EA011551B1

EA011551B1 - Isopentyl carboxanilides for combating undesired micro-organisms

Info

Publication number: EA011551B1
Application number: EA200600779A
Authority: EA
Inventors: Ральф Дункель; Ханс-Людвиг Эльбе; Йорг Нико Гройль; Беноа Хартманн; Ульрике Вахендорфф-Нойманн; Петер Дамен; Карл-Хайнц Кук
Original assignee: Байер Кропсайенс Аг
Priority date: 2003-10-23
Filing date: 2004-10-12
Publication date: 2009-04-28
Also published as: UA84302C2; IL174898A0; JP4783734B2; JP2007509089A; CR8334A; ZA200603061B; DE10352067A1; TW200528435A; EA200600779A1; CN1871218A; CN100522948C

Abstract

The invention relates to novel isopentyl carboxanilides of formula (I),wherein L, R, Rand A have the meaning cited in the description, to several methods for the production of said substances and to the use thereof in order to combat undesired micro-organisms, in addition to intermediate products and to the production thereof.

Description

This invention relates to new isopentylcarboxanilides, to a method for their preparation and to their use for controlling undesirable microorganisms.

Numerous carboxanilides are known to have fungicidal properties (see, for example, No. 0 02/059086, No. 0 00/09482, EP-A-0824099, EP-A-0755927, EP-A-0589301, EP-A-0545099, 1P 11-335364, DR 10-310577 and 1P 10-251240). For example, 1-methyl-I- [2- (3-methylbutyl) phenyl] -3- (trifluoromethyl) -1H-pyrazole-4-carboxamide (from EP-A-0824099) and 2,5-dimethyl- are known. And- [3- (3-methylbutyl) phenyl] -3-furamide (from EP-A-0755927). The effectiveness of these substances is good, but with small consumable quantities in some cases insufficient.

K ¹ is hydrogen;

K ² means hydrogen, fluorine, chlorine, methyl or trifluoromethyl; K ³ is hydrogen or (C1-C ₈ ) alkyl;

where K ¹⁰ means (C ₁ -C ₄ ) alkyl, possibly substituted by fluorine;

K ¹¹ is hydrogen or fluorine and

K ¹² means (C1-C ₄ ) alkyl,

3 11 12 provided that K does not mean trifluoromethyl or difluoromethyl, if K and K mean hydrogen and K means methyl, or

A means a radical of formula (A2) where K ¹³ and K ¹⁴ mean hydrogen and K ¹⁵ means (C1-C ₄ ) alkyl, or A means a radical of formula (A4)

(A2).

(A4), where K ¹⁹ means (C ₁ -C ₆ ) alkyl, or

A means a radical of formula (A11)

P ³ '

R ³⁰ where K ³⁰ means (C ₁ -C ₄ ) alkyl or chlorine and

K ³¹ means (C1-C4) alkyl, possibly substituted by fluorine, provided that K ³¹ does not mean trifluoromethyl, difluoromethyl or methyl, if K ³ means hydrogen and K ³⁰ means methyl.

The compounds according to the invention can, if necessary, exist as mixtures of various possible isomeric forms, in particular stereoisomers, such as E- and Ζ-, threo and erythro, as well as optical isomers, if necessary, also tautomers. The invention encompasses both E and из isomers, as well as threo and erythro and optical isomers, any mixtures of these isomers, as well as all possible tautomeric forms.

New isopentylcarboxylic acid formula (I) can be obtained if:

a) carboxylic acid derivatives of the formula (II) where A is as defined above, and

- 1 011551

X ¹ means a halogen or hydroxy group, to react with an aniline derivative of the formula (III)

where b, I ¹ and I ³ have the meanings given above, if necessary in the presence of a catalyst, if necessary in the presence of a condensing agent, if necessary in the presence of an acid binding agent and if necessary in the presence of a diluent, or

B) isopentone derivatives of formula (V)

where I ¹ , I ² , I ³ and A have the meanings given above, react with hydrazine (or hydrazine hydrate) in the presence of a base and, if necessary, in the presence of a diluent, or

c) isopentene derivatives of the formula (VI)

where I ¹ , I ² , I ³ and A have the values given above, to hydrogenate if necessary in the presence of a diluent and if necessary in the presence of a catalyst, or

b) isopentine derivatives of formula (VII)

where I ¹ , I ² , I ³ and A have the values given above, to hydrogenate, if necessary, in the presence of a diluent and, if necessary, in the presence of a catalyst.

The new isopentylcarboxanilides of formula (I) have very good microbicidal properties and are suitable for controlling unwanted microorganisms both in plant protection and in the protection of materials.

The first group of preferred compounds of formula (I) includes compounds in which (V

B means ι-1;

I ¹ means hydrogen;

I ² means hydrogen, fluorine, chlorine, methyl or trifluoromethyl; I ³ means hydrogen or (C ₁ -C ₆ ) alkyl;

where I ¹⁰ means (C ₁ -C ₂ ) alkyl, possibly substituted by 1-5 fluorine atoms,

I ¹¹ means hydrogen or fluorine and

I ¹² means methyl, ethyl, n-propyl or isopropyl,

3 11 12 provided that I do not mean trifluoromethyl or difluoromethyl, if I and I mean hydrogen and I means methyl, or

- 2 011551

A means a radical of formula (A2) where K ¹³ and K ¹⁴ mean hydrogen and K ¹⁵ means (C ₁ -C ₄ ) alkyl, or A means a radical of formula (A4)

(A2),

(A4), where K ¹⁹ means (C ₁ -C ₆ ) alkyl, or

A means a radical of formula (A11)

where K ³⁰ means methyl, ethyl or chlorine and

K ³¹ means (C ₁ -C ₂ ) alkyl, possibly substituted with 1-5 fluorine atoms, provided that K ³¹ does not mean trifluoromethyl, difluoromethyl or methyl, if K ³ means hydrogen and K ³⁰ means methyl.

The second group of preferred compounds of formula (I) includes compounds in which A is A1.

More preferred are compounds in which A is A1 and b, K ¹ and K ³ are as defined above.

The most preferred compounds are those in which K ³ is hydrogen, and A, B and K ¹ are as defined above.

Description of methods for producing isopentylcarboxanilides of formula (I), as well as intermediates

Method (a), which is the object of claim 5

Claims

claims If 5-fluoro-1,3-dimethyl-1H-pyrazole-4carbonyl chloride and [2- (3-methylbutyl) phenyl] amine chloride are used as starting materials, the implementation of method (a) according to this invention can be clearly represented as Carboxylic acid derivatives used as starting materials in the implementation of method (a) according to this invention are described in general form by formula (II). In this formula (II), the radical A is as defined above, and X1 is preferably a chlorine, bromine or hydroxy group. Carboxylic acid derivatives of formula (II) are known and / or can be obtained by known methods (see AO 93/11117, EP-A-0545099, EP-A-0589301 and EP-A-0589313). Aniline derivatives, also used as starting materials in the process (a) according to the invention, are described in general form by formula (III). In this formula (III), the radicals b, K1 and K3 have the above values. Aniline derivatives of the formula (III), where b is L-1, can be obtained if: e) cyanoanilines of the formula (VIII) where K1 and K2 have the meanings given above in the first stage to react with the Grignard reagent of the formula (IX) where K3 has the meanings given above; X3 means chlorine, bromine or iodine, if necessary in the presence of a diluent, and the alkanoanilines of the formula (X) thus obtained

1. Isopentylcarboxanilides of the formula (I) where b is

K ¹ is hydrogen;

K ² means hydrogen, fluorine, chlorine, methyl or trifluoromethyl;

K ³ is hydrogen or (C1-C ₈ ) alkyl;

And means the radical of the formula (A1) where K ¹⁰ means (C1-C ₄ ) alkyl, possibly substituted by fluorine;

K ¹¹ is hydrogen or fluorine and

K ¹² means (C1-C ₄ ) alkyl,

1- (1-naphthalenyl) -1H-pyrrole-2,5-dione;

1,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or isobutyronitrile, or benzonitrile; amides, such as Ν, Ν-dimethylformamide,,-dimethylacetamide, Ν-methylformanilide, Ν-methylpyrrolidone or hexamethylphosphoric triamide, sulfoxides, such as dimethyl sulfoxide; sulfones such

- 6 011551 as sulfolane; alcohols, such as methanol, ethanol, n- or isopropanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, mixtures with water or pure water.

