Pyrazolcarboxamide and pyrazolthioamide derivatives as fungicides

FIELD: organic chemistry, fungicides, agriculture.

SUBSTANCE: invention describes pyrazolcarboxamide of the formula (I) wherein if X means oxygen atom (O) then R1 represents (C1-C3)-alkoxy-(C1-C3)-alkyl; R2 means (C1-C3)-halogenalkyl; R3 means fluorine (F), chlorine (Cl) or bromine atom (Br), and if X means sulfur atom (S) then R1 means (C1-C3)-alkyl; R2 means (C1-C3)-halogenalkyl; R3 means halogen atom. Also, invention describes a method for preparing compounds of the formula (I), a composition for control of microorganisms and prevention for their attack and damage of plants, and a method for control of phytopathogen organisms, and compound of the formula (V) wherein X means sulfur atom (S); R1 means (C1-C3)-alkyl; R2 means (C1-C3)-halogenalkyl; R3 means chlorine, bromide or iodine atom. Invention provides control and prevention in infection of plants with phytopathogenic microorganisms - fungi in agriculture and horticulture.

EFFECT: valuable agricultural properties of compounds.

9 cl, 4 tbl, 12 ex

 

The present invention relates to new pyrazinecarboxamide and pyrazolidine, which have antibacterial activity, in particular fungicidal activity. The invention also relates to compounds, to agrochemical compositions which contain as active ingredient at least one of these new compounds, obtaining these compositions and the use of active ingredients or compositions in agriculture and horticulture for fighting or preventing infestation of plants by phytopathogenic microorganisms, especially fungi.

Pyrazolecarboxylate of the present invention have the formula I

where

X denotes oxygen or sulphur,

R1represents C1-C3alkyl, C1-C3haloalkyl,1-C3alkoxy-C1-C3alkyl or C1-C3haloalkoxy-C1-C3alkyl;

R2represents C1-C3haloalkyl; and

R3denotes halogen.

With the invention it has been unexpectedly found that the compounds of formula I have improved biological properties, which makes them more acceptable for practical application in agriculture and horticulture.

If in the compounds of formula I are asymmetric carbon atoms is, these compounds are optically active form. The invention relates to the pure isomers, such as enantiomers and diastereoisomers, as well as all possible mixtures of isomers, such as mixtures of diastereomers, racemates or mixtures of racemates.

In the context of the present description, the alkyl means methyl, ethyl, n-propyl and isopropyl. Is understood that the alkyl, as part of other radicals, such as alkoxyalkyl, haloalkyl or haloalkoxy has the above values. The term "halogen" is usually interpreted to mean fluorine, chlorine, bromine or iodine, preferred are fluorine, chlorine or bromine. Assume that the halogen, as part of other radicals, such as haloalkyl or haloalkoxy has the above values. Typical alkoxyalkyl radicals include methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl and methoxypropyl. Typical haloalkaline radicals include pharmacokinetic, diplomatically, trifloromethyl, 2,2,2-triptracker, 3-chloropropoxy, 2,2,3,3,3-pentafluoropropanol, 2,2,2-triptracker and cryptomaterial.

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

Another preferred group of compounds of formula I are compounds in which X denotes the ERU (subgroup B).

In subgroups a and B preferred are compounds in which

R1represents C1-C3alkyl; or

R1stands With1-C3alkoxy-C1-C3alkyl or C1-C3haloalkoxy-C1-C3alkyl;

R2represents C1-C3haloalkyl; or

R2means CF3, CF2H, CFH2, CF2Cl, CF2CF3, CCl3CH2CF3CH2CCl3or CF2CF2CF3; and

R3denotes a fluorine, chlorine or bromine (subgroups AB and BG).

In the subgroup And preferred are compounds in which

R1represents C1-C3alkyl;

R2represents C1-C3haloalkyl; and

R3denotes a fluorine, chlorine or bromine (subgroup A1).

In the subgroup A1 of the most preferred are the compounds of formula I, in which

R2means CF3, CF2H, CFH2, CF2Cl, CF2CF3, CCl3CH2CF3CH2CCl3or CF2CF2CF3(subgroup A2).

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

R1represents C1-C3haloalkyl;

R2represents C1-C3haloalkyl; and

R3denotes a fluorine, chlorine or bromine (subgroup A3).

In the subgroup as well As the preferred are the compounds of formula I, in which

R1stands With1-C3alkoxy-C1-C3alkyl or C1-C3haloalkoxy-C1-C3alkyl;

R2represents C1-C3haloalkyl; and

R3denotes a fluorine, chlorine or bromine (subgroup A4).

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

R1represents C1-C3alkyl;

R2represents C1-C3haloalkyl; and

R3denotes a fluorine, chlorine or bromine (subgroup B1).

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

R2means CF3, CF2H, CFH2, CF2Cl, CF2CF3, CCl3CH2CF3CH2CCl3or CF2CF2CF3(subgroup B2).

In the subgroup B is also preferred are the compounds of formula I, in which

R1represents C1-C3haloalkyl;

R2represents C1-C3haloalkyl; and

R3denotes a fluorine, chlorine or bromine (subgroup B3).

In addition, in the subgroup B is also preferred are the compounds of formula I, in which

R1represents C1-C3alkoxy-C1-C3alkyl or C1-C3haloalkoxy-C1-C3alkyl;

R2represents C1-C3haloalkyl; and

R3the convoy is achet fluorine, chlorine or bromine (subgroup B4).

