O-cyclopropylcarboxanilides and application thereof as fungicides

FIELD: chemistry.

SUBSTANCE: the said invention relates to о-cyclopropylcarboxanilides of general formula (I) , where Het stands for pyrrolyl, pyrazolyl or thiazolyl, each being substituted with R4, R5 and R6 groups; R1, RЗ stand for hydrogen or halogen; R3 stands for С2-12 alkyl, С3-12 cycloalkyl, С3-12 cycloalkyl substituted with С1-3 alkyl, phenyl or halogen-substituted phenyl; and R4, R5 and R6 are independently selected from hydrogen, halogen, С1-4 alkyl or С1-4 haloalkyl, provided that at least one of R4, R5 and R6 is other than hydrogen. Intermediates used in synthesis of I, as well as antimicrobial composition and methods for control and prevention of cultivated plants' infection with phytopathogenic microorganisms are described.

EFFECT: compounds can be used to protect plants from being infected with phytopathogenic microorganisms.

8 cl, 7 tbl, 12 ex

 

This invention relates to novel ortho-substituted cyclopropanecarboxamide, which have antibacterial activity, in particular fungicidal activity. The invention relates also to receive data connections to new intermediate products used in the preparation of these compounds, to agricultural compositions which include at least one of the new compounds as active ingredient, for receiving the said compositions and to the use of the active ingredients or compositions in agriculture or horticulture for fight or prevent contamination of vegetation by phytopathogenic microorganisms, preferably fungi.

In ERA, JP06220035 and JP02129171 describes some ortho-unsubstituted cyclopropanecarboxamide.

This invention provides a compound of formula (I):

where Het represents a 5 - or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulfur, where the ring is substituted by groups R4, R5and R6; R1represents hydrogen or halogen; R2represents hydrogen or halogen; R3represents an optionally substituted C2-12alkyl, optionally substituted C2-1 alkenyl, optionally substituted C2-12quinil, optionally substituted C3-12cycloalkyl, optionally substituted phenyl or optionally substituted heterocyclyl; and R4, R5and R6independently selected from hydrogen, halogen, cyano, nitro, C1-4of alkyl, C1-4halogenoalkane,1-4alkoxy(C1-4)alkyl, and C1-4halogenoalkane(C1-4)alkyl, provided that at least one of R4, R5and R6is not hydrogen.

Halogen represents fluorine, chlorine or bromine.

Each alkyl fragment is a fragment with a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or neopentyl.

Each optional substituents on the alkyl fragment, when present, is independently selected from halogen, hydroxy, cyano, C1-4alkoxyl(=O) -, formyl, nitro, C1-4alkoxy, C1-4halogenoalkane,1-4alkylthio,1-4allogenicity, NS(OR')=N and R R"NN=C(H); where R' and R" independently represent hydrogen or C1-4alkyl.

Alkanniny and alkynylaryl fragments may represent fragments with a straight or branched chain. Alkeneamine fragments, when appropriate, can have (E)- or (Z)-ConfigurationProperty are vinyl, allyl and propargyl.

Each optional substituents on alkenyl or quinil, when present, is independently selected from the optional substituents listed above for the alkyl fragment.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Each optional substituents on cycloalkyl, when one is present, is independently selected from C1-3the alkyl and optional substituents listed above for the alkyl fragment.

The term "heterocyclyl" refers to non-aromatic or aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms, each independently selected from O, S and N. Examples of such rings include 1,3-DIOXOLANYL, tetrahydrofuranyl, morpholinyl, thienyl and furyl.

Each optional substituents on the phenyl or heterocyclyl, when present, is independently selected from C1-6the alkyl and optional substituents listed above for the alkyl fragment. When they are present, the number on the phenyl is up to four optional substituents, each is independently selected.

Each optional substituents on the alkyl fragment, when present, is independently selected from the preferred list, which includes halogen, hydroxy,methoxy, triptoreline, dichloromethoxy, cyano and nitro.

Each optional substituents on alkenyl or quinil, when present, is independently selected from the preferred list, including halogen and cyano.

Each optional substituents on cycloalkyl, when present, is independently selected from the preferred list, including methyl, ethyl, trifluoromethyl, methoxy, triptoreline and cyano.

Each optional substituents on the phenyl or heterocyclyl group, when present, is independently selected from the preferred list, which includes halogen, hydroxy, methoxy, triptoreline, deformedarse and cyano.

Preferably, Het is pyrrolyl, pyrazolyl, thiazolyl, pyridinyl, pyrimidinyl, thiophenyl, furyl, isothiazole or isoxazolyl (more preferably, pyrrolyl, pyrazolyl or thiazolyl), each substituted groups R4, R5and R6.

Preferably, R1and R2independently represent hydrogen or fluorine.

Preferably, R3represents a C2-6alkyl, optionally substituted C3-8cycloalkyl, phenyl, thienyl or furyl.

Preferably, R4, R5and R6independently selected from hydrogen, halogen, C1-4of alkyl, C1-4halogenoalkane and C1-4alkoxy(C1-4)alkyl; in terms of the AI, that at least one of R4, R5and R6is not hydrogen. More preferably, R4, R5and R6independently selected from hydrogen, halogen, methyl,1-2halogenoalkane and methoxymethyl; provided that at least one of R4, R5and R6is not hydrogen.

The compounds of formula (II):

where R3takes the values defined above for the compounds of formula (I)are new compounds and are useful as intermediates in obtaining the compounds of formula (I).

Therefore, another aspect of the present invention is a compound of formula (II), where R3takes the values defined above for the compounds of formula (I).

The compounds of formula (I) and formula (II) may exist in different geometric or optical isomers or tautomeric forms. The invention includes all such isomers and tautomers and mixtures thereof in all ratios, and isotopic forms, such as deuterated compounds.

Compounds are presented below in tables 1-6 illustrate the compounds of this invention.

Table 1 shows the 22 compounds of formula (II), where R3takes the values defined in table 1.

Table X represents the table 2 (when X is 2) and table 3 (when X is equal to 3)

Table 2 represents 80 compounds of formula (Ia):

where R1, R2, R3, R4, R5and R6take the values defined in table 2.

Table 3 represents 80 compounds of formula (Ib)

where R1, R2, R3, R4, R5and R6take the values defined in table 3.

Table 4 presents 50 compounds of formula (Ic):

where R1, R2, R3, R4, R5and R6take the values defined in table 4.

Table 5 represents 54 of the compounds of formula (Id):

where R1, R2, R3and R4take the values defined in table 5.

Table 6 represents 45 of the compounds of formula (Ie):

where R1, R2, R3 and R4take the values defined in table 6.

In this description of the temperature is given in degrees Celsius, "NMR" means a range of nuclear magnetic resonance, "MS" means mass spectrum; and "%" means percent by weight, if appropriate concentrations not specified a different dimension.

In this specification, the following abbreviations are used:

MP - melting point

BP - boiling point

s - singlet

d - doublet

t - triplet

m - multiplet

user. - broadening

DD - doublet of doublets

square - Quartet

ppm - millionths

Table 7 presents the sample the melting temperature and the sample data of NMR spectra obtained using CDCl3as the solvent (unless other terms; if a mixture of solvents, this is indicated as, for example, (CDCl3/d6-DMSO) for some compounds of tables 1-6 (task to present all the characteristic data for all compounds was not intended). Unless otherwise stated, the data refer to a mixture of CIS-/TRANS-isomers of each connection; the connection number that ends with the index "C"refers only to its CIS-isomer, the connection number, which ends in the index "t"refers only to his Proc. of the na-isomer.

