RU2776177C1 - Thiophene carboxamide derivative and agent for controlling a plant disease, containing said derivative - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to a compound based on difluorobiphenyl thiophene carboxamide, represented by the general formula (I), or a salt thereof, applicable as an agent for controlling fungal diseases of plants and exhibiting an excellent control effect at low doses. In the formula (I), Y constitutes a hydrogen atom or a (C1-C4)alkyl; X constitutes a halogen atom or a (C1-C4)alkyl; m constitutes an integer from 0 to 2; R constitutes a hydrogen atom, a (C1-C6)alkyl, a (C2-C6)alkenyl, a (C1-C6)alkyl, which can be substituted with 1-5 halogen atoms, phenyl(C1-C3)alkyl, which can be substituted with a halogen atom, phenyl(C1-C3)alkyl, which can be substituted with a (C1-C4)alkyl, or phenyl(C1-C3)alkyl, which can be substituted with a (C1-C4)alkoxy; R1 constitutes a halogen, (C1-C4)alkyl or (C1-C4)alkyl substituted with 1-3 halogen atoms, and each of R2 and R3 independently constitutes hydrogen, a (C1-C4)alkyl or a halogen. The invention also relates to an agent for controlling fungal diseases of plants for application on agricultural and horticultural plants, a method for controlling fungal diseases of plants, and an application of the compounds by the general formula (I) for producing an agent for controlling fungal diseases of plants.

(I)

EFFECT: creation of a compound suitable for use as an agent for controlling fungal diseases of plants.

7 cl, 2 tbl, 5 ex

Description

Technical field

This application claims priority under Korean Application No. 10-2018-0119984, filed on October 8, 2018, and all contents are disclosed in the application description and drawings incorporated herein by reference.

The present invention relates to a fluoro-substituted derivative of a biphenylthiophenecarboxamide compound, a salt thereof, a structural isomer thereof, and an agricultural and horticultural plant disease control agent containing it as an active ingredient.

Prerequisites for the creation of the invention

To date, many carboxamide-based compounds are already known to have control effects on microorganisms (eg WO 2002/008197 A1, WO 2004/054982 A1, WO 2013/167550 A1 and WO 2017/042142 A1). The activity of such substances in the context of the control is good, but often not satisfactory.

Disclosure

Technical problem

The plant disease control agents for use on agricultural and horticultural plants disclosed in the conventional technology indicated in the above example do not show a practical level of activity in the context of control, hence further study is still needed. In particular, their activity in the context of powdery mildew control is limited. In addition, environmentally friendly compounds are strongly required for modern crop protection agents, and thus plant disease control agents for use on agricultural and horticultural plants that exhibit high activity at low doses are increasingly sought after.

Technical solution

As a result of careful study carried out by the present inventors to solve the above problems, it was found, thereby carrying out the present invention, that the fluoro-substituted derivatives of the thiophenebiphenylcarboxamide-based compound, their structural isomers and salts represented by the general formula (I) of the present invention have a broad spectrum of activity as a fungicide against powdery mildew even at a low dose in addition to a demonstrated excellent control effect as a plant disease control agent for use on agricultural and horticultural plants. In other words, the present invention relates to a thiophenebiphenylcarboxamide-based fluorine-substituted compound or a salt thereof represented by the following general formula 1, a method for their preparation, and a plant disease control agent for use in agricultural and horticultural plants containing them.

The present invention relates to

1) a fluoro-substituted derivative of biphenylcarboxamide or its structural isomer or salt thereof, represented by the following general formula:

(I),

(I)

in the above formula

Y represents a hydrogen atom or (C1-C4)alkyl;

X represents a halogen atom or (C1-C4)alkyl;

m is an integer from 0 to 2;

R represents a hydrogen atom, (C1-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, (C1-C6) alkyl which may be substituted by 1-5 halogen atoms, (C1-C3) alkyl , which may be substituted with (C3-C6)cycloalkyl, (C1-C3)alkyl which may be substituted with phenyl or pyridine, phenyl(C1-C3)alkyl (which may be substituted with a halogen atom), phenyl(C1-C3)alkyl , which may be substituted with (C1-C4) alkyl, or phenyl(C1-C3) alkyl, which may be substituted with (C1-C4) alkoxy;

R1 is (C1-C4)alkyl or (C1-C4)alkyl substituted with 1-3 halogen atoms, and each of R2 and R3 is independently hydrogen, (C1-C4)alkyl or halogen;

2) in said paragraph 1)