The most preferred compounds in the subgroup AB are compounds in which

R1denotes CH3or CH2OCH3; and

R2means CF3, CF2H or CFH2(subgroup b).

In the subgroup In the most preferred are compounds in which

R1denotes CH3; and

R2means CF3(subgroup B1).

Another preferred group are compounds of the subgroup BG, in which

R1denotes CH3or CH2OCH3; and

R2means CF3, CF2H or CFH2(subgroup D).

In the subgroup G most preferred are compounds in which

R1denotes CH3; and

R2means CF3(subgroup G1).

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

Scheme 1

The pyrazole carboxylic acid of formula II is subjected to interaction with an activating agent such as thionyl chloride, pentachloride phosphorus or oxalicacid, in the presence of a solvent at a temperature of from 0°to the temperature of reflux distilled, and carry out the reaction for 30 min - 24 h, obtaining the corresponding acid chloride. Typical solvents are toluene, benzene, XI is the ol, hexane, cyclohexane, chloroform or methylene chloride. The resulting acylchlorides formula III, as a rule, do not release. New carboxamide formula Ia is preferably produced by interaction of the activated carboxylic acid of formula III with an aromatic amine of the formula IV in the presence of a solvent type, toluene, benzene, xylene, hexane, cyclohexane, chloroform or methylene chloride in the presence of an acid binding agent type of triethylamine, the Foundation Hunya, sodium carbonate, potassium carbonate or sodium bicarbonate at a temperature of from 0°to the temperature of reflux distilled. Pyrazolidone formula Ib is obtained by interaction pyrazolecarboxylate Ia with pentasulfide phosphorus or reagent Lawesson in solvent type dioxane, tetrahydrofuran or toluene at temperatures from 0°to the temperature of reflux distilled. Preferably the entire sequence of reactions is depicted in figure 1, is carried out in the same vessel.

The compounds of formula I can also be obtained according to the following reaction scheme 1A.

Scheme 1A

agent VI is a

Obtained "in situ" the pyrazole acid chloride of the carboxylic acid of formula III is subjected to interaction with ortho-galazalinum-phenylamine in the presence of a solvent type, toluene, benzene, KS is Lola, hexane, cyclohexane, THF, chloroform or methylene chloride and in the presence of a base type sodium carbonate, sodium bicarbonate, potassium carbonate, base Hunya, triethylamine or pyridine at temperatures between 0°to the temperature of reflux distilled. Received pyrazolecarboxylate formula Va is subjected to interaction with para-substituted phenylboronic acid (VI) in the presence of a palladium catalyst of the type Pd(P(phenyl)3)4Pd(P(phenyl)3)Cl2, PdCl2dppb, Pd2(dba)3Pd(OAc)2Pd(OAc)2/(ortho-tolyl)3P, Pd(OAc)2/dppf, Pd(PhCN)2Cl2/Ph3As, Pd(CH3CN)2Cl2Pd2(dba)3/P(tert-butyl)3Pd(OAc)2/P(tert-butyl)2biphenyl, Pd(OAc)2/TPPTS, Pd(OAc)2/DCS3Pd(OAc)2/P(O-ISO-Pr)3Pd(OAc)2/2-dimethylamino-2'-dicyclohexylthiourea, Pd(OAc)2/2-dimethylamino-2'-di-tert-butylphosphine, Pd(OAc)2/(ortho-biphenyl)P(cyclohexyl)2in the solvent-type 1,2-dimethoxyethane/water, DMF, DMA, THF/water, dioxane/water, benzene, toluene, xylene, etc. and the Foundation of the type of sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium phosphate, triethylamine, sodium hydroxide, ethylate sodium tert-butyl sodium, silver oxide, barium carbonate, potassium fluoride or cesium fluoride at a temperature of from 0°With up to tempera is URS reflux distilled.

Pyrazolidone formula Ib is obtained by processing pyrazolecarboxylate formula Va R2S5or reagent Lawesson in solvent type dioxane, tetrahydrofuran or toluene at temperatures from 0°to the temperature of reflux distilled getting pyrazolidone formula Vb, and then this pyrazolidone formula Vb is subjected to interaction with the derived Bronevoy acid of formula VI in the presence of a palladium catalyst of the type Pd(P(phenyl)3)4Pd(P(phenyl)3)Cl2, PdCl2dppb, Pd2(dba)3Pd(OAc)2Pd(OAc)2/(ortho-tolyl)3P, Pd(OAc)2/dppf, Pd(PhCN)2Cl2/Ph3As, Pd(CH3CN)2Cl2Pd2(dba)3/P(tert-butyl)3Pd(OAc)2/P(tert-butyl)2biphenyl, Pd(OAc)2/TPPTS, Pd(OAc)2/DCS3Pd(OAc)2/P(O-ISO-Pr)3Pd(OAc)2/2-dimethylamino-2'-dicyclohexylthiourea, Pd(OAc)2/2-dimethylamino-2'-di-tert-butylphosphine, Pd(SLA)2/(ortho-biphenyl)P(cyclohexyl)2in the solvent-type 1,2-dimethoxyethane/water, DMF, DMA, THF/water, dioxane/water, benzene, toluene, xylene, etc. and the Foundation of the type of sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium phosphate, triethylamine, sodium hydroxide, ethylate sodium tert-butyl sodium, silver oxide, barium carbonate, potassium fluoride or cesium fluoride at a temperature is t 0° With up to the temperature of reflux distilled.

The invention relates also to compounds of formulas Va and Vb, in which R1, R2and X have the meanings indicated for the formula I, a R4denotes halogen, preferably chlorine, bromine or iodine.

