6-(1,1-difluoralkyl)-4-aminopicolinates and their application as herbicides

FIELD: chemistry.

SUBSTANCE: in general formula (I) , Y represents -CF2(C1-C3 alkyl); W represents -NR1R2, where R1 and R2 independently represent H or C1-C6 alkyl; and acceptable in agriculture carboxyl or 4-aminogroup derivatives. Invention relates to herbicidal composition, containing formula (I) compound and to method of undesirable vegetation control, which includes contacting of vegetation or place of its location with efficient as herbicide amount of compound of formula (I) in item 1, or its application on soil in order to prevent soot emergence.

EFFECT: obtained are novel compounds which can be used as herbicides.

8 cl, 3 tbl, 7 ex

 

The invention relates to certain new 6-(1,1-diferuloyl)-4-aminopyridinium their derivatives and to the use of these compounds as herbicides.

A number picolinic acids and their pesticidal properties have already been described in this area. For example, U.S. patent 3285925 describes derivatives of 4-amino-3,5,6-trichloropicolinic acid and their use as plant growth regulators and herbicides. U.S. patent 3325272 describes derivatives of 4-amino-3,5-dichlorphenol acid and their use for controlling plant growth. U.S. patent 3317549 describes derivatives of 3,6-dichlorphenol acid and their use as plant growth regulators. U.S. patent 3334108 describes chlorinated derivatives diciplines acids and their use as tools used to destroy parasites. U.S. patent 3234229 describes 4-aminopropan-2-trichloromethylpyridine and their use as herbicides. U.S. patent 3755338 discloses fungicidal properties of 4-amino-3,5-dichloro-6-bromopicolinic. Belgian patent 788756 reveals herbicide properties 6-alkyl-4-amino-3,5-dihalogenoalkane acids. In the work described in Applied and Environmental Microbiology, Vol. 59, No. 7, July 1993, pp. 2251-2256, 4-amino-3,6-dichlorphenol acid identified as a product of anaerobic cleavage of 4-amino-3,5,6-trichloropicolinic acid, the commercial is ski available herbicide picloram. More recently, in U.S. patent 6297197 B1 were described some 4-aminopyridine and their use as herbicides. U.S. patent 5783522 describes some 6-phenylpyridine acids and their use as herbicides, desiccants and tools used for the destruction of the foliage. WO 0311853 describes some of the 6-aryl-4-aminopyridine and their use as herbicides. WO 9821199 describes 6-pyrazolidine and their use as herbicides. U.S. patent 5958837 describes the synthesis of 6-arilpirolului acids and their use as herbicides, desiccants and tools used for defoliation. U.S. patent 6077650 discloses the use of 6-phenylpyruvic acids as bleach, used in pictures, and European patent EP 0972 765 A1 describes the synthesis of 2-, 3 - or 4-arylpyrimidines.

It was found that certain 6-(1,1-diferuloyl)-4-aminopyrine acids and their derivatives are potent herbicides, able to deal with a variety of weeds that are used against woody plants, grasses and sedges, and broadleaf plants and which have a high selectivity with respect to crops. The invention includes compounds of Formula I

in which

Y represents-CF2(C1 -C3alkyl), and

W represents-NO2, -N3, -NR1R2, -N=CR3R4or-NHN=CR3R4,

where R1and R2independently represent H, C1-C6alkyl, C3-C6alkenyl, C3-C6quinil, aryl, heteroaryl, hydroxy, C1-C6alkoxy, amino, C1-C6acyl, C1-C6carbalkoxy, C1-C6allylcarbamate, C1-C6alkylsulfonyl, C1-C6trialkylsilyl or C1-C6dialkylphenol or R1and R2together with the N atom represent a 5 - or 6 - membered saturated or unsaturated cycle which may optionally contain heteroatoms O, S or N; and

R3and R4independently represent H, C1-C6alkyl, C3-C6alkenyl, C3-C6quinil, aryl, heteroaryl or R3and R4together with =C represent a 5 - or 6-membered saturated cycle; and

acceptable in agriculture derivative at the carboxy group or a 4-amino group.

The compounds of Formula I in which Y represents-CF2CH3in which W represents-NR1R2,and R1and R2represent H or C1-C6alkyl are independently preferred.

The invention includes a herbicide composition containing connected to the e of the Formula I and acceptable in agriculture its derivatives at the carboxy group or a 4-amino group in the amount effective for functioning as a herbicide, mixed with auxiliary means or media, are acceptable for use in agriculture. The invention also includes a method of using the compounds and compositions of the present invention for the destruction of unwanted vegetation, or to fight it by drawing connections number with herbicide effects on vegetation or on the place where there is vegetation, but also by making it into the soil until vegetation.

Herbicide compounds of the present invention are derivatives of 4-aminophylline acids of the Formula II

These compounds have substituents, such as Cl atom in position 3, and the group-CF2(C1-C3alkyl), in position 6, while-CF2CH3is the preferred substitute.

The amino group in position 4 may be unsubstituted or substituted by one or more substituents, such as C1-C6alkyl, C3-C6alkenyl, C3-C6quinil, aryl, heteroaryl, hydroxy, C1-C6alkoxy or amino. The amino group can be also converted to amide, carbamate, urea, sulfonamide, silylamine, phosphoramidate, Imin or hydrazone. That is their derivatives can decompose with the formation of the amine. Preferred are unsubstituted or one-deputizing one or two alkyl substituents of the amino group.

Considered to carboxylic acids of Formula I are compounds that actually destroy unwanted vegetation or struggle with it, and usually they are preferred. The analogues of these compounds in which the acid group pikolinos acid converted in this manner to form the related Deputy, which can be transformed into the plant or in the environment in acidic group possessing essentially the same herbicide exposure, included in the scope of this invention. Therefore "acceptable for agriculture derivative"used in the description of the functional group of carboxylic acid located in position -2, defined as any salt, ester, acylhydrazides, imidate, thioimidate, amicin, amide, complex orthoepy, achilleid, allalone, complex tiefer, complex tenoever, complex deciever, nitrile or any other derivative of the acid, well known in this field, which (a) has no significant effect on herbicide activity of the active component, that is, 6-(1,1-diferuloyl)-4-aminophylline acid, and (b) obtained or can be hydrolyzed, oxidized or metabolized in the plant and or soil to Pikalyovo acid, corresponding to the formula I, which, depending on the pH, in dissociated or medicationabana form. Preferred derivatives of carboxylic acids that are acceptable for agriculture, are acceptable for agriculture salts, esters and amides. Similarly, acceptable for agriculture derivative"used to describe the functional group of the amine, in position 4, is defined as any salt, silylamine, phosphorylation, fefinition, phosphoramidate, sulfonamide, zulhilmi, sulfoximine, aminal, hemiaminal, amide, thioamide, carbamate, THIOCARBAMATE, amicin, urea, Imin, nitro, nitroso, azide, or any other derivative containing nitrogen that are well known in this field, which (a) has no significant effect on herbicide activity of the active component, that is, 6-(1,1-diferuloyl)-4-aminophylline acid, and (b) may be hydrolyzed in plants or soil to the free amine corresponding to the formula II. N-Oxides, which are also capable of splitting up the original pyridine, corresponding to the Formula II, also included in the scope of this invention.

