PL224002B1

2-pyridyl ethyl benzamide derivative

Abstract

Compound of general formula (I) in which p is an integer equal to 1, 2, 3 or 4; q is an integer equal to 1, 2, 3, 4 or 5; each substituent X is chosen, independently of the others, as being halogen, alkyl or haloalkyl, at least one of the substituents being a haloalkyl; each substituent Y is chosen, independently of the others, as being halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, amino, phenoxy, alkylthio, dialkylamino, acyl, cyano, ester, hydroxy, aminoalkyl, benzyl, haloalkoxy, halosulphonyl, halothioalkyl, alkoxyalkenyl, alkylsulphonamide, nitro, alkylsulphonyl, phenylsulphonyl or benzylsulphonyl; as to the N-oxides of 2-pyridine thereof; with the exception of N-{2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-ethyl}-2,6-dichlorobenzamide. Method for preparing the compound of general formula (I). Fungicidal composition comprising the compound of general formula (I). Method for treating phytopathogenic diseases.

PL224002B1, drawing sheet 1 — Sheet 1 of 13

Term

Term ended

Expired 8 August 2023, 3.1 years ago.

5 claims: 2 independent, 3 dependent

1
2-Pyridylethylbenzamide derivative with the following general formula:1. Pochodna 2-pirydyloetylobenzamidu o poniższym wzorze ogólnym: w którym: wherein: q is an integer of 1, 2, 3 or 4;q oznacza liczbę całkowitą 1, 2, 3 lub 4;each X is independently halo or haloalkyl with at least one substituent being haloalkyl;każdy podstawnik X oznacza niezależnie fluorowiec lub fluorowcoalkil, przy czym co najmniej jeden z podstawników stanowi fluorowcoalkil;each Y is independently halogen, alkyl, haloalkyl, alkoxy, amino, alkylthio, cyano, ester, hydroxy, benzyl, haloalkoxy, halosulfonyl, alkylsulfonamide, nitro, or alkylsulfonyl, where the alkyl alone or in combination contains 1 to 10 atoms coal;każdy podstawnik Y oznacza niezależnie fluorowiec, alkil, fluorowcoalkil, alkoksyl, grupę aminową, alkilotio, cyjanową, estrową, hydroksylową, benzyl, fluorowcoalkoksyl, fluorowcosulfonyl, alkilosulfonoamid, grupę nitrową, lub alkilosulfonyl, przy czym alkil sam lub w kombinacji zawiera 1 do 10 atomów węgla;as well as N-oxides formed on the 2-pyridine ring, except N- {2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl} -2,6-dichlorobenzamide and excluding the 2-pyridylethylbenzamide derivative of formula general (I "): jak również N-tlenki utworzone na pierścieniu 2-pirydyny, z wyjątkiem N-{2-[3-chloro-5-(trifluorometylo)-2-pirydynylo]etylo}-2,6-dichlorobenzamidu i z wykluczeniem pochodnej 2-pirydyloetylobenzamidu o wzorze ogólnym (I”): w którym: wherein: - X1 is halogen and X2 is haloalkyl containing from 1 to 10 carbon atoms;- X1 oznacza fluorowiec i X2 oznacza fluorowcoalkil zawierający od 1 do 10 atomów węgla;1 1 - Y1 is halogen or haloalkyl containing from 1 to 10 carbon atoms. - Y1 oznacza fluorowiec albo fluorowcoalkil zawierający od 1 do 10 atomów węgla.
5
A method for preventive or curative control of plant pathogenic fungi in crops, characterized in that an effective composition is applied to the seeds, leaves and / or fruit of plants or to the soil in which the plants grow or in which their growth is desired. as defined in any of claims 2-4. 5. Sposób zapobiegawczego lub leczniczego zwalczania grzybów chorobotwórczych dla roślin w uprawach, znamienny tym, że na nasiona, liście i/lub na owoce roślin, albo na glebę, na której rośliny rosną lub na której ich wzrost jest pożądany, nanosi się użytą w ilości skutecznej kompozycję określoną w dowolnym z zastrz. 2-4.

Independent claims2

368 paragraphs in 6 sections, as filed

Description of the invention

The invention relates to novel compounds with fungicidal properties, a fungicidal composition containing these compounds and a method for its use in agriculture as fungicides.

Patent application WO 01/11 965 describes a large family of compounds with fungicidal properties, the general formula comprising the compounds of the present invention. However, in this patent application the presently claimed compounds are not described and their activity as fungicides has not been tested.

Nevertheless, it is always useful in agriculture to use compounds that are more active than those already known to those skilled in the art in order to reduce the amount of active ingredient used by the farmer, but at the same time maintaining an effectiveness at least equivalent to that of the compounds already known.

It has now been found that a number of compounds selected from the large family of compounds have the above-mentioned advantages.