Y represents a hydrogen atom; m is 0; R is (C1-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, (C1-C6) alkyl which may be substituted by 1-5 halogen atoms, (C1-C3) alkyl which may be substituted by (C3-C6)cycloalkyl, (C1-C3)alkyl which may be substituted by phenyl or pyridine, phenyl(C1-C3)alkyl (which may be substituted by a halogen atom), phenyl(C1-C3)alkyl which may be substituted with (C1-C4) alkyl, or phenyl(C1-C3) alkyl which may be substituted with (C1-C4) alkoxy; R1 is (C1-C4)alkyl or (C1-C4)alkyl substituted with 1-3 halogen atoms; and R2 and R3 represent a hydrogen atom;

3) in said paragraph 1)

Y is a hydrogen atom, m is 0, R is (C1-C6)alkyl or (C1-C4)alkyl which may be substituted with 1-3 halogen atoms; R1 is methyl and R2 and R3 are hydrogen atom;

4) structural isomer of the substance specified in point 2);

5) a plant disease control agent for use on agricultural and horticultural plants, characterized in that it contains the compound described in said items 1) to 4) as an active ingredient; or

6) a method for controlling a plant disease, characterized in that the agent of said paragraph 5) is applied to a plant or soil.

Specific details for carrying out the present invention

In accordance with the present invention, a novel fluoro-substituted thiophenebiphenylcarboxamide of the following general formula (I) has been found:

(I).

(I).

In the above formula, the definition of the general formula (I) of the present invention is as follows.

"Halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

An example of "(C1-C6)alkyl which may be substituted with halogen atoms" includes a straight or branched chain alkyl group containing 1-6 carbon atoms, e.g., methyl, ethyl, "normal" propyl, isopropyl, "normal" butyl, isobutyl, secondary butyl, tertiary butyl, "normal" pentyl, neopentyl, and "normal" hexyl; and a straight or branched chain alkyl group containing 1-6 carbon atoms substituted by one or more halogen atoms, which may be the same or different, for example, fluoromethyl, difluoromethyl, trifluoromethyl, perfluoroethyl, chloromethyl, bromomethyl, 1-bromoethyl, 2 ,3-dibromopropyl, etc.

An example of "(C2-C6)alkenyl" includes a straight or branched chain alkenyl group containing 2-6 carbon atoms, e.g. vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-methyl-2-propenyl, 1 -methyl-2-propenyl, 2-methyl-1-propenyl, pentenyl and 1-hexenyl.

An example of "(C2-C6)alkynyl" includes a straight or branched alkynyl group containing 2-6 carbon atoms, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 3 -methyl-1-propynyl, 2-methyl-3-propynyl, pentynyl and 1-hexynyl.

An example of "(C1-C4)alkoxy" includes a straight or branched alkoxy group containing 1-3 carbon atoms, such as methoxy, ethoxy, "normal" propoxy, isopropoxy, "normal" butoxy and isobutoxy.

As the salts of the biphenylthiophenecarboxamide derivative represented by the general formula (I) of the present invention, for example, inorganic acid salts such as hydrochloride, sulfate, nitrate, phosphate; organic acid salts such as acetate, fumarate, maleate, oxalate, methanesulfonate, benzenesulfonate and p-toluenesulfonate; and salts with inorganic or organic ions such as lithium ions, sodium ions, potassium ions, calcium ions and trimethylammonium.

The structural isomers of the thiophenebiphenylcarboxamide derivative represented by the general formula (I) of the present invention may be in (E)-form and (Z)-form.

In the compound represented by the general formula (I) of the present invention, preferably X represents a chlorine atom, a bromine atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl. More preferably X is a group representing a fluorine atom.

Preferably Y is a hydrogen atom, a halogen atom or methyl. More preferably Y is a hydrogen atom.

Preferably R is methyl, ethyl, propyl, propylene, butyl, t-butyl, phenylmethyl, 4-chlorophenylmethyl, 4-fluorophenylmethyl, fluoromethyl, trifluoromethyl, trifluoroethyl or chloroethyl. More preferably R is methyl or trifluoroethyl.

More preferred examples of formula 1 are as follows:

(E)-N-(3',5'-difluoro-4'-((methoxyimino)methyl)-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide,

(E)-N-(4'-((ethoxyimino)methyl)-3',5'-difluoro-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide,

(E)-N-(3',5'-difluoro-4'-((isopropoxyimino)methyl)-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide,

(E)-N-(4'-((tert-butoxyimino)methyl)-3',5'-difluoro-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide,

(E)-N-(4'-(((aryloxy)imino)methyl)-3',5'-difluoro-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide,

(E)-N-(3',5'-difluoro-4'-(((2,2,2-trifluoroethoxy)imino)methyl)-[1,1'-biphenyl]-2-yl)-3- methylthiophene-2-carboxamide and

(E)-N-(4'-(((benzyloxy)imino)methyl)-3',5'-difluoro-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide.