Suitable salts include salts of alkali and alkaline earth metals as well as salts derived from ammonia and amines. Preferred cations include the cations of sodium, potassium, magnesium, and ammonium forms of the crystals

R5R6R7NH+,

where R5, R6and R7each independently represents hydrogen or C1-C12alkyl, C3-C12alkenyl or C3-C12quinil, each of which is optionally substituted by one or more hydroxy, C1-C4alkoxy, C1-C4alkylthio or phenyl groups, provided that R5, R6and R7sterically compatible. Additionally, any two substituent of R5, R6and R7together can be an aliphatic bifunctional part, containing from 1 to 12 carbon atoms and up to two oxygen atoms or sulfur. Salts of compounds of Formula I can be obtained by treatment of compounds of Formula I with a metal hydroxide such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropionate, ballinameen, 2-butoxyaniline, morpholine, cyclododecene or benzylamine. Salts of amines are often the preferred forms of the compounds of Formula I, because they are soluble in water and are suitable for obtaining the required herbicide compositions are water-based.

Suitable esters include esters derived from C1-C12alilovic, C3-C12alkenilovyh or C3-C12alkinilovymi alcohols, such as methanol, and propanol, butanol, 2-ethylhexanol, butoxyethanol, methoxypropanol, allyl alcohol, propargilovyh alcohol or cyclohexanol. Esters can be obtained by the reaction mix pikolinos acid with alcohol using any number of suitable activating agents, such as agents used in the binding peptides, such as dicyclohexylcarbodiimide (DCC) or carbonyldiimidazole (CDI), by reaction of the corresponding acid chloride pikolinos acid corresponding to the Formula I, with an appropriate alcohol or by interaction of the corresponding pikolinos acid corresponding to the Formula I, with an appropriate alcohol in the presence of an acid catalyst.

Suitable amides include amides which are derived from ammonia or from C1-C12alkyl, C3-C12alkenyl or C3-C12quinil - mono - or disubstituted amines, such that, without loss of generality, represent dimethylamine, diethanolamine, 2-methylthiopropionate, ballinameen, 2-butoxyaniline, cyclododecene, benzylamine or cyclic, or aromatic amines, optionally containing or not containing heteroatoms such, which are, among others, aziridine, azetidine, pyrrolidine, pyrrole, imidazole, tetrazole or morpholine. Amides can be obtained through the entries batch is I the corresponding acid chloride pikolinos acid, mixed anhydride or ester of the carboxylic acid corresponding to the Formula I with ammonia or an appropriate amine.

The terms "alkyl", "alkenyl" and "quinil", as well as derivative terms such as "alkoxy", "acyl", "alkylthio" and "alkylsulfonyl"as used herein, include unbranched chain, branched chain and cyclic part. Except where otherwise noted, each may be unsubstituted or substituted by one or more substituents, in addition to other selected from halogen, hydroxy, alkoxy, alkylthio, C1-C6acyl, formyl, cyano, aryloxy or aryl, provided that steric compatibility of deputies and the rules of chemical bonding and rules relating to energy stress. The terms "alkenyl" and "quinil" imply the presence of one or more multiple bonds.

The term "aryl", as well as derivatives terms such as "aryloxy", refers to phenyl, indanernas or naftilos groups, with preference given to phenyl group. The term "heteroaryl"as well as derivatives terms such as "heteroaromatic", refers to 5 - or 6-membered aromatic cycle containing one or more heteroatoms, namely N, O or S. These heteroaromatic cycles may be condensed with other Aro oticheskimi systems. Preferred are the following heteroaryl groups:

Aryl or heteroaryl substituents can be unsubstituted or can be substituted by one or more substituents selected from halogen, hydroxy, nitro, cyano, aryloxy, formyl, C1-C6of alkyl, C2-C6alkenyl, C2-C6the quinil, C1-C6alkoxy, halogenated C1-C6of alkyl, halogenated C1-C6alkoxy, C1-C6acyl, C1-C6alkylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfonyl, aryl, C1-C6OC(O)alkyl, C1-C6NHC(O)alkyl, C(O)OH, C1-C6C(O)Valkila, C(O)NH2C1-C6C(O)NH, C1-C6C(O)N(alkyl)2, -OCH2CH2-, -OCH2CH2CH2-, -OCH2O -, or-OCH2CH2O-, provided that the substituents are sterically compatible and the rules of chemical bonding and rules relating to energy stress, are met. Preferred substituents include halogen, C1-C2alkyl and C1-C2halogenated.

Except where otherwise noted, the term "halogen"includes derivative term, such as "halo"refer to fluorine, chlorine, bromine, and iodine. The terms "halogenated" and "halo is analsexy" refer to alkyl and alkoxygroup, substituted by halogen atoms, the number of which varies from 1 to the maximum number of halogen atoms.

The compounds of Formula I can be obtained by using well-known chemical methods. The necessary source materials are commercially available or can be easily obtained using standard techniques, see U.S. patent 6297197 B1.

The standard sequence of reactions of synthesis, whereby 6-(1,1-diferuloyl)pyridine Formula I can be obtained, shown in schemes 1 and 2:

Scheme 1

Scheme 2

The reaction of compounds alkoxyphenylbenzoates well-known examples in the following links:

(1) Sato, Nobuhiro et al., Synthesis (2001), (10), 1551-1555.

(2) Legros, J.-Y. et. al., Tetrahedron (2001), 57(13), 2507-2514.

(3) Guillier, F. et. al., Synthetic Communications (1996), 26(23), 4421-4436.

(4) Bracher, Franz; et al., Liebigs Annalen der Chemie (1993), (8), 837-9.

Corresponding reactions, such as diflorasone carbonyl, using conventional fluorinating reagents, such as (diethylamino)certified (DAST), give differencialnoe group at position 6.

Corresponding reactions, such as substitution of the corresponding 4-halogenopyrimidines azide, NaN3with subsequent reduction of the corresponding 4-Isidorovich, give the amino group in position 4.

Amino derivatives, is such as 4-N-amide, carbamate, urea, sulfonamide, silylamine and phosphoramidate, can be obtained by reaction of the free amine, for example, with a suitable galogenangidridy acid, chloroformiate, carbamoylation, sulphonylchloride, similiarites or chlorophosphate. Imin or hydrazone can be obtained by reaction of the free amine or hydrazine with a suitable aldehyde or ketone.

Substituted 4-aminoanisole can be obtained by the interaction of the 4-halogenfrei-2-carboxylate, or any other can replace Deputy, in position 4, with substituted amine.

The compounds of Formula I obtained by any of these methods, can be isolated using conventional methods. Usually the reaction mixture is acidified with aqueous solution of acid, such as hydrochloric acid, and extracted with an organic solvent such as ethyl acetate or dichloromethane. Organic solvent and other volatiles can be removed by distillation or evaporation to obtain the desired compounds of Formula I, which can be purified using standard procedures, such as recrystallization or chromatography.