The present invention relates to a group of compounds having the following general formula:

wherein:

q is an integer of 1, 2, 3 or 4;

each X is independently halo or haloalkyl with at least one substituent being haloalkyl;

each Y is independently halogen, alkyl, haloalkyl, alkoxy, amino, alkylthio, cyano, ester, hydroxy, benzyl, haloalkoxy, halosulfonyl, alkylsulfonamide, nitro, or alkylsulfonyl, where the alkyl alone or in combination contains 1 to 10 atoms coal;

as well as N-oxides formed on the 2-pyridine ring, except N- {2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl} -2,6-dichlorobenzamide and excluding the 2-pyridylethylbenzamide derivative of formula general (I "):

wherein:

- X1 is halogen and X2 is haloalkyl containing from 1 to 10 carbon atoms;

1

- Y1 is halogen or haloalkyl containing from 1 to 10 carbon atoms.

The invention also relates to a fungicidal composition which comprises an effective amount of the above-defined compound and an agriculturally acceptable carrier.

Preferably, such a composition further comprises a surfactant.

Preferably, such a fungicidal composition contains from 0.05% to 99% by weight of active ingredient.

The invention further relates to a preventive or curative method of controlling plant pathogenic fungi in crops, consisting in the treatment of seeds, leaves and / or

The fruit of the plants or the soil in which the plants grow or in which their growth is desired is applied with an effective amount of the composition as defined above.

For the purposes of the present invention, the term "halogen" means chlorine, bromine, iodine or fluorine.

For the purposes of the present invention, each alkyl or acyl in the molecule contains from 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, which may be straight or branched chain.

The method of producing the claimed compounds of general formula (Ie) includes:

- the first step, in which the compound of general formula (Ia) is reacted in the presence of a base in an aprotic polar solvent to selectively displace it in position 2: * or with a group of the alkylcyanoacetate type (NC-CH2-CO2Alk) with to obtain a compound of general formula (Ib) according to the scheme:

where:

- X has the meaning given previously;

- Alk is alkyl;

- Q is a nucleofugic group, preferably a halogen or a triflate group;

then the compound of general formula (Ib) thus obtained is subjected to dealkyloxycarboxylation in the presence of an alkali metal halide such as Li-halogen, K-halogen or Na-halogen, at the reflux temperature of a mixture of water and dimethyl sulfoxide according to the Krapcho reaction described in Synthesis, 805, 893 (1982) to obtain a compound of general formula (Ic) according to the scheme:

(in the context of this invention, sodium halide is preferably used) * or with acetonitrile to directly give the compound of formula (Ic) according to the scheme:

- second step in which a compound of general formula (Ic) is reduced to obtain a pyridyl ethanamine of general formula (Id) (or its corresponding ammonium salt, depending on whether or not the medium is acidic) under hydrogen pressure , in the presence of a metal catalyst, in a protic solvent, according to the scheme:

PL 224 002 B1

- the third step, where the compound of general formula (Id) is converted into a compound of general formula (I) by reacting with a benzoyl halide in the presence of a base according to the scheme:

The second step of the described process is carried out in the presence of a metal catalyst. Preferably, the metal catalyst is a nickel, platinum or palladium based catalyst.

The third step of this process is carried out in the presence of a benzoyl halide. Preferably, the benzoyl halide is benzoyl chloride.

From the compound of general formula (I) obtained by the above-described production method, those skilled in the art will be able to prepare 2-pyridine N-oxide derivatives using known methods. Thus, for example, a compound of general formula (I) obtained by the process described herein may be treated with excess metachloroperbenzoic acid (also called m-CPBA) in the presence of a solvent, which may be chloroform, at a temperature ranging from 60 to 80 ° C. C.

The invention also relates to a fungicidal composition containing an effective amount of an active ingredient of general formula (Ie). Accordingly, the invention relates to a fungicidal composition comprising, as an active ingredient, an effective amount of the above-defined compound of general formula (Ie) and an agriculturally acceptable support, carrier or filler.

The term "carrier" as used herein denotes a natural or synthetic organic or inorganic substance with which the active substance is combined for easier application, especially to parts of plants. Generally, such a carrier is inert and should be agriculturally acceptable. The carrier can be a solid or a liquid. Examples of suitable carriers are clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, water, alcohols, in particular butanol, organic solvents, minerals, plants and products derived therefrom. Mixtures of such carriers can also be used.

The composition may also contain additional ingredients. In particular, the composition may further contain a surfactant. The surfactant may be an emulsifier, dispersant or wetting agent of the ionic or non-ionic type, or a mixture of such surfactants. Examples include, for example, polyacrylic acid salts, ligninsulfonic acid salts, phenolsulfonic acid or naphthalenesulfonic acid salts, polycondensation products of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of acid esters sulfosuccinic acid, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylene alcohols or phenols, fatty acid polyol esters and derivatives of the above compounds containing sulfate, sulfonate and phosphate functional groups. In general, the presence of at least one surfactant is essential when the active ingredient and / or the inert support are water-insoluble or when the vector agent for the application is water. Preferably, the surfactant content is in the range of 5% to 40%, based on the weight of the composition.