The compound of the present invention, for example, was prepared according to the following Production Methods 1 and 2, but the production is not limited thereto.

Production method 1

(Wherein R, R1, R2, R3, Xm and Y are as defined in the above formula, and L1 is a leaving group such as a group representing a chlorine atom, a bromine atom or an alkoxy group).

Fluoro-substituted thiophenebiphenylcarboxamide derivatives represented by the general formula (I) can be obtained by carrying out the reaction between the thiophenecarboxylic acid derivative represented by the general formula (II) and the 2-aminobiphenyl derivative represented by the general formula (III) in the presence of a base in an inert solvent . The reaction temperature in this reaction is usually in the range from about -20°C to 120°C, and the reaction time is usually in the range from about 0.1 hour to 48 hours. The number of moles of the 2-aminobiphenyl derivative represented by the general formula (III) used is usually greater by a value ranging from about 0.5 to 4 than the number of moles of the acid derivative A represented by the general formula (II).

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; acetates such as sodium acetate and potassium acetate; alkali metal alcoholates such as potassium tert-butoxide, sodium methoxide and sodium ethoxide; tertiary amines such as triethylamine, diisopropylethylamine and 1,8-diazabicyclo[5.4.0]undec-7-ene; nitrogen-containing aromatic compounds such as pyridine and dimethylaminopyridine; and so on. The number of moles of the base used is usually greater by a value ranging from about 0.5 to 5, compared with the number of moles of the acid derivative A represented by the general formula (II). As the inert solvent, a solvent which does not substantially inhibit the reaction can be used, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; straight chain ethers or cyclic ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitriles such as acetonitrile; esters such as ethyl acetate; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, water, and acetic acid. Such inert solvents may be used alone or in combination of two or more.

Obtaining Method 2

(Wherein R, R1, R2, R3, Xm, Y and L1 are as defined in the above formula, L2 is a leaving group such as a group representing a chlorine atom, a bromine atom and an iodine atom, and L3 is a group B(OH) ₂ or a B(OG2) ₂ group (wherein G2 may be the same or different and is (C1-C10)alkyl, or two G2s may be end-bonded to form CH ₂ CH ₂ or C(CH ₃ )C2(CH ₃ ) ₂ ).

The compound of general formula (V) can be produced by the method relating to the compound (I) of the production method 1.

The fluoro-substituted thiophenecarboxamide derivatives of the present invention represented by the general formula (VII) can be obtained by reacting the thiophenecarboxamide derivative represented by the general formula (V) with a compound represented by the general formula (VI) in an inert solvent in the presence of a catalyst and a base . In this reaction, the reaction temperature is usually in the range from about 20°C to 150°C, and the reaction time is usually in the range from about 0.5 hour to 48 hours. The number of moles of the compound represented by the general formula (V) used is usually greater by a value ranging from about 0.8 to 5, compared with the number of moles of the acid derivative A represented by the general formula (IV). As a catalyst, for example, palladium catalysts such as palladium(II)acetate, tetrakis(triphenylphosphine)palladium(0), complex [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane, and bis dichloride can be used. (triphenylphosphine)palladium(II). The number of moles of the catalyst used is greater by a value ranging from about 0.001 to 0.2 compared to the number of moles of the compound represented by the general formula (V). Examples of the base include inorganic bases such as potassium phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; and acetates such as sodium acetate and potassium acetate. The number of moles of the base used is usually greater by a value ranging from about 0.5 to 10, compared with the number of moles of the acid derivative A represented by the general formula (IV).

In addition, the required compound of general formula (I) can be obtained by reacting a compound of general formula (VII) With an NH ₂ OR compound. Meanwhile, the reaction temperature in this reaction is usually in the range from about -20°C to 100°C, and the period of time for which the reaction is usually carried out is in the range from about 0.5 hours to 24 hours. The number of moles of the NH ₂ OR compound used is usually greater by a value ranging from about 1.0 to 5 compared to the number of moles of the derivative of the compound of general formula (VII). Examples of the base include inorganic bases such as potassium phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; and acetates such as sodium acetate and potassium acetate. The number of moles of the base used is usually greater by a value ranging from about 1.0 to 10 compared to the number of moles of the compound of general formula (VI).

A compound of general formula (VIII) can be obtained by reacting a compound of general formula (VII) with HN ₂ OH hydrochloride. In this case, the hydrochloride HN ₂ OH can be obtained using a reaction duration of 0.5-24 hours at a temperature of from -20°C to 50°C using the number of equivalents based on the compound of formula (VII) in the range of 1.0-4 . Compound (I) can be produced by using L2-R having a suitable L2 from the compound of general formula (VIII) with the method of Production Method 1.

