AU659016B2 - Fungicidal mixtures - Google Patents

Description

6590 16

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S): Schering Aktlengesellschaft ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street, Melbourne, 3000.

INVENTION TITLE: Fungicidal mixtures The following statement is a full description of this invention, including the best method of performing it known to me/us:- 1 a Field of the invention This invention relates to compositions with useful fungicidal properties.

In DDR Patent 151 404 there are described a group of 10 anilinopyrimidine compounds having fungicidal activity. We have now found that particularly valuable fungicidal compositions are obtained when one of the compounds disclosed in this patent, namely 2-anilino-4,6-dimethylpyrimidine, having the common name pyrimethanil, is combined with a fungicide from a different chemical class.

The present invention thus provides a fungicidal composition comprising a) 2-anilino-4,6-dimethylpyrimidine, and b) a fungicidal compound from a different chemical class.

Component is generally a compound selected from a conazole steroid demethylation inhibitor, (ii) a steroid reduction inhibitor based on a l-(3-(4-tert-butylphenyl)-2-methylpropyl] group which is attached via the N-atom to piperidine or 2,6-dimethylmorpholine (iii) a dithiocarbamate fungicide (iv) a phthalimide fungicide in which a chloroalkylthio group is attached via the N-atom to the optionally hydrogenated phthalimide group.

an anilide fungicide (vi) an mbc fungicide.

(vii) a carbamate fungicide (viii) a copper compound fungicide (ix) a tin compound fungicide a strobilurine type fungicide, and (xi) a fungicide selected from the group consisting of chlorothalonil, dimethomorph, fenpiclonil, fluazinam, hymexazol, nuarimol, pencycuron, pyrifenox, thicyofen, 1 probenazole, pyroquilon, tricyclazole, quaternary ammonium compounds, fludioxonil, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one (and mixtures of these two), furmecyclox, 3-iodo-2-propynyl butylcarbamate and 15 sulfur.

Conazoles are defined in ISO standard 257 as compounds based on imidazole or 1,2,4-triazole and containing a halogenated phenyl group. Examples include prochloraz (and its metal complexes especially the manganese or copper complex), propiconazole, flusilazole, hexaconazole, tebuconazole, difenoconazole, bromuconazole, cyproconazole, diniconazole, fenbuconazole, imibenconazole, furconazole, tetraconazole, myclobutanil, penconazole, fluquinconazole, azaconazole, imazalil, triflumizole, epoxiconazole, triticonazole, metconazole and the fungicide having the code No SSF 109.

Examples of type (ii) fungicides include fenpropimorph and fenpropidin.

Examples of type (iii) fungicides include mancozeb and thiram.

Examples of type (iv) fungicides include folpet, captafol and captan.

Examples of type fungicides include a) 3',5'-dichloroanilide fungicides in which the anilino nitrogen comprises a ring carrying two oxo substituents, in positions adjacent the nitrogen, e.g. iprodione, vinclozolin or procymidone, or b) acetanilide fungicides, e.g. metalaxyl or ofurace, c) sulfanilide fungicides, e.g. dichlofluanid, d) benzanilide fungicides, e.g. flutolanil, and e) heteroarylanilide fungicides, e.g. thifluzamide.

Examples of type (vi) fungicides include carbendazim, benomyl and thiophanate-methyl.

Examples of type (vii) fungicides include diethofencarb and propamocarb.

Examples of type (viii) fungicides include Bordeaux mixture, oxine-copper, copper oxychloride and copper naphthenate.

Examples of type (ix) fungicides include tributyltin oxide ard tributyltin naphthenate.

Strobilurine type fungicides (type fungicides) are methyl esters of arylacetic acid in which the acetic acid also carries a methoxymethylene or methoxyimino substituent. The aryl group is usually a 2-substituted phenyl group. Examples of such compounds are those disclosed in a wide number of patent applications, including EPs 178826, 203606, 203608, 206523, 229 074, 226917, 242070, 242081, 243012, 243014, 251082, 256667, 260794, 260832, 267734, 270252, 273572, 274825, 278595, 291196, 299694, 307101, 307103, 310954, 312221, 312243, 329011 and 336211. Specific compounds are those having the having the code Nos BAS 490F and ICIA 5504.