PL 224 002 B1

Optionally, additional ingredients may also be included, e.g. protective colloids, tackifiers, thickeners, thixotropic agents, penetration enhancers, stabilizers, masking agents. Generally speaking, the active ingredients may be combined with any solid or liquid additive according to the usual formulation technique for such formulation.

In general, the composition according to the invention may contain from 0.05 to 99 wt. % of active substance, preferably from 10 to 70% by weight.

The compositions according to the invention can be used in various forms or methods of application. These include means such as an aerosol dispensing device, an encapsulated suspension, a cold fogging concentrate, a dusting powder, an emulsifiable solution, an oil-in-water emulsion, a water-in-oil emulsion, an encapsulated granule, fine granules, a free-flowing concentrate. flow-off for seed treatment, pressurized gas, gas-generating product, granules, heat misting concentrate, macrogranules, microgranules, oil dispersible powder, free-flowing oil-miscible concentrate, oil-miscible liquid, paste, fine plant forms, dry seed treatment powder, pesticide-coated seed, soluble concentrate, soluble powder, seed treatment solution, suspending concentrate ( free-flowing concentrate), ultra-low-volume spraying fluid (ulv), ultra-low-volume spraying suspension (ulv), water-dispersible granules or tablets, water-dispersible powder for treatment with suspension, water-soluble granules or tablets, water-soluble powder for seed treatment, and wettable powder.

Such compositions include not only ready-to-apply compositions to plants or seeds treated with suitable equipment such as spray or dusting apparatus, but also concentrated commercial compositions that must be diluted prior to application to a crop.

The compounds of the invention may also be mixed with one or more insecticides, fungicides, bactericides, acaricide attractants or pheromones, or other compounds with biological activity. The mixtures prepared in this way have a broadened spectrum of activity. Mixtures with other fungicides are particularly preferred.

The fungicidal compositions according to the invention can be used for the curative or preventive control of plant pathogenic fungi in crops. Thus, the invention relates to a method for the curative or preventive control of plant pathogenic fungi in crops, characterized in that the above-defined fungicidal composition is applied to the seeds, plants and or fruit of the plant, or to the soil in which the plant grows or is desired to grow. .

The composition used against plant pathogenic fungi in crops comprises an effective and non-phytotoxic amount of the active ingredient of the general formula (Ie).

The expression "effective and nonphytotoxic amount" means an amount of the compositions of the invention sufficient to control or destroy fungi present or capable of appearing on crops and not causing any significant symptom of phytotoxicity to those crops. This amount may vary widely depending on the type of fungus to be controlled, the type of crop, climatic conditions and the nature of the compounds contained in the fungicidal composition.

The amount can be determined from the results of systematic field trials performed, which is within the capabilities of one of ordinary skill in the art.

The method of treatment according to the invention is useful for the therapeutic treatment of propagation material, such as tubers or rhizomes, as well as seeds, cuttings or pruning cuttings and pricked plants or plants. Such a curative effect may also prove useful in treating the roots. The treatment according to the invention may prove to be useful for the treatment of aerial parts of plants, such as trunks, stems or shoots, leaves, flowers and fruit of plants.

Among the plants that can be protected by the method according to the invention, mention may be made of: cotton, flax, grapevines, horticultural plants, such as Rosaceae sp. (E.g. pome fruits, such as apples and pears, as well as stone fruits, such as apricots, almonds and peaches). , Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaeeae sp., Moraeeae sp., Oleaceae sp., Aetinidaeeae sp., Lauraeeae sp., Musaeeae sp. (E.g. banana etc.), Rubiaeeae sp. ., Theaceae sp., Sterculieeae sp., Rutaeeae sp. (E.g. lemons, oranges and grapefruits), legumes, crops such as Solanaceae sp. (e.g. tomatoes), Liliacae sp., Asteraceae sp. (e.g. lettuce), Umbelliferae sp., Cruciferae

PL 224 002 B1 sp., Chenopodiaeeae sp., Cucurbitaeeae sp., Papilionaeeae sp. (E.g. peas), Rosaeeae sp. (E.g. strawberries), large crop plants such as Graminae sp. (E.g. maize, cereals, such as wheat, rice, barley and triticale), Asteraeeae sp. (e.g. sunflower), Crueiferae sp., e.g. rapeseed, Papilionaeeae sp. (e.g. soybean), Solanaeeae sp. (e.g. potato), Chenopodiaceae sp. (e.g. fodder beet), horticultural and forestry crops, as well as genetically modified homologues of the above plants.

