UA73153C2 - Pyrazolcarboxamide and pyrazolthioamide derivatives as a fungicides - Google Patents

Abstract

Novel pyrazole derivatives of formula (I), wherein: X is oxygen or sulfur; R1 is C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy-C1-C3alkyl or C1-C3haloalkoxy- C1-C3alcyl; R2 is C1-C3haloalkyl; and R3 is halogen. The novel compounds have plant-protective properties and are suitable for protecting plants against infestations by phytopathogenic microorganisms.

Description

Description of the invention

The present invention relates to new pyrazolecarboxamides and pyrazolethioamides, which have bactericidal 2 activity, in particular fungicidal activity. The invention also relates to the preparation of such compounds, agrochemical compositions containing as an active substance at least one of these new compounds, the preparation of the specified compositions and the use of active substances or compositions in agriculture and horticulture to combat or prevent infection of plants with phytopathogenic microorganisms, primarily fungi.

The pyrazolecarboxamides according to the present invention have the formula I c. ke

M n -

In, with Fd de

X stands for oxygen or sulfur,

Ku means C1-C4-C6 alkyl, C1-C6 haloalkyl, C1-C4-C4-C6 alkyl or C1-C6 haloalkyl;

E" means C-Shaloalkyl; and

Ez stands for halogen.

When creating the invention, it was unexpectedly established that compounds of the formula | have improved biological properties that make them more acceptable for practical use in agriculture and horticulture. Gee)

If in the compounds of the formula | asymmetric carbon atoms are present, then these compounds are in an optically active form. The invention relates to pure isomers, such as enantiomers and diastereomers, as well as to all possible mixtures of isomers, for example, mixtures of diastereomers, racemates or mixtures of racemates.

In the context of this description, alkyl means methyl, ethyl, n-propyl and isopropyl. It is intended that alkyl, as part of other radicals such as alkoxyalkyl, haloalkyl, or haloalkylalkyl, has the above meanings. yu

The term "halogen" usually refers to fluorine, chlorine, bromine or iodine, with fluorine, chlorine or bromine being preferred.

It is meant that halogen, as a part of other radicals, such as haloalkyl or haloalkyl, has the above values. Typical alkoxyalkyl radicals include methoxymethyl, ethoxymethyl, propoxymethyl, c methoxyethyl, ethoxyethyl and methoxypropyl. Typical haloalkyl radicals include fluoromethoxymethyl, 3o-difluoromethoxymethyl, trifluoromethoxymethyl, 2,2,2-trifluoroethoxymethyl, 3-chloropropoxymethyl, 2,2,3,3,3-pentafluoropropoxymethyl, 2,2,2-trifluoroethoxyethyl and trifluoromethoxypropyl.

In the group of compounds of formula I, compounds in which X represents oxygen (subgroup A) are preferred.

Another preferred group of compounds of formula I are compounds in which X represents sulfur (subgroup B). "

In subgroups A and B, compounds in which Ki means S.-Szalkyl are predominant; or C 70 Ku means C.4-Salkoxy-C.salkyl or C.-Shaloalkyloxy-C 1-Salkyl; c E" means C-Shaloalkyl; or :з» Bo means SE», Sen, SEN», SESSIONS, USSR», Siv, СНоСЕ», СНССИЗ or СЕРоСЕ»оСЕ У; and

Ez means fluorine, chlorine or bromine (subgroups AB and BG).

In subgroup A, compounds in which

Ku means S.-Szalkil; 7 RE" means S-Szhaloalkyl; and coEz is fluorine, chlorine or bromine (subgroup A1).

In the AT subgroup, the compounds of formula I are the most preferred - in which sl 20 E" means СЕз, СЕН, СЕН», СЕС»СИ, СРС», ССИз, СНоСЕ»С, СНССССИС or СЕ2СРЕССЕ З (subgroup A2).

In subgroup A, compounds of the formula |, c" in which

Ku stands for S-Szhaloalkyl;

RE" means S.-Szhaloalkyl; and 29 Ez represents fluorine, chlorine or bromine (subgroup AZ).

HF) In subgroup A, compounds of the formula |, in which Ku stands for C.4-Czalkoxy-C.-Szalkyl or C.-Szahaloalkyl-C 1-Szalkyl, are also preferred;

RE" means S.-Szhaloalkyl; and 60 Ez means fluorine, chlorine or bromine (subgroup A4).

In subgroup B, compounds of formula Y are preferred, in which

Ku means S.-Szalkil;

E" means C-Shaloalkyl; and because Ez means fluorine, chlorine or bromine (subgroup B1).

