AU2007200796B2 - Synergistic Seed Treatment Compositions - Google Patents

Description

P/00/0II Regulation 3.2 AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT (ORIGINAL) Name of Applicant: Syngenta Participations AG, of Intellectual Property Department, Schwarzwaldallee 215, CH-4058, Basel, Switzerland Actual Inventor: Birgit FORSTER Address for Service: DAVIES COLLISON CAVE, Patent & Trademark Attorneys, of I Nicholson Street, Melbourne, 3000, Victoria, Australia Ph: 03 9254 2777 Fax: 03 9254 2770 Attorney Code: DM Invention Title: Synergistic Seed Treatment Compositions The following statement is a full description of this invention, including the best method of performing it known to us:- C '\NRPonbEDCCORXSMAl7flI OC-24l32 1I

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SYNERGISTIC SEED TREATMENT COMPOSITIONS This is a divisional of Australian Patent Application No. 2002353292, the entire contents of which are incorporated herein by reference. 5 The present invention relates to fungicidal mixtures for the treatment of plant propagation material and to methods of using such mixtures In crop protection. The mixtures according to the Invention comprise at least two fungicidally active components together with a suitable carrier material, wherein component I is 10 1) fludioxonil (= 4-(2,2-dfluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile; The Pesticide Manual, 12th. edition, 2000, 361); and wherein component Il Is IIA) azoxystrobin (-methyl (E)-2-(2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl)-3 methoxyacrylate; The Pesticide Manual, 12th. edition, 2000, 49) or 15 1lI) picoxystrobin (= methyl (E)-3-methoxy-2-[2-(6-trifluoromethyl-2 pyrldyloxymethyl)phenyl]acrylate; The Pesticide Manual, 12th. edition, 2000, 622) or IIC) kresoxim-methyl (= methyl (E)-methoxyimino[2-(o-tolyloxymethyl)phonyl]acetatO; The Pesticide Manual, 12th. edition, 2000,412). 20 In one aspect the invention provides an agrochemical composition comprising at least two active ingredient components together with a suitable carrier, wherein component I is fludioxonil (= 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile) and wherein component II is picoxystrobin (= methyl (E)-3-methoxy-2-[2-(6-trifluoromethyl-2 pyridyloxymethyl)phenyl]acrylate). 25 In another aspect the invention provides agrochemical composition comprising at least two active ingredient components together with a suitable carrier, wherein component I is fludioxonil (= 4-(2,2-difluoro-1,3-benzodioxol-4-y)pyrrole-3-carbonitrife) and wherein component 11 is kresoxim-methyl (= methyl (E)-methoxyimino(2-(o 30 tolyloxymethyl)phenyl]acetate, with the proviso that other fungicides are absent. In a further aspect the invention provides an agrochemical composition comprising I fludioxonil (= 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile) and 1i azoxystrobin (=methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl)-3- C:WRPobnDCCYXS\7877..l.OC-2iV/2011) -2 methoxyacrylate) as sole active ingredients, together with a suitable carrier, wherein the ratio by weight of 1:11 is from 2.5:1 to 1:15. The fungicidal mixtures according to the Invention have very advantageous properties for 5 protecting plants against disease infestation, particularly in the control and prevention of disease infestation on seed and soil. These properties are for example the synergistically enhanced action of mixtures of components I and II. resulting In lower disease infestation, lower rates of application, a t0 longer duration of action and altogether higher crop yields. Another property Improved by the Instant mixtures is summarized as plant vigor. Under the term plant vigor there are understood various sorts of improvements of plants which are not connected to the control of pests. For example such advantageous properties that may be mentioned are improved crop characteristics including: emergence, crop yields, protein content, more developed root 15 system, tillering Increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, less fertilizer needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, increased plant stand and early germination: or any other advantages familiar to a person skilled in the art. Such enhancements were not to be expected from the activity of 20 the individual components. The weight ratio is selected as to give the desired, for example synergistic, action. In general, the weight ratio 1:11 is from 6:1 to 1:30, preferably from 2.5:1 to 1:15. 25 Advantageous mixing ratios of the two active ingredients are 2.5:1, 1.25:1 and 1:6 by weight. The above mentioned mixtures may be mixed with other pesticides, preferably fungicides, resulting in some cases In unexpected synergistic activities. 30 -2A The active ingredient mixtures in question can be used as dressings In the treatment of plant 5 propagation material, especially seed (fruit, tubers, grains) and plant cuttings (e.g. rice), to provide protection against fungus infections on the seed as well as against phytopathogenio fungi which occur In the soil. The active Ingredient mixtures according to the Invention are distinguished by the fact that they are especially Well tolerated by plants and are environmentally friendly. 10 The active ingredient mixtures are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Penicillium, Gaeumannomyces graminis); Basidlomycetes (e.g. the genus Hemileia, Rhizoctonia, Puccinia); Fungi Imperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, 15 Pyricularia and Pseudocercosporella herpotricholdes); Oomycetes (e.g. Phytophthora, Peronospora, Bremia, Pythium, Plasmopara). In a further aspect the compositions of the invention are effective against one or more of Ascomycetes, Basidiomycetes, Fungi imperfecti, and Qomycetes. Target crops for the areas of Indication disclosed herein comprise within the scope of this invention e.g. the following species of plants: cereals (wheat, barley, rye, oats, corn, maize, rice, sorghum and related crops); beet (sugar beet and fodder beet); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard; sunflowers,); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); as well as ornamentals (flowers, shrubs, broad-leaved trees and evergreens, such as conifers). This list does not represent any limitation. The active Ingredient mixtures according to the invention are especially advantageous for the treatment of plant propagation material, especially seeds, of cotton, corn, soybeans, rice and peanuts.

