6-(polysubstituted aryl)-4-aminopicolinates and use thereof as herbicides

FIELD: chemistry.

SUBSTANCE: invention relates to a compound of formula used as herbicides, in which Q1 is H or F; Q2 is a halogen provided that when Q1 is H, Q2 is Cl or Br; R1 and R2 independently denote H, C1-C6-acyl; and Ar is a polysubstituted aryl group selected from a group consisting of

a) , b) , c) in which W1 is a halogen; X1 is C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenalkyl, -NR3R4; Y1 is C1-C4-alkyl, C1-C4-halogenalkyl, halogen or -CN, or when X1 and Y1 are taken together denotes -O(CH2)nO-, in which n=1; and R3 and R4 independently denote H or C1-C4-alkyl; W2 is F or Cl; X2 is F, CI, -CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylthionyl, C1-C4-alkylsulphonyl, C1-C4-halogenalkyl, C1-C4-halogenalkoxy, C1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4-alkoxy, -NR3R4 or fluorinated acetyl; Y2 is a halogen, C1-C4-alkyl, C1-C4-halogenalkyl or -CN, or when W2 is F, Xz and Y2, taken together, denote -O(CH2)nO-, in which n=1; and R3 and R4 independently denote H or C1-C6-alkyl; Y3 is a halogen or -CN; Z3 is F, CI, -NO2, C1-C4-alkoxy, -NR3R4; and R3 and R4 independently denote H; derivatives on the carboxyl group which are suitable for use in agriculture.

EFFECT: compounds are excellent herbicides with a wide range action against weeds and excellent selectivity towards agricultural crops.

19 cl, 7 tbl, 69 ex

 

This application claims the benefit of provisional application U.S. No. 60/758701, filed January 13, 2006, and 60/850145, filed October 6, 2006.

This invention relates, no doubt, to the new 6-(politeley aryl)-4-aminopyridinium and their derivatives and to the use of these compounds as herbicides.

In the art described, a number picolinic acids and their pesticidal properties. In U.S. Patent 6784137 B2 describes a series of 6-aryl-4-aminophylline acids and their derivatives, and their use as herbicides. Now discovered that certain individual subclasses of a number of compounds described in "137", have greatly improved herbicide activity and selectivity.

Now found that certain 6-(politeley aryl)-4-aminopyrine acids and their derivatives are excellent herbicides with a broad spectrum of weeds, grasses and sedges, as well as with broad-leaved and with excellent selectivity to crops. These compounds also possess excellent Toxicological and environmental performance.

This invention relates to compounds of the formula I:

in which

Q1represents H or F;

Q2is halogen, provided that when Q is H, Q2represents Cl or Br;

R1and R2independently represent H, C1-C6-alkyl, C3-C6alkenyl,3-C6-quinil, hydroxy, C1-C6-alkoxy, amino, C1-C6-acyl, C1-C6-carbalkoxy,1-C6-allylcarbamate,1-C6-alkylsulfonyl, C1-C6-trialkylsilyl or1-C6-dialkylphenol or R1and R2taken together with N represent a 5 - or 6-membered saturated ring; and

Ar represents polyamidine aryl group selected from the group consisting of

a)

in which

W1represents halogen;

X1represents F, Cl1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4-halogenated,1-C4-halogenoalkane,1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4-alkoxy, -CN, -NR3R4or fluorinated acetyl or propionyl;

Y1is1-C4-alkyl, C1-C4-halogenated, halogen or-CN, or, when X1and Y1taken together represents-O(CH2)nO-, where n =1 or 2; the

R3and R4independently represent H or C1-C4-alkyl;

b)

in which

W2represents F or Cl;

X2represents F, Cl, -CN, -NO2With1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4-halogenated,1-C4-halogenoalkane,1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4-alkoxy, -NR3R4or fluorinated acetyl or propionyl;

Y2represents halogen, C1-C4-alkyl, C1-C4-halogenated or-CN, or when W2is F, X2and Y2taken together represents-O(CH2)nO-, where n =1 or 2; and

R3and R4independently represent H or C1-C6-alkyl; and

C)

in which

Y3is halogen, -CN or CF3;

Z3represents F, Cl, -CN, -NO2With1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4-halogenated,1-C4-halogenoalkane,1-C4-alkoxysilane the 1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4-alkoxy, -NR3R4or fluorinated acetyl or propionyl; and

R3and R4independently represent H or C1-C6-alkyl; and

suitable in agriculture derivative on the carboxyl group.

Regardless of the preferred compounds of formula I, where Y1, Y2and Y3represent Cl, Br or CF3where W1and W2are Cl or F; where X1or X2are1-C4-alkoxy, C1-C4-dialkoxy,1-C4-halogenated or-NR3R4and where Z represents C1-C4-alkoxy, C1-C4-dialkoxy,1-C4-halogenated or-NR3R4.

This invention relates to herbicide compositions containing effective as a herbicide, the amount of the compounds of formula I, and suitable for agriculture derivative on the carboxyl group in a mixture with suitable agriculture auxiliary substance or medium. The invention also relates to a method of using compounds and compositions of the present invention, in order to destroy or to fight unwanted plants by applying an effective herbicide number of connections on the plants or on the area involved is my plants, as to the soil before emergence of the plants. The invention also relates to intermediate compounds for the preparation of the compounds.

Compounds of the present invention, have a weed-killing activity, are derivatives of 4-aminophylline acids of the formula II:

in which

Q1represents H or F;

Q2is halogen, provided that when Q1is H, Q2represents Cl or Br; and

Ar represents polyamidine aryl group selected from the group consisting of

a)

in which

W1represents halogen;

X1represents F, Cl1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4-halogenated,1-C4-halogenoalkane,1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4-alkoxy, -CN, -NR3R4, fluorinated acetyl or propionyl;

Y1is1-C4-alkyl, C1-C4-halogenated, halogen or-CN, or, when X1and Y1taken together represents-O(CH2)nO-, where n = 1 or 2; and

R3and R4independently presented Aut H or C 1-C4-alkyl;

b)

in which

W2represents F or Cl;

X2represents F, Cl, -CN, -NO2With1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4-halogenated,1-C4-halogenoalkane,1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4-alkoxy, -NR3R4, fluorinated acetyl or propionyl;

Y2represents halogen, C1-C4-alkyl, C1-C4-halogenated or-CN, or when W2is F, X2and Y2taken together, represent-O(CH2)nO-, where n = 1 or 2; and

R3and R4independently represent H or C1-C6-alkyl; and

C)

in which

Y3is halogen, -CN or CF3;

Z3represents F, Cl, -CN, -NO2With1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4-halogenated,1-C4-halogenoalkane,1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxysilane is hydrated With 1-C4-alkoxy, -NR3R4, fluorinated acetyl or propionyl; and

R3and R4independently represent H or C1-C6-alkyl.

These compounds are characterized by the fact that we have Cl or F in the 3-position, H or F in the 5-position and tri - or Tetra-substituted aryl group in 6-position of the pyridine ring. Mostly preferred compounds in which the 3-position is Cl and 5-position is H. Preferred substituted aryl groups include 2,3,4-triple-substituted, 2-fluoro-4,5-triple-substituted and 2-fluoro-4,5,6-Tetra-substituted phenyl group. Particularly preferred substituted aryl groups include those in which Y1, Y2and Y3represent Cl, Br or CF3in which W1and W2are Cl or F; where X1or X2are1-C4-alkoxy, C1-C4-dialkoxy,1-C4-halogenated or-NR3R4in which Z represents C1-C4-alkoxy, C1-C4-dialkoxy,1-C4-halogenated or-NR3R4.

The amino group in 4-position of the pyridine ring may be unsubstituted or substituted by one or more1-C6-alkyl, C3-C6alkenyl,3-C6-quinil, hydroxy, C1-C6-alkoxy or aminosalicylate. Aminor the PAP, in addition, can be converted into an amide, carbamate, urea, sulfanilamide, silylamine or phosphoramidate. Such compounds are able to split up to Amin. Unsubstituted amino group is preferable.

Believe that carboxylic acids of formula I are compounds that really destroy or carry out unwanted plants, and they are usually preferred. The analogues of these compounds in which the carboxyl group is pikolinos acid is converted so as to form a group that can be transformed into plants or the environment carboxyl group, have essentially the same herbicide action and included in the scope of this invention. Therefore, suitable in agriculture derived, when used to describe a carboxyl function in the 2-position, is defined as any salt, ester, acylhydrazides, imidate, thioimidate, amicin, amide, orthoepy, achilleid, allalone, thioether, ether tinuloy acid, thioether tinuloy acid, nitrile or any other well known in the art derived acids, which (a) does not influence significantly on herbicide activity of the active ingredient, i.e. the 6-aryl-4-aminophylline acid, and (b) hydrolyzed (or can be either hydrolyzed), oxidized (or may be oxidized), metabolizes what I (or can be metabolized in plants or soil to Pikalyovo acid of the formula I, which, depending on pH, is dissociated or not dissociated form. Preferred suitable in agriculture derivatives of carboxylic acids are suitable in agriculture salts, esters and amides. Likewise suitable in agriculture derived, when used to describe aminophenol in the 4-position, 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 well known in the art nitrogen-containing derivative, which (a) does not influence significantly on herbicide activity of the active ingredient, i.e. the 6-aryl-4-aminophylline acid, and (b) hydrolyzed (or can be either hydrolyzed) in plants or soil to a free amine of formula II.N-Oxides, which are also able to split up the original picoline formula II, also included in the scope of this invention.

Suitable salts include derivatives of alkali and alkaline earth metals and ammonia and amines. Preferred cations include sodium, potassium, magnesium and cations amine formula:

R5R6R7NH+,

in which each R5, R6and R7 independently represents hydrogen or C1-C12-alkyl, C3-C12alkenyl or C3-C12-quinil, each of which is optionally substituted by one or more hydroxy, C1-C4-alkoxy, C1-C4-alkylthio or phenyl group, provided that R5, R6and R7sterically compatible. Additionally, any two of R5, R6and R7together can represent aliphatic bifunctional group containing 1-12 carbon atoms and up to two atoms of oxygen or sulfur. Salts of compounds of formula I can be prepared by treating compound 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 dissolve in water and are suitable for the preparation of the necessary water main herbicide formulations.

Suitable esters include derivatives of C1-C12-alilovic, C3-C12-alkenilovyh or C3-C12-alkinilovymi alcohols, such as methanol, isopropanol, butanol, 2-ethylhexanol, butoxyethanol, methoxypropanol, allyl alcohol, propargilovyh alcohol and cyclohexanol. Ester which can be prepared via condensation pikolinos acid with alcohol, using any number of suitable activating agents, such as those used in peptide condensation, such as dicyclohexylcarbodiimide (DCC) or carbonyldiimidazole (CDI), by reaction of the corresponding acid chloride pikolinos acid of formula I with an appropriate alcohol, or by reaction of the corresponding pikolinos acid of formula I with a suitable alcohol in the presence of an acidic catalyst. Suitable amides include derivatives of ammonia or C1-C12-alkyl, C3-C12alkenyl or C3-C12-quinil mono - or disubstituted amines, such as, but not limited to, dimethylamine, diethanolamine, 2-methylthiopropionate, ballinameen, 2-butoxyaniline, cyclododecene, benzylamine or cyclic or aromatic amines with or without additional heteroatoms, such as, but not limited to, aziridine, azetidine, pyrrolidine, pyrrole, imidazole, tetrazole or morpholine. Amides can be prepared by reaction of the corresponding acid chloride pikolinos acid mixed anhydride or ester of carboxylic acid of formula I with ammonia or an appropriate amine.

The terms "alkyl", "alkenyl" and "quinil", as well as their derivatives, the terms "alkoxy", "acyl", "alkylthio" and "alkylsulfonyl"as used in the description of the present invention include branched, unbranched chains of the cyclic part. The terms "alkenyl" and "quinil include one or more unsaturated bonds.

The term "aryl", as well as derivative terms such as "aryloxy"refers to phenyl.

If there are no special restrictions, the term "halogen"includes derivative terms such as "halo"refers to fluorine, chlorine, bromine and iodine. The terms "halogenated" or "halogenoalkane" refer to alkyl or alkoxy groups, substituted from one up to the maximum possible number of halogen atoms.

The compounds of formula I can be obtained using well-known chemical methods. The necessary source materials are commercially available or easily synthesized using standard techniques.

6-substituted atypically formula I can be prepared in a number of ways that are well known in the art, for example, by reaction of the appropriate substituted pyridine with easy leaving group in 6-position (III) c ORGANOMETALLIC compound of the type (IV) in an inert solvent in the presence of a catalyst is a transition metal.

In this case "L" can be chlorine, bromine, iodine or triftoratsetata, "metal" can be Mg-halogen, Zn-halogen, tin(C1-C4-alkyl)3, lithium, copper or B(OR8)(OR9), in which R8and R9independently from each other to depict ablaut hydrogen, C1-C4-alkyl or, taken together, form an ethylene or propylene group, and "catalyst" is a catalyst is a transition metal, in particular palladium catalyst such as palladium diacetate, bis(triphenylphosphine)dichloride, palladium (II) or Nickel catalyst such as Nickel acetylacetonate (II), bis(triphenylphosphine)chloride Nickel (II).

Alternatively, the compounds of formula I can be prepared by reaction of the appropriate substituted 6-metastasising pyridine (V) aryl compound of type (VI) in an inert solvent in the presence of a catalyst is a transition metal.

In this case "L" can be chlorine, bromine, iodine or triftoratsetata, "metal" can be Mg-halogen, Zn-halogen, tin(C1-C4-alkyl)3, lithium, copper or B(OR8)(OR9), in which R8and R9independently of one another represent hydrogen, C1-C4-alkyl or, taken together, form an ethylene or propylene group, and "catalyst" is a catalyst is a transition metal, in particular palladium catalyst such as palladium diacetate, bis(triphenylphosphine)dichloride, palladium (II) or Nickel catalyst such as Nickel acetylacetonate (II), bis(triphenylphosphine)chloride Nickel (II).

Reaction with baronowie acids or esters are well and is known and represented by the following links:

(1) W.J. Thompson and J. Gaudino, J. Org. Chem., 49, 5223 (1984);

(2) S. Gronowitz and K. Lawitz, Chem. Ser., 24, 5 (1984);

(3) S. Gronowitz et al., Chem. Ser., 26, 305 (1986);

(4) J. Stavenuiter et al., Heterocycles, 26, 2711 (1987);

(5) V. Snieckus et al., Tetrahedron Letters, 28, 5093 (1987);

(6) V. Snieckus et al., Tetrahedron Letters, 29, 2135 (1988);

(7) M.B. Mitchell et al., Tetrahedron Letters, 32, 2273 (1991); Tetrahedron, 48, 8117 (1992);

(8) JP-A 93/301870.

Reaction with Grignard compounds (metal - Mg-halogen):

(9) L.N. Pridgen, J. Heterocyclic Chem., 12, 443 (1975);

(10) M. Kumada et al., Tetrahedron Letters, 21, 845 (1980);

(11) A. Minato et al., J. Chem. Soc. Chem. Commun., 5319 (1984).

Reaction with tsinkorganicheskih compounds (metal - Zn-halogen):

(12) A. S. Bell et al., Synthesis, 843 (1987);

(13) A.S. Bell et al., Tetrahedron Letters, 29, 5013 (1988);

(14) J.W. Tilley and S. Zawoiski, J. Org. Chem., 53, 386 (1988); see also (9).

Reactions with ORGANOTIN compounds (metal - Sn(C1-C4-alkyl)3):

(15) T.R. Bailey et al., Tetrahedron Letters, 27, 4407 (1986);

(16) Y.Yamamoto et al., Synthesis, 564 (1986); see Also (6).

Condensation III+IV or V+VI may, if necessary, be accompanied by reactions on any ring to get more derivatives of compounds of formula I.

Suitable substituted pyridine formula III in which L is chlorine, bromine, iodine or triftoratsetata, you can easily get the well known methods; see WO 0151468. For example, 6-bromo analogs can be prepared by the recovery of several key intermediates, for example, the corresponding 6-bromo-4-azido, 6-b is ω-4-nitro and N-oxido-6-bromo-4-nitropyridine analogues. These intermediate compounds, in turn, can be prepared as nucleophilic substitution at the 6-bromo-4-halogen analogues with NaN3and electrophilic nitration of the correspondingN-oxido-6-bromopyridine. Alternatively, such analogs can be prepared by direct aminating the corresponding 4,6-dibromo analogues.

4-Namide, urethane, urea, sulfonamidnuyu, silylamine, phosphoramidate derivatives can be prepared by the reaction of free amino groups, for example, with a suitable acid chloride acid, chloroformiate, carbonylchloride, sulphonylchloride, similiarites or chlorophosphate.

Substituted 4-amino analogs can be prepared by reaction of the corresponding 4-halogenfrei-2-carboxylate, or any other capable of substitution of 4-substituted compounds with substituted amine.

The compounds of formula I obtained by any of these methods, you can restore the conventional ways. Typically, the reaction mixture is acidified with aqueous acid, such as hydrochloric acid and extracted with an organic solvent such as ethyl acetate or methylene chloride. Organic solvent and other volatile components can be removed by distillation or evaporation, to obtain the required compound of formula I, which can be cleaned the ü using standard techniques, such as recrystallization or chromatography.

Found that compounds of the formula I are suitable as herbicides before and after germination of noxious plants. They can be used with non-selective (higher) doses of making to deal with a wide range of plants on the area of application, or with a lower dose of application to selective control of harmful plants. The area of application includes pastures and pastures, roadside strips and tracks, power lines and industrial areas, where the desired control of noxious plants. Another use is to combat harmful plants in cultivation of agricultural crops such as corn, rice and cereals. They can also be used to fight harmful plants in cultivation of tree crops such as citrus plants, Apple trees, rubber trees, oil palm, forest and other. It is generally preferable to use the connection after germination noxious plants. In addition, it is generally preferable to use compounds to combat a wide range of woody plants, hardwoods, weeds and sedges. Especially note the use of compounds to fight against harmful plants, when the plants sprout. Despite the fact that each of the 6-aryl-4-aminopyrine the data connection, expressed by formula I, is included in the scope of the present invention, the degree of herbicide activity, selectivity relative to the crop and the spectrum of weed control may vary from those present in the molecule of the substituents. A suitable connection for any particular use as a herbicide can be determined using existing in this description of the information or by using standard tests.

The term herbicide used in this description to denote the active ingredient that kills, fights or, on the other hand, has an adverse effect on plant growth. Effective as a herbicide quantity or number needed to deal with plants is the amount of active ingredient, which adversely modifying effect and includes deviations from natural development, destruction, regulation, desiccation, retardation and the like. Terms of plants and vegetation include sprouted grains, emerging seedlings and rooted vegetation.

Herbicide activity is manifested by the compounds of the present invention, when they are applied directly on the plant or on the area occupied by the plant at any growth stage or before planting and emergence. The observed effect is avisit between plant species, want to fight the growth stage of the plants used parameters dilution and size of the sprayed droplets, the particle size of solid components, the environmental conditions at the time of use, the specific compound, the concrete used excipients and carriers, soil type, and the like, as well as on the number of chemicals used. These and other factors can be selected, as is known in the art to provide non-selective or selective herbicide effect. It is generally preferable to use the compounds of formula I after the appearance of relatively immature harmful vegetation to achieve the maximum degree of weed control.

After germination usually use a dose of addition of 0.1 to 1000 g/ha; for use prior to the emergence typically use doses make 1-2000 g/ha Under certain higher doses mainly non-selective combating a wide variety of harmful vegetation. At lower doses is usually carried out selective struggle and these doses can be used on the space occupied by the crops.