The compounds of formula IV are known from the literature or can be obtained according to reaction scheme 2.

Scheme 2:

The pyrazoles of the formula II are known from the literature or can be obtained according to reaction scheme 3.

Scheme 3:

With the invention it has been unexpectedly found that the new compounds of formula I from a practical point of view have a very valuable range of activities in relation to the protection of plants from diseases caused by fungi and bacteria and viruses.

The compounds of formula I can be applied in the agricultural sector and related fields as active substances for combating plant pests. The new compounds have a very high activity at low application rates, are well tolerated by plants and are safe for the environment. They have a very high curative, preventive and systemic activity and can be used to protect many cultivated plants. The compounds of formula I can be applied to reduce the number or kill pests, for example phytopathogenic microorganisms, which occur on plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) in different crops of useful plants, while protecting against these microorganisms also applies to those parts of plants, which are formed in the later period.

The compounds of formula I can also be used as agents for treating seeds by processing material for breeding plants, particularly seeds (fruit, tubers, grains) and seedlings of plants (e.g. rice), to protect them from fungal infections, as well as from soil pathogenic fungi.

The compounds of formula I, for example, are effective against phytopathogenic fungi belonging to the following classes: imperfect fungi (for example, Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (for example, Rhizoctonia, Hemileia, Puccinia). They also have efficacy against members of the class Ascomycetes (for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and class Oomycetes (for example, Phytophthora, Pythium, Plasmopara). Especially high activity was observed against powdery mildew (Erysiphe spp.). In addition, the new compounds of formula I are effective against phytopathogenic bacteria and viruses (for example, against Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, and is also against tobacco mosaic virus).

Be protected against specified in this description of the diseases of cultivated plants, which fall under the scope of the present invention include, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related crops); beet (sugar beet and fodder beet); pome fruit, stone fruit and berries (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olive, sunflower, coconut, castor, cocoa beans, groundnuts), cucumber plants (pumpkins, cucumbers, melons), fibre plants (cotton, flax, hemp, jute), citrus crops (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers), Laurel crops (avocado, cinnamon tree, camphor tree), or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamental plants.

The compounds of formula I are used in unmodified form or preferably together with auxiliary substances commonly used in cooking techniques preparative forms. For this purpose, on the basis of the known methods is otomat preparative forms, for example mulgirigala concentrates, covering paste, ready to use sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusty, pellets and encapsulated, for example in polymeric substances form. Depending on the type of compositions, treatment methods, such as spraying, spraying in the form of a mist, dusting, scattering, coating or irrigation, is selected depending on the objectives and the prevailing circumstances. The composition can also include additional excipients, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, as well as fertilizers, micronutrient donors or other compositions that contribute to specific impacts.

Acceptable 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 WO 97/33890.

The compounds of formula I, generally used in the form of compositions and can make the habitat or plant, Podles the General processing, simultaneously or sequentially with other compounds. These additional compounds may represent, for example, fertilizers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if necessary with further carriers, surfactants or conducive to the application of adjuvants commonly used in the field of preparative forms.

The compounds of formula I can be mixed with other fungicides, in some cases, unexpectedly can be obtained a synergistic effect. Particularly preferred components of such mixtures are azoles such as azaconazole, bitertanol, propiconazol, difenoconazol, diniconazole, tsyprokonazolu, epoxiconazol, Fluconazol, flusilazol, flutriafol, hexaconazole, imazalil, kabekona, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, peyratout, penconazole, bromuconazole, pirivenas, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinylidene, such as ancymidol, fenarimol or nuarimol; 2-aminopyrimidine, such as bupirimate, dimethirimol or ethirimol; Mohali is s, such as dodemont, fenpropidin, fenpropimorph, spiroxamine or tridemorph; anilinopyrimidines, such as cyprodinil, Pyrimethanil or mepanipyrim; pyrrole, such as fenpiclonil or fludyoksonil; phenylamide, such as benalaxyl, parallaxis, metalaxyl, R-metalaxyl, operas or oxadixyl; benzimidazole, such as benomyl, carbendazim, dibakar, fuberidazole or thiabendazole; dicarboximide, such as chlozolinate, diplozoon, iprodion, mickleton, procymidon or vinclozolin; carboxamide, such as carboxin, fanforum, flutolanil, mepronil, oxycarboxin or leflunamide; guanidine, such as guazatine, Dodin or iminoctadine; strobilurin, such AZOXYSTROBIN, kresoxim-methyl, metamyosyn, SSF-129, methyl-2[(2-trifluoromethyl)pyrid-6-intoximeter]-3-ethoxyacrylate or On-methyloxime methyl ester 2-[α{[(α-methyl-3-trifloromethyl)imino]oxy}-ortho-cholylglycine acid (triperoxonane); dithiocarbamate, such as ferbam, MANCOZEB, MANEB, metiram, propineb, cream, zineb or Tsira; N-holomediterranean, such as captafol, Captan, dichlofluanid, pluromed, folpet or tolyfluanid; copper compounds such as Bordeaux liquid, copper hydroxide, copper oxychloride, copper sulphate, copper oxide(I), marcopper or oxen copper; NITROPHENOL derivatives, such as dinocap or nitrates-isoprop is l; organophosphorus derivatives, such as edifenphos, iprobenfos, isoprothiolane, forgiven, pyrazophos or tolclofos-methyl; compound different from other classes, such as acibenzolar-3-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, CHLOROTHALONIL, having cymoxanil, Dylan, dilamtin, dicloran, dietphenterm, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, verison, fluazinam, glucolipid, fenhexamid, fosetyl aluminum, hymexazol, kasugamycin, metasurfaces, pencycuron, phtalic, polyoxin, provenzal, propamocarb, pyroxylin, jenoxifen, hintzen, sulfur, triazoxide, tricyclazole, triforine, validamycin, (S)-5-methyl-2-methylthio-5-phenyl-3-phenylamino-3,5-dihydroimidazole-4-one (RPA 407213), 3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281), N-allyl-4,5-dimethyl-2-trimethylsilylmethyl-3-carboxamide (MON 65500), 4-chloro-4-CYANOGEN-N,N-dimethyl-5-para-tolylimidazo-1-sulfonamide (IKF-916), N-(1-cyan-1,2-dimethylpropyl)-2-(2,4-dichlorphenoxy)propionamide (AC 382042) or iprovalicarb (SZX 722).