Table 7
Connection< / br>
No.
1H NMR: (ppm, multipletness, number N)TPL< / br>
(°C)
1.3from 0.6 to 0.90 (m, 8H) (CIS and TRANS), of 1.02 (d, 6N) (CIS), 1,11 (6N) (TRANS), to 1.48 (m, 1H) (TRANS), of 1.78 (m, 1H) (CIS), 3,83 (s, 4H) (NH2CIS and TRANS), of 6.68 (m, 4H) (CIS and TRANS), 7,0 (m, 4H) (CIS and TRANS).oil
1.50,6-1,1 (m, 6N) (CIS and TRANS), 0,95-101 (DD, N) (CIS and TRANS), 1,25 (m, 2H) (CIS or TRANS), of 1.40 (m, 2H) (CIS or TRANS), of 1.78 (m, 2H) (CIS or TRANS), 3,85 (s, 4H) (NH2CIS or TRANS), 6,70 (m, 4H) (CIS and TRANS), 7,0 (m, 4H) (CIS and TRANS).oil
1.6t0,52 (m, 1H), 0,80 (m, 1H), 0,97 (s, N), a 1.08 (m, 1H), 1.57 in (m, 1H), 3,85 (s, 2H), of 6.68 (m, 2H), 7,0 (m, 2H).oil
S0,01 (m, 2H), 0,11 (m, 1H), 0,22 (m, 1H), 0,58 (m, 1H), 0.69 (m, 1H), 0,85 (m, 1H), 1,67 (m, 1H), 3,75 (s, 2H) (NH2), of 6.49-6,60 (m, 2H), 6,82-7,00 (m, 2H).oil
1.10t0,01 (m, 2H), 0,30 (m, 2H), 0,55 (m, 2H), 0,72 (m, 2H), 1.28 (in m, 1H), 3,70 (s, N)(NH2), 6,45-6,55 (m, 2H), 6,77-6,85 (m, 2H).oil
1.12of 0.75 (m, 4H) (CIS and TRANS),of 0.97 (m, 2H) (CIS and TRANS), 1,3-1,95 (m, 20N) (CIS and TRANS), 3,88 (s, 4H) (CIS and TRANS), of 6.68 (m, 4H) (CIS and TRANS), 7,01 (m, 4H) (CIS and TRANS).oil
1.130,62-to 1.98 (m, N) (CIS and TRANS), 3,80 (s, 4H) (CIS and TRANS), of 6.65 (m, 4H) (CIS and TRANS), 6,97 (m, 4H) (CIS and TRANS).oil
S110-112
1.17t69-70
Sof 1.29 (m, 1H), of 1.52 (m, 1H), measuring 2.20 (m, 1H), 2,42 (m, 1H), 3,55 (s, 2H), 6,50 (d, 1H), 6,65-6,85 (m, 5H), of 6.99 (t, 1H), to 7.09 (d, 1H).oil
1.18t95-97
S60-62
1.22t0,01-0,1 (m, 4H), 0,42 (m, 2H), 0,99 (s, 3H), 1,01 (m, 1H), 1,21 (m, 1H), 3,55 (s, 2H), 6,45 (m, 2H), 6,78 (m, 2H).oil
2.599-102
2.1775-78
2.1874-79
2.23134-136
2.24110-112
2.3388-92
S111-113
2.34t116-118
S93-95
2.35t134-136
2.450,6-1,90 (m, N) (CIS and TRANS), 4,0 (C, 6N) (CIS and TRANS), 7,0-7,28 (m, 6N) (CIS and the Rance), to 8.0 (s, 1H) (trance), with 8.05 (s, 1H) (Cys), to 8.12 (d, 2H) (TRANS), to 8.20 (d, 2H) (CIS).resin
2.46t116-118
2.52116-118
2.54129-131
2.57107-109
Sresin
2.66t145-147
S104-106
2.67t160-161
Sresin
2.68t148-150
S145-147
2.69t149-150
S119-121
2.76t107-108
S82-84
2.77t109-111
S119-122
2.78t96-97
3.574-78
3.1761-65
3.2392-96
3.33-0,1-of 0.90 (m, N) (CIS and TRANS), of 1.45 (m, 1H) (TRANS), to 1.79 (m, 1H) (Cys), to 3.58 (s, 6N) (CIS and TRANS), 6,82-7,13 (m, 10H) (CIS and TRANS), 7,92 (s, 1H) (NH-TRANS), 8,03 (DD, 1H) (TRANS), 8,10 (s, 1H) (NH-Cys), 8,19 (DD, 1H) (CIS).resin
3.390,63 of-1.83 (m, N) (CIS and TRANS), and 3.72 (s, 6N) (CIS and TRANS), 6,95-7,38 (m, 10H) (CIS and TRANS), with 8.05 (s, 1H) (NH-TRANS), 8,18 (DD, 1H) (TRANS), 8,30 (DD, 1H) (CIS).resin
3.450,6-1,90 (m, N)(CIS and TRANS), 3,70 (s, 6N) (CIS and TRANS), 6,98-7,35 (m, 8H) (CIS and TRANS), 8,08 (users, 2N) (CIS and TRANS), 8,17 (d, 2H) (TRANS), of 8.25 (d, 2H) (CIS).resin
Sof 1.40 (m, 1H), 1,50-of 1.65 (m, 1H), 2,37 (m, 1H), 2,50 (m, 1H), of 3.73 (s, 3H), 6,60-6,70 (m, 5H), 6,97 (m, 2H), 7,18 (m, 3H), of 7.82 (s, 1H) (NH), 8,02 (d, 1H).resin
3.66t146-148
Sof 1.40 (m, 1H), 1.57 in (m, 1H), 2.40 a (m, 2H), and 3.72 (s, 3H), of 6.68 (d, 2H), 6.90 to-was 7.08 (m, 4H), 7,18 (m, 3H), 7,80 (s, 1H), 8,02 (d, 1H).resin
3.68t150-152
3.76resin
S123-126
3.80t94-96
4.1069-74
4.12resin
4.24 /td> 113-115
4.26138-142
5.5resin
5.1283-86
S75-77
5.21t80-82
5.25131-133
5.28115-119
S164-166
5.37t133-135
S160-162
5.40t136-138
S-0,25 (m, 1H), -0,01-0,03 (m, 3H), of 0.60 (s, 3H), of 0.65 (m, 1H), 0,79 (m, 1H), 1,25 (m, 1H), 1,80 (m, 1H), 6,95 (t, 1H), was 7.08 (m, 2H), 7,28 (m, 1H), 8,15 (d, 2H), scored 8.38 (m, 1H), to 8.62 (s, 1H)(NH).resin
5.53t0,01 (m, 4H), of 0.58 (m, 2H), were 0.94 (s, 3H), 1,11 (m, 1H), 1,44 (m, 1H), 6,98 (m, 2H), to 7.09 (m, 1H), 7.23 percent (m, 1H), 8,01 (DD, 1H), 8,10 (d, 1H), 8,35 (DD, 1H), 8,40 (s, 1H).resin
6.10resin

Compounds according to formula (I) can be obtained in accordance with the following synthesis schemes.

