Patent Application
20090081174
The present invention relates to synergistic fungicidal compositions.
In particular, the present invention relates to new synergistic compositions capable of controlling phytopathogens which cause considerable economic damage to agricultural crops.
More specifically, the present invention also relates to the use of compositions comprising mixtures based on a copper (II) salt of phosphorous acid, also called phosphite or phosphonate, with at least another metallic salt of phosphorous acid and the use of compositions comprising mixtures based on a copper (II) salt of phosphorous acid, also called phosphite or phosphonate, alone or mixed with at least another salt of a metal of phosphorous acid and one or more fungicidal compounds.
The use of salts of phosphorous acid as fungicides is generally known in literature, for example in American patent U.S. Pat. No. 4,075,324.
The Applicant has now surprisingly found that copper (II) salts of phosphorous acid are capable of exerting a considerable synergistic effect allowing a higher fungicidal activity to be obtained, than that envisaged on the basis of the activities of single components, when applied in composition with other fungicides, in addition to providing excellent anti-resistance properties.
As resistance phenomena can arise in nature as a result of prolonged treatment with systemic fungicides, it is always important and necessary to find synergies oriented towards anti-resistance strategies.
More specifically, the Applicant has now surprisingly found that mixtures based on copper (II) salts of phosphorous acid and one or more salts of phosphorous acid obtained from metals other than copper, have a considerable synergistic effect, allowing a higher fungicidal activity to be obtained than that envisaged on the basis of the activities of single components and are capable of effectively controlling numerous diseases which can cause damage to crops of great economic interest, such as, vines, potatoes and tobacco.
Said mixtures also have an excellent toxicological and environmental profile, as well as the advantage of having a wider range of use and allowing the dosages of use of copper and also, possibly, of phosphorous acid, to be reduced.
Furthermore, the Applicant has surprisingly found that said mixtures of copper (II) phosphite and other metallic phosphites, in addition to copper (II) phosphite alone, in turn demonstrate a significant synergy with numerous fungicidal products, having common biological targets with those of said copper (II) salt of phosphorous acid.
An object of the present invention therefore relates to a fungicidal composition consisting of mixtures comprising a copper (II) salt of phosphorous acid and at least another metallic salt of phosphorous acid or consisting of mixtures comprising a copper (II) salt of phosphorous acid, alone or mixed with at least another metallic salt of phosphorous acid, and one or more fungicidal compounds.
In particular, the metallic salt of phosphorous acid can be a salt of an alkaline, alkaline-earth metal, an ammonium salt or a salt of Fe, Mn, Zn, Ni, Al, Ti or Se.
Within the spirit of this invention, said mixtures comprising a copper (II) salt of phosphorous acid and at least another metallic salt of phosphorous acid, can be obtained either by mixing the single salts, or by co-precipitation of said salts in a reaction mixture; in both cases, in the above mixture, the copper (II) salt of phosphorous acid and the other metallic salts of phosphorous acid can be present in any proportion, salvation state, structure and crystalline lattice composition.
The salts of an alkaline, alkaline-earth metal, ammonium salt or salts of Fe, Mn, Zn, Ni, Al, Ti or Se, of phosphorous acid can be mono- or dibasic, or they can be mixtures of these in any proportion.
In the fungicidal compositions according to the present invention, said mixtures can also contain salts of alkaline metals in percentages not higher than 10% by weight, such as reaction exchange salts which however do not have a direct fungicidal activity.
As already mentioned, an extension of said synergy concept is to obtain mixtures comprising a copper (II) salt of phosphorous acid alone or in a mixture with at least another metallic salt of phosphorous acid, and with other fungicidal compounds have common biological targets with those of said copper (II) salt of phosphorous acid.
The compound having a fungicidal activity according to the present invention is preferably selected from:
The compounds (1) are described in Italian patent application Nr. MI98A002583.
Compound (2) is described in patent application WO 98/26654 A2.
The compounds (3) are commercial products and their copper salts are described in Italian patent application Nr. MI 2001A002430.
The compounds (4) are easily available on the market.
Compound (5) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 32.
Compound (6) is described in English patent GB 1,500,581.
Compound (7) is described in patent application Wo 96/01559 A1.
Compound (8) is described in English patent GB 2,058,059.
Compound (9) is described in “Phytopathological News” (1978), Vol. 9, page 142.
Compound (10) is described in patent applications EP 550,788 and EP 775,696.
Compound (11) is described in patent application EP 775,696.
Compound (12) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 148.
Compound (13) is described in European patent application EP 382,375.
Compound (14), corresponding to the experimental abbreviation SSF-126, is described in U.S. Pat. No. 5,185,242.
Compound (15) is described in patent application WO 96/01258.
Compound (16) is described in U.S. Pat. No. 4,931,581.
