EA018993B1 - Fungicidal composition - Google Patents

Abstract

A composition suitable for control of diseases caused by phytopathogens comprising:(A) a compound of formula I, wherein Ris difluoromethyl or trifluoromethyl and X is chloro, fluoro or bromo; and (B) is bixafen known for its fungicidal activity; and a method of controlling diseases on useful plants, especially rust diseases on soybean plants.

Description

The invention relates to new fungicidal compositions suitable for controlling diseases caused by phytopathogens, especially phytopathogenic fungi, and to a method for controlling diseases in useful plants, especially soybean rust.

It is known from AO 04/35589 and AO 06/37632 that certain tricyclic amine derivatives and mixtures containing these amine derivatives have biological activity against phytopathogenic fungi. On the other hand, various fungicidal compounds of various chemical classes are widely known as plant fungicides for use on various cereal crops. However, the stability of crops and activity against phytopathogenic plant fungi do not always satisfy the needs of agricultural practice in many cases and aspects. For example, in the past, economically significant phytopathogens were not known in most regions important for soybean crops. However, cases of severe rust damage to soybean crops in South America caused by the harmful fungus Ryakorzog ραοΙινιΊιίζί have recently increased significantly. resulting in significant crop loss. Most common fungicides are not suitable for rust control in soybeans, or their action against Ryakorzog ραοΙινιΊιίζί is not satisfactory.

Based on the aforementioned needs of the agricultural industry for improved resistance and / or increased activity against phytopathogenic fungi, such as Ryakorzoga ραοΙινιΊιίζτ, the present invention proposes a new composition suitable for combating diseases caused by phytopathogens, containing a composition suitable for combating diseases caused by pathogens containing (A) a compound of formula I

where P | is difluoromethyl or trifluoromethyl and X is chlorine, fluorine or bromine; and (B) bixafen.

It was found that the use of component (B) in combination with component (A) unexpectedly and significantly improves the effectiveness of the latter against fungi and vice versa. Additionally, the method of the present invention is effective against a wide range of such fungi that the active ingredients of this method can fight when used separately.

Another aspect of the present invention relates to a method for controlling diseases of useful plants or seed material caused by phytopathogens, which method comprises applying to useful plants, their location or seed material a composition according to the present invention. Preferred is a method that includes applying to useful plants or their location the composition according to the present invention, more preferably to useful plants. Even more preferred is a method that involves applying to the seed of beneficial plants a composition according to the present invention.

The compounds of formula I exist in two different stereoisomers, which are described as separate enantiomers of formulas 1 ₁ and 1 ₁₁

The present invention covers all such stereoisomers and mixtures thereof in any ratio. According to the present invention, a racemic compound of formula (I) means a racemic mixture of compounds of formulas 1 ₁ and 1 _p .

In a preferred embodiment of the present invention, such compositions are represented by compositions that contain, as component A) a compound of formula (I), wherein Cd is difluoromethyl. Other preferred compounds of formula (I) are (9-dichloromethylidenebenzonorbornen-5-yl) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide (compound A-1.1); 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylidenebenzonorbornen-5-yl) amide (compound A-1.2) and (9-dibromomethylidenebenzonorbornen-5-yl) 3-difluoromethyl-1-methyl-1npyrazole amide -4-carboxylic acid (compound A-1.3).

The designation of substituent X as chlorine, fluorine or bromine means that both substituents X have the same meaning.

- 1 018993

1-methyl-3-trifluoromethyl-1H-pyrazole-4-carbon

1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic

-methyl-3-trifluoromethyl-1H-pyrazole-4-carbon

In a preferred embodiment of the present invention, such compositions are represented by compositions that contain, as component A) a compound of formula (I), wherein H1 is trifluoromethyl. Other preferred compounds of formula (I) are:

(9-dichloromethylidenebenzonorbornen-5-yl) acid amide (compound A-1.4);

(9-difluoromethylidenebenzonorbornen-5-yl) acid amide (compound A-1.5) and (9-dibromomethylidenebenzonorbornen-5-yl) acid amide (compound A-1.6).

Particularly preferred compositions of the present invention comprise, as component (A), a compound selected from (9-dichloromethylidenebenzonorbornen-5-yl) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide (compound A-1.1) and (9-Dichloromethylidenebenzonorbornen-5-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide (compound A-1.2), and bixaphene was used as component (B).

Other particularly preferred compositions of the present invention comprise, as component (A), the compound (9-dichloromethylylene benzonorbornen-5-yl) 3-difluoromethyl-1methyl-1H-pyrazole-4-carboxylic acid amide (compound A-1.1) and as component ( C) Bixafen compound.

Compounds of formula (I) can be prepared as described below in Reaction Schemes 1-3.

As shown in scheme 1, the compound of formula (I), where I! and X are as defined above, can be synthesized by reacting a compound of formula (II), where Κ ₁ is as defined above, and I 'is C1 _-5 alkyl, with aniline of formula (III), where X is such as defined above, in the presence of Ν; · ιΝ (ΤΜ8) ₂ at -10 ° C to ambient temperature, preferably in dry THF, as described in THUAPD e! a1. 8ui1e !!, 2001, 1485.