Scheme 1A

The compound of formula (II) [where R3takes the values defined above for the compounds of formula (I)] may be recip is but a sequence of reactions, which begins with the cross-aldol condensation of benzaldehyde with a ketone of the formula CH3C(O)R3[where R3takes the values defined above for the compounds of formula (I)] in the presence of NaOH or KOH in a solvent (such as water or ethanol) and usually by boiling under reflux or, alternatively, the interaction of benzaldehyde with Wittig reagent under standard conditions. Received α,β-unsaturated ketone of formula (III) [where R3takes the values defined above for the compounds of formula (I)]:

can then be converted into compound of formula (IV) [where R3takes the values defined above for the compounds of formula (I)]:

the first interaction with hydrazinehydrate in ethanol by boiling under reflux and then heated (to a temperature in the range of 150-250° (C) in the presence of KOH (distillation of the solvent). After nitration with a mixture of HNO3/H2O or HNO3/acetic angered in refrigerated containers (at temperature in the range from -30°0° (C)obtained o/p-mixture of nitrobenzene of the formula(V) [where R3takes the values defined above for the compounds of formula (I)]:

can then be separated and subjected kata is ticheskamu recovery (Pt/C/H 2or Ra-Ni/H2) in a solvent (such as methanol, ethanol or THF) at room temperature to obtain a crude o/p-mixture of compounds of formula (II), which can then be purified by standard methods.

Alternatively, the compound of formula (II) [where R3takes the values defined above for the compounds of formula (I)] can be obtained by the method shown in the following sequence of reactions, which includes the stage of Pd(II)catalytic aminirovaniya.

Scheme 1B

The compound of formula (VIII) [where R3takes the values defined above for the compounds of formula (I)] is added to the bromine and methanol at a temperature of 5-10°C, after which is added triphenylphosphine in a solvent such as tetrahydrofuran] obtaining the compounds of formula (IX) [where R3takes the values defined above for the compounds of formula (I)], which, in turn, is added to the sodium hydride in a solvent such as DMSO] and then subjected to interaction with 2-bromobenzaldehyde or 2-identilied with obtaining the compounds of formula (X) [where R3takes the values defined above for the compounds of formula (I)and Hal represents a bromine or iodine]. Next, the resulting compound of formula (X) is mixed with HYDR what gingertom in a solvent such as ethanol] and heated to a temperature of education phlegmy, then added potassium hydroxide, and the reaction mixture is maintained at 200-220°within a few hours. The standard procedure for extraction and purification results in the compounds of formula (XI) [where R3takes the values defined above for the compounds of formula (I)and Hal represents a bromine or iodine], which can then be converted into compound of formula (II) mixing with benzophenone, tert-piperonyl sodium, Tris-dibenzylideneacetone (Pd2dba3), racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphtyl (BINAP) and a solvent [such as benzene or toluene], boiling at a temperature of phlegmy usually within a few hours and adding the result [usually raw] dedicated to a mixture of imine hydroxyamine hydrochloride, sodium acetate and solvent [such as methanol]. The resulting mixture is stirred, preferably for about one hour, at room temperature, after which the CIS-/TRANS-mixture of compounds of formula (II) can be extracted with further separation of CIS - and TRANS-isomers using flash chromatography.

Alternatively, in the above-described method of aminirovaniya using a Pd-catalyst system instead of the catalyst-ligand Pd2dba3/BINAP system can be used diacetate pall the Diya/1,1'-bis(diphenylphosphino)ferrocene (dppf).

The reaction scheme 1B is new and involves an inventive step, in particular, the use of stage aminirovaniya using Pd(II)catalyst. Therefore, in accordance with another aspect of the invention provides a method of obtaining compounds of formula (II), where R3takes the values defined above, which includes at least one of the stages of the reaction scheme 1B; in particular, the stage system using Pd(II)catalyst-ligand [where the ligand is selected from a suitable steric specified phosphine (such as BINAP or dppf)] for the interaction of the compounds of formula (XI) [where Hal represents a bromine or iodine; and R3takes the values defined above] with benzophenone optionally in the presence of a base [such as tert-butanolate sodium tert-butanolate potassium, sodium carbonate, potassium carbonate or cesium carbonate] obtaining the compounds of formula (XII) [where R3takes the values defined above].

Examples of reactions aminirovaniya with benzophenones described in the literature (Journal of Organometallic Chemistry, 1999, 576, 125-146; Tetrahedron Letters 1997, 38, 6367-6370).

Scheme 2

Synthesis of amine of the formula (IIA)

[where R3Arepresents hydrogen or methyl] can be carried out sequentially reaction that begins with the reaction of the Wittig on-nitrobenzamide is Yes with ridom [obtained from cyclopropanecarbonitrile in the presence of a strong base, such as NaH, in a solvent such as DMSO at a temperature in the range of 0-85°]. Obtained E/Z-mixture of compounds of formula (VI)

[where R3Arepresents hydrogen or methyl] can be converted into a compound of formula (VII)

the use of the reaction of the Simmons-Smith (Zn/Cu, CH2I2simple ether as solvent) to the olefinic group of the compounds of formula (VI). The recovery of the corresponding nitro compounds of formula (VII) can be carried out using conditions described in scheme 1, to obtain the compounds of formula (IIA).

Scheme 3

The compound of formula (I) can be obtained by the coupling of compounds of formula Het-C(=O)-R* [R* is a halogen, hydroxy or With the1-6alkoxy, preferably chlorine] with the compound of the formula (II), which is obtained as described above, in the presence of a base (such as triethylamine, base Hunya, sodium bicarbonate, sodium carbonate, potassium carbonate, pyridine or quinoline, preferably triethylamine) in a solvent (such as diethylether, methyl tert-butyl ether (TME), THF, dichloromethane, chloroform, N,N-dimethylformamide (DMF) or N-organic (NMP)) during the period of time from 10 minutes to 48 hours (preferably from 12 to 24 hours) and at a temperature in the range from 0°the temperatures of phlegmy (preferably from 20 to 25° C). When R* represents a hydroxyl group, can be used binder [such as benzotriazol-1-yloxytris(dimethylamino)fosfodiesterasa, the acid chloride of bis-(2-oxo-3-oxazolidinyl)phosphinic acid, N,N'-cyclohexylcarbodiimide or 1,1'-carbonyldiimidazole].

Scheme 4

The compound of formula (IA)

[where R3Arepresents hydrogen or methyl] can be obtained by reduction of the nitro group of compounds of formula (VI) [where R3Arepresents hydrogen or methyl] under standard conditions (for example, catalytic reduction or recovery by Besana) and subsequent amidation of the acid chloride to obtain the compounds of formula (VII) [where R3Arepresents hydrogen or methyl]

which is then used in the reaction of the Simmons-Smith (Zn/Cu, CH2I2solvent: a simple ether) to give the compounds of formula (IA).