As it was found that the compounds of Formula I are applicable as prescheduled and post-harvest herbicides. They can be used not izbiratelnyh (higher) rate to combat the vegetation of a wide spectrum of on-site or at a lower rate for the selective control of unwanted vegetation. Applications include grazing land and land suitable for grazing, road curb and right-of-way, transmission line and any industrial areas where controlling undesirable vegetation is necessary. Another application is controlling undesirable vegetation in crops such as wheat. They can also be used for controlling undesirable vegetation in tree crops such as citrus, Apple, rubber tree, oil palm, forest vegetation, and others. Usually prefer to use post-harvest connection. In addition, generally prefer to use these compounds to combat a wide variety of woody plants, broadleaf and grassy weeds and sedges. The use of these compounds for controlling undesirable vegetation in rooted crops especially necessary. While each of the compounds 6-(1,1-diferuloyl)-4-aminopyridine corresponding to the Formula I, is included in the scope of the invention, the degree of herbicide activity, selectivity with respect to crop and get the spectrum of weeds controlled vary, depending on the present deputies. Connect the tion, as herbicide suitable for any particular application can be determined using the information present in this document, and by standard testing.

The term "herbicide" is used herein to refer to the active component, which destroys, regulates, or otherwise adversely modifies the growth of plants. Number, effectively providing herbicide exposure or engaged in the fight against vegetation, represents the number of the active component, which causes the effect of adverse changes and includes a deviation from normal development, destruction, regulation, drying, delay and the like. The terms "plant" and "vegetation" includes sprouted seeds, emerging seedlings and rooted vegetation.

Compounds of the present invention exhibit herbicide activity with their direct application to the plant or at the location of the plant at any stage of development or before planting, or before entering into the phase of earing. The observed effect depends on the plant species, which are subjected to control, phase of plant development, the characteristics of the dilution caused by the connection and the size of the droplets in spraying, the particle size of solid components, the conditions of the physical environment during the application of the herbicide, specific compounds which are used, specific excipients and carriers, soil type, and the like, and the number of the applied chemical. As is well known in this field of knowledge, these and other factors can be adjusted to facilitate non-selective or selective herbicide exposure. Generally speaking, preferably post-harvest application of compounds of the Formula I on the relatively underdeveloped undesirable vegetation to achieve the maximum effect in the fight against weeds.

Commonly used standards applying at the post-harvest application ranges from 1 to 2000 g/ha; when predsjednik the application usually use standards from 1 to 2000 g/ha When setting higher standards application usually get non-selective control of a great variety of unwanted vegetation. Lower rates of application usually lead to electoral control and can be used in areas where the crops.

Often, to be able to deal with a large variety of unwanted vegetation, the best method of applying herbicide compounds of the present invention is its application in conjunction with one or more other herbicides. When used in conjunction with other what herbicide claimed in the present invention compounds can be combined into a common structure with other herbicides or herbicide, by mixing in a mixing tank, or can be applied sequentially with the other herbicide or herbicides. Some of the herbicides that can be used together with the compounds of the present invention, include sulfonamides, such as metosulam, flumetsulam, karenalloy, dicloflam, penoxsulam and florasulam; sulfonylureas, such as chlorimuron, tribenuron, sulfometuron, nicosulfuron, chlorsulfuron, amidosulfuron, triasulfuron, prosulfuron, tritosulfuron, thifensulfuron, sulfosulfuron and metsulfuron; imidazolinone, such as imazaquin, imazapic, imazethapyr, ISAPI, imazamethabenz and imazamox; phenoxyalkanoic acids such as 2,4-D, MCPA, dichlorprop and mecoprop; pyridinecarboxylic acid, such as triclopyr and fluroxypyr, carboxylic acids, such as clopyralid, picloram, aminopyralid and dicamba, dinitroanilines, such as trifluralin, benefin, benfluralin, pendimethalin; chloroacetanilide, such as alachlor, acetochlor and metolachlor; semicarbazone (inhibitors of auxin transport, such as chlorflurazole and diflubenzuron; aryloxyphenoxy, such as fluazifop, haloxyfop, diclofop, clodinafop and fenoxaprop, and other common herbicides, including glyphosate, glufosinate, alfthan, bentazon, clomazone, famiclone is, fluometuron, fomesafen, lactofen, linuron, Isoproturon, Simazine, norflurazon, paraquat, Diuron, diflufenican, picolinafen, cinidon, sethoxydim, tralkoxydim, quinmerac, isoxaben, bromoxynil, metribuzin and mesotrione. Herbicide compounds of the present invention, furthermore, can be used in conjunction with glyphosate and glufosinate to agricultural crops resistant to glyphosate or glufosinate. It is generally preferable to use the compounds according to this invention in combination with herbicides, which have selectivity with respect to the cultivated crop and the rate of application complete the spectrum of weeds controlled by these compounds. In addition, is usually the preferred simultaneous application of the compounds according to the invention and other complementary herbicides or combined drug composition, or in the form of a mixture obtained in the hopper of the mixer.

To improve the selectivity of the compounds of the present invention, as a rule, can be used in combination with known herbicide-Safarli, such as cloquintocet, furilazole, dichlormid, enoxacin, meterail, penconazole, Florasol, dameron, timepart, thiobencarb, felorin and fluxotine. They advanced meters which may be used for controlling undesirable vegetation in many crops, which made them resistant or immune to them or to other herbicides by genetic manipulation or by mutation and selection. For example, rye, wheat, rice, soybean, sugar beet, cotton, canola and other crops that have been converted into resistant or immune to compounds that are inhibitors acetolactate sensitive to them in plants, can be processed. Many crops resistant to glyphosate and glufosinate, can also be treated with these herbicides, or a combination with other herbicides. Some crops (e.g. cotton) were transformed into sustainable culture in relation to euxinum herbicides, such as 2,4-dichlorophenoxyacetic acid. These herbicides can be used to handle such sustainable agricultural crops or other resistant to auxin crops.

When possible the direct use of the compounds 6-(1,1-diferuloyl)-4-aminopyridine corresponding to the Formula I as herbicides, it is preferable to use them in mixtures containing an amount of compound effective as a herbicide, together with at least one auxiliary substance and a carrier, acceptable in agriculture. Suitable excipients or carriers should not be phyto-toxic with respect to valuable crops, in particular, at the concentrations used in the coating compositions in the presence of crops, when carried out selective weed control, and should not chemically interact with the compounds of the Formula I or with other components of the composition. Such mixtures can be prepared for direct use on plants or at their location or they can be concentrates or preparations, which usually before applying diluted with additional carriers and excipients. They can be solids, such as powders, pellets, granules, dispersible in water, or wettable powders, or liquids such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions.

Suitable for agricultural products, excipients and carriers, which are used in obtaining herbicide mixtures according to the invention, are well known to specialists in this field.

Liquid media that can be used include water, toluene, xylene, benzene, vegetable oil, acetone,methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amylacetate, butyl acetate, onomatology ether of propylene glycol and onomatology ether of diethylene glycol, methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, glycerin and the like. Water is usually the best medium for diluting concentrates.

Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgite clay, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fallerovo land, bolls seed cotton, wheat flour, soybean flour, pumice, wood flour, flour from a nutshell, lignin and the like.