Herbicide compounds of the present invention is often used in a mixture with one or more other herbicides to combat a wide variety of time the Noi vegetation. When used in mixture with other herbicides compounds claimed in the present invention, can be mixed with the other herbicide or herbicides, to mix in the tank with the other herbicide or herbicides, or applied sequentially with the other herbicide or herbicides. Some of the herbicides that can be applied in a mixture with compounds of the present invention include: amide herbicides such as ellidaar, beflubutamid, betadex, benzidin, bromobutyl, cafestol, CDEA, chlorine, cobresol, dimethenamid, dimethenamid-P, diphenamid, aprons, atiprimod, phentramin, flupoxam, fomesafen, galasoft, isosorbid, isoxaben, napropamide, naptalam, pethoxamid, propyzamide, heroname and tabulam; anilide herbicides, such as chloranil, zizanie, Komarom, cipramil, diflufenican, etamesonic, tenaculum, flufenacet, flufenisal, mefenacet, mefluidide, meramipop, monolid, nitroanilide, pantanagar, picolinafen and propanil; Alliluyeva herbicides, such as benzoylperoxy, planrep and planrep-M; chloroacetanilide herbicides, such as acetochlor, alachlor, butachlor, buenaflor, delaflor, diacetyl, dimethachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, panahar, turbuhaler, tanishlar and silahlar; sulfanilimide herbicides, such as bentover, perfsuite, perimacular and refloat; sulfa herbicides, such as Azul, carbazoles, tenaculum and oryzalin; herbicides antibiotics, such as milanapos; herbicides - derivatives of benzoic acid such as chloramben, dicamba, 2,3,6-TBA and takamba; herbicides derived by pyrimidinemethanol acid, such as bispyribac and Perminova; herbicides derived by pyrimidinediamine acid, such as pyrithiobac; herbicides - derivatives of phthalic acid, such as chlorthal; herbicides derived pikolinos acid, such as aminopyralid; clopyralid and picloram; herbicides - derivatives of quinoline-carboxylic acids, such as chinkara and hinnerk; herbicides containing arsenic, such as cakaudrove acid, CMA, DSMA, hexaplorum, MAA, MAMA, MSMA, arsenite of potassium and sodium arsenite; herbicides - derivative of benzoylecgonine, such as mesotrione, sulcotrione, deforestion and tembotrione; benzofuranyl alkylsulfonate herbicides, such as belforest and ethofumesate; urethane herbicides, such as Azul, carbocat, chlorproma, dichlormid, tenaculum, carbocylic and thermocarb; carbanilate herbicides, such as Barban, BCPC, carbazoles, carbetamide, CEPC, chlorbutol, chlorpropham, CPPC, desmedipham, Fenicia, phenmedipham, phenmedipham-ethyl, profam and swap; cyclohexenone herbicides, such as aloxide, butoxide, clethodim, chloroxygen, qi is lockside, profoxydim, sethoxydim, tepraloxydim and tralkoxydim; cyclopropylacetylene herbicides, such as isoxaflutole and isoxaflutole; dicarboximide herbicides, such as bestindian, cinidon-ethyl, planesin, flumiclorac, flumioxazin and flubiprofen; dinitroaniline herbicides, such as benfluralin, Butylin, dinitramine, ethalfluralin, fluchloralin, isopropylene, methylpropan, nicraly, oryzalin, pendimethalin, prodiamine, propleuron and trifluralin; dinitroaniline herbicides, such as dinofest, dynapro, dinoseb, dinoseb, dinoterb, DNOC, aminofen and medinotes; herbicides - derivatives of diphenyl ether, such as amoxifen; herbicides - derivatives nitrophenylamino ether, such as acifluorfen, klonipin, bifenox, chlorethoxyfos, chlornitrofen, atiprimod, forgiven, verglichen, Thornicroft, fomesafen, voreloxin, galasoft, lactofen, nitrofen, nitrophorin and oxilorphan; dithiocarbamate herbicides such as dazomet and met; halogenated aliphatic herbicides, such as lorac, chlorophos, dalapon, fluprofen, hexachloroacetone, logmean, bromide, monochloracetic acid, SMA and TCA; imidazolinone herbicides, such as imazamethabenz, imazamox, imazapic, imazapyr, imazighen and imazethapyr; inorganic herbicides, such as sulpham ammonium, borax the chlorate calcium , copper sulfate, is Ulfat iron (II), azide, potassium cyanate potassium, sodium azide, sodium chlorate and sulfuric acid; nitrile herbicides such as bromophenyl, bromoxynil, chloroxine, dichlobenil, jogbani, ioxynil and PERCHLORYL; phosphoarginine herbicides, such as lipophos-methyl, anilofos, bensulide, milanapos, butamifos, 2,4-DEP, DMPA, EBEP, fosamine, glufosinate, GLOBOSAT and piperophos; phenoxy herbicides, such as bromfenac, clomipram, 2,4-DEB, 2,4-DEP, divinamente, dial, Arbon, atiprimod, petercol and Triforce; ferociously herbicides, such as 4-CPA, 2,4-D, 3,4-DA, MCPA, MCPA-thioethyl and 2,4,5-T; herbicides derived proximalen acid, such as 4-CPB, 2,4-DB, 3,4-DB, MCPB and 2,4,5-TB; herbicides derived phenoxypropionic acid, such as laprop, 4-CPP, dichlorprop, dichlorprop-P, 3,4-DP, fenoprop, mecoprop and mecoprop-P; herbicides derived aryloksyfenoksypropionowe acid, such as lorazepam, clodinafop, cloop, cyhalofop, diclofop, fenoxaprop, fenoxaprop-P, pentiumpro, fluazifop, fluazifop-P, haloxyfop, haloxyfop-P, isocaporate, meramipop, propaquizafop, quizalofop, quizalofop-P and triphop; phenylendiamine herbicides, such as dinitramine and prodiamine; pyrazolidine herbicides, such as benzien, pyrazoline, pyrasulfotole, paradoxien, pyroxsulam and topramezone; pyrazolidinone herbicides, such as flatlet, pyraflufen; pyridazinone of gerbic the water, such as creatin, perinatal and peridot; pyridazinone herbicides, such as Bremerton, ozone chloride, dimeadozen, flutter, matterson, norflurazon, oxadiazon and pidyon; pyridine herbicides, such as aminopyralid, clidanac, clopyralid, dithiopyr, fluroxypyr, galaxidi, picloram, picolinafen, pericar, thiazopyr and triclopyr; pyrimidinediamine herbicides, such as primidon and toclaim; herbicides - derived Quaternary ammonium compounds, such as cybercat, ditambah, difenzoquat, Diquat, Mohammad and paraquat; THIOCARBAMATE herbicides, such as butyl, cycloate, di-Allat, EPTC, asbroker, etiolate, itprint, Mediobanca, molinet, arrancars, pebulate, prosulfocarb, perimutter, sulfallate, thiobencarb, thiocarbonyl, three-Allat and vernolate; THIOCARBAMATE herbicides, such as dioxane, EXD and proxy; herbicides - thiourea derivatives, such as meteoron; triazine herbicides such as DIPROPYLENE, triazolam and trihydroxystearin; chlorotriazine herbicides, such as atrazine, Chorazin, cyanazine, ziprin, Eglinton, Ipsen, misoperation, prolatin, progenesis, propazine, subutility, Simazine, terbutylazine and triacetin; methoxythiazole herbicides, such as atraton Mahometan, prometon, sebumeter, Simeon, terbumeton; methyltetrazole herbicides, such as ametrine is high, isoprotein, CYANOGEN is Rin, desmetryn, deltamethrin, melipramin, prometryn, simetryn and terbutryn; triazinone herbicides, such as ameridian, libusin, hexazinone, isomerizing, metamitron, metribuzin; triazole herbicides, such as amitrol, cafestol, aprons and flupoxam; triazolinone herbicides, such as nicarbazin, Banjarmasin, carfentrazone, flucarbazone, propoxycarbazone, sulfentrazone and thiencarbazone-methyl; triazolopyrimidine herbicides, such as karasulu, dicloflam, florasulam, flumetsulam, metosulam, penoksulam and pyroxsulam; herbicides - derivatives of uracil, such as butoverall, bromacil, flourophenyl, isocal, lenacil and terbacil; 3-phenylurazole; herbicides - derivatives of urea, such as benzthiazole, cumyluron, cyclotron, dichloramine, diflubenzuron, Sonoran, Sauron, methabenzthiazuron, monitoron and narure; herbicides derived prilocaine, such as aniston, butuan, chlorbromuron, chlorimuron, chlortoluron, chloroxuron, dameron, Difenoxin, dimefuron, Diuron, fenuron, fluometuron, Flatiron, Isoproturon, linuron, meturon, methyldibromo, metaventure, metobromuron, metoxuron, monolinuron, monuron, neburon, perfluro, finansure, sibron, tetraplodon and thidiazuron; herbicides derived pyrimidinylpiperazine, such as amidosulfuron, azimsulfuron, encultured, chlorite is damage cycloaliphatic, ethoxysulfuron, flazasulfuron, placetocolumn, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, metsulfuron, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron and trifloxysulfuron; herbicides derived triethynylbenzene, such as chlorsulfuron, chinaculture, atomiculture, iodosulfuron, metsulfuron, prosulfuron, thifensulfuron, triasulfuron, tribenuron, triflusulfuron and tritosulfuron; herbicides derived thiadiazolidine, such as butiran, tidiman, tebuthiuron, diazafluoren and thidiazuron; and herbicides, not included in other classes, such as acrolein, allyl alcohol, azafenidin, benazolin, bentazon, benzamycin, booteasy, calcium cyanamide, Cambodian, chlorgenic, jarvenpa, chlorfluazuron, chlorflurazole, cinmetacin, clomazone, CPMF, cresol, ortho-dichlorobenzene, timepart, endothal, formalin, floridon, flurochloridone, flurtamone, fluthiacet, indianian, metasol, methylisothiocyanate, snipercraft, OCH, oxadiargyl, oxadiazon, oxacyclobutane, pentachlorophenol, phenoxazone, acetate finalstate, pinoxaden, prosulfuron, perbenzoic, piritramid, hinkleman, redetail, sulpician, thidiazuron, tridiphane, treemature, tripropionin and tritak. Herbicide is soedineniya of the present invention can, in addition, to use in mixture with glyphosate, glufosinate or 2,4-D resistant to glyphosate, glufosinate or 2,4-D crops. It is generally preferable to use compounds of the invention in combination with herbicides that are selective to the cultivated crop and that complement the spectrum of weed control of these compounds when used in the ava. In addition, it is generally preferable to use the compounds of this invention and other herbicides at the same time, in the form of a combined composition, and tankboy mixture.

Compounds of the present invention is normally used in combination with known herbicide antidotes, such as enoxacin, benthiocarb, brassinolide, cloquintocet (mexyl), simerini, dameron, dichlormid, disilane, timepart, disulfoton, fenchlorphos-ethyl, felorin, Florasol, fluxotine, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, MG 191, MON 4660, naphthalene anhydride (NA), oxybutinin, R29148 and amides ofN-phenylsulfonylacetate acid to enhance their selectivity. They can be used additionally in order to fight harmful vegetation in many crops, which make resistant or immune to them or other herbicides with the gene for the systematic manipulation or mutation, or breeding. For example, you can process corn, wheat, rice, soybean, sugar beet, cotton, rice, canola and other crops that are resistant or immune to compounds that are inhibitors acetolactate-synthase in sensitive plants. Many crops that are resistant to glyphosate and glufosinate, you can also handle both separately and in combination with these herbicides. Some crops (e.g. cotton) made tolerant to euxinum herbicides, such as 2,4-dichlorophenoxyacetic acid. These herbicides can be used to handle such sustainable crops and other crops that are resistant to auxin.

When it is possible to use 6-aryl-4-aminopyridine the compounds of formula I directly as herbicides, it is preferable to use them in mixtures containing an effective herbicide number of connections with at least one suitable in the field of agriculture auxiliary substance or medium. Suitable excipients or carriers should not be phyto-toxic to valuable crops, particularly at the concentrations used in the application of the compositions to behold the objective of weed control in the presence of crops and they must not react chemically with the compounds of formula I or other ingredients of the composition. Such mixtures can be created for use directly on the weeds or the places of their growth, or they can be concentrates or compositions, which are usually diluted with additional carriers or auxiliary substances before use. They can be solids, such as powders, granules, soluble granules, or wettable powders, or liquids, such as, for example, concentrates, emulsions, solutions, emulsions and suspensions.

Suitable in the field of agriculture excipients and carriers that are suitable for the preparation of herbicide mixtures of this invention are well known to specialists in this field of technology.

Liquid media that can be used include water, toluene, xylan, petroleum ether, corn 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. For diluting concentrates as a carrier usually chosen water.

Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgite clay, kaolin clay, diatomaceous earth, chalk, diatom is t, lime, calcium carbonate, bentonite clay, fallerovo earth, cottonseed, wheat flour, soybean flour, pumice, wood flour, nut flour wood, lignin and the like.

In the composition of the present invention it is often desirable to introduce one or more surface-active agents. Such surface-active agents, mainly used in solid and liquid compositions, particularly those which require dilution with carrier before use. Surface-active agents may be anionic, cationic or non-ionic in nature and can be used as emulsifiers, wetting agents, suspendida agents or for other purposes. Standard surface-active agents include salts of alkyl sulphates, such as lauryl of diethanolamine; alkylarylsulfonate salts such as dodecylbenzenesulfonate calcium; the addition products of alkylphenol-accelerated, such as Nonylphenol-C18ethoxylate; addition products alcohol-alkylenes, such as tridecyl alcohol-With16ethoxylate; Soaps, such as sodium stearate; alkylnaphthalene salts such as dibutylaminoethanol sodium; dialkyl ethers sulfosuccinate salts, such as di(2-ethylhexyl)sulfosuccinate sodium; esters of sorbitol, such as sorbitol oleate; the fourth is cnie amines, such as lauryldimethylamine; polietilenglikolya esters of fatty acids, such as polietilenglikolmonostearat; block copolymers of ethylene oxide and of propylene oxide; and salts of mono and dialkyl Postavarul.

Other excipients commonly used in compositions for agriculture include agents that improves the compatibility, anti-foam agents, stabilizing agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, lyophilizers additives, substances that promote penetration agents, giving stickiness, dispersing agents, thickeners, fluid freezing temperature, antimicrobial agents and the like. The composition can also contain other compatible components, for example, other herbicides, plant growth regulators, fungicides, insecticides and the like and can be mixed with liquid fertilizers or solid fertilizers in the form of particles used as carriers such as ammonium nitrate, urea and the like.

The concentration of the active agents in herbicide compositions of the present invention is usually 0.001 to 98% by weight. Often use a concentration of 0.01-90% by weight. In compositions designed for use in the form of concentrates, the active ingredient is typically present at a concentration of 5-98% by weight, preferably 10-90% by weight. T is the cue of the composition is usually diluted with an inert carrier, such as water, before use. The diluted compositions usually applied to the weeds or their places of growth, usually contain of 0.0001-1% by weight of the active ingredient and preferably contain 0.001 to 0.05% by weight.

Presents the composition can be applied to weeds or their growth when using conventional devices for grinding or air nozzles, sprayers and machines for making pellets by adding irrigation water and other conventional known in the art methods.

Many of the starting compounds used for the preparation of compounds of the present invention, for example, 4-amino-3,6-dichloropyridine-2-carboxylic acid, 4-amino-3,5,6-Cryptor-2-cyano, methyl 4-amino-6-bromo-3,5-differencein-2-carboxylate and methyl 4-amino-6-bromo-3-chloropyridin-2-carboxylate, described in U.S. patent 6297197 B1.

Examples:

1. Obtain 3-bromo-6-chloro-2-terfenol

A solution of 1-bromo-4-chloro-2-fervently (20.4 g, 0,100 mol) in tetrahydrofuran (THF; 50 ml) was slowly added to diisopropylamide lithium (LDA; 0.125 mol) in THF (600 ml) at -50°C. After addition the solution was heated to -20°C and then cooled to -50°C and slowly added to the solution of triethylborane (13.5 g, 0,130 mol) in tetrahydrofuran (20 ml) and the temperature was raised to -20°C. Then the mixture was cooled to -70°C. and slowly added to the solution of the Sabbath.arukanai acid (32% in acetic acid, 0,150 mol)and the mixture was heated to ambient temperature. Was added water (250 ml)and the solution was extracted with ethyl acetate (2 × 200 ml). The combined organic phase was dried and concentrated. The black oil was purified column chromatography (20% ethyl acetate in hexane)to obtain 3-bromo-6-chloro-2-terfenol (14.1 g, 0,063 mol):1H-NMR (CDCl3): δ 7,05 (m, 2H), 5,5 (USS, 1H).

The following compounds were obtained according to the method of example 1.

3-bromo-2,6-dichlorphenol:TPL 69-70°C.

3-bromo-2-fluoro-6-cryptomaterial:1H-NMR (CDCl3): δ 7,20 (m, 2H), 5,85 (USS, 1H).

3-bromo-2-chloro-6-terfenol: LC/MS (m/z = 225).

2. Obtain 1-bromo-4-chloro-2-fluoro-3-methoxybenzoyl

A heterogeneous mixture of 3-bromo-6-chloro-2-terfenol (14.4 g, 0,064 mol), methyliodide (13.5 g, 0,096 mol) and potassium carbonate (8.8 g, 0,064 mol) in acetonitrile (100 ml) was boiled under reflux for 2 hours. The mixture was cooled, diluted with water (100 ml) and was extracted with ethyl acetate (2 × 150 ml). The combined extracts were dried and concentrated. The black oil was purified column chromatography (5% ethyl acetate in hexane)to obtain 1-bromo-4-chloro-2-fluoro-3-methoxybenzoyl (14.8 g, 0,062 mol):1H-NMR (CDCl3): δ 7,20 (m, 1H), 7,10 (DD, 1H), 4,0 (s, 3H).

The following compounds were obtained according to the method of example 2.

1-bromo-4-chloro-3-ethoxy-2-torbenson:1H-NMR (CDCl3): δ 7,20 (who, 1H), 7,10 (DD, 1H), 4,20 (kV, 2H), 1,50 (t, 3H).

1-bromo-4-chloro-2-fluoro-3-isopropoxybenzoic:1H-NMR (CDCl3): δ 7,20 (m, 1H), 7,10 (DD, 1H), and 4.5 (m, 1H), 1,40 (d, 6N).

1-bromo-4-chloro-2-fluoro-3-(2-methoxyethoxy)benzene:1H-NMR (CDCl3): δ 7,25 (m, 1H), 7,15 (DD, 1H), 4,25 (t, 2H), 3.75 to (t, 2H), 3,5 (s, 3H).

1-bromo-2-fluoro-3-methoxy-4-cryptomaterial:1H-NMR (CDCl3): δ 7,39 (d, 1H), 7,21 (d, 1H), 6,18 (TT, 1H), 4,24 (dt, 2H).

1-bromo-2,4-dichloro-3-ethoxybenzoyl:1H-NMR (CDCl3): δ to 7.32 (d, 1H), 7,17 (d, 1H), 4,10 (kV, 2H), 1,47 (t, 3H).

1-bromo-2,4-dichloro-3-methoxybenzoyl:1H-NMR (CDCl3): δ to 7.35 (d, 1H), 7,15 (d, 1H), 3,95 (s, 3H).

1-chloro-3,5-debtor-2-methoxybenzoyl: GC-MS (m/z = 178).

1-chloro-3,5-debtor-2-ethoxybenzoyl: GC-MS (m/z = 192), BP. 80-85°C / 30 mm

1,3-dichloro-5-fluoro-2-methoxybenzoyl: GC-MS (m/z = 194).

1-bromo-3-butoxy-4-chloro-2-torbenson: GC-PCI (m/z = 180).

1-bromo-4-chloro-2-fluoro-3-methoxyethoxymethyl: GC-MS (m/z = 269).

1-bromo-2-chloro-4-fluoro-3-methoxybenzoyl: GC-MS (m/z = 239).

3-chloro-5-fluoro-2-methoxybenzaldehyde: GC-MS (m/z = 188).

1,3-debtor-3-ethoxybenzoyl: GC-MS (m/z = 158).

3. Obtain 1-bromo-4-chloro-2-fluoro-5-methoxybenzene

A solution of 4-chloro-2-fluoro-5-methoxyaniline (25,0 g, 0,143 mol) in 10% HBr (250 ml) was cooled to 0°C and slowly added a solution of sodium nitrite (15.0 g, 0,218 mol) in water (20 ml). Was slowly added methylene chloride (50 ml) and copper bromide (30.0 g, 0,244 mol) and then the mixture was heated to ambient temperature and was stirred for those who begins 1 hour. The reaction mixture was filtered through a layer of cellite and was extracted with methylene chloride (2 × 100 ml) and the combined organic phases were dried (sodium sulfate) and concentrated. The chromatography was carried out black oil (5% ethyl acetate in hexane) gave 1-bromo-4-chloro-2-fluoro-5-methoxybenzo (16.6 g, 0,070 mol):1H-NMR (CDCl3): δ 7,20 (m, 1H), 7,05 (DD, 1H), 4.00 points (s, 3H).

4. Obtain 1-bromo-4-chloro-2-fluoro-3-deformational

To a solution of 3-bromo-6-chloro-2-terfenol (1,00 g of 4.44 mmol) and chlorodifluoroacetate sodium in dimethylformamide (DMF; 9 ml) was added potassium carbonate (1.22 g, 5,32 mmol) and water (1.77 ml) and the resulting reaction mixture was heated at 100°C for 4 hours. The solution was cooled to ambient temperature and was added concentrated hydrochloric acid (2.5 ml) and water (4 ml) and stirred at ambient temperature overnight. The solution was cooled in an ice bath and neutralized 2N sodium hydroxide and then extracted with ethyl acetate (2 × 25 ml). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated, obtaining 1-bromo-4-chloro-2-fluoro-3-deformational (1.20 g, 4.2 mmol). This compound was used in the next stage without additional purification.

5. Obtain 1-bromo-4-chloro-3-(2,2-diflorasone)-2-fermental

A solution of 3-bromo-6-chloro-2-terfenol (15,4 g, 0,068 mol) in DMF (25 ml) honey the military was added to a suspension of sodium hydride (60% dispersion in mineral oil) (4.0 g, 0.10 mol) in DMF (100 ml) and the mixture was stirred for 1 hour. Was slowly added a solution of 2,2-diferetiable ether methanesulfonate (17.5 g, 0,109 mol) in DMF (10 ml). The resulting solution was heated at 70°C for 18 hours. The solution was diluted with water (200 ml) and was extracted with ethyl acetate. The combined organic phases were dried (sodium sulfate) and concentrated. The oil residue was purified column chromatography (hexane)to obtain 1-bromo-4-chloro-3-(2,2-diflorasone)-2-torbenson (9.0 g, 0,031 mol):1H-NMR (CDCl3): δ to 7.3 (m, 1H), 7,10 (DD, 1H), x 6.15 (dt, 1H), 4,35 (m, 2H).

The following compounds were obtained according to the method of example 5.

1-bromo-2,4-dichloro-3-(2,2-diflorasone)benzene:1H-NMR (CDCl3): δ 7,35 (m, 1H), 7,15 (DD, 1H), 6,15 (TT, 1H), 4,35 (dt, 2H).

6. Obtain 1-bromo-4-chloro-2-fluoro-3-(methylthio)benzene

A solution of 1-bromo-4-chloro-2-fervently (20.4 g, 0,100 mol) in THF (50 ml) was slowly added LDA (0.125 mol) in THF (600 ml) at -50°C. After addition the solution was heated to -20°C and then cooled to -50°C and slowly added a solution of dimethyl disulfide (18,8 g, 0.20 mol) in tetrahydrofuran (50 ml)and the mixture was heated to ambient temperature. The reaction extinguished with water (200 ml) and was extracted with ethyl acetate (2 × 150 ml) and the combined organic phases were dried (sodium sulfate) and concentrated. The remainder of the red oil was purified column chromate what graphy (5% ethyl acetate in hexane), to obtain 1-bromo-4-chloro-2-fluoro-3-(methylthio)benzene (23.9 g, 0,094 mol):1H-NMR (CDCl3): δ 7,40 (m, 1H), 7,15 (DD, 1H), 2,50 (s, 3H).

The following compounds were obtained according to the method of example 6.

1-bromo-2,4-dichloro-3-(methylthio)benzene:1H-NMR (CDCl3): δ 7,52 (d, 1H), 7,25 (d, 1H), 2,46 (s, 3H).

7. Obtain 3-bromo-6-chloro-2-forventelige

A solution of 1-bromo-4-chloro-2-fervently (20.4 g, 0,100 mol) in THF (50 ml) was slowly added LDA (0.125 mol) in THF (600 ml) at -50°C. After addition the solution was heated to -20°C and then cooled to -50°C and slowly added a solution of DMF (14.6 g, 0.20 mol) in tetrahydrofuran (50 ml)and the mixture was heated to ambient temperature. The reaction extinguished with water (250 ml) and was extracted with ethyl acetate (2 × 150 ml) and the combined organic phases were dried (sodium sulfate) and concentrated. The solid residue was recrystallized from hexane to obtain 3-bromo-6-chloro-2-forbindelse (40,0 g, 0,169 mol): TPL 92-93°C.

The following compounds were obtained according to the method of example 7 by clearing the appropriate electrophile, for example, aldehyde, complex ether or ketone.

1-(3-bromo-6-chloro-2-forfinal)-1-ethanol:1H-NMR (CDCl3): δ 7,40 (m, 1H), 7,15 (m, 1H), 5.40 to (m, 1H), 2,50 (m, 1H), of 1.85 (d, 3H).

3-bromo-2,4-dichlorobenzaldehyde: TPL 96-97°C.

1-(3-bromo-2,4-dichlorophenyl)-1-ethanol:1H-NMR (CDCl3): δ of 7.60 (d, 1H), 7,15 (d, 1H), the 5.45 (m, 1H), 3.0 (d, N), of 1.85 (d, 3H).

1-bromo-4-chloro-3-ethyl-2-torbenson: GC/PCI (m/z = 236).