Among the plants and possible diseases of these plants to be protected by the method according to the invention, the following plants, crops and diseases can be mentioned:

- wheat, in terms of controlling the following grain diseases: fusariosis [Mierodoehium niuale and Fusarium roseum), foul-smelling wheat (Tilletia earies, Tilletia eontrouersa or Tilletia indiea), septoriosis (Septoria nodorum) and pollen knives;

- wheat, in terms of controlling the following diseases of the aerial parts of the plant: cereal stalk fragility (Tapesia yallundae, Tapesia acuiformis), stalk gangrene (Gaeumannomyees graminis), foot blight (F. eulmorum, F. graminearum), cereal rhizoctoniosis Rhizoctonia eerealis), powdery mildew (Erysiphe graminis forma speeie trtici), rusts (Pueeinia striiformis, Pueeinia reeondita) and septoriosis (Septoria trtici and Septońa nodorum);

- wheat and barley, with a view to combating bacterial and viral diseases: e.g. barley yellow mosaic;

- barley, with a view to controlling the following grain diseases: net blotch of barley leaves (Pyrenophora graminea, Pyrenophora teres and Cochliobolus satiuus), pollen head (Ustilago nuda) and fusariosis (Mierodoehium niuale and Fusarium roseum);

- barley, in terms of controlling the following diseases of overhead parts of the plant: cereal stalk fragility (Tapesia yallundae), net blotch of barley leaves (Pyrenophora teres and Cochliobolus satiuus), powdery mildew (Erysiphe graminis forma specie hordeii), dwarf rust (Puccinia hordia) rynchosporosis (Rhynchospońum secalis);

- potato, for the control of tuber diseases (in particular: Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani, potato blight (Phytophthora infestans) and certain viruses (virus Y);

- potato, with regard to controlling the following foliar diseases: potato blight (Altenaria solanii), potato blight (Phytophthora infestans);

- cotton, in terms of combating the following diseases of young plants growing from seeds:

seedling gangrene and vascular fusariosis (Rhizoctonia solani and Fusarium oxysporum) and black root rot (Thielaviopsis basicola);

- the cultivation of protein-providing plants, e.g. peas, for controlling the following seed diseases: anthracnose (Ascochyta pisi, Mycosphaerellapinodes), fusarium disease (Fusarium oxysporum), gray mold (Botrytis cinerea) and pea downy mildew (Pyrenospora pisi);

- cultivating oilseeds, for example oilseed rape, for controlling the following seed diseases: Phoma lingam, Altemaria brassicae and Sclerotinia selerotiorum;

- maize, for the control of grain diseases: Rhizopus sp., Penicillium sp., Trichoderma sp., Aspergillus sp. and Gibberella fugikuroi);

- flax, for the control of seed diseases: Altemaria linicola;

- forest trees, with a view to combating seedlings (Fusarium oxysporum, Rhizoctonia solani);

- rice with the aspect of controlling the following diseases of the aerial parts of the plant: rice blight (Magnaporthe grisea), rhizoctonia solani (Rhizoctonia solani);

- the cultivation of legumes in terms of controlling the following diseases of seeds or young plants growing from seeds: gangrene of seedlings and vascular fusariosis (Fusarium oxysporum, Fusarium roseum, Rhizoctonia solani, Pythium sp.);

- the cultivation of legumes for the control of the following diseases of the aerial parts of the plant: gray mold (Botrytis sp.), powdery mildew (in particular Erysiphe cichoracearum, Sphaerotheca fuliginea and Leueillula taurica), fusarium disease (Fusarium oxysporum, Fusarium roseum, cladosporium sp.) , alternariosis (Altemaria sp.), anthracnose (Colletotrichum sp.), septoriosis (Septoria sp.), rhizoctoniosis (Rhizoctonia solanii), downy mildew (e.g. Bremia lactucae), Peronospora sp., Pseudoperonospora sp., Phytophthora sp.);

- fruit trees, for diseases of the aerial parts of the plant: moniliosis (Monilia fructigenae, M. Iaxa), apple scab (Venturia inaequalis), powdery mildew (Podosphaera leucotricha);

PL 224 002 B1

- grapevines, as regards foliage diseases, in particular gray mold (Botrytis cinerea), grapevine mildew (Uncinula necator), black rot (Guignardia biwelli) and downy mildew (Plasmopara viticola);

- fodder beet, in terms of controlling the following diseases of the aerial parts of the plant: beet leaf spot (Cercospora beticola), powdery mildew (Erysiphe beticola), beetroot ramulariosis (Ramularia beticola).

The fungicidal composition according to the invention can also be used against fungal diseases prone to developing on wood and wood. The term "wood" covers all types of wood and all types of treatment of wood intended for construction work (eg solid wood, high-density wood, laminated wood and plywood). The method of treating wood is contacting it with one or more compounds according to the invention, or a composition according to the invention; and this includes, for example, direct application, spraying, dipping, injection, or any other suitable method.