In subgroup B1, the compounds of formula I are most preferred, in which

E" means СЕз, СЕН, СЕН», СЕС»СИ, СРС», ССИз, СНоСЕ»з, СНСССИз or СЕ2СРЕ»СЕ з (subgroup B2).

In subgroup B, compounds of the formula |, in which

Ku stands for S-Szhaloalkyl;

K" means C,-S-haloalkyl; and

Ez means fluorine, chlorine or bromine (BZ subgroup). 70 In addition, compounds of formula I are also preferred in subgroup B, in which

Ku means C.4-C.sub.4-C.sub.6-C.sub.-S.sub.alkyl or C.-S.sub.5-C.sub.1-C.sub.1-C.sub.1-C.sub.Alkyl;

RE" means S.-Szhaloalkyl; and

Kz means fluorine, chlorine or bromine (subgroup B4).

The most preferred compounds in subgroup AB are compounds in which

Ku means SNuz or СНоОСН"; and

E" means CEz, SEN or SEN" (subgroup B).

In subgroup B, the most preferred are compounds in which

K. stands for SNU"; and

ER" means CE" (subgroup B1).

Another predominant group are compounds of the BG subgroup, in which p

Ku means SNuz or СНоОСН"; and

E" means CEz, SEN or SEN" (subgroup D). and)

In subgroup G, the most preferred are compounds in which

K. stands for SNU"; and c zo ER" means CE" (subgroup G1).

Compounds according to the invention can be obtained according to the following reaction scheme 1. which)

Scheme and "- co

R SOON OO Bosi, or V SOS M t RO, or y

M. m M

And) (0), And AI (does not stand out)

In, in « - - p living 1 Mo nya tt o "OO

I Iv (95) Kk, - sya s 50 se» R.Zh or Laveson's reagent 5 sh solvent toluene, THF, duxan K from 02С to the temperature of dephlegmation t ve

Iv

Ф) В, име) в. 6o Carboxylic acid pyrazole of formula II is reacted with an activating agent, such as thionyl chloride, phosphorus pentachloride or oxalyl chloride, in the presence of a solvent at a temperature from 09C to the reflux temperature, and the reaction is carried out for 30 minutes. - 24 hours, obtaining the corresponding chloride anhydride. Typical solvents are toluene, benzene, xylene, hexane, cyclohexane, chloroform or methylene chloride. The resulting acyl chloride of formula I, as a rule, is not isolated. New carboxamides of the formula Ia are preferably obtained by the interaction of an activated carboxylic acid of the formula I with an aromatic amine of the formula IM in the presence of a solvent such as toluene, benzene, xylene, hexane, cyclohexane, chloroform or methylene chloride in the presence of an acid-binding agent such as triethylamine, Hunig's base , sodium carbonate, potassium carbonate or sodium bicarbonate at a temperature from 09 to the reflux temperature. Pyrazoltisamides of the formula II are obtained by the interaction of pyrazolecarboxamides Ia with phosphorus pentasulfide or Laveson's reagent in a solvent such as dioxane, tetrahydrofuran, or toluene at a temperature from 09C to the reflux temperature.

Preferably, the entire sequence of reactions presented in Scheme 1 is carried out in one vessel.

Compounds of formula I can also be prepared according to reaction scheme 1A below.

Scheme 15 in a, (c) 2 V until 2 h

TO non nivy mon M tm solvent, base "M c

І Kustalogen (С, ВГ, И) | m

V. in ' MI reagent (in the "Ra-catalyst" system

Mvt Riv, or beova " Laveson's reagent 8 OO o 5 v, write sho SHO mm m u u shk

Zhe yiv (g sch a v. Mo v. - Ge) reagent U! "Ra-catalyst" system

Esh shi v. foundations

And co

V. yu pov

M. "-

M. Zh

And Ff p

V. skh i -

IN;

Reagent MI in itself v-3-VN), « 20 The obtained "ip 8yi" pyrazole carboxylic acid chloride anhydride of the formula Sh is subjected to interaction with ortho-halo-substituted phenylamine in the presence of a solvent such as toluene, benzene, xylene, hexane, cyclohexane, THF, chloroform or methylene chloride and in the presence of a base such as sodium carbonate, sodium bicarbonate, potassium carbonate, Hünig's base, triethylamine or pyridine at a temperature from 09C to the reflux temperature. The obtained pyrazolecarboxamide of the formula Ma is subjected to interaction with para-substituted phenylboronic acid (MI) in the presence of a palladium catalyst of the type Pa(P(phenyl)z)m, Pa(P(phenyl)z) Si», -I Rasi»arr, Razh(ara )z, RYAA(OAs)», RYA(OAs)oorto-tolyl)zR, РаІ(OAs)oarry, РІАРІСМ)2СИОРазАv, РІАА(СНУСМ)»СІ»,