It is often desirable to include in the composition of the present invention, one or more surface-active agents. Such surface-active agents, mainly used in solid and liquid compositions, especially those which are made in such a way that before applying them should be diluted with a carrier. Surface-active agents in nature can be anionic, cationogenic or nonionic and may be used as emulsifying means, moisturizers, suspendresume tools or can be used for other purposes. Standard surface-the asset is s agents include alkylsulfate salt, such as diethanolammonium; alkylarylsulfonate, such as qualitydetermination; addition products of alkylphenol to alkilinity, such as addition products of Nonylphenol to C18the ethoxylate; addition products of alcohol to alkilinity, such as addition products tridecylalcohol alcohol to C16the ethoxylate; Soaps, such as sodium stearate; alkylnaphthalene salts such as nutritionallybalanced; complex dialkyl ethers sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; esters of sorbitol, such as sorbifolia; Quaternary amines, such as lauryldimethylamine; esters of polyethylene glycol and of fatty acids, such as polietilenglikolmonostearat; block copolymers of ethylene oxide and of propylene oxide; and salts of mono - and dialkylphosphate esters.

Other excipients commonly used in the compositions used in agriculture include agents that promote compatibility, antifoaming agents, sequestered agents, neutralizing agents and buffers, corrosion inhibitors, dyes, fragrances, tools to facilitate the distribution of funds to facilitate penetration, a means of facilitating adhesion, dispersing agents, thickening agents, the means by which gaudie the freezing point, antimicrobial agents and the like. The composition can also contain other compatible components, for example, other herbicides, growth regulators of plants, fungicides, insecticides and the like, and can be combined in a single composition with liquid fertilizers or solid carriers, representing a fertilizer in the form of particles, such as ammonium nitrate, urea and the like.

The concentration of active ingredients in herbicide compositions according to this invention is usually from 0.001 to 98 mass%. Often use concentrations of from 0.01 to 90 weight percent. In the compositions for use in the form of concentrates, the active ingredient is typically present in a concentration of from 5 to 98 weight percent, preferably from 10 to 90 mass%. Such compositions usually before applying diluted neutral media, such as water. The diluted compositions usually applied to weeds or their location, usually contain from 0.0001 to 1 weight percent active ingredient and preferably contain from 0.001 to 0.05 mass%.

These compositions can be applied to weeds or their location through the use of conventional ground or air dusters, sprayers and apparatus for made the deposits of granular, by addition to irrigation water, as well as other standard methods known to experts in this field.

The following examples are offered to illustrate various aspects of the present invention, and they should not be construed as limitations on the invention. The source materials used to produce compounds of the present invention, such as 3,4,6-trichloropyridin-2-carboxylic acid, described in U.S. patent 6297197 B1.

EXAMPLES

1.Obtain Methyl 6-acetyl-3,4-dichloropyridine-2-carboxylate

Through a solution of methyl 3,4,6-trichloropyridin-2-carboxylate (2.00 g, 8,31 mmol), ethoxyphenylurea (3,09 ml, to 9.15 mmol) and resifted (2,78 g, 18,30 mmol) in dioxane (50 ml) for 15 minutes was barbotirovany nitrogen. Then added dichlorobis(triphenylphosphine)palladium (II) (292 mg, 0.42 mmol) and the mixture is warmed up at 100°C for 3 hours. After cooling, the mixture was concentrated, absorbed with ethyl acetate and filtered through a layer of silica gel. The solvent was removed and then the crude intermediate amoxilonline product was dissolved in a solution of tetrahydrofuran (50 ml) and 1 N. acid HCl (20 ml). After stirring the mixture at room temperature over night, the tetrahydrofuran was removed in vacuo and the remaining aqueous phase was extracted with ethyl acetate. The organic layers merge the Lee, dried (MgSO4) and concentrated. Purification of column chromatography (10% ethyl acetate in hexane) gave methyl 3,4-dichloro-6-acetylpyridine-2-carboxylate (0,98 g, 3.95 mmol) as white solids;1H-NMR (CDCl3): δ to 8.20 (s, 1H), of 4.05 (s, 3H), 2,71 (s, 3H).

Similarly received:

Methyl 6-acetyl-4-amino-3-chloropyridin-2-carboxylate;1H-NMR (CDCl3): δ 7,06 (s, 1H), 6,95 (sh. s, 2H), 1,90 (t, 3H).

2.Obtaining Methyl 3,4-dichloro-6-(1,1-dottorati)pyridine-2-carboxylate

(Diethylamino)certified (DAST, 2.66 ml, 20 mmol) was added to a solution of methyl 6-acetyl-3,4-dichloropyridine-2-carboxylate (0.50 g, 2 mmol) in methylene chloride (25 ml). After stirring for 3 days at room temperature the reaction mixture was poured into a saturated solution of salt. The organic layer was separated and the aqueous phase was extracted with dichloromethane. The organic layers were combined, dried (MgSO4) and concentrated in vacuum. Purification of column chromatography (10% ethyl acetate in hexane) gave methyl 3,4-dichloro-6-(1,1-dottorati)pyridine-2-carboxylate (0.36 g, of 1.33 mmol) as a yellow liquid.1H-NMR (CDCl3): δ a 7.85 (s, 1H), was 4.02 (s, 3H), 2,02 (t, d= 18.7 Hz, 3H).

3.Obtain Methyl 4-amino-3-chloro-6-(1,1-dottorati)pyridine-2-carboxylate (Compound 1)

Sodium azide (26.5 mg, 0.41 mmol) was added to a solution of methyl 3,4-dichloro-6-(1,1-dottorati)pyridine-2-carboxylate (100 is g, of 0.37 mmol) in dimethylformamide (2 ml) and water (0.2 ml). After stirring the reaction mixture for 5 hours at 50°With its extinguished with water, was extracted with diethyl simple ether. The organic phase was dried and concentrated to get the crude compound 4-azide. It is instantly absorbed by methanol (2 ml) and carefully added detribalized (21 mg, 0.55 mmol). After stirring for 10 minutes was added water and the mixture was concentrated. Added ethyl acetate and the mixture was washed with a saturated solution of salt. The organic layer was dried (MgSO4), filtered and concentrated to dryness. The crude product was purified column chromatography (20% ethyl acetate in hexane) to obtain methyl 4-amino-3-chloro-6-(1,1-dottorati)pyridine-2-carboxylate (53 mg, 0.21 mmol) in the form of butter.1H-NMR (CDCl3): δ? 7.04 baby mortality (s, 1H), 4.92 in (sh. s, 2H), 3,98 (s, 3H), of 1.97 (t, d=18.7 Hz, 3H).