In the case of a foliar application, the dose of active compound normally used in the method according to the invention is preferably and generally in the range from 10 to 800 g / ha, more preferably from 50 to 300 g / ha.

In the case of a seed treatment treatment, the dose of active ingredient applied will generally and preferably be in the range from 2 to 200 g / 100 kg of seed, more preferably from 3 to 150 g / 100 kg. It is readily understood that the above-indicated doses are merely exemplary to illustrate the invention. One skilled in the art will know how to adapt the doses used according to the nature of the crop treated.

The fungicidal composition according to the invention can also be applied to genetically modified organisms using the compounds according to the invention or the agrochemical compositions according to the invention. Genetically modified plants are plants into the genome of which the heterologous gene coding for the protein of interest has been permanently integrated. The term "heterologous gene encoding a protein of interest" generally refers to genes which impart new agronomic properties to the transformed plant, or to genes which provide an improvement in the agronomic quality of the transformed plant.

The compositions according to the invention can be used for the preparation of a composition useful for the curative or preventive control of fungal diseases in humans and animals, such as e.g.

The present invention is explained below with reference to the following tables (with compounds shown therein) and examples. The following tables A and B illustrate, in a non-limiting manner, examples of compounds with fungicidal properties. In the tables and examples below, M + 1 represents the peak of the molecular ion plus or minus 1 amu, respectively (atomic mass units) according to the results of the analysis by mass spectroscopy and M (Apcl +) is the molecular ion peak found by mass spectroscopy under chemical ionization conditions under atmospheric overpressure.

Table A.

PL 224 002 B1

<td>Relationship no</td><td>X1</td><td>X2</td><td>X3</td><td>X4</td><td>Y1</td><td>Y2</td><td>Y3</td><td>Y4</td><td>Y5</td><td>M + 1</td>

PL 224 002 B1 cont. table A

PL 224 002 B1 cont. table A

<td>A-119</td><td>Cl</td><td>CF3</td><td>H.</td><td>H.</td><td>O-CF2-CHFCl</td><td>H.</td><td>H.</td><td>Cl</td><td>H.</td><td> 495</td>

<td>A-120</td><td>Cl</td><td>CF3</td><td>H.</td><td>H.</td><td>O-allyl</td><td>H.</td><td>H.</td><td>Cl</td><td>H.</td><td> 419</td>

<td>A-121</td><td>Cl</td><td>CF3</td><td>H.</td><td>H.</td><td>O-allyl</td><td>H.</td><td>H.</td><td>H.</td><td>H.</td><td> 385</td>

PL 224 002 B1 cont. table A

PL 224 002 B1 cont. table A

PL 224 002 B1

Table B.

X3

The following compound preparation examples are provided to illustrate the invention and should not be considered as limiting its scope in any way.

Preparation of methyl [3-chloro-5- (trifluoromethyl) -2-pyridinyl] (cyano) acetate

Procedure: 116 g (2.91 mol,

1.8 eq) of sodium hydride (60% oil suspension). The suspension formed is cooled in an ice-water bath and a solution of 160 g (1.616 mol, 1.0 eq.) Of methyl cyanoacetate in 200 ml of DMF is added dropwise with stirring. After the evolution of gas has ceased completely, 350 g (1.616 mol, 1.0 eq.) Of 2,3-dichloro-5- (trifluoromethyl) pyridine are added with stirring. The mixture thus obtained is stirred overnight at ambient temperature, then 50 ml of methanol are added and the reaction mixture is poured into 5 liters of water. The pH is adjusted to 3-4 with concentrated hydrochloric acid. The yellow precipitate formed, methyl [3-chloro-5- (trifluoromethyl) -2-pyridinyl] cyano) acetate, is filtered off and washed with water and pentane.

Preparation of [3-chloro-5- (trifluoromethyl) -2-pyridinyl] acetonitrile

Procedure: 314 g (1.13 mol, 1 eq.) Of methyl [3-chloro-5- (trifluoromethyl) -2-pyridinyl] (cyano) acetate are dissolved in a solution of 44 ml of water and 1.1 liters of dimethyl sulfoxide. and 22 g (0.38 mol, 0.33 eq.) of sodium chloride. The reaction mixture formed was stirred and heated at 160 ° C until all gas evolution had ceased, then cooled to ambient temperature. Then, 1 liter of water and 0.5 liters of dichloromethane are introduced. After phase separation, the aqueous phase is extracted twice with 0.5 liter of dichloromethane and the phase

The organic mixture is washed twice with 0.5 liters of water each and dried with magnesium sulfate. After concentration, the crude product is diluted in 100 ml of dichloromethane and eluted over a silica pad with 20:80 ethyl acetate / heptane. The resulting filtrate was concentrated to give [3-chloro-5- (trifluoromethyl) -2-pyridinyl] acetonitrile.

