mefenoxam Dinotefuran TI Mófenoxam Thiametboxam iL Cyprodintl Dinoteftiran TI cwoIn! Thiamethoxarn :n___ Azoxystrobin Drnotefuran TI Azoxystrobin TI Tebuconazole Dinotefuran TI Tebuconazole Thiametboxam TI Difenoconazole Dinotefuran TI Difenoconazok Thiamethoxam TI Thiabendazole Drnotefuran TI Thiabendazole Thiamethoxarn IL Fluopyrarn Drnotefuran TI Fluopyram Thiarnethoxam Tl Penflufen Dinotefuran Ti Penflufen Thiamethoxarn iL pyroxad 219!c1'wa IL FuxapyrQxad Thiarnethoxam IL Sedaxane -Clothianidrn TI Sedaxane Nilhiazine TI Fludioxonil çIothhidin Ti Fludioxonil Nithiazine IL Ooduarndrn TI MetaJyI NInazine TI Mefenoxarn Clothiantdrn TI Mefenoxam Nithiazine TI Cyyrodintl Clothianidrn -TI Cyprothnd -Nithtaztne --TI Azoxyobin Clothianidrn TI Azoxystrobin Nithiazine TI Tebuconazole Clothianidin TI Tebuconazole Nithiazine TI Difenoconazole Ciothianidin Ti Difenoconazok Nithiazine TI Thiabendazole Clothianidin Ti Thiabendazole Nithiazine TI Fluopyram Clothianidrn TI Fluopyrarn Nithiazine TI Penflufen --Clothiarudrn TI Penflufen Nithiazine TI Fuxapyroxad ot hianidin -. Ti Fuxapyroxad --Nithiazine :tii: Sedaxanc Flonicamid TI Sedaxane Fipronil IL Fludioxorni Flonicanud TI Fludioxonil Fiprorni IL ±1aiaYt Flomeamid TI MeiyI Fiprorni IL Mefenoxarn Flonicamid TI Mefenoxam Fprorni IL cyP!c*-!! Florncamid TI Cjrprothnil Fiprorni IL Azoxystrobrn Flonicamid TI Azoxystrobrn Fiprorni IL j'ePuc2?zojtL_ F1pnitid JilL 3!k9q* Fipronil TI Difenoconazole Flonicamid TI Difenoconazole Fipronil LL Thiabendazole Flonicamid TI Thiabendazole Fiprorni IL Fluopyrarn f!*d -LL Fluqpyram Fipronil LL!rIuLei Flomcamid TI Penflutèn Fipronil IL Fuxapyroxad Flonicamid TI Fwuipyroxad Fi2romL IL Sedaxane Pyriflugumnazone TI Sedaxane j5etrozine TI Fludioxornl Pypfluqunazone TI Fludioxonil Pymetrozine IL Mc!Sv! . yjfly99iqa1;!*ppe 11 MaxyI Pymetrozine j1_ Mefenoxam Pyrifluqnnazone TI Mefenoxam ?iY2u! 2i!_ Cyprodinil Pynflugwnazone TI Cyprodini_ Pyrnetrozrne iL Azoxy!trobm -Pynfluq3mazone TI Azoxystrobin Pymetrozine _Ii_ Tebuconazole Pyrifluquione Ti Tebueonawle flwtrozine IL Difenoconazole Pyriflugurnazone TI Difenoconazole Pyrnetrozine IL Th4±. Pyrifluqpinazone TI Thiabendazole Pymetrozine J1_ Fluopyram Pyxifluqpinazone 1] Fluoioyram Pyrnetrozine ilL Penflufen Pynfluguinazone TI Penflufbn b'!oz1ne IL Fuxapyroxad Pyrifluciuinazone Ti Fuxapyroxad Pymetrozine TI &tane Sulfoxaflor T Sedaxane Sjirotetramat ]1_ FludioxoniI Sulfoxaflor TI Fludioxonil Spiroteflmat IL M!!*IMJ Ifoxaflor TI Metalaxyl Spirotetrarnat TI Mefenoxam Sulfoxaflor TI Mefenoxam Spirotetramat LL yodini1 Sulfoxatlor iL Cyprodinil irotetramat j:_L Azoxystrobin!ulfoxaflor TI Azoxystrobin Spirotetramat LL 4qcgJe Su Ifoxaflor TI Tcbuconazde Spirotetramat IL Difenoconazole Sulfoxaflor TI Ehfenoconazote Spotetramat TI Thiabendazole Sulfoxaflor TI Thiabendazote Spirotetramat TI Fluopyrarn Sulfoxaflor TI Fluqpyram --Spirotetramat -TI PentlufenSulfoxaflor TI hPa ____________ TI Fuxapyroxad Suifoxaflor TI Fux.apyroxad -Spirotejmma -rn C AB C TI Sedaxane Fludioxonil TI Fludioxonli Sedaxane IL!ea Metalaxxj --TI Fludrnxonrl Metalaxyl Tl Sedaxane Melenoxarn TI Fludioxonii Mefenoxarn TI Sedaxane,>prodrniI TI Ftudioxonil --Cyprodtnil -TI Sedaxane Azoxystrobin TI Fludioxornl Azoxystrobin TI Sedaxane Ic co az ole TI Fludioxonil. Tebuconazole TI Sedaxane Difenoconazole TI Fludioxonil. Difenoconazole TI Sedaxane Thiabendaz ole TI Fludioxonil Thiabendazole LL Sedaxane!1onrm i!_ Fludioxonil Fluopyam _Ij__ Sedaxane Penflufen TI Fludioxonil Penflufen _Ij__ Sedaxane Fuxapyroxad TI Ffud!oxonil Fuxapyrox!d IL Metalaxyl Fiudioxonil IL Mefenoxam Fludioxonil IL Metalaxyl *. -Sedaxare Ti Mefenoxam Sedaxane -IL Metalaxyl Mefenoxam TI Mefenoxam Metalaxyl 2iL Metalaxyl çrodind TI Mefenoxarn cdrni IL Metalaxyl Azoxrobrn TI Mefenoxam Azoxystrobm IL Metalaxyl -Tebuconazole TI Mef!noxam * Tebuconazole IL Metalaxyl Difenoconazole TI Mefenoxarn Difenoconazole __Ij__ Metalaxyl Thiabendazole TI Mçfcnoxarn Thiabendazole LL Metalaxyl Fluopyram Fl Mefenoxam Fluopyrarn IL Metalaxyl Penflufen TI Mefenoxam Penflufen LL Metalaxyl Fuxapyroxad TI Mefenoxam Fuxapyrox.ad cyni Fludioxonij_ TI Azoxystrobrn Fludioxonil LL Cyprodinil Sedaxane TI Azoxystrobrn Sedaxanc _2:i__ Cyprodinil çfcoçajn Ti Azoxystrobin Mefenoxam _i_!