Phytosanitary combination including carvacrol (variants), method, composition and kit containing it

Abstract

FIELD: agriculture.SUBSTANCE: phytosanitary combination with antifungal and insecticidal activity comprises carvacrol and one additional plant protection agent selected from prothioconazole, azoxystrobin, sulfur, cymoxanil, zoxamide, potassium phosphite, fosetyl aluminum or laminarin, azadirachtin, lambda-cyhalothrin and copper oxychloride. The phytosanitary combination is used to combat infections of agricultural plants caused by Oomycetes, Ascomycota, Basidiomycota, and infestations by Hemiptera and Lepidoptera.EFFECT: proposed phytosanitary combination is effective against target pests and non-toxic to helper insects and pollinating insects.12 cl, 2 tbl, 14 ex

Description

[0001] Technical field

[0002] The present invention relates to new phytosanitary combinations including carvacrol, compositions and kits including said combinations, and their use in agriculture as pesticides.

[0003] Technology Level

[0004] Certain chemical substances of natural or synthetic origin are used as plant protection products, where plant protection product means compounds or compositions used in agriculture to at least partially destroy pests that damage crop plants, such as fungi, pathogenic insects, etc., in order to protect the health of these plants and ensure their survival. These plant protection products or phytosanitary products are also sometimes referred to, inappropriately, as parasiticides, fungicides, pesticides, and biocides.

[0005] Carvacrol, or 2-methyl-5-isopropylphenol, having the following formula (I)

[0006] (I),

[0007] is present, for example, in the essential oils of oregano (Origanum spp.) and satureja (Satureja spp.) and has very good antifungal and antibacterial properties, while showing limited toxicity to higher animal species.

[0008] Unlike carvacrol, most compounds exhibiting pesticidal activity capable of protecting plants also exhibit some toxicity to higher animals, such as mammals, fish, poultry, and other species, with a dose-dependent effect. For this reason, there are legal restrictions on the amount of plant protection products that can be applied, such as maximum doses per hectare, which sometimes results in the permitted quantities being insufficient to achieve effective phytosanitary action.

[0009] Furthermore, plant protection products are often effective only against a narrow spectrum of pests, for example, only against fungi or only against insects or mites, etc.

[0010] Therefore, there is a need for affordable new products with phytosanitary action that are truly effective in protecting a wide range of plants and have low toxicity to helper insects and pollinating insects.

[0011] Furthermore, the emergence of resistant fungal strains and insect species creates a need for new broad-spectrum modes of action (MoA) to maintain the restrictive efficacy of approved plant protection products at a satisfactory level.

[0012] Problems of the invention

[0013] The objective of the invention is to create a combination of compounds that have an effective phytosanitary effect that significantly exceeds the activity of a single phytosanitary agent, and which, at the same time, have a reduced impact on the health of higher animals, helper insects and pollinating insects and the environment.

[0014] Another object of the invention is to provide compositions suitable for applying said combinations to plants.

[0015] Another object of the invention is to provide a kit suitable for preparing and applying said combinations to plants.

[0016] Also, the object of the invention is to use such combinations, compositions and kits as antifungal and insecticidal agents.

[0017] Disclosure of invention

[0018] The subject of the invention, according to one of its aspects, is a combination with phytosanitary action, comprising and, on the other hand, consisting of carvacrol and at least one additional plant protection agent selected from

[0019] a) demethylation inhibitors, preferably prothioconazole;

[0020] b) "external quinone" inhibitors, preferably azoxystrobin;

[0021] c) succinate dehydrogenase inhibitors, preferably boscalid;

[0022] d) inhibitors of cellular respiration at the mitochondrial level, preferably fluazinam;

[0023] e) fungicides with multi-site action, preferably copper in active forms, preferably copper oxychloride, and sulfur;

[0024] f) inhibitors of parasite penetration into plant tissue, preferably cymoxanil;

[0025] g) inhibitors of mitosis and cell division, preferably zoxamide;

[0026] h) plant protection inducers, preferably potassium phosphite (or potassium phosphonate), fosetylaluminum and laminarin;

[0027] i) insect growth factor inhibitors, preferably azadirachtin; and

[0028] j) sodium channel modulators, preferably lambda-cyhalothrin.