Alternatively, as shown in Scheme 2, a compound of formula (I) wherein He! is as defined in Scheme 1, Κι and X are as defined above, can be obtained by the interaction of the compounds of formula (II '), where He! is as defined above with aniline of formula (III), where X is as defined above, in the presence of an activating agent such as BOP-C1 (bis- (2-oxo-3-oxazolidinyl) phosphinic acid), and two equivalents of a base, such as triethylamine, in a solvent such as dichloromethane (as described, for example, in 1. CaBe e! a1., BoPFems 1984, 413), or by reacting a compound of formula (II), where He! is as defined above, and O is chlorine, fluorine or bromine, with aniline of formula (III), where X is as defined above, in the presence of one equivalent of a base such as triethylamine or sodium or potassium carbonate or bicarbonate, in a solvent such as dichloromethane, ethyl acetate or Ν, Ν-dimethylformamide, preferably at (-10) -30 ° C. A compound of formula (II) is prepared from a compound of formula (II ') by treatment with a halogenating agent such as thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, 8E ₄ / HE, ΌΑ8Τ (sulfur trifluoride (diethylamino) or Oeho-Piog® (trifluoride [bis ( 2-methoxyethyl) amino] sulfur) in a solvent such as toluene, dichloromethane or acetonitrile.

Compounds (II) and (II ') are usually known compounds and can be obtained as described in the chemical literature, or obtained from commercial sources. Compound (III) is a new compound and can be obtained as described in scheme 3.

- 2 018993

As shown in Scheme 3, the compound of formula (III) can be obtained by Beschamp reduction or other established methods, for example, selective catalytic hydrogenation, nitrogen compounds (E), (E) and (6).

9-dihalomethylidene-5-nitrobenzonorbornenes (E), where X is chlorine, bromine or fluorine, can be obtained by olefination of Wittig ketones (Ό) with the obtained ίΐη δίΐιι dihalogenomethylidene phosphoranes I ' ₃ P = C (I ⁴ ) I ⁵ , where I' is triphenyl, triCl- ₄ alkyl or tridimethylamine, and X is halogen, according to or by analogy with the methods described in H-Ό. Maysh e! A1., Siet. Veg. 118, 2514 (1985), 8.Nahua5Y1 e! A1, Siet. Yeah. 1979, 983 or M. 8nya. Teyayeygop Leyesh, 22, 1421 (1981).

Compounds of formula (I) can be prepared as described in Examples H1-H7.

Example 1. This example illustrates the preparation of (9-dichloromethylidenebenzonorbornenene 5-yl) 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid amide (compound A-1.4)

9-dichloromethylene-5-aminobenzonorbornene (175 mg, 0.729 mmol, prepared as described in Example 6) in dichloromethane (10 ml) was reacted with 1-methyl-3-trifluoromethyl-1H-pyrazolecarboxylic acid (170 mg, 0.874 mmol, 1.2 equiv.) In the presence of bis (2-oxo-3oxazolidinyl) phosphinic acid chloride (278 mg, 1.09 mmol, 1.5 equiv.) And triethylamine (184 mg, 1.821 mmol, 2.5 equiv.) at ambient temperature with stirring for 23 hours. The reaction mixture was extracted with saturated sodium bicarbonate solution and brine, dried over Na ₂ 8 O ₄ and purified by and silica gel in a mixture of ethyl acetate-hexane (1: 1). 210 mg (69% of theory) of (1-methyl-3-trifluoromethyl-1H-pyrazolecarboxylic acid amide (9-dichloromethylidenebenzonorbornen-5-yl) amide (Compound A-1.4, mp 179-181 ° C.) are obtained.

Example 2. In this example, the preparation of 9- (3-pentylidene) -5-nitrobenzonorbornadiene is illustrated.

To a well-mixed solution of isopentyl nitrile (2.31 ml, 1.3 equiv.) In dimethoxyethane (50 ml) at 58 ° C, a mixture of 6-nitroanthranilic acid (2.76 g, 1 equiv.) And 6.6 diethyl fulvene ( 6.45 g of 79% purity, 2.5 equiv.) Dissolved in 25 ml of dimethoxyethane for 8 minutes while the temperature rises to 67 ° C. After 30 minutes, the dark reaction mixture was evaporated and purified on silica gel in hexane-ethyl acetate (20: 1), to give 3.02 g (78%) of the desired product as an oil, which solidified at room temperature (mp. 60- 61 ° C).

Example 3. In this example, the preparation of 9- (3-pentylidene) -5-nitrobenzonorbornene is illustrated.

- 3 018993

9- (3-pentylidene) -5-nitrobenzonorbornobadiene (7.97 g, obtained as described in Example 2) in THF (70 ml) is hydrogenated at 20 ° C in the presence of Ky (PP ₃ ) ₃ C1 (Wilkinson catalyst; 0 , 8 g). The reaction is converted after the absorption of one equivalent of hydrogen. Evaporation and filtration of the crude product on silica gel in a mixture of ethyl acetate-hexane (100: 2) gives the desired product as an oil (7.90 g), which solidifies upon standing at room temperature (mp. 69-56 ° C).

Example 4. In this example, the preparation of 9-oxo-5-nitrobenzonorbornene is illustrated.

9- (3-pentylidene) -5-nitrobenzonorbornene (7.0 g, 27.2 mmol; obtained as described in Example 3), dissolved in dichloromethane (300 ml) and ethanol (5 ml), ozonate (2.8 l 0 ₂ / min, 100 watts, corresponding to 9.7 g of O ₃ / h) at -70 ° C until a stable blue color is obtained (after approximately 15 minutes). The reaction mixture was purged with nitrogen gas. Triphenylphosphine (8.4 g, 32.03 mmol, 1.18 equiv.) Was added and the temperature was raised to 20-25 ° C. After evaporation of the solvent, the residue was purified on silica gel in a 3: 1 hexane-ЕУАс mixture to obtain 5.2 g of compound 36.01 (mp. 112-114 ° С).

Example 5. In this example, the preparation of 9-difluoromethylidene-5-nitrobenzonorbornene is illustrated.