Compound (17) is described in “Brighton Crop Protection Conference—Pests and Diseases” 1996, Congress Records.
Compound (18) is described in European patent application EP 629,616.
Compound (19), also called IKF916, is described in European patent application EP 705,823.
Compound (20) is described in European patent application EP 31,257.
The compounds (21) are described respectively in European patent application EP 219,756 and in “Brighton Crop Protection Conference—Pests and Diseases” 2000, Congress Records.
Compound (22) is described in European patent applications EP 360,701 and EP 611,232.
Compound (23) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 120.
Compound (24) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 339.
Compound (25) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 537.
Compound (26) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 599.
Compound (27) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 252.
Compound (28) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 314.
Compound (29) is described in “The Pesticide Manual”, 1983, VIIth edition, British Crop Protection Council Ed., page 471.
Compound (30) is described in European patent application EP 753,258.
Compound (31) is described in “Brighton Crop Protection Conference—Pests and Diseases” 1998, Congress Records.
Compound (32) is described in patent application WO 01/87822.
Compound (33) is described in “The Pesticide Manual”, 2003, XIIIth edition, British Crop Protection Council Ed.
Compound (34) is a commercial product.
Preferred fungicidal compositions according to the present invention can be selected from
The fungicidal compositions defined as mixture 1, mixture 2, mixture 3 and mixture 4 are particularly preferred.
When they are not commercial products, the single metallic salts of phosphorous acid can be easily obtained in aqueous solution by reaction of phosphorous acid with an inorganic base such as the hydroxide or carbonate of the desired metal, or by reaction of phosphorous acid with an inorganic base, such as sodium or potassium hydroxide and the subsequent reaction with an inorganic salt, for example, chloride, bromide or sulfate of the desired metal, as described in literature in: “GMelins Handbuch Der Anorganischen Chemie” Ed. Verlag Chemie—GMBH—Weinheim.
The fungicidal compositions according to the present invention can be prepared as follows: the mixtures comprising a copper (II) salt of phosphorous acid and at least another metallic salt of phosphorous acid are obtained by mixing the single salts or by co-precipitation of said salts in the reaction mixture.
In this second case, the co-precipitation of the salts is effected starting from phosphites, for example sodium, potassium phosphite, by the shifting of the metallic cation M1 with a mixture, in aqueous solution, of a copper (II) salt and the other desired metallic salt, according to scheme A:
wherein M1 represents a sodium or potassium atom, X represents a halogen, such as chlorine, bromine, iodine or a sulfate group, X1 has the same meaning as X, M2 represents an alkaline earth metal, an ammonium group or a Fe, Mn, Zn, Ni, Al, Ti, Se atom; p is a number greater than 0 and lower than 100 and q is equal to 100-p.
The co-precipitation of a copper (II) salt of phosphorous acid and a salt of an alkaline metal of phosphorous acid is effected starting from the above alkaline salt of phosphorous acid by partial shifting of the metallic cation with a suitable copper (II) salt according to scheme B:
wherein M1, X, p and q have the meanings indicated above.
Analogously mixtures comprising, in addition to copper, two or more metals selected from those listed above, can be prepared.
The fungicidal compositions according to the present invention comprising:
a) a copper (II) salt of phosphorous mixed with at least one salt of an alkaline, alkaline earth metal, an ammonium salt or a salt of Fe, Mn, Zn, Ni, Al, Ti, Se of phosphorous acid;
b) a copper (II) salt of phosphorous acid alone or in a mixture with at least one salt of an alkaline, alkaline earth metal, an ammonium salt, or a salt of Fe, Mn, Zn, Ni, Al, Ti, Se of phosphorous acid, and at least one of the fungicidal compounds (1)-(34);
all have a high fungicidal activity with respect to numerous fungal species.
A further object of the present invention therefore relates to the use of a composition consisting of mixtures comprising a copper (II) salt of phosphorous acid and at least another metallic salt of phosphorous acid or the use of a composition consisting of mixtures based on a copper (II) salt of phosphorous acid, alone or mixed with at least another metallic salt of phosphorous acid and one or more fungicidal compounds, in particular one or more fungicidal compounds (1)-(34), for the control of phytopathogen fungi.
An object of the present invention also relates to a method for the control of phytopathogen fungi in agricultural crops by the application of a fungicidal composition consisting of mixtures comprising a copper (II) salt of phosphorous acid and at least another metallic salt of phosphorous acid or by the application of a composition consisting of mixtures based on a copper (II) salt of phosphorous acid alone or in a mixture with at least another metallic salt of phosphorous and one or more fungicidal compounds, in particular one or more fungicidal compounds (1)-(34).