If necessary, this reaction can be carried out in the presence of a phase transfer catalyst (for example, quaternary ammonium salts such as tetrabutylammonium bromide and benzyltriethylammonium bromide, etc.). As the inert solvent, a solvent which does not substantially inhibit the reaction can be used, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; straight chain ethers or cyclic ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitriles such as acetonitrile; esters such as ethyl acetate; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, water, and acetic acid. Such inert solvents may be used alone or may be used by mixing two or more types.

After completion of the reaction, the compound of interest can be obtained using a conventional method, which can ensure its separation from the reaction system. In general, said compound can be purified by precipitating and filtering the reaction mixture in a suitable solvent, and if necessary, said compound can be obtained by a purification method such as recrystallization, column chromatography, or the like. In the context of the compound to be obtained , structural isomers having different melting points can be obtained. They are all included in the scope of the present invention.

Illustrative examples and NMR data of the fluoro-substituted carboxamide derivative represented by the general formula (I) of the present invention obtained in this way are illustrated in Table 1, but the present invention is not limited thereto.

In Table 1 below, "Me" means methyl group, "Et" means ethyl group, "Pr" means propyl group, "Bu" means butyl group, "Ph" means phenyl group, "n-" means "normal" compound structure, and "i-" means iso, and "t-" means the tertiary structure of the compound.

The compound according to the present invention has a strong fungicidal activity and thus can be used to control fungi and bacteria to control plant diseases in agricultural and horticultural plants.

In a method for controlling plant diseases, it is possible to apply the compound of the present invention to plant parts above ground, stems for propagation, and seeds, and soil at a desired concentration.

The active compound according to the present invention is a plant disease control agent for use in agricultural and horticultural plants, in particular, it is possible to control diseases in plants of rice, fruit trees, vegetables and other crops and flowers.

When the compound of the present invention is used as an active ingredient of a plant disease control agent, it can be used as such without adding other ingredients, but in general it is preferred to use it as an agrochemical composition having a form suitable for use in accordance with a conventional method. receiving pesticides.

The compound of the present invention can be used not only to control plant diseases, but also to protect industrial materials from contamination and degradation by undesirable microorganisms. For example, industrial materials intended to be protected by the active compound of the present invention from being altered or destroyed by microorganisms may be bonding material, paper, plywood, cloth, leather, wood, paint, plastic products, cutting fluids, or any other material that can be damaged or destroyed by microorganisms.

The active compound may be formulated, depending on its particular physical and/or chemical properties, as a solution, emulsion, suspension, powder, foam, paste, granule, aerosol, and conventional formulations such as polymers and microcapsules, in a coating composition. seeds and for use in the ULV heat sink and ULV heater.

Such compositions are obtained by known methods, for example, optionally using surfactants, i.e. emulsifiers and/or dispersing agents and/or foaming agents, for mixing active compounds with carriers, i.e. liquid solvents, liquefied gases located under pressure, and/or solid carriers.

If water is used as the carrier, an organic solvent can also be used as a co-solvent.

In general, the formulations contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight of the active compound.

The active compound of the present invention can be used either alone or in combination with known fungicides, bactericides, acaricides, nematicides or insecticides, for example to extend the spectrum of fungicidal activity or to prevent the development of resistance. In many cases, a synergistic effect is observed, i.e. the activity of the mixture exceeds the activity of the individual ingredients.

The active compound can be used as such, in the form of its composition or in the form obtained from it, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, powders and granules. They are applied by conventional methods, such as spraying, spraying, spraying, scattering, dusting, foaming, spraying, etc. In addition, the active compound can be applied using a microvolume application method, or a formulation based on the active compound, or the active compound itself can be introduced into the soil. Plant seeds can also be processed.

Other antimicrobial active compounds, fungicides, bactericides, herbicides, pesticides, or other active compounds may be added as needed to broaden the spectrum of activity or obtain specific effects such as additional insect protection. It is possible to increase the activity and spectrum of activity of the active compounds used in accordance with the present invention, or compositions, concentrates or most commonly occurring compositions that can be obtained from them. Such mixtures may have a broader spectrum of activity than the compounds of the present invention.

Beneficial effects

The present invention provides a compound showing excellent activity compared to the compounds of the prior art, and in particular, has a wide spectrum of control at a low dose as a plant disease control agent for use in agricultural and horticultural plants.

Implementation of the invention

Hereinafter, the present invention will be more specifically described with reference to Examples and Experimental Examples, but the present invention is not limited to them unless it goes beyond the scope of the main content of the invention.