Unexpectedly it was found that the new compounds of formula (I) possess very useful for practical application range of activities for protection of plants from diseases caused by fungi and bacteria and viruses.

The compounds of formula (I) can be used in the agricultural sector and related fields of application as the active ingredients to combat plant pests. The new compounds have high activity at low application rates, well tolerated by plants and are safe for environment. The compounds possess very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests which occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while protecting those parts of plants which grow later, for example, from phytopathogenic microorganisms.

You can also apply the compounds of formula (I) as a covering agent for the processing of material for propagation, in particular, seeds (fruit, tubers, grains) and cuttings of plants (e.g. rice) for protection against fungal infections as well as against phytopathogenic fungi living in the soil.

In addition, the compounds according to this invention can be used to control fungi in related fields, for example, for the protection of technical materials, including wood and technical materials related to the wood, when storing food, when conducting hygiene etc.

The compounds of formula (I) is effective, for example, from the Oseni phytopathogenic fungi of the following classes: Fungi deuteromycota (for example, Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (for example, Rhizoctonia, Hemileia, Puccinia). In addition, they are also effective against class Ascomycetes (for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (for example, Phytophthora, Pythium, Plasmopara). Wonderful activity detected 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 in the case of tobacco mosaic virus).

In the scope of the present invention includes target crops to be protected, usually including the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomaceous, drupes and juicy fruits (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor bean, cocoa beans, groundnuts); cucurbitaceous plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables plants (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika is sweet); Laurel (avocado, cinnamon, camphor), or t is such plants as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and rubber plants, and ornamental plants.

Compounds of formula I are used in unmodified form or preferably together with the adjuvants, traditionally used in the field of formulation (receipt of drugs). To do this, they are standard ways in the composition of emulsifiable concentrates, pastes applied in the form of coatings, solutions that can directly dispergirujutsja or to dissolve, dilute emulsions, wettable powders, soluble powders, Farrukh Dustov, pellets and encapsulated drugs, for example in polymeric substances. Type compositions, methods of application, such as spraying, spraying, dusting, scattering, coating in the form of a coating or watering, are selected in accordance with the alleged object and existing conditions. The composition may also contain additional adjuvants, such as stabilizers, defoamers, viscosity regulators, binders or substance to improve the adhesiveness, as well as fertilizers, micronutrient donors or other preparations for obtaining special effects.

Suitable carriers and adjuvants can be solid or liquid and are substances used in the technology of the floor is possible drugs for example, natural or regenerated mineral substances, solvents, dispersants, wetting agents, substances for improving adhesiveness, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97/33890.

The compounds of formula (I) are usually used in the form of compositions and can be applied to the area of crop or plant to be treated, simultaneously or sequentially with additional compounds. These additional compounds may represent, for example, fertilizers, 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, in combination with further carriers, surfactants or adjuvants that promote the application, which is usually used in preparation of drugs.

The compounds of formula (I) can be mixed with other fungicides, which in some cases leads to unexpected synergistic activities. Particularly preferred composite components for the mixture are azoles such as azaconazole, BAY14120, bitertanol, bromuconazole, tsyprokonazolu, difenoconazol, diniconazole, epoxy is anasol, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, kabekona, ipconazole, metconazole, myclobutanil, peyratout, penconazole, pirivenas, prochloraz, propiconazole, simionato, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinylidene, such as ancymidol, fenarimol, nuarimol; 2-aminopyrimidine, such as bupirimate, dimethirimol, ethirimol; morpholines such as dodemont, fenpropidin, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, Pyrimethanil; pyrrole, such as fenpiclonil, fludyoksonil; phenylamide, such as benalaxyl, parallaxis, metalaxyl, R-metalaxyl, operas, oxadixyl; benzimidazole, such as benomyl, carbendazim, dibakar, fuberidazole, thiabendazole; dicarboximide, such as chlozolinate, diplozoon, iprodion, mickleton, procymidon, vinclozolin; carboxamide, such as carboxin, fanforum, flutolanil, mepronil, oxycarboxin, leflunomid; guanidine, such as guazatine, Dodin, iminoctadine; strobilurin, such as AZOXYSTROBIN, kresoxim-methyl, metamyosyn, SSF-129, Trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS520; dithiocarbamate, such as ferbam, MANCOZEB, MANEB, metiram, propineb, thiram, zineb, Tsira; N-halogenlithiumcarbenoid, is such as captafol, Captan, dichlofluanid, fluoromica, folpet, tolyfluanid; Cu-containing compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulphate, copper oxide, mankapur, oxen Cooper; NITROPHENOL derivatives such as dinocap, nitrates-isopropyl; organophosphorus derivatives, such as edifenphos, iprobenfos, isoprothiolane, forgiven, pyrazophos, tolclofos-methyl; and compounds of other classes, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionat, chloroneb, CHLOROTHALONIL, cyflufenamid, having cymoxanil, Dylan, declomycin, dicloran, dietphenterm, dimethomorph, SYP-LI90 (proposed name: floorf), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, phenoxyl, fentin, verison, fluazinam, glucolipid, fenhexamid, fosetyl-aluminum, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, metasurfaces, metrafenone, nicobifen, pencycuron, phtalic, polyoxin, provenzal, propamocarb, pyroxylin, jenoxifen, hintzen, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).

The preferred method of applying the compounds of formula (I) or agricultural composition, which contains at least one of these compounds, is a deciduous application. Application frequency and rate of application will depend on the risk of infection corresponding to p is thanom. However, the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by the watering places of growing plants in a liquid preparation or making of compounds in solid form to the soil, e.g. in granular form (soil application). In cultures of the canadian rice such granules can be applied to flooded rice field. The compounds of formula (I) can also be applied to seeds (coating) application of seeds or tubers or liquid drug fungicide or coating a solid preparation in the form of a coating.

Drug [i.e., a composition comprising a compound of formula (I)] and, if necessary, a solid or liquid adjuvant, get in a known manner, typically homogeneous mixing and/or grinding the compound with extenders, e.g. solvents, solid carriers and, optionally, surface-active compounds (surfactants).

Agricultural drugs will usually contain from 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 and 99.8 to 5% wt., solid or liquid adjuvant and 0 to 25 wt.%, preferably from 0.1 to 25 wt.%, Surfactant.

Useful standards applications typically 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 is from 20 g to 600 g A.I/ha When used as a means of impregnation of seeds the usual dose is from 10 mg to 1 g of active ingredient per kg of seeds.

Although it is preferable to manufacture commercial products in the form of concentrates, the end user of the product will usually apply the diluted drugs.

The following examples illustrate, but without limitation, the above-described invention in more detail.

Example 1

This example illustrates the connection No. 1.5.