To a solution of dibromodifluoromethane (6.30 g, 30 mmol) at 0 ° C in THF (50 ml) is added Tris (dimethylamino) phosphane (10.1 g at 97%, the equivalent of 11.2 ml, 60 mmol) in THF (30 ml) for 20 minutes After stirring for 1 hour at room temperature, a solution of 9-oxo-5-nitrobenzonorbornene (6.10 g, 30 mmol; prepared as described in Example 4) in THF (20 ml) was added dropwise to the resulting suspension. 25 minutes, followed by stirring for 21 hours. The suspension was poured onto ice-water and extracted with ethyl acetate. Purification on silica gel in ethyl acetate-hexane (1: 4) gave 4.675 g of 9-difluoromethylidene-5-nitrobenzonorbornene (mp. 99-101 ° C).

Example 6. In this example, the preparation of 9-dichloromethylidene-5-nitrobenzonorbornene is illustrated.

Dry carbon tetrachloride (5.9 g, 33 mmol) was reacted with triphenylphosphine (14.46 g, 55.1 mmol) in dichloromethane (30 ml) at room temperature for 1 h. 9-Oxo-5 nitrobenzonorbornene (5.60 g, 27.56 mmol; obtained as described in Example 4) in dichloromethane (10 ml) was added dropwise and stirred for 20 hours at room temperature. After treatment with water (ice water) and extraction with dichloromethane, the crude product is purified on silica gel in a mixture of ethyl acetate-hexane (1: 4) to obtain the desired 9-dichloromethylidene-5-nitrobenzonorbornene (1.83 g; mp 136-137 ° FROM). A certain amount of the starting material is restored (4.06 g).

Example 7. In this example, the preparation of 9-dibromomethylidene-5 nitrobenzonorbornene is illustrated.

N0

Carbon tetrabromide (4.66 g at 98%, 13.8 mmol) was reacted with stirring with triphenylphosphine (7.23 g, 27.6 mmol) in dichloromethane (50 ml) for 50 minutes at room temperature. 9-Oxo-5-nitrobenzonorbornene (2.8 g, 13.8 mmol; prepared as described in Example 4) in dichloromethane (10 ml) was added dropwise and stirred overnight at room temperature. Treatment with water (ice water) and extraction with dichloromethane, followed by column chromatography (ethyl acetate-hexane, 1: 9) of the crude product, gives the desired product 9dibromomethylidene-5-nitrobenzonorbornene (2.1 g; mp 153-155 ° C).

Table 1. In the table. 1 shows melting points and NMR data, all with CIS1 ₃ as solvent, unless otherwise indicated, for compounds of formula (I). In the table, temperatures are given in degrees Celsius, NMR means nuclear magnetic resonance and the following abbreviations are used:

so pl. = melting point

t.kip. = boiling point, s = singlet, broad. = wide

- 4 018993 d = doublet, dd = doublet of doublets, t = triplet, sq. = quartet, m = multiplet,

ppm = ppm, THF = tetrahydrofuran.

Table 1

Compound so pl. (° C) ^X H-NMR proton shifts 5 (ppm) (SCC1 ₃ ) A-1.1 179-181 8.06 (s, 1H), 7.69 (d, blocked by a wide signal, replaced by C ₂ O, 2H), 7.18 (t, 1H), 7.06 {d, 1H), 4.00 (s ZN), 3.96 (m, 2H), 2.12 (m, 2H), 1.51 (m, 1H), 1.39 (m, 1H). A-1.2 137-143 8.06 (s, 1H), 7.68 (broad d, replaced by C ₂ O, 1H), 7.67 (d, 1H), 7.14 (d, 1H), 4.00 (s, 3H) ), 3.94 (m, 2H), 2.06 (m, 2H), 1.48 (m, 1H), 1.36 (m, 1H).

A-1.3 198-200 8.06 {s, 1H), 7.71 (d, 1H), 7.68 (broad d, replaced by C ₂ O, 1H), 7.18 (t, 1H), 7.05 (d, 1H) ), 4.00 (s, 3H), 3.95 (m, 1H), 3.93 (m, 1H), 2.12 (m, 2H), 1, 50 (m, 1H), 1, 38 (m, 1H). A-1.4 183-188 7.78 (d, 1H), 7.70 (broad d, replaceable ϋ ₂ Ο, 1H), 7.39 (broad s, 1H), 7.16 (t, 1H), 7.01 (d , broad s, 2H), 4.00 (m, 1H), 3.94 (m, 1H), 3.72 (s, 3H), 2.10 (m, 2H), 1.51 (m , 1H); 1.38 (m, 1H). Ά-1.5 133-135 7.76 (d, 1H), 7.70 (br.sd., replaceable with E ₂ O, 1H), 7.39 (br.s, 1H), 7.13 (t, 1H), 7.01 (br .s, 1H), 7.00 (d, 1H), 3.98 (m, 1H), 3.93 (m, 1H), 3.72 (s, 3H), 2.04 (m, 2H) 1.49 (m, 1H); 1.36 (m, 1H). Ά-1.6 155-158 7.79 (d, 1H), 7.70 (broad d, replaceable ϋ ₂ Ο, 1H), 7.39 (broad s, 1H), 7.17 (t, 1H), 7.02 (d , 1H), 7.01 (br s, 1H), 3.98 (s, 1H), 3.91 (s, 1H), 3.72 (s, 3H), 2.11 (m, 2H) 1.50 (m, 1H).

Component (B) is known. (3 ', 4'-dichloro-5-fluoro-1,1'-biphenyl-2-yl) amide (3-difluoromethyl-1-methyl-1Npyrazol-4-carboxylic acid; bixafen is registered under the reg. No СЛ8 581809- 46-3 and described in AO 03/70705.