4.Getting 4-amino-3-chloro-6-(1,1-dottorati)pyridine-2-carboxylic acid (Compound 2)

A solution of lithium hydroxide (159 mg, of 1.27 mmol) in water (6 ml) was added to a solution of methyl 4-amino-3-chloro-6-(1,1-dottorati)pyridine-2-carboxylate (159 mg, to 0.63 mmol) in tetrahydrofuran (6 ml). The mixture was intensively stirred at room temperature overnight and then concentrated almost to dryness. After adding water, the reaction mixture was washed once with ethyl acetate, to adelineadrianaalanaalexa the original substances. Then the aqueous layer was acidified using 1 N. HCl to pH 3 smaller, and were extracted with ethyl acetate. The organic layer was dried (MgSO4), concentrated and the residue triturated in cold hexane to obtain 4-amino-3-chloro-6-(1,1-dottorati)-pyridine-2-carboxylic acid (105 mg, 0.44 mmol) as white solids;1H-NMR (DMSO-d6): δ 7,02 (s, 1H), 6,94 (sh. s, 2H), 1,90 (t, 3H).

Alternative to obtain Methyl 6-acetyl-4-amino-3-chloropyridin-2-carboxylate:

(Diethylamino)certified (2.66 ml, 20 mmol) was added to a solution of methyl 6-acetyl-4-amino-3-chloropyridin-2-carboxylate (0.50 g, 2,19 mmol) in methylene chloride (40 ml). After stirring at room temperature for 3 days the reaction mixture was poured into a saturated solution of salt. The organic layer was separated and the aqueous phase was extracted with dichloromethane. The organic layers were combined, dried (MgSO4) and concentrated in vacuum. The crude residue was dissolved in THF (THF) (25 ml) was added LiOH solution (0,46 g, 10.9 mmol) in water. After stirring over night the day before the half and was washed once with EtOAc. Then acidified with a saturated aqueous solution of citric acid. Was extracted with EtOAc and dried to obtain the crude acid. Was purified using preparative HPLC (70% CH3CN, operative time was 3.5 min) to obtain 4-amino-3-chloro-6-(1,1-dottorati)Piri is in 2-carboxylic acid as a white solid acid, 238 mg (46% for 2 stages).

5.Obtaining herbicide compositions

In the following illustrative compositions parts and percentages are given in mass ratio.

EMULSIFIABLE CONCENTRATES

Stepon C-65
Drug A
wt.%
Connection 126,2
Polyglycol 26-3 (Nonionic emulsifier (deformaty)perpoli-(oxypropylene)block-poly-(oksietilenom). The content of the polyoxyethylene is 12 mol)5,2
Witconate P12-20 (Anionic emulsifier-qualitydetermination - 60 wt.% active)5,2
Aromatic 100 (aromatic solvent number of xylene)63,4
Drug
wt.%
Connection 13,5
Sunspray 11N (paraffin oil)40,0
Polyglycol 26-319,0
Oleic acid1,0
Aromatic solvent number of xylene36,5
Drug
wt.%
Connection 113,2
25,7
Ethomeen T/257,7
Ethomeen T/1518,0
Aromatic solvent number of xylene75,4
The drug D
wt.%
Connection 130,0
Agrimer A1-10LC (emulsifier)3,0
N-methyl-2-pyrrolidone67,0
Drug E
wt.%
Connection 110,0
Agrimul 70-A (dispersant)2,0
Amsul DMAP 60 (thickener)2,0
Emulsogen M (emulsifier)8,0
Attagel 0 (accelerator suspension)2,0
Vegetable oil76,0

These concentrates can be diluted with water to obtain emulsions of suitable concentrations for weed control.

WETTABLE POWDERS

Drug F
wt.%
Connection 226,0
Polyglycol 26-32,0
Polyfon H4,0
Zeosyl 100 (precipitated hydrated SiO2)of 17.0
Baranowska clay + neutral components51,0
The product G
wt.%
Connection 262,4
Polyfon H (sodium salt ligninsulfonate)6,0
Sellogen HR (nitronaphthalene)4,0
Zeosyl 10027,6
Preparation H
wt.%
Connection 21,4
Kunigel VI (medium)30,0
Stepanol ME Dry (humidifier)2,0
Tosnanon GR 31A2,0
Kaolin NK-300 Clay (filler)64,6

The active component is applied on the appropriate media and then mixed and pulverized to obtain a wettable powder having excellent wettability and suspendida ability. The diluting these wettable powders with water gives the opportunity to obtain suspensions of the desired concentration for weed control.

GRANULES, DISPERGIRUJUTSJA IN WATER

The drug I
wt.%
Connection 226,0
Sellogen HR4,0
Polyfon H5,0
Zeosyl 100of 17.0
Kalinicheva clay48,0

The active ingredient is added to gidratirovannom the silicon dioxide, which is then mixed with other components and crushed to powder. Powder aglomerados with water, sieved to obtain granules with a size of -10 to +60 mesh. Dispersive these granules in the water, you can get suspensie the desired concentrations for weed control.

GRANULES

The J drug
wt.%
Connection 25,0
Celetom MP-8895,0

The active ingredient is applied in a polar solvent such as N-methylpyrrolidone, cyclohexanone, gamma-butyrolacetone and so on, to the media Celetom MP 88 or other suitable media. The resulting granules can be applied manually using the machine for the application of granular fertilizers, spraying from an airplane, and so forth, for weed control.

The drug K
wt.%
Connection 21,0
Polyfon H8,0
Nekal BA 772,0
The zinc stearate2,0
Baranowska clayof 87.0

All substances were mixed and crushed to a powder, then added water and clay mixture was stirred to form a paste. The mixture was passed through an extruder to obtain pellets of the desired size.

LIQUID, SOLUBLE IN WATER

The drug L
wt.%
Connection 2to 3.67
Monoethanolamine an acid-base buffer0,5
Water95,83

The active ingredient was dissolved in appropriate amount of water and, optionally, as a buffer was added monoethanolamine. It is permissible to add water-soluble surfactant. Other excipients can be introduced to improve the physical, chemical and/or compositional properties.

6.Assessment of post-harvest activity of herbicides

Seeds selected for test plant species were planted in plastikoperationer with surface area, part of 64 square centimeters, planting a mixture of Grace-Sierra MetroMix® 306, which normally has a pH from 6.0 to 6.8 and contains 30 percent organic matter. Treatment with fungicides and/or other chemical or physical processing was used when it was necessary to ensure good germination and healthy plants. The plants were grown for 7-21 days in the greenhouse, the length of daylight in which was approximately 15 hours. The temperature during the day was maintained in the range from 23 to 29°and during the night - in the range of 22 to 28°C. Nutrients and water was added regularly, and dosvechivanie if necessary, was performed using available above metallogenetic lamps of 1000 watts. Plants used for testing, when they had reached the stage of the first or second true leaf.