Examples of pathogens controlled by the above compositions, together with examples of the application crops, are listed hereunder for purely illustrative and non-limiting purposes:
Plasmopara viticola (vines);
Phytophtora infestans (tomatoes, potatoes)
Phytophtora nicotianae (tobacco, ornamental plants);
Phytophtora palmivora (cacao);
Phytophtora cinnamomi (pineapples, citrus fruit);
Phytophtora capsici (peppers, tomatoes, cucurbits);
Phytophtora cryptogea (tomatoes, plums, ornamental plants);
Phytophtora megasperma (ornamental plants);
Phytophtora citri (citrus fruit);
Peronospora tabacina (tabacco);
Pseudoperonospora cubensis (cauliflowers, cucurbits);
Pseudoperonospora umili (hops);
Phytophtora cactorum (fruit trees);
Phytophtora destructor (onions);
Phytophtora fragarie (strawberries)
Bremia (salad).
The compositions, object of the present invention are capable of exerting a high synergistic fungicidal activity allowing preventive, protective, prophylactic, systemic, curative and de-rooting treatment to be effected.
In the above compositions, the copper (II) salt of phosphorous acid and the other metallic salts of phosphorous acid are preferably present in a ratio varying from 10/90 to 90/10 in equivalent phosphorous acid.
Even more preferably, the copper (II) salt of phosphorous acid and the other metallic salts of phosphorous acid are present in a ratio of 50/50 in equivalent phosphorous acid.
The compositions, object of the present invention, can be used in different quantities in relation to the crop, pathogen, environmental conditions and type of formulation adopted.
The fungicidal compositions according to the present invention generally envisage the following application dosages per hectare:
1,000-4,000 g of salt of phosphorous acid;
5-3,500 g for each fungicide from (1) to (34) present in the composition.
The application of the compositions, object of the present invention, can be effected on all parts of the plant, for example on the leaves, stems, branches and roots, or on the seeds themselves before sowing, or on the ground in which the plant grows.
The compositions according to the present invention can be used in agronomical practice in various forms, such as for example: dry powders, wettable powders, emulsifying concentrates, micro-emulsions, pastes, granulates, solutions, suspensions, etc. The choice of the type of composition will depend on the specific use.
The compositions are prepared in the known way, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, possibly in the presence of surface-active agents.
Solid diluents or supports which can be used are: silica, kaolin, bentonite, talc, infusorial earth, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, sepiolite.
Liquid diluents which can be used, are for example, in addition to water, aromatic compounds (xylols or blends of alkylbenzols), paraffins (petroleum fractions), alcohols (methanol, propanol, butanol, octanol, glycerine), amines, amides (N,N-dimethylformamide, Nmethylpyrrolidone), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone), fatty acids (for example, vegetable oils such as rape oil, sunflower oil), esters (isobutyl acetate, methyl esters of fatty acids obtained for example from the transesterification of vegetable oils).
Sodium salts, calcium salts, triethanolamine or triethylamine of alkylsulfonates, alkylaryl sulphonates, polyethoxylated alkylphenols, fatty alcohols condensed with ethylene oxide, polyethoxylated fatty acids, polyethoxylated esters of sorbitol, ligninsulphonates, can be used as surface-active agents.
The compositions can also contain special additives for particular purposes, such as for example, adhesive agents, such as gum Arabic, polyvinyl alcohol, polyvinyl pyrrolidone.
In the fungicidal compositions, object of the present invention, the concentration of active substances varies from 0.1% to 98% by weight, preferably from 0.5% to 90% by weight.
When desired, other compatible active principles can be added to the compositions, object of the present invention, such as, for example, phyto-regulators, antibiotics, herbicides, insecticides, fertilizers.
The following examples are provided for purely illustrative and non-limiting purposes of the present invention.
350 g of H3PO3 and 350 ml of H2O are charged into a 6 l flask. 563.5 g of KOH dissolved in 700 ml of H2O and previously cooled to about 30° C. are added dropwise under stirring on an ice bath. After a few minutes, the aqueous solution obtained by dissolution of 364 g of CuCl2*2H2O and 313.95 g of CaCl2*2H2O in 3500 ml of H2O is added dropwise. The blue-green precipitate which is formed is left under stirring for 24 hours at room temperature, the flask is then heated bringing the internal temperature to about 80° C. and the mixture is left under stirring for a further 4 hours approximately. The hot mixture is filtered on a Buchner funnel and the solid is washed with 3500 ml of H2O previously heated to about 80° C. After drying in an oven, 652 g of the desired product are obtained.
Elemental analysis [% found (theoretical)]=Cu 20.9 (21.2); Ca 13.0 (13.4); P 20.5 (20.7).