1-(3-bromo-6-chloro-2-forfinal)-2,2,2-triptoreline: GC/PCI (m/z = 304).

1-(3-bromo-6-chloro-2-forfinal)-1-propanol:1H-NMR (CDCl3): δ 7,40 (m, 1H), 7,15 (m, 1H), 5.40 to (m, 1H), 2,50 (m, 1H), 1,90 (m, 4H), and 1.00 (t, 3H).

2-(3-bromo-6-chloro-2-forfinal)-2-propanol:1H-NMR (CDCl3): δ 7,40 (m, 1H), 7,15 (m, 1H), 3.45 points (s, 1H), 1,80 (m, 6N).

8. Obtain 3-chloro-5-fluoro-2-hydroxybenzaldehyde

A solution of 2-chloro-4-terfenol (15.0 g, 102 mmol) in 150 g of 50% sodium hydroxide, water (30 ml) and chloroform (45 ml) was boiled under reflux for 8 hours, was added an additional amount of chloroform (45 ml) every 2 hours. The mixture is then cooled and left to stand for 18 hours and was collected sodium salt. The solid residue suspended in water (200 ml) and the pH was lined up to 1.5 6 N hydrochloric acid and then was extracted with ethyl acetate (2 × 100 ml). The combined extracts were washed with brine, dried and concentrated. The residue was purified by chromatography (1:1 methylene chloride/hexane)to obtain 3-chloro-5-fluoro-2-hydroxybenzaldehyde (5.0 g, 29 mmol): LC/MS (m/z = 174).

9. Obtain 1-bromo-4-chloro-2-fluoro-3-deformational

(Diethylamino)sulfur TRIFLUORIDE (15.3 g, 0,096 mol) was slowly added to a solution of 3-bromo-6-chloro-2-forventelige (7.50 g, to 0.032 mol) in methylene chloride at 0°C and the mixture was stirred for 1 hour at the Les heating the solution to ambient temperature. The reaction was carefully marked with a saturated solution of sodium bicarbonate in water (100 ml) and was extracted with methylene chloride (2 × 75 ml) and the combined extracts were dried (sodium sulfate) and concentrated, obtaining 1-bromo-4-chloro-2-fluoro-3-deformational (7.20 g, 0,028 mol):1H-NMR (CDCl3): δ 7,60 (m, 1H), 7,05 (m, 1H), 7,00 (d, 1H).

The following compounds were obtained according to the method of example 9.

1-bromo-2,4-dichloro-3-deformational: LC/MS ESI (m/z = 271).

1-deformity-3-fluoro-4-iodine-2-methoxybenzoyl: LC/MS (m/z = 302).

2-chloro-4-deformity-3-methoxy-1-nitrobenzene: LC/MS (m/z = 237) (used without full cleaning).

3-chloro-1-deformity-2-methoxybenzoyl LC/MS (m/z = 210).

10. Getting 2-chloro-4-deformity-3-methoxyaniline

A solution of the crude 2-chloro-4-deformity-3-methoxy-1-nitrobenzene in ethanol (50 ml)containing 5% palladium on coal (250 mg), was first made (50 psi) for 5 hours. The solution was filtered and concentrated, obtaining 2-chloro-4-deformity-3-methoxyaniline (1.3 g, 48 mmol): LC/MS (m/z = 207).

11. GettingN-pivaloyl-2-bromo-4-chloro-3-methoxyaniline

To a solution ofN-pivaloyl-4-chloro-3-methoxyaniline (5.0 g, 21 mmol) in tetrahydrofuran (60 ml) at -60°C was addedn-utility (2.5 M, 44 mmol). The solution was heated to 0°C and was stirred for 3 hours. Added ethylenedibromide (9,9 g, 53 mmol) and the solution was stirred for 18 hours prior to quenching of CHL is reed ammonia (saturated solution, 20 ml) and was extracted with ethyl ether (2 × 50 ml). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The residue was purified by chromatography (10% ethyl acetate in hexane)to giveN-pivaloyl-2-bromo-4-chloro-3-methoxyaniline (3.7 g, 1.2 mmol): LC/MS (m/z = 320).

12. Obtain 2-bromo-4-chloro-1-iodine-3-methoxybenzoyl

SolutionN-pivaloyl-2-bromo-4-chloro-3-methoxyaniline (3.7 g, 1.2 mmol) in dioxane (35 ml) was treated with concentrated hydrochloric acid (35 ml) and the solution boiled under reflux for 2 hours. After this, the solution was cooled, the pH was lined up to 10 by adding sodium hydroxide (50% solution) and was extracted with ethyl acetate (2 × 50 ml). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The crude aniline was dissolved in 2N hydrochloric acid was added sodium nitrite (750 mg, 11 mmol) and the solution was stirred for 20 minutes. The solution was poured into a vigorously stirred solution of sodium iodide (3.3 g, 22 mmol) in water (20 ml) and methylene chloride (30 ml) and was stirred for 20 minutes. Then the solution was extracted with methylene chloride (2 × 25 ml) and the combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The residue was purified by chromatography (hexane)to give 2-bromo-4-chloro-1-iodine-3-methoxybenzoyl (1.5 g, 0.6 mmol): LC/MS (m/z = 267).

the Following compounds were obtained according to the method of example 12.

4-chloro-2,6-debtor-5-methyl-1-iadanza: BP. 60-70°C/0,75 mm

2-chloro-4-deformity-3-methoxy-1-iadanza: LC/MS (m/z = 318).

1-chloro-2-deformity-3,5-debtor-4-iadanza: LC/MS (m/z = 324).

13. Obtain 3-chloro-2-methoxy-4-nitrotoluene

A solution of 4-nitro-2-hydroxytoluene (5.0 g, 33 mmol) in chloroform (40 ml) was boiled under reflux and treated with a stream of chlorine for 1 hour. After cooling, the solution was washed with sodium bicarbonate (saturated solution), with brine, dried (sodium sulfate) and concentrated. The residue was dissolved in acetonitrile (75 ml)was treated with potassium carbonate (9.1 g, 66 mmol) and iodomethane (2.5 ml, 5.7 g, 40 mmol) and boiled under reflux for 2 hours. After cooling, the solution was concentrated, and the residue was dissolved in ethyl ether (75 ml) and washed with water (50 ml), with brine, dried (sodium sulfate) and concentrated. The crude product was purified by chromatography on silica gel with 1-5% ethyl acetate in hexane to getting 3-chloro-2-methoxy-4-nitrotoluene (3.0 g, 15 mmol): LC/MS (m/z = 201).

14. Obtain 3-chloro-2-methoxy-4-nitrobenzaldehyde

A solution of 3-chloro-2-methoxy-4-nitrotoluene (1.0 g, 5.0 mmol) in acetic acid (10 ml) and acetic anhydride (10 ml) was cooled to 5°and treated With 1 ml conc. H2SO4. Oxide chromium (VI) (1.4 g, 14 mmol) was added in portions over 10 minutes, at this temperature the tour of the reaction was maintained in the range of 0-5°C. After 30 minutes at this temperature, the mixture was poured into ice water (20 g) and the mixture was extracted with ethyl acetate (2 × 25 ml). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The crude Bissett was combined with water (10 ml), ethanol (10 ml) and concentrated sulfuric acid (1 ml) and boiled under reflux for 40 minutes. After cooling, the mixture was diluted with water (20 ml) and was extracted with ethyl acetate (2 × 50 ml). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The crude mixture was chromatographically (10% ethyl acetate in hexane)to give 3-chloro-2-methoxy-4-nitrobenzaldehyde (400 mg, 1.9 mmol): LC/MS (m/z = 215).

15. Receive (3-bromo-6-chloro-2-forfinal)methanol

To a solution of 3-bromo-6-chloro-2-forventelige (20,0 g, 0,084 mol) in ethanol (250 ml) was added sodium borohydride (6.4 g, has 0.168 mol) and the reaction mixture was stirred at ambient temperature for 1 hour. The mixture was diluted with water (300 ml) and was extracted with ethyl acetate (2 × 200 ml), dried (sodium sulfate) and concentrated. The crude solid residue was recrystallized from hexane, obtaining (3-bromo-6-chloro-2-forfinal)methanol (10.4 g, 0,043 mol):1H-NMR (CDCl3): δ 7.50 for (m, 1H), 7,15 (dt, 1H), 4,90 (s, 2H), 2,10 (USS, 1H).

The following compounds were obtained in accordance with the methodology applied is 15.

1-(3-bromo-6-chloro-2-forfinal)-2,2,2-triptoreline: GC/PCI (m/z = 306).

(3-fluoro-4-iodine-2-methoxyphenyl)methanol: LC/MS (m/z = 282).

16. Obtain 1-bromo-4-chloro-3-vermeil-2-fermental

Solution (diethylamino)sulfur TRIFLUORIDE (7.6 g, 0,047 mol) in methylene chloride (25 ml) was slowly added to (3-bromo-6-chloro-2-forfinal)methanol (10.3 g, 0,043 mol) in methylene chloride (150 ml) at 0°C. the Solution was stirred at ambient temperature for 1 hour. Was carefully added to saturated sodium bicarbonate solution (100 ml) and the mixture was extracted with methylene chloride (2 × 100 ml). The combined organic phases were dried (sodium sulfate) and concentrated. The remainder of the black oil was purified by chromatography (5% ethyl acetate in hexane)to obtain 1-bromo-4-chloro-3-vermeil-2-torbenson (6.20 g, 0,024 mol):1H-NMR (CDCl3): δ at 7.55 (m, 1H), 7,18 (DD, 1H), 5,6 (d, 2H).

The following compounds were obtained according to the method of example 16.

1-bromo-4-chloro-2-fluoro-3-(1-fluoro-1-methylethyl)benzene:1H-NMR (CDCl3): δ 7,42 (m, 1H), 7,10 (m, 1H), 6,05 (DQC, 1H), 1,95 (DD, 6N).

1-bromo-2,4-dichloro-3-(1-foradil)benzene: GC/PCI (m/z = 270).

1-bromo-4-chloro-2-fluoro-3-(1-foradil)benzene: GC/PCI (m/z = 255).

1-bromo-4-chloro-2-fluoro-3-(1,2,2,2-tetraborate)benzene: GC/EI (m/z = 308).

1-bromo-4-chloro-2-fluoro-3-(1-forproper)benzene: GC/EI (m/z = 267).

2-fluoro-4-vermeil-1-iodine-3-methoxybenzoyl: LC/MS (m/z = 284).

17. Obtain 1-bromo-4-chloro-2-fluoro-3-methoxime is Ventola

A solution of 1-bromo-4-chloro-2-fervently (20.4 g, 0,100 mol) in THF (50 ml) was slowly added LDA (0.125 mol) in THF (600 ml) at -50°C. After addition the solution was heated to -20°C and then cooled to -50°C and slowly added to the solution bromomethane (25,0 g, 0,200 mol) in tetrahydrofuran (25 ml)and the reaction mixture was heated to ambient temperature. The reaction extinguished with water (400 ml) and was extracted with diethyl ether (2 × 150 ml). The combined organic phases were dried (sodium sulfate) and concentrated. The residue oil was distilled (70-75°C/0.5 mm)to obtain 1-bromo-4-chloro-2-fluoro-3-methoxymethanol (18.0 g, 0,071 mol):1H-NMR (CDCl3): δ 7.50 for (m, 1H), 7,15 (DD, 1H)and 4.65 (s, 1H), 3,40 (s, 1H).

The following compounds were obtained according to the method of example 17.

1-bromo-4-chloro-2-fluoro-3-methylbenzo:1H-NMR (CDCl3): δ 7,30 (m, 1H), 7,05 (DD, 1H), 2,35 (s, 3H).

18. Obtaining 2-(4-chloro-2-fluoro-3-methoxyphenyl)-[1,3,2]-dioxaborinane

To a solution of 1-bromo-4-chloro-2-fluoro-3-methoxybenzene (10.4 g, 0,043 mol) in diethyl ether (150 ml) at -78°C was slowly added n-utility (2.5 M, 19,0 ml, 0,0475 mol) and the solution was stirred for 30 minutes. Was slowly added a solution of triisopropylsilane (12.0 g, 0,064 mol) in THF (25 ml) and the solution was heated to 0°C. was Added acetylchloride (10.0 g, 0.13 mol). After stirring for 1 hour the solution was concentrated and the solid residue was dissolved the in ethyl acetate (150 ml) and 1N solution of sodium hydroxide (50 ml). To the aqueous phase was added to the ice, which was then acidified enough concentrated hydrochloric acid to obtain a pH of 2. The heterogeneous mixture was extracted with ethyl acetate (2 × 150 ml) and the combined organic phases were dried (sodium sulfate) and concentrated. The solid residue suspended in toluene and was added propane-1,3-diol (6.6 g, 0.09 mol) and the mixture was heated with distillation of water using traps Dean-stark. After 2 hours the mixture was cooled and concentrated. The residue oil was dissolved in methylene chloride (50 ml) and washed with water (25 ml), then dried (sodium sulfate) and concentrated, obtaining 2-(4-chloro-2-fluoro-3-methoxyphenyl)-[1,3,2]-dioxaborinane (6.4 g, 0,062 mol):1H-NMR (CDCl3): δ to 7.15 (m, 1H), 6,95 (DD, 1H), of 4.05 (t, 4H), and 3.8 (s, 3H), 1,95 (t, 2H).

The following compounds were obtained according to the method of example 18.

2-(4-chloro-2-fluoro-5-methoxyphenyl)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ of 7.25 (d, 1H), 7,05 (d, 1H), 4,20 (t, 4H), 4,15 (s, 3H), 2,10 (t, 2H).

2-(4-chloro-2-fluoro-3-ethoxyphenyl)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ 7,30 (m, 1H), 7,05 (DD, 1H), 4,20 (m, 7H), 2.05 is (t, 3H), 1.50 in (t, 3H).

2-(4-chloro-2-fluoro-3-(methylthio)phenyl)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ 7.50 for (m, 1H), 7,18 (DD, 1H), 4,20 (t, 4H), of 2.50 (s, 3H), 2.05 is (t, 2H).

2-(4-chloro-2-fluoro-3-methoxymethyl)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ 7,6 (dt, 1H), 7,25 (DD, 1H), amounts to 4.76 (s, 2H), 4,20 (t, 4H), 3,40 (s, 3H), 2.05 is (t, 2H).

2-(4-chloro-2-CFT is R-3-isopropylphenyl)-[1,3,2]-dioxaborinane: 1H-NMR (CDCl3): δ 7,25 (m, 1H), 7,15 (DD, 1H), 4,5 (kV, 1H), 4,20 (t, 4H), 2.05 is (t, 2H), 1,50 (d, 6N).

2-(4-chloro-2-fluoro-3-deformational)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ of 7.75 (m, 1H), 7,15 (DD, 1H), 6.90 to-to 7.15 (t, 1H), 4,20 (t, 4H), 2.05 is (t, 2H).

2-(4-chloro-2-fluoro-3-formationl)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ of 7.70 (m, 1H), 7,25 (DD, 1H), and 5.8 (d, 2H), 4,20 (t, 4H), 2.05 is (t, 2H).

4-[1,3,2]-dioxaborinane-2-yl-3-fluoro-2-methoxybenzonitrile:1H-NMR (CDCl3): δ 7,40 (m, 1H), and 7.3 (DD, 1H), 4,25 (t, 4H), 4,15 (s, 3H), 2,10 (t, 3H).

2-(4-chloro-2-fluoro-3-methoxyethoxymethyl)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ 7,35 (m, 1H), 7,15 (DD, 1H), 4,25 (m, 6N in), 3.75 (d, 2H), 3,48 (s, 3H), 2,15 (t, 3H).

2-(2,4-dichloro-3-ethoxyphenyl)-[1,3,2]-dioxaborinane:1H-NMR (DMSO-d6): δ 7,40 (d, 1H), 7,29 (d, 1H), 4,08 (m, 4H), of 4.00 (q, 2H), 1,99 (m, 2H), of 1.34 (t, 3H).

2-[4-chloro-2-fluoro-3-(2,2-diplomatogether]-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ was 7.45 (m, 1H), 7,15 (DD, 1H), 6,15 (TT, 1H), to 4.38 (t, 4H), 4,20 (t, 2H), 2,10 (t, 2H).

2-(4-chloro-2-fluoro-5-ethoxyphenyl)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ of 7.25 (d, 1H), 7,05 (d, 1H), 4,20 (t, 4H), to 4.15 (t, 2H), 2,10 (t, 2H), 1,45 (t, 3H).

2-(2,4-dichloro-3-(methylthio)phenyl)-[1,3,2]-dioxaborinane:1H-NMR (CDCl3): δ 7,45-7,28 (m, 2H), 3,86 (m, 4H), 2,42 (s, 3H), of 1.80 (m, 2H).

6-chloro-3-[1,3,2]-dioxaborinane-2-yl-2-perbenzoate:1H-NMR (CDCl3): δ a 7.85 (m, 1H), and 6.25 (m, 1H), 4,20 (m, 4H), 2,10 (m, 2H).

19. Obtain 1-fluoro-2,3-methylenedioxybenzene

Alliquat 336 (methyltris elmonigote, to 0.63 g, 1.6 mmol), dibromomethane (40,7 g of 234.2 mmol) and water (31 ml) were placed in a 500 ml three-neck flask equipped with a dropping funnel, a refrigerator and a magnetic stirrer. In an addition funnel was placed a solution of 3-formeterol (20,0 g, 160 mmol) in 5 n NaOH (80 ml). The mixture in the flask was heated to the boiling temperature and was added dropwise a solution of catechol in 2 hours with good stirring and the resulting black mixture was further heated under reflux for 2 hours. After cooling to room temperature the reaction mixture was diluted with methylene chloride and the layers were separated. The aqueous layer was extracted with methylene chloride and the combined organic layers were dried (Na2SO4c activated carbon). The filtrate is concentrated to constant weight on a rotary evaporator, getting 1-fluoro-2,3-methylenedioxybenzene (14.6 g, 104,2 mmol) as a dark yellow oil:1H-NMR (CDCl3): δ to 6.80 (m, 1H), of 6.68 (m, 2H), 6,04 (s, 2H).

20. Getting 2-fluoro-3,4-methylenedioxyphenylacetic acid

1-fluoro-2,3-methylenedioxybenzene (5.0 g, to 35.7 mmol) was dissolved in THF (70 ml) and the solution was cooled to -65°C. in a bath of dry ice and acetone. Was added via syringe with stirring n-utility (2.5 g, 15.7 ml, or 39.3 mmol). The reaction mixture was heated up to -35°C for 1 hour, then was cooled to -65°C. and treated with trimethylboron (4.1 g,or 39.3 mmol) via syringe. The reaction mixture was slowly heated to room temperature, then the reaction is extinguished 1N HCl (50 ml)was stirred for 15 minutes, then was diluted with ether and the layers were separated. The organic layer was extracted with 1N sodium hydroxide and the extract was separated from the ether and was acidified using 1N hydrochloric acid. The acidic aqueous layer was extracted with two portions of ether and the combined ether extracts were dried (sodium sulfate), filtered and concentrated to an oily residue, which was triturated with dichloromethane. The resulting solid residue was collected by filtration, washed with dichloromethane and dried to obtain 1-fluoro-2,3-methylenedioxyaniline acid (1.4 g, 7.6 mmol) as a yellowish brown solid residue:1H-NMR (DMSO-d6): δ 8,05 (USS, 2H), was 7.08 (DD, 1H), 6,76 (d, 1H), between 6.08 (s, 2H).

The following compounds were obtained according to the method of example 20.

2-fluoro-3-methoxy-4-metilenhloridov acid:1H-NMR (300 MHz, d6-DMSO+H2O): δ 7,32 (USS, 2H), 7,11 (DD, 1H, J=7,2, 5.7 Hz), 6,92 (d, 1H, J=7,2 Hz), 3,74 (s, 3H), 2,19 (s, 3H).

4-bromo-2-fluoro-3-methoxyphenylalanine acid:1H-NMR (300 MHz, DMSO-d6+D2O): δ at 8.36 (USS, 2H), 7,38 (DD, 1H, J=8,4), 7,17 (DD, 1H), 3,82 (d, 3H).

21. Obtaining 2-(2-fluoro-3,4-methylenedioxyphenyl)-[1,3,2]-dioxaborinane

2-fluoro-3,4-methylenedioxyphenylacetone acid (1.4 g, 7.6 mmol) suspended the Wali in toluene and propane-1,3-diole (0.6 g, 7.9 mmol) and the mixture is boiled under reflux for 0.5 hours. The mixture was cooled, filtered through glass wool and concentrated, obtaining 2-(2-fluoro-3,4-methylenedioxyphenyl)-[1,3,2]-dioxaborinane (1.6 g, 7.1 mmol):1H-NMR (DMSO-d6): δ for 7.12 (DD, 1H, J=7,8, 5.7 Hz), 6.75 in (d, 1H), 6,09 (s, 2H), 4,06 (t, 4H), to 1.98 (m, 2H).

22. Obtain 3-bromo-6-chloro-2-perbenzoate

A suspension of 3-bromo-6-chloro-2-forventelige (9.0 g, 0.04 mol) and hydroxyamineO-sulinowo acid (7.50 g, 0.07 mol) in water (300 ml) was heated at 50°C for 18 hours. The suspension was cooled, and the solid residue was collected, receiving 3-bromo-6-chloro-2-perbenzoate (8.8 g, 0.04 mol):1H-NMR (CDCl3): δ of 7.75 (m, 1H), 7,25 (m, 1H).

23. Obtain 3-bromo-2-fluoro-6-chlorobenzamide

Concentrated sulfuric acid (15 ml) were placed in a 100 ml 3-necked flask equipped with internal thermometer, and then heated to 55°C. the acid was added in portions of 3-bromo-2-fluoro-6-chlorobenzonitrile (11,0 g, 47 mmol) and was stirred, maintaining the temperature above 50°C. the Black solution was heated at 65°C for 24 hours, then cooled to room temperature and poured into ice and carefully neutralized with concentrated ammonium hydroxide. The mixture was extracted with two portions of ethyl acetate and the combined organic layers were dried over Na2SO4(with activated carbon). After filtration and concentration which was alocale 3-bromo-2-fluoro-6-chlorobenzamide (11.5g, to 45.5 mmol) as a pale orange solid residue: TPL 157-158°C,1H-NMR (CDCl3): δ rate of 7.54 (t, 1H), 7,14 (DD, 1H),6,03 (USS, 1H), 5,81 (USS, 1H).

24. Obtain 3-bromo-2,6-dichlorobenzamide

3-bromo-2,6-dichlorobenzoyl acid (7.2 g, to 26.7 mmol) was treated with thionyl chloride (30 ml, 400,0 mmol) in a 250 ml round bottom flask and the mixture is boiled under reflux for 1 hour, then cooled to room temperature. Remove approximately one third of the light yellow solution was concentrated in vacuum. The residue was dissolved in THF (16 ml) and treated with concentrated ammonium hydroxide (6 ml) under vigorous stirring. The mixture was distributed between ethyl acetate and saturated NaHCO3and the layers were separated, and the organic layer was dried over Na2SO4. After filtration and concentration was obtained 3-bromo-2,6-dichlorobenzamide (2,19 g) as a foam: TPL 117-119°C,1H-NMR (300 MHz, d6-DMSO): δ 8,10 (USS, 1H), 7,88 (USS, 1H), 7,79 (d, 1H, J=8), 7,44 (d, 1H).