__ yprodrniL -M!Sn1 31 Azoxstrobin iL Cyprodrnil _ Azoxystrobin TI Azoxystrobrn Metalaxayl tL Cyprodinil Tebuconazole Ti Azoxrobin Tebuconazok iL Cyprodimi Difcnoconazole TI Azoxyrobin D ifenoconazole iL Cjprodinii Thiabendazole Ti Azoxystrobrn Thiabendazole TI Cyprodinil Fluqpyram Ti Azoxystrobin Fluopyram _n_ Cyprodrnil!!!gig!B IL Aqitrs*n flfr iLL yprodiniL!93Priat IL M2y!t Fuxapyroxad ir Tebuconazole Fiudioxonit Ti Difenoconazole Fludioxonil TnT Tebuconazole Sedaxane TI Difenoconazole Sedaxane Ti Tebuconazote Mefenoxam Ti Difenoconazole Mefenoxam :tc Tebuconazok yprochrni TI Difenoconazole Cjprodintl LL Tebuconazole Azoxystrobin TI Difenoconazole Azoxystrobin _ii_ Tebuconazoic Metalaxyi TI Difenoconazole Tebuconazoic _ii_ Tebuconazole Difenoconazole TI Difenoconazole Metalaxyi _ii_ Tebuconazoic Ihiabendazo!t TI DIfenoconazole Thiabendazole ilL 1ebuconazole Fluopyram Ti Difenocmnizole Fluopyram TI Tebuconazoic Penflufen Ti Difenoconazole Penfl.ufen TI Tebuconazole Fuxapyroxad Ti Difenoconazole Fuxapyroxad TI Thiabendazole Fludioxonil TI Fluçparn -TI Thiabendazole Sedaxane -TI FIuop -Sedaxane TI Thiabendazole Mefenoxam -TI F1uopyrn Mefenoxam Ti Thiabendazole yprodtnt1 TI Fluopyram Cyprodmil TI Thiabendazole Azoxystrobin -TI Fluopyram Azoxystrobrn 31 hiabendie Tebuconazoic TI FIuopH Tebuconazole TI Thiabendazole Difenoconazole TI Fluqpyram Difenoconazole -TI Thiabendazoic Metalaxyl TI Fluoyyram Tbdazole I 5 IL Thiabendazole!!qgpna___ IL Fluopyram MSY1 _ii_ Thiabendazole Penflufen TI rluopyflffl ?eiflWen _Ii_ 111e4itzoie Fuxapyroxad TI FIuqpyrn Fuxapyroxad IL!!ii4 Fludioxonil TI Fuxapyroxad Fludioxonil IL Sedaxanc TI Fuxpyroxad Sedaxane :a_ Penflufen Mefenoxam TI Fuxapyroxad: MefenQxam IL Penflufen Cyprodinil TI Fuxapyroxad Cyprodinil IL-Penflufen Azoxystrobrn TI Fupyroxad Azoxystrnbrn TI Pen'flufen Tebuconazole TI Fuxaproxad Tebuconazole -19-Penflufen Difenoconazole TI Fuxapyroxad Difenoconazole iL eqflufn Thiabendazole _ii_ Fuxapyroxad Thiabendazole JL Penflufen! ! Fluopyram TI Fuxapyroxad!iuopyr iL Penflufen Metalaxyl Ti Fuxpyroxad Penflufen IL-Penflufen!aproa IL Fuxapyroxad Metálaxyl "TI " means a compound selected from Table I. A, B, C refer to components A, B and C. The present invention also relates to: a method of controlling phytopathogenic diseases on useful plants or on propagation material thereof which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components A, B and C; a method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, to a plant susceptible to attack by a pest, or to plant propagation material susceptible to attack by a pest a combination of components A, B and C; a seed comprising a pesticidal mixture of components A, B and C; a method comprising applying to a seed, e.g. coating, a mixture of components A, B and C. The present invention also includes pesticidal mixtures comprising a component A, B and C in a synergistically effective amount; agricultural compositions comprising a mixture of component A, B and C in a synergistically effective amount; the use of a mixture of component A, B and C in a synergistically effective amount for combating animal pests; the use of a mixture of component A, B and C in a synergistically effective amount for combating phytopatbogenic fungi; a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seets, soils, surfaces or spaces to be protected from animal attack or infestation with a mixture of component A, B and C in a synergistically effective amount; "5 a method for protecting crops from attack or infestation by animal pests and/or phythopathogenic fungi, which comprises contacting a crop with a mixture of component A, B and C in a synergistically effective amount; a method for the protection of seeds from soil insects nd of the seedlings' roots and shoots from soil and foliar insects and/or phythopathogenic fungi comprising contacting the seeds before sowing and/or after prc germination with a mixture ofcomponent A, B and C in a synergistically effective amount; seeds comprising, eg. coated with, a mixture ofcornponent A, B and C in a synergistically effective amount; a method comprising applying to a seed, eg. coating, a mixture of component A, B arid C in a synergistically effective amount; a method of controlling phytopathogenic, e.g. fungal, diseases on useful plants or on propagation material thercof, which comprises applying to the useful plains, the locus thereof or propagation material thereof a combination of components A, B and C in a synergistically effective an omit. In such applications the mixtures of A, B and C will normally be applied in a fungicidally effective amount. The invention also provides a IS method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, to a plant susceptible to attack by a pest, or to plant propagation material susceptible to attack by a pest, a combination of components A, B and C in a synergistically effective amount. in such applications mixtures of A, B and C will normally be a. pplied in an inseeticidally, aearicidally, nematicidally or molluscicidally effective amount. In application components A, B and C may be applied simultaneously or separately.