In this description, the expression composition is used for various mixtures or combinations of components (A) and (B), for example, in a single finished form, in a combined spray mixture consisting of separate compositions of the individual components of the active ingredient, such as a mixed form, and in the form of a combined the use of the individual active ingredients in a sequential application, i.e. one after another over a reasonably short period, such as a few hours or days. The application of components (A) and (B) is not essential for the practice of the present invention.

The compositions of the present invention are effective against harmful microorganisms, such as microorganisms that cause phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.

Compositions according to the present invention are effective especially against phytopathogenic fungi belonging to the following classes: ascomycetes (for example, UepShpa. Robokryaeta, Eguchriye. Moshysha, Musokryaeta 11a, ipsi1a); basidiomycetes (for example, the genus Neshye1a, B ^ oc! osha, Ryakorkoga, Risas, Ikshado, TSheya); Hypn1pregGesb (also known as deuteromycetes; for example, Wo (tuyk, Ne1t1yokrotsht, KKupsyokrotsht, Gikatsht, ерper! Opa, Segsokroga, Anetapa, Rupsiapa and Rokyopheropera, Ropetoma, Ropeto yst, Rkeiboks1egokroga, R1actoraga).

According to the present invention, useful plants typically include the following plant species: grapes; cereals such as wheat, barley, rye or oats; beets such as sugar beets or fodder beets; fruits such as pome fruits, pips or berries, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or black currants; legumes such as beans, lentils, peas, or soybeans; oilseeds such as rapeseed, mustard, poppy, olive, sunflower, coconut, castor oil, cocoa or peanuts; pumpkin crops such as zucchini, cucumber or melon;

- 5 018993 fiber crops such as cotton, flax, hemp or jute; citrus fruits such as orange, lemon, grapefruit or mandarin; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, pumpkin or bell peppers; bay leaves such as avocados, cinnamon or camphor; corn; tobacco; nuts coffee; sugar cane; tea; vine; hop; durian; banana; rubber noses; lawn grass or ornamental crops such as flowers, shrubs, broad-leaved trees, or evergreens, such as conifers. This list is not limiting.

The term useful plants is also understood to include useful plants that remain resistant to herbicides, such as bromoxynil, or classes of herbicides (such as, for example, Л inhibitors, LX inhibitors. For example, primisulfuron, prosulfuron and trifloxisulfuron, ΕΡ3Ρ3 inhibitors (5-enichol 3-phosphate synthase), SZ inhibitors (glutamine synthetase) or PPO (protoporphyrinogen oxidase) inhibitors) as a result of conventional selection methods or genetic engineering. An example of a culture that is resistant to imidazolinones, for example, imazamox, with conventional breeding methods (mutagenesis), is C1eagPe1b® rape (Sapo1a). Examples of crops that are tolerant to herbicides or classes of herbicides using genetic engineering methods include glyphosate and glufosinate resistant maize species commercially available under the trade names IonbnrieabuK. Neglix Ex® and Licensyl®.

The term beneficial plants is also understood to include beneficial plants that are so altered by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, which are known, for example, from bacteria producing toxins, especially of the genus VasShik.

The term beneficial plants is also understood to include beneficial plants that are so altered by the use of recombinant DNA techniques that they are able to synthesize antipathogenic substances with selective action, such as, for example, the so-called pathogenesis-related proteins (ΡΚΡ, see, for example, EP-A -0392225). Examples of such anti-pathogenic substances and transgenic plants capable of synthesizing such anti-pathogenic substances are known, for example, from EP-A-0392225, AO 95/33818 and EP-A-0353191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the above publications.

The term location of a useful plant in this description covers the place where the useful plant grows, where the seed material of the useful plants is sown, or where the seed of the useful plant is placed in the soil. An example of such a location is the field on which a healthy crop is grown.

The term “plant seed” is understood to mean propagating parts of a plant, such as seeds that can be used to propagate the latter, and vegetative material, such as shoot or tuber, for example, potato. For example, seeds (in the narrow sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be given.

Sprouted plants and young shoots that must be carried after germination or after leaving the soil can also be given. Such young shoots can be protected before transplanting with full or partial immersion treatment. Preferably, the plant seed means seeds.

Compositions according to the present invention can also be used in the field of protection of stored goods from damage by fungi. According to the present invention, the term stored goods means natural substances of plant and / or animal origin and their processed forms that are excluded from the natural life cycle and for which long-term storage is desired. Stored products of plant origin, such as plants or parts thereof, for example petioles, leaves, tubers, seeds, fruits or grains, can be protected in a freshly collected state or in a processed form, for example, previously dried, moistened, crushed, ground, pressed or fried. The definition of stored goods also includes wood, either in the form of raw wood, such as building timber, power transmission towers and barriers, or in the form of finished products, such as furniture or objects made of wood. Stored animal products include leather, leather, fur, hair and the like. The compositions of the present invention can prevent undesirable effects such as rotting, discoloration, or mold. Preferably, stored goods mean natural substances of plant origin and / or their processed forms, more preferably fruits and their processed forms, such as apples, stone fruits, berries and citrus fruits, and their processed forms. In another preferred embodiment of the present invention, stored goods mean wood.

Therefore, another aspect of the present invention is a method for protecting stored goods, which comprises applying to the stored goods a composition according to the present invention.

Compositions according to the present invention can also be used in the field of protection of technical materials from damage by fungi. According to the present invention, the term technical material includes paper; Carpets construction; cooling and heating systems; facing plates;

- 6 018993 ventilation and air conditioning systems and the like; preferably technical material means tiles. The compositions of the present invention can prevent undesirable effects such as rotting, discoloration, and mold.