Receiving Example

Example 1

Synthesis of N- (3',5'-difluoro-4'-((methoxyimino)methyl)-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide (compound 1)

To a solution of N- (3',5'-difluoro-4'-formyl-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide (2.30 g, 6.42 mmol) hydrochloride methyl hydroxamide (1.33 g, 2.5 eq.) and sodium acetate trihydrate (2.21 g, 2.5 eq.) were added successively to 15 ml of ethanol at room temperature and stirred for 2 hours. After the completion of the reaction was confirmed by TLC, the organic layer was separated using ethyl acetate (100 ml) and 20 ml of water. The organic layer was dried over magnesium sulfate and concentrated. The resulting white solid was recrystallized using ethyl ether to give 2.01 g of a white solid (81% yield).

¹ H NMR (CDCl ₃ ) δ 2.42 (s, 3H), 4.05 (s, 3H), 6.86 (d, J = 5.1 Hz, 1H), 7.05 (d, J = 8.9 Hz, 2H), 7.25 (m, 3H). 7.36 (t, J = 6.0 Hz, 1H), 7.45 (s, 1H), 8.28 (s, 1H), 8.35 (d, J = 8.3 Hz, 1H)

Example 1-1

Synthesis of N- (3',5'-difluoro-4'-formyl-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide

To a solution of N- (2-bromophenyl)-3-methylthiophene-2-carboxamide (10.2 g, 34.6 mmol) in 100 ml of dimethylformamide was added 25 ml of distilled water, followed by successive addition of 3,5-difluoro-4-formyl -phenylboronic acid (10.9 g, 1.7 eq.), palladium(II) acetate (388 mg, 0.05 eq.) and tribasic potassium phosphate trihydrate (9.0 g, 1.1 eq.). The reaction mixture was stirred at 85 ^° C. for 2 hours under nitrogen atmosphere. After completion of the reaction was confirmed by TLC, ethyl acetate (1000 ml) and brine (100 ml) were added to the reaction mixture to separate the layers, followed by filtration through celite. The filtrate was diluted with ethyl acetate (200 ml) and the organic layer was washed with saturated aqueous Na ₂ CO ₃ (30 ml x 2) and brine (50 ml x 2). The organic layer was dried over magnesium sulfate and concentrated. The resulting concentrate was recrystallized using ethyl ether to give 10.9 g of the above solid (88%).

¹ H NMR (CDCl ₃ ) δ 2.45 (s, 3H), 6.89 (d, 1H), 7.07 (d, 2H), 7.25 (s, 3H). 7.47(m, 2H), 8.23(d, 1H), 10.37(s, 1H)

Example 1-2

Synthesis of N- (2-bromophenyl)-3-methylthiophene-2-carboxamide

To a solution of 2-bromoaniline (50.0 g, 311.3 mmol) and pyridine (25 ml, 1.0 eq.) in tetrahydrofuran (300 ml), .0 equiv.) at 0°C. After 30 minutes, the mixture was stirred for an additional 3 hours at room temperature. Ethyl acetate (100 ml) and water (40 ml) were added to the reaction mixture to separate the organic layer, and the organic layer was washed successively with 1.0 M HCl aqueous solution (30 ml), saturated aqueous sodium hydrogen carbonate solution (30 ml), and brine (50 ml). The organic layers were collected, dried over magnesium sulfate and concentrated. The resulting concentrate was recrystallized using ethyl ether to give 79.8 g of the above white solid (86% yield).

¹ H NMR (CDCl ₃ ) δ 2.65 (s, 3H), 7.0 (m, 2H), 7.36 (m, 2H). 7.56(d, 1H), 8.17(brs, 1H), 8.5(d, 1H)

Table 1 shows NMR data for compounds.