The active ingredient combinations are effective against harmful microorganisms, such as microorganisms, that cause phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria. The active ingredient combinations are effective especially against phytopathogenic fungi belonging to the followIng classes: Ascomycetes e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemiieia, Rhizoctonia, Phakopsora, Puceinia,.

Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g. Botrytis, Heiminthosporiuni, Rhynchosporium, Fusarium, Septoria., Cercospora, Alternaria, Pyricularia and Pseudocereosporella); Oomycetes (e.g. Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudoscierospora, Plasmopara).

The mixtures ofthe present invention can be used to control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Co!eoptera, Siphonaptera, Hyrnenoptera and Isoptera and also other invertebrate pests, for example, acarine, nernatode and moflusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as animal pests. The animal pests which may be controlled by the use of the invention compounds include those animal pests associated with agriculture (which term includes the growing ofcrops for food and fiber products), horticulture and animal husbandry, companion animals, forestry and the storage ofproducts of vegetable origin (such as fruit, grain and timber; those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies). The mixtures of the invention are particularly effective against insects, acarines and/or nematodes.

According to the invention "useful plants" typically comprise the following species of plants: grape vines; cereals, such as wheat, barley, rye or oats; beet, such as sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as marrows, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or mw darins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers. This list does not represent any limitation.

The term tuseful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPI) inhibitors, ALS inhibitors, for example primi.sulfuron, prosuifuron and trifioxysulfuron, EPSPS (5-enoi-pyrovyl-shikimate-3-phosphatc-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imaza ox, by conventional methods of breeding (mutagenesis) is

IS

Clearfield® summer rape Cano1a). Examples ofcrops that have been rendered tolerant to herbicides or classes ofherbicidcs by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.

S

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use ofrecombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from.

toxin-producing bacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as 8-endotoxins, e.g. CrylA(b), CryIA(c), CryiF, CryIF(a2), CryiIA(b), CryILIA, CryllII3(bl) or Cry9c, or vegetative IS insecticidal proteins (VIP).. e.g. VIPI, VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhâbdus spp., such as Photorhabdus luminescens, Xenorhábdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley leetins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidasc, ecdysteroid- UDP-glycosyi-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile horn, one esterase, diuretic hormone receptors, stilbene synthase, bibenzyi synthase, chitinases and giucanascs.