[0029] As used herein, "carvacrol" refers to the compound of formula (I) above, whether it is of natural origin, i.e., obtained by extraction from plants containing it, or produced synthetically. The term "carvacrol" also includes extracts of plants containing carvacrol, such as oils extracted from said plants; in such cases, the amounts of carvacrol specified herein always refer to carvacrol and not to amounts of the extract.

[0030] In this description, "additional plant protection agent" means another compound with antifungal and / or insecticidal activity.

[0031] By "phytosanitary action" is meant the action aimed at protecting plants from parasites; preferably, the phytosanitary action of the combination is antifungal and / or insecticidal.

[0032] According to a preferred embodiment, the combination of the invention comprises carvacrol and at least one additional plant protection agent selected from (a), (d), (e), (f), (g), (h), (i) and (j).

[0033] According to a preferred embodiment, the combination of the invention comprises carvacrol and prothioconazole, preferably in a carvacrol / prothioconazole weight ratio of 40-1 / 1, more preferably 25-1 / 1, such as 20-1 / 1. According to such an embodiment, a higher carvacrol / prothioconazole ratio will preferably be used for seed treatment, and a lower ratio for foliar treatment of plants.

[0034] According to a preferred embodiment, the combination of the invention comprises carvacrol and fluazinam, preferably in a weight ratio of carvacrol / fluazinam of 51 / 1, more preferably 3-1 / 1, such as about 2-1 / 1.

[0035] According to a preferred embodiment, the combination of the invention comprises carvacrol and cymoxanil, preferably in a carvacrol / cymoxanil weight ratio of 10 / 1, more preferably 8-1 / 1, such as about 5-2 / 1.

[0036] According to a preferred embodiment, the combination of the invention comprises carvacrol and zoxamide, preferably in a carvacrol / zoxamide weight ratio of 10-1 / 1, more preferably 8-1 / 1, such as about 5-2 / 1.

[0037] According to a preferred embodiment, the combination of the invention comprises carvacrol and phosphite, preferably in a carvacrol / phosphite weight ratio of 1 / 10-1, more preferably 1 / 8-1, such as about 1 / 4-1.

[0038] According to a preferred embodiment, the combination of the invention comprises carvacrol and copper, preferably in the form of copper oxychloride, preferably in a carvacrol / copper weight ratio of 1 / 10-1, more preferably 1 / 8-1, such as about 1 / 4-1.

[0039] According to a preferred embodiment, the combination of the invention comprises carvacrol and copper, preferably in the form of copper oxychloride, preferably in a carvacrol / copper weight ratio of 10-1 / 1, more preferably 5-1 / 1, such as about 4-1 / 1.

[0040] According to a preferred embodiment, the combination of the invention comprises carvacrol and azadirachtin, preferably in a carvacrol / azadirachtin weight ratio of 20-1 / 1, more preferably 15-2 / 1, such as about 10-3 / 1.

[0041] According to a preferred embodiment, the combination of the invention comprises carvacrol and lambda-cyhalothrin, preferably in a carvacrol / lambda-cyhalothrin weight ratio of 550-40 / 1, more preferably 400-50 / 1, such as about 130-60 / 1.

[0042] According to a preferred embodiment, the combination of the invention comprises carvacrol and laminarin, preferably in a carvacrol / laminarin weight ratio of 15-1 / 1, more preferably 10-3 / 1, such as about 6-7 / 1.

[0043] According to a preferred embodiment, the combination of the invention comprises carvacrol and sulfur, preferably in a carvacrol / sulfur weight ratio of 1-0.1 / 1, more preferably 0.5-0.1 / 1, such as about 0.3-0.2 / 1.

[0044] According to a preferred embodiment, the combination of the invention comprises, and alternatively consists of, carvacrol and at least one additional plant protection agent selected from prothioconazole, cymoxanil, copper, preferably in the form of copper oxychloride, lambda-cyhalothrin and azadirachtin, preferably in the weight ratios given above.

[0045] The combinations according to the invention unexpectedly demonstrate a synergistic effect and, in some cases, allow for a reduction in the dose of crop protection agent in the mixture. It is clear that this result represents significant technical progress, as the addition of carvacrol to another traditional crop protection agent enables effective synergistic antifungal and insecticidal action.