-3 The mixtures of compounds I and I are normally used in the form of compositions. The compounds I and II can be applied to the plant propagation material to be treated either simultaneously or in succession at short interval, for example on the same day, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology. Suitable carriers and adjuvants can be solid or liquid and are the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. In order to treat plant propagation material, especially seed, the compounds I and II can also be applied to the seeds (coating), either by impregnating the tubers or grains with a liquid formulation of each of the active ingredients in succession, or by coating them with an already combined wet or dry formulation. The compounds of the combination are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are therefore formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, or by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomizing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application of the active ingredient mixture are generally from 2 g to 35 g, preferably from 2 g to 20 g, per 100 kg of plant propagation material, especially seed. Preferred rates are from 1 g to 5 g, especially preferred 2.5 g, of compound I and 1 g to 30 g, especially preferred 1 g to 15 g, of compound I per 100 kg of plant propagation material, especially seed. The formulations are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

-4 Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water. The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverized plant residues. Depending upon the nature of the compounds I and I to be formulated, suitable surface active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants. Particularly advantageous application-promoting adjuvants are also natural or synthetic phospholipids of the cephalin and lecithin series, e.g. phosphatidylethanolamine, phos phatidylserine, phosphatidylglycerol and lysolecithin. The agrochemical compositions normally comprise 0.1 to 99 %, especially 0.1 to 95 %, compounds I and II, 99.9 to 1 %, especially 99.9 to 5 %, of a solid or liquid adjuvant and 0 to 25 %, especially 0.1 to 25 %, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The Examples which follow serve to illustrate the invention, "active ingredient" denoting a mixture of compound I and compound II in a specific mixing ratio.