Razhava) z/P(tert-butyl)", PaYa(OAc)P(tert-butyl)biphenyl, OA(OAcS)/TRRTIBZ, Pa(OAc)o/Psuz, and OA(OAcS)P(O-iso- Rg)z, RYA(OAs)/2-dimethylamino-2'-dicyclohexylphosphinobiphenyl, - PaYa(OAs)g/2-dimethylamino-2"-di-tert-butylphosphinobiphenyl, PaYa(OAs)oCorto-biphenyl) P(cyclohexyl) », in a solvent such as 1,2-dimethoxyethane/water, DMF, DMA, THF/water, dioxane/water, benzene, toluene, xylene, etc., and in bases such as sodium carbonate, sodium bicarbonate, potassium carbonate, carbonate cesium, potassium phosphate, triethylamine, sodium hydroxide, sodium ethylate, sodium tert-butylate, silver oxide, barium carbonate, potassium fluoride or cesium fluoride at a temperature from 023 to the reflux temperature.

Pyrazoltidesamides of the formula IB are obtained by treating the pyrazolecarboxamide of the formula Ma RoZ or Laveson's reagent in a solvent such as dioxane, tetrahydrofuran, or toluene at a temperature from 09C to the reflux temperature, obtaining a pyrazoltisamide of the formula MB, and then this pyrazolthiosamide of the formula MB is subjected to interaction with a boronic acid derivative of the formula MI in the presence of a palladium catalyst of the type Pa(P(phenyl)z)y, ko Pa(P(phenyl)»z)SiIz, RasSi»oarr, Raz(avra)z, Rya(OAs)», RAA(OAs)oZorto-tolyl)zR , RY(OAs/arry, RY(RISM)2SIO/RAzAv,

RaYa(SNUSM)»SI», Razh(ava)»z/P(tert-butyl)z, RYA(OAs)P(TRet-butyl)biphenyl, RaYa(OAsO»/TRRTBZ, RaOASsS)/Psuz, in Ra( OAc)P(O-iso-Pg)z, OA(OAc)o/2-dimethylamino-2-dicyclohexylphosphinobiphenyl,

PaYa(OAc)/2-dimethylamino-2'"-di-tert-butylphosphinobiphenyl, PaYa(OAc)oMorto-biphenyl)P(cyclohexyl)", in a solvent of the type 1,2-dimethoxyethanate/water, DMF, DMA, THF/ water, dioxane/water, benzene, toluene, xylene, etc., and bases such as sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium phosphate, triethylamine, sodium hydroxide, sodium ethylate, sodium tert-butylate, silver oxide , barium carbonate, 65 potassium fluoride or cesium fluoride at a temperature from 0oC to the reflux temperature.

The invention also relates to compounds of the formulas Ma and Mb, in which

Ku, B" and X have the values specified for formula I, and K.; means halogen, preferably chlorine, bromine or iodine.

Compounds of formula IM are known from the literature or can be obtained according to reaction scheme 2.

Scheme 2; 1) n-Vii; 2) 8V (Ok).

Kk, x.---B2NNNNnNnnNn - Won),

I am

Hey V! solvent: THF M peren OO

MO, mo, x (X. x halogen) 2

Restoration

Well/catalyst (ROD/S. Ka-nickel Raney) or rieprtchnnnnny and CH, C ge/CH, CoOH vil CT to the temperature of dephlegmation solvent THF, alcohols, aoda M nem

Pyrazoles of formula I! are known from the literature or can be obtained according to reaction scheme 3.

Scheme 3: s o o) ' V.,-- ok ok osi i.soso Pyridim or infa base 2 -y shshshkshK-y Kaya 7 - 5 «- - 6 « « I Zh («- Z I «I oo yo With the 2nd solvent: SIS, or SN.SI.

That is from 1"C to the temperature Kk, with dephlegmation o

AND

K i C.-Cv-alkyl or benzyl | noM-MNA, is) - mono o

Kk, soon shk v. | Shk

Zh- Me, Myu in -- - - 6 ( - 6 "w 3 M | co-solvent: naprikal, alcohols M | 2 in. "M T " from 02С to the temperature of "M n dephlegmation

In, Kk, "

When creating the invention, it was unexpectedly established that the new compounds of formula I from a practical point of view have a very useful range of activities in terms of protecting plants from diseases caused by fungi, as well as bacteria and viruses. "» Compounds of the formula | can be used in the agricultural sector and related industries as active " substances for combating plant pests. The new compounds are characterized by very high activity at low consumption rates, are well tolerated by plants and are safe for the environment. They have very high therapeutic, prophylactic and systemic activity and can be used to protect many cultivated plants. Compounds of the formula | can be used to reduce the number or destroy 2) pests, for example, phytopathogenic microorganisms found on plants or on plant parts (fruits, flowers, leaves, stems, tubers, roots) of various cultures of useful plants, while protection against these microorganisms is also extends to those parts of plants that are formed in a later period. p 50 Compounds of the formula | can also be used as agents for pickling seeds by treating material for plant reproduction, in particular seed material (fruits, tubers, grains) and seedlings of plants (for example, rice), in order to protect them from fungal lesions, as well as from phytopathogenic fungi, that live in the soil.