Preparation of 2- [3-chloro-5- (trifluoromethyl-2-pyridinyl] ethanamine acetate

Procedure: 113 g (0.51 mol, 1 eq.) Of [3-chloro-5- (trifluoromethyl) -2-pyridinyl] acetonitrile are diluted in 2.5 liters of acetic acid and 30 g of palladium (5% on active carbon) are added. ). The reaction mixture thus formed is stirred at ambient temperature under pressure5 hydrogen of 5 x 105 Pa (5 bar). The progress of the reaction is followed by TLC. After [3-chloro-5- (trifluoromethyl) -2-pyridinyl] acetonitrile is completely depleted, the mixture is filtered through Celite pad and then concentrated to dryness to give 2- [3-chloro-5- (trifluoromethyl) -2- acetate. pyridinyl] ethanamine.

Preparation of N- {2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl} benzamides

Procedure: 0.100 g (0.00037 mol, 1.0 eq.) Of 2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethanamine acetate is diluted in 3 ml of dichloromethane, then 0.500 g of polyurethane is added. (4-vinylpyridine). The mixture thus formed was stirred at ambient temperature for 1/2 hour.

Then, 1.2 equivalents of the desired carboxylic acid chloride are added and the reaction mixture is stirred at ambient temperature overnight, then filtered and concentrated to dryness. The crude product is purified by reverse phase HPLC to give the corresponding amide.

In order to compare the activity of the compounds of general formula (I) according to the invention with the activity of the compound described in WO 01/11 965, the following biological activities were tested on a number of fungal diseases.

In vivo test for activity against Altemaria brassicae (altemariosis black cross)

An aqueous solution of the active substance with a concentration of 2 g / liter to be tested is prepared by grinding it in solution 1 or 2.

Solution 1

- water,

- Tween 80 diluted to a concentration of 10% in water; 5 μl / mg of active substance,

- sufficient clay to obtain: active substance + clay = 100 mg.

Solution 2

A concentrated solution containing surfactants and commonly used adjuvants; 200 μl / mg of active substance.

The aqueous solution is diluted with water to the desired concentration.

Radish of the Pernot variety is sown in 50:50 pozzolana / peat substrate and kept at 18-22 ° C. Treatment is carried out by spraying with an aqueous suspension. Untreated control plants are sprayed with water. 24 hours after treatment, the plants are inoculated by spraying with a solution containing Altenaria brassicae spores (40,000 spores / ml) from a 12-day-old culture. Thereafter, the radish plants are kept at 18-20 ° C in a humid atmosphere. After 7-8 days of incubation, the efficacy of the test compounds is assessed in comparison with the control plants.

In vivo activity test against Botrutis cinerea in cucumbers

An aqueous solution of the active substance with a concentration of 2 g / liter to be tested is prepared by grinding it in solution 1 or 2.

Solution 1

- water,

- Tween 80 diluted to a concentration of 10% in water; 5 μl / mg of active substance,

- sufficient clay to provide: active substance + clay = 100 mg.

Solution 2

A concentrated solution containing surfactants and commonly used adjuvants; 200 μl / mg of active substance. The aqueous solution is diluted with water to the desired concentration.

Marketer cucumbers are sown in 50:50 pozzolana / peat substrate and kept at 18-22 ° C. Treatment is carried out by spraying with an aqueous suspension. Untreated control plants are sprayed with water. 24 hours after treatment, the plants are inoculated by spraying with a solution containing Botrytis cinerea spores (150,000 spores / ml) from a 15-day-old culture.

Thereafter, the cucumber plants are kept at 11-15 ° C in a humid atmosphere. After 7-8 days of incubation, the efficacy of the test compounds is assessed in comparison with the control plants.

In vivo activity test against Purenophora teres (net blotch of barley leaves)

An aqueous solution of the active substance with a concentration of 2 g / liter to be tested is prepared by grinding it in solution 1 or 2.

Solution 1

- water,

- Tween 80 diluted to a concentration of 10% in water; 5 μl / mg of active substance,

- sufficient clay to provide: active substance + clay = 100 mg,

Solution 2

A concentrated solution containing surfactants and commonly used adjuvants; 200 μl / mg of active substance. The aqueous solution is diluted with water to the desired concentration.

Barley of the Express variety is sown in 50:50 pozzolana / peat substrate and kept at 12 ° C. Treatment is carried out at the first leaf (10 cm) stage by spraying with an aqueous suspension. Untreated control plants are sprayed with water. 24 hours after treatment, the plants are inoculated by spraying with a solution containing Pyrenophora teres spores (10,000 spores / ml) from a 10-day-old culture.