Method (b), as well as the second stage of method (e) is carried out in the presence of a base. As such, suitable, for example, hydroxides of alkali or alkaline-earth metals, such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide.

The temperature of the reactions in the implementation of method (b), as well as the second stage of method (e) can be varied in a wide range. In general, they operate at a temperature of from 100 to 300 ° C, preferably at a temperature of from 150 to 250 ° C.

In carrying out the process (b) to obtain compounds of formula (I), per mole of isopentone derivative of formula (V) is generally 0.2 to 5 mol, preferably 0.5 to 3 mol of hydrazine (or hydrazine hydrate).

When carrying out the second stage of process (e) to obtain aniline derivatives of formula (III), per mole of alkanonaniline of formula (X) is generally 0.2 to 5 mol, preferably 0.5 to 3 mol of hydrazine (or hydrazine hydrate).

As a diluent in the implementation of methods (c) and (b) all inert organic solvents are suitable. These include predominantly aliphatic or epicyclic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane or decalin; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; alcohols, such as methanol, ethanol, n- or isopropanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixture with water or pure water.

Methods (c) and (b) are carried out in the presence of a catalyst. As such, all catalysts that are commonly used for hydrogenation are suitable. As an example, the following should be mentioned: Raney nickel, palladium or platinum, if necessary on a solid carrier, such as, for example, activated carbon.

Hydrogenation in processes (c) and (b) can be carried out both in the presence of hydrogen in combination with a catalyst, and in the presence of triethylsilane.

The temperature of the reactions in the implementation of methods (c) and (b) can be varied in a wide range. In general, they operate at a temperature of from 0 to 150 ° C, preferably at a temperature of from 20 to 100 ° C.

Methods (c) and (b) are carried out at a hydrogen pressure of from 0.5 to 200 bar, preferably from 2 to 50 bar, more preferably from 3 to 10 bar.

As diluents in the implementation of the first stage of the method (e) all inert organic solvents are suitable. These include predominantly aliphatic or alicyclic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane or decalin; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane.

The temperature of the reactions in the implementation of the first stage of the method (e) can vary in a wide range. In general, they operate at temerature of from 0 to 200 ° C, preferably operate at a temperature of from 20 to 150 ° C.

When carrying out the first stage of process (e) to produce alkanonanilines of formula (X), per mole of cyanoaniline of formula (VIII) is generally 0.2-5 mol, preferably 0.5-3 mol of the Grignard reagent of formula (IX).

As a diluent in the implementation of methods (d) and (11), all inert organic solvents are suitable. These include preferably nitriles, such as acetonitrile, propionitrile, n- or isobutyronitrile, or benzonitrile, or amides, such as Ν, Ν-dimethylformamide,, Ν-dimethyl acetamide, Ν-methylformanilide,-methylpyrrolidone or triamide, hexamethylphosphoric or hexamylphosphoric triamide, or hexamylphosphoric triamide, or triamide, the hexamethylphosphoric triamide, Ν-methylformanilide, ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane.

Methods (d) and (1) are carried out, if necessary, in the presence of a suitable acid acceptor. As such, all conventional inorganic and organic bases are suitable. These include preferably hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates of alkali or alkaline earth metals, such as sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium hydroxide ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or ammonium carbonate, as well as tertiary amines, such as trimethylamine, triethylamine, tributylamine,,-dimeth ilanilin, Ν, Ν-dimethylbenzylamine, pyridine, Ν-methylpiperidine, Ν-methylmorpholine, Ν, Ν-dimethylaminopyridine, diazabicyclooctane (ELVSO), diazabicyclononene (ΌΒΝ) or diazabicycloundecene (ΌΒυ).

- 7 011551

Methods (d) and (k) are carried out in the presence of one or more catalysts.

Salts or palladium complexes are suitable for this. Palladium chloride, palladium acetate, tetrakis- (triphenylphosphine) palladium or bis- (triphenylphosphine) palladium chloride are preferably suitable. It is also possible that the palladium complex is formed in the reaction mixture when the palladium salt and the complex ligand are separately reacted.

As ligands, organophosphorus compounds are preferably meant. By way of example, mention should be made of triphenylphosphine, tri-o-tolylphosphine, 2,2'-bis- (diphenylphosphino) -1,1'binafthyl, dicyclohexylphosphinobiphenyl, 1,4-bis- (diphenylphosphino) butane, bis-diphenylphosphinoferrocene, di (tert -butylphosphino) biphenyl, di (cyclohexylphosphino) biphenyl, 2-dicyclohexylphosphino-2'-S, N-dimethylaminobiphenyl, tricyclohexylphosphine, tri-tert-butylphosphine. However, ligands can be neglected.

Methods (d) and (k) are then carried out, if necessary, in the presence of additionally added metal salts, such as copper salts, for example, media iodide).

The temperature of the reactions in the implementation of methods (d) and (k) can be varied in a wide range. Generally work at a temperature of from 20 to 180 ° C, preferably at a temperature of from 50 to 150 ° C.

When carrying out the process (e) to obtain the isopentene derivatives of the formula (VI), 1 mol of the carboxamide of the formula (XIV) in total is 1-5 mol, preferably 1-3 mol of the alkene of the formula (XV).

In carrying out the process (k) to obtain the isopentin derivatives of the formula (VII), 1 mol of the carboxamide of the formula (XIV) in total is 1-5 mol, preferably 1-3 mol of the alkyne of the formula (XII).

Unless otherwise noted, all of the above methods are usually carried out at normal pressure. However, it is possible to work at elevated or reduced pressure - in general from 0.1 to 10 bar.

The substances according to the invention show high microbicidal activity and can be used to combat undesirable microorganisms, such as fungi and bacteria, in plant protection and in the protection of materials.

Fungicides can be used in the protection of plants for the control of plasmidioforomycetes, oomycetes, chytdiomycetes, cygomycetes, ascomycetes, basidiomycetes and deuteromycetes.

Bactericides can be used in plant protection to combat Rkeibotoiabaseae, YYhohoassas. Ep1egoas1paseaee, Soguyebas1sepaseaee and 81gr1otusse1aseee.

As an example, but not limited to this, it is necessary to name some pathogens of fungal and bacterial diseases that fall under the above generic concepts:

species of the genus Xantomonas (Xa ΐ kotoíac), such as, for example, X Xΐΐии aac satre1pk ru.ogu / ae;

species of the genus Pseudomonas (Rkeibotoiak), such as, for example, Rkeibotoia kupidee ru.1askgutaik;

species of the genus Ervinia (Hisha), such as, for example, Eg \\\ 'ypa atuogua;

species of the genus Pythium (Ru1k1it), such as, for example, Ru1k1it andShtit;

species of the phytophthora species (Rku! ork! koga), such as, for example, Rku! ork! koga tGekishk;

species of the genus psevdoperonosporus (Rkeiboregoiokrog), such as, for example, Rkeiboregoiokroga kitik or Rkeiboregoiokrog sieikE;

species of the plasmopar (P1actorga) genus, such as, for example, P1actorga uyuota;

Bremia (Vget1a) species such as, for example, Vget1a 1as!

species of the genus Peronospore (Regiookrog), such as, for example, Reijoprogga rsH or Regiookrog гgakkyae;

species of the genus Erizif (Eguirke), such as, for example, Eguirke Dgatsk;

species of the genus Spherotek (Broccoli), such as, for example, the Border Cesque;

species of the subsosphere (Robokrkaega), such as, for example, Robokrkaega 1eiso1pska;

species of the genus Venturia decided), such as, for example, Weeshipa shaadiac;

species of the pyrenophore (Rugeiorkoga), such as, for example, Rugeiorkoga 1egek or Rugeiorkoga dgatshea (conidia form: drexler, synonym: helmintosporium);

species of the genus kohliobolyus (Skostius), such as, for example, Skostikyusik kakuik (conidia form: drexler, synonym: helminthosporium);

species of the genus Uromyces (Igotusek), such as, for example, Igotusek arreib1si1ik;

species of the genus Puccinia (Risschsch), such as, for example, Riesssch hesoiby;

species of the genus Sclerotinia (8с1Г1ш1а), such as, for example, 8c1 of 1x1x1;

species of the genus Tilletia (TSheya), such as, for example, TSheya sapek;

species of the genus Ustylago (IkShado), such as, for example, IkShado iiba or IkShado aweiae;