To obtain a concentrated basic solutions of the weighted number, the value of which was determined for each test compound at the maximum dose being tested were placed in a 20 ml glass vial and was dissolved in 4 ml of 97:3.about. (volume/volume) mixture of acetone and dimethyl sulfoxide (DMSO). If the test compound did not dissolve quickly, the mixture was heated and/or treated by ultrasound. To obtain solutions of known concentration for spraying obtained to the centered main solutions were diluted with water mixture, containing acetone, water, isopropyl alcohol, DMSO, Atplus 411 F, concentrate, vegetable oil and surfactant Triton X-155 in the ratio by volume, comprising 48,5:39:10:1,5:1,0:0,02. Solutions for testing, containing the highest concentrations were obtained by dilution of the primary solution in number by a multiple of 2 ml, 13 ml of the mixture, and lower concentrations were obtained by serial dilution of the primary solution. The number of multiples of approximately 1.5 ml of each solution of known concentration was sprayed evenly on each of the containers with the tested plants using atomized sprayer DeVilbiss company, driven by compressed air with a pressure of 2 to 4 psi (140 to 280 kPa)to achieve full coverage of each plant. Control plants were sprayed in the same way water mixture. In this experiment, the rate of application, component 1 h/million, consistent with the application of approximately 1 g/ha

Treated plants and control plants were placed in the greenhouse, such as described above, and watered by the way subsoil irrigation, to prevent washout of the test compounds. After 2 weeks visually compared the condition of the test plants with state of the untreated plants was estimated in percentage on a scale graduated from 0 to 100, p is Acento, where 0 corresponded to no damage to plants, and the numeral 100 corresponded to the complete destruction of the plants.

When applying the conventional probit analysis as described by the authors J. Berkson in the Journal of the American Statistical Society, 48, 565 (1953) and D. Finney in "Probit Analysis" Cambridge University Press (1952), the above data can be used for calculating quantities GR50and GR80that determine how the factors weakening development, which correspond to an effective dose of herbicide required for the complete destruction or control, respectively with 50 or 80 percent of the plants of the target.

Table 1 shows some of the tested compounds used norms of application, types of test plants and the results obtained. The selectivity with respect to the crops of wheat are shown in table 2.

Table 1
Post-harvest treatment (% damage)
ConnectionRate (h/m)XANSTCHEALECHCGSETFA
12451001007565
2 2501001008085
XANST = cocklebur(Xanthium strumarium)< / br>
CHEAL = pigweed white(Chenopodium album)< / br>
ECHCG = plushie millet(Echinochloa crus-galli)< / br>
SETFA = spickle giant(Setaria faberi)
Table 2
Post-harvest treatment (% damage)
ConnectionNormaCHEALAMARETRZAS
11231001000
CHEAL = pigweed white(Chenopodium album)< / br>
AMARE = sirica(Amaranthus retroflexus)< / br>
TRZAS = wheat soft(Triticum aestivum)

7.Assessment predsjedava activity of herbicides

Seeds of the test plants of the desired species were planted in the underlying soil, obtained by mixing loamy soil (43% silt, 19% clay and 38 percent sand, with a pH of 8.1 and organic matter content, comprising 1.5 percent) and sand in the ratio of 70 to 30. Soil was placed in plastic containers with a surface area, component 113 Quadrat is x inches. Treatment with fungicides and/or other chemical or physical processing was used when it was necessary to ensure good germination and healthy plants.

To obtain a concentrated basic solutions of the weighted number, the value of which was determined for each test compound at the maximum dose being tested were placed in a 20 ml glass vial and was dissolved in 4 ml of 97:3.about. (volume/volume) mixture of acetone and dimethyl sulfoxide. If the test compound did not dissolve quickly, the mixture was heated and/or treated by ultrasound. Received basic solutions were diluted 99,9:0,1 a mixture of water and surfactant Tween brands® 155 to obtain solutions of known concentration for application to plants. Solutions for testing, containing the maximum concentrations were obtained by dilution of the primary solution in number by a multiple of 2 ml, 15 ml of the mixture, and lower concentrations were obtained by serial dilution of the primary solution. The number of multiples of approximately 2.5 ml of each solution of known concentration was sprayed evenly over the soil surface (113 cm2each container, the seeds were sown using a 5.0 ml syringe with a glass cylinder firms Cornwall, equipped with a nozzle with a hollow spray brand TeeJet TN-3, to dostijeniyah coverage of the soil in each container. Control containers were sprayed in the same way water mixture.

Treated and control containers were placed in the greenhouse, which supported approximately 15 hours of light per day, and day and night temperatures were maintained respectively in the range from 23 to 29°and in the range of 22 to 28°C. Nutrients and water was added regularly, and dosvechivanie, if necessary, was performed using available above metallogenetic lamps of 1000 watts. Water was added through surface irrigation. After 3 weeks the condition of the test plants, the development and growth of which was compared with the development and growth of the untreated plants was assessed visually, and in percentage on a scale graduated from 0 to 100 percent, where 0 corresponded to no damage to plants, and the numeral 100 corresponded to the complete destruction of plants or lack of development.

Table 3 shows some of the tested compounds used norms of application, types of test plants and the results obtained.

td align="center"> DIGSA
Table 3
Predsjedava treatment (% damage)
ConnectionRate (h/m)CHEALIPOHESETFA
1560100100100100
25601001009895
CHEAL = pigweed white(Chenopodium album)< / br>
IPOHE = Impala plyuschevidnaya(Ipomoea hederacea)< / br>
DIGSA = creeping weed (large)(Digitaria sanguinalis)< / br>
SETFA = spickle giant(Setaria faberi)

1. The compound of the formula I

in which

Y represents-CF2(C1-C3alkyl); and

W represents-NR1R2,

where

R1and R2independently represent N or C1-C6alkyl; and

acceptable in agriculture derivative at the carboxy group or a 4-amino group.

2. Compounds according to claim 1, in which Y represents-CF2CH3.

3. The compound according to claim 1, in which Y represents-CF2CH3, and W represents-NH2.

4. Herbicide composition containing the compound of the formula I according to claim 1 in an effective amount as a herbicide in the mixture with acceptable in agriculture auxiliary substance or medium.

5. The method of controlling undesirable vegetation, which comprises contactyou is their vegetation or its location with effective as a herbicide, a number of the compounds of formula I according to claim 1, or applying it to the soil to prevent the emergence of seedlings.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: compound of formula (I) wherein X represents H or F; Y represents C1-C4 alkyl;C1-C4 alkyl substituted C1-C4 by the group alkoxy; C1-C4 alkyl substituted by the group C1-C4 thioalkoxy, or C2-C3 alkenyl; and agriculturally acceptable salts and esters of carboxylic acid group. The compounds have herbicide potency. The herbicide composition and the method of weed control using the compound of formula (I) are also described.

EFFECT: production of the compound characterized with herbicide potency.

4 cl, 5 tbl, 14 ex

FIELD: organic chemistry, medicine, biochemistry, pharmacy.

