Benzoylpyridine derivative or its salt, fungicide comprising its as active component, methods for its preparing and intermediate compounds for its preparing

FIELD: organic chemistry, chemical technology, fungicides.

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

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

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

17 cl, 36 tbl, 4 ex

 

The scope of the invention

The present invention relates to a new derived benzoylpyridine or its salts, containing as the active ingredient of the fungicide, the method of its production and to intermediate compounds for its receipt.

Background of the invention

Derivatives benzoylpyridine, which are analogues of the compounds of the present invention may be the compounds disclosed, for example, in WO99/41237, WO99/38845, WO96/17829, JP-A-7-309837 and JP-A-2-275858. However, they differ from the compounds of the present invention. In addition, the objectives of using these compounds differ from the purpose of using the compounds of the present invention.

Many of the commonly used fungicides differ in specific characteristics in terms of combating pests that cause diseases of plants. Some of them (fungicides) are somewhat weaker therapeutic action compared to preventive action, and some residual effect that lasts only a relatively short period of time, so in some cases, their ability to control pests it turns out in practice to be insufficient. Accordingly, it was highly desirable to create new connections, which would be very effective against pests that cause diseases of age is th.

Description of the invention

The authors of the present invention made intensive studies to overcome the above problems and as a result discovered that by using the compounds represented by formula (I)as the active ingredient provides excellent preventive effect and curative action against various plant diseases, especially against powdery mildew of barley, vegetables, fruit and flowering plants, and thus was accomplished the present invention.

Thus, the present invention relates to a derivative of benzoylpyridine represented by the formula (I)or its salt

where X represents a halogen atom, a nitro-group is substituted with alkoxygroup, replaced alloctype, replaced cycloalkanes, hydroxyl group, substituted hydrocarbon group substituted with allylthiourea, cyano, carboxyl group, which can be esterificated or lidirovat, or replacing the amino group; n is 1, 2, 3 or 4; R1represents a substituted alkyl group; R2represents a substituted alkyl group substituted with alkoxygroup, replaced alloctype, replaced cycloalkanes or hydroxyl group; and m is 1, 2, 3, or 4, provided that when m equals the least 2, R2may contain an oxygen atom with the formation of condensed rings (except when the pyridine ring is substituted bentilee group in 2-position; the pyridine ring substituted by alkoxygroup, a hydroxyl group or benzyloxypropionic in the 3-position; and n equals 1, m equals 1 or 2), a fungicide containing it as active ingredient, the method of its production and intermediate connection to retrieve.

The halogen atom denoted by X may be, for example, fluorine, chlorine, bromine or iodine, and preferably can be used, for example, fluorine, chlorine or bromine. The alkoxy fragment in original alkoxygroup marked each of X and R2may be, for example, C1-6alkoxy (such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, out-butoxy or tert-butoxy), and preferably may be, for example, C1-4alkoxy (such as methoxy or ethoxy). In addition, secondary substituents replaced alkoxygroup can be from 1 to 5 substituents, which may be the same or different and which are selected from the group consisting of aryl, aryloxy, hydroxyl, nitro, nitroxy, halogen (such as fluorine, chlorine, bromine or iodine), halogenoalkane (such as C1-4halogenoalkane, as, for example, CF3On or HCF2O), cycloalkyl, amino, alkylthio and cyano. Of these is replaced alkoxygroup preferred the unsubstituted alkoxygroup, particularly preferred C1-4alkoxygroup.

As the aryl fragment in original alloctype, denoted as X, you can specify a polycyclic group condensed type, such as naphthyl and phenyl, preferably phenyl. Secondary Deputy have replaced alloctype may be, for example, halogen, alkyl, alkoxy or hydroxyl. From delegate aryloxy most preferred fenoxaprop.

Cycloalkyl fragment in the original cycloalkene denoted by X, is usually a fragment containing from 3 to 10 carbon atoms, and monocyclic group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclooctyl, and may also be referred to polycyclic group condensed type. However, the preferred monocyclic group. Secondary Deputy delegate of cycloalkanes may be, for example, halogen, alkyl, alkoxy or hydroxyl. Of these replaced cycloalkyl most preferred cyclohexyloxy.

Hydrocarbon fragment in the substituted hydrocarbon group represented by X may be, for example, group C1-6alkyl (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl)2-6alkenyl (such as vinyl, allyl, Isopropenyl or 3-methyl-2-butenyl)2-6quinil (that is Oh how ethinyl, 1-PROPYNYL or 2-PROPYNYL)3-6cycloalkyl (such as cyclopropyl, cyclopentyl or cyclohexyl), or With6-10aryl. In addition, secondary substituents of the substituted hydrocarbon groups can be from one to five substituents, which may be the same or different and which are selected from the group consisting of aryl, aryloxy, hydroxyl, nitro, nitroxy, halogen (such as fluorine, chlorine, bromine or iodine), halogenoalkane (such as C1-4halogenoalkane, as, for example, CF3On or HCF2O), cycloalkyl, amino, alkylthio and cyano. Of these substituted hydrocarbon groups are preferred substituted alkyl groups and particularly preferred alkyl groups. In addition, among the alkyl groups are the most preferred C1-4alkyl groups.

Fragment of alkylthio in original allylthiourea denoted by X may be, for example, C1-6alkylthio (such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutyric or tert-butylthio) and preferably C1-4alkylthio (such as methylthio or ethylthio). Of these alkylthio, which may have substituents, preferred allylthiourea, especially preferred C1-4allylthiourea. Secondary substituents at substitutable ancilliary can be from one to five substituents, which may be the same who or different and which are selected from the group consisting of aryl, aryloxy, hydroxyl, nitro, nitroxy, halogen (such as fluorine, chlorine, bromine or iodine), halogenoalkane (such as C1-4halogenoalkane, as, for example, CF3On or HCF2O) and cyano.

Carboxyl group which may be esterified or liderovna, designated as X may be, for example, carboxyl group which may be esterified, such as C1-6alkoxycarbonyl group (as, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, solutionline group or tert-butoxycarbonyl group), nitroxy-C1-4-alkoxycarbonyl group (such as 2-nitroacetanilide group or 3-nitrosoperoxycarbonate group), phenyl-C1-4-alkoxycarbonyl group (such as benzyloxycarbonyl group or penetrationonline group); or a carboxyl group which may be liderovna, such as carnemolla group, C1-6monoacylglycerols group (such as methylaminomethyl group, ethylaminomethyl group, propylaminoethyl group, isopropylaminocarbonyl group, butylaminoethyl group, isobutyleneisoprene group or tert-butylaminothio is supplemented flax group), C1-6dialkylaminoalkyl group (such as dimethylaminocarbonylmethyl group, diethylaminocarbonylmethyl group, dipropylenetriamine group, diisopropylaminoethyl group, dibutylaminoethanol group or isobutyleneisoprene group), nitroxy-C1-4-alkylaminocarbonyl group (such as 2-nitrosylmyoglobin group or 3-nitrosoperoxycarbonate group), phenyl-C1-4-alkylaminocarbonyl group (such as benzylaminocarbonyl group or penetrationonline group)3-6-cycloalkylcarbonyl group (such as cyclopropanecarbonyl group), cyclopentanecarbonyl group or cyclohexyloxycarbonyl group, cyclic aminocarbonyl group (such as morpholinosydnonimine group, piperidinecarboxylate group, pyrrolidinecarbonyl group or tiomorfolina group) or aminocarbonyl group.

The substituted amino group denoted by X may be, for example, amino group or alkylamino, such as monoalkylamines or dialkylamines. The alkyl fragment in alkylamine (monoalkylamines or dialkylamines) is preferably C1-4alkyl. Secondary substituents in the substituted amino group can be from one to n is t Vice, which may be the same or different and which are selected from the group consisting of aryl, aryloxy, hydroxyl, nitro, nitroxy, halogen (such as fluorine, chlorine, bromine or iodine), halogenoalkane (such as C1-4halogenlampe, as, for example, CF3On or HCF2O), cycloalkyl, amino, alkylthio and cyano.

The alkyl fragment in the substituted alkyl group denoted by each of R1and R2preferably represents C1-6alkyl (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl), and among them, preferred C1-4alkyl. Secondary substituents of the substituted alkyl groups can be from one to five substituents, which may be the same or different and which are selected from the group consisting of aryl, aryloxy, hydroxyl, nitro, nitroxy, halogen (such as fluorine, chlorine, bromine or iodine), halogenoalkane (such as C1-4halogenoalkane, as, for example, CF3On or HCF2O), cycloalkyl, amino, alkylthio and cyano. Of these substituted alkyl groups are preferred unsubstituted alkyl group, and particularly preferred C1-4an alkyl group. Among them, most preferred methyl group.

The alkoxy fragment in the original alkoxygroup, denoted as R2preferably is C1-6alkoxy (such as metox is, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy), and among them, preferred C1-4alkoxy. Secondary substituents of the substituted alkyl groups can be from one to five substituents, which may be the same or different and which are selected from the group consisting of aryl groups, alloctype, hydroxyl group, nitro group, nitroxide, halogen atoms (such as fluorine, chlorine, bromine or iodine), halogenlamp (such as C1-4halogenlampe, as, for example, CF3On or HCF2O), cycloalkyl group, amino group, allylthiourea and ceanography. Of these replaced alkoxygroup preferred the unsubstituted alkoxygroup.

As the aryl fragment in original alloctype denoted by R2you can specify polycyclic group condensed type, such as naphthyl and phenyl, preferably phenyl. Secondary substituents replaced alloctype can be, for example, halogen atom, alkyl group, alkoxygroup or hydroxyl group. Of these replaced aryloxy most preferred unsubstituted fenoxaprop.

Cycloalkenyl fragment in original cycloalkene denoted by R2usually is a fragment, which contains from 3 to 10 carbon atoms, and monocyclics the th group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclooctyl, and polycyclic group condensed type. However, the preferred monocyclic group. Secondary Deputy have replaced cycloalkanes may, for example, be a halogen atom, alkyl, alkoxy or hydroxyl. Of these replaced cycloalkyl most preferred unsubstituted cyclohexyloxy.

And finally, aryl fragment, cycloalkyl group and allylthiourea in the secondary substituent in the composition of the substituent denoted by X, R1and R2have the meanings mentioned for the substituents denoted by X, R1, R2and R3.

The compound represented by formula (I)may form a salt with the acidic compound, and it can form, for example, inorganic salt, such as hydrochloride, hydrobromide, phosphate, sulfate or nitrate, or organic salt such as acetate, benzoate, para-toluensulfonate, methanesulfonate or propanesulfonate.

The preferred method of carrying out the invention

Some preferred variants derived benzoylpyridine represented by the formula (I)shown below. These compounds can be combined with each other. In addition, these compounds are useful as fungicides.

R2', R2"and R2"'have the meanings specified the s to R 2and X1X2X3and X4have the meanings specified above for X.

(1) Derived benzoylpyridine represented by the formula (I')or its salt

where X, n and R1have the above for General formula (I) values, R2'represents a substituted alkyl group substituted with alkoxygroup, replaced alloctype, replaced cycloalkanes or hydroxyl group, p is 1, 2 or 3, and R2"is replacing alkoxygroup or hydroxyl group, provided that at least two of R2'and R2"may contain oxygen atom with the formation of the condensed ring (excluding the case when the pyridine ring is substituted benzoyl group in 2-position; the pyridine ring substituted by alkoxygroup, a hydroxyl group or benzyloxypropionic in the 3-position; and n is 1, p is 1).

(2) Derived benzoylpyridine or its salt according to the above item (1), which is represented by formula (I")

where X represents a halogen atom, a nitro-group is substituted with alkoxygroup, replaced alloctype, replaced cycloalkanes substituted hydrocarbon group substituted with allylthiourea, cyano, carboxyl group which may be esterified or liderovna, or Deputy who returned the amino group; n is 1, 2, 3 or 4; R1represents an alkyl group; R2'represents a substituted alkyl group substituted with alkoxygroup, replaced alloctype or replaced cycloalkanes; p is 1, 2 or 3; and each of R2"and R2"'is replacing alkoxygroup.

(3) Derived benzoylpyridine or its salt according to the above item (2), where X represents a halogen atom, a nitro-group is substituted with alkoxygroup, replaced cycloalkanes, alkyl group, substituted alkylthiols or amino group.

(4) Derived benzoylpyridine or its salt according to the above item (3)represented by the formula (I"):

where X represents a halogen atom, a nitro-group is substituted with alkoxygroup, replaced cycloalkanes, alkyl group, substituted alkylthiols or replacing the amino group; n is 1, 2, 3, or 4; R1represents an alkyl group; R2represents a substituted alkyl group substituted with alkoxygroup, replaced alloctype or replaced cycloalkanes; p is 1, 2 or 3; each of R2"and R2"'is replacing alkoxygroup (excluding the case when the pyridine ring is substituted bentilee group in 3-position, and the pyridine ring contains a group of CF3at least one of 2,6-is alogene).

(5) Derived benzoylpyridine or its salt according to the above item (1)represented by the formula (I"')

where X represents a halogen atom, substituted alkoxygroup, an alkyl group, a group of CF3or allylthiourea; n is 1, 2, 3 or 4; R1represents an alkyl group; R2represents a substituted alkyl group substituted with alkoxygroup or replaced cycloalkanes; p is 1, 2 or 3; and each of R2"and R2"'is replacing alkoxygroup.

(6) Derived benzoylpyridine or its salt according to the above item (5)represented by the formula (I"')

where X represents a halogen atom, substituted alkoxygroup, an alkyl group, a group of CF3or allylthiourea; n is 1, 2, 3, or 4; R1represents an alkyl group; R2'represents a substituted alkyl group substituted with alloctype or replaced cycloalkanes; p is 1, 2 or 3; each of R2"and R2"'is replacing alkoxygroup (excluding the case when the pyridine ring is substituted by a benzoyl group at the 3-position, and the pyridine ring contains a group of CF3at least one of 2,6-positions).

(7) Derived benzoylpyridine or its salt according to the above item (5) or (6), where the halo atom is s, presents X is a fluorine atom or a chlorine atom.

(8) Derived benzoylpyridine or its salt according to the above item (5) or (6), where n is 3 or 4.

(9) Derived benzoylpyridine or its salt according to the above item (5) or (6)in the case when n is 1 or 2, halogen atom represented by X is a fluorine atom or a chlorine atom.

(10) Derived benzoylpyridine or its salt according to the above item (5)represented by the formula (I"")

where X represents a halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; n is 1, 2 or 3; R1represents an alkyl group; R2'is alkoxygroup; p is 1, 2 or 3; and each of R2"and R2"'is alkoxygroup.

(11) Derived benzoylpyridine or its salt according to the above item (10)represented by formula (I"")

where X represents a halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; n is 1, 2 or 3; R1represents an alkyl group; R2'is alkoxygroup; p is 1, 2 or 3; and each of R2"and R2"'is alkoxygroup (excluding the case when the pyridine ring is substituted by a benzoyl group at the 3-position, and the pyridine ring gr contains the foam CF 3at least one of 2,6-positions).

(12) Derived benzoylpyridine or its salt according to the above item (8)represented by the formula (I"')

where In represents-SH4=when a is-N=; is-N=, when a represents-CH=; each of X1and X2who are independent from each other, represents a halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; X3represents a hydrogen atom, halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; X4represents a hydrogen atom, halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; R1represents an alkyl group; R2'is alkoxygroup; p is 1, 2 or 3; and each of R2"and R2"'is alkoxygroup.

(13) Derived benzoylpyridine or its salt according to the above item (8)represented by the formula (I"')

where In represents-SH4=when a is-N=; is-N=, when a represents-CH=; each of X1and X2who are independent from each other, represent a halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; X3represents a hydrogen atom, a halo atom is s, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; X4represents a hydrogen atom, halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; R1represents an alkyl group; R2'is alkoxygroup; p is 1, 2 or 3; and each of R2"and R2"'is alkoxygroup (excluding the case when a is-CH=, and b is-N=, a X2represents a group of CF3).

The compound represented by formula (I)or its salt can be obtained in accordance with known method of obtaining similar compounds (such as the method disclosed in WO 96/17829). However, as the preferred way to specify methods 1-3 are presented in the following diagrams. Here X, R1, R2n and m in the formula have the above values. One of the substituents represented by M1in the formula (II) and M2in the formula (III), represents the cyano and the other is a metal atom, or a mixed salt; Deputy represented by W in the formula (V) represents a halogen atom or triftormetilfullerenov; one of the substituents represented by M3in the formula (VI) and M4in the formula (VII)represents a formyl group and the other represents a metal atom or a mixed salt.

Im the 1

The method of obtaining the compound represented by formula (I), which includes the implementation of the condensation reaction of the compound represented by formula (II), and compounds represented by formula (III), getting aminosilane represented by the formula (VIII)

where X, R1, R2n and m have the previously indicated meanings, Z represents a metal atom or a mixed salt, and implementation of hydrolysis of the compounds obtained.

Metal atom denoted by each of the M1and M2in formulas (II) and (III)may be, for example, a typical atom of metal, such as lithium, magnesium, zinc or copper; or the transition metal atom, such as palladium or ruthenium. In addition, instead of the metal atom can be used a mixed salt of the metal atom.

The compound of formula (II), where M1represents a cyano, and a compound of the formula (III), where M2is cyano, can be obtained in a known manner, such as disclosed in Journal of the Chemical Society, Perkin transactions 1 pages 2323-2326, 1999.

The condensation reaction to obtain aminosidine carried out in a suitable solvent (such inert solvents as tetrahydrofuran, diethyl ether, dimethoxyethane, hexane, benzene, toluene, methylene chloride, or mixtures) at the reaction temperature from -100 to 70°C, preferably from -80 to 30�B0; C. This reaction is preferably carried out in an atmosphere of inert gas, for example nitrogen or argon.

Aminosidine resulting from the condensation reaction, hydrolyzing known way and is converted into a compound represented by the formula (I). The hydrolysis reaction can be conducted in the presence of, for example, water, alcohol or mixtures thereof. In method 1 the condensation reaction and the hydrolysis reaction is usually carried out continuously and do not emit any aminosidine. In addition, to obtain compounds represented by formula (I), with high yield, it is preferable to carry out the hydrolysis reaction after the condensation reaction is fully completed.

Method 2

The method of obtaining the compound represented by formula (I), which includes the implementation of the condensation reaction of the compound represented by formula (IV)and compounds represented by formula (V), with compounds represented by the formula (IX)

where X, R1, R2n and m have the previously indicated meanings, and implementation of oxidative delanerolle in the presence of a base.

The reaction for obtaining a compound represented by the formula (IX), during the first half of method 2 is usually carried out in the presence of a base, preferably in a solvent. The base that can be used is in this reaction, may be, for example, lithium hydride, sodium hydride, sodium methoxide, ethoxide or sodium tert-piperonyl potassium. The solvent may be, for example, tetrahydrofuran, diethyl ether, benzene, toluene, methylene chloride, chloroform or DMF, or a mixture of these solvents. This reaction is preferably carried out at a temperature from 0 to 100°C. furthermore, it is preferably carried out in an atmosphere of inert gas, for example nitrogen or argon. In addition, in those cases when you want to accelerate the reaction, you can add benzosulfimide sodium or a pair of toluensulfonate sodium.

The reaction of oxidative delanerolle on stage last half of method 2 is carried out in the presence of a base. The base can be, for example, sodium hydride, potassium hydride, sodium carbonate or potassium carbonate. In addition, if necessary, you can use interphase catalyst (such as benzyltriethylammonium or tetrabutylammonium). This reaction is usually carried out in a suitable solvent (such as an inert solvent, such as methylene chloride, chloroform, 1,2-dichloroethane, benzene, toluene, DMF or DMSO, or in water-containing solvents, or their mixtures), at the reaction temperature from 0 to 50°C.

Method 3

The method of obtaining the compound represented by formula (I), which includes the implementation of the EOI is to interact compounds represented by formula (VI)and compounds represented by formula (VII), with phenylenediamine represented by the formula (X)

(where X, n, m, R1and R2have mentioned previously for formula (I) values), and the implementation of the oxidation reaction of the obtained compound.

Each of the metal atoms denoted by M3and M4in method 3 can be, for example, a typical atom of metal, such as lithium, magnesium, zinc or copper; or the transition metal atom, such as palladium or ruthenium. In addition, instead of the metal atom can be used a mixed salt of the metal atom.