The preferred method of making the compounds of formula I or agrochemical composition comprising at least one of these compounds is the treatment of the leaves. The multiplicity of treatments and the consumption rate depends on the risk of infection by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots and the soil (systemic action) if the feeding habitats of plants with a liquid composition or if compounds applied to the soil in solid form, for example, in the form of granules (soil application). The cultivation of paddy rice such granules can be made on flooded rice field. For seed treatment of compounds of formula I also can be applied to seeds (coating) either by impregnating the seeds or tubers liquid fungicide composition or by coating them with a solid composition.

Preparative form, i.e. the compositions containing the compound of the formula I and optionally a solid or liquid adjuvant, get known method, typically by thorough mixing and/or grinding the compound with extenders, e.g. solvents, solid carriers and optionally with surface-active substances (surfactants).

The agrochemical compositions usually contain 0.1 to 99 wt.%, preferably from 0.1 to 95 wt.% the compounds of formula I, from about 99.9 to 1 wt.%, preferably from 99,8 to 5 wt.% solid or liquid adjuvant and 0 to 25 wt.%, preferably from 0.1 to 25 wt.% surface-active substances.

The preferred consumption rates generally range from 5 g to 2 kg of active ingredient (A.I.) per hectare (ha), preferably from 10 g to 1 kg A.I/ha, most preferably from 20 to 600 g A.I/ha When used for seed consumption rates range from 10 mg to 1 g of active ve is esta per 1 kg of seeds.

Despite the fact that as provided in the sale of the compositions is typically more preferred concentrated compositions, the end user, as a rule, use a diluted composition.

The above-described invention are illustrated by the following examples, which in no way intended to limit its scope. Temperatures are given in degrees Celsius. The following abbreviations are used: tPLrefers to melting point; tKiprefers to the boiling point. "NMR" refers to a range of nuclear magnetic resonance. MS denotes the mass spectrum. "%" means%by weight, if not specified, the corresponding concentrations are given in other units.

Example 1

(4'-Chlorobiphenyl-2-yl)amide 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid

A solution containing 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (0.68 g) and oxacillin (0,49 g) in methylene chloride (30 ml), stirred for 2 h at room temperature in the presence of catalytic amount of DMF. The resulting solution of the acid chloride is then added at 0°to a solution containing 4'-chlorobiphenyl-2-ylamine (0.71 g) and triethylamine (0.36 g) in 15 ml of methylene chloride. After removal of the solvent using a vacuum created by a water vacuum pump, the residue is dissolved in etelaat the te/water. An ethyl acetate phase is extracted twice with water. After drying the organic phase over Na2SO4the solvent is distilled using a vacuum created by a water vacuum pump, the residue is purified by chromatography on columns (silica gel; eluent: ethyl acetate/hexane=1:1). Obtain 0.8 g (4'-chlorobiphenyl-2-yl)amide 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid in the form of brownish crystals with tPL144-146°C.

Example 1 (reaction mix Suzuki)

(4'-Chlorobiphenyl-2-yl)amide 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid

A solution containing (2-bromophenyl)amide 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (0.64 g), 4-chlorobenzophenone acid (0.29 grams), powdered sodium carbonate (0.25 g) and tetrakis(triphenylphosphine)palladium (0.04 g) in 25 ml of 1,2-dimethoxyethane (DME) and 2 ml of water, maintained at a temperature of reflux distilled within 20 hours After cooling, the solvent is removed using a vacuum created by water-jet pump, and the residue is dissolved in ethyl acetate/water. An ethyl acetate phase is washed twice with water and with brine and dried over sodium sulfate. After distillation of the solvent to obtain the crude product, which is optionally purified using chromatography on columns (silica gel; eluent: ethyl acetate/hexane=1:1) and recrystallized Ismail-tert-butyl ether (MTBE). After cleaning they receive 0.6 g of product; tPL145-146°C.

Similarly, using the methods described above receive the following compounds of formula I.