In the context of the present invention there are to be understood by 8-endotoxins, for example CrylA(b), CryiAc), CrylF, CrylF(a2), CrylIA(b), CryillA, CryIIIl3(b 1) or Ciy9c, or vegetative insecticidal proteins (VIP), for example V P1, VIP2,. VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced reco.mbinantiy by a new combination of different domains of those proteins w (see, for example, WO 02/15701). An example for a truncated toxin is a truncated CrytA(b), which is expressed in the Bt! I maize from Syngenta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. En such amino acid replacements, preferably non-naturally present S protease recognition sequences are inserted into the toxin, such as, for example, in the case of CryIllA0S5, a cathepsin-D-*recognition sequence is inserted into a CrylliA toxin (see WO 03/018810) Examples of such toxins or transgenie plants capable of synthesising such toxins are disclosed, for example, n EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processcs for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-typc deoxyribonucleic acids and their preparation are known, for example., from WO 95/34656, EP-A..0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lcpidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them. are commercially available.

Exan pies of such plants are: YieidGard® (maize variety that expresses a CrylA(b) toxin); VieldOard R.ootworm® (maize variety that expresses a CryHIB(bI) toxin); YieldGard Plus® (maize variety that expresses a CryIA(b) and a Crylill3(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferasc (PAT) to achieve tolerance to the herbicide giufosinate am.monium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Boligard I® (cotton variety that expresses a Cryi.A(c) toxin); Boligard li® (cotton variety that expresses a CryiA(c) and a CryliA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CryIlIA toxin); NatureGard® and Protecta®.

Further examples of such transgenic crops are: I % JUl 1 Maize from Syngenta Seeds SAS, Chemin de 1'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/O5/i 0. Genetically modified Zi.a map which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioldes) by transgenic expression ofa truncated Cry1A(b toxin. Sti 1 maize also transgenicaily expresses the enzyme PAT to achieve tolerance to the herbicide giufosinate amrnonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number CIFR/96/05/i 0. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (C)strinia,nthiialis and Sesamia nonagrioides) by transgenic expression of a CryEA(b) toxin. 8t176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

3. M1R604 Maize from Syngenta Seeds SAS, Chemin de lHobit 27, F-31 790 St Sauveur, France, registration number C1F.R/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CryillA toxin. This toxin is Cry3AO55 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, 8-1150 Brussels, Belgium, registration number CIDE/02/9. MON 863 expresses a CryIliB(bi) toxin and has resistance to certain Colcoptera insects.

5. lIt 531 Cotton from Monsanto Europe S,A. 270-272 Avenue de Tervuren, 8-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-I 160 Brussels, Belgium, registration number /NL/00/i0. Genetically modified maize for the expression of the protein Cryl F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide giufosinate ammoniurn, 7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-i 150 Brussels, Belgium, registration number C10B1021M3103. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kursiaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

Transgcnic crops of insect-resistant plants are also described in BATS (Zentrurn für Biosicherheit und Nachhaltigkeit, Zentrurn BATS, Clarastrasse 13, 4058 l3asel,Switzerland) Report 2003, th1*......L1kitaI!1 The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as,, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenie substances and transgenic plants capable of synthesising such antipathogenic substances are known., for example, from EP-A-0 392 225., WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KPI, KP4 or KP6 toxins; stilbene synthascs; bibcnzyl synthases; chitinases; giucanases; the so-called "pathogenesis-related proteins" PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/338 18) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resist-ance genes", as described in WO 03/00Q906.

Useful plants of elevated interest in connection with present invention are cereals; soybean; rice; oil seed rape; pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes, potatoes, cucurbi.ts and lettuce.

The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sow. or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

The term "plant propagation materiaL" is understood to denote generative parts ofa plant, such as seeds, which can be used for the multiplication oftbe btter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young piants which are to be transplanted after germination or after emergence from the soil, may also be mentioned These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.

A further aspect of the instant invention is a method of protecting natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms against attack of fungi and/or animal pests, which comprises applying to.

said natural substances of plant and/or animal origin or their processed forms a is combination of components A, B and C in a synergistically effective amount.

According to the instant invention, the term "natural substances of plant origin, which have been taken from the natural life cycle" denotes plants or parts thereof which have been harvested from the natural life cycle and which are in the freshly harvested form.

Examples of such natural substances of plant origin are stalks, leafs, tubers, seeds, fruits or grains. According to the instant invention, the term "processed form of a natural substance of plant origin" is understood to denote a form of a natural substance of plant origin that is the result of a modification process. Such modification processes can be used to transform the natural substar.ce of plant origin in a more storable form of such a substance (a storage good). Examples of such modification processes are pre-drying, moistening, crushing, comminuting, grounding, compressing or roasting. Also failing under the definition of a processed form of a natural substance of plant origin is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.