The compound of formula (VI)where the Deputy denoted by M3is the formyl group, and a compound of the formula (VII)where the Deputy denoted by M4is a formyl group, can usually be obtained by a known method such as the method disclosed in Journal of Organic Chemistry, vol.57, pages 6847-6852, 1992.

Phenylenediamines represented by the formula (X)obtained from the compounds represented by formula (VI)and compounds represented by formula (VII), can be oxidized by known methods using containing metal oxidizing agent such as manganese dioxide or chromic acid, the oxidation method according Sarno (Swern) (dimethyl sulfoxide+ oxalicacid) or by the oxidation method and with the use of ruthenium (tetrapropylammonium+N-methylmorpholin-N-oxide), and converted into the compound represented by formula (I).

Further disclosed a method of implementation of the method 3.

(1) a method of obtaining a compound represented by the formula (I), which includes the interaction of the substituted benzaldehyde represented by the formula (VI-1)

(where R1, R2and m have the previously indicated meanings, and salts of substituted pyridine derivative with the metal represented by formula (VII-1)

(where X have the previously indicated meanings, Z represents a metal atom or a mixed salt) to obtain phenylenediamine represented by the formula (X), and its oxidation.

(2) a method of obtaining a compound represented by the formula (I), which includes the engagement of salt substituted derivative of benzene with the metal represented by formula (VI-2):

(where R1, R2and m have the previously mentioned meanings and Z represents a metal atom or a mixed salt), and substituted peredelanaya represented by the formula (VII-2)

(where X have the previously indicated values), with phenylenediamine represented by the formula (X), and its oxidation.

Below are the preferred varieties phenylpyridine the La, represented by formula (X), which is an intermediate compound to obtain a compound represented by the formula (I).

(1) Phenylenediamines represented by formula (X')

where X, n and R1have mentioned previously for formula (I) values, R2'represents a substituted alkyl group substituted with alkoxygroup, replaced alloctype, replaced cycloalkanes or hydroxyl group, p is 1, 2 or 3; and R2"is replacing alkoxygroup or hydroxyl group, provided that at least two of R2'and R2"may contain an oxygen atom with the formation of the condensed ring (excluding the case when the pyridine ring is substituted benzoyl group in 2-position; the pyridine ring substituted by alkoxygroup, a hydroxyl group or benzyloxypropionic in the 3-position; and n is 1, p is 1).

(2) Phenylenediamines above p.(1)represented by the formula (X")

where X represents a halogen atom, a nitro-group is substituted with alkoxygroup, replaced alloctype, replaced cycloalkanes substituted hydrocarbon group substituted with allylthiourea, cyano, carboxyl group which may be esterified or liderovna, or substituted and is infogruppu; n is 1, 2, 3 or 4; R1represents an alkyl group; R2'represents a substituted alkyl group substituted with alkoxygroup, replaced alloctype or replaced cycloalkanes, p is 1, 2 or 3, and each of R2"and R2"'is replacing alkoxygroup.

(3) Phenylenediamines above p.(2), where X represents a halogen atom, a nitro-group is substituted with alkoxygroup, replaced cycloalkanes, alkyl group, substituted alkylthiols or replacing the amino group.

(4) Phenylenediamines above p.(2) or (3), where the pyridine ring is substituted by a benzoyl group at the 4-position.

(5) Phenylenediamines above p.(1)represented by the formula (X"')

where X represents a halogen atom, substituted alkoxygroup, an alkyl group, a group of CF3or allylthiourea; n is 1, 2, 3 or 4; R1represents an alkyl group; R2'represents a substituted alkyl group substituted with alkoxygroup or replaced cycloalkanes; p is 1, 2 or 3; and each of R2"and R2"'is replacing alkoxygroup.

(6) Phenylenediamines above p.(5)represented by formula (X'")

where X represents a halogen atom, alkoxygroup, Alki is inuu group, group CF3or allylthiourea; n is 1, 2 or 3; R1represents an alkyl group; R2'is alkoxygroup; p is 1, 2 or 3; and each of R2"and R2"'is alkoxygroup.

(7) Phenylenediamines above p.(5) or (6), where the pyridine ring is substituted by a benzoyl group at the 4-position.

(8) Phenylenediamines above p.(6), represented by formula (X'"')

where In represents-SH4=if a is-N=; is-N=, if a represents-CH=; each of X1and X2independently from each other represents a halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; X3represents a hydrogen atom, halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; X4represents a hydrogen atom, halogen atom, alkoxygroup, an alkyl group, a group of CF3or allylthiourea; R1represents an alkyl group; R2'is alkoxygroup; p is 1, 2 or 3; and each of R2"and R2"'is alkoxygroup.

(9) Phenylenediamines above p.(8), where a is-N=.

In addition, the compound represented by formula (I)can optionally enter the electrophilic substituents or nucleophile. The EU is ü connection, represented by formula (I)can be converted to a compound represented by formula (I-a) or (I-b), which is illustrated in the following diagram. In addition, the compound represented by formula (I), you can enter a Deputy radically. Here, in the formula (I-a) E is an electrophilic reagent, and in the formula (I-b) Nu represents a nucleophilic reagent.

n' and n" have the previously indicated for n values.

The reaction for obtaining a compound represented by formula (I-a), is varied properly depending on the electrophilic agent, and the reaction is usually run by known methods or are represented here by the way. For example, you can use the above method 1. Nucleophilic substitution to obtain the compound represented by formula (I-b), vary appropriately depending on the nucleophilic agent, and the reaction is usually run by known methods or are represented here by the way. For example, in the case ethoxymethylene reagent is preferable to conduct the reaction in the presence of an inert solvent, such as ethanol or dioxane, toluene or octane, at the reaction temperature from 0 to 120°C for an appropriate period of time. Ethoxymethylene the reagent is used in an amount of from 0.1 to 10 molar equivalents, preferably from 0.5 to 5 mol what's equivalents.

In addition, the compound represented by the formula (1-C) (the compound of formula (I), where X represents a halogen atom), can be further converted into the compound represented by formula (I-d) resulting from the removal of the Deputy-halogen, which is represented in the following diagram. In response, further illustrated in the diagram, you can properly use catalytic hydrogenation, the reaction of hydrogen transport or reaction of metal recovery. In the diagram Hal represents a halogen atom.

The catalytic hydrogenation can be performed in the presence of a catalyst in an atmosphere of hydrogen gas at normal pressure or at elevated pressure in an appropriate solvent. The catalyst which can be used may be, for example, a catalytic system comprising platinum, palladium, rhodium, ruthenium, Nickel, or iridium. The solvent can be used, for example, water, alcohol (such as methanol or ethanol, ethyl acetate, acetic acid, dioxane, ether, benzene or hexane. In this case, the catalyst is used in quantities of from 0.01 to 1.2 moles based on the compound represented by formula (I-c). Furthermore, the reaction can be conducted in the presence of a base such as triethylamine or sodium bicarbonate. In addition, it is possible to use known reactivatable, such as the reaction of hydrogen transport (e.g., using palladium-on-charcoal, monitorial as a source of hydrogen or sodium dihydrophosphate), or the reaction for reduction of the metal (for example, samarium diiodide).

Below are specific examples of the preparation of derivative benzoylpyridine represented by the formula (I), and intermediates for their production (the names of the compounds in the examples of the preparation is based on the IUPAC nomenclature, and position of the substituents may differ from those presented in the following tables).

Example obtain 1

Obtaining 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2,6-dichloro-4-triptoreline (compound No. 3)

(a) 14 ml (20 mmol) n-utility (1.5 M hexane solution) is added dropwise at 0°With the solution containing 2.9 ml (21 mmol) of Diisopropylamine dissolved in 62 ml of tetrahydrofuran, followed by stirring for 30 minutes the Solution is cooled to -20°With, add to the resulting solution containing 4.0 g (19 mmol) of 2,6-dichloro-4-triptoreline dissolved in 5 ml of tetrahydrofuran, followed by stirring for 5 min, and the obtained add a solution containing 3.8 g (18 mmol) of 2,3,4-trimetoksi-6-methylbenzaldehyde dissolved in 7 ml of tetrahydrofuran, followed by stirring for 1.5 hours. To the mixture is added 30 ml of water for the termination of the reaction and the tetrahydrofuran is distilled off under reduced pressure. Conduct extraction with ethyl acetate, the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, obtaining 6.2 g (yield 81%) (2,3,4-trimetoksi-6-were)(2,6-dichloro-4-trifluoromethyl-3-pyridyl)methanol (oily brown substance).

(b) 14 g oxide magnesium are added to a solution containing 5.4 g (2,3,4-trimetoksi-6-were)(2,6-dichloro-4-trifluoromethyl-3-pyridyl)methanol obtained in stage (a) and dissolved in 140 ml of toluene, followed by stirring at boiling under reflux under heating for 6 hours. The mixture is cooled, then filtered and the toluene is distilled off under reduced pressure, obtaining 4.4 g (yield 81%) of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2,6-dichloro-4-triptoreline connection # 3; TPL 81-83°).

Example of getting 2

Obtaining 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2-chloro-4-triptoreline (compound No. 11) and 3-(2,3,4-trimetoksi-6-methylbenzoyl)-4-triptoreline (compound No. 7)

2.4 ml (17 mmol) of triethylamine and 0.3 g of 5% palladium-on-coal added to a solution containing 3.4 g (8.0 mmol) of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2,6-dichloro-4-triptoreline (compound No. 3)obtained in the example of obtaining 1, dissolved in 50 ml of methanol, with sleduyushim by stirring in an atmosphere of hydrogen for 6.5 hours. The mixture is filtered, add to it 50 ml of water and the methanol is distilled off under reduced pressure. Conduct extraction with ethyl acetate, the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving 1.7 g (yield 55%) of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2-chloro-4-triptoreline (compound No. 11; TPL 110-112° (C) and 1.1 g (yield 37%) of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-4-triptoreline (compound No. 7; TPL 59-62°).

Example for the preparation of 3

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2,5-dichloro-3-triptoreline (compound No. 90)

(a), 17 ml (25 mmol) of n-utility (1.5 M hexane solution) are added dropwise at 0°With the solution containing 3.6 ml (25 mmol) of Diisopropylamine dissolved in 60 ml of diethyl ether, followed by stirring for 45 minutes the Solution is cooled to -78°With, add to the resulting solution containing 6.0 g (24 mmol) of 2,3,6-trichloro-5-triptoreline dissolved in 8 ml of diethyl ether, followed by stirring for 5 min, and to the resulting add a solution containing 5.0 g (24 mmol) of 2,3,4-trimetoksi-6-methylbenzaldehyde dissolved in 12 ml of toluene, followed by stirring for 1 hour. To the mixture is added 30 ml of water is La the end of the reaction, the aqueous layer was extracted with ethyl acetate and then the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure, obtaining (2,3,4-trimetoksi-6-were)(2,3,6-trichloro-5-trifluoromethyl-4-pyridyl)methanol (TPL 131-135°).

(b) and 2.7 ml (19 mmol) of triethylamine and 0.9 g of 5% palladium-on-coal added to a solution containing (2,3,4-trimetoksi-6-were) (2,3,6-trichloro-5-trifluoromethyl-4-pyridyl)methanol obtained in stage (a), dissolved in 200 ml of methanol, followed by stirring in a hydrogen atmosphere for 14 hours. The mixture is filtered, add 30 ml of water and the methanol is distilled off under reduced pressure. Conduct extraction with ethyl acetate, the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving of 2.38 g (yield 24%) (2,3,4-trimetoksi-6-were)(2,5-dichloro-3-trifluoromethyl-4-pyridyl)methanol (So PL-165°).

(c) 14 g of manganese dioxide are added to a solution containing 3.5 g (8.2 mmol) of (2,3,4-trimetoksi-6-were)(2,5-dichloro-3-trifluoromethyl-4-pyridyl)methanol obtained in stage (b), dissolved in 100 ml of toluene, followed by stirring at boiling under reflux under heating for 6 hours. The mixture of the OHL the support, then filtered and the toluene is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, obtaining 3.1 g (yield 89%) of 4-(2,3,4-trimetoksi-6-methyl-benzoyl-2,5-dichloro-3-triptorelin (compound No. 90; TPL 106-109°).

Example 4

Obtaining 3-(4,5-dimethoxy-2-methylbenzoyl)-2-methoxy-4-triptoreline (compound No. 32)

0.9 g (16 mmol) of sodium methoxide are added to a solution containing 1.5 g (4.2 mmol) of 3-(4,5-dimethoxy-2-methylbenzoyl)-2-chloro-4-triptoreline synthesized according to the method of example obtaining 1 and dissolved in 20 ml of toluene, followed by stirring at boiling under reflux by heating for 4 hours. The mixture is cooled and then add to it 20 ml of water to the end of the reaction, the aqueous solution is extracted with ethyl acetate, the organic layer is dried over anhydrous sodium sulfate and filtered, using a cake of silica gel. The solvent is distilled off under reduced pressure, obtaining 1.5 g (yield 99%) of 3-(4,5-dimethoxy-2-methylbenzoyl)-2-methoxy-4-triptoreline (connection # 32; TPL 125-127°).

Example of getting 5

Obtain 3-[4,5-(methylenedioxy)-2-methylbenzoyl]-2-chloro-4-triptoreline (compound No. 13)

(a) 3.2 ml (62 mmol) of bromine are added dropwise at 0°With the solution containing 7.0 ml (58 mmol) of 3,4-(methylenedi the XI)toluene and 5.5 ml (68 mmol) of pyridine, dissolved in 110 ml of dichloromethane, followed by stirring for 30 min, and the temperature was raised to room temperature, followed by stirring for 22 hours. The mixture was washed with aqueous sodium hydroxide solution, dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, obtaining 13 g (yield 99%) of 2-bromo-4,5-(methylenedioxy)toluene.

(b) 13 ml (20 mmol) n-utility (1.5 M hexane solution) are added dropwise at -78°to a solution containing 4.0 g (19 mmol) of 2-bromo-4,5-(methylenedioxy)toluene, dissolved in 50 ml of tetrahydrofuran, followed by stirring for 30 min, and the obtained add 1.5 ml (19 mmol) of dimethylformamide, followed by stirring for 70 minutes To the mixture is added 30 ml of water to the end of the reaction and the tetrahydrofuran is distilled off under reduced pressure. Conduct extraction with chloroform, the organic layer is dried over anhydrous sodium sulfate, filtered, using a cake of silica gel, and the solvent is distilled off under reduced pressure, obtaining 3.1 g (yield 99%) of 2-methyl-4,5-(methylenedioxy)benzaldehyde (TPL 84-86°).

(c) Using 1.5 g (8.3 mmol) of 2-chloro-4-triptoreline and 1.4 g (8.2 mmol) of 2-methyl-4,5-(methylenedioxy)benzaldehyde according to the method of the stud and (a) example of getting 1 obtain 2.1 g (yield 73%) of (2-methyl-4,5-(methylenedioxy)phenyl)(2-chloro-4-trifluoromethyl-3-pyridyl)methanol (TPL 127-130°).

(d) Using 1.5 g (4.3 mmol) of (2-methyl-4,5-(methylenedioxy)phenyl)(2-chloro-4-trifluoromethyl-3-pyridyl)methanol obtained in stage (C), and 8.0 g (92 mmol) of manganese dioxide according to the method of stage (b) example of receive 1 receive 0.3 g (yield 22%) of 3-[4,5-(methylenedioxy)-2-methylbenzoyl]-2-chloro-4-triptoreline (compound No. 13; TPL 119-122°).

An example of obtaining 6

Obtain 3-(5-benzyloxy-4-methoxy-2-methylbenzoyl)-2-chloro-4-triptoreline (compound No. 27)

(a) a Solution of 2-methoxy-4-METHYLPHENOL (6,91 g) in dimethylformamide (15 ml) was added dropwise to a suspension of sodium hydride (2.4 g) in dimethylformamide (20 ml) under ice cooling, followed by stirring for 30 minutes To obtained is added dropwise dimethylformamide (15 ml) solution of benzylbromide (9,41 g) and received to add a catalytic amount of tetrabutylammonium, followed by stirring at the same temperature for 30 minutes the Temperature was raised to room temperature and stirring is continued over night. The reaction solution was poured into water (250 ml) and extracted with ethyl acetate (100 ml) three times. An ethyl acetate phase washed with water (100 ml) three times and then washed with an aqueous solution of sodium chloride (100 ml). After drying over magnesium sulfate the solvent is distilled off under reduced pressure, the residue is purified on a chromatographic column with silica the LEM (hexane-ethyl acetate), receiving 11.4 g of 4-benzyloxy-3-methoxytoluene (TPL 38-39° (C) quantitatively, and the structure of the product is confirmed using a range of nuclear magnetic resonance.

(b) 4-benzyloxy-3-methoxytoluene (8.0 g) is dissolved in dimethylformamide (30 ml) and to the resulting added dropwise dimethylformamide solution (15 ml) of N-bromosuccinimide (6,36 g), followed by stirring at room temperature over night. The reaction solution was poured into ice water (400 ml) and precipitated in the precipitated crystals are collected by filtration, adequately washed with water and dried over night, receiving at 10.64 g of 4-benzyloxy-2-bromo-5-methoxytoluene (TPL 110-111° (C) almost quantitatively, and the structure of this compound is confirmed by using the spectrum of nuclear magnetic resonance.

(c) Hexane solution (17 ml) n-utility added dropwise to tertrahydrofuran ring solution (190 ml) of 4-benzyloxy-2-bromo-5-methoxytoluene (7,83 g) at -78°C for 20 min, followed by stirring at the same temperature for 1 hour. To the resulting added dropwise tertrahydrofuran ring solution (10 ml) dimethylformamid Yes (of 3.73 g) at -78°C, followed by stirring at the same temperature for 1 hour. The temperature is gradually increased to room temperature, and stirring is continued over night. The reaction solution was poured the aqueous solution of ammoniaand (200 ml) and extracted with ethyl acetate (150 ml) twice. An ethyl acetate phase is washed with an aqueous solution of sodium chloride (100 ml) twice, dried over magnesium sulfate and the solvent is distilled off under reduced pressure. The residue is purified on a chromatographic column with silica gel (hexane-ethyl acetate), obtaining 3,14 g (yield 48%) of 5-benzyloxy-4-methoxy-2-methylbenzaldehyde (TPL 107-109° (C), and its structure is confirmed using a range of nuclear magnetic resonance.

(d) Hexane solution (11,4 ml) n-utility added dropwise to tertrahydrofuran ring solution (45 ml) Diisopropylamine (2,81 g) at 0°C, followed by stirring for 1 hour to obtain tertrahydrofuran ring solution sitedisability. The solution is cooled to -50°and received gradually add tertrahydrofuran ring solution (7.5 ml) of 2-chloro-4-triptoreline (2,81 g), followed by stirring at the same temperature for 30 minutes the Solution is cooled to -78°and received gradually add tertrahydrofuran ring solution (37.5 ml) of 5-benzyloxy-4-methoxy-2-methylbenzaldehyde (of 3.97 g), followed by stirring at the same temperature for 1 hour. To the resulting add saturated aqueous solution of ammoniaand (50 ml), the temperature was raised to room temperature, the mixture was poured into saturated aqueous sodium bicarbonate solution (50 ml), extracted with ethyl acetate (150 ml) twice. This is acetato phase is washed with an aqueous solution of sodium chloride (100 ml), dried over magnesium sulfate and the solvent is distilled off under reduced pressure. The residue is purified on a chromatographic column with silica gel (hexane-ethyl acetate), obtaining 6,48 g (yield 96%) of (5-benzyloxy-4-methoxy-2-were)(2-chloro-4-trifluoromethyl-3-pyridyl)methanol as a red-yellow oily substance, the structure of which is confirmed by using the spectrum of nuclear magnetic resonance.

(e) (5-benzyloxy-4-methoxy-2-were)(2-chloro-4-trifluoromethyl-3-pyridyl) methanol (5.9 g) was dissolved in a mixed solvent consisting of anhydrous methylene chloride (50 ml) and acetonitrile (5 ml), and obtained consistently add tetrapropylammonium (95 mg), N-methylmorpholin-N-oxide (2.38 g) and molecular sieves 4A (6.8 g), followed by stirring in a stream of argon at room temperature for three nights. The reaction mixture was distilled off under reduced pressure, the resulting residue is suspended in methylene chloride and filtered through celite; the remainder appropriately washed with methylene chloride (200 ml). The solvent is distilled off under reduced pressure, and the residue is purified on a chromatographic column with silica gel (hexane-ethyl acetate), obtaining the is 4.93 g (yield 84%) of 3-(5-benzyloxy-4-methoxy-2-methylbenzoyl)-2-chloro-4-triptoreline (compound No. 27; TPL 116-117° (C), the structure of which is confirmed by using the SP is Ctra nuclear magnetic resonance.