25. Obtain 3-bromo-6-chloro-2-foronline

Sodium hydroxide (4.0 g, 100.0 mmol) was dissolved in water (70 ml) in a 250 ml round bottom flask and the resulting solution was cooled in an ice bath and treated with bromine (4.7 g, 29.7 mmol), to obtain a yellow solution. 3-bromo-2-fluoro-6-chlorobenzoxazole (5.0 g, to 19.9 mmol) was slowly added as a solid with vigorous stirring and oranzhevo the mixture was boiled under reflux for 2 hours. The cooled reaction mixture was diluted with dichloromethane and the layers were separated and the dichloromethane was dried (Na2SO4). Crystallization of the concentrated filtrate from cold hexane gave 3-bromo-6-chloro-2-ftoranila (2.8 g, 12.6 mmol) as a grayish white solid residue: TPL 61-62°C,1H-NMR (CDCl3): δ 6,94 (DD, 1H), 6,83 (DD, 1H), 4,16 (USS, 2H).

The following compounds were obtained according to the method of example 25.

3-bromo-2,6-dichloroaniline: TPL 71-72°C.

26. GettingN-(3-bromo-6-chloro-2-forfinal)-N,N-dimethylamine

3-bromo-6-chloro-2-ftoranila (2.5 g, 11.1 mmol) was dissolved in THF (25 ml) purged with nitrogen, 250 ml round bottom flask and treated with 37% formaldehyde (0.84 g, 2.1 ml, 27.8 mmol), dichloride dibutyrate (0.07 g, 0.22 mmol) and phenylsilane (1,33 g, 12.3 mmol) and stirred at room temperature under nitrogen atmosphere for 48 hours. The reaction mixture was concentrated in vacuo, and purified flash chromatography on silica gel (hexane)to giveN-(3-bromo-6-chloro-2-forfinal)-N,N-dimethylamine (2.0 g, 7.9 mmol) in butter form:1H-NMR (CDCl3): δ 7,19 (DD, 1H),? 7.04 baby mortality (DD, 1H), 2,88 (s, 3H), 2,87 (s, 3H).

The following compounds were obtained according to the method of example 26.

N-(3-bromo-6-chloro-2-forfinal)-N,N-diethylamino:1H-NMR (300 MHz, CDCl3): δ 7.24 to (DD, 1H), 7,07 (DD, 1H), and 3.16 (DD, 4H), 1,01 (t, 6N).

N-(3-bromo-2,6-dichlorophenyl)-N,N-dimethylamine:1 H-NMR (300 MHz, CDCl3): δ 7,33 (d, 1H), 7,13 (d, 1H), 2,88 (C, 6N).

N-(2-chloro-4,6-differenl)-N,N-dimethylamine: colorless oil.1H-NMR (300 MHz, CDCl3): δ 6,93 (DDD, 1H), 6.73 x (m, 1H), 2,82 (d, 6N).

27. GettingN-(3-bromo-2-forfinal)-Nof methylamine

3-bromo-6-chloro-2-ftoranila (1.2 g, 5.2 mmol) was dissolved in THF (12 ml) in a 100 ml round bottom flask and was treated with Tetra-N-butylammonium bromide (0.015 g, 0.05 mmol) and powdered sodium hydroxide (0,83 g of 20.9 mmol) under stirring. After 5 minutes, the black mixture was treated with dimethylsulfate (1.3 g, 10.4 mmol) and the mixture was heated at 60°C for 2 hours. Monitoring by TLC (hexane:ethyl acetate 20/1) showed the presence of a quantity of original substance. Added additional dimethylsulfate (0.66 g, 5.2 mmol) and continued heating for 1.5 hours, then stirred at room temperature overnight. The reaction mixture was distributed between diethyl ether and water, the layers were separated and the aqueous phase was extracted with ether. The combined ether layers were washed with water and dried (MgSO4). Filtration, concentration and purification with flash chromatography on silica gel (hexane) gaveN-(3-bromo-6-chloro-2-forfinal)-Nmethylamine (0,81 g) as a colorless oil:1H-NMR (300 MHz, CDCl3): δ 6,93 (DD, 1H, J=8,4), 6,83 (DD, 1H), 4.00 points (USS, 1H), 3,09 (d, 3H).

28. Obtaining 1,3-ditto the-2-iodine-4-methoxy-5-methylbenzoyl

A solution of 1,5-debtor-2-methoxy-3-methylbenzene (0.65 g, 4.1 mmol) in THF (1 ml) was added LDA (4.3 mmol) in THF (10 ml) at -55°C and the solution was stirred for 45 minutes. Added solid iodine (1,15 g, 4.5 mmol) and the solution was heated to ambient temperature. The solution was diluted with ethyl acetate and washed with sodium bicarbonate (saturated solution, 15 ml) and sodium thiosulfate (saturated solution, 15 ml), dried (sodium sulfate) and concentrated. The residue was purified by chromatography (hexane)to give 1,3-debtor-2-iodine-4-methoxy-5-methylbenzoyl:1H-NMR (300 MHz, CDCl3): δ 6,72 (DD, 1H), 3,84 (d, 3H), and 2.26 (s, 3H).

The following compounds were obtained according to the method of example 28.

3,5-debtor-4-iodine-2-methoxybenzonitrile: TPL 106-110°C.

N-(6-chloro-2,4-debtor-3-itfinal)-N,N-dimethylamine:1H-NMR (300 MHz, CDCl3): δ 6,98 (DD, 1H), 2,82 (d, 6N).

1,3-dichloro-5-fluoro-4-iodine-2-methoxybenzoyl: GC-MS (m/z = 320).

1,3-debtor-2-iodine-4-methoxy-5-methylbenzoyl:1H-NMR (CDCl3): δ 6,72 (DD, 1H), 3,84 (d, 3H), and 2.26 (s, 3H).

2,3-debtor-4-iodine-benzonitrile: LC/MS (m/z = 265).

3-chloro-1-deformity-5-fluoro-4-iodine-2-methoxybenzoyl: LC/MS (m/z = 336).

2 ethoxy-1,3-debtor-4-iadanza: GC-MS (m/z = 284).

1,3-debtor-2-iodine-4-methoxy-5-methylbenzoyl:1H-NMR (CDCl3): δ 6,72 (DD, 1H), 3,84 (d, 3H), and 2.26 (s, 3H).

3,5-debtor-4-iodine-2-methoxybenzonitrile: TPL 106-110°C.

(6-chloro-2,4-debtor-3-itfinal)dimethylamine:1H-NMR (CDCl 3): δ 6,98 (DD, 1H), 2,82 (d, 6N).

2,4,6-Cryptor-3-iodine-benzonitrile: LC/MS (m/z = 283).

1-bromo-3,5-debtor-4-iodine-2-methoxybenzoyl: LC/MS (m/z = 349).

1,3-dichloro-5-fluoro-4-iodine-2-methoxybenzoyl: GC-MS (m/z = 320).

29. Obtain 1-chloro-3,5-debtor-4-iodine-2-methoxybenzoyl

To a solution of 1-chloro-3,5-debtor-2-methoxybenzene (2.0 g, 0.01 mol) in THF at -75°C. was added n-utility (2.5 M in hexane, 6,7 ml) and the resulting solution was stirred at -75°C for 1 hour. Solution was added iodine (5.1 g, 0.02 mol) in THF (10 ml) and the reaction mixture was heated to ambient temperature. The reaction mixture was diluted with ethyl ether (50 ml) was added aqueous sodium thiosulfate (10%, 50 ml) and was stirred for 1 hour. After separation of the phases the organic phase was dried (Na2SO4) and concentrated, obtaining 1-chloro-3,5-debtor-4-iodine-2-methoxybenzoyl in the form of a white solid residue: TPL 62-64°C.

The following compounds were obtained according to the method of example 29.

1-chloro-2-ethoxy-3,5-debtor-4-iadanza: GC-MS (m/z = 178).

30. Obtain 3-fluoro-4-iodine-2-methoxybenzonitrile.

Sodium hydride (60 mg, 2.5 mmol) suspended in DMF (15 ml) and treated with dry methanol (120 ál, 96 mg, 3.0 mmol). After stirring for 10 minutes at 25°C. the solution was cooled to -25°C. and was treated with 2,3-debtor-4-iodine-benzonitrile (500 mg, 1.9 mmol). After 25 minutes, the mixture was suppressed by the addition of 10% solution lim is authorized acid (5 ml) and was heated to 25°C. The mixture was extracted with ethyl ether (2 × 15 ml), the combined ether phases were washed with water (5 ml), with brine, dried (sodium sulfate) and evaporated to obtain 3-fluoro-4-iodine-2-methoxybenzonitrile (500 mg, 1.8 mmol): LC/MS (m/z = 277).

31. Obtain 3-fluoro-4-iodine-2-methoxybenzaldehyde.

3-fluoro-4-iodine-2-methoxybenzonitrile (1.0 g, 3.6 mmol) was dissolved in toluene (7 ml), cooled to 0°C and treated portions 25% by weight of diisobutylaluminium (DIBAL) in toluene (3.1 ml, 4.7 mmol). After 30 minutes the reaction was suppressed by the addition of methanol (5 ml), poured in 1M sulfuric acid (15 ml) and was extracted with ethyl acetate (2 × 15 ml). The combined extracts were washed with water (5 ml), with brine, dried (sodium sulfate) and evaporated to obtain 3-fluoro-4-iodine-2-methoxybenzaldehyde (450 mg, 1.6 mmol): LC/MS (m/z = 260).

32. Obtain 3-chloro-4-iodine-2-methoxyaniline.

3-chloro-2-methoxyaniline (1 g, 6.4 mmol) was dissolved in methylene chloride (10 ml) in a 250 ml round bottom flask and treated with water (10 ml), NaHCO3(1.1 g, 12.7 mmol) and iodine (1,61 g, 6.4 mmol) and the resulting mixture was boiled under reflux for 2 hours, after which TLC (hexane/ethyl acetate 4:1) showed almost complete conversion. The reaction mixture was diluted with ethyl acetate and washed with saturated Na2S2O3. The organic layer was separated and dried (Na2 SO4). Filtration, concentration and purification with flash chromatography on silica gel (hexane/ethyl acetate 8:1) gave 0.71 g of a red oil, which, as defined, is a mixture of 2.5:1 3-chloro-4-iodine-2-methoxyaniline and source connections:1H-NMR (300 MHz, CDCl3): δ was 7.36 (d, 1H, J=8,4 Hz), 6,45 (d, 1H, J=8,4 Hz), 4,10 (USS, 2H), 3,82 (s, 3H).Other experiments with an excess of iodine gave similar results. The mixture was combined with a mixture of previous experience and used without further purification.

33. Getting 4-chloro-2,6-debtor-3-methylaniline

A solution of 2,6-debtor-3-methylaniline (15 g, 105 mmol) in acetic acid (80 ml) was heated to 70°C. and added dropwise over 20 minutes a solution of sulfurylchloride (16.0 g, 115 mmol) in acetic acid (40 ml). The temperature was kept for 3 hours, then cooled and concentrated. The residue was dissolved in water (100 ml) and the pH was brought to 9 2N sodium hydroxide and then extracted with methylene chloride (2 × 75 ml) and the combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The residue was distilled, obtaining 4-chloro-2,6-debtor-3-methylaniline (12.2 g, 69 mmol): BP. 55-65°C/55 mm

34. Obtain 1-bromo-3-chloro-4-iodine-2-methoxybenzoyl

A mixture of 3-chloro-2-methoxyaniline and 3-chloro-4-iodine-2-methoxyaniline (2.8 g, a 2.5:1) was dissolved in dioxane (20 ml) and the resulting solution was cooled in Leda the Oh bath, processing 48% HBr (20 ml). Then dark purple mixture was treated with NaNO2(1.4 g, a 19.5 mmol) in water (6 ml) under vigorous stirring. After 10 minutes, was added CuBr (5,1 g, 35.5 mmol) and the mixture was removed from the ice bath was heated to room temperature and was stirred for 0.5 hour. Dark purple mixture was diluted with ethyl acetate and water, then filtered through celite using ethyl acetate. The layers were separated and the organic layer was washed with a saturated solution of sodium sulfite and saturated solution of ammonium chloride and dried (Na2SO4). Filtration, concentration and purification with flash chromatography on silica gel (hexane) gave 2,95 g of colorless oil, which, as defined, is a mixture of 2.3:1 1-bromo-3-chloro-2-methoxybenzene and 1-bromo-3-chloro-4-iodine-2-methoxybenzene, which was used without further purification:1H-NMR (300 MHz, CDCl3): δ 7,49 (d, 1H), 7,19 (d, 1H), 3,90 (s, 3H).

35. Obtain 1-chloro-3,5-debtor-4-trimethylsilylimidazole

To a solution of 3,5-debtor-1-chlorobenzene (10.0 g, 67 mmol) and tetramethylaniline (TMEDA; 7,8 g, 67 mmol) in THF (75 ml) at -75°C. was added n-utility (2,5M, 68 mmol) and the resulting solution was stirred for 30 minutes. Solution was added trimethylsilylpropyne (7.6 g, 70 mmol) in THF (15 ml) and the solution was heated to ambient temperature and was stirred for 25 hours. Added chlorine is the ID of ammonia (saturated solution, 15 ml) and the mixture was extracted with ethyl ether (2 × 100 ml) and the combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The residue oil was distilled, obtaining 1-chloro-3,5-debtor-4-trimethylsilanol (13,0 g, 60 mmol): BP. 70-75°C.

36. Obtaining 6-chloro-2,4-debtor-3-trimethylbenzaldehyde

A solution of 1-chloro-3,5-debtor-4-trimethylsilylimidazole (1.5 g, 6.8 mmol) in THF (10 ml) was added to a solution of tetramethylpiperidine lithium (14 mmol) in THF (15 ml) at -75°C. the Solution was stirred for 2 hours, then was added DMF (1.5 g, 20 mmol) and the solution was heated to ambient temperature. The reaction was suppressed with a saturated solution of ammonium chloride (25 ml) and was extracted with ethyl acetate (2 × 25 ml) and the combined extracts were dried (sodium sulfate) and concentrated. The residue was purified by chromatography (hexane)to obtain 6-chloro-2,4-debtor-3-trimethylbenzaldehyde (1.4 g, 5.6 mmol): LC/MS (m/z = 248).

37. Obtaining 6-chloro-2,4-debtor-3-identilied

A solution of 6-chloro-2,4-debtor-3-trimethylbenzaldehyde (600 mg, 2.4 mmol) in methylene chloride (7 ml) was cooled to 0°C and treated with a solution of jodhpured (780 mg, 4.8 mmol) in methylene chloride (10 ml) and stirred at ambient temperature for 2 hours. Added more jodhpured (900 mg) and the solution boiled under reflux for 40 min is so The solution was cooled and washed with sodium bisulfite (15 ml, 5% solution), water (10 ml) and saturated sodium bicarbonate solution (10 ml). The organic phase was dried (sodium sulfate) and concentrated, obtaining 6-chloro-2,4-debtor-3-identilied (620 mg, 3.9 mol): LC/MS (m/z = 302).

38. Obtain 1-bromo-2,4-debtor-5-methoxybenzoyl

To a solution of 1,3-dibromo-4,6-diferente (10.0 g, 37 mmol) in THF (50 ml) at -20°C was added isopropylaniline (2.0 M in THF, 42 mmol) and the resulting mixture was heated to 0°C and was stirred for 30 minutes. Added trimethylboron (4.7 g, 45 mmol) and the mixture was stirred at ambient temperature for 1 hour. The solution was re-cooled to -20°C and was added peracetic acid (32%, 50 mmol) and the solution was stirred at ambient temperature for 30 minutes. Then the solution is extinguished sodium bisulfite (5% solution, 75 ml) and then acidified using 6N hydrochloric acid and was extracted with ethyl ether (2 × 75 ml). The combined extracts were dried (sodium sulfate) and concentrated. The crude phenol was dissolved in acetonitrile (40 ml) was added potassium carbonate (10 g, 74 mmol) and jodean (5.7 g, 40 mmol) and stirred at ambient temperature for 20 hours. The solution was concentrated and the residue was dissolved in water (50 ml) and was extracted with ethyl ether (2 × 75 ml) and the combined extracts were washed salt is a solution, was dried (sodium sulfate) and concentrated. The residue was purified by chromatography (hexane)to obtain 1-bromo-2,4-debtor-5-methoxybenzo (2.0 g, 8.6 mmol): LC/MS (m/z = 223).

39. Getting 2-chloro-4,6-debtor-1-iodine-3-methoxybenzoyl

A solution of 4-chloro-2,6-debtor-1-iodine-3-methoxybenzoyl (2.0 g, 6.6 mmol) in THF (7 ml) was added LDA (8.0 mmol) in THF (15 ml) at -55°C and the reaction mixture was stirred for 2 hours. The solution was diluted with ethyl ether (50 ml) and washed with ammonium chloride (saturated solution, 25 ml), with brine and then dried (sodium sulfate) and concentrated. The residue oil was purified by chromatography with reversed phase (70% acetonitrile in water)to obtain 2-chloro-4,6-debtor-1-iodine-3-methoxyphenol (500 mg, 1.7 mmol): LC/MS (m/z = 304).

40. Getting 4-chloro-3-(dimethylamino)-2-ftorhinolonovy acid

N-(3-bromo-6-chloro-2-forfinal)-N,N-dimethylaniline (0.88 g, 3.5 mmol) was dissolved in ether (10 ml) dried in a drying Cabinet, purged with nitrogen, 50 ml 3-necked flask equipped with a thermometer. The solution was cooled to -60°C. in a nitrogen atmosphere. Was added dropwise via syringe n-utility (0,23 g, 3.6 mmol, 1,45 ml of 2.5 M solution), keeping the temperature below -55°C. After 0.5 hours was added via syringe trimethylboron (0.40 g, 0.38 mmol) and the reaction mixture was heated to room temperature. Added 1N HCl (3.5 ml) and the mixture was stirred for 0.5 hour. Specieslevel water and ether and the ether layer was separated and dried over PA 2SO4. Filtration and concentration gave 0,753 g of a foam which is triturated with hexane. The resulting solid residue was collected by filtration and dried to obtain 4-chloro-3-(dimethylamino)-2-ftorhinolonovy acid (0.5 g, 2.3 mmol) as off-white solid residue: using1H NMR (DMSO-d6) found that the residue is a mixture of what, apparently, is Bronevoy acid and anhydrides. The solid residue was used without further purification and characterization.

The following compounds were obtained according to the method of example 40.

4-chloro-3-(diethylamino)-2-ftorhinolonovy acid:1H-NMR (300 MHz, DMSO-d6+ D2O): δ compared to 8.26 (USS, 2H), 7,26 (m, 2H), 3,05 (kV, 4H), of 0.91 (t, 6N).

2,4-dichloro-3-dimethylaminobenzophenone acid. The substance was isolated as an oily mixture Bronevoy acid and anhydride and used without further purification or characterization.

2-chloro-4-fluoro-3-methoxyphenylalanine acid (used without purification)

41. Obtain [3-chloro-2-fluoro-3-(4,4,5,5-tetramethyl-{1,3,2}dioxaborolan-2-yl)phenylethylamine

N-(3-bromo-6-chloro-2-forfinal)-Nmethylamine (0.84 g, 3.5 mmol) was dissolved in DMF (10 ml) purged with nitrogen, 50 ml 3-necked flask and the resulting solution was purged with nitrogen for 0.5 hours. At the same time was added bis(pinacolato)is boron (0,98 g, 3.9 mmol), potassium acetate (1.04 g, 10.6 mmol) and the complex [1,1'-bis(diphenylphosphino)ferrocene]dichloride palladium (II) · CH2Cl2(0.14 g, 0.18 mmol) and the mixture was heated to 110°C. by blowing nitrogen to 60°C. and, then, in the outdoor atmosphere of nitrogen for 1.5 hours. The reaction mixture was cooled to room temperature and distributed between ethyl acetate and hydrochloric solution and the layers were separated. The aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with brine and dried (Na2SO4). Filtration, concentration and purification with flash chromatography on silica gel (hexane:ethyl acetate / 5:1) gave [3-chloro-2-fluoro-3-(4,4,5,5-tetramethyl-{1,3,2}dioxaborolan-2-yl)phenylethylamine (0.85 grams): light green solid residue:1H-NMR (300 MHz, CDCl3): δ 7,05 (m, 2H), 3.96 points (USS, 1H), 3,06 (d, 3H), of 1.35 (s, N).

42. Obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-thiomethyl)phenyl)pyridine-2-carboxylic acid (compound 1).

A solution of methyl ester 4-amino-3,6-dichloropyridine-2-carboxylic acid (2.6 g, 0.012 mol), 2-(4-chloro-2-fluoro-3-dimethylphenyl)-[1,3,2]dioxaborinane (4.1 g, to 0.016 mol), 1,4-bis(diphenylphosphino)butane (0,610 mg, 0,0015 mol) and cesium fluoride (6.7 g, 0.045 mol) in acetonitrile (75 ml) was degirolami nitrogen for 15 minutes. Added palladium acetate (0,30 g 0,0015 mol) and the mixture is boiled under reflux for 4 hours. React the mixture was extinguished with water and was extracted with ethyl acetate (2 × 100 ml) and the combined extracts were dried (sodium sulfate) and concentrated. The solid residue was purified by chromatography (25-40% ethyl acetate in hexane)to obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-dimethylphenyl)pyridine-2-carboxylic acid (2.0 g, of 0.005 mol):1H-NMR (DMSO-d6): δ for 7.78 (t, 1H), 7,50 (d, 1H), 7,25 (s, 1H), 3,95 (s, 3H), of 2.50 (s, 3H).

The following compounds were obtained according to the method of example 42 (in some cases, instead of ether used untreated Bronevoy acid).

Methyl ester of 4-amino-3-chloro-6-(4-chloro-3-cyano-2-forfinal)pyridine-2-carboxylic acid (compound 2): TPL 189-190°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxymethyl)pyridine-2-carboxylic acid (compound 3): TPL 116-117°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-deformational)pyridine-2-carboxylic acid (compound 4): TPL 145-146°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-formationl)pyridine-2-carboxylic acid (compound 5):1H-NMR (CDCl3): δ with 8.05 (dt, 1H), 7,25 (d, 1H), 7,15 (s, 1H), 5,65 (DD, 2H), 4.95 points (USS, 2H), 4.00 points (s, 3H).