The names quoted for these compounds are the nonproprietary common names and the chemical structure can be found for example by reference to the "Pesticide Manual", ninth edition, 1991, published by the British Crop Protection Council. Of those not mentioned in the Pesticide Manual the full chemical names are as follows: bromuconazole [4-bromo-2-(2,4-dichlorophenyl)> tetrahydro-2-furanyl]methyl] 1H-1, 2, 4-triazole fluquinconazole -3-(2,4-dichlorophenyl)-6-fluoro- 2- (lH-1, 2, 4-triazol-l-yl) 4 (3H) -quinazolinone epoxiconazole 1-[3-(2-chlorophenyl)-2-(4-fluorophenyl) oxiran-2-ylmethyl] 1H-l, 2, 4-triazole triticonazole 5-(4-chlorophenyl)methylenel-ylmethyl) cycloheptanol metconazole 5- (4-chlorobenzyl) 2-dimethyl- 1- (lH-l, 2, 4-triazol-i-ylmethyl) cyclopentanol thifluzamide 2' dibromo-2-methyl-4 '-trifluoromethoxy-4 -trifluoromethyl- 1, fludioxonil 4- 2-difluoro-l, 3-benzodioxol- 4-yl) pyrrole-3-carbonitrile, SSF 109 1-(4-chlorophenyl)-2-(1H-1,2,4triazol-1-yl) cycloheptanol BAS 490F methyl -methoximino(a-(o-tolyoxy) o-toly] acetate ICIA 5504 methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phertyl}-3-methoxyacrylate We have found that the compositions of the invention have advantageous properties over the individual components and that synergism is often demonstrated, and yield of crop may be increased.

The weight ratio of component to component can vary over wide ranges. Suitable ranges of to are from 25:1 to 1:25, especially 5:1 to In addition, other pesticides may be employed in conjunction with the active ingredients described above providing they do not adversely affect the interaction between the fungicidal components.

The compositions of the invention are active against a wide range of fungi, e.g. powdery mildew (Erysiphe graminis) on cereal crops such as wheat, barley, oats and rye and other foliar diseases such as glume blotch (Septoria nodorum), leaf blotch (Rhynchosporium secalis), eyespot (Pseudocercosporella herpotrichoides) and rusts Puccinia graminis). Certain compositions of the present invention can be used to control seed-borne organisms such as bunt (Tilletia caries) on wheat, loose smut (Ustilago nuda and Ustilago hordei) on barley and oats, leaf spot (Pyrenophora avenae) on oats and leaf stripe (Pyrenophora graminis) on barley. The compositions can also be applied to rice for control of rice blast (Pyricularia oryzae), to horticultural crops such as apple trees for the control of apple scab (Venturia inaequalis), roses and other ornamentals for the control of powdery mildew (Sphaerotheca pannosa), rust and black spot, to many crops, for the control of Botrytis cinerea, to turf for the control of dollar spot (Sclerotinia homeocarpa) and to stored produce for the control of storage rot organisms of citrus fruit, potatoes, sugar beet, apples, pears etc., Penicillium spp., Aspergillus spp. and Botrytis spp.). Other diseases that may be combatted include Helminthosporium spp. and Cercospora spp.

SThe compositions of the invention may be employed in many 10 forms and are often most conveniently prepared in aqueous form immediately prior to use. One method of preparing such a composition is referred to as "tank mixing" in which the ingredients in their commercially available form are mixed together by the user in a quantity of water.

In addition to tank mixing immediately prior to use, the compositions containing 2-anilino-4,6-dimethylpyrimidine may be formulated into a more concentrated primary composition which is diluted with water or other diluent before use. Such compositions may comprise a surface active agent in addition to the active ingredients and examples of such compositions are as follows.

Si It can be a dispersible solution which comprises the active i.gredients dissolved in a water-miscible solvent with the addition of a dispersing agent. Alternatively it can comprise the ingredients in the form of a finely ground powder in association with a dispersing agent and intimately mixed with water to give a paste or cream which can if desired be added to an emulsion of oil in water to give a dispersion of active ingredients in an aqueous oil emulsion.

An emulsifiable concentrate comprises the active ingredient dissolved in a water-immiscible solvent which is formed into an emulsion with water in the presence of an emulsifying agent.

A granular solid comprises the active ingredients associated with powder diluents such as kaolin, which mixture is granulated by known methods. Alternatively it comprises the active ingredients adsorbed )r absorbed or a pre-granular diluent, for example Fuller's earth, attapulgite or limestone grit.

1 0 A dispersible or wettable powder usually comprises the active ingredients in admixture with a suitable surfactant and an inert powder diluent such as china clay.

444 Another suitable concentrate is a flowable suspension 15 concentrate which is formed by grinding the active ingredients with water, a wetting agent and a suspending agent.

In some circumstances it may be desirable to combine two types of formulation e.g. one of the components is present S"in an emulsifiable concentrate and the second component is oi' dispersed as a powder in this concentrate.

The concentrate of the active ingredients (when used as the sole active components) in a composition for direct application to the crop by conventional ground methods is preferably within the range of 0.001 to 10 per cent by weight of the composition, especially 0.005 to 5 per cent by weight, but more concentrated compositions containing up to 40 per cent may be desirable in t'he case of aerial sprays.