Example of getting 7

Obtaining 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2-methylthio-4-triptoreline (compound No. 50)

Meantioned sodium (0.32 g) is added to dimethylformamide solution (15 ml) 0.9 g of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2-chloro-4-triptoreline (compound No. 11) at room temperature, followed by stirring for 1 hour. The mixture was poured into water (50 ml) and extracted with ethyl acetate. An ethyl acetate phase is dried over sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified on a chromatographic column with silica gel (hexane-ethyl acetate)to give 0.54 g (yield 58%) of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2-methylthio-4-triptoreline (compound No. 50; pale yellow oily substance), the structure of which is confirmed by using the spectrum of nuclear magnetic resonance.

Example obtain 8

Getting 5-(2,3,4-trimetoksi-6-methylbenzoyl)-3-acetyl-2, 6-dichloro-4-triptoreline (compound No. 62)

(a) and 9.6 ml (14 mmol) of n-utility (1.5 M hexane solution) are added dropwise to tertrahydrofuran ring (16 ml) solution of 2.0 ml (14 mmol) of Diisopropylamine at 0°C, followed by stirring for 30 minutes the Solution is cooled to -50°to the add tertrahydrofuran ring (11 ml) solution of 2.9 g (7 mmol) of (2,3,4-trimetoksi-6-were)(2,6-dichloro-4-trifluoromethyl-3-pyridyl)methanol is followed by stirring for 30 min, then the solution is cooled to -78°and received to add an excessive amount of acetaldehyde followed by stirring for 2 hours. To the mixture is added 30 ml of water to the end of the reaction, the tetrahydrofuran is distilled off under reduced pressure. The mixture is extracted with ethyl acetate, the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving 2.5 g (yield 78%) (2,3,4-trimetoksi-6-were)(2,6-dichloro-5-(1-hydroxyethyl)-4-trifluoromethyl-3-pyridyl)methanol.

(b) 10 g of manganese dioxide are added to toluene (80 ml) solution of 2.3 g (5 mmol) of (2,3,4-trimetoksi-6-were)(2,6-dichloro-5-(1-hydroxyethyl)-4-trifluoromethyl-3-pyridyl)methanol obtained in stage (a), followed by stirring at boiling under reflux by heating for 1 hour. The reaction solution is cooled to room temperature, then filtered, and the toluene is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving 1.5 g (yield 66%) of 5-(2,3,4-trimetoksi-6-methylbenzoyl)-3-acetyl-2,6-dichloro-4-triptoreline (compound No. 62; TPL 109-112°).

Example of getting 9

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2-chloro-3-t is iformity-5-methoxypyridine (compound No. 123)

(a) 70,0 ml (106 mmol) of n-utility (1.5 M hexane solution) is added dropwise to a solution of 15.0 ml (107 mmol) of Diisopropylamine in diethyl ether (120 ml) at 0°C, followed by stirring for 1 hour. The solution is cooled to -78°to the add a solution of 22.1 g (102 mmol) of 2,3-dichloro-5-triptoreline in diethyl ether (10 ml) followed by stirring for 30 min and then add to the resulting toluene solution (40 ml) to 21.0 g (100 mmol) of 2,3,4-trimetoksi-6-methylbenzaldehyde, followed by stirring for 2 hours. To the mixture is added 30 ml of water to the end of the reaction, the aqueous layer was extracted with ethyl acetate and then the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving 24.8 g (yield 58%) (2,3,4-trimetoksi-6-were)(2,3-dichloro-5-trifluoromethyl-4-pyridyl)methanol (TPL 95-98°).

(b) 2.1 g of 5% palladium-on-coal added to a methanol solution (200 ml) 24.8 g (58,1 mmol) (2,3,4-trimetoksi-6-were)(2,3-dichloro-5-trifluoromethyl-4-pyridyl)methanol obtained in stage (a), and 9.50 ml (68.2 mmol) of triethylamine, followed by stirring in an atmosphere of hydrogen for 4 hours. The mixture is filtered, add to it 50 ml of water and the methanol is distilled off under reduced is the making. The aqueous layer was extracted with ethyl acetate and the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving 15.9 g (yield 70%) (2,3,4-trimetoksi-6-were)(3-chloro-5-Cryptor-methyl-4-pyridyl)methanol (TPL 102-105°).

(c) 45 g of manganese dioxide is added to the toluene solution (220 ml) 15.9 g (40,6 mmol) (2,3,4-trimetoksi-6-were) (3-chloro-5-trifluoromethyl-4-pyridyl)methanol obtained in stage (b), followed by stirring at boiling under reflux under heating for 2 hours. The mixture is filtered and the solvent is distilled off under reduced pressure, obtaining 14.9 g (yield 94%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-chloro-5-triptoreline (compound No. 102; TPL 75-77°).

(d) to 16.4 g (304 mmol) of sodium methoxide is added to the toluene solution (150 ml) of 18.5 g (47,5 mmol) 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-chloro-5-triptoreline obtained in stage (C), and 16.6 ml (95,4 mmol) hexamethylphosphorotriamide, followed by stirring at boiling under reflux by heating for 30 minutes To the mixture, water is added to the end of the reaction, the aqueous layer was extracted with ethyl acetate and the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent distillate is ut under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving of 11.7 g (yield 64%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-methoxy-5-triptoreline (compound No. 122; TPL 103-106°).

(e) of 6.1 g (28 mmol) of m-chloroperbenzoic acid (m-SRV) add to chloroformate solution (100 ml) 5.6 g (15 mmol) 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-methoxy-5-triptoreline (compound No. 122) at 0°C, followed by stirring at room temperature for 18 hours. The reaction solution was washed with a saturated aqueous solution of sodium hydroxide and the solvent is distilled off under reduced pressure, obtaining 5.8 g (yield 99%) 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-methoxy-5-triptorelin-N-oxide (TPL 128-134°).

(f) 1.8 ml (19 mmol) of phosphorus oxychloride is added to 4 ml of toluene and 8 ml of dimethylformamide at 0°C, followed by stirring for 10 min, and to the resulting add 4.0 g (10 mmol) 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-methoxy-5-triptorelin-N-oxide, followed by stirring for 20 minutes Stirring is carried out at room temperature for 2 hours, and then the reaction solution was poured into ice-cold water to complete the reaction. The aqueous layer was extracted with ethyl acetate, then the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled PR is the reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving 3.57 g (yield 85%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2-chloro-3-trifluoromethyl-5-methoxypyridine (compound No. 123; TPL 117-119°).

Example 10

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2-bromo-3-trifluoromethyl-5-methoxypyridine (compound No. 124)

Using 7.2 g (18 mmol) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-methoxy-5-triptorelin-N-oxide, 7 ml of toluene and 17 ml of dimethylformamide and 10 g (35 mmol) of bronocice phosphorus, by way of example, the receiving stage 9 (f) obtain 4.1 g (yield 49%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2-bromo-3-trifluoromethyl-5-methoxypyridine (compound No. 124; TPL 145-147°).

Example of getting 11

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2,3,5-trichloropyridine (compound No. 186)

(a) and 17.2 ml (to 26.7 mmol) n-utility (of 1.56 M hexane solution) is added dropwise to a solution of 2.7 g (to 26.7 mmol) Diisopropylamine in diethyl ether (20 ml) at 0°C, followed by stirring for 1 hour. The solution is cooled to -78°With, to the obtained toluene are added dropwise a solution of 4.8 g (to 26.7 mmol) of 2,3,5-trichloropyridine and then to the obtained toluene are added dropwise a solution of 5.0 g (24,0 mmol) of 2,3,4-trimetoksi-6-methylbenzaldehyde, followed by stirring for 30 minutes the Temperature is brought to room temperature and remesiana carry out further for 1 hour. To the mixture is added 30 ml of water to the end of the reaction, and extraction add ethyl acetate. The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, gaining 6.7 g (yield 72%) of amorphous (2,3,4-trimetoksi-6-were)(2,3,5-trichloro-4-pyridyl)methanol.

(b) 16.2 g of manganese dioxide is added to the toluene solution (180 ml) 5.6 g (2,3,4-trimetoksi-6-were)(2,3,5-trichloro-4-pyridyl)methanol obtained in stage (a), followed by stirring at boiling under reflux under heating for 3 hours. After the mixture is cooled, it is filtered and the solvent is distilled off under reduced pressure, obtaining 4.7 g (yield 87%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2,3,5-trichloropyridine (compound No. 186; TPL 60-61°).

Example 12

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)for 3,5-dichloropyridine (compound No. 191)

4.6 g (6,9 mmol) of triethylamine and 1.8 g of 10% palladium-on-coal added to a methanol solution (280 ml) of 17.8 g (4.6 mmol) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2,3,5-trichloropyridine (compound No. 186), followed by stirring in an atmosphere of hydrogen at room temperature for 7 hours. The mixture is filtered and the solvent is distilled off under reduced pressure. Obtained the way the crude product is purified on a chromatographic column with silica gel, getting 11.6 g (yield 72%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)for 3,5-dichloropyridine (compound No. 191; TPL 109-111°).

Example of getting 13

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-chloro-5-methoxypyridine (compound No. 244)

5.0 g (2.8 mmol) of hexamethylphosphorotriamide and 1.1 g (2.1 mmol) of sodium methoxide is added to the toluene solution (60 ml) 5.0 g (1.4 mmol) 4-(2,3,4-trimetoksi-6-methylbenzoyl)for 3,5-dichloropyridine (compound No. 191), followed by stirring at boiling under reflux under heating for 5 hours. After the mixture is cooled, add to it 50 ml of water to complete the reaction and add to the resulting ethyl acetate for extraction. The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, obtaining 3.4 g (yield 69%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-chloro-5-methoxypyridine (compound No. 244; pale yellow oily substance).

Example of getting 14

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2,3-dichloro-5-methoxypyridine (compound No. 193)

(a) Chloroformate (60 ml) solution of 3.4 g (1 mmol) 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-chloro-5-methoxypyridine (compound No. 244) is cooled with ice, to the resulting added 4.1 g (1.6 mmol) of m-chloroperbenzoic acid with the respective stirring under ice cooling for 2 hours, and stirring is continued at room temperature for 2 hours. To the mixture is added 30 ml of 0.5 mol/l aqueous solution of sodium hydroxide to the end of the reaction, the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure, obtaining 3.5 g (yield 85%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-chloro-5-methoxypyridine-N-oxide (So pl. 160-166°).

(b) 5 ml of dimethylformamide is added to 2.5 ml of toluene, the mixture is cooled with ice and add to it dropwise 1.3 ml (1.4 mmol) of phosphorus oxychloride. The mixture is stirred under ice cooling for 10 minutes, to the resulting add 2.5 g (0.7 mmol) 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-chloro-5-methoxypyridine-N-oxide. After the mixture is stirred under ice cooling for 30 min, the temperature was adjusted to room temperature, followed by stirring for 2 hours. To the mixture is added 30 ml of water to complete the reaction and add to the resulting ethyl acetate for extraction. The organic layer is dried over anhydrous sodium sulfate, filtered and purified through column chromatography with silica gel, obtaining 2.0 g (yield 76%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2,3-dichloro-5-methoxypyridine (compound No. 193; TPL 98-99°).

Example get 15

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2-bromo-3-chloro-5-methoxypyridine (compound No. 245)

5 ml dim teleformula added to 2.5 ml of toluene, the mixture is cooled with ice and add to it dropwise 0.7 g (0.2 mmol) of oxybromide phosphorus. After the mixture is stirred under ice cooling for 10 minutes, to the resulting type of 0.42 g (0.1 mmol) 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-chloro-5-methoxypyridine-N-oxide obtained in example obtain 14(a). After the mixture is stirred under ice cooling for 30 min, the temperature was adjusted to room temperature, followed by stirring for 2 hours. To this mixture 10 ml of water to complete the reaction and add to the resulting ethyl acetate to effect the extraction. The organic layer is dried over anhydrous sodium sulfate, filtered and purified through column chromatography with silica gel, getting 0.32 g (yield 65%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-2-bromo-3-chloro-5-methoxypyridine (compound No. 245; TPL 97-99°).

Example 16

Getting 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-bromo-5-methylpyridine (compound No. 228)

(a) to 57.0 ml (88,9 mmol) n-utility (of 1.56 M hexane solution) is added dropwise to a solution of 12.5 ml of 89.2 mmol) Diisopropylamine in dietpower ether (110 ml) at 0°C, followed by stirring for 60 minutes the Solution is cooled to -78°With, add to the resulting toluene (80 ml) solution of 20 g (85 mmol) of 3,5-dibromopyridine, followed by stirring for 5 min, and then to policenauts toluene (50 ml) solution 21,0 g (100 mmol) of 2,3,4-trimetoksi-6-methylbenzaldehyde, followed by stirring for 2 hours. To the mixture is added 50 ml of water to the end of the reaction, the aqueous layer was extracted with ethyl acetate, and the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, getting to 11.8 g (yield 31%) (2,3,4-trimetoksi-6-were)(3,5-dibromo-4-pyridyl)methanol (yellow oily substance).

(b) tertrahydrofuran ring (15 ml) solution of 2.0 g (4.6 mmol) of (2,3,4-trimetoksi-6-were)(3,5-dibromo-4-pyridyl)methanol obtained in stage (a), cooled to -78°C, K obtained are added dropwise to 6.0 ml (9.4 mmol) of n-utility (of 1.56 M hexane solution), followed by stirring for 5 min, and the obtained add 0.5 ml (8.0 mmol) under the conditions, followed by stirring for 2.5 hours. Add 20 ml of water and the tetrahydrofuran is distilled off under reduced pressure. The aqueous layer was extracted with ethyl acetate, the organic layer is dried over anhydrous sodium sulfate, filtered and the solvent is distilled off under reduced pressure. Thus obtained crude product was then purified through column chromatography with silica gel, receiving of 0.44 g (yield 25%) (2,3,4-trimetoksi-6-were)(3-bromo-5-methyl-4-pyridyl)methanol.

(c) 3 g of manganese dioxide are added to toluene (30 ml) solution of 0.43 g (1.1 mmol) of (2,3,4-trimetoksi-6-methyl is enyl) (3-bromo-5-methyl-4-pyridyl)methanol obtained in stage (b), followed by stirring at boiling under reflux under heating for 2 hours. The mixture is filtered, the solvent is distilled off under reduced pressure, and the thus obtained crude product was then purified through column chromatography with silica gel, getting to 0.23 g (yield 54%) of 4-(2,3,4-trimetoksi-6-methylbenzoyl)-3-bromo-5-methylpyridin (connection # 228; TPL 88-93°).

Example of getting 17

Obtaining 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2,6-dichloro-4-methylpyridine (compound No. 320)

(a)Synthesis of 3-cyano-2,6-dichloro-4-methylpyridine

The mixture was 4.76 g (32 mmol) of 3-cyano-2,6-dihydroxy-4-methylpyridine and 26 g (133 mmol) of dichloride of phenylphosphonic acid was stirred at 150°C for 2 days. The reaction mixture was poured into ice water (200 ml) and filtered through celite followed by rinsing with toluene (100 ml). The aqueous layer was twice extracted with ethyl acetate (100 ml) and combined with the organic layer, followed by washing with water (100 ml) (twice) and saturated aqueous sodium chloride (100 ml), dried over magnesium sulfate and drove away the solvent under reduced pressure. The residue was purified column chromatography on silica gel (hexane-ethyl acetate) to obtain the 5.45 g of pale yellow crystals of 3-cyano-2,6-dichloro-4-methylpyridine.1H-NMR (400 MHz, Dl3): δ (ppm) at 2.59 (s, 3H), 7,28 (s, 1H).

(b) Sintez,6-dichloro-3-formyl-4-methylpyridine

1.54 g (8,23 mmol) of 3-cyano-2,6-dichloro-4-methylpyridine was dissolved in methylene chloride (40 ml), cooled to -70°and then slowly dropwise added a toluene solution (1M, 10 ml) hydride diisobutylaluminum. After stirring at -78°C for 15 minutes, the liquid temperature was raised to room temperature and continued stirring overnight. Because the original substance have not been fully consumed, the liquid was again cooled to -78°again added a toluene solution of hydride diisobutylaluminum and continued stirring at -78°C for 15 minutes and at room temperature over night. The reaction mixture was poured into 1N. hydrochloric acid solution and three times were extracted with methylene chloride (50 ml). Methylenchloride layer was sequentially washed with a saturated solution of sodium bicarbonate (100 ml), saturated aqueous sodium chloride (100 ml) and dried over magnesium sulfate, and then drove away the solvent under reduced pressure. The residue was purified column chromatography on silica gel (hexane-ethyl acetate) to obtain the 0,81 g of 2,6-dichloro-3-formyl-4-methylpyridine.1H-NMR (400 MHz, Dl3): δ (ppm) 2,60 (s, 3H), 7,20 (s, 1H), 10,52 (s, 1H).

(C) Synthesis of (2,3,4-trimetoksi-6-were)(2,6-dichloro-4-methyl-3-pyridyl)methanol (Intermediate compound No. 302)

A solution of 3,4,5-trimetoksi-2-brontolo the La (1,53 g, 5.9 mmol) in tetrahydrofuran (25 ml) was cooled to -78°and was added dropwise n-BuLi (1.5 M solution in hexane, 4 ml) followed by stirring at the same temperature for 40 minutes to obtain 2,3,4-trimetoksi-6-methylphenylene. Then thereto was added dropwise a solution of 2,6-dichloro-3-formyl-4-methylpyridine (0,93 g, 4.9 mmol) in tetrahydrofuran (5 ml) followed by stirring at -78°C for 1 hour. For completion of the reaction was added saturated aqueous solution of ammonium chloride (15 ml) and the temperature of the reaction mixture was raised to room, then the reaction mixture was poured into saturated sodium bicarbonate solution and twice were extracted with ethyl acetate (100 ml). An ethyl acetate layer was washed saturated aqueous sodium chloride (100 ml), dried over magnesium sulfate and drove away the solvent under reduced pressure. The residue was purified by chromatography on silica gel (hexane-ethyl acetate) to give 0.73 g of pale yellow oily (2,3,4-trimetoksi-6-were)(2,6-dichloro-4-methyl-3-pyridyl)methanol.1H-NMR (400 MHz, Dl3): δ (ppm) of 2.20 (s, 3H), 2,41 (s, 3H), 3.46 in (s, 3H), of 3.77 (s, 3H), of 3.80 (s, 3H), of 6.26 (d, J=6,4 Hz, 1H), 6,46 (s, 1H), 7,03 (s, 1H).

(d) Synthesis of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2,6-dichloro-4-methylpyridine

1.06 g (2,85 mmol) (2,3,4-trimetoksi-6-were)(2,6-dichloro-4-methyl-3-pyridyl)methanol was dissolved in toluene (50 ml) and added to 4.23 g (clean the TA: 88%, 42.8 mmol) of manganese dioxide followed by heating for 5 hours at boiling temperature under reflux. The liquid was allowed to cool and the reaction mixture was filtered through celite, and then the residue was washed with ethyl acetate (100 ml). The filtrate and wash solution were combined and the solvent is kept under reduced pressure, followed by purification column chromatography on silica gel (hexane-ethyl acetate) to obtain the 0,81 g of pale yellow oily 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2,6-dichloro-4-methylpyridine.1H-NMR (400 MHz, Dl3): δ (ppm) 2,31 (s, 3H), of 2.45 (s, 3H), of 3.32 (s, 3H), of 3.73 (s, 3H), 3,88 (s, 3H), 6,56 (s, 1H), 7,18 (s, 1H).