The compositions of the present invention are particularly effective against powdery mildew; rust; all types of leaf spot; cercosporosis and mold; especially against sper1op. Riessh, Yeguz1rNe, RugeporNoga and Tareya in cereals; Soybean Cornea; No He1a in coffee; RNgadpiNsht at roses; LNeppapa in potatoes, tomatoes and pumpkin plants; 8s1egoysha in the lawn, vegetables, sunflower and rapeseed; black rot, rubella, powdery mildew, gray mold and drying of grapes; Fruits with stegee in the fruit; Mopshsha spr. at fruits and Reshsht spr. in the fruit.

The compositions of the present invention are also particularly effective against seed-borne and soil-borne diseases, such as Liveria sp. , Eizagsht topShGogte, Eizagsht oxysporum, Eizagsht rgoNGegaSht, Eizagsht zo1ap1, Rizalit zid1i1tap8, Saitappotusez dgat1shz, Ne1tsh1Nozrogsht spp., MyugoyosNit shua1e, PHOTO spp., RugeporNoga dgatshea, Rupsyapa oguhae, Rbl / oShota zo1at, Ud / oShota segeaNz, 8s1egoNy and spr., 8p1opa spr., 8pNase1o1Nesa henNapa, Tzhena spr., TurNi1a shsagpay, IgosuzNS Ossina, IzShado spr. or WEShShsht spr .; in particular, against cereal pathogens such as wheat, barley, rye or oats; maize; rice; cotton soybeans; a lawn; sugar beets; rapeseed; potatoes; legumes such as peas, lentils or chickpeas; and sunflower.

The compositions of the present invention are also particularly effective against post-harvest diseases, such as WoNuyz steega, Co11e1o1g1cNpt tizae, Schuyapa liaaa, Rizapit zetnitsit, SeoNsnit saiNiit, Moensha Gnpsesuidae, Monoceridae, Retshit zo1nit, Reshshsht N1dNa1it or Reshshsht expands, in particular, against pathogens in fruits, such as pome fruits, for example apples and pears, stone fruits, for example peaches and plums, citrus fruits, melon, papaya, kiwi, mango, berries strawberries , Avocados, pomegranates and bananas, and nuts.

The compositions of the present invention are particularly useful for controlling the following diseases of the following cultures: LNHapap species in fruits and vegetables; LzsosNu1a species in legumes; VNUNZ stega for strawberries, tomatoes, sunflowers, legumes, vegetables and grapes; Segosozroga agasH1Shco1a in peanuts; Composition of zaois in cereals; types of Co11e1o1g1sNpt in legumes; Eguz1rNe species in cereals; for example, Eguz1PNe dgaplits in wheat and Eguz1pNe dgaplits in barley; Eguz1RNe SyuNogaseeagit and 8rNaego1Nesa Guindea in pumpkin; Rizalit species in cereals and maize; Saytappotuzez dgaiiishz in cereal and lawn grasses; Species of Ne1tsh1Nozrogsht grazed in corn, rice and potatoes; No11е1а уаз1аίπχ in coffee; MyugoyosNit species in wheat and rye; Garbage on a banana; types of RNcortex in soybeans, for example, RNcortex rasNuph! soybeans; Rysshya species in cereals, broadleaf crops and perennial crops; for example, Riesshsha HesopNia in wheat, Rhyshsha siuGotiz in wheat and Rhyshsha HesopNa in barley; Species of Rzeyiosegseozroge11a in cereals, for example, Rzeyiosegseozrogea 11a Negro1g1sNo1ez in wheat; RNgadtysht tpsgopaSt at roses; RoyozrNaega species in fruits; types of Rugepor Foot in barley, for example, Rugepor Foot 1 in barley; Rupsyapa uguhay rice; Katyapa soi-judge in barley; Types of Kyoto / Shota in cotton, soybeans, cereals, corn, potatoes, rice and lawn grasses, for example KYhoslosha zo1ap1 in potatoes, rice, lawn grasses and cotton; KNupsNozropt zesNz in barley, KNupsNozrosht zesNz in rye; 8c1egoNesha species in lawn grasses, lettuce, vegetables and rapeseed, for example, 8c1egoya ss1egoogogit in rape and 8c1egoya Noteosagra in lawn grasses; species of sper1op in cereals, soybeans and vegetables, for example, sper1op 1grn in wheat, 8p1opa will help in wheat and 8lpop1 in soy; 8pNase1o1Nesa henNapa in corn; TSheia species in cereals; ipshpia pesparas stpida parsonum and parsnipidae in grapes; Igosuz NZ OSSIIa in rye; The igotusias has fallen in beans; Ishado species in cereals and maize; UepShpa species in fruits, for example, UepShpa tes. | IAZ in apples; MopShsha species in fruits; Resheshsht species in citrus and apples.

In general, the mass ratio of component (A) to component (B) is from 2000: 1 to 1: 1000. A non-limiting example of such masses, ratios is the ratio of the compound of formula 1: the compound of formula B-2 = 10: 1. The mass ratio of component (A) to component (B) is preferably from 100: 1 to 1: 100; more preferably from 20: 1 to 1:50.

