AU766275B2 - Fungicidal combinations comprising a 4-phenoxyquinoline - Google Patents

Description

AUSTRALIA

PATENTS ACT 1990 DIVISIONAL APPLICATION NAME OF APPLICANT: Noi~vacaL 4C A ISEC ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street Melbourne, 3000.

INVENTION TITLE: "Fungicidal combinations comprising a 4-phenoxyquinoline" The following statement is a full description of this invention, including the best method of performing it known to us: -1A- FUNGICIDAL COMBINATIONS COMPRISING A 4-PHENOXYQUINOLINE This application is a divisional of Australian Patent Application No. 81041/98, the entire contents of which are incorporated herein by reference.

The present invention relates to novel fungicidal compositions for the treatment of phytopathogenic diseases of crop plants, especially phytopathogenic fungi, and to a method of combatting phytopathogenic diseases on crop plants.

It is known that certain phenoxyquinoline derivatives have biological activity against phytopathogenic fungi, e.g. from EP-A-0326330 where their properties and methods of preparation are described. On the other hand azole fungicides, morpholines and aminopyrimidines are widely known as plant fungicides for application in various crops of cultivated plants. However, crop tolerance and activity against phytopathogenic plant fungi do not always satisfy the needs of agricultural practice in many incidents and aspects.

It has now been found that the use of a) a 4-phenoxyquinoline of formula I C F ot (I Cl in association with b) either a morpholine fungicide of formula III

H

3

C

0 N-R H3C 3 wherein

"R

9 is C8- 1 5 cycloalkyl, C 8 -isalkyl or C 14 alkylphenyl-C 1 -alkyl, with the proviso that the compound of formula III is not tridemorph, and the salts of such morpholine fungicide; or a compound of formula V -2-

CH

3

C

H

3

H

3 C CH2-CH-CH,-N

CH

3 or a compound of formula VI Cl C CO-N O (VI)

H

3

CO

OCH3 is particularly effective in combatting or preventing fungal diseases of crop plants. These combinations exhibit synergistic fungicidal activity.

The combinations according to the invention may also comprise more than one of the active components if broadening of the spectrum of disease control is desired.

Salts of the morpholine active ingredients are prepared by reaction with acids, hydrohalo acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, or sulfuric acid, phosphoric acid or nitric acid, or organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, lactic acid, succinic acid, S citric acid, benzoic acid, cinnamic acid; oxalic acid, formic acid, benzensulfonic acid, ptoluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid and 1,2-naphtalenedisulfonic acid The active ingredient combinations are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes the genus Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella herpotrichoides (Tapesia spp.)); Oomycetes Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).

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, rice, sorghum -3and related crops); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor); or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (flowers, shrubs, broad-leaved trees and evergreens, such as conifers). This list does not represent any limitation.

The combinations according to the present invention are particularly effective against powdery mildews.and rusts; Rhynchosporium and Pyrenophora, and leptosphaeria:fungi; in particular against pathogens of monocotyledoneous plants such as cereals, including wheat and barley.

The amount of combination of the invention to be applied, will depend on various factors such as the compound employed, the subject of the treatment (plant, soil, seed), the type of treatment spraying, dusting, seed dressing), the purpose of the treatment (prophylactic or therapeutic), the type of fungi to be treated and the application time.

Particularly preferred mixing partners of the compounds of formula III are those wherein R 9 is cyclododecyl (commonly known as dodemorph). Predominantly, the cis-positioning of the methyl groups at the morpholine ring is present in the compounds of formula III when used in the combinations of the invention.

The compound of formula V is commonly known as fenpropidin.

The compound of formula VI is commonly known as dimethomorph.

The specific compounds b) mentioned in the preceding paragraphs are commercially available. Other compounds falling under the scope of the various groups of component b) -4are obtainable according to procedures analogous to those known for preparing the commercially available compounds.

Specific combinations according to present invention are: compound of formula I with a second fungicide selected from the group dodemorph, fenpropidin or dimethomorph.

The most preferred combinations according to present invention are those of fenpropidin with the compound of formula I.