Example of getting 18

Obtaining 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2,5-dichloro-4-methylpyridine (Compound No. 321)

(a) Synthesis of 2-amino-3-bromo-5-chloropyridine

25,34 g (197 mmol) of 2-amino-5-chloropyridine and 16,16 g (197 mmol) of sodium acetate was dissolved in 120 ml of acetic acid and was heated to 43°S, then for 1.5 hours was added dropwise at a temperature of 43-45°From 31.5 g (10,2 ml, 197 mmol) of bromine in acetic acid (10 ml). The reaction mixture was allowed to cool, and then it was poured into ice water, the solution was made weakly alkaline (pH 8-9) by adding 1 n sodium hydroxide (200 ml)and then solid sodium hydroxide and was extracted with 100 ml ethyl acetate (5 times). An ethyl acetate layers were combined, sequentially industry is Ali twice 100 ml of 10% aqueous solution of sodium sulfite and 100 ml saturated aqueous solution of sodium chloride, was dried over sodium sulfate and filtered. The solvent drove under reduced pressure to get 40,0 g of the crude crystals of 2-amino-3-bromo-5-chloropyridine.

1H-NMR (400 MHz, Dl3): δ (ppm) to 4.98 (user., 2N), to 7.67 (d, J=2.0 Hz, 1H), of 7.97 (d, J=2.0 Hz, 1H).

(b) Synthesis of 3-bromo-5-chloro-2-hydroxypyridine

40,0 g of the crude crystals of 2-amino-3-bromo-5-chloropyridine was dissolved in a solution of concentrated hydrochloric acid (52 ml) in water (326 ml) and cooled in a bath of ice - sodium chloride. While maintaining the solution temperature below -1°gradually over a period of 80 minutes was added dropwise an aqueous solution (109 ml) of 13.6 g of sodium nitrite (purity 98%, 193 mmol) and the reaction mixture was stirred for 20 minutes at 0°and then overnight at room temperature. The obtained crystals were collected by filtration, washed with 100 ml of water and then 100 ml of hexane and dried at 40°With under reduced pressure to get 28,86 g of the crude crystals of 3-bromo-5-chloro-2-hydroxypyridine.

(c) Synthesis of 3-bromo-2,5-dichloropyridine

28,86 g of the crude crystals of 3-bromo-5-chloro-2-hydroxypyridine was dissolved in 35 ml of dimethylformamide and gradually within 4 hours was added dropwise and 31.7 g (19.3 ml) of phosphorus oxychloride. The reaction mixture was heated to 70°C and stirred at the same temperature for 3 days. After the mixture javalikecalc, it was poured into ice water (500 ml) and the resulting crystals were collected by filtration, washed sufficiently 300 ml of water and dried at room temperature and reduced pressure for 8 hours and after slightly noticeable sublimation) at atmospheric pressure for 1 week with getting 21,33 g of the crude crystals of 3-bromo-2,5-dichloropyridine.

1H-NMR (400 MHz, Dl3): δ (ppm) of 7.95 (d, J=2.0 Hz, 1H), 8,32 (d, J=2.0 Hz, 1H).

(d) Synthesis of 2,5-dichloro-3-formylpyridine

10.0 g (to 44.1 mmol) 3-bromo-2,5-dichloropyridine in anhydrous diethyl ether (250 ml) was cooled to -78°in argon atmosphere and gradually dropwise added to 29.4 ml of n-utility (1.5 M solution in hexane, to 44.1 mmol). The resulting mixture was stirred at -78°C for 1 hour. To the obtained solution of 2,5-dichloro-3-pyridyldithio gradually dropwise added with 3.27 g (to 44.1 mmol) ethylformate in 20 ml of anhydrous diethyl ether and the resulting mixture was stirred at -78°C for 2 hours. After confirming the completion of reaction by TLC the reaction was completed by adding to the reaction mixture of 23 ml of a saturated aqueous solution of ammonium chloride, and then 200 ml of water. After heating to room temperature the reaction mixture 3 times was extracted with 150 ml of ethyl acetate and an ethyl acetate layers were combined, washed with 200 ml saturated aqueous solution of sodium chloride, sushi is whether over sodium sulfate and filtered. The solvent is kept under reduced pressure and the residue was purified on a column of silica gel with getting 4.83 g of 2,5-dichloro-3-formylpyridine (yield 62%).

1H-NMR (400 MHz, Dl3): δ (ppm) 8,18 (d, J=2.4 Hz, 1H), 8,56 (d, J=2.4 Hz, 1H), 10,38 (s, 1H).

(e) Synthesis of 2,5-dichloro-3-dimethoxypyrimidine

8,55 g (to 48.6 mmol) of 2,5-dichloro-3-formylpyridine was dissolved in 60 ml of methanol and heated for 12 hours with 15,47 g (146 mmol) of meteorophobia and 0.61 g (2.4 mmol) of p-toluensulfonate pyridinium while boiling under reflux. After cooling, volatiles drove away under reduced pressure, mixed with 100 ml of water and 3 times was extracted with 100 ml of ethyl acetate. An ethyl acetate layers were combined, dried over magnesium sulfate, filtered and the solvent drove away under reduced pressure. The residue was purified on a column of silica gel with getting 9.60 g of 2,5-dichloro-3-dimethoxypyrimidine (yield 89%).

1H-NMR (400 MHz, Dl3): δ (ppm) 3,40 (C, 6N), 5,52 (s, 1H), 7,94 (d, J=2.4 Hz, 1H), with 8.33 (d, J=2.4 Hz, 1H).

(f) Synthesis of 2,5-dichloro-3-dimethoxymethyl-4-methylpyridine

5.0 g (to 22.5 mmol) of 2,5-dichloro-3-dimethoxypyrimidine was dissolved in 100 ml of anhydrous tetrahydrofuran and cooled to -78°in argon atmosphere, and then was added dropwise to 26.3 ml finelite (0,94 M solution in cyclohexane-diethyl ether, to 24.7 mmol). The resulting mixture was stirred at -78°With those who tell 4 hours from receipt of 2,5-dichloro-3-dimethoxymethyl-4-pyridyldithio. Then was added dropwise to 6.39 g (45 mmol) under the conditions in 25 ml of tetrahydrofuran and the mixture was stirred at -78°C for 1 hour and then overnight at room temperature. After adding 100 ml of water the reaction mixture was extracted with 3 times 100 ml of ethyl acetate. An ethyl acetate layers were combined, washed with saturated aqueous sodium chloride, dried over magnesium sulfate and filtered. The solvent is kept off and the residue was purified on a column of silica gel to obtain 0.51 g of 2,5-dichloro-3-dimethoxymethyl-4-methylpyridine (output of 9.6%).

1H-NMR (400 MHz, Dl3): δ (ppm) to 2.57 (s, 3H), 3.46 in (C, 6N), USD 5.76 (s, 1H), of 8.27 (s, 1H).

(g) Synthesis of 2,5-dichloro-3-formyl-4-methylpyridine

0.51 g (of 2.16 mmol) of 2,5-dichloro-3-dimethoxymethyl-4-methylpyridine was dissolved in 40 ml of dimethylformamide and stirred with 20 ml of 1 N. hydrochloric acid at room temperature over night. After adding 40 ml of water the reaction mixture was neutralized with an aqueous solution of sodium hydroxide and was extracted 3 times with 50 ml diethyl ether. Diethylamine layers were combined, dried over magnesium sulfate and filtered. The solvent is kept off and the residue was purified on a column of silica gel. The purified product is then subjected deacetylases, because the NMR analysis showed the presence of a residue of the original substance. The purified product was dissolved in 1 ml acetic sour the s and was stirred at room temperature overnight. The reaction was monitored using HPLC and found that some percentage of the original substance remained unreacted. Therefore, the reaction mixture was heated at 50-60°and then, when 70-80°C. the Reaction mixture was allowed to cool and after adding 20 ml of water the reaction mixture was neutralized with an aqueous solution of sodium hydroxide and was extracted 3 times with 50 ml diethyl ether. Layers of diethyl ether were combined, washed with 3 times 50 ml of water, dried over magnesium sulfate and filtered. The solvent drove away with getting 0,22 g of 2,5-dichloro-3-formyl-4-methylpyridine.

1H-NMR (400 MHz, Dl3): δ (ppm) to 2.67 (s, 3H), 8,48 (s, 1H), 10,52 (s, 1H).

(h) Synthesis of (2,3,4-trimetoksi-6-were)(2,5-dichloro-4-methyl-3-pyridyl)methanol

To 0,30 g (1,16 mmol) 3,4,5-trimetoksi-2-bromthymol in tetrahydrofuran (6 ml), cooled to -78°C. in the argon atmosphere was added dropwise 0.75 ml of n-utility (1.5 M solution in hexane, 1.13 mmol) and the resulting mixture was stirred at this temperature for 30 minutes to obtain 2,3,4-trimetoksi-6-methylphenylene. Then was added dropwise to 0.22 g (1,16 mmol) of 2,5-dichloro-3-formyl-4-methylpyridine in tetrahydrofuran (2 ml) and the resulting mixture was stirred at -78°C for 1 hour. For completion of the reaction was added sequentially 1.5 ml of a saturated aqueous solution of ammonium chloride and 40 ml of water. The reaction is th the mixture was heated to room temperature and 3 times was extracted with 40 ml ethyl acetate. An ethyl acetate layers were combined, washed with 40 ml saturated aqueous solution of sodium chloride, dried over magnesium sulfate and filtered. The solvent is kept under reduced pressure and the residue was purified on a column of silica gel to obtain 0.14 g (2,3,4-trimetoksi-6-were)(2,5-dichloro-4-methyl-3-pyridyl)methanol (output 32,4%).

1H-NMR (400 MHz, Dl3): δ (ppm) to 2.18 (s, 3H), of 2.50 (s, 3H)and 3.59 (s, 3H), 3,81 (s, 3H) 3,85 (s, 3H), 6.42 per (user., 1H), 6,50 (s, 1H), compared to 8.26 (s, 1H).

(i) Synthesis of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-2,5-dichloro-4-methylpyridine (Compound No. 321)

0.14 g (0.38 mmol) of (2,3,4-trimetoksi-6-were)(2,5-dichloro-4-methyl-3-pyridyl)methanol was dissolved in 5 ml of toluene and heated for 2 hours with 0.67 g (6.8 mmol) of activated manganese dioxide with stirring and boiling under reflux. After the reaction mixture was allowed to cool, it was filtered through celite and the filter cake was washed sufficiently with toluene and then with ethyl acetate. The filtrate and washing liquid were combined and the solvent was removed by distillation under reduced pressure, the residue was purified on a column of silica gel to obtain 0.10 g of the desired product.

TPL 77-79°C.1H-NMR (400 MHz, Dl3): δ (ppm) is 2.37 (s, 3H), of 2.53 (s, 3H), 3,30 (s, 3H), 3,76 (s, 3H), 3,92 (s, 3H), 6,60 (s, 1H), 8,32 (s, 1H).

Example of getting 19

Obtaining 3-(2,3,4-trimetoksi-6-mative the zoilus)-5-chloro-2-methylpyridine (Compound No. 322)

(a) Synthesis of 5-chloro-3-dimethoxymethyl-2-methylpyridine

3.0 g (13.5 mmol) of 2,5-dichloro-3-dimethoxypyrimidine was dissolved in 30 ml of 1,4-dioxane and heated for 6 hours with 5.6 g (40,5 mmol) of potassium carbonate, 1.56 g (1.35 mmol) tetranitroaniline and 1.69 g of trimethylboroxine (50% solution in tetrahydrofuran, to 6.75 mmol) under stirring and boiling under reflux. Since it was detected the presence of unreacted educt was added 0.84 g (3.35 mmol) of trimethylboroxine and the reaction mixture was heated under stirring and boiling under reflux for another 6 hours. After the reaction mixture was allowed to cool, it was filtered through celite and the filter cake washed with 15 ml of ethyl acetate and 15 ml of tetrahydrofuran. The filtrate and wash liquid were combined, the solvent was removed by distillation under reduced pressure and the residue was purified on a column of silica gel with getting 0,81 g of 5-chloro-3-dimethoxymethyl-2-methylpyridine (30%yield).

1H-NMR (400 MHz, Dl3): δ (ppm) to 2.55 (s, 3H), and 3.31 (s, 6N), 5,44 (s, 1H), a 7.85 (d, J=2.4 Hz, 1H), to 8.41 (d, J=2.4 Hz, 1H).

(b) Synthesis of 5-chloro-3-formyl-2-methylpyridine

0,81 g (4 mmol) of 5-chloro-3-dimethoxymethyl-2-methylpyridine was dissolved in 1.6 ml of acetic acid and stirred at room temperature for 3 hours and then at 60-70°in the course of 23.5 hours. The reaction with whom thou gave to be cooled and, after adding 30 ml of water was neutralized with an aqueous solution of sodium hydroxide and 3 times was extracted with 50 ml diethyl ether. Diethylamine layers were combined, washed with water (50 ml), dried over magnesium sulfate and filtered. The solvent is kept under reduced pressure and the residue was purified on a column of silica gel with a mixture of desired product and educt approximately 1:1. The mixture was dissolved in 5 ml of acetic acid and stirred at 60-70°for 23.5 hours. The reaction mixture was allowed to cool, and then subjected to processing and cleaning, as described above, with the receipt of 0.30 g of 5-chloro-3-formyl-2-methylpyridine (yield 48%).

1H-NMR (400 MHz, Dl3):δ (ppm) of 2.86 (s, 3H), 8,08 (d, J=2.4 Hz, 1H), 8,65 (d, J=2.4 Hz, 1H), 10.30 a.m. (s, 1H).

(C) Synthesis of (2,3,4-trimetoksi-6-were)(5-chloro-2-methyl-3-pyridyl)methanol

To 0.50 g (1,91 mmol) 3,4,5-trimetoksi-2-bromthymol in tetrahydrofuran (10 ml), cooled to -78°C. in the argon atmosphere was added dropwise 1.3 ml of n-utility (1.5 M solution in hexane, of 1.95 mmol) and the resulting mixture was stirred at the same temperature for 30 minutes to obtain 2,3,4-trimetoksi-6-methylphenylene. Then was added dropwise to 0.30 g (1,93 mmol) 5-chloro-3-formyl-2-methylpyridine in tetrahydrofuran (3 ml) and the resulting mixture was stirred at -78°C for 2 hours. For completion of the reaction was sequentially added 26 ml of a saturated aqueous solution of ammonium chloride and 70 ml of water. The reaction mixture was heated to room temperature the s and 3 times was extracted with 70 ml of ethyl acetate. An ethyl acetate layers were combined, washed with 70 ml of saturated aqueous solution of sodium chloride, dried over magnesium sulfate and filtered. The solvent is kept under reduced pressure and the residue was purified on a column of silica gel to obtain 0.33 g (2,3,4-trimetoksi-6-were)(5-chloro-2-methyl-3-pyridyl)-methanol (yield 51,4%).

1H-NMR (400 MHz, Dl3): δ (ppm) of 2.25 (s, 3H), of 2.50 (s, 3H), of 3.64 (s, 3H), 3,81 (s, 3H), a 3.87 (s, 3H), 5,98 (d, J=7,6 Hz, 1H), of 6.52 (s, 1H), 7,75 (user., 1H), of 8.37 (d, J=2.4 Hz, 1H).

(d) Synthesis of 3-(2,3,4-trimetoksi-6-methylbenzoyl)-5-chloro-2-methylpyridine (Compound No. 322)

0.33 g (0.98 mmol) of (2,3,4-trimetoksi-6-were)(5-chloro-2-methyl-3-pyridyl)methanol was dissolved in 12 ml of toluene and heated for 2 hours under stirring and boiling under reflux with 1.73 g (17.5 mmol) of activated manganese dioxide. After the reaction mixture was allowed to cool, it was filtered through celite and the filter cake was washed sufficiently with toluene and then with ethyl acetate. The filtrate and wash liquid were combined, drove under reduced pressure to remove solvent and the residue was purified on a column of silica gel with getting 0,22 g of the desired product (yield 67%).

TPL 49-50°C.1H-NMR (400 MHz, Dl3): δ (ppm), and 2.27 (s, 3H), 2,74 (s, 3H), of 3.54 (s, 3H), 3,81 (s, 3H), 3, 92 (s, MN), to 6.58 (s, 1H), to 7.61 (d, J=2.4 Hz, 1H), 8,54 (d, J=2.4 Hz, 1H).

Example the floor is placed intermediate connection

Below is an example of obtaining 2,3,4-trimetoksi-6-methylbenzaldehyde, which is used as intermediate compounds in the above examples produce 1, 3, 9, 11 and 16.

Getting 2,3,4-trimetoksi-6-methylbenzaldehyde

128 g (0.7 mol) 3,4,5-trimethoxyphenol dissolved in dry methylene chloride (100 ml), dropwise gradually added to a solution of 112 g (0.84 mol) of aluminofluoride in dry methylene chloride (500 ml) under cooling with ice. The mixture is stirred at the same temperature for 45 min, it is gradually added dropwise to the solution at 88.5 g (0.77 mol) dichlorodimethyl ether in dry methylene chloride over 2 hours. Stirring is continued at the same temperature for 2 hours, and the mixture is gradually brought to room temperature, followed by stirring at room temperature over night. The reaction mixture is poured into 1 l of ice water, methylenchloride phase out, and the aqueous phase is twice extracted with 200 ml of methylene chloride. Extract and methylenchloride phase unite, successively washed with 200 ml water, 200 ml of saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate and the solvent is distilled off under reduced pressure. In the remainder of the injected embryos for crystallization and the resulting crystals are collected by filtration, washed with hexane and dried air is, getting 128 g of 2,3,4-trimetoksi-6-methylbenzaldehyde (TPL 55-57°).

The compounds obtained according to the methods of examples obtain 1-19 presented in the following tables 1-18.

Compounds represented by formulas (I-1) to (I-9) in the tables are the following compounds. In addition, in the tables, Me represents methyl group, Et represents ethyl group, Butyl is boutelou group, ISO-Propyl represents ISO-propyl group, Ph represents a phenyl group, Allyl represents allyl group, a Hexyl represents tsiklogeksilnogo group, Benzyl represents a benzyl group, Propargyl represents a propargyl group and Pencil is pentelow group.