The compositions of the invention are particularly useful for treating seeds, especially cereal seeds, in order to control, particularly, seed-borne diseases. The seeds can be treated in conventional manner using a variety of formulation types, such as dusts, solutions in an organic solvent or aqueous formulations such as flowable suspension concentrates. If cereal grain is to be stored in a store room or container it is sometimes convenient to treat the store room or containers with a composition according to the invention instead of, or in addition to, treatment of the cereal grain itself. A suitable rate of application for a seed dressing is from 0.005 to 5.0 g 0 2-anilino-4,6-dimethylpyrimidine per kilogram of seed, such as for example fro 0.01 to 1.0 g per kilogram of seed.

Alternatively the composition of the invention can be applied directly to plants by, for example, spraying or dusting either at the time which the fungus has begun to appear on the plant or before the appearance of fungus, as a protective measure. In both cases the preferred mode of application is by foliar spray. When the composition of the invention is applied directly to the plant a suitable rate of application is from 0.005 to 2 kilograms per ,,44 hectare, preferably from 0.1 to 1 kilogram per hectare.

The invention thus includes a method of combating phytopathogenic fungi which comprises applying to the fungus or its locus a mixture according to the invention.

The invention is illustrated in the following Example which describe in vitro experiments in which a synergistic effect was observed.

Example 2-Anilino-4,6-dimethylpyrimidine and component (b) fungicides were incorporated into molten agar in amounts to give the required concentration of active ingredient in the agar. The molten agar was then poured into petri 0 dishes and allowed to set. 5 mm mycelial plugs of an agar culture of the specified fungus were transferred to the centre of each plate with the mycelium surface down. The dishes were incubated at 20 0 C. The colony diameters were then measured at various times and the percentage control 15 of growth in comparison with the growth in a dish of agar, used as a standard, which had been Aimilarly inoculated but contained no active ingredient, was calculated.

To indicate the existence of synergism between the active components the results were treated in the manner described by Colby "Calculating Synergistic and S, Antagonistic Responses of Herbicide Combinations" in Weeds 1967 15, 20-22). In this method the "expected" percent control of growth, E, of the combination compared with untreated control is given by the equation

AF

E=A+F-

AF

100 where A is the control by 2-anilino-4,6-dimethylpyrimidine, used alone at a given concentration and F is the control by component used alone at a given concentration. If the observed control of the mixture is greater than E the results indicate synergism. In Table I evidence of synergism is shown at the given rates.

1) Prochloraz a) Pyricularia oryzae Concentration Concentration of 2-anilino- of 4,6-dimethyl- prochloraz observed control 0%) Expected control (E in pyrimidine (ppm) (ppm) 25 0 0 0.25 0.25 0 0 0 0.25 0.05 0.05 0.25 0.05 0.25 0.05 5 76.7 85.5 76.3 85.9 80.3 87.7 2) Chiorothalonil a) Botrytis cinerea Concentration (Qoncentration of 2-anilino- of 4,6-dimeth~lyl- chiorothalonil pyriinidine (ppm) (ppm) observed control Expected control (E in 0.25 1.25 0 0 0 0.25 0.25 0.25 1.25 0 0 0.05 0.25 1.25 0.05 0.25 1.25 1.25 3) Fenpropidin a) Bot-rytis cinerea Concentration Concentration of 2-anilino- of 4,6-dirnethyl- fenpropidin pyrimidine (ppm) (ppm) observed control Expected control (E in 0.25 0.25 1.25 0.25 1.25 0.25 0.25 b) Gaeumanriomyces grarninis Concentration Concentration of 2-anilino- of 4,6-dimethyl- fenpropidin pyrimidine (ppm) (ppm) observed control Expected control (E in 0.25 0 6 0.05 0.25 1.25 0.05 0.25 1.25 0.25 0.25 0.25 4) Prooiconazole a) Pseudocercosporella herpotrichoides Concentration Concentration Observed of 2-anilino- of control 4,6-dimethyl- propiconazole 006) pyrimidine (ppm) (ppm) Expected control (E in 0.05 0.25 0 0. 05 0.25 0 0 0.05 0. 0.05 Flusilazole a) Botrytio cinez-ea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of flusilazole (ppm) Observed control