Compounds of formula I, for example, are effective against phytopathogenic fungi belonging to the 99 following classes: imperfect fungi (e.g.

GF) Segsozroga and AiYCsegpagia) and Vavzidiotusefgez (for example, KPigosiopia, Neptiiiiia, Rissippia). They are also effective against representatives of Azotuseiez classes (for example, Mepishgia and Eguzirpe, Rodozrnaega de Mopiiipia, Opsiptsia) and Ootuseiez classes (for example, Rnuiorpiipoga, Ruipisht, Riaztoraga). Especially high activity was found in relation to true powdery mildew (Eguzirpe spp.). In addition, new compounds of the formula 60 | are effective against phytopathogenic bacteria and viruses (for example, against Hapitopaz spp.,

Rzeidotopaz srr., Egmipia atuiomoga, as well as in relation to the tobacco mosaic virus).

Cultivated plants subject to protection in relation to the diseases indicated in this description, which fall under the scope of this invention, include, for example, the following types of plants: cereals (wheat, barley, rye, oats, rice, corn, sorghum and related crops); beet (sugar beet and fodder beet); grains, because stone and berry crops (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), legumes (beans, lentils, peas, soybeans), oil crops (rapeseed, mustard, poppy, olives, sunflowers, coconuts, castor beans, cocoa beans, peanuts), cucumber plants (pumpkins, cucumbers, melons), fibrous plants (cotton, flax, hemp, jute), citrus crops (oranges, lemons, grapefruits, tangerines), vegetable crops ( spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, sweet pepper), laurel crops (avocado, cinnamon tree, camphor tree) or plants such as tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper , grapes, hops, bananas and natural rubber trees, as well as decorative plants.

Formula compounds ! used in an unmodified form or preferably together with auxiliary substances, which are usually used in the technology of preparation of preparative forms. For this purpose, preparative forms are prepared on their 7/0 basis by known methods, for example, emulsifiable concentrates, coating pastes, ready-to-use solutions that are sprayed or diluted, diluted emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulated, for example, in polymeric substances, forms. Depending on the type of compositions, processing methods such as spraying, misting, dusting, spreading, coating or watering are selected depending on the objectives and /5 prevailing circumstances. The compositions may also include additional auxiliary substances, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, as well as fertilizers, donors of trace elements or other compositions that contribute to the achievement of specific effects.

Suitable carriers and excipients can be solid or liquid and are compounds that are used in the field of preparative forms, for example, natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in UUO 97/33890.

The compounds of formula I are generally applied in the form of compositions and can be applied to the habitat or to the plant to be treated simultaneously or sequentially with other compounds. These additional compounds can be, for example, fertilizers or donors of trace elements or other drugs that affect the growth of plants. They may also be selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several such preparations, if necessary with additional i) carriers, surface-active substances or adjuvants, which facilitate the application, which are commonly used in the industry preparative forms.