[0046] If desired or necessary, the combination of the invention may comprise carvacrol and two or more plant protection agents defined above.

[0047] According to one embodiment, the combination of the invention comprises carvacrol and only one additional plant protection agent as defined above.

[0048] The subject of the invention, according to another of its aspects, is a method for obtaining a phytosanitary effect, in particular, obtaining an antifungal and / or insecticidal effect in the agricultural field, comprising administering an effective amount of the combination according to the invention for growing plants in need thereof.

[0049] According to one embodiment, the method of the invention comprises simultaneously administering the components of the combination.

[0050] According to such an embodiment, for example, it is possible to ad hoc mix a composition comprising carvacrol with at least one composition comprising one additional plant protection agent as defined above and dilute the mixture with water before applying it to agricultural crops. Such mixing can, for example, take place in suitable containers, such as drums, where plant protection agents are typically diluted before application to plants; the dilution is carried out to obtain a suitable concentration of the active ingredients. Indeed, it is known that plant protection agents are sold as concentrated compositions and must be diluted before application; they are typically diluted with water in containers such as drums.

[0051] However, alternatively, it is possible to apply the components of the combination to crops individually for a short period of time.

[0052] Compositions comprising carvacrol and compositions comprising an additional plant protection agent are known and commercially available.

[0053] As an example, such compositions may be in solid form, such as in the form of wettable or soluble powders, microgranules or granules that dissolve or disperse in water, etc., or in liquid form, such as in the form of concentrated water-based suspensions, solutions, emulsifiable concentrates, microcapsule suspensions, etc.

[0054] Such compositions may include, in addition to the active ingredients, also certain excipients, such as those commonly used in the technical field.

[0055] The term "excipients" in the present description refers to components that are added to the composition to enhance its stability, to ensure its storage and to obtain mixtures suitable for application to plants. Commonly used excipients include, for example, solvents; diluents; surfactants; stabilizers; colorants; plant penetrating agents; pH regulators such as organic or inorganic acids; antifoaming agents; thickeners; anti-drift agents, etc.

[0056] The phytosanitary composition according to the invention preferably comprises carvacrol in a concentration range from 5 wt.% to 80 wt.% relative to the total weight of the finished product.

[0057] The amounts of the combination used depend on the type of treatment being carried out, such as preventive or curative, as well as the type and sanitary condition of the crop being treated, seasonality, etc. A person skilled in the art can select the most appropriate amount of the composition to achieve the desired effect, also based on the examples given in the following experimental section.

[0058] The experimental section presents some analyses conducted by the Applicant by mixing and diluting with water one composition containing carvacrol and one composition containing an additional crop protection product (defined in the tables as "partner"). As can be seen, the combination results in a synergistic effect, which in some cases allows for a reduction in the dosage of the additional crop protection product typically applied to agricultural crops.

[0059] It has been established that this result represents a surprising and unexpected technical effect that solves the problem of reducing the dosage required to obtain a phytosanitary effect.

[0060] The subject of the invention, according to another of its aspects, is also a kit comprising at least one composition comprising carvacrol and at least one composition comprising one additional plant protection agent as defined above.

[0061] According to a preferred embodiment, the invention comprises at least one composition comprising carvacrol in concentrated form and at least one composition comprising one other plant protection agent as defined above in concentrated form.

[0062] Compositions in kits containing carvacrol and at least one other plant protection product, intended for mixing and subsequent dilution before application to plants requiring phytosanitary treatment.

[0063] The term "combination" as used herein includes both mixtures of carvacrol and at least one other plant protection product in concentrated form and said mixtures in diluted form, preferably diluted with water.

[0064] The kit according to the invention may contain, in addition to the compositions defined above, also instructions indicating how to mix, dilute and apply the combination according to the invention to plants.

[0065] The subject of the invention, according to another aspect thereof, is also a composition comprising a combination according to the invention and one or more conventional excipients / auxiliaries, such as, for example, solvents; diluents; surfactants; stabilizers; colorants; impregnating agents for plants; pH regulators, such as organic or inorganic acids, antifoaming agents, thickeners, anti-drift agents, etc.