According to the instant invention, the term "natural substances of animal origin, which have been taken from the natural life cycle and/or their processed forms" is understood to denote material of animal origin such as skin, hides, leather, furs, hairs and the like.

The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mould.

A preferred embodiment is a method ofprotecting natural substances ofplant origin, S which have been taken from the natural life cycle, and/or their processed forms against attack of fungi and/or animal pests, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a combination of components A, B and C in a synergistically effective amount.

A further preferred embodiment is a method of protecting fruits, preferably pornes, stone fruits, soft fruits and citrus fruits, which have been taken from the natural life cycle, and/or their processed forms, which comprises applying to said fruits and/or their processed forms a combination of components A, B and C in a synergistically effective amount.

The combinations of the present invention may also be used in the field of protecting industrial material against attack of fungi. According to the instant invention, the term "industrial material" denotes non-living materials which have been prepared for use in industry. For example, industrial materials which are intended to be protected against attack of fungi can be glues, sizes, paper, board, textiles, carpets, leather, wood, constructions, paints, plastic articles, cooling lubricants, aquacous hydraulic fluids and other materials which can be infested with, or decomposed by, microorganisms. Cooling and heating systems, ventilation and air conditioning systems and pans of production plants, for example cooling-water circuits, which may be impaired by multiplication of microorganisms may also be mentioned from amongst the materials to be protected. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.

The combinations of the present invention may also be used in the field of protecting technical material against attack of fungi. According to the instant invention, the term "technical material" includes paper; carpets; constructions; cooling and heating systems; ventilation and air conditioning systems and the like. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.

The combinations according to the present invention are particularly effective against powdery mildews; rusts; leafspot species; early blights and molds; especially against Septoria, Puccinia, Erysiphc, Pyrenophora and Tapesia in cereals; Phakopsora in soybeans; Fiemilcia in coffee; Pliragmidium in roses; Alternaria in potatoes, tomatoes and eucurbits; Scierotinia in turf, vegetables, sunflower and oil sccd rape; black rot, red fire, powdery mildew, grey mold and dead arm disease in vine; Botrytis cinerea in fruits; Monilinia spp. in fruits and Penicilhium spp. in fruits.

The combinations according to the present invention are furthermore particularly effective against seedborne and soilborne diseases, such as Alternaria spp., Ascochyta.

spp., Botrytis cinerea, Cercospora spp, Claviceps purpurea, Cochliobolus sativus, Colletotrichum spp., Epicoecum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusariurn prolifèratum, Fusarium solani, Fusarium subglutinars, GAumannomyces graminis, Helminthosporium spp, Mierodoehium nivale, Phorna spp, Pyrenophora graminea, Pyricularia oryzae, Rhizoctonia solani, Rhizoctonia cerealis, Sclerotinia spp., Septoria spp., Sphacelotheca reilliana, Tilietia spp., Typhula incarnata, Uroeystis occulta, Ustilago spp. or Verticillium spp.; in particular against pathogens of cereals, such as wheat, barley, rye or oats; maize; rice; cotton; soybean; turf; sugarbeet; oil seed rape; potatoes; pulse crops, such as peas, lentils or chickpea; and sunflower.

The combinations according to the present invention are ftirthermore particularly effective against post harvest diseasese such as Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotriehum candidum, Monilinia fructicota, Monilinia fruetigena, Monilinia laxa, Mucor piriformis, Penicilium italicum, Penicilium soliturn, Penicillium digita turn or Penicillium expansum in particular against pathogens of fruits, such as pomefruits, for example apples and pears, stone fruits, for example peaches and plums, citrus, melons, papaya, kiwi, mango, berries, for example strawberries, avocados, pomegranates and bananas, and nuts.

The combinations according to the invention are particularly useful for controlling the following plant diseases: Alternaria species in fruit and vegetables, Aseochyta species in pulse crops, Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes, Cercospora arachidicola in peanuts, Cochiiobolus sativus in cereals, Colletotrichum species in pulse crops.

Erysiphe species in cereals, S Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Fusarium species in cereals and maize, GAum.annomyces graminis in cereals and lawns, Helminthosporium species in maize, rice and potatoes, Hemileia vastatrix on coffee, Microdochium. species in wheat and rye, Phakopsora species in soybean, Puccinia species in cereals, broadleaf crops and perrenial plants, Pseudocercosporella species in cereals, Phragmidium mucronatuin in roses, Podosphaera species in fruits, Pyrenophora species in barley, Pyricularia oryzae in rice, Ramularia collo-cygni in barley, Rhizoctonia species in cotton, soybean, cereals, maize, potatoes, rice and lawns, Rhynchosporiuin secalis in barley and rye, Scierotinia species in lawns, lettuce, vegetables and oil seed rape, Septoria species in cereals, soybean and vegetables, Sphacelotheca reilliana in maize, Tilletia species in ccreals, Uncinula necator, Guignardia bidwellii and Phomopsis viticola in vines, Urocystis occulta in rye, Ustilago species in cereals and maize, Venturia species in fruits, Monilinia species on fruits, Penicillium species on citrus and apples.