Table 1
Compounds represented by formula (I-1)
No.(X)nR1(R2)mPhysical properties
1 2-Cl, 6-ClMe4’-MeO, 5’-MeOTPL 108-110°
22-Cl, 6-ClMe4’-MeO, 5’-MeTPL 123-126°
32-Cl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 81-83°
42-Cl, 6-ClMe4’-MeOColorless oily substance
5No substitutionMe4'-MeO, 5’-MeOOily yellow substance
6No substitutionMe4'-MeO, 5'-MeTPL 63-65°
7No substitutionMe4'-MeO, 5'-MeO, 6'-MeOTPL 59-62°
8No substitutionMe4’-MeOPale-yellow oily substance
92-ClMe4'-MeO, 5’-MeOTPL 82-86°
102-ClMe4'-MeO, 5'-MeTPL 86-89°
112-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 110-112°
122-ClMe4'-Me, 5'-Me, 6'-MeTPL 88-95°
132-Cl Me4',5'-(-OCH2O-)TPL 119-122°
142-ClMe4'-MeOPale-yellow oily substance
152-ClEt4'-MeO, 5'-MeO, 6'-MeO 
162-ClISO-propyl4'-MeO, 5'-MeO, 6'-MeO 
172-ClMe3'-MeO, 4'-MeO, 5’-MeO, 6'-MeO 
182-ClMe4'-MeO, 5'-EtOTPL 89-90°
192-ClMe4'-MeO, 5'-ISO-propyl-O-Pale-yellow oily substance
202-ClMe4'-MeO, 5'-Allyl-O- 
212-ClMe4'-MeO, 5'-Propargyl-O- 
222-ClMe4’-MeO, 5'-CF3CH2O- 
232-ClMe4'-MeO, 5'-Hexyl-O-TPL 85-86°

Table 2
Compounds represented by formula (I-1)
No.(X)n R1(R2)mPhysical properties
242-ClMe4'-MeO, 5'-(CH3)2N(CH2)2O- 
252-ClMe4'-MeO, 5'-CH3S(CH2)2O- 
262-ClMe4'-MeO, 5'-PhO-A viscous substance
272-ClMe4'-MeO, 5'-benzyl-O-TPL 116-117°
282-ClMe4'-MeO, 5'-CH3Soo- 
292-ClMe4'-MeO, 5'-CH3LLC- 
302-MeO, 6-MeOMe4'-MeO, 5'-MeO, 6'-MeOTPL 93-94°
312-Cl, 6-MeOMe4'-MeO, 5'-MeO, 6'-MeOTPL 85-87°
322-MeOMe4'-MeO, 5'-MeOTPL 125-127°
332-isopropyl-O-Me4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
342-CF3CH2About-Me4'-MeO, 5'-MeO, 6'-MeOTPL 80-82°
352-CH3O(CH2)2O-Me4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
362-CH3S(CH2)2About-Me4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
372-PhO-Me4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
382-benzyl-O-Me4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
392-cyclohexyl-O-Me4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
402-allyl-O-Me4'-MeO, 5'-MeO, 6'-MeOTPL 85-86°
412-propargyl-O-Me4'-MeO, 5'-MeO, 6'-MeOTPL 121-124°
422-(CH3)2N(CH2)2O-Me4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
432-Cl, 5-IUMe4'-MeO, 5'-MeO, 6'-MeOTPL 161-162°
442-Cl, 5-allylMe4'-MeO, 5'-MeO, 6'-MeO 
45Me4'-MeO, 5'-MeO, 6'-MeO 
462-Cl, 5-CH3O(C=O)-Me4'-MeO, 5'-MeO, 6'-MeO 
472-Cl, 5-CH3(C=O)-Me4'-MeO, 5'-MeO, 6'-MeOTPL 127-129°

Table 3
Compounds represented by formula (I-1)
No.(X)nR1(R2)mPhysical properties
482-Cl, 5-EtMe4'-MeO, 5'-MeO, 6'-MeO 
492-MeO, 5-MeMe4'-MeO, 5'-MeO, 6'-MeOTPL 103-105°
502-MeSMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
512-Me2NMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
522-Cl, 5-(CH3)2N (=O)-Me4'-MeO, 5'-MeO, 6'-MeO 
532-CNMe4'-MeO, 5'-MeO, 6'-MeOTPL 140-144°
54 2-Cl, 5-Cl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 114-116°
552-Cl, 5-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 149-151°
562-MeO, 5-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 100-103°
572-OH, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
582-Cl, 5-Me, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 101-104°
592-Cl, 5-allyl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
602-Cl, 5-propargyl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeO 
612-Cl, 5-CH3O(C=O)-, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 107-111°
622-Cl, 5-CH3(C=O)-, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 109-112°
632-Cl, 5-Et, 6-ClMe4'-MeO, 5'-MeO, 6'-MeO 
642-Cl, 5-(CH3)2N (=O)-Me4'-MeO, 5'-MeO, 6'-MeO 
655-MeMe4'-MeO, 5'-MeO, 6'-MeOPale yellow oily the e substance
665-allylMe4'-MeO, 5'-MeO, 6'-MeO 
675-propargylMe4'-MeO, 5'-MeO, 6'-MeO 
685-CH3O(C=O)-Me4'-MeO, 5'-MeO, 6'-MeO 
695-CH3(C=O)-Me4'-MeO, 5'-MeO, 6'-MeOTPL 110-113°
705-EtMe4'-MeO, 5'-MeO, 6'-MeO 

Table 4
Compounds represented by formula (I-1)
No.(X)nR1(R2)mPhysical properties
715-(CH3)2N (=O)-Me4'-MeO, 5'-MeO, 6'-MeO 
722-CH3O(CH2)2O-,Me4'-MeO, 5'-MeOTPL 77-81°
     
742-MeOMe4'-MeO, 5'-MeO, 6'-MeOTPL 81-82°
752-EtOMe 4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
762-MeSMe4'-MeO, 5'-MeO, 6'-MeOTPL 98-102°
772-OHMe4'-MeO, 5'-MeO, 6'-MeOTPL 167-173°
782-NH2Me4'-MeO, 5'-MeO, 6'-MeOTPL 115-118°
792-CH3NHMe4'-MeO, 5'-MeO, 6'-MeOTPL 150-157°
802-CH3SooMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
812-isopropyl-OMe4'-MeO, 5'-MeO, 6'-isopropyl-O-Pale-yellow oily substance
822-Cl, 6-ClEt4'-MeO, 5'-MeO, 6'-MeOTPL 105-108°
832-ClMe4'-MeO, 5'-(4-MeO-benzyl)-O-TPL 123-125°
842-MeMe4'-MeO, 5'-MeO, 6'-MeOTPL 100-103°
852-Me, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
862-Me, 5-BrMe4'-MeO, 5'-MeO, 6'-MeO 
Table 5
Compounds represented by formula (I-2)
No.(X)nR1(R2)mPhysical properties
872-PhO, 5-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 147-150°
882-OH, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 

Table 6
Compounds represented by formula (I-2)
No.(X)nR1(R2)mPhysical properties
892-Cl, 5-ClMe4'-MeO, 5'-MeOTPL 120-125°
902-Cl, 5-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 106-109°
91No substitutionMe4'-MeO, 5'-MeOTPL 98-101°
92No substitutionMe4'-MeO, 5'-MeO, 6'-MeOTPL 104-107°
932-MeO, 5-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 130-134°C
942-MeO 5-ClMe 4'-MeO, 5'-MeOTPL 151-156°
952-Br, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
962-MeS, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
972-CN, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
982-Cl, 5-Cl, 6-ClMe4'-MeO, 5'-MeOTPL 139-141°
992-Cl, 5-Cl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 113-115°
1005-Cl, 6-C1Me4'-MeO, 5'-MeOTPL 94-97°
1015-ClMe4'-MeO, 5'-MeOTPL 90-91°
1025-ClMe4'-MeO, 5'-MeO. 6'-MeOTPL 75-77°
1035-Cl, 6-C1Me4'-MeO, 5'-MeO, 6'-MeOTPL 72-74°
1045-Cl, 6-MeOMe4'-MeO, 5'-MeO, 6’-MeOTPL 143-146°
1055-Cl, 6-MeOMe4'-MeO, 5'-MeOTPL 112-115°
1065-Cl, 6-EtOMe4'-MeO, 5'-MeO, 6'-MeOTPL 82-84°
107MeO Me4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
1085-Cl, 6-n-Propyl-OMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
1096-EtOMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
1105-Cl, 6-n-Butyl-OMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
1116-n-Propyl-OMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
1126-n-Bugil-OMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance

Me
Table 7
Compounds represented by formula (I-2)
No.(X)nR1(R2)mPhysical properties
1135-Cl, 6-Propargyl-OMe4'-MeO, 5'-MeO, 6'-MeOTPL 131-133°
1145-Cl, 6-n-Pentyl-OMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
1155-Cl, 6-OHMe4'-MeO, 5'-MeO, 6'-MeOTPL 152-154°
1166-n-Pentyl-OMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
1175-Cl, 6-CH3S(CH2)2AboutMe4-MeO, 5'-MeO, 6'-MeOTPL 62-64°
1185-Cl, 6-Allyl-OMe4'-MeO, 5'-MeO, 6'-MeOPale-yellow oily substance
1195-Cl, 6-CH3O(CH2)2AboutMe4'-MeO, 5'-MeO, 6'-MeOTPL 78-80°
1202-MeO, 5-MeOMe4'-MeO, 5'-MeO, 6'-MeOtell 135-139°
1212-MeOMe4'-MeO, 5'-MeO, 6'-MeOTPL 97-100°
1225-MeOMe4'-MeO, 5'-MeO, 6'-MeOTPL 103-106°
1232-Cl, 5-MeOMe4'-MeO, 5'-MeO, 6'-MeOTPL 117-119°
1242-Br, 5-MeOMe4'-MeO, 5'-MeO, 6'-MeOTPL 145-147°
1252-Me, 5-MeOMe4'-MeO, 5’-MeO, 6'-MeO 
1262-Et, 5-MeO4'-MeO, 5'-MeO, 6'-MeO 
1272-n-Propyl, 5-MEOMe4’-MeO, 5'-MeO, 6'-MeO 
1282-Allyl, 5-MEOMe4’-MeO, 5'-MeO, 6'-MeO 
1292-Propargyl, 5-MEOMe4'-MeO, 5'-MeO, 6'-MeO 
1302-EtO, 5-MeOMe4’-MeO, 5'-MeO, 6’-MeOTPL 110-112°
1312-CN, 5-MeOMe4’-MeO, 5'-MeO, 6'-MeOTPL 117-120°
1322-MeS, 5-MeOMe4'-MeO, 5’-MeO, 6'-MeOTPL 154-159°
1335-MeMe4’-MeO, 5’-MeO, 6'-MeOTPL 98-105°
1345-BrMe4’-MeO, 5’-MeO, 6'-MeO 
1355-FMe4'-MeO, 5'-MeO, 6'-MeO 

4-Me, 5-Cl
Table 8
Compounds represented by formula (I-3)
No.(X)nR1(R2)mPhysical properties
1366-ClMe4'-MeO, 5'-MeO, 6’-MeOOily yellow substance
Table 9
Compounds represented by formula (I-4)
No.(X)nR1(R2)mPhysical properties
137No substitutionMe4'-MeO, 5'-MeO, 6’-MeO 
Table 10
Compounds represented by formula (I-5)
No.(X)nR1(R2)mPhysical properties
1385-Cl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 109-111°
Table 11
Compounds represented by formula (I-6)
No.(X)nR1(R2)mPhysical properties
1394-MeMe4'-MeO, 5'-MeO, 6'-MeO 
140Me4'-MeO, 5'-MeO, 6'-MeO 
1414-Me, 5-BrMe4'-MeO, 5'-MeO, 6'-MeO 

Table 12
No.Formula(X)nR1(R2)pR3Physical properties
142(I-7)2-MeOMe5'-MeOMeOTPL 90-91°
143(I-7)2-Cl, 4-ClMe5'-MeOPh 
144(I-7)2-Cl, 4-ClMe5'-MeO, 6'-MeOMeO 
145(I-7)2-Cl, 4-MeOMe5'-MeO, 6'-MeOMeO 
146(I-7)2-MeO, 4-ClMe5'-MeO, 6'-MeOMeO 
147(I-7)2-F, 4-FMe5'-MeO, 6'-MeOMeO 
148(I-7)2-F, 4-MeOMe5'-MeO, 6'-MeOMeO 
149(I-7)2-MeO, 4-FMe5'-MeO, 6'-MeOMeO 
150(I-7)2-Cl, 4-Cl, 5-ClMe5'-MeO, 6'-MeOMeO 
151(I-7)2-Me, 4-MeMe5'-MeO, 6'-MeOMeO 
152(I-7)2-Me, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeO 
153(I-7)2-Me, 4-Me, 5-BrMe5'-MeO, 6'-MeOMeO 
154(I-7)2-Me, 4-MeOMe5'-MeO, 6'-MeOMeO 
155(I-7)2-Me, 4-MeO, 5-ClMe5'-MeO, 6'-MeOMeO 
156(I-7)2-Me, 4-MeO, 5-BrMe5'-MeO, 6'-MeOMeO 
157(I-7)2-MeO, 4-MeMe5'-MeO, 6'-MeOMeO 
158(I-7)2-MeO, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeOTPL 84-88°
159(I-7)2-MeO, 4-Me, 5-Br Me5'-MeO, 6'-MeOMeOTPL 111-114°
160(I-7)2-Me, 4-ClMe5'-MeO, 6'-MeOMeO 
161(I-7)2-Me, 4-Cl, 5-ClMe5'-MeO, 6'-MeOMeO 
162(I-7)2-Me, 4-Cl, 5-BrMe5'-MeO, 6'-MeOMeO 
163(I-7)2-Cl, 4-MeMe5'-MeO, 6'-MeOMeO 
164(I-7)2-Cl, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeO 
165(I-7)2-Cl, 4-Me, 5-BrMe5'-MeO, 6'-MeOMeO 
166(I-7)2-CF3, 4-CF3, 5-ClMe5'-MeO, 6'-MeOMeO 

Table 13
No.Formula(X)nR1(R2)pR3Physical properties
167(I-7)2-Cl,4-CF3A 6-CF3 Me5'-MeO, 6'-MeOMeOTPL 117-118°
168(I-7)2-CF3, 4-CF3, 5-MeMe5’-MeO, 6'-MeOMeO 
169(I-7)2-CF3, 4-CF3, 5-EtMe5'-MeO, 6'-MeOMeO 
170(I-7)2-CF3, 4-CF3A 5-AlpinMe5'-MeO, 6'-MeOMeO 
171(I-7)2-CF3, 4-CF3, 5-n-PropylMe5'-MeO, 6'-MeOMeO 
172(I-7)2-CF3, 4-CF3A 5-PropargylMe5'-MeO, 6'-MeOMeO 
173(I-7)2-CF3, 4-CF3, 5-Me, 6-ClMe5'-MeO, 6'-MeOMeO 
174(I-7)2-CF3, 4-CF3, 5-Et, 6-ClMe5'-MeO, 6'-MeOMeO 
175(I-7)2-CF3, 4-CF3, 5-Allyl, 6-ClMe5'-MeO, 6'-MeOMeO 
176(I-7)2-CF3/sub> , 4-CF3, 5-n-Propyl, 6-ClMe5'-MeO, 6'-MeOMeO 
177(I-7)2-CF3, 4-CF3A 5-Propargyl, 6-ClMe5'-MeO, 6'-MeOMeO 
178(I-7)2-CF3, 4-CF3Me5'-MeO, 6'-MeOMeO 
179(I-7)2-CF3, 5-CF3A 6-ClMe5'-MeO, 6'-MeOMeO 
180(I-7)2-CF3, 5-CF3Me5'-MeO, 6'-MeOMeO 
181(I-7)2-CF3, 4-Me, 5-CF3Me5'-MeO, 6'-MeOMeO 
182(I-7)2-CF3, 4-Et, 5-CF3Me5'-MeO, 6'-MeOMeO 
183(I-7)2-CF3, 4-Allyl, 5-CF3Me5'-MeO, 6'-MeOMeO 
184(I-7)2-CF3, 4-n-propyl, 5-CF3Me5'-MeO, 6'-MeOMeO 
185(I-7)2-CF3, 4-Propargyl, 5-CF3Me5'-MeO, 6'-MeOMeO 
186(I-8)2-Cl, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMeOMP 60-61°
187(I-8)2-MeO, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMeOTPP 128-134°

Table 14
No.Formula(X)nR1(R2)pR3Physical properties
188(I-8)2-EtO, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
189(I-8)2-MeO, 3-MeO, 5-ClMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
190(I-8)2-MeO, 3-MeOMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
191(I-8)3-Cl, 5-ClMe5’-MeO, 6’-MeOMeOTPL 109-111°
192(I-8)3-ClMe 5'-MeO, 6'-MeOMeOTPL 90-94°
193(I-8)2-Cl, 3-Cl, 5-MeOMe5'-MeO, 6'-MeOMeOTPL 98-99°
194(I-8)2-Cl, 3-Cl, 5-EtOMe5'-MeO, 6'-MeOMeOTPL 110-114°
195(I-8)2-Cl, 3-MeO, 5-MeOMe5'-MeO, 6'-MeOMeO 
196(I-8)2-Cl, 3-EtO, 5-MeOMe5'-MeO, 6'-MeOMeO 
197(I-8)3-MeOMe5'-MeO, 6'-MeOMeO 
198(I-8)3-EtOMe5'-MeO, 6'-MeOMeO 
199(I-8)2-Cl, 3-MeO, 5-ClMe5'-MeO, 6'-MeOMeOTPP. 80-86°
200(I-8)2-Cl, 3-EtO, 5-ClMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
201(I-8)3-BrMe5'-MeO, 6'-MeOMeOTPL 106-107°
202(I-8)3-Br, 5-Br Me5'-MeO, 6'-MeOMeOTPL 108-110°
203(I-8)3-Br, 5-MeOMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
204(I-8)2-F, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
205(I-8)2-MeO, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
206(I-8)2-EtO, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
207(I-8)2-MeO, 3-MeO, 5-FMe5'-MeO, 6'-MeOMeO 
208(I-8)3-F, 5-FMe5'-MeO, 6'-MeOMeO 
209(I-8)3-FMe5'-MeO, 6'-MeOMeO 
210(I-8)3-Me, 5-MeOMe5'-MeO, 6'-MeOMeOPale-yellow oily substance

Table 15
No.Formula(X)nR1 (R2)pR3Physical properties
211(I-8)2-Cl, 3-Me, 5-MeOMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
212(I-8)2-Br, 3-Me, 5-MeOMe5'-MeO, 6'-MeOMeO 
213(I-8)3-Me, 5-NoMe5'-MeO, 6'-MeOMeOTPL 117-122°
214(I-8)2-Cl, 3-Me, 5-Meno5’-MeO, 6'-MeOMeO 
215(I-8)2-Br, 3-Me, 5-HeMe5'-MeO, 6'-MeOMeO 
216(I-8)3-Et, 5-MeOMe5'-MeO, 6'-MeOMeO 
217(I-8)3-Allyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
218(I-8)3-n-Propyl, 5-MEOMe5'-MeO, 6'-MeOMeO 
219(I-8)3-Propargyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
220 (I-8)2-Cl, 3-Et, 5-MeOMe5'-MeO, 6'-MeOMeO 
221(I-8)2-Cl, 3-Allyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
222(I-8)2-Cl, 3-n-Propyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
223(I-8)2-Cl, 3-Propargyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
224(I-8)2-Br, 3-Et, 5-MeOMe5'-MeO, 6'-MeOMeO 
225(I-8)2-Br, 3-Allyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
226(I-8)2-Br, 3-n-Propyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
227(I-8)2-Br, 3-Propargyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
228(I-8)3-Me, 5-BrMe5'-MeO, 6'-MeOMeOTPL 88-93°
229(I-8)3-Et, 5-BrMe5'-MeO, 6'-MeOMeO
230(I-8)3-Allyl, 5-BrMe5'-MeO, 6'-MeOMeO 
231(I-8)3-n-Propyl, 5-BrMe5'-MeO, 6'-MeOMeO 
232(I-8)3-Propargyl, 5-BrMe5'-MeO, 6'-MeOMeO 
233(I-8)3-Me, 5-Br, 6-ClMe5'-MeO, 6'-MeOMeO 
234(I-8)3-Et, 5-Br, 6-ClMe5'-MeO, 6'-MeOMeO 

 
Table 16
No.Formula(X)nR1(R2)pR3Physical properties
235(I-8)3-Allyl, 5-Br, 6-ClMe5'-MeO, 6'-MeOMeO 
236(I-8)3-n-Propyl, 5-Br, 6-ClMe5'-MeO, 6'-MeOMeO 
237(I-8)3-Propargyl, 5-Br, 6-ClMe5'-MeO, 6'-MeOMeO
238(I-8)3-Me, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
239(I-8)3-Et, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
240(I-8)3-Allyl, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
241(I-8)3-n-Propyl, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
242(I-8)3-Propargyl, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
243(I-8)3-MeO, 5-MeOMe5'-MeO, 6'-MeOMeORed oily substance
244(I-8)3-MeO, 5-ClMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
245(I-8)2-Br, 3-Cl, 5-MeOMe5'-MeO, 6'-MeOMeOTPL 97-99°
246(I-8)2-Br, 3-Br, 5-BrMe5'-MeO, 6'-MeOMeO 
247(I-8)2-Cl, 3-Br, 5-Br Me5'-MeO, 6'-MeOMeO 
248(I-8)2-Br, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMeO 
249(I-8)2-Cl, 3-MeO, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
250(I-8)2-Br, 3-MeO, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
251(I-8)3-EtO, 5-EtOMe5'-MeO, 6'-MeOMeOTPL 106-109°
252(I-8)3-EtO, 5-ClMe5'-MeO, 6'-MeOMeOTPL 98,5-99,5°
253(I-8)2-Br, 3-EtO, 5-ClMe5'-MeO, 6'-MeOMeO 
254(I-8)2-Br, 3-Cl, 5-EtOMe5'-MeO, 6'-MeOMeOTPL 113-115°
255(I-8)2-Cl, 3-Br, 5-EtOMe5'-MeO, 6'-MeOMeO 
256(I-8)2-Br, 3-Br, 5-EtOMe5'-MeO, 6'-MeOMeO 
257(I-8)2-Br, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMEO 
258(I-8)2-Cl, 3-EtO, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeO 