350 g of H3PO3 and 350 ml of H2O are charged into a 6 l flask. 563.5 g of KOH dissolved in 700 ml of H2O and previously cooled to about 30° C. are added dropwise under stirring on an ice bath. After a few minutes, the aqueous solution obtained by dissolution of 364 g of CuCl2*2H2O and 613.9 g of ZnSO4*7H2O in 3500 ml of H2O is added dropwise. The blue precipitate which is formed is left under stirring for 24 hours at room temperature, the flask is then heated bringing the internal temperature to about 80° C. and the mixture is left under stirring for a further 4 hours approximately. The hot mixture is filtered on a Buchner funnel and the solid is washed with 3500 ml of H2O previously heated to about 80° C. After drying in an oven, 699 g of the desired product are obtained.
Elemental analysis [% found (theoretical)]=Cu 18.6 (21.2); Zn 16.6 (13.4); P 18.4 (20.7); K 4.18 (0).
350 g of H3PO3 and 350 ml of H2O are charged into a 6 l flask. 563.5 g of KOH dissolved in 700 ml of H2O and previously cooled to about 30° C. are added dropwise under stirring on an ice bath. After a few minutes, the aqueous solution obtained by dissolution of 364 g of CuCl2*2H2O and 360.86 g of MnSO4*H2O in 3500 ml of H2O is added dropwise. The blue precipitate which is formed is left under stirring for 24 hours at room temperature, the flask is then heated bringing the internal temperature to about 80° C. and the mixture is left under stirring for a further 4 hours approximately. The hot mixture is filtered on a Buchner funnel and the solid is washed with 3500 ml of H2O previously heated to about 80° C. After drying in an oven, 451.7 g of the desired product are obtained.
Elemental analysis [% found (theoretical)]=Cu 20.3 (21.4); Mn 16.8 (18.5); P 20.0 (20.9); K 1.49 (O).
350 g of H3PO3 and 350 ml of H2O are charged into a 6 l flask. 563.5 g of KOH dissolved in 700 ml of H2O and previously cooled to about 30° C. are added dropwise under stirring on an ice bath. After a few minutes, the aqueous solution obtained by dissolution of 480.4 g of CuCl2*2H2O and 238.2 g of MnSO4*H2O in 3500 ml of H2O is added dropwise. The blue precipitate which is formed is left under stirring for 24 hours at room temperature, the flask is then heated bringing the internal temperature to about 80° C. and the mixture is left under stirring for a further 4 hours approximately. The hot mixture is filtered on a Buchner funnel and the solid is washed with 3500 ml of H2O previously heated to about 80° C. After drying in an oven, 482 g of the desired product are obtained.
Elemental analysis [% found (theoretical)]=Cu 27.7 (28.2); Mn 10.9 (12.2); P 18.0 (20.9); K 0.97 (0).
The following mixtures can be obtained with an analogous procedure:
Leaves of cultivar Merlot vines, grown in vases, in a conditioned environment (20±1° C., 70% relative humidity) are treated by spraying both sides of the leaves with the mixtures under examination dispersed in an aqueous solution containing a 0.3% of tween 20.
After remaining 7 days in a conditioned environment, the plants are infected on the lower side with an aqueous suspension of spores of Plasmopara viticola (200,000 spores per cm3).
The plants are kept in a humidity saturated environment, at 21° C., for the incubation period of the fungus and, at the end of this period (7 days), the fungicidal activity is evaluated according to an evaluation percentage scale from 100 (healthy plant) to 0 (completely infected plant).
From the data indicated in tables 1-2, it is possible to verify the synergistic effect of the mixtures, consisting of the mixtures being examined, compared with the expected efficacy using the Limpel formula (“Pesticide Science” (1987), vol. 19, pages 309-315):
E=x+y−(xy/100)
wherein:
When the fungicidal activity found experimentally is greater than the value of E, this activity is considered synergistic.
Leaves of potato plants, of the Primura variety, grown in vases, in a conditioned environment (20±1° C., 70% relative humidity) are treated by spraying both sides of the leaves with the mixtures under examination dispersed in an aqueous solution containing 0.3% of tween 20.
After remaining 7 days in a conditioned environment, the plants are infected on the lower side with an aqueous suspension of spores of Phytophthora infestans (100,000 spores per cm3).
The plants are kept in a humidity saturated environment, at 18-24° C., for the incubation period of the fungus and, at the end of this period (7 days), the fungicidal activity is evaluated according to an evaluation percentage scale from 100 (healthy plant) to 0 (completely infected plant).
From the data indicated in tables 3-6, it is possible to verify the synergic effect of the mixtures, consisting of the mixtures being examined, compared with the expected efficacy using the Limpel formula.
acid.
| Number | Date | Country | Kind |
|---|---|---|---|
| MI2005A001019 | May 2005 | IT | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2006/005157 | 5/29/2006 | WO | 00 | 12/19/2007 |