The combinations according to the present invention are furthermore particularly effective against the following animal pests: Myzuspersicae (aphid), Aphis gossypil (aphid), Aphisfabac (aphid, Lygus spp. (capsids), Dysdercus spp. (capsids), Niiaparva:a lugens (planthopper), Nephoteuixe inaIceps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Lepiocorisa spp. (stinkbugs), Frank/iniefla occidenialis (thrip), Thrips spp. (thrips), Lcpzinoiarsa decern/ineaia (Colorado potato beetle), Antionomus grandi (boll weevil), Aonidieiia spp. (scale insects), Triakurodes spp.

S (white flies), flemish, labaci (white fly), Osirinia nubilalis (European corn borer), Spodopiera lilionhlis (cotton leafworrn), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton boUworm), Helicoverpa zea (cotton bollworrn), Sylepta derogata (cotton leafroller), Pleris brassicac (white butterfly), Piwella xylosielia (diamond back moth), Agrotis spp. (cutwornis), Chilo suppressalis (rice stern boreO, to Locustajnigraioria (locust), floniocetes terrninf/ira (locust), Diabrotica spp.

(rootworms), Panonychus u/mi (European red mite), Panonychus din (citrus red mite), Tetranychus urticac (twospotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyiocopiruta oleivora (citrus rust mite)., Pülyphagotarsonetnus laws (broad mite), Brev:alpus spp. (flat mites), Boophilus microplus caffle tick), LJ*ermace,uor variabilis (American dog tick), Qenocephalides fells teat flea), Liriomyza spp.

(leafrniner, Musca domes: lea (housefly), Aedes aegypti (mosquito), Anopheles spp.

(mosquiioes, Culex spp. (mosquitoes), Luciilia spp. (blowflies), B/a/u/ia germanica (cockroach), Peripianeta americana (cockroach), Blat/a orientalis (cockroach), termites of the Mastotermitidac (for example Masiotermes sppj, the Kalotermitidae (for example JVeotermes sppj, the Rhinotermitidae (for example C'optoierines.fbrmosanus, Reticulisermesfiavipes, K speraw, K virginicus, K hesperus, and K sanionensis) and the Termitidae (for example Giobiterines suj/'ureus), Solenopsis geminata (fire ant), Monomoriwn pharaonis (pharaoh's ant), Dainaiinia spp. and Linognathus spp (biting and sucking lice), Meloidogync spp. (root knot nematodes), Globodera spp. and 1-Jeterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchuius spp4eitrus nematodes), Haernonchus contortus (barber pole worm), Caenorhabdi:is elegansjvinegar eeiworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras retlcuiatum (slug).

The amount of a combination of the invention to be applied, will depend on various factors, such as the compounds employed; the subject of the treatment., such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting or seed dressing; the purpose of the treatment, such as, for example prophylactic or therapeutic; the type of fImgi and/or animal pest to be controlled or the application time.

The mixtures comprising a compound of formula I, e.g. those selected from table 1, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, Le. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from Table 1 and the active ingredients as described above is not essential for working the present invention.

Synergistic activity is present when the fungicidal and/or animal pesticidal activity of the composition of.A + B + C is greater than the sum of the fungicidal and/or pesticidal activities of A, B and C and/or A and (B + C), and/or (A + B) and C, and/or (A + C) and B. The method of the invention comprises applying to the useful plants, the locus thereof or propagation material thereof in admixture or separately, a synergistically effective aggregate amount of component A, B and C. Some of said combinations according to the invention have a systemic action and can be used as foliar, soil and seed treatment pesticides.

With the combinations according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms and/or animal pests which occur in plants or in pans of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms and/or animal pests.

The combinations of the present invention are of particular interest for controlling a large number of fungi and/or animal pests in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.

The combinations according to the invention are applied by treating the fungi and/or animal pests the usefifi ptants, the locus thereof the propagation materiaL thereof the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials threatened by fungus and/or animal pests, attack with a combination of components A, B and C in a synergistically effective amount.

The combinations according to the invention may be applied before or after infection or contamination of the useful plants, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials by the ftmgi and/or animal pests.

When applied to the useful plants the compound of formula I is applied at a rate of 1 to 500 g a.i./ha in association with I to 5000 g al/ha, particularly I to 2000 g a,iiha, of a compound of each of components B and C, depending on the class of chemical employed as components B and C. Generally for plant propagation material, such as seed treatment, application rates can vary from 0.001 to lOg / kg of seeds of active ingredients for compounds of form. ula 1, When the combinations of the present invention are used for treating seed, rates of 0.001 to S g of a compound of formula I per kg of seed, preferably from 0.01 to ig per kg of seed, and 0.001 to 50 g each of a compound of component B and C per kg of seed, preferably from 0.01 to 10 g per kg of seed, are generally sufficient. When component C is not a thngicidc 0.001 to 5 g of a compound of component C per kg of seed, preferably from 0.01 to 1 g per kg of seed, are generally: sufficient.