Compounds of formula I can be mixed with other fungicides, and in some cases, a synergistic effect can unexpectedly be obtained. Particularly preferred components of such mixtures are azoles, such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxyconazole, and fluquinconazole , flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, "pr tetraconazole, fenbuconazole, metconazole, myclobutanil, pefurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triaddimefon, triadimenol, triflumizole, or triticonazole; pyrimidinylcarbinols such as ancymidol, me ) fenarimol or nuarimol; 2-aminopyrimidines such as bupyrimate, dimethylmol or ethyrimol; morpholines such as iododemorph, fenpropidine, fenpropimorph, spiroxamine or tridemorph; anilinopyrimidines such as cyprodinil, pyrimethanil or mepanipyrim; pyrroles such as fenpiclonil or fludi oxonyl; phenylamides such as benalaxyl, furalaxyl, metalaxyl, K-metalaxyl, ofuras or oxa Dixyl; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole or thiabendazole; dicarboximides such as clozolinate, diclozolin, iprodione, myclozolin, procymidone or vinclozolin; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin p»)c or tifluzamide; guanidines such as guazatin, dodine or iminoctadine; strobilurins, such as azoxystrobin, kresoxim-methyl, methominostrobin, 55ЗЕ-129, methyl-2|((2-trifluoromethyl)pyrid-b-yloxymethyl|-3-methoxyacrylate;» or O-methyloxime of methyl ether 2-(94МКо-methyl- 3-trifluoromethylbenzyl)imino|oxy)-ortho-tolylglyoxylic acid (trifluorooxystrobin); dithiocarbamates such as ferbam, mancoceb, maneb, metiram, propineb, triam, zineb or ciram; M-halomethylthiodicarboximides, such as captafol, captan, dichlofluanid, fluromide, folpet-i or tolifluanid; compounds that contain copper, such as Bordeaux liquid, copper hydroxide, copper oxychloride, copper sulfate, copper oxide(!), mancoper, or copper oxide; nitrophenol derivatives such as dinocab or o-nitrothal-isopropyl; organophosphorus derivatives, such as edifenfos, iprobenfos, isoprothiolane, phosdifen, pyrazofos - or tolclofos-methyl; compounds from various other classes such as acibenzolar-5-methyl, anilazine, blasticidin-5, quinomethionate, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomesin, dicloran, dietofencarb, dimethomorph, o dithianone, etridiazole, famoxadone, phenamidon, fentin, ferimzone , fluazinam, flusulfamide, phenhexamide, se»fosetyl aluminum, himexazole, kasugamycin, metasulfocarb, pencicuron, phthalide, polyoxins, probenazole, propamocarb, pyrochilone, quinoxifen, hintozen, sulfur, triazoxide, tricyclazole, triforin, validamycin, (5)-5- methyl-2-methylthio-5-phenyl-3-phenylamino-3,5-dihydroimidazol-4-one (EPA 407213), 5 Z,o-dichloro-M-(3-chloro-1-ethyl-1-methyl- 2-oxopropyl)-4-methylbenzamide. (KN-7281),

M-allyl-4,5-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MOM 65500), iF) 4-chloro-4-cyano-M,M-dimethyl-5-para-tolylimidazole-1-sulfonamide (IKE- 916), as IM-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AS 382042) or iprovalicarb (52X 722).

A preferred method of applying a compound of formula I or an agrochemical composition that includes at least one of these compounds is foliar application. The frequency of treatments and the consumption rate depend on the risk of infection with the corresponding pathogen. However, the compounds of the formula I can also penetrate into the plant through the roots from the soil (systemic action) when the place of residence of the plant is saturated with a liquid composition or, if the compounds are introduced into the soil in a solid form, for example, in the form of granules (soil application). When cultivating paddy rice, such granules can be applied to a flooded rice field. For the treatment of seed material compounds of the formula | can also be applied to 65 Seeds (coating) either by impregnating the grains or tubers with a liquid fungicide composition or by coating them with a solid composition.

Preparative forms, that is, compositions containing a compound of formula I and, if necessary, a solid or liquid adjuvant, are obtained by a known method, as a rule, by thoroughly mixing and/or grinding the compound with fillers, for example, with solvents, solid carriers and optionally with surfactants (surfactants).

Agrochemical compositions, as a rule, contain from 0.1 to 9Omas. 96, preferably from 0.1 to 9Ubmas. 906 compounds of formula I, from 99.9 to wt. 95, preferably from 99.8 to 5 mass. 95 solid or liquid adjuvant and from 0 to 25 wt. 9o, preferably from 0.1 to 25 mass. 95 surfactants.

Preferable rates of consumption, as a rule, are from 5 g to 2 kg of active substance (d.r.) per hectare (ha), /o preferably from 7Og to kg d.r./ha, most preferably from 20 to bOOg d.r. /Ha. When used for pickling seeds, the rate of consumption is from 1 mg to 1 g of active substance per kg of seeds.

Although concentrated compounds are generally preferred as commercially available compositions, diluted compositions are generally used by the end user.

The invention described above is illustrated by the following examples, which are in no way intended to limit its scope.

Temperatures are in degrees Celsius. The following abbreviations are used:

Idl. means the melting point; iod means boiling point. "'NMR" means nuclear magnetic resonance spectrum. MS means mass spectrum. "90" means mass. 95, unless indicated that the corresponding concentrations are presented in other units.