Methyl ester of 4-amino-3-chloro-6-(4-cyano-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 6):1H-NMR (CDCl3): δ of 7.70 (m, 1H), 7,20 (DD, 1H), 7,10 (d, 1H), 4.95 points (USS, 2H), 4.00 points (s, 3H).

Methyl ester of 4-amino-3-chloro-6-(2,4-dichloro-3-ethoxyphenyl)pyridine-2-carboxylic acid (compound 7): TPL 132-133°C.

Methyl ester of 4-amino-3-chloro-6-[4-dichloro-2-fluoro-3-(2,2-dottorato and)phenyl]pyridine-2-carboxylic acid (compound 8): TPL 134-136°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-5-ethoxyphenyl)pyridine-2-carboxylic acid (compound 9): TPL 115-116°C.

Methyl ester of 4-amino-3-chloro-6-[2,4-dichloro-3-(2,2-diflorasone)phenyl]pyridine-2-carboxylic acid (compound 10): TPL 113-115°C.

Methyl ester of 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(methoxyethoxy)phenyl]pyridine-2-carboxylic acid (compound 11): TPL 89-90°C.

Methyl ester of 4-amino-3-chloro-5-fluoro-6-(2-fluoro-3,4-methylenedioxyphenyl)pyridine-2-carboxylic acid (compound 12): TPL 151-152°C.

Methyl ester of 4-amino-3-chloro-6-(2,4-dichloro-3-methylthiophenyl)pyridine-2-carboxylic acid (compound 13):1H-NMR (CDCl3): δ was 7.45 (d, 1H), 7,40 (d, 1H), 6,98 (s, 1H), equal to 4.97 (USS, 2H), 3,98 (s, 3H), of 2.44 (s, 3H).

Methyl ester of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 14): TPL 172-173°C.

Methyl ester of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-5-methoxyphenyl)pyridine-2-carboxylic acid (compound 15): TPL 168-169°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-forfinal)pyridine-2-carboxylic acid (compound 16): TPL 104-106°C.

Methyl ester of 4-amino-3-chloro-6-[4-chloro-3-(diethylamino)-2-forfinal)pyridine-2-carboxylic acid (compound 17): TPL 120-121°C.

43. Obtain methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2-fluoro-5-methoxyphenyl)pyridine-2-carboxylic acid (compound 18).

The solution met the business ester 4-acetylamino-3,6-dichloropyridazine acid (4.3 g, to 0.016 mol), 2-(4-chloro-2-fluoro-5-methoxyphenyl)-[1,3,2]-dioxaborinane (4.5 g, 0.018 mol), cesium fluoride (3.5 g, 0,025 mol) and 1,4-bis(diphenylphosphino)butane (0,360 g, 0,0016 mol) in acetonitrile (100 ml) was degirolami nitrogen for 15 minutes before adding palladium acetate (0,180 g, 0,0016 mol) and the solution boiled under reflux for 18 hours. Was added water (150 ml) and the resulting solid residue was collected and dried to obtain methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2-fluoro-5-methoxyphenyl)pyridine-2-carboxylic acid (4.5 g, 0.012 mol): TPL 180-182°C.

The following compounds were obtained according to the method of example 43.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2-fluoro-3-were)pyridine-2-carboxylic acid (compound 19): TPL 151-152°C.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 20): TPL 159-160°C.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2-fluoro-3-ethoxyphenyl)pyridine-2-carboxylic acid (compound 21):1H-NMR (CDCl3): δ 9,00 (USS, 1H), 8,00 (m, 1H), 7,60 (m, 1H), 7,25 (s, 1H), 4,25 (kV, 2H), 4.00 points (s, 3H), of 2.35 (s, 3H), 1.50 in (t, 3H).

Methyl ester of 4-acetylamino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 22):1H-NMR (CDCl3): δ of 8.90 (s, 1H), with 8.05 (s, 1H), 7,40 (d, 1H), 7,30 (d, 1H), of 4.05 (s, 3H), of 3.95 (s, 3H), of 2.35 (s, 3H).

Methyl ester of 4-acetylamino-3-chloro-6-(2-fluoro-3,4-meth is mendicity)pyridine-2-carboxylic acid: TPL 132-134°C.

Methyl ester of 4-acetylamino-3-chloro-6-(2,4-dichloro-3-ethoxy-2-forfinal)pyridine-2-carboxylic acid:1H-NMR (CDCl3): δ 8,86 (s, 1H), 8,00 (USS, 1H), 7,37 (d, 1H), 7,26 (d, 1H), 4,11 (kV, 2H), 4.00 points (s, 3H), 2,32 (s, 3H), of 1.47 (t, 3H).

Methyl ester of 4-acetylamino-3-chloro-6-[2,4-dichloro-3-(2,2-diflorasone)phenyl]pyridine-2-carboxylic acid:1H-NMR (CDCl3): δ 8,81 (s, 1H), 8,10 (USS, 1H), 7,32 (d, 1H), 7,29 (d, 1H), 6,16 (TT, 1H), 4,22 (TD, 2H), 3,95 (s, 3H), of 2.28 (s, 3H).

44. Obtain methyl ester of 4-acetylamino-3-chloro-6-(2,4-debtor-3-were)pyridine-2-carboxylic acid (compound 23).

A solution of 1-bromo-2,4-debtor-3-methylbenzene (2.10 g, 0.09 mol), methyl ester 4-acetylamino-3-chloro-6-trimethylaniline-2-carboxylic acid (4,00 g, 0.01 mol), 1,4-bis(diphenylphosphino)butane (0,140 g 0,0003 mol) and cesium fluoride (4.5 g, 0.03 mol) in acetonitrile (100 ml) was degirolami nitrogen. Added palladium acetate (0,70 g 0,0003 mol) and the mixture is boiled under reflux for 2 hours. The reaction mixture was filtered through celite and the filtrate was diluted with water (200 ml) and then extracted with ethyl acetate (2 × 150 ml). The combined organic phase was dried and concentrated and the solid residue was purified by chromatography (50% ethyl acetate in hexane)to obtain methyl ester of 4-acetylamino-3-chloro-6-(2,4-debtor-3-were)pyridine-2-carboxylic acid (0.800 to g, 0.002 mol): TPL 152-153°C.

The following compounds the Oia received in accordance with the method of example 44.

Methyl ester of 4-acetylamino-3-chloro-6-(2,4-dichloro-3-were)pyridine-2-carboxylic acid (compound 24): TPL 172-174°C.

45. Receive (2-fluoro-3-methoxy-4-triptoreline)-trimethylstyrene.

Dioxane (28 mg) was added to the dried in a drying Cabinet, purged with nitrogen, 100 ml 3-necked flask equipped with a fridge and a magnetic stirrer was purged with nitrogen for 15 minutes. Added hexamethyldisilane (5.0 g, of 15.3 mmol) and 1-bromo-2-fluoro-3-methoxy-4-(trifluoromethyl)benzene (3.8 g, a 13.9 mmol) and aeration was continued for 5 minutes. Added 1,4-bis(diphenylphosphino)butane (0.6 g, 1.4 mmol) and palladium acetate (0.3 g, 1.4 mol) and the free space of the reaction vessel was purged with nitrogen when heated to the boiling temperature under stirring. Then the reaction was stirred while boiling under reflux in an open atmosphere of nitrogen for 6 hours. TLC (hexane) showed complete disappearance of starting compound. The cooled reaction mixture was concentrated and purified flash chromatography on silica gel (hexane)to obtain (2-fluoro-3-methoxy-4-triptoreline)trimethylsilane (3,93 g, 11.0 mmol) in butter form:1H-NMR (CDCl3): δ 7,31 (d, 1H), 7,11 (DD, 1H), 3,98 (d, 3H), 0,38 (s, N). All signals have corresponding satellites tin.

The following compounds were obtained according to the method of example 45.

(3 butoxy-4-chloro-2-CFT is henyl)trimethylsilane (used without purification).

4-chloro-2-fluoro-3-(1-fluoro-1-methylethyl)trimethylsilane (used without purification).

46. Obtain methyl ester of 4-acetylamino-3-chloro-6-(2-fluoro-3-methoxy-4-triptoreline)pyridine-2-carboxylic acid.

In dried in a drying Cabinet, purged with nitrogen, 100 ml 3-necked flask equipped with a fridge and a magnetic stir bar was dissolved methyl-4-acetylamino-3,6-dichloropyridine-2-carboxylate (1.2 g, 4.6 mmol) and (2-fluoro-3-methoxy-4-triptoreline)trimethylsilane (1.7 g, 4.6 mmol) in acetonitrile (15 ml) and the resulting solution was re-purged with nitrogen for 15 minutes. Added cesium fluoride (2.1 g, a 13.9 mmol), 1,4-bis(diphenylphosphino)butane (0.2 g, 046 mmol) and palladium acetate (0.1 g, 0.46 mmol) and the free space in the reaction vessel was purged with nitrogen under stirring as the reaction mixture was heated to boiling point. Then the reaction mixture was stirred in an open atmosphere of nitrogen for 5 hours, after which TLC (hexane:ethyl acetate / 1:2) showed complete conversion of the parent compound. The cooled reaction mixture was filtered through celite using ethyl acetate, and the filtrate was concentrated and purified flash chromatography on silica gel (hexane:ethyl acetate/2:1)to give methyl ester of 4-acetylamino-3-chloro-6-(2-fluoro-3-methoxy-4-triptoreline)pyridine-2-carboxylic acid (0,19 g, 0.46 mmol) of the butter form: 1H-NMR (CDCl3): δ 9,03 (d, 1H), 8,02 (USS, 1H), 7,68 (Ust, 1H), 7,42 (USD, 1H), 4,03 (d, 3H), 4,01 (s, 3H), of 2.33 (s, 3H).

The following compounds were obtained according to the method of example 46.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-3-butoxy-2-forfinal)pyridine-2-carboxylic acid: LC/ESI (m/z = 428).

Methyl ester of 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(1-fluoro-1-methylethyl)phenyl]pyridine-2-carboxylic acid (compound 25): TPL 122-123°C.

47. Obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-5-nitrophenyl)pyridine-2-carboxylic acid.

Was added methyl-4-amino-3-chloro-6-(4-chloro-2-forfinal)pyridine-2-carboxylate (1.0 g, 3.2 mmol) as a solid substance to intensively mixed with concentrated sulfuric acid (16 ml) at 0°C. was Added sodium nitrate (0,29 g, 3.5 mmol) to the mixture and the resulting yellow solution was stirred at 0°C for 1.5 hours, then diluted with a large amount of ice and warmed up to room temperature. The solution was filtered to remove solids, and then the filtrate was extracted 3 times with ethyl acetate and the combined an ethyl acetate layers washed with saturated aqueous NaHCO3and dried (Na2SO4). Filtration and concentration gave the methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-5-nitrophenyl)pyridine-2-carboxylic acid (0.96 g, 2.7 mmol) as a yellow solid residue: TPL 161-163°C:1 H-NMR (CDCl3): δ 8,73 (d, 1H), was 7.36 (d, 1H), 7,24 (d, 1H), 4,93 (USS, 2H), was 4.02 (s, 3H).

48. Obtain methyl ester of 4-amino-3-chloro-6-(5-amino-4-chloro-2-forfinal)pyridine-2-carboxylic acid.

Iron powder (0,78 g, a 13.9 mmol) was added to a suspension of methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-5-nitrophenyl)pyridine-2-carboxylate (0.5 g, of 1.39 mmol) in acetic acid (20 ml) in a 100 ml round bottom flask. The mixture was heated to 85°C for 15 minutes, then cooled to room temperature and filtered through celite using ethanol, and the filtrate was concentrated in vacuum. The residue was distributed between ethyl acetate and saturated NaHCO3the layers were separated, the aqueous phase was extracted with ethyl acetate and the combined organic phases were dried (Na2SO4). Filtration and concentration gave the methyl ester of 4-amino-3-chloro-6-(5-amino-4-chloro-2-forfinal)pyridine-2-carboxylic acid (0,44 g of 1.33 mmol) as a light brown solid residue: TPL 99-101°C.

49. Obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-5-dimethylamino-2-forfinal)pyridine-2-carboxylic acid (compound 26).

Methyl-4-amino-3-chloro-6-(5-amino-4-chloro-2-forfinal)pyridine-2-carboxylate (0,38 g, 1.13 mmol) was dissolved in THF (10 ml) purged with nitrogen, 250 ml round bottom flask and treated with 37% formaldehyde (0,068 g, 0.17 ml of 2.27 mmol), dichloride dibutyrate (0,007 g, is 0.023 mmol) and phenylsilane (is 0.135 g, 1.25 m is ol) and stirred at room temperature for 72 hours. The reaction mixture was concentrated in vacuo, and purified flash chromatography on silica gel (hexane:ethyl acetate / 2:1)to obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-5-dimethylamino-2-forfinal)pyridine-2-carboxylic acid (0,283 g, 0.8 mmol) in the form of friable white balance: TPL 113-115°C,1H-NMR (CDCl3): δ 7,66 (d, 1H), 7,14 (d, 1H), 7,14 (d, 1H), 4,91 (USS, 2H), 3,99 (s, 3H), and 2.79 (s, 6N).

50. Obtain methyl ester of 4-acetylamino-3-chloro-6-yodellin-2-carboxylic acid.

To a solution of methyl ester 4-acetylamino-3-chloro-6-trimethylindolenine-2-carboxylic acid (21,0 g, 54 mmol) in methylene chloride (200 ml) was added iodine (13,7 g, 108 mmol) and the solution was stirred for 1 hour at ambient temperature. The solution was filtered through a layer of celite and then washed with sodium thiosulfate (50 ml, 10% solution), dried (sodium sulfate) and concentrated. The residue was purified by chromatography (10% ethyl acetate in hexane)to obtain methyl ester of 4-acetylamino-3-chloro-6-iodine-pyridine-2-carboxylic acid (5.6 g, 18 mmol): GC-MS (m/z = 354).

51. Obtain methyl ester of 4-amino-3-chloro-6-iodine-pyridine-2-carboxylic acid.

To a solution of methyl ester 4-acetylamino-3-chloro-6-yodellin-2-carboxylic acid (5.0 g, 14 mmol) in methanol (25 ml) was added acetylchloride (1 ml) and the solution boiled under reflux for 1 hour. The solution was cooled and to allali water (25 ml) and the precipitate collected. Recrystallization from methanol gave methyl ester of 4-amino-3-chloro-6-yodellin-2-carboxylic acid (3.5 g, 11 mmol): TPL 152-153°C.

52. Obtain methyl ester of 4-amino-6-(4-bromo-2-fluoro-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid (compound 27).

A solution of methyl ester 4-amino-3-chloro-6-yodellin-2-carboxylic acid (1.1 g, 3.0 mmol), 4-bromo-2-fluoro-3-methoxyphenylacetic acid (1.3 g, 4.5 mmol) and cesium fluoride (0,60 g, 4.0 mmol) in dimethoxyethane (2 ml) and water (2 ml) was purged with nitrogen for 15 minutes before adding dichlorobis(triphenylphosphine)palladium (0.25 g, 0.4 mmol) and then heated at 85°C for 2 hours. The reaction mixture was diluted with water (15 ml) and was extracted with ethyl acetate (2 × 15 ml). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The residue was purified by chromatography (33% ethyl acetate in hexane)to give methyl ester of 4-acetylamino-6-(4-bromo-2-fluoro-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid (1.2 g, 2.8 mmol): TPL 164-165°C.

The following compounds were obtained according to the method of example 52.

Methyl ester of 4-acetylamino-3-chloro-6-(2,4,6-Cryptor-3-methoxyphenyl)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-(2,4-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 28): TPL 114-115°C.

Marked the th ether 4-acetylamino-3-chloro-(2-chloro-4-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 29): TPL 153-154,5°C.

53. Obtain methyl ester of 4-acetylamino-3-chloro-6-[2,4-dichloro-3-(1-foradil)phenyl]pyridine-2-carboxylic acid.

A solution of 2,4-dichloro-3-(1-foradil)bromine benzol (3.4 g, 12.5 mmol), methyl ester 4-acetylamino-3-chloro-6-trimethylaniline-2-carboxylic acid (4.7 g, 12.5 mmol), copper iodide (0.4 g, 2.1 mmol), cesium fluoride (3.6 g, 25 mmol) and dichlorobis(triphenylphosphine) palladium (0.14 g, 2 mmol) in DMF (50 ml) was heated at 70°C for 2 hours. Was added water (100 ml) and the mixture was extracted with ethyl acetate (2 × 100 ml). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The residue was purified by chromatography (15-30% ethyl acetate in hexane)to obtain methyl ester of 4-acetylamino-3-chloro-6-[2,4-dichloro-3-(1-foradil)phenyl]pyridine-2-carboxylic acid which was used without further purification.

The following compounds were obtained according to the method of example 53.

Methyl ester of 4-acetylamino-3-chloro-(2,6-debtor-3-methoxy-4-were)pyridine-2-carboxylic acid: TPL 134-136°C.

Methyl ester of 4-acetylamino-3-chloro-6-(4-cyano-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid: TPL 146-147°C.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-3-dimethylamino-2,6-differenl)pyridine-2-carboxylic acid: (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2,6-di is top-3-methoxyphenyl)pyridine-2-carboxylic acid: (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(2,4-dichloro-6-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid: (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2,6-debtor-3-ethoxyphenyl)pyridine-2-carboxylic acid: (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-[4-chloro-2-fluoro-3-(1-foradil)phenyl]pyridine-2-carboxylic acid: (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-[2,4-dichloro-3-(deformity)phenyl]pyridine-2-carboxylic acid (compound 30): TPL 152-153°C.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-3-ethyl-2-forfinal)pyridine-2-carboxylic acid: GC/PCI (m/z = 236).

Methyl ester of 4-acetylamino-3-chloro-6-[4-chloro-2-fluoro-3-(1,2,2,2-tetraborate)phenyl]pyridine-2-carboxylic acid (compound 31): LC/MS ESI (m/z = 456).

Methyl ester of 4-acetylamino-3-chloro-6-[4-chloro-2-fluoro-3-(1-forproper)phenyl]pyridine-2-carboxylic acid (compound 32): LC/MS ESI (m/z = 416).

Methyl ester of 4-acetylamino-3-chloro-6-(2,3,4-tryptophanyl)pyridine-2-carboxylic acid (compound 33): TPL 169-171°C.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyethoxymethyl)pyridine-2-carboxylic acid (compound 34): TPL 122-123°C.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2-fluoro-3-deformational)pyridine-2-carboxylic acid (compound 35): TPL 146°C.

Methyl e is Il-4-acetylamino-3-chloro-6-(4-deformity-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(2-fluoro-4-vermeil-3-methoxyphenyl)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2,6-debtor-3-were)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-6-(2-bromo-4-chloro-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-6-(4-bromo-2,6-debtor-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(3-deformity-2,4,6-tryptophanyl)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(2-chloro-4-deformity-3-methoxyphenyl)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2,6-debtor-3-deformational)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(2-chloro-4,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-(2,4-debtor-3-ethoxyphenyl)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-ACET is a melamine-3-chloro-6-(4-chloro-3-cyclopropyl-2-forfinal)pyridine-2-carboxylic acid (used without additional purification).

Methyl ester of 4-acetylamino-3-chloro-6-[4-chloro-2-fluoro-3-(2,2,2-TRIFLUOROACETYL)phenyl]pyridine-2-carboxylic acid (used without additional purification).

54. Obtain methyl ester of 4-amino-3-chloro-6-(2-fluoro-3-methoxy-4-were)pyridine-2-carboxylic acid (compound 36).

A solution of methyl ester 4-amino-3,6-dichloropyridine-2-carboxylic acid (0.24 g, 1.1 mmol), 2-fluoro-3-methoxy-4-methylphenylacetic acid (0,30 g, and 1.63 mmol) and cesium fluoride (3.0 g, 3,26 mmol) in dimethoxyethane (2 ml) and water (2 ml) was purged with nitrogen for 15 minutes before adding dichlorobis(triphenylphosphine) palladium (0.07 g, 0.1 mmol) and then heated at 85°C for 2 hours. The reaction mixture was diluted with water (15 ml) and was extracted with ethyl acetate (2 × 15 ml). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The residue was purified by chromatography (33% ethyl acetate in hexane)to obtain methyl ester of 4-amino-3-chloro-6-(2-fluoro-3-methoxy-4-were)pyridine-2-carboxylic acid (0.08 g, 0.2 mmol): TPL 95-96°C.

The following compounds were obtained according to the method of example 52.

Methyl ester of 4-amino-3-chloro-6-[2,4-dichloro-3-(dimethylamino)phenyl]pyridine-2-carboxylic acid (compound 37):1H-NMR (300 MHz, CDCl3): δ 7,30 (d, 1H), 7,19 (d, 1H), 6,93 (s, 1H), 4,88 (USS, 2H), 3.96 points (s, 3H), 2,88 (C, 6N).

Methyl ester of 4-amino-3-chloro-6-[4-chloro-2-CFT is R-3-(methylamino)phenyl]pyridine-2-carboxylic acid (compound 38): TPL 148-149°C.

Methyl ester of 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(methoxycarbonyl)phenyl]pyridine-2-carboxylic acid (compound 39):1H-NMR (300 MHz, CDCl3): δ 7,53 (d, 1H), 7,37 (d, 1H), 6,94 (s, 1H), equal to 4.97 (USS, 2H), of 3.97 (s, 3H), of 3.96 (s, 3H).

Methyl ester of 4-acetylamino-3-chloro-6-(4-cyano-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid: TPL 146-147°C.

Methyl ester of 4-acetylamino-3-chloro-6-[4-chloro-3-(dimethylamino)-2,6-differenl]pyridine-2-carboxylic acid:1H-NMR (300 MHz, CDCl3): δ to 8.70 (s, 1H), 8,03 (USS, 1H), 7,03 (DD, 1H), 4.00 points (s, 3H), and 2.83 (d, 6N), 2,32 (s, 3H).

Methyl ester of 4-acetylamino-3-chloro-6-(2,6-debtor-3-methoxy-4-were)pyridine-2-carboxylic acid: TPL 134-136°C.

Methyl ester of 4-acetylamino-6-(4-bromo-2-chloro-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid: TPL 129-130°C.

Methyl ester of 4-acetylamino-3-chloro-6-(4-chloro-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 40): TPL 144-144,5°C.

55. Obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-ethoxyphenyl)pyridine-2-carboxylic acid (compound 41).

To a solution of methyl ester 4-acetylamino-3-chloro-6-(4-chloro-2-fluoro-3-ethoxyphenyl)pyridine-2-carboxylic acid (0.5 g, 0,0013 mol) in methanol (10 ml) was added acetylchloride (1 ml) and the solution boiled under reflux for 1 hour. Was added water (2 ml) and the resulting solid residue was collected and dried to what to teach methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-ethoxyphenyl)pyridine-2-carboxylic acid: TPL 154-156°C.