It was unexpectedly found that certain mass ratios of component (A) to component (B) are able to increase the synergistic effect. Therefore, another aspect of the present invention includes compositions where component (A) and component (B) are present in the composition in amounts that provide a synergistic effect. Such a synergistic effect is evident from the fact that the fungicidal activity of the composition containing component (A) and component (B) is greater than the total fungicidal activity of component (A) and component (B). Such synergistic activity increases the action of component (A) and component (B) in two ways. Firstly, the amount of application of component (A) and component (B) is reduced, while the effect remains the same, which means that the mixture of active ingredients reaches a high degree of phytopathogenic control, even where two separate components were ineffective in such a low application volume. Secondly, there is a significant expansion in the spectrum of phytopathogens that can be combated.

- 7 018993

A synergistic effect exists where the effect of the combination of active ingredients is greater than the sum of the actions of the individual components. The expected action E for this combination of active ingredients obeys the so-called SOBU formula and can be calculated as follows (SOBB.Z.E. Ca1ci1a1dd kuyegd1k11s aib agIadoshkos gekropkek οί Nsgyshs sotpayoi. Aeebk, Uo-22.

ppm = milligrams of active ingredient (= ai) per liter of sprayable mixture;

X =% action of the active ingredient A) using r ppm of the active ingredient;

Υ =% action of the active ingredient B) using c. | ppm of the active ingredient.

According to ΟΟίΒΥ. expected (additive) effect of the active ingredients A) + B) using p + s. | ppm of the active ingredient is Ε = Χ + Υ- (Χ · Υ) / 100.

If the observed action (O) is greater than the expected action (E), then the combination action is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to the positive value of the difference (OE). In the case of a completely complementary addition of activities (expected activity), the indicated difference (OE) is zero. A negative value of the indicated difference (OE) indicates a loss of activity compared to the expected activity.

However, in addition to the actual synergistic effect with respect to fungicidal activity, the compositions according to the present invention also have other unexpected favorable properties. Examples of such beneficial properties include: more favorable degradability; improved toxicological and / or ecotoxicological behavior; or improved characteristics of useful plants, including: germination, yield, more developed root system, improved shoot formation, increased plant height, larger leaf blades, fewer dead leaves, stronger shoots, greener leaves, reduced fertilizer requirement, reduced seed consumption , more productive shoots, earlier flowering, earlier ripening of grains, less lodging of plants, increased shoot growth, improved plant power and early germination.

Some compositions according to the present invention have a systemic effect and can be used as fungicides for treating foliage, soil and seeds.

Using the compositions according to the present invention, it is possible to inhibit or destroy phytopathogenic microorganisms that exist in plants or in parts of plants (fruits, flowers, leaves, stems, tubers, roots) of various useful plants, while protecting parts of plants that grow later from phytopathogenic damage microorganisms.

Compositions according to the present invention can be applied to phytopathogenic microorganisms, beneficial plants, their locations, their seed, stored goods or technical materials affected by microorganisms.

Compositions according to the present invention can be applied before or after infection of beneficial plants, seeds, stored goods or technical materials with microorganisms.

The amount of composition to be applied according to the present invention depends on various factors, such as the compounds used; an object of processing, such as, for example, plants, soil or seeds; type of treatment, such as, for example, spraying, dusting or dressing seeds; the purpose of the treatment, such as, for example, prevention or treatment; the type of fungi to be fought, or the time of application.

When used on useful plants, component (A) is usually applied in an amount of 5-2000 g ai / ha, preferably 10-1000 g ai / ha, for example 50, 75, 100 or 200 g ai / ha, usually in combination with 1-5000 g ai / ha, preferably 2-2000 g ai / ha, for example 100, 250, 500, 800, 1000, 1500 g ai / ha component (B).

In agricultural practice, the amount of applied composition according to the present invention depends on the type of effect desired and usually ranges from 20 to 4000 g of composition per hectare.

If the composition according to the present invention is used for seed treatment, the amount of 0.001-50 g of the compound of component (A) per kg of seeds, preferably 0.01-10 g per kg of seeds, and 0.001-50 g of the compound of component (B) per kg of seeds, preferably from 0.01 to 10 g per kg of seed is usually sufficient.

The composition according to the present invention can be applied in any conventional form, for example, in the form of a double package, in the form of powder for dry seed treatment (Ό8), emulsion for seed treatment (Ε8), fluid concentrate for seed treatment (E8), seed treatment solution (B8), a water dispersible seed treatment powder (AZ), an encapsulated seed treatment suspension (CE), a seed treatment gel (CE), a concentrated emulsion (EC), a concentrated suspension (ZS), a suspension emulsion (ZE), an encapsulated suspensions (SZ), water-dispersible granules (AC), emulsifiable granules (EU), water-in-oil emulsions (EO), oil-in-water emulsions (EA), microemulsions (IU), dispersions in oil (ΟΌ), fluid powder (OE) mixed with oil miscible with oil, liquid (S), soluble concentrate (S), suspension of ultra-low volume (S), liquid of ultra low volume (S), technical concentrate (TK), dispersible concentrate

- 8 018993 (OS), wettable powder (^ P) or any technically feasible composition in combination with agriculturally acceptable adjuvants.

Such compositions can be prepared by conventional methods, for example, by mixing the active ingredients with at least one suitable inert adjuvant for the composition (for example, diluents, solvents, fillers and optional other ingredients for the compositions, such as surfactants, biocides, antifreeze, binders substances, thickeners and compounds that provide a promoting effect). Conventional sustained release formulations may also be used if sustained exposure is required. Preferably, compositions applied in sprayable forms, such as water dispersible concentrates (e.g. EC, 8C, OS. OE. 8E, E ^, EO and the like), wettable powders and granules, may contain surfactants such as wetting agents and dispersing agents, and other compounds that provide a promoting effect, for example, a condensation product of formaldehyde and naphthalene sulfonate, alkylaryl sulfonate, lignin sulfonate, fatty alkyl sulfate and ethoxylated alkyl phenol and ethoxylated fatty alcohol.