Example 1 (4-Chlorobiphenyl-2-yl)amide of 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid ko; SOM V,

CC sch te i sn,

The solution containing 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (0.68g) and oxalyl chloride (0.49g) in methylene chloride (30ml) was stirred for 2 hours. at room temperature in the presence of about a catalytic amount of DMF. The resulting solution of hydrogen chloride is then added at 02C to a solution containing 4-chlorobiphenyl-2-ylamine (0.71g) and triethylamine (0.36g) in 15ml of methylene chloride. After removing the solvent using a vacuum created by a water jet pump, the residue is dissolved in ethyl acetate/water. o The ethyl acetate phase is extracted twice with water. After drying the organic phase over Ma 2504, the solvent is distilled off using a vacuum created by a water jet pump, the residue is purified using column chromatography (silica gel; eluent: ethyl acetate/hexane-1:1). 0.8 g of (4-chlorobiphenyl-2-yl)iamide of 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid is obtained in the form of brownish "crystals" with (dl 144-14620.

Example 1 (Suzuki coupling reaction) - 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid c (4-Chlorobiphenyl-2-yl)amide. we EzS SOM

AND; 4

In th; What about sleep c - c «cl 20 A solution containing (2-bromophenyl)amide. 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (0.64 g), 4-chlorobenzeneboronic acid (0.29 g), powdered sodium carbonate (0.25 g) and tetrakis(triphenylphosphine)palladium (0 ,04 g) in 25 bml of 1,2-dimethoxyethane (DME) and 2 ml of water, kept at the temperature of reflux for 20 hours. After cooling, the solvent is removed using a water jet pump vacuum and the residue is dissolved in ethyl acetate/water. The ethyl acetate phase is washed 22 times with water and brine and dried over sodium sulfate. After distilling off the solvent, it is obtained

HF) crude product, which is further purified by column chromatography (silica gel; eluent: ethyl acetate/hexane-1:1) or recrystallized from methyl tert-butyl ether (MTBE). After purification, 0.bg of the product is obtained; (dl 1145-1462.

In a similar way, using the methods described above, the following compounds of the formula I. sova mim ya rov are obtained

Z snz SEZ (|VGIO clear svryu 8513 sbnosoo letlez 613 sen oko mem 7 en senovyui in a dream of a dream vo ov ovo ov ov kyu that sea of snow 2 1sn sen oyu in my dream my dream lo obnaosna sv bo bossa sv kyu oo tolerable sv byu 2 bnosna sv kyu v5-v 125127 clear vovi s with vors ov v o all sen ev sn senses all senovov s zo sni sen yus ovv y ovo ev - va snoosna s sv s vv dbnyusna sv 8 7 oy snosyua sev y, ovo snosyua sv kv speni sensiv sni sn ok h zv 1sna own manifestation

Table 2 . and?

X OO

In! - -I g M g) | eat

M. m - 1

K, syu"

Кк, Уа, УЙ зв Гма, УВИ о ю ов о яю бю ов ооо о ясни snogo 42 1snz ob so zol 8 | obnz oz voo lotlov yaya1snz otv 0101 pet yavo1snz sezstavyui bo 46 snoosniaZ| СЕоН |сССОо ato (bnaosna static yav (bnyusni styan ogo in (bnyusna sv o ) bnyusna ov at 00 ov obnyusnya sv 10 of the main 0000 in rosn update o sna snorovie, ov

I'm going to sleep 000 ve (bnaosna stov

C obnyusn sleep 8000 o (bnyusna o 5,000 va (bnaosna stv in

The owl has its own 1B

Examples of compositions of compounds of the formula

According to the methods described in MUO 97/33890, compositions of compounds of formula I!, such as

Emulsifiable concentrates, solutions, granules, duets and wettable powders.

Biological examples: Fungicidal activity i)

Example B-1: Activity against Rissipia hesopaiia on wheat (brown rust of wheat)

One-week-old Agip wheat plants are treated with the composition of the tested compound (0.0295 active ingredient) in a spray chamber. 1 day after treatment, wheat plants are inoculated by spraying the studied plants with a spore suspension (1 x 1097 uredospores/ml). After incubation for 2 days at 202C and 9595 relative humidity, the plants are kept in a greenhouse for 8 days at 202 and 609b5 relative humidity. Symptoms of the disease are evaluated 10 days after inoculation. --

Compounds from table | showed activity in this study (lesion "20905"). Compounds 1, 2, 5, 6, 17, 22 and 23 almost completely prevented lesions (lesions 0-595). at

Example B-2: Activity against Rhodozryaega Ieisoihisna on apple trees (true powdery mildew of apple trees)

Five-week-old seedlings of apple trees of the Msipiuoz variety are treated with the composition of the tested compound (0.002905 active substance) in a spray chamber. 1 day after treatment, apple plants are inoculated by "shaking plants infected with true apple powdery mildew over the tested plants.