The following compounds were obtained according to the method of example 55.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 42): TPL 141-142°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-5-methoxyphenyl)pyridine-2-carboxylic acid (compound 43):1H-NMR (CDCl3): δ of 7.60 (d, 1H), 7,25 (s, 1H), 7,20 (m, 1H), 4.95 points (USS, 2H), of 4.05 (s, 3H), of 3.95 (s, 3H).

Methyl ester of 4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 44): TPL 168-170°C.

Methyl ester of 4-amino-3-chloro-6-(2-fluoro-3-methoxy-4-triptoreline)pyridine-2-carboxylic acid (compound 45): TPL 144-146°C.

Methyl ester of 4-amino-3-chloro-6-(2-fluoro-3,4-methylenedioxyphenyl)pyridine-2-carboxylic acid (compound 46): TPL 139-141°C.

Methyl ester of 4-amino-3-chloro-6-(2,4-debtor-3-were)pyridine-2-carboxylic acid (compound 47): TPL 129-130°C.

Methyl ester of 4-amino-3-chloro-6-(2,4-dichloro-3-were)pyridine-2-carboxylic acid (compound 48):1H-NMR (CDCl3): δ 7,30 (d, 1H), 7,25 (d, 1H), 6,95 (s, 1H).

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-were)pyridine-2-carboxylic acid (compound 49): TPL 116-118°C.

Methyl ester of 4-amino-3-chloro-6-[4-chloro-3-(dimethylamino)-2,6-differenl]pyridine-2-carboxylic acid (compound 50):1H-NMR (300 MHz, CDCl3): δ 7,00 (DD, 1H), for 6.81 (s, 1H), 4,93 (USS, 2H), 3.96 points (s, 3H), of 2.81 (d, 6N.

Methyl ester of 4-amino-3-chloro-6-(2,6-debtor-3-methoxy-4-were)pyridine-2-carboxylic acid (compound 51): off-white foam,1H-NMR (300 MHz, CDCl3): δ 6,83 (s, 1H), 6,74 (DD, 1H), 4,88 (USS, 2H), of 3.97 (s, 3H), of 3.84 (d, 3H), of 2.28 (s, 3H).

Methyl ester of 4-amino-6-(4-bromo-2-chloro-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid (compound 52): TPL 154-155°C.

Methyl ester of 4-amino-3-chloro-6-(2-chloro-4-deformity-6-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 53): LC/MS (m/z = 380).

Methyl ester of 4-amino-3-chloro-6-(4-chloro-3-deformity-2,6-differenl)pyridine-2-carboxylic acid (compound 54): LC/MS (m/z = 383).

Methyl ester of 4-amino-3-chloro-(2-chloro-4,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 55): LC/MS (m/z = 348).

Methyl ester of 4-amino-3-chloro-6-(2,4,6-Cryptor-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 56): HPLC-MS (m/z = 346).

Methyl ester of 4-amino-3-chloro-6-(2,4-dichloro-6-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 57): HPLC-MS (m/z = 378).

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 58): HPLC-MS (m/z = 362).

Methyl ester of 4-amino-3-chloro-6-(4-dichloro-2,6-debtor-3-ethoxyphenyl)pyridine-2-carboxylic acid (compound 59): HPLC-MS (m/z = 376).

Methyl ester of 4-amino-3-chloro-6-(4-dichloro-3-butoxy-2-forfinal)pyridine-2-carboxylic acid (compound 60): LC/MS ESI (m/z = 386).

Methyl is the fir 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(1-foradil)phenyl]pyridine-2-carboxylic acid (compound 61): LC/MS ESI (m/z = 360).

Methyl ester of 4-amino-3-chloro-6-(2,4-dichloro-3-deformational)pyridine-2-carboxylic acid (compound 62): LC/MS ESI (m/z = 380).

Methyl ester of 4-amino-3-chloro-6-[2,4-dichloro-3-(1-fluoro-1-ethylphenyl]pyridine-2-carboxylic acid (compound 63): LC/MS ESI (m/z = 362).

Methyl ester of 4-amino-3-chloro-6-(4-chloro-3-ethyl-2-forfinal)pyridine-2-carboxylic acid (compound 64): TPL 120-122°C.

Methyl ester of 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(1,2,2,2-tetraborate)phenyl]pyridine-2-carboxylic acid (compound 65): LC/MS ESI (m/z = 414).

Methyl ester of 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(1-forproper)phenyl]pyridine-2-carboxylic acid (compound 66):1H-NMR (300 MHz, CDCl3): δ of 7.90 (m, 1H), 7,25 (m, 1H), 7,10 (s, 1H), 5,96 (DQC, 1H), 4,90 (USS, 2H), of 4.05 (s, 3H), 2,30 (m, 1H), 2.05 is (m, 1H), of 1.05 (t, 3H).

Methyl ester of 4-amino-3-chloro-6-(2,3,4-tryptophanyl)pyridine-2-carboxylic acid (compound 67): TPL 163-164°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyethoxymethyl)pyridine-2-carboxylic acid (compound 68): TPL 99°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-deformational)pyridine-2-carboxylic acid (compound 69): TPL 164°C.

Methyl ester of 4-amino-3-chloro-6-(2,4-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 70): LC/MS (m/z = 328).

Methyl ester of 4-amino-3-chloro-6-(4-deformity-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 71): TPL 145-147°C.

Methyl ester-amino-3-chloro-6-(2-fluoro-4-vermeil-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 72): LC/MS (m/z = 342).

Methyl ester of 4-amino-3-chloro-6-(2,4-debtor-5-methoxyphenyl)pyridine-2-carboxylic acid (compound 73): TPL 128-130°C.

Methyl ester of 4-amino-3-chloro-6-(2-chloro-4-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 74): TPL 145-146°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-2,6-debtor-3-were)pyridine-2-carboxylic acid (compound 75): LC/MS (m/z = 346).

Methyl ester of 4-amino-6-(2-bromo-4-chloro-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid (compound 76): LC/MS (m/z = 405).

Methyl ester of 4-amino-6-(4-bromo-2,6-debtor-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid (compound 77): LC/MS (m/z = 407).

Methyl ester of 4-amino-3-chloro-6-(3-deformity-2,4,6-tryptophanyl)pyridine-2-carboxylic acid (compound 78): LC/MS (m/z = 366).

Methyl ester of 4-amino-3-chloro-6-(2-chloro-4-deformity-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 79): TPL 134-136°C.

Methyl ester of 4-amino-3-chloro-6-(2,4-debtor-3-ethoxyphenyl)pyridine-2-carboxylic acid (compound 80): TPL 158-159°C.

Methyl ester of 4-amino-3-chloro-6-(4-chloro-3-cyclopropyl-2-forfinal)pyridine-2-carboxylic acid (compound 81): TPL 135-136,5°C.

Methyl ester of 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(2,2,2-TRIFLUOROACETYL)phenyl]pyridine-2-carboxylic acid (compound 82): LC/MS (m/z = 410).

56. Obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methanesulfonyl)pyridine-2-carboxylic acid (compound 83) the methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methanesulfonyl)pyridine-2-carboxylic acid (compound 84).

To a solution of methyl ester 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methylthiophenyl)pyridine-2-carboxylic acid (0.800 to g, 2 mmol) in methylene chloride (20 ml) was slowly added peracetic acid (32% in acetic acid, of 0.004 mol). The reaction mixture was extinguished sodium bisulfite (10% in water, 20 ml) and was extracted with methylene chloride (20 ml). The organic phase was dried (sodium sulfate) and concentrated. The solid residue was purified by chromatography (15-50% ethyl acetate in hexane). The first fraction was the methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methanesulfonyl)pyridine-2-carboxylic acid (0,250 g, 0.7 mmol): TPL 108-110°C. the Second fraction was the methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methanesulfonyl)pyridine-2-carboxylic acid (0,100 g, 0.03 mmol): TPL 122-124°C.

57. Obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-ftormetilirovaniya)pyridine-2-carboxylic acid (compound 85).

To a solution of methyl ester 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methylthiophenyl)pyridine-2-carboxylic acid (1.50 g, 4.1 mmol) in acetonitrile (40 ml) was added 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane-bis(tetrafluoroborate) (F-TEDA; SELECTFLUORTMfluorinating agent; 1.48 g, 8.2 mmol) and the solution was stirred at ambient temperature for 2 hours. Was added a saturated solution of sodium bicarbonate (25 ml) and the solution was extracted with methylene chloride (2 × 50 ml). Unite the military extracts were dried (sodium sulfate) and concentrated, and the residue was purified by chromatography (20-50% ethyl acetate in hexane)to obtain methyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-ftormetilirovaniya)pyridine-2-carboxylic acid (0.09 g, 0.2 mmol): TPL 104-105°C.

58. Obtaining the ethyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 86).

To a solution of methyl ester 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (200 mg, 0.9 mmol) in ethanol (5 ml) was added a catalytic amount of tetraisopropoxide titanium, and the solution boiled under reflux for 2 hours. The solution was cooled and distributed between ethyl acetate (10 ml) and water (10 ml) and the organic phase was dried (sodium sulfate) and concentrated. The residue was passed through a layer of silica gel (1:1 ethyl acetate:hexane)to give ethyl ester of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (150 mg, 0.6 mmol): TPL 74-75°C.

The following compounds were obtained according to the method of example 58.

2-butoxyethoxy ether 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 87): LC/MS (m/z = 430).

Butyl ester of 4-amino-3-chloro-6-(4-chloro-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 88): LC/MS (m/z = 404).

Butyl ester of 4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 8): LC/MS ESI (m/z = 402).

Butyl ester of 4-amino-3-chloro-6-(4-bromo-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 90): LC/MS ESI (m/z = 430).

Butyl ester of 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(1-foradil)phenyl]pyridine-2-carboxylic acid (compound 91): LC/MS ESI (m/z = 402).

2-butoxyethoxy ether 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 92): TPL 72-74°C.

59. Getting 4-amino-3-chloro-6-(4-cyano-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid.

A suspension of 4-acetylamino-3-chloro-6-(4-cyano-2,6-debtor-3-methoxyphenyl)pyridine (of 0.13 g, 0.33 mmol) in methanol (5 ml) was treated with 1N sodium hydroxide (1.7 ml) and stirred at ambient temperature for 1 hour. The solution was diluted with water (15 ml) and was acidified using 1N hydrochloric acid (1.7 ml) and the collected solid residue (0,095 g). Analysis1H NMR showed 4-amino-3-chloro-6-(4-cyano-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid and impurities. The substance was used without further purification.

The following compounds were obtained according to the method of example 59.

4-amino-3-chloro-6-(2,6-debtor-3-methoxy-4-were)pyridine-2-carboxylic acid (compound 93): TPL 167-168°C.

4-amino-3-chloro-6-(4-chloro-2,6-debtor-3-dimethylaminophenyl)pyridine-2-carboxylic acid (compound 94): TPL 171-172°C.

60. Obtain methyl ester of 4-amino-3-chloro-6-(4-cyano-2,6-debtor-3-methoxyphenyl)the feast of the DIN-2-carboxylic acid (compound 95).

A suspension of 4-amino-3-chloro-6-(4-cyano-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid in tetrahydrofuran (10 ml) and methanol (3 ml) was treated with trimethylsilyldiazomethane (0.64 g, and 0.28 ml of a 2M solution in hexane) at ambient temperature. After 1 hour the reaction mixture is extinguished acetic acid (2 ml) and water (10 ml). The mixture was extracted with ethyl acetate (2 × 20 ml) and the combined extracts were dried (Na2SO4) and concentrated. The residue was purified by chromatography (30-100% ethyl acetate in hexane)to give methyl ester of 4-amino-3-chloro-6-(4-cyano-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (0.083 g, 0.24 mmol):1H-NMR (CDCl3): δ to 7.15 (DD, 1H), 6,85 (s, 1H), 4,98 (USS, 2H), 4,08 (d, 3H), 3,98 (s, 3H).

61. Getting 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-(2,2-diflorasone)phenyl)pyridine-2-carboxylic acid (compound 96).

A solution of methyl ester 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-(2,2-diflorasone)phenyl)pyridine-2-carboxylic acid (0,300 g, 0,0008 mol) in methanol (5 ml) and sodium hydroxide (1N, 2 ml) was treated with boiling under reflux for 1 hour and then acidified to pH 3 (concentrated hydrochloric acid) and cooled. The resulting solid residue was collected and dried, obtaining 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-(2,2-diflorasone)phenyl)pyridine-2-carboxylic acid (0,270 g 0,0007 mol): TPL 183-184°C Dec.

The following connections floor is made in accordance with the method of example 61.

4-amino-3-chloro-(2,4-debtor-3-were)pyridine-2-carboxylic acid (compound 97): TPL 189-190°C Dec.

4-amino-3-chloro-6-(2,4-dichloro-3-were)pyridine-2-carboxylic acid (compound 98): TPL 170-172°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-were)pyridine-2-carboxylic acid (compound 99): TPL 179-181°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 100): TPL 174-175°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-5-methoxyphenyl)pyridine-2-carboxylic acid (compound 101):1H-NMR (DMSO-d6): δ 13,80 (USS, 1H), 7,55 (m, 2H), 7,25 (s, 1H), 3,95 (s, 3H).

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-ethoxyphenyl)pyridine-2-carboxylic acid (compound 102): TPL 177-178°C Dec.

4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 103): TPL 179-180°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methylthiophenyl)pyridine-2-carboxylic acid (compound 104):1H-NMR (DMSO-d6): δ 13,80 (USS, 1H), of 7.90 (t, 1H), 7,55 (d, 1H), 7,10 (s, 1H), 6,95 (USS, 2H), 2,50 (s, 3H).

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxymethyl)pyridine-2-carboxylic acid (compound 105): TPL 187-188°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-deformational)pyridine-2-carboxylic acid (compound 106): TPL 182-183°C Dec.

4-amino-3-chloro-6-(2-fluoro-3-methoxy-4-triptoreline)pyridine-2-carboxylic acid (compound 107): TPL 177-178°C Dec.

4-amino-3-chloro-6-(2-fluoro-3,methylenedioxyphenyl)pyridine-2-carboxylic acid (compound 108): TPL 202-203°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-5-ethoxyphenyl)pyridine-2-carboxylic acid (compound 109): TPL 178-179°C Dec.

4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 110): TPL 187-188°C Dec.

4-amino-3-chloro-6-(4-chloro-5-dimethylamino-2-forfinal)pyridine-2-carboxylic acid (compound 111): TPL 180-181°C Dec.

4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-forfinal)pyridine-2-carboxylic acid (compound 112): TPL 185-186°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyethoxymethyl)pyridine-2-carboxylic acid (compound 113): TPL 169-170°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-formationl)pyridine-2-carboxylic acid (compound 114):1H-NMR (DMSO-d6): δ 8,00 (dt, 1H), 7,50 (DD, 1H), 6.90 to (USS, 2H), ceiling of 5.60 (DD, 1H).

4-amino-3-chloro-5-fluoro-6-(2-fluoro-3,4-methylenedioxyphenyl)pyridine-2-carboxylic acid (compound 115): TPL 179-180°C.

4-amino-3-chloro-6-[4-chloro-3-(diethylamino)-2-forfinal]pyridine-2-carboxylic acid (compound 116): TPL 174-175°C.

4-amino-3-chloro-6-[2,4-dichloro-3-(dimethylamino)phenyl]pyridine-2-carboxylic acid (compound 117): TPL 177-178°C.

4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(methylamino)phenyl]pyridine-2-carboxylic acid (compound 118): TPL 185-186°C.

4-amino-3-chloro-6-(2-fluoro-3-methoxy-4-were)pyridine-2-carboxylic acid (compound 119): TPL 178-179°C.

4-amino-6-(4-bromo-2-fluoro-3-methoxyphenyl)-3-chloropyridin-2-carbonatite (compound 120): TPL 176-177°C.

4-amino-6-(4-bromo-2-chloro-3-methoxyphenyl)-3-chloropyridin-2-carboxylic acid (compound 121): TPL 192-193°C.

4-amino-3-chloro-6-(4-chloro-2-fluoro-5-methoxyphenyl)-5-herperidin-2-carboxylic acid (compound 122): TPL 180-181°C.

4-amino-3-chloro-6-(4-chloro-2-chloro-3-methoxyphenyl)-5-herperidin-2-carboxylic acid (compound 123): TPL 178-179°C.

4-amino-3-chloro-6-(4-chloro-3-butoxy-2-forfinal)pyridine-2-carboxylic acid (compound 124): TPL 157-158°C Dec.

4-amino-6-[2,4-dichloro-3-(1-foradil)phenyl]pyridine-2-carboxylic acid (compound 125): TPL 169-170°C Dec.

4-amino-3-chloro-6-(2,4-dichloro-3-deformational)pyridine-2-carboxylic acid (compound 126): TPL 182-183°C Dec.

4-amino-3-chloro-6-[2,4-dichloro-3-(1-fluoro-1-methylethyl)phenyl]pyridine-2-carboxylic acid (compound 127): TPL > 250°C.

4-amino-3-chloro-6-(4-chloro-3-ethyl-2-forfinal)pyridine-2-carboxylic acid (compound 128): TPL 192-193°C Dec.

4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(1,2,2,2-tetraborate)phenyl]pyridine-2-carboxylic acid (compound 129): TPL 175-176°C Dec.

Methyl ester of 4-amino-3-chloro-6-[4-chloro-2-fluoro-3-(1-forproper)phenyl]pyridine-2-carboxylic acid (compound 130): TPL 165-167°C Dec.

4-amino-3-chloro-6-(2,3,4-tryptophanyl)pyridine-2-carboxylic acid (compound 131): TPL 178-179°C Dec.

4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyethoxymethyl)pyridine-2-carboxylic acid (compound 132): TPL 159°C Dec.

4-amino-3-the ENT-6-(4-chloro-2,6-debtor-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 133): LC/MS (m/z = 293).

4-amino-3-chloro-6-(4-chloro-3-deformedarse-2-fluoro-phenyl)pyridine-2-carboxylic acid (compound 134): TPL 179°C Dec.

62. Getting triethylammonium salt 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 135).

To a solution of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (1.0 g, 3.1 mmol) in methanol (30 ml) was added triethylamine (10 ml) and the solution was stirred at ambient temperature for 1 hour and then concentrated to obtain triethylammonium salt 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (1,1 g, 2.6 mmol):1H-NMR (DMSO-d6): δ 7,60 (m, 1H), 7,45 (m, 1H), 7,00 (s, 1H), 4.00 points (s, 3H), 3.00 for (t, 6N)and 1.15 (kV, N).

The following compounds were obtained according to the method of example 62.

triethylammonium salt 4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)pyridine-2-carboxylic acid (compound 136):1H-NMR (DMSO-d6): δ at 7.55 (d, 1H), 7,435 (d, 1H), 7,00 (s, 1H), 4.00 points (s, 3H), 3.00 for (t, 6N)and 1.15 (kV, N).

63. Obtaining herbicide compositions

The following presents the compositions of parts and percentages are expressed by weight.

Concentrates of emulsions

The composition And
weight%
Connection 126,2
Polyglycol 26-3
Non-ionic emulsifier (di-sec-butyl)phenyl-poly(oxypropylene)block polymer with (oksietilenom). The content of the polyoxyethylene is 12 moles.
5,2
Witconate P12-20 (anionic emulsifier - dodecylbenzenesulfonate calcium - 60% by weight activity)5,2
Aromatic 100 (aromatic solvent of xianbao number)63,4
Part B
weight%
Connection 123,5
Sunspray 11N (paraffin oil)40,0
Polyglycol 26-319,0
Oleic acid1,0
Aromatic solvent of xianbao number36,5
The composition of
weight%
The connection 1413,2
Stepon C-6525,7
Ethomeen T/257,7
Ethomeen T/1518,0
Aromatic solvent of xianbao number35,4
Part D
weight%
The connection 1830,0
Agrimer A1-10LC (emulsifier)3,0
N-methyl-2-pyrrolidone67,0
Composition E
weight%
The connection 4110,0
Agrimul 70-A (dispersant)2,0
Amsul DMAP 60 (thickener)2,0
Emulsogen M (emulsifier)8,0
Attagel 50 (additive that promotes the formation of suspension)2,0
Vegetable oil76,0/td>

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

Wettable powders

Composition F
weight%
Connection 9526,0
Polyglycol 26-32,0
Polyfon H4,0
Zeosyl 100 (precipitated hydrated SiO2)of 17.0
Clay Barden + inert additives51,0
The composition G
weight%
Connection 10162,4
Polyfon H (sodium salt of lignosulfonate)6,0
Sellogen HR (naphthalenesulfonate sodium)4,0
Zeosyl 10027,6
Composition H
weight%
Connection 1091,4
Kunigel V1 (medium)30,0
Stepanol ME Dry (wetting)2,0
Tosnanon GR 31A (binding agent)2,0
Kaolin NK-300 (filler)64,6

The active ingredient is used with the appropriate media and then mixed and pulverized to obtain a wettable powders of excellent wettability and the ability to form a suspension. Diluting these powders water can be obtained suspension of a suitable concentration for weed control.

Granules, forming a dispersion in water

Part I
weight%
Connection 6326,0
Sellogen HR4,0
Polyfon H5,0
Zeosyl 100of 17.0
Kalinicheva clay 48,0

The active ingredient was added to the hydrate of silicon dioxide, which is then mixed with other ingredients and crushed to powder. The powder stick together under the action of water and sieved to obtain granules with sizes corresponding to the sizes of the sieves from -10 to +60 mesh. Dispersive these granules in water to obtain a suspension of suitable concentrations for weed control.

Granules

Composition J
weight%
The connection 1145,0
Celeton MP-8895,0

The active ingredient was added to a polar solvent, such asN-organic, cyclohexanone, γ-butyrolactone, etc. to the media Celetom MP-88 or other suitable media. The resulting granules can be applied manually, by using the machine to make pellets, aircraft, etc. in order to deal with weeds.

Composition K
weight%
Connection 117 1,0
Polyfon H8,0
Nekal BA 772,0
The zinc stearate2,0
Clay Bardenof 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 is cut using a die cutter to obtain pellets of the desired size.

Water-soluble liquid

Composition L
weight%
Connection 136to 3.67
pH buffer monoethanolamine0,5
Water95,83

The active ingredient was dissolved in a suitable amount of water and added additional monoethanolamine as a buffer. You can add a water-soluble surfactant. You can add other excipients to improve the physical, chemical and/or properties of the composition.

64. Measurement of herbicide activity after the appearance of the Assembly.

The seeds or nuts required test species of plants were planted in seed mix, Sun Gro MetroMix®306, which normally has a pH of 6.0-6.8 and contains 30% organic matter, in plastic pots with a surface area of 64 square centimeters. If necessary to ensure good germination and healthy plants used fungicide treatment and/or other chemical or physical processing. Plants were grown in a period of 7-21 days in a greenhouse with approximately 15 hour photoperiod, maintaining a temperature in the range of 23-29°C during the day and 22-28°C at night. Regularly added nutrients and water and, if necessary, provide additional light through the top 1000 W metallogenica lamps. The plants used in the test, when they reached the first or second true leaf stage.