Table 17
No.Formula(X)nR1(R2)pR3Physical properties
259(I-8)2-Br, 3-EtO, 5-Cl, 6-ClMe5'-MEO, 6'-MeoMEO 
260(I-8)2-Cl, 3-EtO, 5-Cl, 6-BrMe5’-MeO, 6'-MeoMeO 
261(I-8)2-Br, 3-EtO, 5-Cl, 6-BrMe5'-MeO, 6'-MeOMeO 
262(I-8)2-F, 3-F, 5-F, 6-FMe5'-MeO, 6'-MeOMeOTPL 85-87°
263(I-8)2-Br, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
264(I-8)2-F, 3-Me, 5-FMe5'-MeO, 6'-MeOMeO
265(I-8)2-Br, 3-F, 5-F, 6-BrMe5'-MeO, 6'-MeOMeO 
266(I-8)2-Cl, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
267(I-8)2-Br, 3-Br, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
268(I-8)2-Cl, 3-Cl, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeO 
269(I-8)3-Br, 5-FMe5'-MeO, 6'-MeOMeO 
270(I-8)2-Br, 3-F, 5-F, 6-FMe5'-MeO, 6'-MeOMeO 
271(I-8)3-F, 5-CH3Me5'-MeO, 6'-MeOMeO 
272(I-8)3-Cl, 5-CH3Me5'-MeO, 6'-MeOMeOTPP. 84-88°
273(I-8)3-F, 5-MeOMe5'-MeO, 6'-MeOMeO 
274(I-8)2-Cl, 3-CF3A 6-CF3Me5'-MeO, 6'-MeOMeOPL 85-88°
275(I-8)3-CF3A 6-CF3Me5'-MeO, 6'-MeOMeO 
276(I-8)3-CF3, 5-Me, 6-CF3Me5'-MeO, 6'-MeOMeO 
277(I-8)3-CF3A 5-EF3A 6-CF3Me5'-MeO, 6'-MeOMeO 
278(I-8)3-CF3, 5-Allyl, 6-CF3Me5'-MeO, 6'-MeOMeO 
279(I-8)3-CF3, 5-n-Propyl, 6-CF3Me5'-MeO, 6'-MeOMeO 
280(I-8)3-CF3A 5-Propargyl, 6-CF3Me5'-MeO, 6'-MeOMeO 
281(I-8)2-Cl, 3-CF3, 5-CF3A 6-ClMe5'-MeO, 6'-MeOMeO 
282(I-8)2-Cl, 3-CF3, 5-CF3Me5'-MeO, 6'-MeOMeO 

td align="center"> Formula
Table 18
No.(X)nR1(R2)pR3Physical properties
283(I-8)3-CF3, 5-CF3Me5'-MeO, 6'-MeOMeO 
284(I-9)3-Cl, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeOTPL 144-147°
285(I-9)3-F, 5-F, 6-FMe5'-MeO, 6'-MeOMeO 
286(I-9)3-Br, 5-BrMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
287(I-1)2-MeOMe5'-cyclohexyl-OMeOTPL-100°
288(I-8)2-Me, 3-Cl, 6-ClMe5'-MeOMeOTPL 111-113°
289(I-8)2-Me, 3-Cl, 6-ClEt5'-MeOMeOTPL 88-94°
290(I-8)2-Me, 3-ClMe5'-MeOMeOTPL 117-118°
291(I-8)2-Cl, 3-Br, 5-MeOMe 5'-MeO, 6'-MeOMeOBrown oily substance
292(I-8)2-Br, 3-Br, 5-MeOMe5'-MeO, 6'-MeOMeOYellow oily substance
293(I-7)2-MeO, 4-Br, 5-ClMe5'-MeO, 6'-MeOMeOTPL 92-94°
294(I-7)2-MeO, 4-Et, 5-ClMe5'-MeO, 6'-MeOMeOYellow oily substance
295(I-7)2-MeO, 4-Cl, 5-ClMe5'-MeOMeOTPL 139-141°
296(I-7)2-MeO, 4-Cl, 5-ClMe5'-EtOMeOTPL 110-112°
297(I-7)2-EtO, 4-Br, 5-ClMe5'-MeO, 6'-MeOMeOYellow oily substance
298(I-7)2-EtO, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeOYellow oily substance
299(I-7)2-EtO, 4-Cl, 5-BrMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
300(I-7)2-MeO, 4-Cl, 5- Me5'-MeO, 6'-MeOMeOColorless oily substance
301(I-7)2-MeO, 4-MeO, 5-IMe5'-MeO, 6'-MeOMeOColorless oily substance
302(I-7)2-MeO, 4-MeS, 5-ClMe5'-MeO, 6'-MeOMeOTPL 98-104°
303(I-7)2-MeO, 4-MeO, 5-ClMe5'-MeO, 6'-MeOMeOTPL 93-94°
304(I-7)2-MeO, 4-Br, 5-BrMe5'-MeO, 6'-MeOMeOTPL 149-150°
305(I-7)2-MeO, 4-Br, 5-IUMe5'-MeO, 6'-MeOMeOTPL 140-142°
306(I-7)2-MeO, 4-CF3, 5-BrMe5'-MeO, 6'-MeOMeOTPL 128-129°
307(I-7)2-MeO, 4-Cl, 5-ClMe5'-MeO, 6'-MeOMeOTPL 84-86°

Table 18 (continued)
No.Formula(X)nR1(R2)p R3Physical properties
308(I-7)2-Cl, 4-Cl, 5-IUMe5'-MeO, 6'-MeOMeOTPL 78-80°
309(I-7)2-Cl, 4-Cl, 5-IMe5'-MeO, 6'-MeOMeOOily substance
310(I-7)2-F, 4-I, 5-IUMe5'-MeO, 6'-MeOMeOTPL 140-141°
311(I-7)2-F, 4-Me, 5-MeMe5'-MeO, 6'-MeOMeOTPL 91-92°
312(I-7)2-MeO, 4-Me, 5-MeMe5'-MeO, 6'-MeOMeOTPL 84-86°
313(I-7)2-EtO, 4-Me, 5-MeMe5'-MeO, 6'-MeOMeOTPL 74-75°
314(I-7)2-MeS, 4-Me, 5-MeMe5'-MeO, 6'-MeOMeOOily substance
315(I-7)2-MeO, 4-Cl, 5-BrMe5'-MeO, 6'-MeOMeOTPL 84-87°
316(I-7)2-MeO, 4-Cl, 5-IUMe5'-MeO, 6'-MeOMeOTPL 88-90°
317(I-7)2-MeO, 4-ethinyl, 5-ClMe5'-MeO, 6'-MeOMeOTPL 113-115°
318(I-7)2-MeO, 4-CH2F, 5-ClMe5'-MeO, 6'-MeOMeOTPL 82-84°
319(I-7)2-MeO, 4-Me, 5-ClMe5'-MeOMeOTPL 129-130°
320(I-7)2-Cl, 4-Me, 6-ClMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
321(I-7)2-Cl, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeOTPL 77-79°
322(I-7)2-Me, 5-ClMe5'-MeO, 6'-MeOMeOTPL 49-50°

Compounds represented by formula (X), which is used as intermediate compounds obtained by the methods in accordance with examples of the preparation 1, 3, 5, 6, 8, 9, 11 and 16, are presented in the following tables 19-36.

Compounds represented by General formulas (X-1) to (X-9) in the tables are the following compounds.

In addition, in these tables, Me represents methyl group, Et represents ethyl group, Butyl is boutelou group,ISO-Propyl represents ISO-propyl group, Ph represents a phenyl group, Allyl represents allyl group, a Hexyl represents tsiklogeksilnogo group, Benzyl represents a benzyl group, Propargyl represents a propargyl group and Pencil is pentelow group.

Table 19
Compounds represented by formula (X-1)
No.(X)nR1(R2)mPhysical properties
12-Cl, 6-ClIU4'-MeO, 5'-MeOA viscous substance
22-Cl, 6-ClMe4'-MeO, 5'-MeA viscous substance
32-Cl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOA viscous substance
42-Cl, 6-ClMe4'-MeOA viscous substance
5No substitutionMe 4'-MeO, 5'-MeO 
6No substitutionMe4'-MeO, 5'-Me 
7No substitutionMe4'-MeO, 5'-MeO, 6'-MeOTPL 132-135°
8No substitutionMe4’-MeO 
92-ClMe4'-MeO, 5'-MeO 
102-ClMe4'-MeO, 5'-Me 
112-ClMe4’-MeO, 5’-MeO, 6'-MeOA viscous substance
122-ClMe4'-Me, 5'-Me, 6'-MeTPL 125-127°
132-ClMe4',5'-(-och2Oh)TPL 127-130°
142-ClMe4'-MeO 
152-ClEt4'-MeO, 5'-MeO, 6'-MeO 
162-ClISO-Propyl4'-MeO, 5'-MeO, 6'-MeO 
172-ClMe3'-MeO, 4'-MeO, 5’-MeO, 6'-MeO 
182-ClMe4'-MeO, 5'-EtOViscous substances, the
192-ClMe4'-MeO, 5'-ISO-Propyl-OA viscous substance
202-ClMe4'-MeO, 5'-Allyl-O 
212-ClMe4'-MeO, 5'-Propargyl-O 
222-ClMe4'-MeO, 5'-CF3CH2About- 
232-ClMe4'-MeO, 5'-Hexyl-OA viscous substance

Table 20
Compounds represented by formula (X-1)
No.(X)nR1(R2)mPhysical properties
242-ClMe4’-MeO, 5'-(CH3)2N(CH2)2O- 
252-ClMe4'-MeO, 5'-CH3S(CH2)2O- 
262-ClMe4'-MeO, 5'-PhO- 
272-ClMe4'-MeO, 5'-Benzyl-O-A viscous substance
282-ClMe 4'-MeO, 5'-CH3Soo- 
292-ClMe4'-MeO, 5'-CH3LLC- 
302-MeO, 6-MeOMe4'-MeO, 5'-MeO, 6’-MeO 
312-Cl, 6-MeOMe4’-MeO, 5'-MeO, 6’-MeO 
322-MeOMe4'-MeO, 5'-MeO 
332-ISO-Propyl-OMe4'-MeO, 5'-MeO, 6'-MeO 
342-CF3CH2O-Me4'-MeO, 5'-MeO, 6’-MeO 
352-CH3O(CH2)2About-Me4'-MeO, 5'-MeO, 6'-MeO 
362-CH3S(CH2)2O-Me4'-MeO, 5'-MeO, 6’-MeO 
372-PhO-Me4’-MeO, 5'-MeO, 6’-MeO 
382-Benzyl-O-Me4'-MeO, 5'-MeO, 6’-MeO 
392-Hexyl-O-Me4’-MeO, 5'-MeO, 6’-MeO 
402-Allyl-O-Me4’-MeO, 5'-MeO, 6'-MeO 
2-Propargyl-O-Me4'-MeO, 5'-MeO, 6'-MeO 
422-(CH3)2N(CH2)2O-Me4’-MeO, 5'-MeO, 6’-MeO 
432-Cl, 5-NoMe4’-MeO, 5'-MeO, 6'-MeO 
442-Cl, 5-AllylMe4'-MeO, 5'-MeO, 6'-MeO 
452-Cl, 5-PolartMe4’-MeO, 5'-MeO, 6’-MeO 
462-Cl, 5-CH3O(C=O)-Me4’-MeO, 5'-MeO, 6'-MeO 
472-Cl, 5-CH3(C=O)-Me4’-MeO, 5'-MeO, 6’-MeO 

Table 21
Compounds represented by formula (X-1)
No.(X)nR1(R2)mPhysical properties
482-Cl, 5-EtMe4'-MeO, 5’-MeO, 6'-MeO 
492-MeO, 5-MeMe4'-MeO, 5’-MeO, 6’-MeO 
502-MeSMe4'-MeO 5'-MeO, 6'-MeO 
512-Me2NMe4'-MeO, 5-MeO, 6’-MeO 
522-Cl, 5-(CH3)2N (=O)-Me4'-MeO, 5'-MeO, 6’-MeO 
532-CNMe4'-MeO, 5’-MeO, 6'-MeO 
542-Cl, 5-Cl, 6-ClMe4'-MeO, 5'-MeO, 6’-MeOA viscous substance
552-Cl, 5-ClMe4’-MeO, 5'-MeO, 6’-MeO 
562-MeO, 5-ClMe4’-MeO, 5’-MeO, 6'-MeO 
572-OH, 5-ClMe4'-MeO, 5’-MeO, 6’-MeO 
582-Cl, 5-Me, 6-ClMe4'-MeO, 5’-MeO, 6’-MeOA viscous substance
592-Cl, 5-Allyl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOA viscous substance
602-Cl, 5-Propargyl, 6-ClMe4'-MeO, 5'-MeO, 6’-MeO 
612-Cl, 5-CH3O(C=O)-, 6-ClMe4'-MeO, 5’-MeO, 6’-MeOTPL 133-135°
622-Cl, 5-CH3CH(OH)-, 6-ClMe4’-MeO, 5'-MeO, 6'-MeO TPL 141-158°
632-Cl, 5-Et, 6-ClMe4'-MeO, 5’-MeO, 6'-MeO 
642-Cl, 5-(CH3)2N (=O)-Me4'-MeO, 5-MeO, 6’-MeO 
655-MeMe4'-MeO, 5’-MeO, 6’-MeO 
665-AllylMe4'-MeO, 5’-MeO, 6’-MeO 
675-PropargylMe4'-MeO, 5’-MeO, 6'-MeO 
685-CH3O(C=O)-Me4'-MeO, 5’-MeO, 6'-MeO 
695-CH3(C=O)-Me4'-MeO, 5’-MeO, 6'-MeO 
705-EtMe4'-MeO, 5’-MeO, 6’-MeO 

Table 22
Compounds represented by formula (X-1)
No.(X)nR1(R2)mPhysical properties
715-(CH3)2N (=O)-Me4'-MeO, 5'-MeO, 6’-MeO 
722-CH3O(CH2 )2About-Me4'-MeO, 5'-MeO 
732-(6'-phenyl)-O-Me4’-MeO, 5’-MeO, 6’-O- (2-Pyridyl) 
742-MeOMe4'-MeO, 5'-MeO, 6’-MeO 
752-EtOMe4'-MeO, 5'-MeO, 6'-MeO 
762-MeSMe4'-MeO, 5'-MeO, 6'-HE 
772-HEMe4'-MeO, 5'-MeO, 6'-MeO 
782-NH2Me4'-MeO, 5'-MeO, 6'-MeO 
792-CH3NHMe4'-MeO, 5'-MeO, 6'-MeO 
802-CH3SooMe4'-MeO, 5'-MeO, 6'-MeO 
812-ISO-Propyl-O-Me4'-MeO, 5'-MeO, 6'-ISO-Propyl-O- 
822-Cl, 6-ClEt4'-MeO, 5'-MeO, 6’-MeO 
832-ClMe4'-MeO, 5'-(4-MeO-Benzyl)OA viscous substance
842-MeMe4'-MeO, 5'-MeO, 6’-MeO 
85 2-Me, 5-ClMe4'-MeO, 5'-MeO, 6’-MeO 
862-Me, 5-BrMe4'-MeO, 5'-MeO, 6'-MeO 
Table 23
Compounds represented by formula (X-2)
No.(X)pR1(R2)mPhysical properties
872-PhO, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
882-HE, 5-ClMe4'-MeO, 5'-MeO, 6’-MeO 

106
Table 24
Compounds represented by formula (X-2)
No.(X)nR1(R2)mPhysical properties
892-Cl, 5-ClNo4'-MeO, 5'-MeOTPL 134-136°
902-Cl, 5-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 162 to 165°
91No substitutionMe4'-MeO, 5'-MeO 
92No substitutionMe4'-MeO, 5'-MeO, 6'-MeO TPL 101-106°
932-MeO, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
942-MeO, 5-ClMe4'-MeO, 5'-MeO 
952-Br, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
962-MeS, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
972-CN, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
982-Cl, 5-Cl, 6-ClMe4'-MeO, 5'-MeOTPL 156-158°
992-Cl, 5-Cl, 6-ClMe4'-MeO, 5'-MeO, 6’-MeOTPL 131-135°
1005-Cl, 6-ClMe4'-MeO, 5'-MeOA viscous substance
1015-ClMe4'-MeO, 5'-MeO 
1025-ClMe4'-MeO, 5'-MeO, 6'-MeOTPL 102-105°
1035-Cl, 6-ClMe4'-MeO, 5'-MeO, 6'-MeOTPP. 95-98°
1045-Cl, 6-MeOMe4'-MeO, 5'-MeO, 6'-MeO 
1055-Cl, 6-MeOMe4'-MeO, 5'-MeO 
5-Cl, 6-EtOMe4'-MeO, 5'-MeO, 6'-MeO 
1076-MeOMe4'-MeO, 5'-MeO, 6'-MeO 
1085-Cl, 6-n-Propyl-OMe4'-MeO, 5'-MeO, 6'-MeO 
1096-EtOMe4'-MeO, 5'-MeO, 6'-MeO 
1105-Cl, 6-n-Butyl-OMe4'-MeO, 5'-MeO, 6'-MeO 
1116-n-Propyl-OMe4'-MeO, 5'-MeO, 6'-MeO 
1126-n-Butyl-OMe4'-MeO, 5'-MeO, 6'-MeO 

Table 25
Compounds represented by formula (X-2)
No.(X)nR1(R2)mPhysical properties
1135-Cl, 6-Propargyl-OMe4'-MeO, 5'-MeO, 6'-MeO 
1145-Cl, 6-n-Pentyl-OMe4'-MeO, 5'-MeO, 6'-MeO 
1155-Cl, 6-HEMe4'-MeO, 5'-MeO, 6'-MeO 
16 6-n-Pentyl-OMe4'-MeO, 5'-MeO, 6'-MeO 
1175-Cl, 6-CH3S(CH2)2AboutMe4'-MeO, 5'-MeO, 6'-MeO 
1185-Cl, 6-Allyl-OMe4’-MeO, 5'-MeO, 6'-MeO 
1195-Cl, 6-CH3O(CH2)2OMe4'-MeO, 5'-MeO, 6'-MeO 
1202-MeO, 5-MeOMe4’-MeO, 5'-MeO, 6'-MeO 
1212-MeOMe4'-MeO, 5'-MeO, 6'-MeO 
1225-MeOMe4'-MeO, 5'-MeO, 6'-MeO 
1232-Cl, 5-MeOMe4'-MeO, 5'-MeO, 6'-MeO 
1242-Br, 5-MeOMe4'-MeO, 5'-MeO, 6'-MeO 
1252-Me, 5-MeOMe4'-MeO, 5'-MeO, 6'-MeO 
1262-Et, 5-MeOHe4'-MeO, 5'-MeO, 6'-MeO 
1272-n-Propyl, S-MeOMe4’-MeO, 5'-MeO, 6'-MeO 
1282-All, 5-MeOMe4'-MeO, 5'-MeO, 6'-MeO/td>  
1292-Propargyl, 5-MEOMe4'-MeO, 5’-MeO, 6'-MeO 
1302-EtO, 5-MeOMe4’-MeO, 5'-MeO, 6'-MeO 
1312-CN, 5-MeOMe4'-MeO, 5’-MeO, 6'-MeO 
1322-MeS, 5-MeOMe4'-MeO, 5'-MeO, 6'-MeO 
1335-MeMe4'-MeO, 5'-MeO, 6'-MeO 
1345-BrMe4'-MeO, 5'-MeO, 6’-MeO 
1355-FMe4'-MeO, 5’-MeO, 6'-MeO 

Table 26
Compounds represented by formula (X-3)
No.(X)nR1(R2)mPhysical properties
1366-ClMe4'-MeO, 5’-MeO, 6'-MeOA viscous substance
Table 27
Compounds represented by formula (X-4)
No.(X) nR1(R2)mPhysical properties
137No substitutionMe4'-MeO, 5'-MeO, 6'-MeO 
Table 28
Compounds represented by formula (X-5)
No.(X)nR1(R2)mPhysical properties
1385-Cl, 6-ClMe4’-MeO, 5'-MeO, 6’-MeOTPP. 71-73°
Table 29
Compounds represented by formula (X-6)
No.(X)nR1(R2)mPhysical properties
1394-MeMe4'-MeO, 5'-MeO, 6'-MEO 
1404-Me, 5-ClMe4'-MeO, 5'-MeO, 6'-MeO 
1414-Me, 5-BrMe4'-MeO, 5'-MeO, 6'-MeO 