The weight ratio of is so selected as to give a synergistic fungicidal action. In general the weight ratio of a) b) is between 10 1 and 1 50. The synergistic action of the composition is apparent from the-fact that the fungicidal action of the composition of a) b) is greater than the sum of the fungicidal actions of a) and b).

Where the component b) is a morpholine fungicide of formula III the weight ratio of is for example between 1:1 and 1:10, especially 1:2 and 1:10, and more preferably 1:3 to 1:8.

Where component b) is the fungicide of formula V, the weight ratio of a) b) is for example o. between 1:1 and 1:10, especially 1:2 and 1:10, and more preferably 1:3 and 1:8.

:i Where component b) is the fungicide of formula VI, the weight ratio of a) b) is for example between 1:1 and 1:20, especially 1:3 and 1:15, and more preferably 1:4 and 1:10.

The method of the invention comprises applying to the treated plants or the locus thereof in admixture or separately, a fungicidally effective aggregate amount of a compound of formula I and a compound of component b).

o The term locus as used herein is intended to embrace the fields on which the treated crop plants are growing, or where the seeds of cultivated plants are sown, or the place where the seed will be placed into the soil. The term seed is intended to embrace plant propagating material such as cuttings, seedlings, seeds, germinated or soaked seeds.

The novel combinations are extremely effective on a broad spectrum of phytopathogenic fungi, in particular from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal combinations are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The combinations are applied by treating the fungi or the seeds, plants or materials threatened by fungus attack, or the soil with a fungicidally effective amount of the active ingredients.

The agents may be applied before or after infection of the materials, plants or seeds by the fungi.

The novel combinations are particularly useful for controlling the following plant diseases: Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugarcane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Septoria tritici in wheat wheat, Rhynchosporium secalis on barley Botrytis cinerea (gray mold) in strawberries, tomatoes and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides (Tapesia spp.) in wheat and barley, Pyrenophera teres in barley Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.

When applied to the plants the compound of formula I is applied at a rate of 50 to 200 g/ha, particularly 75 to 150 g/ha, e.g. 75, 100, or 125g/ha, in association with 50 to 1500 g/ha, particularly 60 to 1000 g/ha, e.g. 75 g/ha, 80 g/ha, 100 g/ha, 125 g/ha, 150 g/ha, 175 g/ha 200 g/ha, 300 g/ha, 500 g/ha, or 1000 g/ha of a compound of component depending on the class of chemical employed as component Where the component b) is a morpholine fungicide of formula III for example 250 to 500 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula V for example 300 to 450 g a.i./ha is applied in association with the compound of formula I, where the component b) is the compound of formula VI for example 100 to 900 g a.i./ha is applied in association with the compound of formula I.

In agricultural practice the application rates depend on the type of effect desired, and range from 0.02 to 3 kg of active ingredient per hectare.

When the active ingredients are used for treating seed, rates of 0.001 to 50, and preferably from 0.01 to 10g per kg of seed are generally sufficient.

The invention also provides fungicidal compositions comprising a compound of formula I and a compound of component b).

The composition of the invention may be employed in any conventional form, for example in the form of a twin pack, an instant granulate, a flowable or a wettable powder in combination with agriculturally acceptable adjuvants. Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate adjuvants (diluents or solvents and optionally other formulating ingredients such as surfactants).

Suitable carriers and adjuvants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binding agents or fertilisers. Such carriers are for example described in WO 96/22690.

Particularly formulations to be applied in spraying forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, 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, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g.

as slow release capsules or microcapsules.

In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to agriculturally acceptable surfactant and 10 to 99.99% solid or liquid adjuvant(s), the active agent consisting of at least thee compound of formula I together with a compound of component and optionally other active agents, particularly guazatin and fenpiclonil.

Concentrate 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.

Examples for specific formulations-combination are as disclosed e.g. in WO 96/22690, e.g.

for wettable powders, emulsifiable concentrate, dusts, extruder granules, coated granules, suspension concentrate.

Slow Release Capsule Suspension 28 parts of a combination of the compound of formula I and a compound of component or of each of these compounds separately, are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanatemixture This mixture is emulsified in a mixture of -8- 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerisation reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.