Weighted amount determined using the largest dose that needs to be tested, each test substance was placed in 25 ml glass test tube and was dissolved in 4 ml of 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO)to obtain a concentrated basic solutions. If the test substance is poorly dissolved, the mixture was heated and/or irradiated with ultrasound. The obtained concentrated base solutions were diluted with 20 ml of an aqueous mixture containing acetone, water, isopropyl who Peart, DMSO, concentrate vegetable oil Atplus 411F and surfactant Triton®X-155 in the ratio 48,5:39:10:1,5:1,0:0,02 volume/volume to obtain a solution for spraying, containing the highest dose of application. Additional doses of making the received serial dilution 12 ml of solution with a high dose of a solution containing 2 ml 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO), and 10 ml aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, concentrate vegetable oil Atplus 411F and surfactant Triton®X-155 in the ratio 48,5:39:10:1,5:1,0:0,02 volume/volume to get 1/2X, 1/4X, 1/8X 1/ 16X dose high dose. The required quantities of substances determine, based on a 12 ml volume used at the dose of 187 l/ha Prepared mixture of the compound used on the plants using the top sprayer Mandela, equipped with nozzles E, calibrated to deliver 187 l/ha) on land used 0,503 per square meter at the height of the spray 18 inches (43 cm) above the average height of the layer of plants. Control plants were sprayed in the same way using a single solvent.

Treated plants and control plants were placed in a greenhouse as described above, and watered with groundwater irrigation to prevent flushing of the tested compounds. After 14 days the status of subjects of age is th, when compared with plants not subjected to treatment, was determined visually and evaluated from 0 to 100%, where 0 = no damage and 100 corresponds to complete destruction.

When using the conventional probit analysis as described by 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 to calculate values GR50and GR80that determine how factors reduce growth, which correspond to the effective doses of herbicide required to eradicate or control 50% or 80%, respectively, of a plant target.

Table 1 presents some subjects substances used doses are entered, the tested plant species and results.

20
Table 1.
Weed control after germination.
Control %
Connection # Dose
(g ai/ha)
ABUTHAMARECHEAL
114085100100
2140859080
314010010080
414010010085
51401003590
61409010095
71401009095
81408010095
914085100100
1014090 100100
11140909580
12140100100100
1314010010090
14140100100100
15140100100100
16140100100100
17140100100100
25140100100100
26 140100100100
2714010090100
2814010010095
29140954098
301401009095
32140608050
33140959590
36140100100100
37140100100100
38140100100100
39140907595
401409595100
41140958598
42140100100100
43140100100100
44140100100100
451401008095
46140100 10095
47140100100100
48101988085
491401008090
50140100100100
51140100100100
5214010010095
53140708095
54140100100100
55 10010090
56140100100100
57140100100100
58140100100100
591401009090
60140559090
61140100100100
62140100100100
63140100100100
6414095100100
651409510090
661409010095
67140100100100
6814095100100
69140100100100
70140100100100
711401008085
7214010080
7314090100100
7414010090100
751401009595
76140100100100
77140100100100
7814090100100
791409590100
8014010010095
81 10010095
8214010010095
83140908585
84140807570
8514010095100
86140100100100
87140100100100
9014010085100
9114095100100
92140100100100
93140100100100
94140100100100
951401008590
961405010090
97140658580
98140907080
99140809090
100140100 100100
101140100100100
102140808595
10314095100100
104140858080
105140959885
1061409010090
1071401008090
10814010010095
110 140809085
112140100100100
114140958595
115140100100100
1161408090100
117140100100100
118140100100100
11914010010095
120140100905
1211401009590
123140100100100
12614090100100
12714090100100
129140859590
130140809595
131140100100100
1341409510090
ABUTH - canetic Theophrastus (Abutilon theophrasti)
AARE - amaranth spiked (Amaranthus retroflexus)
CHEAL - white pigweed (Chenopodium album)

65. Evaluation of herbicide activity before germination.

Seeds required test species of plants were planted on the underlying soil prepared by mixing clay soils (43% silt, 19% clay, 38% sand, with a pH of 8.1 and organic matter content of 1.5%) and sand in the ratio of 70 to 30. The underlying soil was placed in plastic pots with a surface area of 113 square inches. If necessary to ensure good germination and healthy plants, used fungicide treatment and/or other chemical or physical processing.

Weighted amount determined using the largest dose that needs to be tested, each test substance was placed in 25 ml glass test tube and was dissolved in 6 ml 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO)to obtain a concentrated basic solutions. If the test substance is poorly dissolved, the mixture was heated and/or irradiated with ultrasound. The obtained concentrated base solutions were diluted with 18 ml of 0.1% volume/volume aqueous solution of the surfactant Tween®20, to obtain solutions for spraying containing the highest dose of application. Additional doses of making the received serial dilution of 12 ml with Vysokogorsky in solution, containing 3 ml of 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO), and 9 ml of 0.1% volume/volume aqueous solution of the surfactant Tween®20 to get 1/2X, 1/4X, 1/8X 1/16X dose high dose. The required quantities of substances determine, based on a 12 ml volume used at the dose of 187 l/ha Prepared mixture of compounds used by plants using the top sprayer Mandela, equipped with nozzles E, calibrated to deliver 187 l/ha) on land used 0,503 per square meter at the height of the spray 18 inches (43 cm) above the average height of the layer of plants. Control plants were sprayed in the same way using a single solvent.

The treated pots and control pots were placed in a greenhouse, maintaining approximately a 15-hour photoperiod and temperature in the range of 23-29°C during the day and 22-28°C at night. Regularly added nutrients and water and, if necessary, provide additional light through the top 1000 W metallogenica lamps. Water was added through the top irrigation. After 20-22 days the condition of the tested plants that have sprouted and grew, when compared with plants that emerged and grew up, was determined visually and evaluated from 0 to 100%, where 0 = no damage and 100 corresponds to complete destruction or absence of the shoots.

Table 2 presents some subjects substances used doses are entered, the tested plant species and results.

99
Table 2.
Weed control before germination.
Control %
Connection # Dose
(g ai/ha)
ABUTHAMARECHEAL
11408010090
31409810095
10280405080
12140100100100
14140100100100
1514060100100
1614090100100
26140101090
2714010010090
41140805090
42140100100100
4314098100100
44140953095
49140100100
50140100100100
5214010010090
58140100100100
591409010060
62140100100100
63140100100100
6414080100100
70140100100100
74140 1009595
77140100100100
8214090100100
93140100100100
94140100100100
95140909090
96140207040
9914010010095
100140100100100
101140100100100
10214085950
10312390100100
10414010010080
10514010010095
1081409010090
1101401004040
11114035100100
11214010010 100
1131400055
115140100100100
11614010010075
121140100100100
122140100100100
123140100100100
125140100100100
13114090100100
ABUTH - kanati is Theophrastus ( Abutilon theophrasti)
AMARE - amaranth spiked (Amaranthus retroflexus)
CHEAL - white pigweed (Chenopodium album)

66. Evaluation of herbicide activity in transplanted rice-padde.

The seeds or nuts of required weed species of test plants were planted in coarse soil (peat), obtained by blending non-sterilized mineral soil (28% silt, 18% clay, 54% sand, with a pH of 7.3-7.8 and organic matter content of 1%) and water at a ratio of 100 kg of soil in 19 l of water. Prepared peat distributed in 250 ml aliquots in 480 ml of solid plastic pots with a surface area of 91.6 square centimeter, leaving in each pot 3 cm of space above the earth. Rice seeds were planted in seed mix, Sun Gro MetroMix®306, which normally has a pH of 6.0-6.8 and contains 30% organic substances in plastic trays. The seedlings in the second and third growth stage sheet was transplanted in 650 ml of peat, in 960 ml of solid plastic pots with a surface area of 91.6 square inch for 4 days before applying the herbicide. "Rice field" created by filling water 3 cm of the pot above the surface of the earth. If necessary to ensure good germination and healthy plants used fungicide treatment and/or other chemical or physical processing. The plants were grown within 4-14 days in the greenhouse, maintaining CA is approximately 14 hour photoperiod and temperature in the range of 29°C during the day and 26°C at night. Nutrients were added in the form of Osmocote (17:6:10 N:P:K + minor nutrients) 2 g in each pot. Regularly added to the water to keep the flooding, and provide more light using the top 1000 W metallogenica lamps. The plants used in the tests, when they reached the second or third true leaf stage.

Weighted amount determined using the largest dose that needs to be tested, each test substance was placed in a 120 ml glass test tube and was dissolved in 20 ml of acetone, to obtain a concentrated basic solutions. If the test substance is poorly dissolved, the mixture was heated and/or irradiated with ultrasound. The obtained concentrated base solutions were diluted with 20 ml of 0.01% vol/vol aqueous solution of the surfactant Tween®20. Received dose make 1/2X, 1/4X, 1/8X, 1/16X high doses of making the required quantity of base solution in water layer "rice fields". Control plants were sprayed in the same way using a single solvent.

Treated plants and control plants were placed in a greenhouse as described above, and, if necessary, adding water to keep the flooding. After 3 weeks the condition of the test plants, when compared with plants not subjected to processing the e, was determined visually and evaluated from 0 to 100%, where 0 = no damage and 100 corresponds to complete destruction.

Table 3 presents some subjects substances used doses are entered, the tested plant species and results.

Table 3.
Herbicide activity for transplanted rice.
Control %
Connection # Dose
(g ai/ha)
ORYSAECHCGMOOVACYPDISCPJU
4of 17.5001009570
57002010010090
7701010000 10085
173507010010090
27of 17.504510010099
387005010010095
41of 17.5105010010090
42of 17.554010010090
447005090100 95
4635020100100100
52700609910095
58of 17.503010010050
6135080100100100
70700451009595
773507010010099
86 70102510010095
887010100100100100
897008510010090
90of 17.503010010090
913509910010099
92of 17.50401009990
100of 17.510 3010010080
10370104010010095
1203504010010095
125705100100100100
135of 17.5103010010085
1363501510010080
ORYSA - rice (Orysa sativavar. Japonica)
ECHCG - chicken millet (Echinochloa crus-galli)
SCPJU - reed sitnikovky (Scirpus juncoides)
CYPDI - si is ü heterogeneous ( Cyperus difformis)
MOOVA - Monochoria vaginal (Monochoria vaginalis)

67. Evaluation of herbicide activity after germination in cereal grains.

Seeds required test species of plants were planted in seed mix, Sun Gro MetroMix®306, which normally has a pH of 6.0-6.8 and contains 30% organic matter, in plastic pots with a surface area 103,2 square centimeter. If necessary to ensure good germination and healthy plants, used fungicide treatment and/or other chemical or physical processing. The plants were grown during 7-36 days in a greenhouse with approximately 14 hour photoperiod, maintaining the temperature in the range of 18°C during the day and 17°C at night. Regularly added nutrients and water and, if necessary, provide additional light through the top 1000 W metallogenica lamps. The plants used in the test, when they reached the second or third true leaf stage.

Weighted amount determined using the largest dose that needs to be tested, each test substance was placed in 25 ml glass test tube and was dissolved in 8 ml 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO)to obtain a concentrated basic solutions. If the test substance is poorly dissolved, the mixture of the load, the Wali and/or irradiated with ultrasound. The obtained concentrated base solutions were diluted with 16 ml of an aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, concentrate vegetable oil Agridex and surfactant Triton®X-77 in the ratio 64,7:26,0:6,7:2,0:0,7:0,01 volume/volume to obtain a solution for spraying, containing the highest dose of application. Additional doses of making the received serial dilution 12 ml of solution with a high dose of a solution containing 4 ml 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO), and 8 ml aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, concentrate vegetable oil Agridex and surfactant Triton®X-77 in the ratio 48,5:39:10:1,5:1,0:0,02 volume/volume to get 1/2X, 1/4X, 1/8X 1/16X dose high dose. The required quantities of substances determine, based on a 12 ml volume used at the dose of 187 l/ha Prepared mixture of the compound used on the plants using the top sprayer Mandela, equipped with nozzles E, calibrated to deliver 187 l/ha) on land used 0,503 per square meter at the height of the spray 18 inches (43 cm) above the average height of the layer of plants. Control plants were sprayed in the same way using a single solvent.

Treated plants and control plants were placed in a greenhouse as described above, and watered by the Yu underground irrigation to prevent flushing of the tested compounds. After 20-22 days the condition of the test plants, when compared with plants not subjected to treatment, was determined visually and evaluated from 0 to 100%, where 0 = no damage and 100 corresponds to complete destruction.

Table 4 presents some subjects substances used doses are entered, the tested plant species and results.

Table 4.
Control after emergence of several major weeds in cereal crops.
Control %
Connection # Dose
(g ai/ha)
TRZASHORVSGALAPLAMPUPAPRHVERPE
13551085808050
14350 090959565
16of 17.51010951009595
17of 17.5008010010099
267001080959540
27of 17.5559910010050
36705095999950
38of 17.550859510099
42of 17.555991009960
43700565998530
443510565999060
45of 17.500901009080
507000 951009560
513500957010030
56700101009910095
58of 17.5001001009960
61of 17.510085999075
653515585959040
70 of 17.500991009960
71of 17.50095959550
73700095999560
77of 17.500991009965
87of 17.50010010010050
90of 17.501099 1009525
91of 17.52010901006045
92of 17.500991009530
100of 17.5105901009565
10170105609910060
1033500609510075
120 of 17.50080959550
133of 17.5001009910070
135of 17.5009010010060
TRZAS - soft wheat (Triticum aestivum)
HORVS - barley seed (Hordeum vulare)
GALAP - cleaver (Galium aparine)
LAMPU - purple dead-nettle (Lamium purpureum)
PAPRH - Mac - Samosata (Papaver rhoeas)
VERPE - Veronica Persian (Veronica persica)

68. Evaluation of herbicide protection after germination in cereal grains.

Seeds required test species of plants were planted in seed mix, Sun Gro MetroMix®306, which normally has a pH of 6.0-6.8 and contains 30% organic matter, in plastic pots with a surface area 103,2 square centimeter. If necessary to ensure good Prora is food and healthy plants used fungicide treatment and/or other chemical or physical processing. The plants were grown during 7-36 days in a greenhouse with approximately 14 hour photoperiod, maintaining the temperature in the range of 18°C during the day and 17°C at night. Regularly added nutrients and water and, if necessary, provide additional light through the top 1000 W metallogenica lamps. The plants used in the test, when they reached the second or third true leaf stage.

Processing includes processing the connection 42 and cloquintocet separately and in combination. Weighted number was placed in 25 ml glass vials and dissolved in a volume of 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO)to obtain a basic solution 9 mg AI/ml. Concentrated base solutions were diluted to 3 ml AI/ml by adding 2 volumes of aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, concentrate vegetable oil Agridex and surfactant Triton®X-77 in the ratio 64,7:26,0:6,7:2,0:0,7:0,01 volume/volume. A diluted solution prepared by mixing 1 volume 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO) and 2 volumes of aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, concentrate vegetable oil Agridex and surfactant Triton®X-77 in the ratio 64,7:26,0:6,7:2,0:0,7:0,01 volume/volume. The required quantities of substances determine, based on a 12 ml volume used is when the dose of 187 l/ha Solutions for spraying mixtures of cloquintocet and compound 42 was obtained by adding a basic solution to a suitable amount of diluent to get a 12 ml solution for spraying with a ratio of active ingredient 1:1, 1:2 and 1:4 (herbicide:safener). Prepared mixture used on the plants using the top sprayer Mandela, equipped with nozzles E, calibrated to deliver 187 l/ha) on land used 0,503 per square meter at the height of the spray 18 inches (43 cm) above the average height of the layer of plants. Control plants were sprayed in the same way using a single solvent.

Treated plants and control plants were placed in a greenhouse as described above, and watered with groundwater irrigation to prevent flushing of the tested compounds. After 3 weeks the condition of the test plants, when compared with plants not subjected to treatment, was determined visually and evaluated from 0 to 100%, where 0 = no damage and 100 corresponds to complete destruction.

Used the equation Colby, to determine the estimated weed-killing effect of the mixture (Colby, S.R. 1967. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 15:20-22).

Used the following equation to calculate the expected activity of the mixture, sod is Rasa two ingredients, A and B:

Expected = A + B - (A × B/100)

A = observed efficacy of the active ingredient And at the same concentration as used in the mixture.

In = the observed efficacy of the active ingredient At the same concentration as used in the mixture.

Table 5 presents some subjects substances used doses are entered, the tested plant species and results.

Table 5.
Protection from herbicide damage to crops
Use
Dose (g ai/ha)
Control %
Connection # 42clockvine
atoxyl
TRZASHORVWGALAPPAPRH
ObExObExObExObEx
35
70
0
0
35
40
-
-
0
15
-
-
99
100
-
-
100
100
-
-
0
0
0
0
35
70
140
280
0
0
0
0
-
-
-
-
0
0
0
0
-
-
-
-
0
0
0
0
-
-
-
-
0
0
0
0
-
-
-
-
35
35
35
35
70
140
0
0
0
35
35
35
0
0
0
0
0
0
100
100
100
99
99
99
100
100
100
100
100
100
70
70
70
70
140
280
0
0
0
40
40
40
0
0
0
15
15
15
100
100
100
100
100
100
100
100
100
100
100
100
TRZAS - soft wheat (Triticum aestivum)
HORVW barley - common (Hordeum vulgare)
GALAP - cleaver (Galium aparine)
PAPRH - Mac - Samosata (Papaver rhoeas)
Ob - observed value
Ex - estimated, the calculated value

69. Evaluation of herbicide activity of the mixture after germination in cereal crops.

Seeds required test species of plants were planted and grown as described in "Evaluation of herbicide protection after germination in cereal crops".

The processing includes processing the connection (listed in tables 6 and 7), flexibilisation ether (E) and monoethanolamine (MEA) salt clopyralid separately and in combination. Weighted number was placed in 25 ml glass vials and dissolved in a volume of 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO)to obtain a basic solution of 4.5 mg AI/ml If the test substance is poorly dissolved, the mixture was heated and/or irradiated with ultrasound. Concentrated base solutions were diluted to 1.5 ml AI/ml by adding 2 volumes of aqueous mixture containing acetone, water, from the propyl alcohol, DMSO, concentrate vegetable oil Agridex and surfactant Triton®X-77 in the ratio 64,7:26,0:6,7:2,0:0,7:0,01 volume/volume. A diluted solution prepared by mixing 1 volume 97/3 volume/volume mixture of acetone and dimethyl sulfoxide (DMSO) and 2 volumes of aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, concentrate vegetable oil Agridex and surfactant Triton®X-77 in the ratio 64,7:26,0:6,7:2,0:0,7:0,01 volume/volume. The required quantities of substances determine, based on a 12 ml volume used at the dose of 187 l/ha Solutions for spraying fluroxypyr E, clopyralid MEA and mixtures experimental compounds were obtained by adding a basic solution to a suitable amount of diluent to get a 12 ml solution for spraying with the active ingredients in combinations of two and three. Prepared mixture used on the plants using the top sprayer Mandela, equipped with nozzles E, calibrated to deliver 187 l/ha) on land used 0,503 per square meter at the height of the spray 18 inches (43 cm) above the average height of the layer of plants. Control plants were sprayed in the same way using a single solvent.

Treated plants and control plants were placed in a greenhouse as described above, and watered with groundwater irrigation to prevent flushing IP is ytheme compounds. After 3 weeks the condition of the test plants, when compared with plants not subjected to treatment, was determined visually and evaluated from 0 to 100%, where 0 = no damage and 100 corresponds to complete destruction.

Used the equation Colby, to determine the estimated weed-killing effect of the mixture (Colby, S.R. 1967. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 15:20-22).

Used the following equation to calculate the expected activity of mixtures containing two ingredients, A and B:

Expected = A + B - (A × B/100)

A = observed efficacy of the active ingredient And at the same concentration as used in the mixture.

In = the observed efficacy of the active ingredient At the same concentration as used in the mixture.

Used the following equation to calculate the expected activity of the mixture containing the three ingredients, A, B and C:

Expected = A + B + C - (A × B + B × C + And × C)/100+ (A × V × C)/10000

A = observed efficacy of the active ingredient And at the same concentration as used in the mixture.

In = the observed efficacy of the active ingredient At the same concentration as used in the mixture.

C = observed efficacy of the active ingredient With at the same concentration as used in the mixture.

In the tables the x 6 and 7 presents some subjects substances, used doses are entered, the tested plant species and results.

Table 6.
Protection and synergistic activity of mixtures of herbicides.
Use
Dose (g ai/ha)
Control %
TRZASHORVWMATCH
Conn. 93Conn. 74Conn. 58Fluroxypyr
I
Clopyralid
MEA
ObExObExObEx
0
0
0
0
0
0
0
0
0
0
35
35
35
0
35
0
0
0
-
-
0
0
0
0
-
-
0
20
0
25
-
-
20
35
-
-
-
-
0
35
0
35
15
0
-
15
10
0
-
10
45
85
-
56
-
-
35
35
-
-
0
35
0
35
25
10
-
25
0
0
-
0
10
80
-
28
-
-
-
-
35
35
0
35
0
35
35
30
-
35
15
10
-
15
0
70
-
20
TRZAS - soft wheat (Triticum aestivum)
HORVW barley - common (Hordeum vulgare)
MATCH - camomile (Matricaria chamomilla)
E - methylheptanoic ether
MEA - monoethanolamine salt
Ob - observed values is
Ex - estimated, the calculated value

Table 7.
Protection and synergistic activity of mixtures of herbicides.
Use
Dose (g ai/ha)
Control %
TRZASHORVWMATCH
Conn.
42
Clopyralid
MEA
Fluroxypyr
I
ObExObExObEx
35
70
0
0
0
0
30
45
-
-
25
30
-
-
50
60
-
-
0
0
35
70
0
0
0
0
-
-
0
0
-
-
5
40
-
-
0
0
0
0
35
70
0
0
-
-
0
0
-
-
0
0
-
-
0
0
35
70
35
70
0
0
0
0
0
0
0
0
20
20
5
40
35
70
35
70
0
0
25
40
30
45
15
25
30
30
99
100
52
76
35
70
0
0
35
70
30
35
30
45
15
20
25
30
0
90
50
60
35br/> 70
35
35
70
35
70
70
35
35
35
70
35
70
35
30
30
20
10
30
30
45
30
30
45
15
25
15
15
25
25
30
25
25
30
70
99
99
99
70
52
76
70
52
62
TRZAS - soft wheat (Triticum aestivum)
HORVW barley - common (Hordeum vulgare)
MATCH - camomile (Matricaria chamomilla)
E - methylheptanoic ether
MEA - monoethanolamine salt
Ob - observed value
Ex - estimated, the calculated value

1. The compound of formula 1

in which Q1represents H or F;
Q2is halogen, provided that when Q1is H, Q2represents CL or Br;
R1and R2independently represent H, C1-C6-acyl; and
AG is polyamidine aryl group selected from
the group consisting of
a)

in which W1represents halogen;
X1is1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenated, -HR3R4;
Y1is1-the 4-alkyl, C1-C4-halogenated, halogen or-CN, or, when X1and Y1taken together represents-O(CH2)nO-, in which n=1; and R3and R4independently represent N or C1-C4-alkyl;
b)

in which W2represents F or CL;
X2represents F, CL, -CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4- alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4- halogenated, C1-C4-halogenoalkane,1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4-alkoxy, -NR3R4or fluorinated acetyl;
Y2represents halogen, C1-C4-alkyl, C1-C4-halogenated or-CN, or when W2is F, X2and Y2taken together, represent-O(CH2)nOh,
in which n=1; and
R3and R4independently represent N or C1-C6-alkyl; and
C)

in which Y3is halogen or-CN;
Z3represents F, Cl, -NO2With1-C4-alkoxy, -NR3R4;
R3and R4independently represent H; and
suitable in agriculture derivatives of carboxylic gr is the group.