To a mixture of 17.4 g (0.1 mol) of (2-isobutylthiazole)benzene and 80 mg of acetic anhydride added a solution of 6.0 g (0,095 mol) of nitric acid and 40 ml of acetic anhydride so that the temperature of the mixture is maintained at a constant level -30°C. the resulting reaction mixture is stirred for 1 hour at -30°and then for 2 hours at 0°C. the Mixture is then poured into 500 ml ice water and extracted three times with hexane. The hexane phases are combined and washed twice with 5% aqueous bicarbonate solution. The organic phase is dried over sodium sulfate and the solvent is distilled off in a water jet vacuum pump, receiving the crude reaction product. Purification with flash chromatography over silica gel (eluent: ethyl acetate/hexane 1:10) results of 10.5 g of yellow oil (mixture of para - and ortho-nitrosamino), which directly and the use in the next stage. This mixture of isomers [consisting of 10.5 g (0,048 mol) of 1-(2-isobutylthiazole)-2-nitrobenzene and 1-(2-isobutylthiazole)-4-nitrobenzene] dissolved in 110 ml of ethanol and hydronaut over 5% Pt/C catalyst within 45 minutes. After absorption of theoretical amount of hydrogen the catalyst is filtered off and the solvent is removed in vacuum. The crude mixture of isomers of aniline purified flash chromatography (eluent: ethyl acetate/hexane 1:2).

Output: 6,38 g 2-(2-isobutylthiazole)phenylamine in the form of a yellow oil (mixture of CIS - and TRANS-isomers).

Example 2

This example illustrates the connection 3.17.

A solution of 0.35 g (0,0018 mol) of 1-methyl-4-cryptomaterial-3-carboxylic acid and 0.24 g (0,0019 mol) of oxalicacid in 15 ml of methylene chloride is stirred for 3 hours at room temperature in the presence of two drops of absolute DMF. Then a solution of the carboxylic acid is added slowly to a solution of 0.34 g (0,0018 mol) of 2-(2-isobutylthiazole)phenylamine, 0.27 g (0,0027 mol) of triethylamine and 10 ml of methylene chloride. The resulting mixture is stirred for 16 hours at room temperature. The solvent is removed in vacuum and the crude product is transferred in ˜100 ml of ethyl acetate. An ethyl acetate phase is washed twice with water, the organic phase is dried and again the solvent is distilled off in a water jet vacuum pump. Neo is ewenny the product was then purified flash chromatography (eluent: hexane/ethyl acetate/methylene chloride 1:2:2).

Yield: 0.52 g of 2-(2-isobutylthiazole)phenyl]amide 1-methyl-4-trifluoromethyl-1H-pyrrole-3-carboxylic acid as a white powder (mixture of CIS - and TRANS-isomers).

Example 3

This example illustrates the formation of compounds No. s and 1.10t.

Stage 1

In capacity for sulfonation to the absolute DMSO (600 ml) is added NaH (12.8 g, 0.32 mol). The mixture is heated at 80°C for 90 minutes, then at room temperature portions add cyclopropanemethylamine (136,5 g, 0.32 mol). The resulting suspension is stirred for 30 minutes at room temperature, then added dropwise a solution of 2-bromobenzaldehyde (59,4 g, 0.32 mol) in absolute DMSO (100 ml). The resulting mixture is heated at 50°C for 4 hours, then poured into 2.5 liters of ice water. Extraction with ethyl acetate, drying over sodium sulfate and distillation of the solvent in a water jet vacuum pump to yield the crude product. The product is purified by vacuum distillation.

Output: 77,6 g E-3-(2-bromophenyl)-1-cyclopropylamino in the form of a yellow oil (BP. 125-130°at 0.3 mbar).

Stage 2

In the flask for sulfating mixture of E-3-(2-bromophenyl)-1-cyclopropylamino (77,6 g, 0,309 mol) and hydrazine hydrate is added (23,2 g, 0,464 mol) in ethanol (25 ml) is refluxed for 2 hours. Then add poroshkoobraz the initial potassium hydroxide (85%) (24.4 g, of 0.37 mol) and excess hydrazine hydrate is added and the solvent is distilled off. The remaining mixture is heated at 205-210°C for 3 hours. The obtained resin is dissolved in ethyl acetate (500 ml) at a temperature of 50°and the organic phase is washed twice with water. Drying an ethyl acetate phase over sodium sulfate and distillation of the solvent in a water jet vacuum pump to yield the crude product, which was purified flash chromatography on silica gel (eluent: hexane/methylene chloride 7:1).

Output: to 61.2 g of 2-(2-bromophenyl)bacillophobia in the form of a slightly yellow oil (mixture of CIS - and TRANS-isomers).

Stage 3

A mixture of 2-(2-bromophenyl)bacillophobia (28.5 g, 0.12 mol), benzophenones (26,1 g, 0.144 mol), tert-butoxide sodium (16,1 g has 0.168 mol), Tris-dibenzylideneacetone (Pd2dba3) (0,43 g, 0,474 mmol), racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) (0,83 g of 1.34 mmol) and absolute toluene (450 ml) is refluxed under nitrogen atmosphere for 6 hours. Then the solvent is removed in a water-jet pump vacuum and the residue is transferred into ethyl acetate (750 ml). The organic layer is washed three times with brine and dried over sodium sulfate. The solvent is evaporated, give crude product. The product was then purified flash chromatography on silica gel (eluent: hexane/methylene chloride 5:1).

Output: 39.9 g of the mixture of CIS - and TRANS-isome what s benzhydrylidene-(2-bicyclopentyl-2-ylphenyl)amine in the form of a brownish oil.

Stage 4

In the flask for sulfating hydroxyamine hydrochloride (0.35 g, 0,0048 mol), sodium acetate (0,53 g, 0,0064 mol) and absolute methanol (30 ml) was stirred at room temperature for about 15 minutes. Then added dropwise a solution benzhydrylidene-(2-bicyclopentyl-2-ylphenyl)amine (0.9 g, 0,00267 mol) in methanol (15 ml). The resulting mixture was stirred for 1 hour at room temperature. The mixture is diluted with ethyl acetate (250 ml), the organic phase is washed twice with water. The organic phase is dried (sodium sulfate) and the solvent is distilled off in a water jet vacuum pump, give crude product. Final purification and separation of CIS - and TRANS-isomers hold flash chromatography (eluent: hexane/ethyl acetate 5:1).

Yield: 0.21 g of TRANS - and 0.15 g of CIS-2-bicyclopentyl-2-ilfenomeno in the form of a brownish oil.

Examples of drugs for compounds of formula (I)

Techniques for obtaining preparations of compounds of formula I, such as emulsifiable concentrates, solutions, granulates, dusty and wettable powders described in WO 97/33890.

Examples of biological testing: fungicidal activity

Example-1: Effect onPuccinia reconditaon wheat (leaf rust of wheat)

Plants wheat cultivar Arina 1 week to process drug test compound (0.02% of active ingredient) in the camera oprys the air traffic management. The day after the processing plants wheat inoculant spraying pilot plant spore suspension (1×105uredospore/ml). After a period of incubation at 20°C and 95% relative humidity (O.V.) duration 2 days the plants kept in the greenhouse for 8 days at 20°and 60% O.V. incidence is assessed 10 days after inoculation.

Compounds of tables 2, 3, 4 and 5 show good activity in this experience (<20% infestation). Infection is prevented virtually completely (0-5% infestation) each of the connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.33, 2.45, 2.46t, 2,76c, 2.76t, s, 2.77t, 3.5, 3.17, 3.23, 3.33, 3.45, 3.76, 4.10, 4.12, 4.26, 5.5, 5.12, 5.21c and 5.37c.