Species of the genus Pelicularia (REShapa), such as, for example, Reshsshapa kakakp;

species of the genus Pyrikularia (Rupschapa), such as, for example, Rupschapa oghuhe;

species of the genus Fusarium (Rikagsht), such as, for example, Rikagsht syltogit;

Botrytis (Wo! guIk) species of the genus, such as, for example, Wo! guIkegegea;

- 8,011,551 species of the septoria genus (SriUpa). such as, for example, serptisol is liable;

species of the genus leptosperia (Boschidae), such as, for example, Béréricorne;

species of the genus of churches (Segokrog), such as, for example, Segokrog gap;

species of the genus Alternaria (Aietpapa), such as, for example, Aiyetpapa gakkyue;

species of the genus Pseudocerkosporella (Rkeibosetsroctera 11a), such as, for example, Rkeibosettsrote 11a Negro1ls1kpbek;

Species of the genus Rhizoctonia (Kyhosgosha), such as, for example, Pli / os1osha koash.

Biologically active substances according to this invention also show a strong strengthening effect on plants, therefore, they are suitable for mobilizing the plant’s own protective forces against damage by undesirable microorganisms.

By strengthening plants (forming resistance) substances should be understood in this regard, such substances that are able to stimulate the plant defense system in such a way that the treated plants with subsequent inoculation with undesirable microorganisms show good resistance to these microorganisms.

Under undesirable microorganisms in this case should be understood phytopathogenic fungi, bacteria and viruses. Therefore, the substances according to this invention can be used to protect plants for a certain period of time after treatment from damage by these pathogens. The period of time during which protection is achieved generally lasts from 1 to 10 days, preferably from 1 to 7 days after the treatment of plants with biologically active substances.

Good tolerance by plants of biologically active substances in concentrations that are necessary to combat plant diseases, allow the treatment of aerial parts of plants, plants and seed material and soil.

Moreover, the biologically active substances according to the present invention can be particularly successfully used to combat plant diseases of grain crops, for example, species of the puccinia genus (Risasha), diseases of grapes, horticultural crops, and vegetable crops, such as species of the botrytis genus (Wo1tIk) , species of the genus Venturia (Uep1shta) or species of the genus Alternaria (Aietpapa).

Biologically active substances according to this invention are also suitable for increasing the size of the crop. In addition, they have minimal toxicity and are well tolerated by plants.

Biologically active substances according to this invention can also be used, if necessary, in certain concentrations and consumable quantities as herbicides, to affect plant growth, and also to combat animal pests. They can also be used if necessary as intermediate and starting products for the synthesis of other biologically active substances.

According to this invention, it is possible to treat plants in whole or in part of plants. A plant is understood to mean all plants and plant populations, such as desirable and undesirable wild and cultivated plants (including naturally occurring cultivated plants). Cultivated plants can be plants that can be obtained by traditional methods of cultivation and optimization or by methods of biotechnology and genetic engineering, or a combination of these methods, including transgenic plants and including plant varieties, protected and unprotected by law to protect varieties. Plant parts should be understood to include all aboveground and underground parts and plant organs, such as a sprout, a leaf, a flower, and a root, including, for example, leaves, needles, stems, stems, flowers, fruits and seeds, as well as roots, tubers, rhizomes. Parts of the plant also include the commercial product of the crop, as well as vegetative and generative propagation material, such as cuttings, tubers, rhizomes, cuttings and seeds.

The treatment of plants or plant parts according to the present invention with a combination of biologically active substances occurs directly or by affecting their environment, habitat or storage areas by conventional methods, for example, dipping, spraying, steaming, spraying, dispersing, applying, squirting, and breeding material, especially seeds, by forming single or multi-layered shells on them.

You can use the substances according to this invention to protect technical materials from damage or their destruction by unwanted microorganisms.

Under the technical materials should be understood in this regard non-living materials that are prepared for use in engineering. For example, technical materials that should be protected from microbial change or destruction can be adhesives, adhesives, paper and cardboard, textiles, leather, wood, paints and varnishes and plastic products, coolants and other materials that can be affected by microorganisms. or be destroyed by them. Within the framework of the materials to be protected, it is also necessary to name parts of production plants, for example, water cooling circuits, which may be damaged due to the multiplication of microorganisms. In the framework of this invention, adhesives, adhesives, paper and cardboard, textiles, leather, wood, paints and varnishes, coolants and heat transfer fluids, particularly preferably wood, should be mentioned as technical materials.

For example, bacteria, fungi, yeast, algae and mucus organisms should be mentioned as microorganisms that can cause destruction or alteration of technical materials. Preferably, the biologically active substances of the present invention act on fungi, especially mold fungi, which stain and destroy wood fungi (basidiomycetes), as well as on mucus organisms and algae.

It should be called, for example, microorganisms of the following genera:

alternaria (Liegepapa), of such species as Liepupeanne; Aspergillus (LkregdShik), such species as LkregdShik shdeg; Hetomium (CLAIN), such species as CLAINI; Koniofor (Soshoryb), such species as Soshorybeard! apa; Lentinus (Lepepek), such as Lepepean Tsdppt;

penicillium (Resch), such as Reshsshsh d1aSit; polyporus (Po1urogi8), of such species as Po1urogi§ urosis;

aureobasidium (LigeiOiysht), such species as LigeoIiysht ri11i1ap8; sclerophus (Steromyobacter), such species as Sylpacid Steriopathy;

Trichoderma (Tpsyobegta), such species as Tpsyoegta utbe; Escherichia (Exichepsia), such species as Exichepsa soi;

Pseudomonas (Rkeibotopak), such species as Rkeiyotopak aegidshok; stafillokok (§1aryby1osossi8), such species as §1aryby1ssossi8 aigeik.

Biologically active substances, depending on their respective physical and / or chemical properties, can be converted into conventional formulations and preparations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, microcapsules in polymeric substances and into coating masses. seed material, as well as recipes for obtaining IVU (ultralow volume) - cold and warm fog.

These formulations are prepared by conventional methods, for example by mixing biologically active substances with fillers, i.e. with liquid solvents, liquefied gases under pressure, and / or solid fillers, if necessary using surfactants, i.e. emulsifiers and / or dispersants and / or blowing agents. In the case of using water as a filler, for example, organic solvents can be used as an auxiliary solvent. Aromatic compounds, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffinic hydrocarbons, for example, petroleum fractions, are mainly suitable as liquid solvents, alcohols, such as butanol or glycol, also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solution erator, such as dimethylformamide or dimethyl sulphoxide, and also water. Liquefied gaseous fillers are understood to be liquids that are gaseous at ordinary temperatures and normal pressure, for example, working gases for aerosols, such as halohydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid fillers are, for example, natural rock flour, such as kaolin, clay, talc, quartz, chalk, attapulgite, montmorillonite or diatomaceous earth, and synthetic solid rock flour, such as highly dispersed silicic acid, aluminum oxide and silicates. For example, crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic origin, as well as granules of organic materials, such as sawdust, coconut shells, corncobs and tobacco stalks. Suitable emulsifying and / or blowing agents are, for example, non-ionic and anionic emulsifiers, such as fatty acid esters of polyoxyethylene, fatty alcohol esters of polyoxyethylene, such as alkylaryl polyglycols, alkyl sulfonates, alkyl sulfates, arylsulfonates, and protein hydrolysates. Suitable dispersants are, for example, ligninsulfate waste solutions and methylcellulose.

The formulations and preparations means may be used to improve adhesion, such as carboxymethylcellulose, natural and synthetic powdered, granular or latex-like polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue, and organic dyes such as alizarin, azo and metal phthalocyanine dyes, and microcomponents such as salts of iron, manganese, boron, copper, cobalt, molybdenum can be used and zinc.