The compositions of the present invention may also contain other pesticides, such as, for example, fungicides, insecticides or herbicides.

The seed dressing composition is applied to the seeds by known methods using the compositions of the present invention and a diluent in a form suitable for the seed dressing composition, for example, in the form of an aqueous suspension or dry powder that adheres well to the seeds. Such seed treatment compositions are known in the art. Seed dressing compositions may contain the individual active ingredients or a combination of the active ingredients in an encapsulated form, for example, sustained release capsules or microcapsules.

Typically, compositions contain from 0.01 to 90% by weight of active agent, from 0 to 20% of an agriculturally acceptable surfactant, and from 10 to 99.99% of solid or liquid inert fillers and adjuvants of the composition, where the active ingredient contains at least a compound of component (A) together with a compound of component (B), and optionally other active agents, especially microbiocides or preservatives, or the like. Concentrated forms of compositions typically contain from about 2 to about 70% by weight of active agent. Application forms of the composition may, for example, contain from 0.01 to 20 wt.%, Preferably from 0.01 to 5 wt.% Of the active agent. Although commercial products are preferably in the form of concentrates, the end user typically uses diluted compositions.

The methods of the present invention also provide a good opportunity to control other harmful fungi often found in soy plants. The most important fungal diseases in soybeans is Ryakorkoga rasugYa, Msgokraega bgyika, Segsokroga ktkisY, Segsokroga Korpi 8er1og1a d1us1pek and S.o11eYu1ps11shp 1gipsa1it, some of which include so-called complex disease of late varieties and ShahosYusha ko1apg Sogupekroga sakkiso1a, 8s1egoysha ks1egoyogit and 8s1egoksht HT1 £ ki.

As described above, for the term beneficial plant, the term soybean plant includes all soybean plants and all variants, including transgenic plants. The term soybean plant preferably includes glyphosate tolerant soybean plants.

Glyphosate tolerance is understood to mean plants which, when applying the methods, are resistant to glyphosate or resistant to glyphosate. Glyphosate-tolerant plants are made glyphosate-tolerant by conventional selection or transgenic manipulations that provide glyphosate resistance. Some examples of such preferred transgenic plants that are resistant to glyphosate are described in US patents 5914451; 5,866,775; 5,804,425; 5776760; 5,633,435; 5,627,061; 5,463,175; 5,312,910; 5,310,667; 5,188,642; 5,145,783; 4971908 and 4940835. The use of folded transgenic objects in a plant is also being considered.

Folded transgenic objects, including additional signs of herbicide resistance, such as resistance to ΗΡΡϋ inhibitors, sulfonylureas, glufosinate and bromxinyl, are widely used and described in readily available sources. Folded transgenic objects can also be targeted for signs of resistance to other pesticides, such as an insecticide, nematicide, fungicide, etc., which can be obtained by routine selection or administration of a transgenic object. Glyphosate tolerant transgenic cereal lines for use in the methods of the present invention include, for example, Coipbir Veabu® 8ObEap 40-3-2.

A transgenic plant refers to a plant that contains genetic material that is absent (i.e., exogenous) in a wild type of plant of the same species, its variety or cultivars. The genetic material may include a transgene, an insertion mutagenesis object (such as transposon or T-DNA insertion mutagenesis), an activation labeling sequence, a mutated sequence, a homologous recombinant object, or a sequence modified by chemotherapy. Typically, foreign genetic material is manually introduced into the plant, but any method known to one skilled in the art can be used. Transgenic

- 9 018993 the plant may contain an expression vector or expression polygenic cluster. An expression cassette typically contains a polypeptide-coding sequence operably linked (i.e., under regulatory control) to a suitable inducible or constitutive regulatory sequence that allows expression of the polypeptide. A polygenic expression cluster can be introduced into the plant by transformation or selection after transformation of the parent plant. As described above, a plant refers to a whole plant, including seedlings and mature plants, as well as parts of a plant, such as seeds, fruits, leaves or roots, plant tissues, plant cells or any other plant material, for example, a plant explant, and his offspring, and to ίη νίίτο systems that mimic biochemical or cellular components or processes in a cell.

The following examples serve to illustrate the invention, the active ingredient means a mixture of component (A) and component (B) in a specific ratio.

Examples of compositions

Wettable Powders a) B) active ingredient [A): B) = 1: 3 (a), 1: 1 (b)] 25% 75% sodium lignosulfonate 5% - sodium lauryl sulfate 3% 5% diisobutylnaphthalenesulfonate sodium - 10% (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% kaolin 62% -

The active ingredient is thoroughly mixed with other components of the composition and the mixture is thoroughly ground in a suitable mill to obtain wettable powders that can be diluted with water to give suspensions of the desired concentration.

Dry Seed Powders a) B) active ingredient [A): B) = 1: 3 (a), 1: 1 (b)] 25% 75% light mineral oil 5% 5% highly dispersed silicic acid 5% - kaolin 65% - talc - 20

The active ingredient is thoroughly mixed with other components of the composition and the mixture is thoroughly ground in a suitable mill to obtain powders that can be used directly for seed treatment.

Emulsifiable concentrate:

active ingredient (A): B) = 1: 6) 10% octylphenol ether polyethylene glycol (4-5 3% mole of ethylene oxide) calcium dodecylbenzenesulfonate 3% polyglycol ether castor oil (35 4% mole of ethylene oxide) cyclohexanone thirty% xylene mixture fifty%

Emulsions of any desired degree of dilution, which can be used to protect plants, can be obtained from this concentrate by dilution with water.