Example b-2: Effect on Podosphaera leucotricha Apple (powdery mildew of apples)

Seedlings of Apple varieties McIntoch 5 weeks treated with the drug test compounds (0,002% active ingredient) in the chamber of the spray. Later, one day after processing pilot plants inoculant shaking over them plants infected with powdery mildew of Apple. After a period of incubation at 22°and 60% O.V. and a light regime of 14/10 hours light/dark) duration of 12 days to assess the level of disease.

Compounds of tables 2, 3 and 4 show good activity in this experience. Connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.33, 2.45, 2.46t, 3.5, 3.17, 3.23, 3.33, 3.45, 4.10 and 4.12 each exhibit high efficiency is ü (< 20% infestation).

Example b-3: Effect onVenturia inaequalisApple (Apple scab)

Seedlings of Apple varieties McIntosh 4 weeks treated with the drug test compound (0.02% of active ingredient) in the chamber of the spray. The day after the processing pilot plants inoculant by spraying a spore suspension (4×105conidia/ml). After an incubation period lasting for 4 days at 21°and 95% O.V. plants are placed in a greenhouse for 4 days at 21°and 60% O.V. After an additional 4 days incubation period at 21°and 95% O.V. assess the level of disease.

Compounds of tables 2 and 3 show good activity in this experience. Connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.33, 2.45, 2.46t, 3.5, 3.17, 3.23, 3.33 and 3.45, each, show a high efficiency (<20% infestation).

Example b-4: Effect onErysiphe graminisbarley (powdery mildew of barley)

Plants of barley varieties Express 1 week to process drug test compound (0.02% of active ingredient) in the chamber of the spray. The day after the processing of barley plants inoculant by shaking the plants infected with powdery mildew, on experimental plants. At the end of the incubation period in the greenhouse at 20°/18°C (day/night) and 60% O.V. duration 6 days assess the level of disease.

Compounds of tables 2, 3 and 4 show choir is Shui activity in this experience. Connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.45, 2.46t, s, 2.77t, 3.5, 3.17, 3.23, 3.45, 4.10 and 4.12, each, show a high efficiency (<20% infestation).

Example B-5: Effect onBotrytis cinereaApple (Botrytis fruit of the Apple tree)

On the fruit of the Apple cultivars Golden Delicious drill 3 holes and fill each with drops of the drug test compound with a volume of 30 ál (0,002% active ingredient). Two hours after treatment at point of use connection with a pipette and put 50 ál of a suspension of spores of B. cinerea (4×105conidia/ml). After an incubation period lasting 7 days in a growth chamber at 22°To assess the level of disease.

Compounds of tables 2, 3, 4, 5 and 6 show good activity in this experience. Connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.33, 2.45, 2.46t, 2,76c, 2.76t, s, 2.77t, 3.5, 3.17, 3.23, 3.33, 3.76, 3.45, 3.76, 4.10, 4.12, 4.26, 5.5, 5.12, 5,21c and 5.37c, each, show a very high efficiency (<10% infection).

Example B-6: Effect on grapes Botrytis cinerea (Botrytis grapes)

Seedlings of Gutedel grape 5 weeks treated with the drug test compounds (0,002% active ingredient) in the chamber of the spray. Two days later, after processing pilot plants inoculant by spraying a spore suspension (1×106conidia/ml). At the end of the incubation period duration of 4 days in the greenhouse at 21°and 95% O.V. assess the level of disease.

Compounds of tables 2, 3, 4, 5 and 6 show good activity in this experience. Connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.45, 2.46t, 2,76c, 2.76t, s, 2.77t, 3.5, 3.17, 3.23, 3.33, 3.39, 3.76, 4.10, 4.12, 4.26, 5.5, 5.12, 5,21c and 5.37c, each, show a very high efficiency (<10% infection).

Example B-7: the Effect onBotrytis cinereatomatoes (tomato Botrytis)

Plants of tomato varieties Roter Gnom 4 weeks treated with the drug test compounds (0,002% active ingredient) in the chamber of the spray. Two days after treatment pilot plants inoculant by spraying a spore suspension (1×105conidia/ml). After an incubation period lasting 4 days in a growth chamber at 20°and 95% O.V. assess the level of disease.

Compounds of tables 2, 3, 4, 5 and 6 show good activity in this experience. Connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.33, 2.45, 2.46t, 2,76c, 2.76t, s, 2.77t, 3.5, 3.17, 3.23, 3.39, 3.45, 3.76, 4.10, 4.12, 4.26, 5.5, 5.12, 5,21c and 5.37c, each, show a very high efficiency (<10% infection).

Example B-8: the Effect onPyrenophora teresbarley Net blotch of barley)

Plants of barley varieties Express 1 week to process drug test compounds (0,002% active ingredient) in the chamber of the spray. Two days after treatment pilot plants inoculant by spraying a spore suspension (3×104conidia/ml). After a period of incubation at 20°and 95% O.V. duration 2 days the plants kept in the greenhouse for 2 days at 20° C and 60% O.V. Level of disease assessed 4 days after inoculation.

Compounds of tables 2, 3, 4, 5 and 6 show good activity in this experience. Connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.33, 2.45, 2.46t, 2,76c, 2.76t, s, 2.77t, 3.5, 3.17, 3.23, 3.39, 3.45, 3.76, 4.10, 4.12, 4.26, 5.5, 5.12, 5,21c and 5.37c, each, show a very high efficiency (<20% infestation).

Example B-9: the Effect onSeptoria nodorumwheat (Septoria leaf spot of wheat)

Plants wheat cultivar Arina 1 week to process drug test compound (0.02% of active ingredient) in the chamber of the spray. One day after processing pilot plants inoculant by spraying a spore suspension (5×105conidia/ml). After a period of incubation at 20°and 95% O.V. duration 1 day plants kept in a greenhouse for 10 days at 20°and 60% O.V. incidence estimate on the 11th day after inoculation.

Compounds of tables 2, 3 and 4 show good activity in this experience. Connections 2.5, 2.17, 2.18, 2.23, 2.24, 2.33, 2.45, 2.46t, 2,76c, 2.76t, s, 2.77t, 3.5, 3.17, 3.23, 3.33, 3.39, 3.45, 3.76, 4.10 and 4.12, each, show a very high efficiency (<20% infestation).

1. The compound of formula (I)

where Het is pyrrolyl, pyrazolyl or thiazolyl, each substituted groups R4, R5and R6;

R1represents hydrogen or Galaga is;

R2represents hydrogen or halogen;

R3represents a C2-12alkyl, C3-12cycloalkyl, C3-12cycloalkyl, substituted C1-3the alkyl, phenyl or phenyl substituted by halogen; and

R4, R5and R6independently selected from hydrogen, halogen, C1-4the alkyl or C1-4halogenoalkane provided that at least one of R4, R5and R6is not hydrogen.

2. The compound of formula (I) according to claim 1, where R1represents a hydrogen or fluorine.

3. The compound of formula (I) according to claim 1, where R2represents a hydrogen or fluorine.

4. The compound of formula (I) according to claim 1, where R3represents a C2-6alkyl, C3-8cycloalkyl,3-8cycloalkyl, substituted C1-3the alkyl, phenyl or phenyl substituted by halogen.