- 10 011551

Formulations and preparations generally contain from 0.1 to 95% by weight of biologically active substances, preferably from 0.5 to 90% by weight.

The biologically active substances according to the invention can be used as such or in their formulations, as well as in mixtures with known fungicides, bactericides, acaricides, nematicides or insecticides, for example, in order to expand the range of action or prevent the development of resistance. In many cases, a synergistic effect is obtained, i.e. the efficiency of the mixture is higher than the sum of the effectiveness of the individual components.

The following compounds are suitable partners for blends.

Fungicides:

2. Isopentylcarboxamide formula (I) according to claim 1, where

B means

I ¹ means hydrogen;

I ² means hydrogen, fluorine, chlorine, methyl or trifluoromethyl;

I ³ means hydrogen or (C1- _C6 ) alkyl;

And means a radical of the formula (A1) where I ¹⁰ means (C1-C ₂ ) alkyl, possibly substituted by 1-5 fluorine atoms;

I ¹¹ means hydrogen or fluorine and

I ¹² means methyl, ethyl, n-propyl or isopropyl,

2-amino-4-methyl-L-phenyl-5-thiazolecarboxamide; 2-chloro-y- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridine carboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile;

actinovate; cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol; methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1 -yl) -1H-imidazole-5-carboxylate; potassium bicarbonate;

L- (6-methoxy-3-pyridinyl) cyclopropanecarboxamide;

L-butyl-8- (1,1-dimethylethyl) -1-oxaspiro [4.5] decan-3-amine; sodium tetrathiocarbonate;

as well as copper salts and copper preparations, such as Bordeaux mixture; copper hydroxide; copper naphthenate; copper oxychloride; copper sulfate; kufraneb; copper oxide; mancopper; oxine copper.

Bactericides:

Bronopol; dichlorophene; nitrapirin; nickel dimethyldithiocarbamate; Kasugamycin; octylinone; furancarboxylic acid; oxytetracycline; probenazole; streptomycin; tecophthalm; copper sulfate and other copper compounds.

Insecticides / acaricides / nematicides:

abamectin; ABC-9008; acephate; acequinocyl; acetamiprid; acetoprole, acrinatrine,-1022; ΆΚΌ-3059; ΑΚΌ-3088; alanicarb, aldicarb, aldoxycarb, allethrin, allethrin 1K-isomers, alpha

- 11 011551 cypermethrin (alpha-metrin), amidoflumet, aminocarb, amitraz, avermectin, ΑΖ 60541, azadirachtin, azamethiphos, azinposmethyl, azinphosethyl, azocyclotin;

VasShik roryas, VasShik Krzyaspsik, VasShik KiY1Shk, VasShik 1Nig1p§1sp515. Vashe bifenaze, bifenthrin, binapacryl, bioallethrin, bioallethrin-8-cyclophthalomas butathiophos, butocarboxim, butoxycarboxyme, bu ilpirida, kadusaf a) hlovaportrin, chromafenozide, cis-cypermethrin, cis-resmethrin, cis-permethrin, clotsitrin, cloetocarb, clofentezin, clotianidine, clotiazoben, codeleone, coumaphos, cyanophenphos, cyanofos, cyclopene, zylenophenophen, cyloprene, cyloophenphos, cyanophos, cycloprinoscobene, codeleone, coumaphos, cyanophenphos, cyanophos, cycloprene, cyleophenophen, cyloprene, cylophenophos, cyanophos, cyclopene, zylenophenophos, cyloprin, cyloophenphos, cyclophenezine otrin, cyhexatin, cypermethrin, cyphenothrin (1B-trans-isomer), cyromazine, ΌΌΤ, deltamethrin, demeton-8-methyl, demeton-8-methylsulfone, diafenthiuron, dialifos, diazinon, dichlorofenthion, dichloros, dicofol, dos, dihydin, diazinon, dichlorofenthion, dichloros, dicofol, diacinone, dichlorofenthion, dichlorophen, dicofurin dimetos, dimethylphenols, dino ethiofencarb, ethiprole, ethion, etoprofos, etofenprox, ethoxazole e, frimthat, fenfacrin , fluprocyrinate, flucycloxuron, flucitrinate, flufenerime, flufenoxuron, mefur, flufenprox, flumethrin, flupirazofos, flutenzin (flufenzin), fluvalinate, phonophos, formethanate, formotionion, phosphomethane, phastiazate, cream, phfophos, phonophos, formethanate, formotionion, phosphomethane, phastiazate, cream, phfophos, phonophos, formetanate, formotionion, phosphomethane, phastiazate, cream, phfophos, phonophos, formethanate, formotionion, phosphomethane, phastiazate, cream, phfophos, phonophos, formethanate, formotionion, phosphomethane, phostiate, ceffosfan, phfophos, formetanate RB;

gamma cialis , iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin, japanilure, cadetrin, nuclear polyhedron viruses, kinoprene;

lambda milbemectin, milbemycin, ΜΚΙ-245, 0Ν-45700, monocrotophos, moxidectin, ΜΤΙ-800, frost, N ^ 104, N ^ 170, N0184, N ^ 194, N ^ 196, niclosamide, nicotine, nitenpyram, nitiazine,- 0001, NN1-0101, NN1-0250, NN1-9768, Novaluron, Noviflumuron, 0Κ-5101, 0Κ-5201, 0Κ-9601, 0Κ-9602, 0-9701, 0Κ-9802, ometoate, oxamyl, oxymemetonmet silt, RassIotussk Gitokogsik, parathionmethyl, parathion (-ethyl), permethrin (cis-, trans-), kerosene, PH-6045, phenotrin (1B-trans-isomer), fentoate, forate, fosalone, phosmet, phosphamidone, phosphocarb, foxim piperonium, piromal , pyrimidiphen, pyriproxifen, quinalphos, resmethrin, V -5849, ribavirin, WI-12457, WI-15525, 8-421, 8-1833, salition, sebufos, 8Ι-0009, silafluofen, spinosad, spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos, 8ΖΙ-121;

tau-fluvalinat cycles of thioxan liprole, verbutin, UsgysShsht 1ssapy, e L-108,477, ^ I-40027, uv-5201, 5301-uv, uv-5302, HMS, ksililkarb, of ZA-3274;

zeta-cypermethrin, zolaprofos, ΖΧΙ-8901, compound 3-methylphenylpropylcarbamate (tsumacide), compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-azabicyclo [3.2. 1] octane-3-carbonitrile (reg. No.-CA8 185982-80-3) and the corresponding 3-endoisomers (reg. No.-CA8 185984-60-5) (cf. ^ 0-96 / 37494, ^ 0-98 / 25923), as well as preparations that contain insecticidal plant extracts, nematodes, fungi or viruses.

It is also possible to mix with other known biologically active substances, such as herbicides, or with fertilizers and growth regulators, protective substances or chemicals.

- 12 011551

Moreover, the compounds of formula (I) according to the invention have very good antifungal properties. They have a very wide range of antifungal effects, especially against dermatophytes and sprout fungi, mold and diphasic fungi (for example, against Candida species (Saiblba), such as Saibliba Fujik, Saiblb §1aBga1a), as well as Er1bigurus Parosit, aspert species, asparagus types, and asparagus types, asparagus types, asparagus types, asparagus types, as well as Epiphysis, as well as Er1begtor and Phytocum fungi. such as AkregdShik shdeg and AkregdShik 1it1da1i8, Trichophyton species (TpsNoru! OIs) such as Tps1yur11u1op tei1adgoru1e8, types microspores (Myugokrogoi) such as Myugokrogoi sai18 and aiboshii. The listing of these mushrooms is by no means a limitation of the covered spectrum of fungi, but is only illustrative.

Biologically active substances can be used, as such, in the form of their formulations or working forms prepared from them, such as ready-to-use solutions, suspensions, powders for spraying, pastes, soluble powders, pollination agents and granules. The application occurs in the usual way, for example by pouring, spraying, spraying, foaming, spreading, etc. Further, it is possible to introduce a biologically active substance by the method of І1га-Bo \\ 'Ao1shpe (ultra small volumes) or inject the formulation with the biologically active substance or the biologically active substance into the soil. You can also process the seed of plants.