[0066] A person skilled in the art is well able to select the most suitable excipients to formulate each combination of the invention into a composition that is stable during storage and can be applied to plants in a suitable manner.

[0067] The compositions of the invention are prepared according to conventional methods known in the art, for example, by mixing the components and excipients for a convenient period of time. Preferably, the compositions of the invention are then packaged in suitable multi-dose or single-dose containers.

[0068] For use, the combination and composition according to the invention, after dilution as known to a person skilled in the art, is used for treatment (spraying foliage, fertigation of soil) of plants in need thereof, or by precise and localized application to seeds.

[0069] The subject of the invention, according to another of its aspects, is the use of the combination, kit, and composition according to the invention as phytosanitary agents, in particular as antifungal and / or insecticidal agents, in the field of agriculture. As an example, the combination, composition, and kit according to the invention can be used as an antiparasitic agent, in particular an antifungal and / or insecticidal agent, for herbaceous and woody plants, such as corn, apple, wheat, grapes, tomatoes, eggplant, etc.

[0070] According to a preferred embodiment, the subject of the invention is the use of a combination, composition and kit according to the invention for the prevention or treatment of various fungal infections, for example, but not limited to, infections caused by Oomycetes, Aschomycota, Basidiomycota, for example, Pythium, V. inaequalis, P. recondita, P. viticola, P. infestans.

[0071] According to a preferred embodiment, the subject of the invention is the use of the combination, composition and kit of the invention as an insecticide for the control of various plant pests, including, but not limited to, Hemiptera, Lepidoptera, such as D. plantaginea and H. Armigera.

[0072] According to one embodiment, the combination of carvacrol and demethylation inhibitors, preferably prothioconazole, is particularly suitable for treating cereal crops, such as, but not limited to, rice, corn and wheat.

[0073] According to one embodiment, the combination of carvacrol and "external quinone" inhibitors, preferably azoxystrobin, is particularly suitable for treating nightshade crops, such as, but not limited to, eggplant, tomato, pepper and potato.

[0074] According to one embodiment, a combination of carvacrol and multi-purpose fungicides, preferably copper in active forms, preferably copper oxychloride, is particularly useful in the treatment of grapes.

[0075] According to one embodiment, the combination of carvacrol and growth factor inhibitors, preferably azadirachtin, is particularly useful in the treatment of horticultural plants.

[0076] The subject of the invention, according to one of its aspects, is a method for obtaining an antifungal and / or insecticidal effect in the agricultural field, comprising using an effective amount of a combination, composition or kit according to the invention for growing plants in need thereof.

[0077] Experimental Section

[0078] The effectiveness of some representative combinations of the invention was confirmed by analyses, the results of which are presented in the following Tables 1 and 2.

[0079] The tests were carried out in a greenhouse for the period of time specified in Table 1.

[0080] In tables

[0081] - another plant protection product in the combination is indicated in the tables as “partner”;

[0082] - "target" represents the parasite to be reduced / destroyed;

[0083] - "EC" means emulsifiable concentrate;

[0084] - "l" means liter;

[0085] - "SC" means concentrated suspension;

[0086] - "CS" means microcapsule suspension;

[0087] - "gai" means grams of active ingredient;

[0088] - "ha" means one hectare;

[0089] - "ratio" means the mass ratio of carvacrol / partner;

[0090] - "mixture efficiency" means the efficiency of the combination shown in % of the disease control, in relation to the "untreated" plant, and the following calculation is made:

[0091] A= % disease in untreated plant,

[0092] B= % of disease in the treated plant,

[0093] % of disease control = [(AB) / A]×100;

[0094] - Synergy is estimated by calculation using the Colby equation. To determine the Colby coefficient, which determines whether the effect of an active ingredient (in this case, carvacrol) on another active ingredient can be classified as "SYNERGISTIC", it is necessary to consider the efficacy of the product based only on carvacrol (X), the efficacy of the product selected based only on the partner (additional crop protection product) (Y), and the observed efficacy of the mixture (O). From the first two values, the theoretical efficacy (E) can be calculated using the Gowing equation or the Limpel equation. Then, the effect is defined as synergistic if the results of O are greater than E. The following is an example of calculating the effect assessment of the carvacrol + prothioconazole mixture (Test 1, Table 1):

[0095] X = 65%,

[0096] Y=39%,

[0097] E = X + [Y(100-X)] / 100,

[0098] E = 65 + [39(100-65)] / 100 = 78.65;

[0099] or

[0100] E = X + Y-(XY / 100),

[0101] E = 65 + 39-(2535 / 100) = 78.65.