After incubation for 12 days at 22 C and bObo relative humidity and a light regime of 14/10 h. - with (day/night) the signs of the disease are assessed. and Compounds from Table 1 showed activity in this experiment. Compounds 1, 2, 5, 6, 17, 22 and 23 showed high efficacy (2096 lesions).

Example B-3: Activity against Mepitzgia ipaedzaiis on apple trees (apple scab)

Four-week-old seedlings of apple trees of the Msipiozp variety are treated with the composition of the tested compound (0.0295 active substance) in a spray chamber. 1 day after the treatment, apple plants are inoculated by spraying the studied plants with a spore suspension (4x102 conidia/ml). After incubation for 4 days at 2190 and 95965 relative humidity, the plants are kept in a greenhouse for 4 days at 212C and 609b5 relative humidity. After additional incubation for 4 days at 212 and 9595 relative humidity, signs of 1 20 disease are assessed.

The compounds from Table 1 showed high activity in this experiment. Compounds 1, 2, 5, 6, 17, 22 and 23 showed very high efficiency (lesion "209b5).

Example B-4: Activity against Eguzirpe agatipis on barley (true powdery mildew of barley)

One-week-old barley plants of the Ehrgezz variety are treated with the composition of the tested compound (0.0290 active substance 25) in a spray chamber. 1 day after treatment, barley plants are inoculated by

GF) shaking plants infected with true powdery mildew over the tested plants. After incubation in a greenhouse for 6 days at 202С/182С (day/night) and 609o relative humidity, signs of the disease are assessed.

The compounds from Table 1 showed activity in this experiment. Compounds 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (lesions "2096"). bo Example B-5: Activity against Voiguiis sipegea on apple trees (gray rot of apples)

Holes are drilled in apples of the Soidep Oeiiisishyuiz variety and each one is filled with drops of ZOmcl of the composition of the tested compound (0.00295 active substance). In 2 hours after treatment, 500 μl of B. sipegea spore suspension (4 x 109 conidia/ml) are introduced into the treated areas with a pipette. After incubation for 7 days at 22 C in the vegetation chamber 65, the signs of the disease are evaluated.

The compounds from Table 1 showed activity in this experiment. Compounds 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (lesion "10965").

Example B-6: Activity against sipegea on grapes (gray rot of grapes)

Five-week old bunches of Osheae grapes! treated with the composition of the tested compound (0.00295 active substance) in the spray chamber. 2 days after treatment, the grape plants are inoculated by spraying the studied plants with a spore suspension (1 x 1059 conidia/ml). After incubation in a greenhouse for 4 days at 21 C and a relative humidity of 9595, the signs of the disease are assessed.

The compounds from Table 1 showed activity in this experiment. Compounds 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (lesion "10965"). 70 Example B-7: Activity against Vogguiis sipegea on tomatoes (gray rot of tomatoes

Four-week-old tomato plants of the Koieg Spot variety are treated with the composition of the tested compound (0.00290 active substance) in a spray chamber. 2 days after treatment, tomato plants are inoculated by spraying the studied plants with a spore suspension (1x10 5 conidia/ml). After incubation in a vegetative chamber for 4 days at 202C and a relative humidity of 9595, the signs of the disease are evaluated.

The compounds from Table 1 showed activity in this experiment. Compounds 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (lesion "10965).

Example B-8: Activity in relation to Rougeporpnog (hegesis on barley (reticulate spotting of barley)

One-week-old barley plants of the Ehrgezz variety are treated with the composition of the tested compound (0.002905 active substance) in a spray chamber. 2 days after treatment, barley plants are inoculated by spraying the studied plants with a spore suspension (3 x 10 7 conidia/ml). After incubation for 2 days at 209C and a relative humidity of 9595, the plants are kept in a greenhouse for 2 days at 202C and a relative humidity of 60905. Disease signs are assessed 4 days after inoculation.

The compounds from Table 1 showed activity in this experiment. Compounds 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (lesions "2096"). with

Example B-9: Activity against Zeriogia podogyta on wheat (septoriasis of wheat leaves) Ge)

One-week-old Agip wheat plants are treated with the composition of the tested compound (0.0295 active ingredient) in a spray chamber. 1 day after treatment, wheat plants are inoculated by spraying the studied plants with a spore suspension (5 x 102 conidia/ml). After incubation for 1 day at 20 202C and 9595 relative humidity, the plants are kept in a greenhouse for 10 days at 209C and 6O09p relative humidity. Symptoms of the disease are evaluated 11 days after inoculation. is)

Compounds from table | showed activity in this experiment. Compounds 1, 2, 5, 6, 17, 22 and 23 showed high "- efficiency (lesion "2096). co

Claims (10)