The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

-9- Biological Examples 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, S.R. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967): ppm milligrams of active ingredient per litre of spray mixture X action by active ingredient I using p ppm of active ingredient Y action by active ingredient II using q ppm of active ingredient.

According to Colby, the expected (additive) action of active ingredients 1+11 using p+q ppm of

X.Y

active ingredient is E X Y 100 If the action actually observed is greater than the expected action then the action of the combination is superadditive, i.e. there is a synergistic effect.

Alternatively the synergistic action may also be determined from the dose response curves according to the so-called WADLEY method. With this method the efficacy of the a.i. is determined by comparing the degree of fungal attack on treated plants with that on untreated, similarly inoculated and incubated check plants. Each a.i. is tested at 4 to 5 concentrations.

The dose response curves are used to establish the EC90 concentration of a.i. providing disease control) of the single compounds as well as of the combinations (EC 9 0observed).

The thus experimentally found values of the mixtures at a given weight ratio are compared with the values that would have been found were only a complementary efficacy of the components was present (EC 90 (A+B)expected). The EC90 (A+B)expected is calculated according to Wadley (Levi et al., EPPO- Bulletin 16, 1986, 651-657): a+b EC 90 expected a b obsered EC90 observed wherein a and b are the weight ratios of the compounds A and B in the mixture and the indexes refer to the observed EC 90 values of the compounds A, B or the given combination A+B thereof. The ratio EC90 (A+B)expected EC90 (A+B)obseved expresses the factor of interaction In case of synergism, F is >1.

Example B-1: Residual-protective action against Venturia inaequalis on apples Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip point with an aqueous spray mixture prepared from a wettable powder formulation of the active ingredient mixture and infected 24 hours later with a conidia suspension of the fungus. The plants are incubated for 5 days at 90-100 relative humidity and stood in a greenhouse for a further 10 days at 20-24°C. Fungus infestation is evaluated 12 days after infection.

Example B-2: Action against Botrytis cinerea on apple fruits Artificially damaged apples are treated by dropping a spray mixture of the active ingredient mixture onto the damage sites. The treated fruits are then inoculated with a spore suspension of the fungus and incubated for one week at high humidity and about 20*C. The fungicidal action of the test compound is derived from the number of damage sites that have begun to rot.

Example B-3: Action against Podosphaera leucotricha on apple shoots Apple cuttings with about 15 cm long fresh shoots are sprayed with a spray mixture of the active ingredient mixture. The treated plants are infected 24 hours later with a conidia suspension of the fungus and placed in a climatic chamber at 70 relative humidity and 0 C. Fungus infestation is evaluated 12 days after infection.

Example B-4: Action against Drechslera teres on barley barley plants of the "Golden Promise" variety are sprayed with a spray mixture of the active ingredient mixture. The treated plants are infected 24 hours later with a conidia suspension of the fungus and incubated in a climatic chamber at 70 relative humidity and 20-22 0 C. Fungus infestation is evaluated 5 days after infection.

-11 Example B-5 Efficacy against Erysiphe graminis f.sp. tritici on wheat Five to ten wheat seeds c.v. "Arina" are sown in plastic pots of 7 cm diameter and grown for 7 to 12 days at 20°C, 50-70% rH. When the primary leaves have fully expanded, the plants are spray treated with aqueous spray liquors containing the single compounds, or mixtures thereof (hereinafter All compounds are used as experimental or commercially available formulations, combinations are applied as tank mixtures. The application comprises foliar spraying to near runoff (three pots per treatment). 24 hours after the application or 24 hours before application, the plants are inoculated in a settling tower with fresh spores of Erysiphe graminis f. sp. tritici. The plants are then incubated in a growth chamber at 20°C, 60% rH.

Seven days after the inoculation, the percentage of infection on primary leaves is evaluated.

The efficacy of the a.i. is determined by comparing the degree of fungal attack on treated plants with that on untreated, similarly inoculated and incubated check plants. Each a.i. is tested at 4 to 5 concentrations. The synergie factor is calculated according to the COLBY method.