Thereafter, the barley plants are kept at 18 ° C in a humid atmosphere. After 8-15 days of incubation, the efficacy of the test compounds is assessed in comparison with the control plants.

In vivo activity test against Seotoria tritici (wheat septoriosis)

An aqueous solution of the active substance with a concentration of 2 g / liter to be tested is prepared by grinding it in solution 1 or 2.

Solution 1

- water,

- Tween 80 diluted to a concentration of 10% in water; 5 μl / mg of active substance,

- sufficient clay to provide: active substance + clay = 100 mg.

Solution 2

A concentrated solution containing surfactants and commonly used adjuvants; 200 μl / mg of active substance. The aqueous solution is diluted with water to the desired concentration.

Scipion wheat is sown in 50:50 pozzolana / peat substrate and kept at 12 ° C. Treatment is carried out at the first leaf (10 cm) stage by spraying with an aqueous suspension. Untreated control plants are sprayed with water. 24 hours after treatment, the plants are inoculated by spraying with a solution containing Septoria tritici spores (500,000 spores / ml) from a 7-day-old culture.

PL 224 002 B1

Thereafter, the wheat plants are kept at 18-20 ° C in a humid atmosphere for 72 hours and then under a relative humidity of 90%. 21-28 days after infection, the efficacy of the test compounds is assessed in comparison with the control plants.

The efficacy of the test compounds is estimated at doses of 500 g / ha, 250 g / ha or 330 ppm, as percentage of control with respect to untreated plants. Under these conditions, good efficacy is defined as greater than 80% efficacy. Average efficacy is defined as efficacy ranging from 50 to 80%. Poor Efficacy is defined as efficacy ranging from 10-50%, and Zero Efficacy is defined as less than 10% efficacy.

When used at a concentration of 500 g / ha, the following compounds showed good to medium efficacy against pathogenic fungi:

Altenaria brassicae: A-6, A-7, A-9, A-13, A-14, A-25.

Botrytis cinerea: A-7, A-9, A-25.

Pyrenophora teres: A-5, A-6, A-7, A-9, A-25, A-27.

Septoria tritici: A-5, A-6, A-7, A-16, A-18, A-21, A-22, A-23, A-24, A-25.

When used at a concentration of 250 g / ha, the following compounds showed good to medium efficacy against pathogenic fungi:

Altenaria brassicae: A-28, A-29, A-41, A-73, A-173.

Botrytis cinerea: A-73.

Pyrenophora teres: A-73.

The following compounds used at a concentration of 330 ppm showed good to medium efficacy against pathogenic fungi:

Altenaria brassicae: A-44, A-47, A-48, A-49, A-52, A-60, A-61, A-62, A- 71, A-72, A-73, A-74, A- 75, A-76, A-77, A-79, A-80, A-83, A-84, A-85, A-86, A-87, A-89, A-92, A-92, A-96, A-98, A-99, A-100, A-107, A-110, A-112, A-113, A-117, A-122, A-123, A-124, A- 125, A-127, A-128, A- 133, A-134, A-135, A-136, A-137, A-138, A-139, A-140, A-141, A-142, A-143, A-144, A-146, A-147, A-148, A-150, A-151, A-152, A-156, A- 157, A-158, A-159, A- 162, A-165, A-166, A-167, A-168, A-169, A-170, A-171, A-173, A-174, A-175, A-176, A-177, A-178, A-179, A-180, A- 181, A-182, A-183, A-184, A-185, A-186, A-187, A-188, A-189, A- 194.

Botrytis cinerea: A-73, A-170, A-172, A-173, A-174, A-175, A-187.

Pyrenopkora teres: A-44, A-61, A-73, A-83, A-87, A-89, A-96, A-117, A- 125, A-133, A-134, A-140 , A-167, A-173, A-174, A-187.

Under these conditions:

- N- {2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl} -2,6-dichlorobenzamide at a concentration of 330 ppm and 250 g / ha showed poor and no efficacy against Altenaria brassicae, respectively, and at a concentration of 250 g / ha and 330 ppm, zero efficacy against Botrytis cinerea;

- N- {methylcarbamoyl-2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl} -4-phenylbenzamide, disclosed in WO 01/11 965 (see compound 316 in Table D), in at a concentration of 250 g / ha, it showed poor efficacy against Altenaria brassicae and Septoria tritici and zero efficacy against Botrytis cinerea;

- N- {1-ethylcarbamoyl-2- (3-chloro-5- (trifluoromethyl) -2-pyridinyl} ethyl} nitrobenzamide, also disclosed in WO 01/11 965 (see compound 307 in table D) at a concentration of 250 g / ha showed zero efficacy against Altenaria brassicae and Botrytis cinerea;