31
Table 1
Conn.No.R1R2R3XPhys. data, tPL°
1CH3CF3ClO144-146
2CH3CF3FO149-151
3CH3CF3BrO
4CH3CF3IO
5CH3CF2HClO161-162
6CH3CF2NFO144-145
7CH3CF2HBrO
8CH3CF2HI O
9CF3CF3ClO
10CF3CF3FO
11CH3CF2HFO
12CH3CF2HClO
13CF2HCF3FO
14CF2HCF3ClO
15CF2HCF3FO
16CF2HCF3ClO
17CH3CF2CF3FO146
18CH2Och3CF3ClO
19CH2Och3CF3FO
20CH2OCF3CF3ClO
21CH2OCF3CF3FO
22CH3CF3ClS85-86
23CH3CF3FS125-127
24CH3CF3BrS
25CH3CF3IS
26CH3CF2HFS
27CH3CF2HClS
28CH3CF2HBrS
29CH3CF2HIS
30CF3CF3ClS
CF3CF3FS
32CH2OCH3CF3ClS
33CH2OCH3CF3FS
34CH2OCF3CF3ClS
35CH2OCF3CF3FS
36CH3CF2HClS
37CH3CF2NFS
38CH3CF2CF3FS

Table 2

td align="center"> I
Conn. No.R1R2R4XPhys. data, tPL°C
39CH3CF2NClO
40CH3CF2HBrO
41CH3CF2HFO
42CH3CF3ClO120-121
43CH3CF3BrO127-128
44CH3CF3IO176-177
45CH3CF3CF2BrO
46CH2OCH3CF2HClO
47CH2OCH3CF2HBrO
48CH2Och3CF2HIO
49CH2OCH3CF3ClO
50CH2OCH3CF3Br O
51CH2OCH3CF3IO
52CH3CF2HClS
53CH3CF2HBrS
54CH3CF2HIS
55CH3CF3ClS107-108
56CH3CF3BrS109-110
57CH3CF3IS98-99
58CH3CF3CF2BrS102-103
59CH2OCH3CF2HClS
60CH2OCH3CF2HBrS
61CH2OCH3CF2HS
62CH2OCH3CF3ClS
63CH2OCH3CF3BrS
64CH2OCH3CF3IS

Examples of compositions of compounds of formula I

According to the methods described in WO 97/33890 receive compositions of compounds of formula I, such as mulgirigala concentrates, solutions, granules, dusty and wettable powders.

Biological examples: Fungicidal activity

Example-1: Activity against Puccinia recondita on wheat (leaf rust of wheat)

A one-week plant wheat cultivar Arina is treated with a composition of the test compound (0.02% of active substance) in the chamber for spraying. After 1 day after treatment of wheat plants inoculant by spraying pilot plant spore suspension (1×105uredospore/ml). After incubation for 2 days at 20°C and 95%relative humidity, the plants kept in the greenhouse for 8 days at 20°C and 60%relative humidity. The symptoms assessed 10 days after inoculation.

Soedinenii table 1 showed activity in this experiment (defeat < 20%). Connection 1, 2, 5, 6, 17, 22 and 23 is almost completely warned defeat (defeat 0-5%).

Example b-2: Activity against Podosphaera leucotricha on Apple trees (powdery mildew of apples)

Five-week Apple varieties Mclntosh is treated with a composition of the tested compounds (0,002% active ingredient) in the chamber for spraying. After 1 day after treatment plants Apple trees inoculant by shaking plants infected with powdery mildew of Apple, on experimental plants. After incubation for 12 days at 22°C and 60%relative humidity and a light regime of 14/10 h (day/night) evaluate the 15 signs of illness.

Compounds from table 1 showed activity in this experience. Connection 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (defeat <20%).

Example b-3: Activity against Venturia inaequalis on Apple trees (Apple scab)

Four weeks Apple varieties Mclntosh treated with the composition of the test compound (0.02% of active substance) in the chamber for spraying. After 1 day after treatment plants Apple trees inoculant by spraying pilot plant spore suspension (4×105conidia/ml). After incubation for 4 days at 21°C and 95%relative humidity, the plants kept in the greenhouse for 4 days at 21°C and 60%relative humidity. On the Le additional incubation for 4 days at 21° C and 95%relative humidity assess the symptoms of the disease.

Compounds from table 1 showed high activity in this experiment.

Connection 1, 2, 5, 6, 17, 22 and 23 showed a very high efficiency (defeat <20%).

Example b-4: Activity against Erysiphe graminis on barley (powdery mildew of barley)

Weekly plants of barley varieties Express is treated with a composition of the test compound (0.02% of active substance) in the chamber for spraying. After 1 day after treatment of barley plants inoculant by shaking plants infected with powdery mildew, above the test plants. After incubation in the greenhouse for 6 days 20°/18°C (day/night) and 60%relative humidity assess the symptoms of the disease.

Compounds from table 1 showed activity in this experience. Connection 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (defeat <20%).

Example B-5: Activity against Botrytis cinerea on Apple trees (grey rot of apples)

In apples Golden Delicious drill 3 holes and fill each dropwise 30 μl of the composition of the tested compounds (0,002% active ingredient). After 2 h after treatment in place of processing the pipette contribute 50 μl of a suspension of spores VSEGEI (4×105conidia/ml). After incubation for 7 days at 22°in growth chamber assess the symptom of the disease.

Compounds from table 1 showed activity in this experience. Connection 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (defeat <10%).

Example B-6: Activity against Botrytis cinerea on grapes (grey rot)

Five weeks shank grapes Gutedel is treated with a composition of the tested compounds (0,002% active ingredient) in the chamber for spraying. 2 days after treatment the plants grapes inoculant by spraying pilot plant spore suspension (1×105conidia/ml). After incubation in the greenhouse for 4 days at 21°C and relative humidity of 95% evaluate the signs of the disease.

Compounds from table 1 showed activity in this experience. Connection 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (defeat <10%).

Example B-7: Activity against Botrytis cinerea on tomatoes (grey rot of tomatoes)

Four weeks old plants of tomato varieties Roter Gnom is treated with a composition of the tested compounds (0,002% active ingredient) in the chamber for spraying. 2 days after treatment the plants tomatoes inoculant by spraying pilot plant spore suspension (1×10 conidia/ml). After incubation in a growth chamber for 4 days at 20°C and relative humidity of 95% evaluate the signs of the disease.