Table 1

connection no. R1 R2,
R3 Y xm R ¹ H NMR (300 MHz, solvent) one Me H H - Me (CDCl ₃ ) δ 2.42 (s, 3H), 4.05 (s, 3H), 6.86 (d, J = 5.1 Hz, 1H), 7.05 (d, J = 8.9 Hz, 2H), 7.25 (m, 3H). 7.36 (t, J = 6.0 Hz, 1H), 7.45 (s, 1H), 8.28 (s, 1H), 8.35 (d, J = 8.3 Hz, 1H) 2 Me H H - t-Bu (CDCl ₃ ) δ 1.38 (s, 9H), 2.41 (s, 3H), 6.88 (d, J = 5.0 Hz, 1H), 7.01 (d, J = 8.9 Hz, 2H), 7.25 (m, 3H). 7.43 (t, J = 6.0 Hz, 1H), 7.59 (s, 1H), 8.23 (s, 1H), 8.34 (d, J = 8.3 Hz, 1H) 3 Me H H - Et (CDCl ₃ ) δ 1.35 (t, J = 7.1 Hz, 3H), 2.42 (s, 3H), 4.31 (q, J = 7.1 Hz, 2H), 6.89 ( d, J = 5.0 Hz, 1H), 7.04 (d, J = 8.8 Hz, 2H), 7.26 (m, 3H). 7.44 (t, J = 9.0, 1H), 7.55 (s, 1H), 8.29 (s, 1H), 8.35 (d, J = 8.2 Hz, 1H) four Me H H - i-Pr (CDCl ₃ ) δ 1.33 (d, J = 6.2 Hz, 6H), 2.42 (s, 3H), 4.54 (m, 1H), 6.89 (d, J = 5.0 Hz, 1H), 7.04 (d, J = 8.7 Hz, 2H), 7.26 (m, 3H). 7.44 (t, J = 6.0, 1H), 7.55 (s, 1H), 8.26 (s, 1H), 8.36 (d, J = 8.3 Hz, 1H) 5 Me H H - benzyl (CDCl ₃ ) δ 2.42 (s, 3H), 5.28 (s, 2H), 6.89 (d, J = 5.0 Hz, 1H), 7.04 (d, J = 8.7 Hz, 2H), 7.35(m, 9H), 7.53(br, 1H), 8.36(m, 2H) 6 Me H H - 4-F-benzyl (CDCl ₃ ) δ 2.42 (s, 3H), 5.23 (s, 2H), 6.89 (d, J = 5.0 Hz, 1H), 7.06 (m, 5H), 7, 26 (m, 3H), 7.44 (m, 3H), 7.52 (br, 1H), 8.34 (m, 2H) 7 Me H H - 4-Cl-benzyl (CDCl ₃ ) δ 2.42 (s, 3H), 5.23 (s, 2H), 6.89 (d, J = 5.0 Hz, 1H), 7.04 (d, J = 8.8 Hz, 2H), 7.26(m, 3H), 7.35(m, 4H), 7.44(m, 1H), 7.52(s, 1H), 8.33(s, 1H), 8.35 (d, J = 8.3 Hz, 1H) eight Me H H - 4-OCH ₃ -benzyl (CDCl ₃ ) δ 2.42 (s, 3H), 3.81 (s, 3H), 5.20 (s, 2H), 6.90 (m, 3H), 7.03 (d, J = 8 .8 Hz, 2H), 7.26 (m, 3H), 7.43 (m, 3H), 7.53 (br, 1H), 8.31 (s, 1H), 8.35 (d, J = 8.3Hz, 1H) 9 Me H H - CH ₂ CF ₃ (CDCl ₃ ) δ 2.43 (s, 3H), 4.60 (q, J = 8.5 Hz, 2H), 6.90 (d, J = 5.1 Hz, 1H), 7.07 ( d, J = 9.0 Hz, 2H), 7.27 (m, 3H). 7.46 (m, 2H), 8.32 (d, J = 8.3 Hz, 1H), 8.40 (s, 1H) ten Me H H - _{CH2CH2Cl _} (CDCl ₃ ) δ 2.43 (s, 3H), 3.82 (t, J = 5.9 Hz, 2H), 4.46 (t, J = 5.8 Hz, 2H), 6.90 ( d, J = 5.1 Hz, 1H), 7.06 (d, J = 9.0 Hz, 2H), 7.27 (m, 3H). 7.46 (t, J = 6.0 Hz, 1H), 7.53 (s, 1H), 8.35 (d, J = 9.0 Hz, 1H), 8.60 (s, 1H) eleven Me H H - allyl (CDCl ₃ ) δ 2.43 (s, 3H), 4.74 (d, 2H), 5.3 (m, 2H), 6.05 (m, 1H), 6.90 (d, J = 5 .1 Hz, 1H), 7.06 (d, J = 9.0 Hz, 2H), 7.27 (m, 3H). 7.46 (t, J = 6.0 Hz, 1H), 7.53 (s, 1H), 8.35 (d, 2H) 12 Me H H 4-F Me (CDCl ₃ ) δ 2.43 (s, 3H), 4.06 (s, 3H), 6.90 (d, J = 5.0 Hz, 1H), 7.03 (m, 3H), 7, 16 (m, 1H), 7.30 (d, J = 5.0 Hz, 1H), 7.41 (br, 1H), 8.25 (m, 2H) 13 Me H H 4-F t-Bu (CDCl ₃ ) δ 1.38 (s, 9H), 2.42 (s, 3H), 6.90 (d, J = 5.1 Hz, 1H), 7.00 (m, 3H), 7, 15 (m, 1H), 7.30 (d, J = 5.1 Hz, 1H), 7.43 (br, 1H), 8.23 (s, 1H), 8.23 (m, 1H) fourteen Me H H 4-F CH ₂ CF ₃ (CDCl ₃ ) δ 2.43 (s, 3H), 4.59 (q, J = 8.5 Hz, 2H), 6.90 (d, J = 5.0 Hz, 1H), 7.00 ( dd, J = 8.6, 3.0 Hz, 1H), 7.05 (d, J = 8.7 Hz, 2H). 7.16 (td, J = 6.0, 3.0 Hz, 1H), 7.30 (d, J = 5.0 Hz, 1H), 7.38 (s, 1H), 8.21 (dd , J = 9.1, 5.2 Hz, 1H), 8.38 (s, 1H) fifteen Me H H 4-F _{CH2CH2Cl _} (CDCl ₃ ) δ 2.43 (s, 3H), 3.81 (t, J = 5.8 Hz, 2H), 4.46 (t, J = 5.8 Hz, 2H), 6.90 ( d, J = 5.0 Hz, 1H), 7.03 (m, 3H), 7.16 (m, 1H), 7.30 (d, J = 5.0 Hz, 1H), 7.41 ( br, 1H), 8.23(m, 1H), 8.35(s, 1H)