-12- Results Table 1 (curative application) Quino- Fenpro- Ratio activity activity SF xyfen pidin observed expected Colby mg a.i./l mg a.i./l 0.05 1 0.1 3 0.25 6 4 1 7 7 8 16 24 34 0.05 0 1 1:25 41 30 1.4 0.05 1:1 17 8 2.2 0.05 1:2 15 9 1.6 0.05 1:5 25 17 0.1 2:1 16 10 1.6 0.1 1:1 21 11 1.9 0.1 1:5 37 26 1.4 0.25 1:1 30 21 1.4 0.25 1:2 48 29 1.7 2:1 40 20 2 1:1 58 27 2.2 0.05 1:2 48 35 1.3 0.05 0.05 1:1 40 1 -13- Table 2 (protective application) Quinoxyfen Fenpropidin Ratio activity activity SF observed expected Colby mg a.i./I mg a.i./l 0.05 0 0.1 1 0.25 3 1 2 4 12 1 12 2 0.05 1:5 7 4 0.1 2:1 6 2 3 0.1 1:1 11 3 3.6 0.1 1:2,5 16 5 3.2 0.1 1:5 17 13 1.3 0.25 2,5:1 14 5 2.8 0.25 1:1 12 7 1.7 0.05 1:2 11 1 11 0.05 1:5 23 12 1.9 0.05 0.5 1:10 4 2 2 Example B-7: Activity against Uncinula necator Grape plants, 4 weeks old (4-5 leaves), are sprayed to near run off with a suspension containing 250 mg/1 of active ingredient. The deposit is then allowed to dry. One day later, the treated plants are inoculated by dusting freshly harvested conidia over the test plants; then the plants were incubated in a growt chamber for 10-14 days at +22°C and 70% r.h.

P:\OPER\Mal\2410198 spcdoc-24A40)l -14- The efficacy of the test compounds is determined by comparing the degree of fungal attack with that on untreated, similarly inoculated check plants.

The mixtures according to the invention exhibit good activity in these examples.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will 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.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

Claims (2)

1. A method of combatting phytopathogenic diseases on crop plants which comprises applying to the crop plants or the locus thereof being infested with said phytopathogenic disease an effective amount of a synergistic combination of a) a 4-phenoxyquinoline of formula I CI O0 F I(I) Cl N in association with b) either a morpholine fungicide of formula III HC 0 N-R, (III) H 3 C 3 wherein R is Ca-iscycloalkyl, C 8 15 alkyl or Ci-alkylphenyl-C.4alkyl, with the proviso that the compound of formula III is not tridemorph, and the salts of such morpholine fungicide; or a compound of formula V CH CH, H 3 C CHc-CH-CHN CH 3 or a compound of formula VI •eo P:\OPERUgc\46219-01 Is spa.doc-05A8/03

16- C1 _C CO--N O (VI H 3 CO CH OCH, 2. A method according to claim 1 wherein the component b) is selected from the group comprising dodemorph, fenpropidin and dimethomorph. 3. A method according to claim 2 wherein the component b) is fenpropidin. 4. A method according to any of claims 1 to 3 wherein the components a) and b) are applied in a quantity producing a fungicidal disease controlling effect. A fungicidal composition comprising a fungicidally effective synergistic S*combination of a) a 4-phenoxyquinoline of formula I according to claim 1 in association with S 20 b) either a morpholine fungicide of formula Ill, or a compound of formula V, or a compound of formula VI, as defined in claim 1. 6. A composition according to claim 5 the weight ratio of a) to b) is between 10: 1 and 1 7. A composition according to claims 5 or 6 wherein the component b) is selected from the group comprising dodemorph, fenpropidin and dimethomorph. 8. A composition according to claim 7 wherein the component b) is fenpropidin. P:\OPERUgC\46219411 Isi spadoc-06/10803 -17- 9. A method of combating phytopathogenic diseases according to claim 1 substantially as hereinbefore described with reference to the Examples. DATED this 6 t h day of August, 2003 Syngenta Participations AG by DAVIES COLLISON CAVE Patent Attorneys for the Applicant ooo -e-s-