Compounds from table 1 showed activity in this experience of Connection 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (defeat <10%).

Example B-8: Activity against Pyrenophora teres on barley net blotch of barley)

Weekly plants of barley varieties Express is treated with a composition of the tested compounds (0,002% active ingredient) in the chamber for spraying. 2 days after processing barley plants inoculant by spraying pilot plant spore suspension (3×104conidia/ml). After incubation for 2 days at 20°C and relative humidity of 95% of the plants kept in the greenhouse for 2 days at 20°C and relative humidity 60% of the Symptoms assessed 4 days after inoculation.

Compounds from table 1 showed activity in this experience. Connection 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (defeat <20%).

Example B-9: Activity against Septoria nodorum on wheat (Septoria leaf blotch of wheat)

A one-week plant wheat cultivar Arina is treated with a composition of the test compound (0.02% of active substance) in the chamber for spraying. After 1 day after treatment of wheat plants inoculant by spraying pilot plant spore suspension (5×105conidia/ml). After incubation for 1 day at 20°C and 95%relative humidity, the plants kept in the greenhouse for 10 days at 20°and 60%of the relative humidity. The symptoms assessed in 11 days after inoculation.

Compounds from table 1 showed activity in this experience. Connection 1, 2, 5, 6, 17, 22 and 23 showed high efficiency (defeat <20%).

Comparative example 1:

When testing evaluated the biological activity of the claimed compounds No. 18, characterized in table 1, and the known compound No. 37, characterized in table 1 (the description of EP 0589301, p.29).

Both compounds have almost identical structure except that in the known compound No. 37 pyrazol ring substituted in position 1 metal group, while the claimed compound No. 18 instead of the specified substituent contains another Deputy ethoxymethylene group (both groups represented a structural formula selected Chernin font). The tests were carried out according to the following procedure:

Action against Plasmopara viticola (downy mildew) on grapes:

Disks cut from the vine leaves were placed in a medium of agar in a multiple-cell tablets (24 cells). Then each plate was treated with a solution of the test compound. Each of the above compounds were tested at various concentrations, which are expressed in Muscat./million and is shown in the table.

After drying, vertannes leaf disks were inoculable spore suspension of the fungus fluffy mold (downy mildew fungus). After an incubation period of 7 days in each tablet was evaluated protective fungicidal activity of the test compounds. The results were expressed in % protective fungicide for each compound at various concentrations.

Table 3
ConnectionConcentration, miscast./million
2006020
Connection # 18 (claimed invention)70700
Connection # 37 (invention)000

Presented in table 3 clearly indicate that the claimed compound No. 18 shows a very high level of antifungal activity against Plasmopara viticola in that time as well-known compound No. 37 completely ineffective in the tested concentrations.

Conclusion:

The above results of biological tests confirm that the claimed compound No. 18 shows an unexpectedly high fungicidal activity compared with the closest analogue described in EP 0589301. Given the similarity of the structures of the studied compounds, it can be argued that what is shown is e superiority of the claimed compounds for fungicidal activity is completely unexpected and could not be predicted in advance by an expert in the field of technology studied the prior art.

Comparative example 2:

When testing evaluated the biological activity of the claimed compounds No. 22, characterized in table 1, and the known compound No. 37, characterized in table 1 (the description of EP 0589301, p.29).

Both compounds have almost identical structure except that in the known compound No. 37 pyrazol ring substituted in position 4 carbonyl fragment, while the claimed compound No. 22 instead of the specified fragment contains a thiocarbonyl fragment (both fragments in the presented structural formulas highlighted in black font). The claimed compound No. 22 can be considered as timidly similar known compounds No. 37. The tests were carried out according to the following procedure:

Action against Botrytis cinerea on tomatoes:

Four weeks old plants of tomato varieties "Roter Gnom" were treated with the drug, prepared on the basis of the test compounds (concentration of active ingredient 0,002%) in the chamber for spraying. Each of the above compounds were tested at various concentrations, which are expressed in Muscat./million and are shown in table. Two days after treatment, the test plants tomatoes were inoculable by spraying a spore suspension (1×105is Onidi/ml). After the incubation in the growth chamber for 4 days at a temperature of 20°C and relative humidity of 95% assessed signs of disease. The results were expressed in % protective fungicide for each compound at various concentrations.

Table 4
ConnectionConcentration, miscast./million
2020,20,02
Compound No. 22 (claimed invention)100807050
Connection # 37 (invention)8070100

Presented in table 4 clearly indicate that the claimed compound No. 22 significantly more active at low concentrations compared with the known from the prior art compound No. 37. In particular, the claimed compound No. 22 shows a very high level of protective fungicide at a concentration of 0.2 miscast./million, that is, when the concentration value which is smaller than the concentrations of 2 miscast./million, which is a known compound No. 37 shows approximately the same level of protective action is Oia. Moreover, compound No. 22 has a protective fungicidal activity against Botrytis cinerea even at very low concentration of 0.02 miscast./million (degree of protection 50%), in contrast to this well-known compound No. 37 completely ineffective at this concentration (degree of protection 0%).

Conclusion:

The above results of biological tests confirm that the claimed compound No. 22 shows an unexpectedly high fungicidal activity compared with the closest analogue described in EP 0589301. Given the similarity of the structures of the studied compounds, it can be argued that such a manifestation of the superiority of the claimed compounds for fungicidal activity is completely unexpected and could not be predicted in advance by an expert in the field of technology who has studied the prior art.