When using the biologically active substances according to the present invention as fungicides, the consumption amounts can be varied over a wide range depending on the method of application. When processing parts of plants, the consumption of biologically active substances are in the range from 0.1 to 10,000 g / ha, preferably from 10 to 1000 g / ha. When treating seed, the consumable amount of the biologically active substance generally lies in the range from 0.001 to 50 g per 1 kg of seed, preferably from 0.01 to 10 g per 1 kg of seed. When tillage, the consumable amount of biologically active substances are in the range from 0.1 to 10,000 g / ha, preferably from 1 to 5,000 g / ha.

As mentioned above, according to this invention, it is possible to treat plants in whole or in part. In a preferred embodiment of the invention, wild-grown or obtained by traditional biological growing methods such as crossing or protoplast fusion, plant species and plant varieties, as well as parts thereof, are processed. In another preferred embodiment, transgenic plants and plant varieties are processed, which are obtained by genetic engineering methods, if necessary, in combination with traditional methods (genetically modified organisms) and their parts. The concept of parts and parts of plants are explained above.

Particularly preferably, according to the invention, the plants are treated according to standard commercial quality or used varieties. Plant variety is understood to be plants with new properties (Tgab), which are grown using both traditional methods and by mutagenesis or recombinant DNA technologies. These can be varieties, breeds, bio and genotypes.

Depending on the plant species or varieties, their location and growing conditions (soil, climate, vegetation period, nutrition), super-additive (synergistic) effects can also occur as a result of the treatment according to this invention. For example, it is possible to reduce consumption quantities and / or expand the range of effects, and / or enhance the effectiveness of substances and agents used in accordance with this invention, better plant growth, increased tolerance to dryness or to the content of water and salts in the soil, increased flowering productivity, facilitating harvesting, accelerating ripening, increasing the size of the crop, improved quality and / or increased nutritional value of the crop, increased storage stability and / or processability that exceed actually expected effects.

Preferred transgenic plants (obtained using genetic engineering technologies) that are treated according to this invention include all plants that were obtained by genetic engineering modifications of the genetic material, which gave these plants particularly advantageous valuable properties (Tgab). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to the content of water and salts in the soil, increased flowering productivity, easier harvesting, accelerated ripening, increased crop size, improved quality and / or increased nutritional value of the product of the crop, increased storage stability and / or processability of the product of the crop. Other and especially prominent examples of such properties are increased plant protection from animals and microbial pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses, as well as increased plant tolerance to certain herbicidal biologically active substances. As an example of transgenic plants, important cultivated plants are mentioned, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed, and fruit plants (with fruits such as apples, pears, citrus fruits and grapes), corn, soybeans, potatoes, cotton, tobacco, and rape are particularly prominent. As properties (Tgab), the increased protection of plants against insects, arachnids, nematodes and gastropods (snails) with the help of toxins formed in plants, especially

- 13 011551 which are produced in plants by means of genetic material from VashShik T1shppsch515 (for example, through the genes Cyu1A (a), Cygu1A (b), Cyu1A (c), Cyu11A, Cyu111A, Cyu111B2, Cygu9s, Cygu2Ab, Cygu3A, and Cype1A, Cygu11A, Cyu111B2, Cygu9s, Cyu2Ab, Cygu3A, and Circuit1, Cygu11A, Cygu111B2, Cycu9s, Cygu1A2, Cygu3A, and Cype1A2 combinations) (hereinafter referred to as B1-plants). As properties (Tgike), the increased resistance of plants to fungi, bacteria, and viruses is also particularly emphasized due to systemic acquired resistance (HUchschysNs Ax. | Speed Vschchsph. 8AK.). systemine, phytoalexin, elicytoren and resistance genes and related proteins and toxins. As properties (Tgayk), the increased tolerance of plants to certain herbicidal biologically active substances, such as imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example, PAT gene), is particularly emphasized. Genes that confer the desired desired properties (Tgike) in transgenic plants can occur in combination with each other.

Examples of B1 plants include the varieties of corn, cotton, soybeans and potatoes, which are sold under the trade names ΥΙΕΕΌ SAKE® (for example, corn, cotton, soy), KposOSh® (for example, corn), §1гЫпк® (for example, corn ), BO11Dagb® (cotton), LisoGop® (cotton) and Li ^ GeaT® (potatoes).

Examples of herbicide-tolerant plants include varieties of corn, cotton, and soybeans, which are sold under the trade names Koipbir Keabu® (glyphosate tolerance, for example, corn, cotton, soybeans), Hygienic Ypk® (phosphinotricin tolerance, for example, soybeans), for example, phosphonotricin tolerance, for example, soybeans, phosphorotropic tolerance, for example, phosphonotricin tolerance. , ΙΜΙ® (imidazolinone tolerance) and 8T8® (sulfonylurea tolerance, such as corn).

As herbicide-resistant plants (usually grown on herbicide tolerance), varieties that are marketed under the name CleagPe1b® (for example, maize) should be mentioned. Needless to say, these statements are also valid for varieties that will be developed in the future and will appear in the future on the market of plant varieties with these or new, developed in the future, properties (Tgike).

These plants can be particularly preferably treated with compounds of the general formula (I) or mixtures of biologically active substances according to the invention. The preferred ranges indicated above for biologically active substances or mixtures are also valid for the treatment of these plants. Particularly preferred treatment of plants specifically indicated in this text compounds or mixtures.

The preparation and use of biologically active substances according to this invention is shown in the following examples.

Examples of obtaining compounds

Example 1

To a solution consisting of 388.5 mg (2.2 mmol) of 5-fluoro-1,3-dimethyl-1H-pyrazole-4carbonyl chloride and 0.45 ml (3.2 mmol) of triethylamine in 20 ml of tetrahydrofuran is added 326 , 5 mg (2.0 mmol) [2- (3-methylbutyl) phenyl] amine (ΙΙΙ -1). The reaction mixture is stirred for 90 minutes at 60 ° C, filtered through silica gel and the solvent is distilled off. After purification on a chromatographic column (gradient cyclohexane / ethyl acetate), 592 mg (98% of theory) of 5-fluoro-1,3-dimethyl-L- [2- (3-methylbutyl) phenyl] -1H-pyrazole are obtained. -4-carboxamide with 1OD (pH 2.3) = 3.12.

Analogously to example 1, as well as in accordance with the instructions given in the general description of the methods, receive the compounds of formula (Ι) given in table. one.

- 14 011551

Table 1

I (ΐ)

ns ^ mon,

Example K ¹ to ² to ³ BUT 1ODP 2 n n SNS ^NES UU 1 SN _E 3.42 3 n n SNS ° zhU ABOUT 4.14 four n n n 3, 90 five n n SNS & 4.13 6 n and n -H 3.87 7 n n SNS 4.15 eight n n n ά 3.78 9 n n n ά 3, 76 ten n n n ^{g, 0} \ _ / CH, 3, 68 eleven n n SNS X 1 ch ₃ 3.28

- 15 011551

12 Η Η SNS XN ^H 1 F ₃ 3, 91 13 Η 4-C1 C ₂ H ₅ 4.96 14 Η 4-C1 from _{2 to} ₅ ά 5.02 15 Η 4-C1 from _{2 to} ₅ ^l , / U SI ·, 4.29 sixteen Η Η SNS Ή Νγ3 C1 4.54 17 Η Η C ₂ H ₅ ^N L / w ⁿ ₃ 3.68 18 Η Η C ₂ H ₅ "P 3.59 1.9 Η 4-C1 C ₂ N ₅ ^PRN % - / SN _e 4,10 20 Η 4-Γ SNS ^N L / gGK | y ^to sn ₃ 3.34 21 Η 4-Γ SNS Have 4.14 22 Η 4-Γ SNS 1 cN _e 3.34 23 Η 4-Γ SNS '¥ 1 ch ₃ 3.57 24 Η 4-Γ SNS ^p, cn Νγ8 sn ₃ 4.05

- 16 011551

Preparation of starting materials of the formula (III) Example (ΙΙΙ-1).