Sprayable powders a) B) active ingredient [A): B) = 1: 6 (a), 1:10 (b)] 5% 6% talc 95% - kaolin - 94%

Ready-to-use powders are prepared by mixing the active ingredient with carriers and grinding the mixture in a suitable mill. Such powders can also be used for dry seed dressing.

- 10 018993

Extruded granules active ingredient (A): B) = 2: 1) sodium lignosulfonate alkylnaphthalene sodium sulfonate kaolin% wt./mass.

fifteen%

2%

1%

82%

The active ingredient is mixed and ground with other components of the composition, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Suspension Concentrate:

active ingredient (A): B) = 1: 8)

40% propylene glycol nonylphenol ether polyethylene glycol (15 mol ethylene oxide) sodium lignosulfonate carboxymethyl cellulose silicone oil (as a 75% emulsion in water) water

10%

6%

10%

1%

32%

The finely divided active ingredient is thoroughly mixed with other components of the composition to obtain a suspension concentrate that can be diluted in water to any desired concentration. Such dilutions can be processed and protected from infection by microorganisms living plants and seeds, by spraying, watering or immersion.

Bulk concentrate for seed treatment:

active ingredient (A): B) = 1: 8) 40% propylene glycol 5% butanol copolymer PO / EO 2% tristirolphenol ethoxylate (with 10-20 moles EO) 2% 1,2-benzisothiazolin-3-one 0.5% monoazo-pigment calcium salt 5% silicone oil (as a 75% emulsion in water) 0.2% water 45.3%

The finely divided active ingredient is thoroughly mixed with other components of the composition to form a suspension concentrate that can be diluted in water for application to the seeds. Such dilutions can be processed and protected against infection by microorganisms seed material by spraying, watering or immersion.

Biological Examples

Example B1: fungicidal action against Segocroc agasulophyta (syn. Musocerea agiaSyysch), brown spotting of peanuts.

Conidia of mushrooms from the cryogenic storage is mixed directly into the nutrient broth (KDB potato-dextrose broth). After placing (DMSO) a solution of the test compounds in a microtiter plate (96-well), a nutrient broth containing mushroom spores is added. Test plates were incubated at 24 ° C and growth inhibition was evaluated after 7 days. The expected fungicidal effect is calculated by the Colby method. The results are shown in table. IN 1:

Fungicidal action against Segsokrog agasYuyuoa

Table B.1

Compound A-1.1 Bixafen ppm ppm % activity 0,0313 70 0.0156 20

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0.0078 0 0.0030 0 0,0313 70 0.0156 20 0.0078 0 0.0039 0 Expected Action (CoLb) 0,0313 0.0156 90 76 0.0156 0,0313 90 76 0.0156 0.0156 70 36 0.0156 0.0078 fifty 20 0.0156 0.0039 fifty 20 0.0078 0.0156 fifty 20 0.0039 0.0156 fifty 20

Example B2. Fungicidal action against Mopoagaoke 11a ηίναΐίδ (syn.

Conidia of mushrooms from the cryogenic storage is mixed directly into the nutrient broth (KDB potato-dextrose broth). After placing (DMSO) a solution of the test compounds in a microtiter plate (96-well), a nutrient broth containing mushroom spores is added. Test plates were incubated at 24 ° C and growth inhibition was evaluated after 4 days. The expected fungicidal effect is calculated by the Colby method. The results are shown in table. IN 2.

Table B2. Fungicidal action against Mopoagaoye 11a schua118

Table B2

Compound A-1.1 Bixafen ppm ppm % activity 0.0625 fifty 0,0313 20 0.2500 20 0,1250 0 0.0625 0 0,0313 0 Expected Action (Co1yy) 0.0625 0.2500 90 60 0.0625 0,1250 90 fifty 0.0625 0.0625 70 fifty 0.0625 0,0313 70 fifty 0,0313 0,1250 fifty 20 0,0313 0.0625 fifty 20

CLAIM

Claims (12)

1. A composition for controlling diseases caused by phytopathogens, comprising: (A) a compound of formula (I) wherein I ₁ is difluoromethyl or trifluoromethyl and X is chlorine, fluorine or bromine; and (B) a bixafen compound. 2. The composition according to claim 1, where component (A) is a compound of formula (I), where I ₁ is difluoromethyl. 3. The composition according to claim 1, where component (A) is a compound of formula (I), where I ₁ is difluoromethyl and X is chlorine. 4. The composition according to claim 1, where component (A) is a compound of formula (I), where I ₁ is difluoromethyl and X is fluorine. 5. The composition according to claim 1, where component (A) is a compound of formula (I), where I! is difluoromethyl and X is bromo. 6. The composition according to claim 1, where component (A) is (9-dichloromethylidenebenzonorbornene-5yl) amide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid or (9-difluoromethylidenebenzonorbornen-5-yl) amide 3 -difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid and component (B) is bixafen. - 12 018993 7. The composition according to claim 1, where component (A) is (9-dichloromethylidenebenzonorbornene-5yl) amide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid and component (B) is bixafen. 8. The composition according to claim 1, where component (A) is (9-difluoromethylidenebenzonorbornene-5yl) amide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid and component (B) is bixafen. 9. The composition according to claim 1, where the mass ratio (A) :( B) is from 2000: 1 to 1: 1000. 10. A method of combating diseases of useful plants or their seed caused by phytopathogens, which includes applying to a useful plant, their location or their seed the composition according to claim 1. 11. A method of combating diseases of soy plants caused by phytopathogens, which comprises applying to a soy plant or its location a composition according to claim 1. 12. The method according to claim 11, where the phytopathogen is Ranocorpus rasibiota.