Physico-chemical constants of some of the claimed compounds, see table 1.

Continuation of table 1
Connection # StructureTemperature plavleniya
18150-153°
19148-150°

1. Pyrazolecarboxylate formula I

where X is oxygen;

R1stands With1-C3alkoxy-C1-C3alkyl;

R2represents C1-C3haloalkyl;

R3denotes a fluorine, chlorine or bromine,

or where X denotes sulfur;

R1represents C1-C3alkyl;

R2represents C1-C3haloalkyl;

R3denotes halogen.

2. The compound of formula I according to claim 1, in which X denotes sulfur, and R1stands With1-C3alkyl, and R3denotes a fluorine, chlorine or bromine.

3. The compound of formula I according to claim 2. in which R2means CF3, CF2H, CFH2, CF2CF3, CCl3CH2CF3CH2CCl3or CF2CF2CF3.

4. The compound of formula I according to claim 1, in which X denotes sulfur, and R1denotes CH3and R2means CF3, CF2H and CFH2.

5. The compound of formula I according to claim 4, in which R1denotes CH3and R2means CF3.

6. The method of obtaining compounds of formula I, including interaction of the initial products according to the scheme

where R1, R2and R3have the values listed DL the formula I in claim 1, a R4denotes chlorine, bromine or iodine.

7. Composition for combating microorganisms and prevent their attacks and defeats of their plants, in which the active ingredient is a compound according to claim 1 in combination with an acceptable carrier.

8. A method of combating phytopathogenic organisms or preventing the destruction of their cultural plants by applying a compound of formula I according to claim 1 to the plants, their parts or their habitat.

9. The compound of formula V

where X denotes sulfur;

R1stands With1-C3alkyl;

R2represents C1-C3haloalkyl;

R3denotes chlorine, bromine or iodine.

Priority items:

09.12.1999 according to claim 2 and 3;

14.12.1999 according to claims 1, 7 and 8;

11.11.2000 on claims 4 to 6 and 9.



 

Same patents:

The invention relates to N-piperidino-5-(4-bromophenyl)-1-(2,4-dichlorophenyl)-4-aripirazole-3-carboxamide, its pharmaceutically acceptable salt and solvate, which are strong antagonists of cannabinoid ST1receptors

The invention relates to substituted 1-phenylpyrazol-3-carboxamide formula (Ia) in which R1xis in position 4 or 5 and denotes the group-T-CONRaRbin which T represents a direct bond or (C1-C7-alkylen; NRaRbdenotes a group selected from (a), (b), (C); R5and R6denote, independently of one another, hydrogen, (C1-C6)-alkyl, (C3-C8)-alkenyl or R5and R6together with the nitrogen atom to which they are linked, represent a heterocycle selected from pyrrolidine, piperidine, research, piperazine, substituted in position 4 by Deputy R9; R7denotes hydrogen, (C1-C4)-alkyl or benzyl; R8denotes hydrogen, (C1-C4)-alkyl, or R7and R8together with the carbon atom to which they are attached, form a (C3-C5-cycloalkyl; R9denotes hydrogen, (C1-C4)-alkyl, benzyl or a group-X-NR'5R'6in which R'5and R'6represent, independently from each other, (C1-C6)-alkyl; R10denotes hydrogen, (C1-C4)-alkyl; s= 0-3; t=0-3, provided that (s+t) in the same group greater than or equal to 1; the divalent radicals a and E together with the atom is which in addition, may be substituted by one or more (C1-C4-alkilani; R2xand R3xdenote, independently of one another, hydrogen, (C1-C6)-alkyl, (C3-C8-cycloalkyl, (C3-C8-cyclooctylmethyl provided that R2xand R3xdo not simultaneously denote hydrogen or R2xand R3xtogether form tetramethylene group; and their pharmaceutically acceptable salts

The invention relates to new compounds for combating pests, in particular derivatives carbanilide and fungicide-insecticidal tool based on them

The invention relates to pyrazole derivative of the formula I, where1means the group - NRR1R2or group-OR2, g2- g6the same or different and independently of one another denote hydrogen, halogen, C1-4alkyl, C1-4alkoxyl, trifluoromethyl, or C1-4allylthiourea; w2-w6the same or different and independently of one another denote hydrogen, halogen, C1-4alkyl, C1-4alkoxy or trifluoromethyl, provided that at least one of the substituents g2-g6and one of the substituents w2-w6different from hydrogen; R1means hydrogen or C1-4alkyl; R2- nah3-15-carbocyclic radical, unsubstituted or mono - or multiply substituted WITH1-4by alkyl; R3is hydrogen or the group CH2-R6; R4and R5each independently of one another denote hydrogen or C1-4alkyl; or R4means hydrogen and R5and w6together form an ethylene radical; R6means hydrogen, or when the deputies of the g2g3, g4, g5and/or g6different from1-4of alkyl, R6means hydrogen, C1-4alkyl or C1-5alkoxyl, and their salts

The invention relates to pyrazole derivative of the General formula I

< / BR>
in which R1is phenyl, substituted cyclo(lower)alkyl, hydroxy(lower)alkyl, cyano, lower alkylenedioxy, carboxy, (lower alkoxy)carbonyl group, a lower alkanoyl, lower alkanoyloxy, lower alkoxy, phenoxy or carbamoyl, optionally substituted lower alkyl;

R2is halogen, halo(lower)alkyl, cyano, carboxy, (lower alkoxy)carbonyl group, carbamoyl, optionally substituted by alkyl;

R3is phenyl, substituted lower alkylthio, lower alkylsulfonyl, or lower alkylsulfonyl, provided that when R1is phenyl, substituted lower alkoxy, then R2represents halogen or halo(lower)alkyl,

or their pharmaceutically acceptable salts

FIELD: organic chemistry, insecticides, chemical technology.