A solution consisting of 8.0 g (0.045 mol) of 1- (2-aminophenyl) -3-methylbutan-1-one (X-1), 6.8 g (0.135 mol) of hydrazine hydrate and 7.6 g (0.135 mol) potassium hydroxide in 90 ml of triethylene glycol, heated for 6 hours at a temperature of 210 ° C. For processing at room temperature add water and ethyl acetate. The organic phase is again washed with water, dried over magnesium sulphate and the solvent is distilled off under reduced pressure. After purification on a chromatographic column (cyclohexane / ethyl acetate 3: 1), 5.3 g (71.5% of theory) of [2- (3-methylbutyl) phenyl] amine are obtained.

An example (W-2).

2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine;

2-phenylphenol; 8-hydroxyquinoline sulfate; acibenzolar-8-methyl; aldimorph; amidoflumet;

ampropylphos; ampropylphosphate; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; benomyl; benthiavalicarbizopropyl; benzamacryl; benzamethacrylate; bilanaphos; binapacryl; biphenyl; betertanol; Blasticidin-8; bromuconazole; bupirimate; butobiobate; butylamine; calcium polysulfide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamide; carvone; quinomethionate; chlobenthiazone; chlorphenazole; Chloroneb; chlorothalonil; chlozolinate; chlosylacon; cyazofamide; cyflufenamide; cymoxanil; cyproconazole; cyprodinil; ciprofuram; Dagger C, Debacarb; dichlofluanid; dichlone; dichlorophene; diclocyme; diclomezine; dicloran; diethofencarb; difenoconazole; diflumetorim; dimethyromol; dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap; diphenylamine; dipirition; ditalimfos; dithianon; Dodin; Drazoxolone; Edifenphos; epoxiconazole; ethaboxam; ethyrimol; etridiazole; famoxadone; fenamidone; phenapanil; fenarimol; fenbuconazole; fenfuram; fenhexamide; fenitropane; phenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-A1, fosetyl sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazole; imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris- (albesyl); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovalentione; Kazugamycin; kresoximmethyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; metasulfocarb; metforoxam; metiram; metominostrobin; metsulfovaks; Mildiomycin; miklobutanil; myclozolin; natamycin; nicobifen; nitrotalisopropyl; Noviflumuron; nuarimol; ofurase; orizastrobin; oxadixyl; oxolinic acid; oxpoconazole; hydroxycarboxine; oxyfentiine; paclobutrazole; pefurasoate; penconazole; penzicuron; fosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz; procymidone; propamocarb; propanosinenatrium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilone; Piroxyfur; pyrrolnitrin; quinconazole; quinoxyfen; Quintocene; simeconazole; spiroxamine; sulfur; tebuconazole; tecophthalm; teknazene; tetcyclacis; tetraconazole; thiabendazole; titsiofen; tifluzamide; thiophanatemethyl; thiram; thioximide; tolclofosmetil; tolylfluanid; triadimefon; triadimenol; triazbutyl; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; triflumisole; triforine; triticonazole; uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide;

(28) -Y- [2- [4 - [[3- (4-chlorophenyl) -2-propynyl] oxy] -3-methoxyphenyl] ethyl] -3-methyl-2 - [(methylsulfonyl) amino] butanamide;

3. Isopentylcarboxanilides of the formula (I) according to claim 1 or 2, wherein A is A1.

4. Isopentylcarboxanilides of the formula (I) according to claim 1 or 2, where I ³ means hydrogen.

5. The method of producing compounds of formula (I) according to claim 1, characterized in that the carboxylic acid derivatives of the formula (II) where A has the meanings given in claim 1, and

X ¹ is halogen or hydroxy,

- 27 011551 is reacted with an aniline derivative of the formula (III) where b, K ¹ and K ³ have the meanings given above, if necessary in the presence of a catalyst, if necessary in the presence of a condensing agent, if necessary in the presence of an acid binding agent, and necessary in the presence of a diluent.

6. Agent for controlling undesirable microorganisms, characterized in that it contains at least one isopentylcarboxanilide of formula (I) according to claim 1, along with fillers and surfactants.

7. The use of isopentylcarboxanilides of the formula (I) according to claim 1 for the control of undesirable microorganisms.

8. The method of combating undesirable microorganisms, characterized in that the isopentylcarboxanilides of formula (I) according to claim 1 are applied to the microorganisms and to their habitats.

9. A method of obtaining agents for combating undesirable microorganisms, characterized in that the isopentylcarboxanilides of formula (I) according to claim 1 are mixed with fillers and / or surfactants.

where a) K ^1-B means ((C1-C8) alkyl) carbonyl, and K ^3-B means (C1-C8) alkyl or b) K ^1-B means hydrogen, and K ^3-B means hydrogen or (C1 -C ₈ ) alkyl and K ² has the meanings given in paragraph 1.

11. Isopentone derivatives of the formula (V) where K ¹ , K ² , K ³ and A have the meanings given in paragraph 1.

12. Isopenten derivatives of the formula (VI) where K ¹ , K ² , K ³ and A have the meanings given in paragraph 1.

13. Isopentine derivatives of the formula (VII) where K ¹ , K ² and K ³ have the meanings given in paragraph 1;

A has the values given in paragraph 1, with the exception of A1.

14. Alkanonanilina formula (X) where K ¹ , K ² and K ³ have the meanings given in paragraph 1.

A means a radical of formula (A2) where I ¹³ and I ¹⁴ means hydrogen and I ¹⁵ means (C1-C ₄ ) alkyl, or A means a radical of formula (A4) where I ¹⁹ means (C1-C ₆ ) alkyl, or

And means the radical of the formula (A11) where I ³⁰ means methyl, ethyl or chlorine and

I ³¹ means (C1-C ₂ ) alkyl, possibly substituted with 1-5 fluorine atoms, provided that I ³¹ does not mean trifluoromethyl, difluoromethyl or methyl, if I ³ means hydrogen and I ³⁰ means methyl.

A means a radical of formula (A2)

- 26 011551 where I ¹³ and I ¹⁴ mean hydrogen and I ¹⁵ means (C1-C ₄ ) alkyl, or A means a radical of formula (A4) where I ¹⁹ means (C1-C ₆ ) alkyl, or

And means radical (formula (A11) where I ³⁰ means (C1-C ₄ ) alkyl or chlorine and

I ³¹ means (C1-C ₄ ) alkyl, possibly substituted by fluorine, provided that I ³¹ does not mean trifluoromethyl, difluoromethyl or methyl, if I ³ means hydrogen and I ³⁰ means methyl.

3.23 g (15 mmol) of No. [2- (3,3-dimethylbut-1-ynyl) phenyl] acetamide (XIII-1) are placed in 40 ml of methanol. 0.5 g of palladium on carbon (5%) is added and finally it is hydrogenated in an autoclave for 20 hours at 4 bar of hydrogen pressure. After separation of the catalyst and removal of the solvent, 3.1 g (94% of the theory) of No. [2- (3,3-dimethylbutyl) phenyl] acetamide with 1 D (pH 2.3) = 2.69 are obtained.

Example (ΙΙΙ-3).

0.5 g (2.3 mmol) of No. [2- (3,3-dimethylbutyl) phenyl] acetamide (ΙΙΙ-2) are placed in 20 ml of 2n. hydrochloric acid and stirred for 5 hours at a temperature of 100 ° C. After cooling, it is extracted with ethyl acetate 3 times in 20 ml each time. The organic phase is separated, dried over sodium sulfate and the solvent is distilled off. 390 mg (79% of theor.) Of 2- (3,3-dimethylbutyl) phenylamine hydrochloride are obtained with 1 D (pH 2.3) = 2.20.

Obtaining starting materials of the formula (V)

Example (ν-1).