Table 30
No.Formula(X)nR1(R2)pR3Physical properties
142(X-7)2-MeOMe5'-MeOMeOA viscous substance
143(X-7)2-Cl, 4-ClMe5'-MeOPhO 
144(X-7)2-Cl, 4-ClMe5'-MeO, 6'-MeOMeO 
145(X-7)2-Cl, 4-MeOMe5'-MeO, 6'-MeOMeO 
146(X-7)2-MeO, 4-ClMe5'-MeO, 6'-MeOMeO 
147(X-7)2-F, 4-FMe5'-MeO, 6'-MeOMeO 
148(X-7)2-F, 4-MeOMe5'-MeO, 6'-MeOMeO 
149(X-7)2-MeO, 4-FMe5'-MeO, 6'-MeOMeO 
150(X-7)2-Cl, 4-Cl, 5-ClMe5'-MeO, 6'-MeOMeO 
(X-7)2-Me, 4-MeMe5'-MeO, 6'-MeOMeO 
152(X-7)2-Me, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeO 
153(X-7)2-Me, 4-Me, 5-BrMe5'-MeO, 6'-MeOMeO 
154(X-7)2-Me, 4-MeOMe5'-MeO, 6'-MeOMeO 
155(X-7)2-Me, 4-MeO, 5-ClMe5'-MeO, 6'-MeOMeO 
156(X-7)2-Me, 4-MeO, 5-BrMe5'-MeO, 6'-MeOMeO 
157(X-7)2-MeO, 4-MeMe5'-MeO, 6'-MeOMeO 
158(X-7)2-MeO, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeOA viscous substance
159(X-7)2-MeO, 4-Me, 5-BrMe5'-MeO, 6'-MeOMeOA viscous substance
160(X-7)2-Me, 4-ClMe5'-MeO, 6'-MeOMeO 
161 (X-7)2-Me, 4-Cl, 5-ClMe5'-MeO, 6'-MeOMeO 
162(X-7)2-Me, 4-Cl, 5-BrMe5'-MeO, 6'-MeOMeO 
163(X-7)2-Cl, 4-MeMe5'-MeO, 6'-MeOMeO 
164(X-7)2-Cl, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeO 
165(X-7)2-Cl, 4-Me, 5-BrMe5'-MeO, 6'-MeOMeO 
166(X-7)2-CF3, 4-CF3A 6-ClMe5'-MeO, 6'-MeOMeO 

Table 31
No.Formula(X)nR1(R2)pR3Physical properties
167(X-7)2-Cl, 4-CF3A 6-CF3Me5'-MeO, 6'-MeOMeOA viscous substance
168(X-7)2-CF3, 4-CF3, 5-MeMe5'-MeO, 6'-MeOMeO 
169(X-7)2-CF3, 4-CF3, 5-EtMe5'-MeO, 6'-MeOMeO 
170(X-7)2-CF3, 4-CF3, 5-AllylMe5'-MeO, 6'-MeOMeO 
171(X-7)2-CF3, 4-CF3, 5-n-PropylMe5'-MeO, 6'-MeOMeO 
172(X-7)2-CF3, 4-CF3A 5-PropargylMe5'-MeO, 6'-MeOMeO 
173(X-7)2-CF3, 4-CF3, 5-Me, 6-C1Me5'-MeO, 6'-MeOMeO 
174(X-7)2-CF3, 4-CF3, 5-Et, 6-ClMe5'-MeO, 6'-MeOMeO 
175(X-7)2-CF3, 4-CF3, 5-Allyl, 6-ClMe5'-MeO, 6'-MeOMeO 
176(X-7)2-CF3, 4-CF3, 5-n-Propyl, 6-ClMe5’-MeO, 6'-MeOMeO 
177(X-7)2-CF3, 4-CF3A 5-Propargyl, 6-ClMe5'-MeO 6'-MeO MeO 
178(X-7)2-CF3, 4-CF3Me5'-MeO, 6'-MeOMeO 
179(X-7)2-CF3, 5-CF3A 6-ClMe5'-MeO, 6'-MeOMeO 
180(X-7)2-CF3, 5-CF3Me5'-MeO, 6'-MeOMeO 
181(X-7)2-CF3, 4-Me, 5-CF3Me5'-MeO, 6'-MeOMeO 
182(X-7)2-CF3, 4-E, 5-CF3Me5'-MeO, 6'-MeOMeO 
183(X-7)2-CF3, 4-Allyl, 5-CF3Me5'-MeO, 6'-MeOMeO 
184(X-7)2-CF3, 4-n-Propyl, 5-CF3Me5'-MeO, 6'-MeOMeO 
185(X-7)2-CF3, 4-Propargyl, 5-CF3Me5'-MeO, 6'-MeOMeO 
186(X-8)2-Cl, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMeO
187(X-8)2-MeO, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMeO 

Table 32
No.Formula(X)nR1(R2)pR3Physical properties
188(X-8)2-EtO, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMeO 
189(X-8)2-MeO, 3-MeO, 5-ClMe5'-MeO, 6'-MeOMeO 
190(X-8)2-MeO, 3-MeOMe5'-MeO, 6'-MeOMeO 
191(X-8)3-Cl, 5-ClMe5'-MeO, 6'-MeOMeOTPL 136-140°
192(X-8)3-ClMe5'-MeO, 6'-MeOMeOTPL 160-162°
193(X-8)2-Cl, 3-Cl, 5-MeOMe5'-MeO, 6'-MeOMeO 
194(X-8)2-Cl, 3-Cl, 5-EtOMe5'-MeO, 6'-MeOMeO  
195(X-8)2-Cl, 3-MeO, 5-MeOMe5'-MeO, 6'-MeOMeO 
196(X-8)2-Cl, 3-EtO, 5-MeOMe5'-MeO, 6'-MeOMeO 
197(X-8)3-MeOMe5'-MeO, 6'-MeOMeO 
198(X-8)3-EtOMe5'-MeO, 6'-MeOMeO 
199(X-8)2-Cl, 3-MeO, 5-ClMe5'-MeO, 6'-MeOMeO 
200(X-8)2-Cl, 3-EtO, 5-ClMe5'-MeO, 6'-MeOMeO 
201(X-8)3-BrMe5'-MeO, 6'-MeOMeOTPL 168-169°
202(X-8)3-Br, 5-BrMe5'-MeO, 6'-MeOMeOA viscous substance
203(X-8)3-Br, 5-MeOMe5'-MeO, 6'-MeOMeOTPL 90-93°
204(X-8)2-F, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
205(X-8)2-MeO, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
206(X-8)2-EtO, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
207(X-8)2-MeO, 3-MeO, 5-FMe5'-MeO, 6'-MeOMeO 
208(X-8)3-F, 5-FMe5'-MeO, 6'-MeOMeO 
209(X-8)3-FMe5’-MeO, 6'-MeOMeO 
210(X-8)3-Me, 5-MeOMe5'-MeO, 6'-MeOMeO 

td align="left"> 3-Me, 5-Br, 6-Cl
Table 33
No.Formula(X)nR1(R2)pR3Physical

properties
211(X-8)2-Cl, 3-Me, 5-MeOMe5'-MeO, 6'-MeOMeO 
212(X-8)2-Br, 3-Me, 5-MeOMe5'-MeO, 6'-MeOMeO 
(X-8)3-Me, 5-MeMe5'-MeO, 6'-MeOMeO 
214(X-8)2-Cl, 3-Me, 5-MeMe5'-MeO, 6'-MeOMeO 
215(X-8)2-Br, 3-Me, 5-MeMe5'-MeO, 6'-MeOMeO 
216(X-8)3-Et, 5-MeOMe5'-MeO, 6'-MeOMeO 
217(X-8)3-Allyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
218(X-8)3-n-Propyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
219(X-8)3-Propargyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
220(X-8)3-Cl, 3-Et, 5-MeOMe5'-MeO, 6'-MeOMeO 
221(X-8)2-Cl, 3-Allyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
222(X-8)2-Cl, 3-n-Propyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
223(X-8) 2-Cl, 3-Propargyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
224(X-8)2-Br, 3-Et, 5-MeOMe5'-MeO, 6'-MeOMeO 
225(X-8)2-Br, 3-Allyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
226(X-8)2-Br, 3-n-Propyl, 5-MeOMe5'-MeO, 6'-MeOMeO

ir
 
227(X-8)2-Br, 3-Propargyl, 5-MeOMe5'-MeO, 6'-MeOMeO 
228(X-8)3-Me, 5-BrMe5'-MeO, 6'-MeOMeOA viscous substance
229(X-8)3-Et, 5-BrMe5'-MeO, 6'-MeOMeO 
230(X-8)3-Allyl, 5-BrMe5'-MeO, 6'-MeOMeO 
231(X-8)3-n-Propyl, 5-BrMe5'-MeO, 6'-MeOMeO 
232(X-8)3-Propargyl, 5-BrMe5'-MeO, 6'-MeOMeO 
233(X-8)Me5'-MeO, 6'-MeOMeO 
234(X-8)3-Et, 5-Br, 6-ClMe5'-MeO, 6'-MeOMeO 

Table 34
No.Formula(X)nR1(R2)pR3Physical properties
235(X-8)3-Allyl, 5-Br, 6-ClMe5'-MeO, 6’-MeOMeO 
236(X-8)3-n-Propargyl, 5-Br, 6-ClMe5'-MeO, 6'-MeOMeO 
237(X-8)3-Propargyl, 5-Br, 6-ClMe5'-MeO, 6'-MeOMeO 
238(X-8)3-Me, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
239(X-8)3-Et, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
240(X-8)3-Allyl, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
241(X-8) 3-n-Propyl, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
242(X-8)3-Propargyl, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
243(X-8)3-MeO, 5-MeOMe5'-MeO, 6'-MeOMeO 
244(X-8)3-MeO, 5-ClMe5'-MeO, 6'-MeOMeO 
245(X-8)2-Br, 3-Cl, 5-MeOMe5'-MeO, 6'-MeOMeO 
246(X-8)2-Br, 3-Br, 5-BrMe5'-MeO, 6'-MeOMeO 
247(X-8)2-Cl, 3-Br, 5-BrMe5'-MeO, 6'-MeOMeO 
248(X-8)2-Br, 3-Cl, 5-ClMe5'-MeO, 6'-MeOMeO 
249(X-8)2-Cl, 3-MeO, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeO 
250(X-8)2-Br, 3-MeO, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeO 
251(X-8)3-EtO, 5-EtO Me5'-MeO, 6'-MeOMeO 
252(X-8)3-EtO, 5-ClMe5'-MeO, 6'-MeOMeO 
253(X-8)2-Br, 3-EtO, 5-ClMe5'-MeO, 6'-MeOMeO 
254(X-8)2-Br, 3-Cl, 5-EtOMe5'-MeO, 6'-MeOMeO 
255(X-8)2-Cl.3-Br,5-EtOMe5'-MeO, 6'-MeOMeO 
256(X-8)2-Br, 3-Br, 5-EtOMe5'-MeO, 6'-MeOMeO 
257(X-8)2-Br,3-Cl,5-ClMe5'-MeO, 6'-MeOMeO 
258(X-8)2-Cl, 3-EtO, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeO 

Table 35
No.Formula(X)nR1(R2)pR3Physical properties
259(X-8)2-Br, 3-EtO, 5-Cl, 6-ClMe5'-MeO, 6'-eO Meo 
260(X-8)2-Cl, 3-EtO, 5-Cl, 6-BrMe5'-MeO, 6'-MeOMeo 
261(X-8)2-Br, 3-EtO, 5-Cl, 6-BrMe5'-MeO, 6'-MeOMeO 
262(X-8)2-F, 3-F, 5-F, 6-FMe5'-MeO, 6'-MeOMeoA viscous substance
263(X-8)2-Br, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
264(X-8)2-F, 3-Me, 5-FMe5'-MeO, 6'-MeOMeO 
265(X-8)2-Br, 3-F, 5-F, 6-BrMe5'-MeO, 6'-MeOMeO 
266(X-8)2-Cl, 3-F, 5-FMe5'-MeO, 6'-MeOMeO 
267(X-8)2-Br, 3-Br, 5-Br, 6-BrMe5'-MeO, 6'-MeOMeO 
268(X-8)2-Cl, 3-Cl, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeO 
269(X-8)3-Br, 5-FMe5'-MeO, 6'-MeOMeO  
270(X-8)2-Br, 3-F, 5-F, 6-FMe5'-MeO, 6'-MeOMeO 
271(X-8)3-F, 5-CH3Me5'-MeO, 6'-MeOMeO 
272(X-8)3-Cl, 5-CH3Me5'-MeO, 6'-MeOMeO 
273(X-8)3-F, 5-MeOMe5'-MeO, 6'-MeOMeO 
274(X-8)2-Cl, 3-CF3A 6-CF3Me5'-MeO, 6'-MeOMeOTPL 154-158°
275(X-8)3-CF3A 6-CF3Me5'-MeO, 6'-MeOMeO 
276(X-8)3-CF3, 5-Me, 6-CF3Me5'-MeO, 6'-MeOMeO 
277(X-8)3-CF3, 5-E, 6-CF3Me5'-MeO, 6'-MeOMeo 
278(X-8)3-CF3, 5-Allyl, 6-CF3Me5'-MeO, 6'-MeOMeo 
279(X-8)3-CF3, 5h-Propyl, 6-CF3Me5'-MeO, 6'-MeOMeO 
280(X-8)3-CF3A 5-Propargyl, 6-CF3Me5'-MeO, 6'-MeOMeo 
281(X-8)2-Cl, 3-CF3, 5-CF3A 6-ClMe5'-MeO, 6'-MeOMeO 
282(X-8)2-Cl, 3-CF3, 5-CF3Me5'-MeO, 6'-MeOMeO 

Table 36
No.Formula(X)pR1(R2)pR3Physical properties
283(X-8)3-CF3, 5-CF3Me5'-MeO, 6'-MeOMeO 
284(X-9)3-Cl, 5-Cl, 6-ClMe5'-MeO, 6'-MeOMeOTPL 97-99°
285(X-9)3-F, 5-F, 6-FMe5'-MeO, 6'-MeOMeO 
286(X-9)3-Br, 5-BrMe5'-MeO, 6'-MeOMeOTPL 114-117°the
287(X-7)2-MeO, 4-Br, 5-ClMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
288(X-7)2-MeO, 4-Cl, 5-ClMe5'-MeOMeOThese NMR (table 37)
289(X-7)2-MeO, 4-Cl, 5-ClEt5'-EtOMeOThese NMR (table 37)
290(X-7)2-EtO, 4-Br, 5-ClMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
291(X-7)2-EtO, 4-Cl, 5-BrMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
292(X-7)2-MeO, 4-Cl, 5-IMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
293(X-7)2-MeO, 4-Br, 5-BrMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
294(X-7)2-MeO, 4-CF3, 5-BrMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
295(X-7)2-MeO, 4-Cl, 5-ClMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
296(X-7)2-Cl, 4-Cl, 5-MeMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
297(X-7)2-Cl, 4-Cl, 5-IMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
298(X-7)2-F, 4-I, 2-MeMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
299(X-7)2-MeO, 4-Cl, 5-BrMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
300(X-7)2-MeO, 4-CH2F, 5-ClMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
301(X-7)2-MeO, 4-Me, 5-ClMe5'-MeOMeOThese NMR (table 37)
302(X-7)2-Cl, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeOPale-yellow oily substance
303(X-7)2-Cl, 4-Me, 5-ClMe5'-MeO, 6'-MeOMeOThese NMR (table 37)
304(X-7)2-Me, 5-ClMe5'-MeO, 6'-MeO These NMR (table 37)

Anything to add the s to the table 36: data for compounds of table. 36

No. tabl1H-NMR (Dl3, 400 MHz): δ (ppm)
287of 2.33 (s, 3H), 3.46 in (s, 3H), of 3.77 (s, 3H), 3,82 (s, 3H), of 3.94 (s, 3H), 5,33 (d, 1H, J=10.4 Hz), 6,17 (d, 1H, J=10.4 Hz), 6.48 in (s, 1H), of 8.06 (s, 1H)
288to 2.42 (s, 3H), 3,70 (s, 3H), of 3.77 (d, 1H, J=11,6 Hz), 3,86 (s, 3H), of 4.00 (s, 3H), 6,32 (d, 1H, J=11,6 Hz), to 6.58 (s, 1H), 6,72 (s, 1H), 8,18 (s, 1H)
289of 1.30 (t, 3H, J=6.8 Hz), to 2.35 (s, 3H), 3,74 (d, 1H, J=11.2 Hz), of 3.78 (s, 3H), 3,86 (q, 2H, J=6.8 Hz), 3,93 (s, 3H), 6,24 (d, 1H, J=11.2 Hz), 6,50 (s, 1H), 6,65 (s, 1H), 8,11 (s, 1H)
290of 1.41 (t, 3H, J=4.4 Hz), 2,24 (s, 3H), of 3.77 (s, 3H), 3,82 (s, 3H), 4.09 to (s, 3H), of 4.44 (q, 2H, J=4.4 Hz), are 5.36 (d, 1H, J=9.6 Hz), 6,34 (d, 1H, J=9.6 Hz), 6.48 in (s, 1H), 7,98 (s, 1H)
291of 1.35 (t, 3H, J=4.4 Hz), of 2.33 (s, 3H), 3,49 (s, 3H), of 3.77 (s, 3H), 3,83 (s, 3H), of 4.44 (q, 2H, J=4.4 Hz), 5,38 (d, 1H, J=10.0 Hz), 6,23 (d, 1H, J=10.0 Hz), 6.48 in (s, 1H), 8,17 (s, 1H)
292of 2.34 (s, 3H), 3,51 (s, 3H), of 3.77 (s, 3H), 3,82 (s, 3H), of 3.95 (s, 3H), 5,31 (d, 1H, J=10.4 Hz), 6,23 (d, 1H, J=10.4 Hz), 6,47 (s, 1H), at 8.36 (s, 1H)
2932,24 (s, 3H), 3,53 (s, 3H), of 3.77 (s, 3H), 3,83 (s, 3H), of 3.97 (s, 3H), 4,50-4,65 (user., 1H), 6,28-6,34 (user., 1H), 6.48 in (s, 1H), 8,16 (s, 1H)
294of 2.35 (s, 3H), 3,29 (s, 3H), 3,74 (s, 3H), 3,82 (s, 3H), 3,90 (s, 3H), 4,86-4,88 (user., 1H), to 6.19-6.22 per (user., 1H), 6,51 (s, 1H), 8,31 (s, 1H)
2952,32 (s, 3H), 3,52 (s, 3H), of 3.77 (s, 3H), 3,82 (s, 3H), 4,11 (s, 3H), 5,32 (d, 1H, J=10.0 Hz), 6,21 (d, 1H, J=10.0 Hz), 6,55 (s, 1H), 8,07 (s, 1H)
296of 2.10 (s, 3H), and 2.26 (s, 3H)and 3.59 (s, 3H), of 3.73 (s, 3H), of 3.77 (s, 3H), of 5.15 (d, 1H, J=9,2 Hz), 6,41 (d, 1H, J=9,2 Hz), 6.42 per (s, 1H), 8,08 (s, 1H)
297to 2.18 (s, 3H), 3,62 (s, MN), 3,76 (s, 3H), 3,81 (s, 3H), 5,02 (users, 1H), 6,41 (users, 1H), 6,46 (s, 1H), to 8.57 (s, 1H)
298of 2.21 (s, 3H), 2,42 (s, 3H), and 3.72 (s, 3H), 3,79 (s, 3H), 3,81 (s, 3H), equal to 4.97 (d, 1H, J=10.0 Hz), 6,07 (d, 1H, J=10.0 Hz), 6,46 (s, 1H), 7,86 (s, 1H)
2992,17 (s, 3H), of 2.33 (s, 3H), of 3.54 (s, 3H), 3,79 (s, 3H), of 3.84 (s, 3H), of 3.97 (s, 3H), 5,32 (d, 1H, J=10.0 Hz), 6,23 (d, 1H, J=10.0 Hz), of 6.49 (s, 1H), 8,21 (s, 1H)
3002,32 (s, 3H), 3,37 (s, 3H), of 3.75 (s, 3H), 3,79 (s, 3H), 3,81 (s, 3H), 4,28 (d, 1H, J=6.0 Hz), 5,59 (DD, 1H, J=10.4 Hz and 46.8 Hz), 5,97 (DD, 1H, J=10.4 Hz and 46.8 Hz), 6,27 (d, 1H, J=6.0 Hz), 6,47 (s, 1H), 8,08 (s, 1H)
301of 2.26 (s, 3H), of 2.38 (s, 3H), of 3.69 (s, 3H), 3,85 (user., 1H), a 3.87 (s, 3H), of 4.00 (s, 3H), 6,13 (s, 1H), to 6.57 (s, 1H), 6,72 (s, 1H), 8,11 (s, 1H)
303to 2.18 (s, 3H), of 2.50 (s, 3H)and 3.59 (s, 3H), 3,81 (s, 3H), 3,85 (s, 3H), 6.42 per (user., 1H), 6,50 (s, 1H), compared to 8.26 (s, 1H)
304of 2.25 (s, 3H), of 2.50 (s, 3H), of 3.64 (s, 3H), 3,81 (s, 3H), a 3.87 (s, 3H), 5,98 (d, J=7,6 Hz, 1H), of 6.52 (s, 1H), of 7.75 (s, 1H), of 8.37 (d, J=2.4 Hz, 1H)

Derived benzoylpyridine represented by the formula (I)or its salt can be used as an active ingredient or a fungicide, especially as an active ingredient for agricultural and horticultural fungicide. As agricultural and horticultural NGF is of Izida it effectively to combat such diseases, as piricularia, brown spot and stem canker sheaths of rice (Oryza sativa); powdery mildew, scab, rust, snow mold, the head smut, ocellar spot, leaf spot or blight flakes of barley (Hordeum vulgare); melanosis or scab of citrus (Citrus); grey mould, powdery mildew, Alternaria leaf spot or scab of Apple (Malus pumila); scab or black spot of pear (Pyrus serotina, Pyrus ussuriensis, Pyrus coiroiunis); Rhizoctonia, scab, or caused by a bacterium Fomitopsis rot of peach (Prunus persica); Anthracnose, glomerulosa rot, powdery mildew or downy mildew of grape (Vitis vinifera); Anthracnose or circular leaf spot of Japanese persimmon (Diospyros kaki); Anthracnose, powdery mildew, black mycosphaerellaceae rot or downy mildew of pumpkin (Cucumis melo); brown mottling, leaf mold or late blight of tomato (Lycopersicon esculentum); spotting Kress (Brassica sp., Raphanus sp., etc); brown spot and late blight of potato (Solanum tuberosum); powdery mildew of strawberry (Fragaria chiloensis); gray mold or stem rot of different cereals. It has an excellent effect particularly in the fight against powdery mildew of barley and vegetables and piricularia of Fig. In addition, it is also effective for controlling soil diseases caused by phytopathogenic is the present moment, such as Fusarium, Pythium, Rhizoctonia, Verticillium and Plasmodiophora.