The weight ratio of A to B and A to C may generally be between i 000: 1 and I: 1000.

in other embodiments that weight ratio of A to B may be between 500: I to 1: 500, for example between 100:' 1 to 1: 100, for example between I: $0 to 50: 1, for example 1 to 20: 1. In other embodiments that weight ratio of A to C may be between 50.0: 1 to I: 500, for example between 100: I to: 100, for example between I: 50 to 50: I, for example I: 20 to 20: I. In other embodiments that weight ratio of B to C may be between 500: I to 1: 500, for example between 100: I to I: 100, for example between t: 50 to 50: I, for example 1: 20 to 20: I. In cases where component C is component S 0 arid component C2, the above rates arid ratios apply separately to Cl and Cl The invention also provides pesticidat mixtures comprising a combination of components A, B and C as mentioned above e.g. in a synergistically effective amount, together with an agriculturally acceptable carrier, and optionally a surfactant. I0

The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed tretment (ES), a flowabie concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (OF), an emulsion concen-trate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an. emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TIC), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with ap.propriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting. efficacy is intended.

Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (eg. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene suiphonate, an aikylarylsuiphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, tg. as an aqueous suspension or In a dry powder form having good adherence to the S seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination ofactive ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. A typical a t&k-mix formulation for seed treatment application comprises 0.25 to 80%, especially I to 75 %, of the desired ingredients, and 99.75 to 20 %, especially 99 to 25 %, of a solid or liquid auxiliaries (including, for example, a solvent such as watery, where the auxiliaries can be a surfactant in an amount of 0 to 40 %, especially 0.5 to 3034, based on the tank-mix formulation. A typical pre-mix fonti ulation for seed treatment application comprises 0.5 to 99.9 0/s, especially I to 95 %, of the desired ingredients, and 99.5 to 0.1 34, especially 99 to 5 %, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 04, especially 0.5 to 40 %, based on the pie-mix formulation.

In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula I together with a compound of component B, and optionally other active agents, particularly microbiocides or conservatives or the like, Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.

A synergistic. effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components.

The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, SR. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967): ppm milligrams of active ingredient & a.i.) per liter of spray mixture X = % action by active ingredient A) using p ppm of active ingredient Y = % action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredients A)4-B) using x.Y p±q ppm of active ingredient is E = X + -____ If the action actually observed (0) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect In mathematical terms the synergism factor SF corresponds to OlE. In the agricultural practice an SF of? 1.2 indicates significant improvement over the purely complementary addition of activities (ex. cted activity), while an SF of 0.9 in the practical application routine signals a loss of activity compared to the expected activity.

Claims (15)