-5 Formulation Examples Wettable powders a) b) C) active ingredient (1:11 = 1:6(a), 1:2(b), 1:1(c)] 25% 50% 75% sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether - 2 % (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration. Dusts a) b) c) active ingredient [1:11 = 1:6(a), 1:2(b), 1:10(c)] 5% 6% 4% Talcum 95% - Kaolin - 94% mineral filler - 96% Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can be used for dry dressings for seed. Suspension concentrate active ingredient (1:11 = 1:8) 40% propylene glycol 10% nonylphenol polyethylene glycol ether 6 % (15 mol of ethylene oxide) sodium lignosulfonate 10% carboxymethylcellu lose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % water 32 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspen sion concentrate from which suspensions of any desired dilution can be obtained by dilution -6 with water. Using such dilutions plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Biological Examples A synergistic effect exists, for example, 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, S.R. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (= a.i.) per litre of spray mixture X = % action by active ingredient I using p ppm of active ingredient Y = % action by active ingredient I using q ppm of active ingredient. According to Colby, the expected (additive) action of active ingredients 1+11 using p+q ppm of active ingredient is E = X+ Y -Y 100 If the action actually observed (0) is greater than the expected action (E), then the action of the combination is superadditive, i.e. there is a synergistic effect. Al) Rhizoctonia solanil Cotton (Damping off on Cotton) A defined amount of mycelium of R. solani is blended with soil and trays are filled with the inoculated soil. The formulated test mixtures are applied to cotton seeds (cv. Sure Grow 747). The treated cotton seeds are then sown into the inoculated soil. Until germination the trays are stored at 200 C and a rel. humidity of 90% in the dark. After germination the trays are transferred to 250 C and a rel. humidity of 70% with a photoperiod of 14h. The evaluation is done by counting the emerged cotton plants and the number of emerged and diseased plants. The mixtures +IIA, l+11B and l+IlC according to the instant invention show good synergistic action.

P OPERWALUT OI85229 New Div doc-2202/OO7 -7 The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from 5 it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates. Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will 10 be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

Claims (17)

1. An agrochemical composition comprising at least two active ingredient 5 components together with a suitable carrier, wherein component I is fludioxonil (= 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile) and wherein component II is picoxystrobin (= methyl (E)-3-methoxy-2-[2-(6-trifluoromethyl-2 pyridyloxymethyl)phenyl acrylate). 10

2. An agrochemical composition comprising at least two active ingredient components together with a suitable carrier, wherein component I is fludioxonil (= 4-(2,2 difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile) and wherein component 11 is kresoxim methyl (= methyl (E)-methoxyimino[2-(o-tolyloxymethyl)phenyl]acetate, with the proviso that other fungicides are absent. 15

3, A composition according to either claim 1 or claim 2, wherein the ratio by weight of 1:ll is 5:1 to 1:30.

4. A composition according to either claim 1 or claim 2, wherein the ratio by weight of 20 1:11 is from 2.5:1 to 1:15.

5. A composition according to either claim 1 or claim 2, wherein the ratio by weight of 1:11 is 2.5:1, 1.25:1 or 1:6. 25

6. A composition according to any one of claims 1 to 5 which is effective against one or more of Ascomycetes, Basidiomycetes, Fungi imperfecti, and Oomycetes.

7. An agrochemical composition comprising I fludioxonil (= 4-(2,2-difluoro-1,3 benzodioxol-4-yl)pyrrole-3-carbonitrile) and 11 azoxystrobin (=methyl (E)-2-{2-[6-(2 30 cyanophenoxy)pyrimidin-4-yloxyl phenyl)-3-methoxyacrylate) as sole active ingredients, together with a suitable carrier, wherein the ratio by weight of 1:11 is from 2.5:1 to 1:15.

8. A composition according to claim 7, wherein the ratio by weight of 1:11 is 2.5:1, 1.25:1 or 1:6. C: NR P.n h lD CTRX\2797 74 H_ I. DOC-2 4 A 2010

9. A composition according to either claim 7 or claim 8 which is effective against one or more of Ascomycetes, Basidiomycetes, Fungi imperfecti, and Oomycetes. 5 10. A method of protecting plants against plant diseases by treating plant propagation material with (i) a composition defined in any one of claims I to 9, or (ii) component I and component 11, as defined in claim 7, as sole active ingredients, where the weight ratio of I to II is 2.5:1 to 1:15, in any desired sequence or simultaneously.

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11. A method according to claim 10 wherein rates of I and II is from 2 to 35 grams per 100kg of plant propagation material.

12. A method according to either claim 10 or claim 11, wherein seed is treated. 15

13. A method according to claim 12, wherein seed of cotton, corn, soybeans, rice or peanuts is treated.

14. Plant propagation material which has been treated in accordance with any one of claims 10 to 13. 20

15. A composition according to any one of claims 1-9 substantially as hereinbefore described.

16. A method according to any one of claims 10 to 13 substantially as hereinbefore 25 described.

17. A plant propagation material according to claim 14 substantially as hereinbefore described.