SUBSTANCE: invention describes derivative of 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole of the general formula (1): wherein A means: (A-1) , (A-2) , (A-3) and (A-4) and wherein X represents C-halogen; R1 represents (C1-C4)-alkyl group or halogen-(C1-C4)-alkyl group; A represents any group among (A-1) - (A-4) wherein R4 represents hydrogen atom or (C1-C4)-alkyl group; n = 0, 1 or 2 under condition that R1 represents halogen-(C1-C4)-alkyl group with exception for perhalogenalkyl group when A represents (A-1) and n = 0, and that n doesn't equal 0 when A represents (A-4). Also, invention describes derivative of pyrazole of the formula (2): wherein A means: (A-1) and Y means: (Y-1) , (Y-2) and (Y-3) wherein X, R2, R3 and R4 have values given above; R5 represents hydrogen atom; A represents (A-1); Y means any group among (Y-1) - (Y-3); Z represents halogen atom that are intermediate compounds used for synthesis of the compound (1). Invention describes methods for preparing compounds of the formula (1) and (2) and insecticide comprising compound of the formula (1) as an active component. Insecticide shows high systemic activity, high safety and reduced harmful effect on environment in vicinity areas of its applying.

EFFECT: improved methods for preparing, valuable insecticide properties of compound.

11 cl, 9 tbl, 19 ex

FIELD: organic chemistry, agriculture, fungicide compositions.

SUBSTANCE: invention relates to compounds of formula I

, wherein R1 and R2 are hydrogen or C1-C4-alkyl; X is C3-C8-cycloalkyl, phenyl or styryl, as well as method for production thereof and fungicide composition containing the same. Compounds of present invention have fungicide activity and are useful in effective controlling of deleterious fungi.

EFFECT: compounds and fungicide composition with improved effectiveness.

3 cl, 2 tbl, 4 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: claimed mixture from herbicides and antidotes contains (A) herbicidically active substance based on phenylsulfonylureas of formula I and salts thereof (in formula R1 is hydrogen or C1-C6-alkyl; R2 is C1-C3-alkyl; R3 is C1-C3-alkoxy; R4 is hydrogen or C1-C4-alkyl; Hal is fluorine, chlorine, bromine, or iodine); and (B) antidote of formulae II or III , wherein X is hydrogen, halogen, C1-C4-alkyl; C1-C4-alkoxy, nitro or C1-C4-haloalkyl; Z is hydroxyl, C1-C8-alkoxy, C3-C6-cycloalkoxy, C2-C8-alkenyloxy, C2-C8-alkynyloxy; R5 is C1-C2-alkandiyl chain optionally substituted with one or two C1-C4 alkyl residues or (C1-C3-alcoxy)carbonyl; W is bivalent heterocyclic residue; n = 1-5; in weight ratio herbicide/antidote of 100:1-1:100. Also disclosed is method for protection of cultural plants against phytotoxic side effect of herbicidically active substance of formula I. Claimed method includes antidote application of formulae II or III on plant, plant parts, plant seeds or seeding areas before or together with herbicidically active substance in amount of 0.005-0.5 kg/hectare in weight ratio of 100:1-1:100.

EFFECT: mixture for effective selective weed controlling in cultural plant, particularly in maize and grain cultures.

8 cl, 2 ex, 7 tbl

The invention relates to the field veterinariia and is intended for combating parasites in animals

The invention relates to a means for protection against phyto-toxic side effects of herbicidal

The invention relates to biphenylamine General formula I

< / BR>
and their salts, where R1means H or F; R2means H, halogen, C1-C4-alkyl; R3means of CH3; connection I use for combating phytopathogenic fungi

FIELD: organic chemistry, agriculture.

SUBSTANCE: claimed mixture from herbicides and antidotes contains (A) herbicidically active substance based on phenylsulfonylureas of formula I and salts thereof (in formula R1 is hydrogen or C1-C6-alkyl; R2 is C1-C3-alkyl; R3 is C1-C3-alkoxy; R4 is hydrogen or C1-C4-alkyl; Hal is fluorine, chlorine, bromine, or iodine); and (B) antidote of formulae II or III , wherein X is hydrogen, halogen, C1-C4-alkyl; C1-C4-alkoxy, nitro or C1-C4-haloalkyl; Z is hydroxyl, C1-C8-alkoxy, C3-C6-cycloalkoxy, C2-C8-alkenyloxy, C2-C8-alkynyloxy; R5 is C1-C2-alkandiyl chain optionally substituted with one or two C1-C4 alkyl residues or (C1-C3-alcoxy)carbonyl; W is bivalent heterocyclic residue; n = 1-5; in weight ratio herbicide/antidote of 100:1-1:100. Also disclosed is method for protection of cultural plants against phytotoxic side effect of herbicidically active substance of formula I. Claimed method includes antidote application of formulae II or III on plant, plant parts, plant seeds or seeding areas before or together with herbicidically active substance in amount of 0.005-0.5 kg/hectare in weight ratio of 100:1-1:100.

EFFECT: mixture for effective selective weed controlling in cultural plant, particularly in maize and grain cultures.

8 cl, 2 ex, 7 tbl

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