5. (2-Bicyclopentyl-2-yl-phenyl)amide 3-deformity-1-methyl-1H-pyrazole-4-carboxylic acid represented by the formula

6. The compound of formula (II)

where R3has the meanings given in claim 1.

7. Composition for combating microorganisms and prevent infection of their plants and contaminated plants, where the active ingredient is a compound of formula (I) according to claim 1 in combination with a suitable n is Cetelem.

8. The way to fight or prevent infestation of cultivated plants by phytopathogenic microorganisms by application of the compounds of formula (I) according to claim 1 to the plants, or parts, or the place of their growth.



 

Same patents:

FIELD: organic chemistry, fungicides.

SUBSTANCE: invention describes pyrazolylcarboxanilides of the formula (I) wherein R means difluoromethyl or trifluoromethyl group; R1 and R2 mean independently of one another halogen atom or (C1-C6)-alkyl; R3 means fluorine atom, and agent and method for control of undesirable fungi using compounds of the formula (I), and novel intermediate substances - derivatives of aniline and halogenpyrazolcarboxanilides. Compounds of the formula (I) elicit fungicide properties and can be used in protection of plants.

EFFECT: valuable properties of compounds and agent.

15 cl, 8 tbl, 10 ex

FIELD: organic chemistry, insecticides.

SUBSTANCE: invention relates to compounds of the formula (1) , their N-oxides and salts that can be used in agriculture wherein values A, B, J, R1, R3, R4 and n are given in the invention claim. Also, invention describes a method for control of arthropoda pests to provides high productivity that comprises applying the effective dose of compound of the formula (1) on arthropoda pests and in medium of their habitation, and a the composition with arthropocide activity comprising compounds of the formula (1).

EFFECT: valuable properties of compounds and composition.

23 cl, 34 tbl, 759 ex

FIELD: organic chemistry, agriculture, insecticides.

SUBSTANCE: invention relates to a substituted anilide derivative of the formula (I): wherein R1 represents hydrogen atom, (C1-C6)-alkyl group; R2 represents hydrogen atom, halogen atom or halogen-(C1-C6)-alkyl group; R3 represents hydrogen atom, halogen atom, (C1-C6)-alkyl group, hydroxyl group or (C1-C6)-alkoxy-group; t = 1; m = 0; each among X that can be similar or different represents (C2-C8)-alkyl group, hydroxy-(C1-C6)-alkyl group or (C3-C6)-cycloalkyl-(C1-C6)-alkyl group; n = 1 or 2; Z represents oxygen atom; Q means a substitute represented by any of the following formulae: Q1-Q3, Q6, Q8-Q12, Q14-Q19, Q21 and Q23 (wherein each among Y1 that can be similar or different represents halogen atom, (C1-C6)-alkyl group, and so on); Y2 represents (C1-C6)-alkyl group or halogen-(C1-C6)-alkyl group; Y3 represents (C1-C6)-alkyl group, halogen-(C1-C6)-alkyl group or substituted phenyl group; p represents a whole number from 1 to 2; q represents a whole number from 0 or 2; r represents a whole number from 0 to 2. Also, invention proposes a chemical for control of pests of agricultural and fruit crops. The chemical comprises substituted anilide derivative of the formula (I) as an active component and represents insecticide, fungicide or acaricide. Also, invention proposes a method for addition of the chemical for control of pests of agricultural and fruits crops. Also, invention proposes aniline derivative represented by the general formula (II): wherein R1 represents hydrogen atom, (C1-C6)-alkyl group; R2 represents hydrogen atom, halogen atom or halogen-(C1-C6)-alkyl group; R3 represents hydrogen atom, halogen atom, (C1-C6)-alkyl group, hydroxyl group or (C1-C6)-alkoxy-group; t = 1; m = 0; each among X that can be similar or different represents (C2-C8)-alkyl group, hydroxy-(C1-C6)-alkyl group or (C3-C6)-cycloalkyl-(C1-C6)-alkyl group; n = 1 or 2. Invention provides the development of anilide derivative as insecticide, fungicide and acaricide against pests of agricultural and fruit crops.

EFFECT: valuable properties of compound.

5 cl, 6 tbl, 27 ex

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 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

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to novel compounds of the formula (I): wherein R1 represents halogen atom; R2 represents halogen atom; R3 represents (C1-C4)-alkyl; X represents nitrogen atom (N) or -CH; n = 0-3 under condition that when X represents -CH then n= 1 at least. Also, invention relates to novel compounds of the formula (II): wherein R1 represents halogen atom; R2 represents halogen atom; R3 represents hydrogen atom (H) or (C1-C4)-alkyl; X represents N or -CH; n = 0-3 under condition that when X represents -CH then n = 1 at least. Also, invention relates to a method for synthesis of compound of the formula (I), a method for synthesis of compound of the formula (II) and to a method for synthesis of compound of the formula (III) given in the invention description. Also, invention describes intermediate compounds of the formula (4) given in the invention description. Invention provides synthesis of novel biologically active compounds that can be used as insecticides, and a method for their synthesis.

EFFECT: valuable properties of compounds.

24 cl, 3 tbl, 19 ex

FIELD: organic chemistry, fungicides.

SUBSTANCE: invention describes pyrazolylcarboxanilides of the formula (I) wherein R means difluoromethyl or trifluoromethyl group; R1 and R2 mean independently of one another halogen atom or (C1-C6)-alkyl; R3 means fluorine atom, and agent and method for control of undesirable fungi using compounds of the formula (I), and novel intermediate substances - derivatives of aniline and halogenpyrazolcarboxanilides. Compounds of the formula (I) elicit fungicide properties and can be used in protection of plants.

EFFECT: valuable properties of compounds and agent.

15 cl, 8 tbl, 10 ex

FIELD: organic chemistry, chemical technology, herbicides.

SUBSTANCE: invention describes derivatives of pyrazole of the general formula [I]: wherein R1 means (C1-C6)-alkyl group; R2 means (C1-C3)-halohenalkyl group; R3 means hydrogen atom,(C1-C3)-alkyl group that can be substituted with one or some substitutes chosen from group substitutes α or formyl group; R4 means hydrogen atom or (C1-C3)-halogenalkyl group (under condition that R4 represents (C1-C3)-halogenalkyl group in case when R3 means hydrogen atom or formyl group, and R4 represents hydrogen atom or (C1-C3)-halogenalkyl group in case when R3 means (C1-C3)-alkyl group that can be substituted with one or some substitutes chosen from group of substitutes α). Also, invention describes methods for synthesis of indicated derivatives of pyrazole that are intermediate compounds used in synthesis of derivatives of isoxazoline showing the excellent herbicide activity and selectivity with respect to cultural plants and weeds.

EFFECT: improved method of synthesis, valuable properties of compounds.

15 cl, 16 tbl, 40 ex

FIELD: organic chemistry.

SUBSTANCE: invention describes insecticide-acaricide substance used against extoparasites in dogs and cats. Substance represents derivative of phenylpyrazole of the formula (I) wherein in pyrazole structure cyano-group, trifluoromethylsulfenyl group and amino-group are bound at 3, 4 and 5 positions, respectively, and chlorine atoms are bound to phenyl cycle at 2 and 6 positions, and trichlorosilyl group is bound at 4 position. Substance protects dogs and cats against infection with fleas for 65 days after treatment and for 45 days after treatment of cats, and against infection with mites for 35 days, not less. In acute experiment toxicity of substance is characterized by value LD50 above 1300 mg/kg after its administration in stomach to dogs.