At room temperature, 355.0 mg (2.0 mmol) of 1- (2-aminophenyl) -3-methylbutan-1-it is added to a solution consisting of 388.5 mg (2.2 mmol) of 5-fluoro-1 chloride , 3-dimethyl-1H-pyrazole-4-carbonyl and 0.45 ml (3.2 mmol) of triethylamine in 20 ml of tetrahydrofuran. The reaction mixture is stirred for 1.5 hours at 60 ° C, filtered through silica gel and the solvent is distilled off. After purification on a chromatographic column (cyclohexane / acetic acid ester: 3/1), 577.7 mg (1.8 mmol, 88% of theor.) [2- (3-methylbutyryl) phenyl] amide 5-fluoro-1 are obtained, 3-dimethyl-1H-pyrazole-4-carboxylic acid with 10 P (pH 2.3) = 3.42.

Analogously to the example (ν-1), as well as in accordance with the instructions given in the general description of the reactions, the compounds of formula (V) obtained in Table 1 were obtained. 2

- 17 011551

Example (νΐΙ-1).

table 2

Example Κ ¹ κ ² κ ³ Α 1ODP ν-2 Η Η Η ^Η Α / ο 4.30 ν-3 Η Η Η 4.33 ν-4 Η Η Η ά 4.53 ν-5 Η Η Η ά 4.35 ν-6 Η Η Η ά 4.30 ν-7 Η Η Η 4.44

Obtaining starting materials of the formula (VII)

190 mg (1.0 mmol) of 2-trifluoromethylbenzoic acid, 178 mg (0.83 mmol) of 2- (3,3-dimethylbut-1inyl) phenylamine, 215 mg (1.67 mmol), Ν-diisopropylethylamine and 583 mg (1.25 mmol) RuBgOR (bromo-tris- (pyrrolidino) phosphonium hexafluoride) is stirred in 8 ml of acetonitrile for 4 days at room temperature. To the mixture is added 10 ml of ethyl acetate / water 1: 1, the organic phase is separated and washed with 10 ml of a saturated solution of ammonium chloride and finally 10 ml of water. The organic phase is separated, the solvent is distilled off and dried, then 950 mg of crude product is obtained. After purification on a chromatographic column of silica gel 60 (petroleum ether / ethyl acetate 10: 1 ethyl acetate), 110 mg of the No. [2- (3,3-dimethylbut-1-ynyl) phenyl] -2-trifluoromethylbenzamide [1 GD (pH 2.3) = 4.55].

Analogously to the example (νΐΙ-1), as well as in accordance with the instructions given in the general descriptions of the methods of preparation, receive the compounds of formula (VII), given in table. 3

- 18 011551

Table 3

An example (X-!).

A solution of 29.5 g (0.25 mol) of anthranilic (o-aminobenzoic) nitrile in 150 ml of tetrahydrofuran is added dropwise, under reflux, to a suspension consisting of 18.2 g (0.75 mol) of magnesium, 375 ml 2 M solution of isobutyl magnesium bromide in tetrahydrofuran and 15 ml of diethyl ether. After heating for 5 hours with reverse distillation, 100 ml of water are fed to the reaction mixture at 0 ° C and the pH is adjusted to 6 with hydrochloric acid. The organic phase is washed with water and dried over magnesium sulfate. The solvent is distilled off in vacuo and purified on silica gel (eluent: petroleum ether / acetone 95: 5) to obtain 11.0 g (25% of theory.) 1- (2-aminophenyl) -3-methylbutan-1-one with 1ODP (pH 2.3) = 2.89.

Obtaining starting materials of the formula (XIII)

An example (HS-1).

> ^sn C η, ο-'Ύη,

25.7 g (120 mmol) of orthobromoacetanilide, 5.05 g (7.2 mmol) of bis- (triphenylphosphine) palladium (II) chloride and 1.37 g (7.2 mmol) of iodide medica) are placed in 450 ml of triethylamine in argon atmosphere. Finally, 17.8 g (180 mmol) of 3,3-dimethyl-1-butine is added dropwise at room temperature over 10 minutes and stirred for 5 hours at 50 ° C. The reaction mixture is poured into 2 l of water, extracted with diethyl ether 3 times in 250 ml each time, dried over sodium sulfate and the solvent is distilled off. After purification on a chromatographic column of silica gel 60 with methylene chloride, 25.9 g of N- [2- (3,3-dimethylbut-1-ynyl) phenyl] acetamide with 1 DF (pH 2.3) = 3.03 are obtained.

The determination of 1ODP values given in the preceding tables and in the examples of preparation is carried out in accordance with the EEC-directive 79/831 Ap. U.A8 using HPLC (high-resolution liquid chromatography) on a column with reversed phases (C 18). Temperature: 43 ° C.

- 19 011551

The determination is carried out in the acidic region at a pH value of 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluent; linear gradient from 10 to 90% acetonitrile.

Calibration is carried out with unbranched alkan-2-ones (with 3-16 carbon atoms), for which 1 PD-values are known (determination of 1 CD-values depending on the retention time in a linear extrapolation between two consecutive alkanones).

The lambda max values are determined on the basis of UV spectra in the range from 200 to 400 nm at the maximum of the chromatographic signal.

Application Examples

Example A. Test for Robokryaega (apple) / protective.

Solvent:

24.5 weight.h. acetone,

24.5 weight.h. dimethylacetamide.

Emulsifier:

weight.h. alkyl aryl polyglycol ether.

For the preparation of a suitable recipe for the biologically active substance, 1 wt. including biologically active substances with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test the protective activity of young plants are sprayed with the specified expenditure amount of the drug biologically active substances. After the spray coating has dried on, the plants are inoculated with an aqueous suspension of the spores of the pathogen of apple powdery mildew of Robokryaega leiso ps1a. After that, the plants are placed in a greenhouse at a temperature of about 23 ° C and a relative humidity of about 70%.

10 days after the inoculation, an evaluation takes place. At the same time, 0% means efficiency, which corresponds to the effectiveness of the control, whereas the efficiency of 100% means that no damage is observed.

Table A

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Example B. Test for νοηΐιιπα (apple) / protective.

Solvent:

24.5 weight.h. acetone,

24.5 weight.h. dimethylacetamide.

Emulsifier:

weight.h. alkyl aryl polyglycol ether.

To test the protective activity of young plants are sprayed with the specified expenditure amount of the drug biologically active substances. After drying, the spraying of the plant is inoculated with an aqueous suspension of conidia of the apple scab pathogen νοηοιιπα taediaS and left for 1 day in an incubation cabin at a temperature of about 20 ° C and a relative humidity of 100%. After that, the plants are placed in a greenhouse at a temperature of about 21 ° C and a relative humidity of about 90%.

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Table B

Test for UsgIipa (apple) / protective

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Example C. Test for Wobusch (beans) / protective.

Solvent:

24.5 weight.h. acetone,

24.5 weight.h. dimethylacetamide.

Emulsifier:

weight.h. alkyl aryl polyglycol ether.

To test the protective activity of young plants are sprayed with the specified expenditure amount of the drug biologically active substances. After drying the spray from spraying on each sheet put two small pieces of agar, overgrown with ΒοΙιγΙίδ skhegea. Inoculated plants are placed in a darkened chamber at a temperature of about 20 ° C and a relative humidity of 100%.

2 days after the inoculation, the magnitude of the lesion spots on the leaves is evaluated. At the same time, 0% means efficiency, which corresponds to the effectiveness of the control, whereas the efficiency of 100% means that no damage is observed.

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Example Ό. Risse 1 (wheat) / protective test.

Solvent: 50 weight.h. Ν,-dimethylacetamide.

Emulsifier: 1 weight.h. alkyl aryl polyglycol ether.

To test the protective activity of young plants are sprayed with the specified expenditure amount of the drug biologically active substances. After the spray coating has dried on, the plants are inoculated with a Risas hesobby conidial suspension. Plants are left for 48 hours in an incubation cabin at a temperature of 20 ° C and a relative humidity of 100%.

After that, the plants are placed in a greenhouse at a temperature of about 20 ° C and a relative humidity of 80% to create favorable conditions for the development of rust pustules.

Table Ό

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Example E. Test for 8yeary! Jesa (cucumber) / protective.

Solvent: 49 weight.h. ,-Dimethylformamide.

Emulsifier: 1 weight.h. alkyl aryl polyglycol ether.