SUBSTANCE: invention relates to compounds inhibiting activity of hormone-sensitive lipase and represented by structure of the formula: (XXXXIVa)

and the formula (XXXXIVb): wherein R1ap and R2ap are chosen independently from (C1-C6)-alkyl, aryl wherein each (C1-C6)-alkyl and aryl can be substituted optionally with one or some substitutes chosen independently from halogen atom, (C1-C6)-alkyl under condition that if R1ap and R2ap are similar then they are not methyl or ethyl, and wherein between substitutes R1ap and R2ap can be a covalent bond optionally, and wherein R5ap, R6ap and R7ap are chosen independently from hydrogen atom and fluorine atom (F), and R4ap is chosen from hydrogen atom, sulfanyl, halogen atom, amino-, nitro-group, (C1-C6)-alkyl, heteroaryl, (C3-C8)-heterocyclyl wherein each among sulfanyl, amino-group, (C1-C6)-alkyl, heteroaryl, (C3-C8)-heterocyclyl can be substituted optionally with one or some substitutes chosen independently from hydroxy-, oxo-group, halogen atom, (C1-C6)-alkyl, aryl, heteroaryl wherein each among (C1-C6)-alkyl, aryl, heteroaryl can be substituted optionally with one or some substituted chosen independently from oxo-group, halogen atom, amino-group, (C1-C6)-alkyl, (C3-C8)-heterocyclyl wherein each among amino-group, (C1-C6)-alkyl, (C3-C8)_heterocyclyl can be substituted optionally with one or some substitutes chosen independently from oxo-group, (C1-C6)-alkyl wherein (C1-C6)-alkyl can be substituted optionally with one or some substitutes chosen independently from oxo-group under condition that R4ap is not methyl. Also, invention relates to a pharmaceutical composition and using these compounds for preparing a medicinal agent used for inhibition of lipolytic activity of hormone-sensitive lipase. Invention describes compounds that can be useful in treatment and prophylaxis of clinical disorders wherein decrease of activity of hormone-sensitive lipase is desirable.

EFFECT: valuable medicinal and biochemical properties of compounds and pharmaceutical composition.

8 cl, 1 tbl, 602 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of 4-phenylpyridine of the general formula: (I) wherein R means halogen or halogen atom; R1 means -(C≡C)mR1' or -(CR'=CR'')mR1'; X means -C(O)N(R8)-, -N(R8)C(O)- or -N(R8)-(CH2)p- wherein m = 0-4 and p = 1-2; values of radicals R1', R2, R3', R3, R4, R4', R8, R' and R'' are given above, and to their pharmaceutically acceptable acid-additive salts and a medicinal agent based on thereof. New compounds are neurokinine-1 antagonists and can be used as medicinal agents in treatment of diseases mediated by neurokinine-1 receptors.

EFFECT: valuable medicinal properties of derivatives.

13 cl, 119 ex

FIELD: chemical technology.

SUBSTANCE: method for preparing tetrachloropicolinic acid involves interaction of 2-cyanopyridine and chlorine in liquid phase in the melt at temperature 120-200°C under pressure up to 0.6 MPa in the presence of catalysts wherein phosphorus chlorides and oxychlorides are used in the mole ratio of 2-cyanopyridine to catalyst = 1:(0.1-1.0) followed by dissolving the reaction mixture in inert solvent, addition of water at temperature 70-80°C, decomposition of phosphorus chlorides at increased temperature to yield hydrogen chloride and phosphoric acid, separation of phosphoric acid from organic layer and the following addition of sulfuric acid to organic layer and hydrolysis of residue by heating the mixture to 120-140°C. Method provides increasing yield and purity of the end product, simplifying technology, reducing cost for its preparing.

EFFECT: improved preparing method.

2 cl, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing tetrachloropicolinic acid. Method involves interaction of 2-cyanopyridine with chlorine in presence of catalysts wherein phosphorus chlorides are used in the amount 2-60 weight % of the initial load of 2-cyanopyridine, and phosphorus oxychlorides also. The chlorination process is carried out in the melt at temperature 120-200°C and under pressure up to 0.6 MPa followed by dosing the reaction mass into a mixture of water with sulfuric acid, and then hydrolysis is carried out in the presence of phosphoric acid formed after hydrolysis of phosphorus chlorides. The end product is isolated by the known procedures. Method provides simplifying the process by using the standard equipment, improving ecological indices and reducing energy consumptions.

EFFECT: improved preparing method.

2 cl, 6 ex

FIELD: organic chemistry, chemical technology, fungicides.

SUBSTANCE: invention describes derivative of benzoylpyridine of the formula (I) or its salt:

wherein X represents halogen atom, (C1-C6)-alkoxy-group optionally substituted with a substitute taken among halogen atom, phenyl, methoxy-, methylthio-, dimethylamino-group, vinyl or ethynyl; phenoxy-group, (C3-C6)-cycloalkoxy-group, hydroxyl group, (C1-C6)-alkyl group, (C2-C6)-alkenyl group, CF3, (C1-C6)-alkylthio-group, (C1-C6)-alkoxycarbonyl group, (C1-C6)-dialkylaminocarbonyl group, (C1-C6)-alkylcarbonyloxy-group, (C1-C6)-alkylcarbonyl group, amino-group, (C1-C4)-alkylamino-group or di-(C1-C4)-alkylamino-group; n represents 1, 2, 3 or 4; R1 represents (C1-C6)-alkyl group; R2 represents (C1-C6)-alkyl group, (C1-C6)-alkoxy-group optionally substituted with phenyl, phenoxy-group, (C3-C10)-cycloalkyloxy-group or hydroxyl group; m = 1, 2 or 3 under condition that if m = 2 then R2 can form ring -OCH2O- (with exception when pyridine ring is substituted with benzoyl group at 2-position; pyridine ring is substituted with (C1-C6)-alkoxy-group, hydroxyl group or benzyloxy-group; n = 1; m = 1 or 2). Also, invention describes fungicide comprising compound of the formula (I) or it salt as an active component, methods for preparing derivatives of benzoylpyridine, phenylpyridylmethanol that is an intermediate compounds used for synthesis of compound of the formula (I). Invention provides fungicide properties of compound of the formula (I) or its salt.

EFFECT: improved method for preparing, valuable properties of compounds.

17 cl, 36 tbl, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing some 4-aminopicolinic acids by electrochemical reduction. Invention relates to a method for selective reduction of halogen substitutes at position 5 of halogenated 4-aminopicolinic acids in the presence of halogen substitutes at positions 3 and 6. Invention represents a method for preparing 4-amino-3-halogenpicolinic acid of the formula (I): wherein X represents Cl or Br atom; Y represents H, Cl or Br atom. Method involves passing direct or alternating current from anode to cathode through 4-amino-3,5-dihalogenpicolinic acid solution of the formula (II): wherein and Y are given above and wherein both X represent either Cl atom or Br atom at cathode potential from -0.4 to -1.7 V relatively to the comparison electrode Ag/AgCl (3.0 M Cl-) and extraction of product under condition that when X represents Cl atom then Y doesn't mean Br atom. Invention provides possibility for selective reduction of halogenated amino-containing group pyridines.

EFFECT: improved method for preparing.

8 cl, 3 ex

FIELD: chemistry of metalloorganic compounds, medicine, oncology.

SUBSTANCE: invention relates to derivatives of platinum tetrachloride and to a method for their preparing also. Invention proposes compounds of the formula PtCl4 x 2 Li wherein Li represents N-(2-nitroxyethyl)nicotinamide or N-(2-nitroxyethyl)isonicotinamide, or nicotine hydroxamic acid, or isonicotine hydroxamic acid. Also, invention proposes a method for preparing these compounds that involves interaction of pyridine carboxylic acid nitroxyethylamides or hydroxamic acids, or their hydrochlorides with potassium hexachloroplatinate followed by isolation of the end product. Invention provides synthesis of the unknown early chelate platinum compounds that are physiologically active substances and can be used in medicinal practice instead cisplatin as effective anti-metastatic medicinal agents with low toxicity.