M%

Expected control (E in 1.25 0 0 1.25 1.25 0.05 0.25 0.25 6) Mancozeb a) Pyricularia oryzae Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of mancozeb (ppm) observed control Expected control (E in 0.05 0 1 0.25 0 23 0.05 0.05 0.05 0.05 0.25 7) Thiran, a) Botrytis cinerea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of thiram (ppm) observed control Expected control (E in 0.05 0.25 1.25 0.05 0.25 1.25 1.25 1.25 1.25 1.25 8! Trrodione a) Botrytis cinerea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of iprodione (ppm) Observed control Expected control (E in 0.25 0 0.25 0 0.05 0.05 9) Enoxiconazole a) Botrytis cinerea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of epoxiconazole (ppm) observed control Expected control (E in 0.05 0 4 0.25 0 17 1.25 0 0. 05 0.25 1.25 1.25 1.25 1.25 1.25 Bromuconazole a) Scierotinia sclerotiorum Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of bromuconazole (ppm) Observed control Expected control (E in 0.05 0.25 0.05 0.05 0.05 0. 05 0.25 11) Cyproconazole a) Botrytis cinerea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of cyproconazole (ppm) Observed control Expected control (E in 0.25 0 11 1.25 0 23 1.25 1.25 1.25 0.25 1.25 b) Scierotiun rolfsii Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of cyproconazole (ppm) observed control Expected control (E in 0. 05 0.25 0 0. 05 0.25 0 0 0.05 0.05 0. 12) Diniconazole a) Botrytis cinerea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of diniconazole (ppm) observed control

I.)

Expected control (E in 0.25 1.25 0 0 0 0.25 0.25 0.25 1.25 1.25 0.05 0.25 1.25 0.05 0.25 1.25 0.05 0.25 1.25 b) Scierotinia scierotiorum Concentration of 2-anilino- 4,6-dimethylpyrimidine (ppm) Concentration of diniconazole (ppm) observed control Expected control (E in 0.25 0 :1 1.25 0 9 0.25 0.25 1.25 0.05 0.25 0.05 0.25 0.05 0.25 13) Flucguinconazole a) Fusariua nivale Concentration Concentration of 2-anilino- of 4,6-dimethyl- fluquinconazole pyrimidine (ppm) (ppm) observed control Expected control (E in 0.25 0 12 1.25 0 0.25 0.25 1.25 1.25 0.25 1.25 0.25 1.2'5 0.25 1.25 14) Tebuconazole a) Botrytis cinerea Concentration Concentration of 2-anilino- of 4, 6-dimethyl- tebuconazole pyrimidine (ppm) (ppm) observed control Expected control (E in 1.25 1.25 1.25 1.25 12593 82 Vinclozolin a) Scierotium r-olfsii Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) concentration of vinclozolin (ppm) observed control Expected control (E in 0.25 0 6 1.25 0 14 0.05 0.05 0.05 0.25 1.25 16) Benomnvl a) F~ 2sariurn nivale Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of benomyl (ppm) observed control Expected control- (E in 0.25 0 0.25 0 0.01 0.01 38 22 17) Difenoconazole a) Botrytis cinerea Concentration Concentration of 2-anilino- of 4,6-dimethyl- difenoconazole pyrimidine (ppm) (ppm) Observed control Expected control (E in 1.25 0 1.25 0 1.25 1.25 18) Hexaconazole a) Botrytis cinerea Concentration of 2-anilino- 4,6-dimethylpyrimidine (ppm) Concentration of hexaconazole (ppm) Observed control Expected control (E in 1.25 0 18 0.05 0.25 1.25 0.05 0.25 1.25 1.25 1.25 1.25 19) Thiophanate-methyl a) Botrytis cinerea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of thiophanatemethyl (ppm) Observed control Expected control (E in 1.25 1.25 1.25 1.25 Hymexazol a) BotrytIs cinerea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of hymexazol (ppm) IQbserved ccoritrol Expected control (E in 0.25 0 26 1.25 0 1. 1.25 1.25 0.25 1.25 21) ofurace a) Fusarium nivale Concentration of 2-anilino- 4, 6-dimethylpyrimid mne (ppm) Concentration of ofurace (ppm) Observed control Expected control (E in 1.25 0 1.25 0 0.05 0.05 22) BAS 490F a) BotrytiS cinerea Concentration of 2-anilino- 4, 6-dimethylryr imidine (ppm) Concentration of BAS 490F (ppm) Observed control Expected control (E in 0. 1.25 0. 1.25 1.25 0. 0. 05 1.25 23 ICIA 5504 a) Botrytis cinerea Concentration of 2-anilino- 4, 6-dimethylpyrimidine (ppm) Concentration of ICIA 5504 (ppm) Observed control Expected control (E in 0.05 0.05 0.05 0.05 25a Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

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Claims (1)

1. 3. The stepo, features, compositions and oompo disclosed herein or referred to or ind n the specification and/or cl this application, individu collectively, and any and all combinations S oif ny two or more of said otepo or featureo. i I i lII DATED this EIGHTH day of JUNE 1993 Schering Aktiengesellschaft by DAVIES COLLISON CAVE Patent Attorneys for the applicant(s) ABSTRACT There is provided a fungicidal composition comprising 2-anilino-4,6-dimethylpyrimidine and another fungicide. The compositions have synergistic properties. e i o i i