The following describes examples from bioactivity assays.

Experimental example 1

Wheat leaf rust control effects test

A predetermined amount of the compound of the present invention, corresponding to the test concentration, was dissolved in 10% acetone and then sprayed onto the leaves of single leaf wheat (species: Baegjoong) grown in a round pot (6 x 7 cm, diameter x height). One day after application, wheat plants were inoculated by spraying a spore suspension prepared with spores obtained from wheat leaves infected with wheat leaf rust pathogen ( Puccinia recondita ). After an inoculation period of 1 day at 20° C. under humid conditions, the plants were kept in the chamber for 14 days at constant temperature and humidity under constant light conditions. After 15 days of treatment with the compound, the occurrence rate of the disease was evaluated according to the following equation (1), and the control value was determined according to the following criteria.

(Equation 1)

Control value (%) = (1-X/Y) x 100,

where

X: area ratio of diseased leaves of treated plants

Y: area ratio of diseased leaves of untreated plants

Criteria

0: Reference value less than 9%

1: reference value of 10-29%

2: control value of 30-49%

3: reference value of 50-69%

4: control value of 70-89%

5: 90-100% control value

As a result of the above test, the compounds of the present invention showed excellent control effects in terms of active ingredient concentration of 200 ppm and spray dose amount of 30 ml, and in particular, compounds No. 1, 4 and 9 showed high activity, meeting criterion 5.

Experimental example 2

Rice Rhizoctonia Control Effects Test

A predetermined amount of the compound of the present invention corresponding to the test concentration was dissolved in 10% acetone and then sprayed onto the leaves of a 5-leaf rice plant (species: Chucheongbyeo) grown in a round pot (6 x 7 cm, diameter x height). One day after application, rice plants were inoculated by spraying a mycelial culture suspension of rice bran pathogen ( Rhizoctonia solani ) obtained by culturing in a rice bran culture medium, and incubated to induce disease development for 5 days under a humid environment at 30°C. After 5 days of treatment with the compound, the incidence of disease was evaluated according to Equation (1) of Experimental Example 1, and the control value was determined according to the criteria of Experimental Example 1.

As a result of the above test, the compound of the present invention showed an excellent control effect at an active ingredient concentration of 200 ppm and a spray dose amount of 30 ml, and in particular, the compound No. 1 showed high activity corresponding to criterion 5 in Equation 1 above.

Experimental Example 3

Control effects test on cucumber powdery mildew

A predetermined amount of the compound of the present invention corresponding to the test concentration was dissolved in 10% acetone and then sprayed onto the leaves of a single-leafed cucumber (species: Baekdadagi) grown in a round pot (6 x 7 cm, diameter x height). One day after application, cucumber plants were inoculated by spraying a spore suspension prepared with spores obtained from cucumber leaves infected with cucumber powdery mildew ( Sphaerotheca fusca ) pathogen. After an incubation period of 1 day at 20° C. under humid conditions, the plants were kept in a chamber for 12 days at constant temperature and humidity under constant light conditions. After 13 days of treatment with the compound, the occurrence rate of the disease was evaluated according to the equation (1) of Experimental Example 1, and the control value was determined according to the criteria of Experimental Example 1.

As a result of the above test, the compound of the present invention exhibits an excellent control effect at an active ingredient concentration of 200 ppm and a spray dose amount of 30 ml, and in particular, the compound No. 1, 2, 3, 4, 5, 6, 7, 8 , 9, 10, 11, 12, 13 and 14 showed high activity, meeting criterion 5 in equation 1 above.