[0102] In the specific case, since the observed % disease control is “O=98%”, and therefore O is greater than E, the effect of carvacrol on the efficacy of prothioconazole at the doses shown in Test 1 of Table 1 is determined to be “SYNERGISTIC” (see S. R. Colby, “Weeds”, Vol. 15, No. 1 (1967), pages 20-22, Ed. Cambridge University Press), with Colby’s coefficient being O - E = 19.35.

[0103]

[0104]

[0105]

[0106] As can be concluded from the results, combinations with carvacrol according to the invention demonstrate very interesting synergistic effects (Table 1). In some cases, combinations with significantly lower doses of the additional plant protection product (partner) were tested (Table 2), and good efficacy against pathogens was also observed.

[0107] The combination of 300 g / l carvacrol, EC + 240 g / l zoxamide, SC, was also tested on grape crops, and in this case also very interesting results were obtained.

[0108] Therefore, the combinations of the invention have shown that they are particularly useful as phytosanitary agents, in particular as antifungal and / or insecticidal agents for agriculture.

Claims

1. A phytosanitary combination with antifungal and insecticidal activity, comprising carvacrol and one additional plant protection product selected from: a) prothioconazole; b) azoxystrobin; c) sulfur; d) cymoxanil; e) zoxamide; f) potassium phosphite, fosetyl aluminum or laminarin; g) azadirachtin; h) lambda-cyhalothrin.

2. The combination according to claim 1, characterized in that the additional plant protection agent is selected from: prothioconazole, azoxystrobin, zoxamide, potassium phosphite, fosetyl aluminum or laminarin, azadirachtin, lambda-cyhalothrin.

3. The combination according to paragraph 1 or 2, characterized in that - the mass ratio of carvacrol and prothioconazole is (40-1):1; - the mass ratio of carvacrol and cymoxanil is (10-1):1; - the mass ratio of carvacrol and zoxamide is (10-1):1; - the mass ratio of carvacrol and potassium phosphite is 1:(10-1); - the mass ratio of carvacrol and azadirachtin is (20-1):1; - the mass ratio of carvacrol and lambda-cyhalothrin is (550-40):1; - the mass ratio of carvacrol and laminarin is (15-1):1; and - the mass ratio of carvacrol and sulfur is (1-0.1):

1.

4. A combination according to any one of claims 1 to 3, characterized in that it comprises carvacrol and one additional plant protection agent selected from prothioconazole, cymoxanil, lambda-cyhalothrin or azadirachtin.

5. A phytosanitary combination with antifungal and insecticidal activity, including carvacrol and copper oxychloride in a mass ratio of 2:1 or 1:1.

23.

6. A method for treating plants, including the use of an effective amount of a combination according to any of paragraphs 1-5, for antifungal and insecticidal protection of grown plants.

7. The method of claim 6, which comprises mixing carvacrol and one additional plant protection product, diluting the combination, preferably with water, and applying an effective amount of the resulting liquid mixture to plants in need thereof.

8. A phytosanitary composition with antifungal and insecticidal activity, comprising a combination according to any one of claims 1-5 and at least one conventional excipient.

9. Use of a combination according to any of paragraphs 1-5 as a phytosanitary agent with antifungal and insecticidal activity.

10. A phytosanitary kit for treating plants, comprising a composition containing carvacrol and a composition containing one additional plant protection agent selected from prothioconazole, azoxystrobin, copper oxychloride, aluminum fosetyl, sulfur, cymoxanil, zoxamide, potassium phosphite, azadirachtin, lambda-cyhalothrin, laminarin.

11. Use of the kit according to item 10 as a product with antifungal and insecticidal activity.

12. Use according to item 11 for combating infection caused by Oomycetes, Aschomycota, Basidiomycota, and infestations by Hemiptera, Lepidoptera.

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