2. The compound according to claim 1, in which R1and R2represent N.

3. The compound according to claim 1, in which Q1is N.

4. The compound according to claim 1, in which Q2is CL.

5. The compound according to claim 1, in which Q1is N, and Q2is CL.

6. The compound according to claim 1, in which AG is

in which W1represents halogen;
X1is1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenated, -NR3R4;
Y1is1-C4-alkyl, C1-C4-halogenated, halogen or-CN, or, when X1and Y1taken together represents-O(CH2)nO-, in which n=1; and R3and R4independently represent N or C1-C4-alkyl.

7. The connection according to claim 6, in which W1represents CL or F.

8. The connection according to claim 6, in which X1represents C1-C4-alkoxy, C1-C4-halogenated or-NR3R4.

9. The connection according to claim 6, in which Y1represents CL, Br or-CF3.

10. The compound according to claim 1, in which AG is

in which W2represents F or CL;
X2represents F, CL, -CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio,1-C4 -alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4-halogenated,1-C4-halogenoalkane,1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4-alkoxy,
-NR3R4, fluorinated acetyl;
Y2represents halogen, C1-C4-alkyl, C1-C4-halogenated or-CN, or when W2is F, X2and Y2taken together, represent-O(CH2)nO-, in which n=1; and R3and R4independently represent N or C1-C6-alkyl.

11. The connection of claim 10, in which X2represents C1-C4- alkoxy, C1-C4-alkylthio,1-C4-halogenated or-NR3R4.

12. The connection of claim 10, in which Y2represents CL, Br or-CF3.

13. The compound according to claim 1, in which AG is

in which Y3is halogen or-CN;
Z3represents F, Cl, -NO2With1-C4-alkoxy, -NR3R4; and R3and R4independently represent N.

14. The connection 13, in which Y3is Cl.

15. The connection 13, in which Z3represents C1-C4- alkoxy or-NR3R4.

16. Herbicide composition containing effective in the quality of the ve herbicide amount of the compounds of formula I according to claim 1 in a mixture with acceptable in agriculture auxiliary substance or medium.

17. A method of combating harmful vegetation, which comprises contacting an effective herbicide quantities of the compounds of formula I according to claim 1 with vegetation or occupy the surface or applying it to the soil to prevent the emergence of vegetation.

18. The compound of formula ArMetal, in which AG is polyamidine aryl group selected from the group consisting of

in which W1represents halogen;
X1is1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenated or-NR3R4;
Y1is1-C4-alkyl, C1-C4-halogenated, halogen or-CN, or, when X1and Y1taken together represents-O(CH2)nO-, in which n=1; and R3and R4independently represent N or C1-C4-alkyl;

in which W2represents F or CL;
X2represents F, CL, -CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, C1-C4-halogenated, C1-C4-halogenoalkane,1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy-substituted C1-C4 -alkoxy,
-NR3R4or fluorinated acetyl;
Y2represents halogen, C1-C4-alkyl, C1-C4-halogenated or-CN, or when W2is F, X2and Y2taken together, represent-O(CH2)nO, where n=1; and R3and R4independently represent N or C1-C6-alkyl; and

in which Y3is halogen, -CN;
Z3represents F, Cl, -NO2With1-C4-alkoxy or-NR3R4;
R3and R4independently represent H; and
Metal is (C1-C4-alkyl)3tin or B(OR8)(OR9), in which R8and R9independently of one another represent hydrogen, C1-C4-alkyl.

19. Connection p selected from the group consisting of:
2-(4-chloro-2-fluoro-3-methoxyphenyl)-[1,3,2]-dioxaborinane;
2-(4-chloro-2-fluoro-5-methoxyphenyl)-[1,3,2]-dioxaborinane;
2-(4-chloro-2-fluoro-3-ethoxyphenyl)-[1,3,2]-dioxaborinane;
2-(4-chloro-2-fluoro-3-(methylthio)phenyl)-[1,3,2]-dioxaborinane;
2-(4-chloro-2-fluoro-3-methoxymethyl)-[1,3,2]-dioxaborinane;
2-(4-chloro-2-fluoro-3-isopropoxyphenyl)-[1,3,2]-dioxaborinane;
2-(4-chloro-2-fluoro-3-deformational)-[1,3,2]-dioxaborinane;
2-(4-chloro-2-fluoro-3-formationl)-[1,3,2]-dioxaborinane;
4- [1,3,2]-dioxaborinane-2-yl-3-fluoro-2-methoxybenzonitrile;
2-(4-CHL is R-2-fluoro-3-methoxyethoxymethyl)-[1,3,2]-dioxaborinane;
2-(2,4-dichloro-3-ethoxyphenyl)-[1,3,2]-dioxaborinane;
2-[4-chloro-2-fluoro-3-(2,2-diflorasone)phenyl]-[1,3,2]-dioxaborinane;
2-(4-chloro-2-fluoro-5-ethoxyphenyl)-[1,3,2]-dioxaborinane;
2-(2,4-dichloro-3-(methylthio)phenyl)-[1,3,2]-dioxaborinane;
2-fluoro-3,4-methylenedioxyphenylacetic acid;
2-fluoro-3-methoxy-4-methylphenylacetic acid;
4-bromo-2-fluoro-3-methoxyphenylacetic acid;
2-(2-fluoro-3,4-methylenedioxyphenyl)-[1,3,2]-dioxaborinane;
4-chloro-3-(diethylamino)-2-ftorhinolonovy acid;
2,4-dichloro-3-dimethylaminopropionic acid;
2-chloro-4-fluoro-3-methoxyphenylacetic acid;
3-chloro-2-fluoro-3-(4,4,5,5-tetramethyl-{1,3,2}-dioxaborolan-2-yl)phenylmethyl;
(2-fluoro-3-methoxy-4-triptoreline)trimethylstyrene;
(3 butoxy-4-chloro-2-forfinal)trimethylstyrene; and
4-chloro-2-fluoro-3-(1-fluoro-1-methylethyl)trimethylstyrene.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a dialkyltin compound, involving: a reaction for redistribution of alkyl groups and/or a reaction for dealkylation of a composition of a deactivated form of a catalyst based on dialkyltin, which is formed during synthesis of an ester derivative using a dialkyltin-based catalyst. The dialkyltin-based catalyst is a compound of at least one type selected from a group comprising a dialkyltin compound of formula (1) and tetraalkyldistanoxane of formula (2): (1) (where each of R1 and R2 independently denote a straight or branched alkyl group containing 1-12 carbon atoms, each of X1 and X2 independently denotes a substitute of at least one type selected from a group comprising an alkoxy group, an acyloxy group and a halogen atom, a and b independently denote an integer from 0 to 2 and a+b=2, and c and d independently denote an integer from 0 to 2 and c+d=2; (2), (where each of R3, R4, R5 and R6 independently denote a straight or branched alkyl group containing 1-12 carbon atoms, each of X3 and X4 independently denote a substitute of at least one type selected from a group comprising an alkoxy group, an acyloxy group and a halogen atom, and e, f, g and h independently denote an integer from 0 to 2, e+f=2 and g+h=2). The ester derivative is a compound of at least one type selected from a group comprising a carboxylic ester, a carbamate and isocyanate.

EFFECT: method enables production of versions of dialkyltin alkoxide compounds in active form in form of dialkyltin alkoxide compounds.

37 cl, 34 ex, 7 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to separation and extraction of tialkyl tin dialkoxide from a catalyst composition of alkyl tin alkoxide used as a catalyst during synthesis of ether or carbonate. The invention describes a method of separating and extracting dialkyl tin dialkoxide from an alkyl tin alkoxide catalyst composition which cannot be separated through distillation for use in production a carbonate which contains a high-boiling deactivated component having boiling point higher than 250°C at normal pressure, and an active component having two tin-carbon bonds on each tin atom in the alkyl tin alkoxide, involving the following steps: (1) reaction of the alkyl tin alkoxide catalyst composition with an alcohol and/or carbonate to obtain a reaction solution which contains a product formed from the active component; and (2) distillation of the reaction solution obtained at step (1) so as to separate and extract dialkyl tin dialkoxide from the product formed from the active compound.

EFFECT: efficient separation and extraction from an alkyl tin alkoxide catalyst composition which cannot be separated through distillation, where said composition contains a high-boiling deactivated component and a dialkyl tin dialkoxide active component.

17 cl, 24 ex, 2 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to compounds with general formula (I) and its isomers, where R1 is a hydrogen atom of an alkyl C1-4 group with a straight or branched chain, or a phenyl group, thienyl group or furyl group, optionally substituted with one or more alkyl C1-4 groups with a straight or branched chain, C1-4 alkoxy groups with a straight or branched chain, or halogen atoms; R2 is a hydrogen atom or an alkyl C1-4 group with a straight or branched chain, or a phenyl, benzyl, thienyl or furyl group, optionally substituted with a methylenedioxy group, or one or more alkyl C1-4 groups with a straight or branched chain, or C1-4 alkoxy-, hydroxyl-, trifluoromethyl- or cyano-group with a straight or branched chain, or halogen atoms, as well as to a method of producing said compound. The invention also relates to new intermediates with general formula (II) and their production.

EFFECT: radioligands A3 with antagonistic action are obtained and described, labeled with iodine isotopes with mass number 125, which have high specific activity.

16 cl, 3 ex, 2 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: description is given of a method of obtaining alkoxides of alkyl tin, which involves dehydration reaction of at least one alkyl tin compound, used as the initial compound and chosen from organo-tin compounds, with tin-oxygen-tin bonds, and hydroxy compounds, used as a reagent, with obtaining of alkoxide of alkyl tin, corresponding the given initial material and reagent, where the given initial compound and the given reagent are continuously put into a reactor. Low boiling components, containing water are taken out of the above mentioned reactor with continuous removal of the reaction liquid, containing alkoxide of alkyl tin from the lower part of the reactor.

EFFECT: obtaining alkoxides of alkyl tin.

1 cl, 24 ex, 14 dwg

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of acetylene organotin compounds of the general formula: R4-nSn(C≡CR1)n wherein R means lower alkyl; R1 means phenyl, hexinyl, trimethylsilylethynyl and others; n = 3 or 4. In aims for simplifying and safety of the method invention proposes carrying out synthesis of these compounds by interaction of alkyltrihalides tin or tetrahalides tin with 1-alkynes in the presence of secondary-tertiary aliphatic amine and zinc chloride in hydrocarbon solvent medium at temperature 20-70°Cand in the mole ratio tetrahalide tin : 1-alkyne : zinc chloride : amine = 1:4:4.2:8.4, respectively, or in the mole ratio alkyltrichlorotin : 1-alkyne : zinc chloride : amine = 1:3:3.1:6.2, respectively, in yields 48-82%.

EFFECT: improved method of synthesis.

2 cl, 8 ex

FIELD: chemistry of metalloorganic compounds, catalysts.

SUBSTANCE: invention relates to a metalloorganic compound and catalytic composition comprising indicated metalloorganic compound of the general formula (I): [HC(CRR'R'')(CRR'R'')]+[M2X9]- wherein R means hydrogen atom (H) or M1R1R2R3; R' means M1R4R5R6; R'' means H, (C1-C12)-alkyl; M means Zr or Hf; M' means Si or Sn; X means halogen atom; R1-R6 mean (C1-C12)-alkyl. Also, invention relates to a method for homo- and co-polymerization of isoolefins or olefins in the presence of indicated metalloorganic compound. Described catalytic system based on compound of the formula (I) shows high activity in the co-polymerization reaction of isobutylene.

EFFECT: valuable chemical and catalytic properties of compound.

10 cl, 2 tbl, 14 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing complexes of 2-isopropoxy-2-methylvinyl trichlorophosphonium hexachlorometals of the general formula: [(I-PrO-C(CH3)=CHP+Cl3)nMCln-6] wherein M means Sn; n = 2; M means Sb or Bi; n = 3. Method involves interaction of diisopropyl ester with phosphorus pentachloride in the inert solvent medium followed by treatment of formed compound with tin, antimony of bismuth dichloride. Before treatment of formed compound with the corresponding anhydrous metal dichloride nitromethane as a polar solvent is added to its in the amount 1.1-1.25 mole per 1 mole of phosphorus pentachloride, and mixture is heated to temperature above 55°C up to formation of the end product. Method provides increasing yield of the end product.

EFFECT: improved preparing method.

3 ex

The invention relates to an improved process for the preparation of organometallosiloksanov General formula YAlk2SnOMnRmYn-m-1[where M is a metal selected from the group of CA, Zn, Cu, Al, Si, Ge, Sn, Ti, Fe, Mn, Co, Cr; Y=OR' (R'is alkyl 1 - 4C) or O2CR '(R" is alkyl, cycloalkyl with 6-11C); R is alkyl with 1 to 4C, vinyl, phenyl; n is the valence of the metal M, m=0-2, m-n1] by the interaction of dialkanolamides with alkoxides or acylate the above metals M

The invention relates to a method of extracting complex diesters distannoxane from reaction mixtures containing these compounds

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of dialkoxyorganoboranes, particularly to a method for synthesis of dialkoxyorganoboranes via ester exchange. The invention also relates to a method for synthesis of organo-oxazaborolidine catalysts (organo-CBS) and trialkylboroxins which are enantioselective catalysts for reducing ketones.

EFFECT: efficient method for synthesis of dialkoxyorganoboranes.

5 cl, 4 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to a compound of formula (I) where one of R1 and R2 represents -NH-X-Y-Z, and another represents -OH; where X represents -(CH2)m- where m is equal to 0, 1, 2, 3 or 4; Y represents carborane where at least one boron atom represents 10B; and Z represents H; and its pharmaceutically acceptable salts, solvates and stereoisomers. Also, the pharmaceutical compositions, application of the compound of formula (I) and a method of producing the compound of formula (I) are offered.

EFFECT: production of the compounds effective for boron neutron capture therapy.

15 cl, 6 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to organic electroluminescent devices based on compounds of formula

where Y, Z is selected from N, P, P=O, C=O, O, S, S=O and SO2; Ar1, Ar2, Ar3 are selected from benzene, naphthaline, anthracene, phenanthrene, pyridine, pyrene or thiophene, optionally substituted with R1; Ar4, Ar5, Ar6, Ar7 are selected from benzene, naphthaline, anthracene, phenanthrene, pyridine, pyrene, thiophene, triphenylamine, diphenyl-1-naphthylamine, diphenyl-2-naphthylamine, phenyldi(1-naphthyl)amine, phenyldi(2-naphthyl)amine or spirobifluorene, optionally substituted with R1; E is a single bond, N(R1), O, S or C(R1)2; R1 denotes H, F, CN, alkyl, where the CH2 can be substituted with -R2C=CR2 -, -C=C-, -O- or -S-, and H can be substituted with F, optionally substituted aryl or heteroaryl, where R1 can form a ring with each other; R2 denotes H, aliphatic or aromatic hydrocarbon; X1, X4, X2, X3 are selected from C(R1)2, C=O, C=NR1, O, S, S=O, SO2, N(R1), P(R1), P(=O)R1, C(R1)2-C(R1)2, C(R1)2-C(R1)2-C(R1)2, C(R1)2-O and C(R1)2-O-C(R1)2; n, o, p, q, r and t are equal to 0 or 1; s = 1.

EFFECT: obtaining novel compounds - emission layer dopants, and novel electroluminescent devices based on said compounds which emit a blue colour.

18 cl, 91 ex, 6 tbl

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to application of compound, which has the following structure , where R10b represents halogen, R7b represents H, and R1b is selected from negative charge, H and salt anti-ion, or its pharmaceutically acceptable salt as medication for treatment of infection, caused by yeasts, fungi or bacteria, in animal, as well as for obtaining medication for treatment of infection, onychomycosis in humans. Also claimed are pharmaceutical preparation, method of treating onychomycosis in humans, method of inhibiting fungi-induced infection development in humans.

EFFECT: invention makes it possible to increase efficiency of treating infections, caused by yeasts, fungi or bacteria.

61 cl, 20 ex, 12 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of producing 6-[3-(1-adamantyl)-4-methoxyphenyl]-2-naphthoic acid of formula (I) through a Suzuki reaction between 3-adamantyl-4-methoxyphenylcarboxylic acid of formula (II) and 6-bromo-2-naphthoic acid of formula (III), wherein the reaction between compounds (II) and (III) is carried out at temperature between 60 and 110°C for between 30 minutes and 24 hours in an inert gas atmosphere in the presence of a palladium catalyst and a base in a polar solvent, followed by treatment with an acid. The invention also relates to use of compounds of formulae (II) and (III) to produce a compound of formula (I).

EFFECT: single-step method enables to obtain desired product with high output.

13 cl, 2 dwg, 3 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to derivatives of 13(l)-N-{2-N-(closo-monocarbadodecaboran-1-yl)-methyl]aminoethyl}amide-15(2), 17(3)-dimethyl ether of chlorine e6 of general formula

, where M=Cs, Na, manifesting properties of photosensitiser.

EFFECT: compounds can be used in medicine as agents for boron neutron capture therapy (BNCT) and photodynamic therapy (FDT) of malignant neoplasms.

2 ex, 1 tbl, 2 dwg

FIELD: medicine.

SUBSTANCE: invention refers to nanocrystalline compounds of formula (I) AOx-(L-Men+)i where AOx represents metal oxide where A it specified from Ti or Zr, x=2; Men+ represents metal ion exhibiting antibacterial activity, specified from Ag+ and Cu++, where n=1 or 2; L represents a bifunctional molecule, or a organic or metal-organic molecule able to get bound with metal oxide and ion metal Men+ simultaneously; where the organic molecule is specified from pyridine, dipyridyl, tripyridyl, functionalized with carboxylic groups (-COOH), boronic groups (-B(OH)2), or phosphonic groups (-PO3H2), or 4-mercaptophenylboronic acids; where the metal-organic molecule represents a metal-organic complex containing organic ligand coordinated with central metal atom and containing boronic (-B(OH)2), phosphonic (-PO3H2) or carboxylic (-COOH) functional group, and the groups are coordinated with central metal atom and able to get bound with metal ions with antibacterial activity; where specified organic ligand coordinated with central metal atom is specified from pyridine, dipyridyl, tripyridyl functionalized with carboxylic groups (-COOH), boronic groups (-B(OH)2), or phosphonic groups (-PO3H2), or 4-mercaptophenylboronic acids; i represents a number of groups L-Men+ bound with nanoparticle AOx. Also, there are offered a composition exhibiting antibacterial and/or antiviral activity, dermatological compositions, application of nanocrystalline compounds, a method of nanocrystalline compounds regeneration.

EFFECT: nanocrystalline compounds show effective antibacterial action.

27 cl, 4 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a novel carboranyl derivative of fluorinated porphyrins of general formula I , where Ia: M=2H, R=o-CB10H10C-, Ib: M=2M, R=o-C6H5-CB10H10C-, Ic: M=2H, R=-CB11H11-Cs+, Id: M=Cu, R=-CB11H11-Cs+, Ie: M=Pd, R=-CB11H11-Cs+, If: M=2H, R=-CB11H11-Na+, Ig: M=Cu, R=-CB11H11-Na+, Ih: M=Pd, R=-CB11H11-Na+,having photosensitiser properties. The invention also discloses methods for synthesis of said compounds.

EFFECT: compounds which exhibit photosensitiser properties can be used in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) of oncological diseases.

6 cl, 8 ex, 1 tbl

FIELD: medicine, pharmaceutics.

SUBSTANCE: described are structure and manufacturing of antibiotics which include borinic acid complexes, in particular derivatives of hydroxyquinoline, imidazole and picolinic acid, together with compositions of said antibiotics and methods of application of antibiotics and compositions as bactericidal and fungicidal preparations as well as therapeutic medications for treatment of diseases caused by bacteria and fungi.

EFFECT: obtaining antibiotics which include borinic acid complexes.

51 cl, 1 ex, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to chelate complexes of gadolinium (III). Complexes of Gd3+ with 4-dihydroxyborophenylamine (DHBPA) have formula Gd(DHBPA)3, and complexes of Gd3+ with DHBPA and monosaccharide (M), which is in the inner sphere of the complex, have formula: M3[Gd(DHBPA)3]. DHBPA molecules enter the coordination sphere of gadolinium through nitrogen and oxygen atoms of the alanine fragment. Monosaccharides, e.g. fructose and/or ribose, form outer-sphere complexes on hydroxyl groups of borophenyl in DHBPA, built in the inner coordination sphere of Gd3+.

EFFECT: obtaining new compounds.

2 cl, 3 ex, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to novel compound of general formula (I): , where Ar1 is a phenyl group substituted with 1-3 halogen atoms; Ar2 is a phenyl group which can be substituted with a halogen, alkoxyalkyl, alkoxyhalogenalkyl, or pyridyl group which can be substituted with halogenalkyl; X is -S-, -SO- or -SO2-; Y is a hydrogen atom, -NR1R2 (where R1 is a hydrogen atom, lower alkyl group or hydroxy group; and R2 is a hydrogen atom, lower alkyl group which can be substituted, lower alkanoyl group, alkoxycarbonyl group which can be substituted, lower alkoxy group which can be substituted, amino group which can be substituted; or R1 and R2 together with a nitrogen atom with which they are bonded form a piperidine, morpholine, azetidine or piperazine ring, which can be substituted wiht a hydroxy group) or -OR1', where R1 is a hydrogen atom); Z is an oxygen atom or sulphur atom; and R is a hydrogen atom or a lower alkyl group; or to salts thereof. The invention also relates to a medicinal agent and a pharmaceutical composition which inhibit production/secretion of β- amyloid protein, to use of said compounds to prepare a medicinal agent and to a method of treating diseases caused by abnormal production or secretion of β- amyloid protein.

EFFECT: novel compounds which can inhibit production/secretion of β- amyloid protein and which can be used in treating Alzheimer disease or Down syndrome are obtained and described.

30 cl, 136 ex, 1 tbl

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