1. Claims 1. A pesticidal mixture comprising a component A, a component B and a component C, wherein component A is an enantiomeric mixture of a compound of formula [that is enantiomerically enriched for the S enantiomerA A (1)wherein the symbol * indicates the chiral centre; A' and A.2 are C-I!, or one of A' and A2 is C-H and the other is N; R' is a group selected from P1 to P11 rt)ccN RI 0 P2 P3 P4 P5 P6 T0 PlO P11 R2 is chiorodifluoromethyl or trifluoromethyl; R3 is 3,5dibromo-phenyl, 3,5-diehlorophenyi, 3,4-diehiorophenyl, 3,5-dichloro-4 fluoro-phenyl or 3,4,5-trichioro-phenyl; R4 is hydrogen, methyl or cyano; R5 is hydrogen; or R4 and R5 together form a bridging 1,3-butadiene group; component B is a compound selected from Sedaxane, Fludioxonil, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazoic, Difenoconaxole, Thiabendazole, Fluopyram, Penflufen and Fuxapyroxad; and I0 component C is a compound selected from an insecticide, a fungicide and a nematicide, which insecticide is selected from neonicotinoids, carbamates, diamides, spinosyns, phenylpyrazoles, pyrethroids, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat; which fungicide is selected from Azoxystrobin, Trifloxystrobin, Fluoxastrobin, Cyproconazolé, Difenoconazole, Prothioconazole, Tebuconazole, Triticonazole, Fludioxonil, Thiabendazole, ipeonazole, Cyprodinii, Myclobutanil, Metalaxyl, Mefenoxam, Sedaxane, Fluopyram, Penflufen, Fuxapyroxad, Fluopyrarn, and Penthiopyrad; which nematicide is selected from Ahamectin, carbamate nematicides organophosphorus nematicides, Captan, Thiophanate-methyl, Thiabendazole, a compound of formula.X,N $ F Fxwherein n isO, I or 2 and the thiazole ring may be optionally substituted, Bacillus firmus, Bacillus cereus, Bacillus subtilis, and Pasteuria penetrans; wherein components B and C are different.
2. 2. A pesticidal mixture according to claim 1, wherein A' and A2 are C-H.
3. 3. A pesticidal mixture according to claim I, wherein component A is an enantiomerie mixture of a compound selected from compound I to 11 that is enantiornericaily enriched for the S enantiomer ci I Ci (Ia) S wherein the symbol * indicates the location of the chirai centre; Nt RI R2 1 Me 2 Me HN"CFH 4.N
4. 4 Me H o Mc H 6 Mc 3$ 7 Me H 8 Mc 9 Me Me H H Me H 4. A pesticidal mixture according to any one of claims I to 3, wherein component A is at Least 80% enantiomerically enriched for the S cnantiomer.
5. 5. A pesticidal mixture according to any one of claims I to 3, wherein component A is at least 90% enantiomerically enriched for the S enantiomer.
6. 6. A. pesticidal mixture according to any one of claims I to 5, wherein component C is a compound selected from Thiamethoxain, Clothianidin, Nithiazine, Fionicamid, Imidacloprid, Acetamiprid, Dinotefuran, Nitenpyram, Thiacloprid, Thiodicarb, Aldicarb, Carbofliran, Furadan, Fenoxycarb, Carbaryl, Sevin, Ethienocarb, Fenobucarb, Chlorantraniliprole, Cyantraniliprole, Fiubendiamide, Spinosad. Spinetoram, Cyhalothrin, Lambda-cyhatothrin, Garnma-cyhalothrin, Tefluthrin, Fipronil, Azoxystrobin, Trifloxystrobin, Fiuoxastrobin, Cyproconazole, Difenoconazole, Prothioconazole, Tebuconazole, Triticonazole, Fludio.xonii, Thiabendazole, Ipconazole, Cyprodinil, Myclobutanil, Metalaxyl, Mefenoxam, Sedaxane, Ftuopyram, Penflufen, Fuxapyroxad, Abarneclin, Aldicarb, Thiodicarb, Carbofuran, Carbosulfan, Oxamyl, Aldoxycarb, Ethoprop, Methornyt, L3enomyl, Alanycath, Iprodione, Phenarniphos, Fensulfothion, Terbufos, Fosthiazte, Dimethoate, Phosphocarb, Dichiofenthion, Isamidofos, Fosthietan, Isazofos, Ethoprophos, Cadusafos, Terbufos, Chiorpyrifos, Dichiofenthion, Heterophos, Isamidofos, Mecarphon, Phorate, Thionazin, Triazophos, Diamidafos, Fosthietan, Phosphamidon, Imicyafos, Captan, Thiophanate-methyl, Thiabetdazoie, a compound of formula X, Pyrifiuquinazone, Pymetrozine, Sulfoxailor and Spirotetrm at., Bacillus firmus, Bacillus subtilis and Pasteuria penetrans.
7. 7. A pesticidal mixture according to any one of claims I to 5, wherein component C is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chlorpyrifos, Thiodicarb, Chiorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis, and Pasteuria penetrans.
8. 8. A pesticidal mixture according to any one of claims I to 5, wherein component C is a compound selected from lmidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefuran, Thiamethoxam, Clothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat.
9. 9. A pesticidal mixture according to any one of claims I to 5, wherein component C is a compound selected from Sedaxane, Fludioxonil, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenoconazole, Thiabcndazole, Fluopyram, Penflufen and Fuxapyroxad, provided that components B and C are different.
10. 10. A. pesticidal. mixture according to any one of claims I to 5, wherein the pesticidal mixture comprises, as component C, component Ci and component C2, wherein component Cl is a compound selected from Tefluthrin, Lambda-cyhaiothrin, Abamectin, Spinosad, Spinetorarn, Chiorpyrifos, Thiodiearb, Chlorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis, and Pasteuria penetrans, and component C2 is a compound selected from lmidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefuran, Thiarrethoxam, Clothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifiuquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat.
11. 11. A pesticidal mixture according to any one of claims I to 10, wherein the mixture comprises an agricultural acceptable carrier and optionally a surfactant, 3?
12. 12. A pesticidal mixture according to any one of claims I to 11, wherein the weight ratio of A to each of components B and C is 1000:1 to 1:1000.
13. 13. A method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components A, B and C, wherein components A, B and C are as defined in any one of claims 1 to 12.
14. 14. A method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, to a plant susceptible to attack by a pest, or to plant propagation material susceptible to attack by a pest, a combination of components A, B and C, wherein components A, B and C are as defined in any one of claims I to 12.
15. 15. A seed comprising a pesticidal mixture as defined in any one of claims 1 to 12.16. .A method comprising applying to a seed a mixture as defined in any one of claims Ito 12.