EFFECT: improved preparing method, enhanced and valuable medicinal properties of compounds.

2 cl, 3 ex

The invention relates to new derivatives of benzene or pyridine of the formula (I)

where R denotes H, C1-C7alkyl and halogen; R1denotes H or halogen, provided that in the 4th position R1not denotes bromine or iodine; R2denotes H or CF3; R3denotes N or C1-C7alkyl; R4denotes H, halogen, C1-C7alkyl and others; R5denotes N or C1-C7alkyl; X represents-C(O)N(R5)-, -N(R5)-C(O)- or-C(O)O-; Y represents -(CH2)n-, -O-, -S-, -SO2-, -C(O)- or N(R5’)-; R5’means (ness.)alkyl; Z represents =N-, -CH= or-C(C1)=; n denotes a number from 0 to 4; and their pharmaceutically acceptable salts

The invention relates to new triaromatic the vitamin D analogues of General formula (I):

where R1- CH3or-CH2HE, R2-CH2HE, X-Y - linkage of formula (a) or (C)

where R6- H, lower alkyl, W is O, S or-CH2-, Ar1, Ar2the cycles of formula (e), (j), (k), (m)

R8, R9, R11, R12- H, lower alkyl, halogen, HE, CF3,

R3-

where R13, R14- lower alkyl, CF3, R15- H, acetyl, trimethylsilyl, tetrahydropyranyl, or their salts

FIELD: agriculture, veterinary science.

SUBSTANCE: composition contains alphametrin, surface-active agent, alcohol, solvent chloracetophos, glycerine and dimethylsulfoxide; isopropyl alcohol - as alcohol, neonol - as surface-active agent, in the following ratio of components, wt %: alphametrin 5-10, chloracetophos 5-10, neonol AF 9-10, isopropyl alcohol 10-15, dimethylsulfoxide 3-6, glycerine 3-6, solvent remaining part. The composition contains propylene glycol and mixed benzine-oil solvent for rubber-processing industry with final boiling point of 80-120°C or mixed benzine-oil solvent with final boiling point of 50-170°C taken in the weight proportions equal to 1:(7-8) as a solvent.

EFFECT: increasing the composition efficiency.

3 tbl

FIELD: agriculture, chemistry.

SUBSTANCE: description is given to the application of a compound with formula (I) or its salt (compound (B), R1n means n R1 radicals, where R1 is a halogen; n is equal from 1 to 3; R2 and R3 stand for hydrogen, (C1-C6)alkyl; R4 stands for hydrogen or (C1-C12)alkyl to increase weed suppression activity of one or more aryloxiphenoxipropionate herbicides (A) chosen from phenoxaprop-P-ethyl, clodinafop-propargyl and diclofop-methyl or their agriculturally appropriate salts where weight proportion of the above components (A):(B) is equal to from 1:10 to 100:1.

EFFECT: improving weed control.

8 cl, 3 tbl, 3 ex

FIELD: agriculture.

SUBSTANCE: composition contains in wt %: polymer preparation Catapol - 0.05-0.2, furacilin - 0.005-0.015, dimethylsulfoxide - 0.1, water - remaining part.

EFFECT: increasing antibacterial activity of the composition.

7 ex, 11 tbl, 1 dwg

FIELD: medicine; pharmacology.

SUBSTANCE: presented are anilides of nicotinic acid of general formula I , where R means atom of hydrogen, halogen or benzyloxy-group, R' means atom of hydrogen or halogen, X means 2-furyl, 2-pyridyl, 3-pyridyl unsubstituted or substituted with phenyl halogen atom with fungicidal activity.

EFFECT: new compound are effective for hazardous fungi.

3 tbl, 6 ex

FIELD: agriculture.

SUBSTANCE: invention consists in use of preparations from rhizomes, roots, stalks, inflorescences and leaves of the serpent grass Polygonum bistorta L., which prepare in the officinal way, as means of controlling fresh-water mollusks. Using the specified means treat places of dwelling of fresh-water mollusks on a pasture or a box of the lowered pond.

EFFECT: provides practically utter annihilation of mollusks and their layings within three - six days.

6 ex

FIELD: agriculture.

SUBSTANCE: invention consists in use of preparations from rhizomes, roots, stalks, inflorescences and leaves of the marsh cinquefoil Comarum palustre L., which prepare in the officinal way, as means of controlling fresh-water mollusks. Using the specified means treat places of dwelling of fresh-water mollusks on a pasture or a box of the lowered pond.

EFFECT: provides practically utter annihilation of mollusks and their layings within three - six days.

6 ex

FIELD: agriculture.

SUBSTANCE: invention consists in use of preparations from roots, flowering branches, and leaves of the willow weed Lythrum salicaria L., which prepare in the officinal way, as means of controlling fresh-water mollusks. Using the specified means treat places of dwelling of fresh-water mollusks on a pasture or a box of the lowered pond.

EFFECT: provides practically utter annihilation of mollusks and their layings within three - six days.

6 ex

FIELD: biotechnologies.

SUBSTANCE: extract of purple Echinacea is prepared at the temperature of 60-70°C and ratio of water - ethanol mixture (1:1) and herbal raw materials 1:25-1:50 with further thermal melting of ballast proteins, their separation by means of centrifugation with further addition of 0.05-0.075% of nano-fraction of grape seeds and sterilisation of preparation with autoclaving.

EFFECT: makes it possible to increase growth-stimulating activity of product.

2 tbl, 7 ex

FIELD: agriculture.

SUBSTANCE: herbicidal composition is made on the bases of 3.6-dichlorpyridine-2-carboxylic acid and substituted arylsulfonylheterylcarbamide. As a derivative of 3.6-dichlorpyridine-2-carboxylic acid it contains alcohol esters of C7-C10 356- dichlorpyridine-2-carboxylic acid or their mixtures, at the following components ratio, wt %: C7-C10 alcohol esters; 3,6-dichlorpyridine-2-carboxylic acid or their mixture - 40-75; substituted arylsulfonylheterylcarbamide - 1-5; surface -active agent 15-35; carrying agent - the remaining.

EFFECT: increases consistency of composition.

3 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: in pyridylmethylanilides of heterocyclic acids of general formula I R stands for atom of hydrogen halogen or benzyloxy-group, R' stands for atom of hydrogen or halogen, X stands for 2-phuryl or 2-pyridyl.

EFFECT: increase of compound efficiency against harmful fungi.

1 cl, 3 tbl, 5 ex

FIELD: agriculture.

SUBSTANCE: herbicidal composition is made on the bases of 3.6-dichlorpyridine-2-carboxylic acid and substituted arylsulfonylheterylcarbamide. As a derivative of 3.6-dichlorpyridine-2-carboxylic acid it contains alcohol esters of C7-C10 356- dichlorpyridine-2-carboxylic acid or their mixtures, at the following components ratio, wt %: C7-C10 alcohol esters; 3,6-dichlorpyridine-2-carboxylic acid or their mixture - 40-75; substituted arylsulfonylheterylcarbamide - 1-5; surface -active agent 15-35; carrying agent - the remaining.

EFFECT: increases consistency of composition.

3 cl, 2 tbl, 12 ex

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