To test the protective activity of young cucumber plants are sprayed with the indicated consumable quantities of the drug of biologically active substances. One day after the treatment, the plants are inoculated with a spore suspension of 8rLaHyiGyedtea. In conclusion, the plants are placed in a greenhouse at a relative humidity of 70% and a temperature of 23 ° C.

7 days after the inoculation, an evaluation takes place. At the same time, 0% means efficiency, which corresponds to the effectiveness of the control, whereas the efficiency of 100% means that no damage is observed.

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Table E

- 3 011551 where I ¹ , I ² and I ³ have the meanings given above, in the second stage, subject to interaction with hydrazine (or hydrazine hydrate) in the presence of a base (for example, an alkali or alkaline earth metal hydroxide, such as sodium hydroxide or potassium) and, if necessary, in the presence of a diluent.

Among the aniline derivatives of the formula (III), compounds of the formula (III) mean (C ₁ -C ₈ ) alkyl or where a) I ^1- b means ((C ₁ -C ₈ ) alkyl) carbonyl, and I ^3-b

B) I ^1- b means hydrogen, and I ^3- b means hydrogen or (C ₁ -C ₈ ) alkyl and

I ² has the above values.

These aniline derivatives are the object of claim 10.

The Grignard reagents of formula (IX) are known or can be obtained by known methods.

Alcanonanilines of formula (X), used as intermediates in the implementation of method (e), which are new compounds, are the object of 14 claims.

Hydrazine (or hydrazine hydrate), which is also used as a reagent in the above method (e), is a known chemical for synthesis.

Method (b).

If 2-iodo-L- [2- (3-methylbutanoyl) phenyl] benzamide, as well as hydrazine and base are used as the starting material, the implementation of method (b) can be visualized as a scheme

Isopentone derivatives used as starting materials in the implementation of method (b) are described in general form by formula (V). In this formula (V), the radicals I ¹ , I ² , I ³ and A have the above values.

Isopentone derivatives of formula (V), which are new compounds, are the object of paragraph 11 of the claims.

They are received if:

I) carboxylic acid derivatives of the formula (II) where A has the meanings given above and

X ¹ means a halogen or hydroxy group, to react with alkanonanilines of the formula (X) where K ¹ , I ² and I ³ have the meanings given above, if necessary in the presence of a catalyst, if necessary in the presence of a condensing agent, if necessary in the presence of a coupling agent acid, and if necessary in the presence of a diluent.

Carboxylic acid derivatives of formula (II), used as starting materials in the implementation of method (I), have already been described above in connection with method (a) according to this invention.

The alkanonanilines of formula (X), also used as starting materials in the implementation of method (I) according to the invention, have already been described in connection with method (e) above.

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Method (s).

If as the starting material, one uses {2- [3,3-dimethylbut-1-en-1-yl] phenyl} -5-fluoro1,3-dimethyl-1H-pyrazole-4-carboxamide, as well as hydrogen, implementation of the method (c) can be clearly described in the form of a diagram

The derivatives of isopentene, used as starting materials in the implementation of method (c), are described in general form by formula (VI). In this formula (VI), the radicals B ¹ , B ² , B ³ and A have the above values.

The isopentene derivatives of formula (VI), which are new compounds, are the object of clause 12 of the claims.

They are received if:

d) carboxamides of the formula (XIV) where K ¹ , B ² and A have the meanings given above, and X ⁵ means chlorine, bromine, iodine or -080 ₂ CP ₃ , is reacted with alkenes of the formula (XV) where B ³ matters , above, in the presence of a catalyst, if necessary in the presence of a base and if necessary in the presence of a diluent.

Carboxamides used as starting materials in the implementation of method (e) are described in general form by formula (XIV). In this formula (XIV), the radicals B ¹ , B ² and A have the above values, and X ⁵ preferably means bromine or -080 ₂ CP ₃ .

The carboxamides of formula (XIV) are known or can be obtained by known methods (see \ Y0 02/08195 and \ Y0 02/08197).

Alkenes, also used as starting materials in the implementation of method (e), are known.

Method (b).

If L- [2- (3,3-dimethylbut-1-in-1-yl) phenyl] -5-fluoro1,3-dimethyl-1H-pyrazole-4-carboxamide is used as the starting material, as well as hydrogen, then The implementation of the method (e) according to this invention can be visualized as a diagram

Isopentine derivatives used as starting materials in the process (b) are described in general terms by formula (VII). In this formula (VII), the radicals B ¹ , B ² , B ³ and A have the above values.

The isopentine derivatives of formula (VII), where A does not mean A1, are new compounds that are the subject of claim 13.

The isopentine derivatives of formula (VII) are obtained if:

11) carboxamides of the formula (XIV) where B ¹ , B ² and A have the meanings given above, and X ⁵ means chlorine, bromine, iodine or -080 ₂ CP ₃ , are reacted with alkynes of the formula (XII) (XIV).

- 5 011551 κΐ sn ₃ n-ΞΖ- \ (XII), ch ₃ where I ³ has the values given above, in the presence of a catalyst, if necessary in the presence of a base and if necessary in the presence of a diluent.

The carboxamides of formula (XIV) used as starting materials in the implementation of method (11). already described above in connection with the above method (e).

Reaction conditions.

As a diluent in the implementation of methods (a) and (I), all inert organic solvents are suitable. These include predominantly aliphatic, epicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; or amides, such as Ν, Ν-dimethylformamide,,-dimethylacetamide, Ν-methylformanilide,-methylpyrrolidone or hexamethylphosphoric triamide.

Methods (a) and (I) are carried out, if necessary, in the presence of a suitable acid acceptor. As such, all conventional inorganic and organic bases are suitable. These include preferably hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates of alkali or alkaline earth metals, such as sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium hydroxide ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or ammonium carbonate, as well as tertiary amines, such as trimethylamine, triethylamine, tributylamine,,-dimeth ilanilin, Ν, Ν-dimethylbenzylamine, pyridine, Ν-methylpiperidine, Ν-methylmorpholine, Ν, Ν-dimethylaminopyridine, diazabicyclooctane (ELVSO), diazabicyclononene (ΌΒΝ) or diazabicycloundecene (ΌΒυ).

Methods (a) and (I) are, if necessary, carried out in the presence of a suitable condensing agent. As such, all condensing agents commonly used for this kind of amidation reactions can be used. For example, you can call the substances that form a halide acid, such as phosgene, phosphorotribromide, phosphorotrichloride, phosphorus pentachloride, phosphoroxychloride or thionyl chloride; anhydrides forming substances such as chloroformic acid ethyl ester, chloroformic acid methyl ester, chloroformic acid isopropyl ester, chloroformic acid isobutyl ester, or methanesulfonyl chloride; carbodiimides, such as Ν, Ν'-dicyclohexylcarbodiimide (OCC), or other common condensing agents, such as phosphorus pentoxide, polyphosphoric acid,, Ν'-carbonyldiimidazole, 2-ethoxy-L-ethoxycarbonyl-1,2 dihydrochin-hygidine, imine-azidazole, 2-ethoxy-L-ethoxycarbonyl-1,2 dihydroghinine-imidazole; triphenylphosphine / carbon tetrachloride or bromotripirrolidinophosphonium-hexafluorophosphate.

Methods (a) and (I) are optionally carried out in the presence of a catalyst. As an example, 4-dimethylaminopyridine, 1-hydroxybenzotriazole or dimethylformamide should be mentioned.

The temperature of the reactions in the implementation of methods (a) and (I) can be varied in a wide range. As a rule, they operate at a temperature of from 0 to 150 ° C, preferably at a temperature of from 0 to 80 ° C.

In carrying out the process (a) according to the invention, to obtain a compound of formula (I), per mole of carboxylic acid derivative of formula (II) is generally 0.2-5 mol, preferably 0.5-2 mol of aniline derivative of formula (III).

In carrying out the method (I) for producing a compound of the formula (V), per mole of the carboxylic acid derivative of the formula (II) is generally 0.2-5 mol, preferably 0.5-2 mol of alkanonaniline of the formula (X).

As diluents in the implementation of the method (b), as well as the second stage of the method (e), all inert organic solvents are suitable. These include predominantly aliphatic, epicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,

4 ^