Experimental example 4

Test of Control Effects on Cucumber Sclerotinia Disease

A predetermined amount of the compound of the present invention corresponding to the test concentration was dissolved in 10% acetone and then sprayed onto the leaves of a single-leafed cucumber (variety: Baekdadagi) grown in a round pot (6 x 7 cm, diameter x height). One day after application, cucumber plants were inoculated by spraying a mycelial liquid culture suspension of cucumber sclerotinia pathogen ( Sclerotinia sclerotiorum ) and incubated for 4 days under constant light and high humidity conditions at 25°C to induce disease development. Four days after treatment with the compound, the occurrence rate of the disease was evaluated according to Equation (1) of Experimental Example 1, and the control value was determined according to the criteria of Experimental Example 1.

As a result of the above test, the compound of the present invention showed an excellent control effect at an active ingredient concentration of 200 ppm and a spray dose amount of 30 ml, and in particular, the compound No. 1 showed high activity corresponding to criterion 5 in Equation 1 above.

Experimental Example 5

Compound No. 1 and the following four compounds as a comparative control compound were evaluated for control of cucumber powdery mildew as described in Experimental Example 3.

Compound A: 3-(difluoromethyl)-N-(4'-((methoxyimino)methyl)-[1,1'-biphenyl]-2-yl)-1-methyl-1H-pyrazole-4-carboxamide (compound I-11 of WO 2002/008197 A1).

Compound B: N-(4'-((methoxyimino)methyl)-[1,1'-biphenyl]-2-yl)-3-methylthiophene-2-carboxamide (Compound I-47 of WO 2002/008197 A1) .

Reference Compound C: 3-(difluoromethyl)-N-(3'-fluoro-4'-((methoxyimino)methyl)-[1,1'-biphenyl]-2-yl)-1-methyl-1H-pyrazol- 4-carboxamide (compound I-114 of WO 2002/008197 A1).

Compound D: 5-chloro-N-(3',5'-difluoro-4'-((methoxyimino)methyl)-[1,1'-biphenyl]-2-yl)-3-(difluoromethyl)-1 -methyl-1H-pyrazole-4-carboxamide (compound 23 from WO 2013/167550 A1).

[Table 2]

Processing concentration Connection 1 activity Comparative Compound Activity A B C D 10ppm 5 0 one 0 one

Industrial Applicability

The compound of the present invention is applicable as a plant disease control agent for use on agricultural and horticultural plants, which has a wide control spectrum with a low amount of the horticultural and agricultural disease treatment agent, and exhibits an excellent control effect.

Claims (16)

1. A difluorobiphenylthiophenecarboxamide compound represented by the following general formula (I):

(I) or its salt, in the above formula Y represents a hydrogen atom or (C1-C4)alkyl; X represents a halogen atom or (C1-C4)alkyl; m is an integer from 0 to 2; R represents a hydrogen atom, (C1-C6)alkyl, (C2-C6)alkenyl, (C1-C6)alkyl which may be substituted by 1-5 halogen atoms, phenyl(C1-C3)alkyl which may be substituted by halo, phenyl(C1-C3)alkyl which may be substituted with (C1-C4)alkyl, or phenyl(C1-C3)alkyl which may be substituted with (C1-C4)alkoxy; R1 is halogen, (C1-C4)alkyl or (C1-C4)alkyl substituted with 1-3 halogen atoms, and each of R2 and R3 is independently hydrogen, (C1-C4)alkyl, or halo. 2. A compound according to claim 1 or a salt thereof, where Y is a hydrogen atom and m is 0. 3. The compound according to any of the previous paragraphs or its salt, where Y represents a hydrogen atom; m is 0; R is (C1-C6)alkyl, (C2-C6)alkenyl, (C1-C6)alkyl which may be substituted by 1-5 halogen atoms, phenyl(C1-C3)alkyl which may be substituted by halogen atom, phenyl (C1-C3)alkyl which may be substituted with (C1-C4)alkyl, or phenyl(C1-C3)alkyl which may be substituted with (C1-C4)alkoxy; R1 is (C1-C4)alkyl or (C1-C4)alkyl substituted with 1-3 halogen atoms; and R2 and R3 represent a hydrogen atom. 4. The compound according to any of the preceding paragraphs, or a salt thereof, wherein Y is a hydrogen atom, m is 0, R is (C1-C6)alkyl or (C1-C4)alkyl which may be substituted by 1-3 halogen atoms; R1 is methyl; and R2 and R3 are hydrogen. 5. Means for the control of fungal diseases of plants for use in relation to agricultural and horticultural plants, containing as an active ingredient a compound of General formula (I) according to any one of paragraphs. 1-4 or its salt. 6. A method for controlling fungal diseases of plants, involving the use of an effective amount of a compound of general formula (I) according to any one of paragraphs. 1-4 or its salts. 7. The use of compounds of General formula (I) according to any one of paragraphs. 1-4 or salts thereof to obtain a plant fungal disease control agent for use in agricultural and horticultural plants.