The formula of the invention is 1. Pyrazolcarboxamide of the formula that "zh ee Fe 5 y y I" MN tire - 45 in. o ha - where X means oxygen; 1 50 Ku means C.4-Szalkoxy-C.4-Szalkyl or C.-Szahaloalkyl-C 4-Szalkyl; RE" means S.-Szhaloalkyl; and c" Kz means fluorine, chlorine or bromine; or in which X is sulfur and Ku is C.sub.1-C alkyl, C.sub.3-C.haloalkyl, C.sub.4-C.sub.alkoxy-C.sub.-C.sub.alkyl or C.4-C.sub.4-C.sub.haloalkyl-C.sub.1-S.sub.alkyl; 99 RE" means S.-Szhaloalkyl; and HF) Ez means halogen. 2. The compound of the formula | according to claim 1, in which X means sulfur, K. means S.-Szalkil; and Kz means fluorine, chlorine or bromine. 60 3. The compound of formula I according to claim 2, in which Bo stands for CE", Sen, SEN", SER»SE», SS», СНоСЕ», СНоССИ» or СЕРоСЕ»оСЕ in. 4. Compound of the formula | according to claim 1, in which X represents sulfur; Ku stands for C 1 -C 3 -Alkoxy-C 4 -C 3 -Alkyl or C 4 -C 3 -Alkyl -C 4 -C 3 -Alkyl; and because Ez means fluorine, chlorine or bromine. 5. The compound of formula I according to claim 1, in which X represents sulfur; Ku means СНз or СНоОСН"; K" means CEz, SEN or SEN". 6. The compound of formula I according to claim 5, in which K. means СНу», and Ko means -СЕз. 7. The compound of the formula | according to claim 1, selected from the group that includes: (4-bromobiphenyl-2-yl)amide. 1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid 70, (4-iodobiphenyl-2-yl)amide. 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid, (4-chlorobiphenyl-2-yl)amide. 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid, (4-fluorobiphenyl-2-yl)amide. 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid, (4-bromobiphenyl-2-yl)amide. 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid and (4-iodobiphenyl-2-yl)amide. 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid. 8. The method of obtaining compounds of formula I, which involves the interaction of the starting products in accordance with a) the scheme of E e , SOS vosh, or sva sch Psiva or SHI M em - M. (8) i (osa Y t K, Kk. r E v nd . - R.v. or Laveson's reagent c) and" solvent toluene, THF, dioxane from 0" to the temperature M of deflagration | | N - - :;; -shfshayaalsh shvu llnnonyazhj l lshlshl 5 -oyu ly f« n« (95) | IV R, - c and where X, Ku, K» and Kz have the values specified for the formula | in claim 1; or c» b) according to scheme F) name) 60 b5 or V sosi o /nm e M Y | Hn pc Kk, IM - in, vistvii ee " on lu n. m I! p aa 2 v. Kk. 170 TI o I E system of "Ro-catalyst" MI solvent, | | H base M. Y F Ha 5-0. von, V. M Ra c) according to the scheme and sosi nm o and Z r M | And (8) tm Kk, And | H - 33 -----7--А-Д--йА-77- E vi stevia av, tm ' V i viii aa | cha s PI v, oyu v "- Zh o M Zo R.v or Laveson's reagent | | nn - ----5th- M. eE Y m" Kk, " system of "Rocatapizer" in s solvent, Z . base E i? --shzh - - i - - -- i l--zhl -4 -- - shf6yo II KI Ra V(on;, -m FI V. M | Iv (95) Kk. - with c 20 where Ku, K» and Kz have the values specified for the formula | in claim 1, and Ka means chlorine, bromine or iodine. 9. A composition for combating microorganisms and preventing their attack and damage to plants, in which the active substance is a compound according to claim 1 in combination with a suitable carrier. 10. The method of combating phytopathogenic microorganisms or preventing their damage to cultivated plants by applying the compound of the formula | according to claim 1 for plants, their parts or places of their growth. 59 11. Compound of formula M; (M) o x name) E yu IV ZM Kk, KE, be where X means oxygen; Ku means C.4-Szalkoxy-C.4-Szalkyl or C.-Szahaloalkyl-C 4-Szalkyl; or wherein X is sulfur; Ku means C.sub.1-Salkyl, C.sub.1-S.haloalkyl, C.sub.1-S.sub.4-C.sub.4-S.sub.alkyl or C.sub.-S.sub.1-S.sub.4-C.sub.4-S.sub.alkyl; RE" means S.-Szhaloalkyl; and Ku stands for chlorine, bromine, or iodine. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2005, M 6, 15.06.2005. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. s shchi 6) so IS) "- so i - - with . and? -I (95) - c 50 syu» ime) 60 b5