EFFECT: valuable properties of substance.

2 ex

FIELD: herbicides, agriculture.

SUBSTANCE: invention describes a herbicide agent with selective effect comprising a combination of biologically active substances and involving the following components: (a) compound of the formula (I) given in the invention description wherein Q1 means oxygen atom (O); Q2 means O; R1 means alkyl with number of carbon atoms from 1 to 6; R2 means alkyl with number of carbon atoms from 1 to 6; R3 means alkyl with number of carbon atoms from 1 to 6 substituted if necessary with (C1-C4)-alkoxyl or alkoxy-group with number of carbon atoms from 1 to 6; R4 means alkyl with number of carbon atoms from 1 to 6 or cycloalkyl with number of carbon atoms from 3 to 6, and salts of compounds of the formula (I) also, and (b) compound improving compatibility with crop plants and chosen from compounds of the following group: AD-67, cloquintocet-methyl, dichloramide, phenchlorazol-ethyl, flurazol, furylazol, isoxadiphen-ethyl, mefenpir-diethyl, MON-7400, compound of the formula (IId) given in the invention description, compound of the formula (IIe) given in the invention description wherein per 1 weight part of compound of the formula (I) or its salt is taken from 0.4 to 200 weight parts of compound of the group (b). Proposed herbicide agent prevents damage of crop plats and can be used for selective control against weeds in cultures of useful plants, for example, cereals and maize.

EFFECT: valuable properties of herbicide agent.

7 cl, 36 tbl, 3 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to 5-substituted alkylaminopyrazole derivatives of formula I , wherein R1 is CN; W is C-halogen; R1 is halogen; R3 is C1-C3-haloalkyl, C1-C3-haloalkoxy; R4 is hydrogen, C1-C6-alkenyl, C2-C6-alkynyl, C3-C7-cycloalkyl, COR8; A is C1-C12-alkylene; R5 is hydrogen, C3-C6-alkenyl, -(CH )qR7 or NR10R11; R5 is C1-C6-haloalkyl; as well as method for animal exogenous and endogenous pest controlling; pesticide composition and application of said compounds for production of veterinary drug. 5-Substituted alkylaminopyrazole derivatives are useful in pest controlling, including insects, arachnids and helminthes, such as nematodes.

EFFECT: new pesticide derivatives.

9 cl, 12 tbl, 20 ex

FIELD: organic chemistry, herbicides.

SUBSTANCE: invention describes novel derivatives of the formula (I): wherein R1 are similar or different and mean hydrogen atom (H),-CN, (C1-C8)-alkyl, (C1-C8)-alkoxy-group; A means phenyl, pyrazolyl wherein each of them is bound to X through carbon atom and substituted with one or two radicals comprising (C1-C8)-alkyl, (C1-C8)-halogenalkyl; X means oxygen atom (O); R2 and R3 mean H; m means O; R6 means H, (C1-C8)-alkyl, (C1-C8)-alkylsulfonyl substituted with halogen atom; B means [(C1-C8)-alkyl]-carbonyl, [(C3-C6)-cycloalkyl]-carbonyl wherein each radical is not substituted or substituted with one or some radicals chosen from a row comprising halogen atom, (C1-C8)-alkoxy-group and [(C1-C8)-alkoxy]-carbonyl, (C1-C8)-alkylsulfonyl substituted with halogen atom, [(C2-C8)-alkenyl]-carbonyl, phenylcarbonyl substituted with one some radicals chosen from a row comprising halogen atom, (C1-C8)-alkyl and -NO2, or di-[(C1-C8)-alkyl]-aminosulfonyl, formyl or group of the formula -CO-CO-R1 wherein R1 means (C1-C8)-alkyl or phenyl-substituted [(C2-C8)-alkenyl]-carbonyl, furancarbonyl, thienylcarbonyl, halogen-substituted phenylaminocarbonyl, dimethylaminosulfonyl or group of the formula: or wherein W means oxygen or sulfur atom; T means O; R11 means unsubstituted (C1-C8)-alkyl or substituted with halogen atom; R12 and R13 are similar or different and mean H, unsubstituted (C1-C8)-alkyl, with exception for N-hydroxy-N-[(6-phenoxy-2-pyridyl)methyl]-acetamide, and a herbicide agent comprising compound of the formula (I) and accessory substances used usually in preparing agents for plants protection. Proposed compounds possess the herbicide activity and therefore they can be used agriculture.

EFFECT: valuable properties of compounds and agents.

3 cl, 2 tbl, 8 ex

Herbicide agent // 2303872

FIELD: organic chemistry, herbicides.

SUBSTANCE: invention describes a herbicide agent comprising a combination of active components consisting of (a) substituted thene-3-ylsulfonylaminocarbonyl triazolinone of the general formula (I) wherein R1 means alkyl with 1-6 carbon atoms; R2 means alkyl with 1-6 carbon atoms; R3 means alkyl, alkoxy-, alkylthio-group with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms; R4 means alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, or its salt, and (b) compound chosen from group of herbicides given in the description and taken in the synergetic ratio. The proposed agent shows synergetic effect.

EFFECT: valuable property of herbicide agent.

6 cl, 107 tbl, 1 ex

FIELD: chemical plant protection.

SUBSTANCE: invention provides herbicidal agent containing (A) herbicidally active amount of one compound described by general formula I, wherein R1 represents C1-C6-alkyl, R2 hydrogen, R4 halogen or C1-C6-alkyl, R4, R5, and R5 are hydrogen atoms, R7 represents C1-C6-alkyl, and a=2; and (B) antidote-active amount of one compound of general formula II or III, in which R8, R9, R10, independently from each other, represent C1-C4-alkyls, weight ratio of herbicide-to-antidote component ranging from 3:1 to 0.75:1. Method of controlling weeds among cultural plants consists in a treatment of weeds with herbicidal agent.

EFFECT: achieved high selectivity of herbicidal agent when used in wheat and corn crops.

5 cl, 7 ex

FIELD: organic chemistry, insecticides.

SUBSTANCE: invention describes anthranilic acid diamides of the formula (Ia): wherein A and B mean oxygen atom (O); J means compound of the formula (J-1): ; K in common with atoms bound with its forms phenyl cycle substituted optionally with 1 or 2 R4; R1 means hydrogen atom (H); R2 means H; R3 means (C1-C6)-alkyl; each among R4 means independently (C1-C6)-alkyl; each among R5 means independently H, (C1-C6)-alkyl, (C1-C6)-halogenalkyl, (C2-C6)-alkoxycarbonyl or W; W means phenyl substituted optionally with one-two substitutes chosen independently from R6; each among R6 means independently (C1-C4)-alkyl or halogen atom; m = a whole number 1-3; n = a whole number 1-2. Proposed compounds possess insecticide activity. Also, invention describes a method for control of insects and a composition used in control of insects based on compound of the formula (Ia).

EFFECT: valuable properties of compounds and composition.

6 cl, 15 tbl, 7 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

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