- N- {1-ethylcarbamoyl-2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl} benzamide and N- {1-methylcarbamoyl-2- [3-chloro-5- (trifluoromethyl) -2 -pyridinyl] ethyl} benzamide, also disclosed in WO 01/11 965 (see compounds 304 and 314 in Table D), at a concentration of 250 g / ha showed poor efficacy against Septoria tritici and zero efficacy against Botrytis cinerea; and

- N- {1-ethylcarbamoyl-2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl} -4-chlorobenzamide, N- {1-ethylcarbamoyl-2- [3-chloro-5- (trifluoromethyl) ) -2-pyridinyl] ethyl} -2-bromobenzamide and N- {1-methylcarbamoyl-2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl} -4-methoxybenzamide, also disclosed in the patent application WO 01/11 965 (see compounds 306, 310 and 315 in Table D), at a concentration of 250 g / ha, showed zero efficacy against Botrytis cinerea.

Contents6

54 members in 31 offices

This recordMember, by publication datePriority claim21 more offices are in the list below

Priority claims8

Priority claims
Document	Office	Kind	Date
02356159	European Patent Office (EPO)	A	2002-08-12
02356159	European Patent Office (EPO)	A	2002-08-12
0305233	France	A	2003-04-29
0305233	France	A	2003-04-29
023561590	–	–	–
0305233	–	–	–
EP20020356159	–	–	–
FR20030005233	–	–	–

Members54

Family members, oldest first
Document	Office	Kind
EP1389614A1	European Patent Office (EPO)	A1	2004-02-18
CA2492173A1	Canada	A1	2004-02-26
WO2004016088A2	World Intellectual Property Organization (WIPO)	A2	2004-02-26
AU2003266316A1	Australia	A1	2004-03-03
WO2004016088A3	World Intellectual Property Organization (WIPO)	A3	2004-03-25
TW200415991A	Taiwan Province of China	A	2004-09-01
AR040852A1	Argentina	A1	2005-04-20
MXPA05001580A	Mexico	A	2005-04-25
MA27335A1	Morocco	A1	2005-05-02
EP1531673A2	European Patent Office (EPO)	A2	2005-05-25
KR20050071476A	Republic of Korea	A	2005-07-07
BR0313340A	Brazil	A	2005-07-12
RU2005106877A	Russian Federation	A	2005-07-20
ECSP055594A	Ecuador	A	2005-08-11
CN1674784A	China	A	2005-09-28
US2005234110A1	United States of America	A1	2005-10-20
JP2005535714A	Japan	A	2005-11-24
PL375269A1	Poland	A1	2005-11-28
EP1531673B1	European Patent Office (EPO)	B1	2006-01-04
IL166335A0	Israel	A0	2006-01-16
IL166335D0	Israel	D0	2006-01-16
AT314808T	Austria	T	2006-02-15
ATE314808T1	Austria	T1	2006-02-15
DK1531673T3	Denmark	T3	2006-03-06
DE60303147D1	Germany	D1	2006-03-30
ES2250921T3	Spain	T3	2006-04-16
HK1080329A	Hong Kong, China	A	2006-04-28
HK1080329A1	Hong Kong, China	A1	2006-04-28
NZ537608A	New Zealand	A	2006-04-28
SI1531673T1	Slovenia	T1	2006-06-30
ZA200500294B	South Africa	B	2006-08-30
DE60303147T2	Germany	T2	2006-08-31
OA19202A	African Intellectual Property Organization (OAPI)	A	2006-10-13
UA78361C2	Ukraine	C2	2007-03-15
CN1319946C	China	C	2007-06-06
AU2003266316B2	Australia	B2	2007-10-25
RU2316548C2	Russian Federation	C2	2008-02-10
KR100853967B1	Republic of Korea	B1	2008-08-25
US7572818B2	United States of America	B2	2009-08-11
IL166335A	Israel	A	2010-11-30
CA2492173C	Canada	C	2011-04-26
TWI343785B	Taiwan Province of China	B	2011-06-21
JP4782418B2	Japan	B2	2011-09-28
FR14C0045I1	France	I1	2014-07-18
LU92504I2	Luxembourg	I2	2015-01-02
FR14C0045I2	France	I2	2015-01-09
PL410411A1	Poland	A1	2015-03-16
PL410412A1	Poland	A1	2015-03-16
BRPI0313340B1	Brazil	B1	2015-08-18
PL222168B1	Poland	B1	2016-07-29
PL224002B1This record	Poland	B1	2016-11-30
PL224003B1	Poland	B1	2016-11-30
HUS1400037I1	Hungary	I1	2017-08-28
BE2014C015I2	Belgium	I2	2022-08-09

2-pyridyl ethyl benzamide derivative

Abstract

Term

PL 224 002 B1

PL 224 002 B1

PL 224 002 B1

PL 224 002 B1

PL 224 002 B1

PL 224 002 B1

Priority claims8

Members54

Numbers

Titles2

Classification