The compound of the present invention can be used in combination with agricultural auxiliaries for various drugs fungicides containing this compound, such as dusty, granules, granular, wettable powders, wettable powders, aqueous suspensions, oily suspensions, water-soluble powders, emulsifiable concentrates, aqueous solutions, pastes, aerosols or microdose Farrukh Dustov. The compound of the present invention can be prepared in the form of any drugs that are usually used in agriculture or horticulture, unless satisfied the objectives of the present invention. As auxiliary substances, which can be used to obtain preparations, you can specify, for example, a solid carrier such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, a mixture of kaolin and sericite, clay, sodium carbonate, sodium bicarbonate, Glauber's salt, zeolites or starch; solvents such as water, toluene, xylene, naphtha, dioxane, acetone, isophorone, methyl-isobutylketone, chlorobenzene, cyclohexane, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone or alcohol; anionic surface-active agents or distributing agents, such as salts of fatty acids, benzoate, alkylsulfonate, diallylmalonate, polycarboxylate, salt alilovic esters of sulfuric acid, alkyl sulphates, alkylarylsulfonate, sulfates alkyldiphenyl ethers, salts of esters of sulphuric acid and alcohol, alkyl sulphonates, alkylarylsulphonates, arylsulfonate, ligninsulfonate, disulfonate alkyldiphenylamine simple ether, polystyrenesulfonate, salts of esters alkylphosphoric acid, alkylaromatic, stellarisware, salt of ester of sulfuric acid and polyoxyethylene Olkiluoto simple ether, sulphatepolyacrylamide-alkylsilanes simple ester, salt of ester of sulfuric acid and polyoxyethylene-alkylsilanes simple ether, fosfatidilinositola-Olkiluoto simple ester, salt of polyoxyethylene-alkylarylsulfonate of ester or salt condensate naphtalenesulfonic acid and formalin; nonionic surface-active or distributing agents, such as sorbitane esters of fatty acids, glycerol esters of fatty acids, polyglyceryl fatty acids, ethers of polyglycols and alcohols-derivatives of fatty acids, acetylglycine, acetylaspartic, oxyalkylene block polymers, polyoxyethylene alkalemia esters, polyoxyethylene-alkylacrylate ethers, polyoxyethylene-steelarrow simple ether is, alkalemia ethers of polyoxyethyleneglycol, polyoxyethylene esters of fatty acids, polyoxyethylenesorbitan esters of fatty acids, polyoxyethyleneglycol esters of fatty acids, utverjdenie the polyoxyethylene castor oil or polyoxypropylene esters of fatty acids; vegetable oils or mineral oils, such as olive oil, Kapok oil, castor oil, palm oil, camelliae oil, coconut oil, sesame oil, corn oil, rice oil, peanut oil, cottonseed oil, linseed oil, Tung oil or liquid paraffin. Known excipients can be selected from excipients, which are known in the field of agriculture and horticulture, not going beyond the subject of the present invention. In addition, you can use excipients that are commonly used, such as increasing the volume of agents, thickeners, agents preventing the deposition of anti-freezing agents, dispersion stabilizers, agents that reduce damage plants, or agents that protect against powdery mildew. Typically, the ratio in the mixture of the compounds of the present invention to the auxiliary substance is 0.005:99,995 to 95:5, preferably from 0.2:99,8 to 90:10. Such compositions, in practice, you can use either the to they are or when diluted their diluent, such as water, to the desired concentration and, if necessary, to add the spray agent. The concentration of the compounds of the present invention varies depending on the treated plants, method of application, form of the drug or the dose and, therefore, cannot be specified in General. However, in the case of processing leaves the concentration of the compounds as the active ingredient is usually from 0.1 to 10,000 million-1preferably from 1 to 2000 million-1. In the case of soil treatment, the concentration is usually from 10 to 100000 g/ha, preferably from 200 to 20,000 g/ha

The preparation of a fungicide containing compound of the present invention, or diluted product can be applied to any of the commonly used methods of application, such as dispersion (dispersion, spraying, misting, spraying tiny particles spreading in the form of grains or drawing on the water), soil (e.g., mixing or irrigation) or surface application (for example, coating, deposition of dust or surface coating). In addition, it can be made using the so-called ultra-low volumes. In this way, the preparation may contain 100% active ingredient.

The fungicide of the present invention can be mixed or used, for example, instead of the ones with other agricultural chemical, such as insecticide, miticide, nematocide, fungicide, antiviral agent, an attractant, a herbicide or a plant growth regulator. Sometimes in that case it is possible to achieve even greater effect.

Examples of compounds active ingredients (common name; including the compounds being considered), insecticides, miticides or nematicides, i.e. pesticides, of the above agricultural chemicals include organic phosphorus compounds such as profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos-methyl, Arafat, prothiofos, fosthiazate, fastcars, cadusafos and disulfoton;

connection type carbamates such as carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, carbosulfan and benfuracarb;

derivatives delicatessen, such as cartap and thiocyclam;

organic chlorine compounds, such as dicofol and tetradifon;

organic metal compounds, such as terbutaline;

PYRETHROID compounds such as fenvalerate, permethrin, cypermethrin, deltamethrin, cigalotrin, tefluthrin, etofenprox and plutopress;

connection type benzoylacetone, such as diflubenzuron, chlorfluazuron, teflubenzuron and flufenoxuron;

compounds such juvenile hormone, such as methoprene;

connection is ireasoning type, such as pyridaben;

connection pyrazol type, such as fenpyroximate, fipronil, tebufenpyrad, amiprol, tolefree and acetool;

the neonicotinoids, such as Imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, neinteen and dinotefuran;

connection of hydrazine, such as tebufenozide, methoxyfenozide and chromafenozide;

compounds of the pyridine type such as peridural and flonicamid;

connection type tetronic acid, such as spirodiclofen;

connection type strobilurin, such as flociprin;

dinitrosobenzene, organic sulfur compounds, compounds of the type of urea, connection type, triazine, compounds of the type of hydrazone and other compounds, such as buprofezin, hexythiazox, amitraz, Chlordimeform, selflove, triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb, achiezer, etoxazole, cyromazine and 1,3-dichloropropene; AKD-1022 and IKA-2000. In addition, the fungicide of the present invention can be mixed or used in conjunction with microbial pesticide, such as agent W, or pathogenic virus insect, or an antibiotic, such as avermectin, milbemycin, spinosad or emamectin benzoate.

Among other agricultural chemicals examples of compounds of the active ingredients of fungicides (common name; including consideration of the is to be placed) include compounds of the type pyrimidinamine, such as mepanipyrim, Pyrimethanil and cyprodinil, connection type pyridinoline, such as fluazinam;

connection type azole, such as triadimefon, bitertanol, triflumizole, itaconate, propiconazol, penconazole, flusilazol, myclobutanil, tsyprokonazolu, tebuconazol, hexaconazole, vorconizole-CIS, prochloraz, metconazole, ipconazole, tetraconazole, expomanagement and ipconazole;

connection type finokalia, such as chinomethionat;

connection type dithiocarbamate, such as MANEB, zineb, MANCOZEB, polycarbamate, metiram and propineb; or

organic chlorine compounds, such as phtalic, CHLOROTHALONIL, hintzen;

connection type antifungals, such as benomyl, thiophanate-methyl, carbendazim and cyazofamid;

connection type cyanoacetamide, such as having cymoxanil;

connection type phenylamide, such as metalaxyl, metalaxyl M, oxadixyl, operas, benalaxyl, parallaxes and zeroforum;

connection type sultanovoy acid, such as dichlofluanid;

copper compounds such as copper hydroxide and Oxine Copper;

connection type isoxazol such as hydroxyethoxy;

organophosphorus compounds such as fosetyl-Al, calcots-methyl, 3-benzyl O,O-diisopropylphosphoramidite, O-ethyl S,S-diphenyltetrazolium and aluminum ethyl hydrophosphate;

connection type N-halogenoalkane, such as APTN and folpet;

connection type dicarboximide, such as procymidone, iprodione and vinclozolin;

connection type benzanilide, such as flutolanil, mepronil and zoxamide;

connection type piperazine, such as triforine;

compounds of the pyridine type such as pirivenas;

connection type carbinol, such as fenarimol and flutriafol;

connection type piperidine, fenpropidin;

connection type of the research, such as fenpropimorph;

ORGANOTIN compounds, such as fistinginaction and fantinato;

connection type urea, such as pencycuron;

connection type cinnamic acid, such as dimethomorph;

connection type carbamate, such as dietphenterm;

connection type cyanoferrate, such as fludyoksonil and fenpiclonil;

connection type strobilurin, such as AZOXYSTROBIN, kresoxim-methyl, etaminophen, Trifloxystrobin, picoxystrobin: (S 500F);

connection type oxazolidinone, such as famoxadone;

connection type thiazolecarboxamide, such as ethaboxam;

connection type silylamine, such as silthiofam;

connection type amenableto amino acids, such as iprovalicarb and benthiavalicarb;

connection type imidazolidine, such as fenamidone;

connection type hydroxyanisole, such as fenhexamid;

join the be the of zolsulphonate, such as glucolipid;

connection type, oxime esters, such as cyflufenamid;

connection type phenacemide, such as phenoxyl;

connection type a triazole, such as semiconical;

connection type anthraquinone; connection type crotonic acid; antibiotics and other compounds, such as isoprothiolane, tricyclazole, pyroxylin, dilamtin. Pro. benzene, jenoxifen, propanecarboxylate, spiroxamine, chlorpicrin, dazomet and METAM-sodium; BJL-993, BJL-994, S-510, S-505, MTF-753 and UIBF-307.

Below are some test cases for agricultural and horticultural fungicides of the present invention. However, these examples in no way limit the present invention.

In each of the tests to determine the efficiency of suppression of diseases (control) on the basis of the following criteria.

[control]:[the Degree of the outbreak: visual observation]

5: Not visible neither lesions nor the sporogony

4: Area of lesions, number of lesions or square sporogony is less than 10% of the corresponding values for untreated instances

3: Area of lesions, number of lesions or square sporogony is less than 40% from the corresponding values for untreated instances

2: the Area of lesions, number of lesions, or the area of the sporogony of the composition is scored less than 70% of the corresponding values for untreated instances

1: Area of lesions, number of lesions or square sporogony is at least 70% of the corresponding values for untreated specimens.

TEST EXAMPLE 1

The test for determining the protective effect against powdery mildew of wheat

Wheat (cultivar Norin-61-go) grown in plastic pots with a diameter of 7.5 cm, and when the wheat reaches the stage of half leaves, it is sprayed with 10 ml of a solution containing a certain concentration of the compounds of the present invention, by using a sprayer. After drying the solution infect wheat, causing conidiospore fungus powdery mildew, then wheat contain thermostatted chamber at 20°C. After 6-8 days after inoculation explore the area of the sporogony to determine the rate control using the above criteria. In the above connection№№1, 2, 8, 47, 58, 61, 62, 69, 73, 76, 77, 78, 83, 87, 91, 107, 110, 112, 114, 117, 119, 138, 250, 262 and 274 demonstrated results that match the performance of control 4 or above at a concentration of 500 million-1and connections№№3, 4, 5, 6, 7, 9, 10, 11, 13, 14, 18, 19, 23, 27, 30, 31, 32, 33, 34, 35, 36, 38, 40, 41, 43, 49, 50, 51, 54, 55, 56, 59, 65, 72, 74, 75, 82, 84, 89, 90, 92, 93, 94, 99, 100, 101, 102, 103, 104, 105, 106, 108, 109, 111, 113, 118, 120, 121, 122, 123, 124, 133, 136, 142, 158, 159, 186, 187, 188, 189, 190 191, 192, 193, 194, 199, 200, 210, 211, 213, 228, 243, 245, 249 252, 254, 272, 287, 288, 289, 290, 291, 292, 293, 294, 296, 297, 298, 299, 300, 302, 303, 304, 305, 306, 307, 30, 309, 310, 311, 312, 313, 314, 315, 316, 320 and 321 demonstrated results that match the performance of control 4 or above at a concentration of 125 million-1.

TEST EXAMPLE 2

The test for determining the protective effect against piricularia rice

Rice (variety: Nihonbare) grown in plastic pots with a diameter of 7.5 cm, and when the rice reaches the stage of half leaves, it sprayed with 10 ml of a solution containing a certain concentration of the compounds of the present invention by using a sprayer. After drying of the solution figure infect, causing the suspension conidiospore mushroom piricularia rice, then rice is kept in a box for insulinopenia at 20°within 24 hours, and then contain in a thermostatted chamber at 20°C. Through 6-11 days after inoculation examine the number of affected areas to determine the rate control using the above criteria. The result of the above compounds, compounds№№31, 56, 76, 90, 103, 136, 158, 293, 294, 307, 308, 309, 314, 315, 316 and 321 demonstrated results that match the performance of control 4 or above at a concentration of 500 million-1and compound No. 50, 74, 75 and 102 showed results that match the performance of control 4 or above at a concentration of 125 million-1.

TEST EXAMPLE 3

The test for determining the protective effect against powdery R is si eggplant

Eggplant (sort Senryo-2-go) grown in plastic pots with a diameter of 7.5 cm, and when the plants eggplant reach stage two of the leaves, sprayed with 10 ml of a solution containing a certain concentration of the compounds of the present invention, by using a sprayer. After drying the solution eggplant infect, causing conidiospore fungus powdery mildew of eggplant, then eggplant contain in a thermostatted chamber at 20°C. After 16 days after insulinopenia explore the area of the sporogony to determine the rate control using the above criteria. The result of the above connections№№1, 3, 5, 7, 92, 101 and 103 showed the results corresponding to the performance control 4 or above at a concentration of 500 million-1and connection No. 9, 11, 55, 90 and 102 showed results that match the performance of control 4 or above at a concentration of 125 million-1.

TEST EXAMPLE 4

The test for determining the protective effect against powdery mildew of cucumbers

Cucumber (variety Suyo) grown in plastic pots with a diameter of 7.5 cm, and when the cucumbers have reached the point of half of the leaves, sprayed with 10 ml of a solution containing a certain concentration of the compounds of the present invention, by using a sprayer. After drying the solution cucumbers, Sara the Ute, causing the suspension conidiospore fungus powdery mildew, then cucumbers contain in a thermostatted chamber at 20°C. After 7-11 days after insulinopenia explore the area of the sporogony to determine the rate control using the above criteria. The result of the above compounds compound No. 98 showed results that match the performance of control 4 or above at a concentration of 500 million-1and connections№№1, 5, 7, 9, 49, 55, 74, 90, 92, 93, 102, 103, 123, 124, 158, 159, 293, 294, 296, 297, 299, 300, 302, 303, 304, 305, 306, 307, 308, 313, 314, 315, 316 and 321 demonstrated results that match the performance of control 4 or above at a concentration of 125 million-1.

The following are examples of compositions containing the compounds of the present invention. However, examples in no way limit the dose of the compositions, dosage forms, etc.

EXAMPLE COMPOSITIONS 1

(1) the Compound of the present invention 20 weight. parts

(2) Clay 72 weight. parts

(3) Matrilineality 8 weight. parts

The above components are mixed until homogeneous, getting a wettable powder.

EXAMPLE COMPOSITION 2

(1) the Compound of the present invention 5 weight. parts

(2) Talc 95 weight. parts

The above components are mixed until homogeneous, receiving the dust.

An EXAMPLE of the COMPOSITION 3

(1) Connect this izaberete the Oia 20 weight. parts

(2) N,N-dimethylacetamide 20 weight. parts

(3) Alkylphenolic ether of polyoxyethylene 10 weight. parts

(4) Xylene 50 weight. parts

The above components are mixed to homogeneity and diluted getting emulsifiable concentrate.

An EXAMPLE of the COMPOSITION 4

(1) Clay 68 weight. parts

(2) Matrilineality 2 wescast

(3) Polyoxyethylene-alkylarylsulfonate 5 weight. parts

(4) a Fine-grained silicon dioxide 25 weight. parts

A mixture of the above components and the connection of the present invention are mixed in a weight ratio of 4:1, receiving a wettable powder.

An EXAMPLE of the COMPOSITION 5

(1) the Compound of the present invention 50 weight. parts

(2) the Oxidized polyalkylphenols-triethanolamine 2 wescast

(3) Silicone 0.2 weight. part

(4) Water 47,8 weight. part

The above components are mixed until smooth and crushed, getting the original solution, and then add to it

(5) Polycarboxylic sodium 5 weight. parts

(6) Anhydrous sodium sulfate 42.8 weight. parts

Then all mix until smooth, granularit and dried, obtaining granulated wettable powder.

An example of a COMPOSITION of 6

(1) the Compound of the present invention 5 weight. parts

(2) Polyoxyethylene-octylphenoxy ether 1 weight. part

(3) Polyoxyethylenated 0.1 weight. part

(4) Powdered calcium carbonate 93,9 the EU. part

The above components (1)to(3) are pre-mixed to homogeneity and diluted with an appropriate amount of acetone, diluted with a mixture of sprayed component (4) and the acetone is removed, obtaining granules.

An EXAMPLE of the COMPOSITION 7

(1) the Compound of the present invention to 2.5 weight. part

(2) N-methyl-2-pyrrolidone 2.5 weight. parts

(3) Soybean oil 95,0 weight. parts

The above components are mixed to homogeneity and diluted, getting composition of ultra-low volume.

An EXAMPLE of the COMPOSITION 8

(1) the Compound of the present invention 20 weight. parts

(2) the Oxidized polyalkylphenols-triethanolamine 2 weight. part

(3) Silicone 0.2 weight. part

(4) Resin xanthan 0.1 weight. part

(5) ethylene Glycol 5 weight. parts

(6) Water 72,7 weight. part

The above components are mixed until smooth and crushed, getting aqueous suspension.

Industrial applicability

As mentioned above, derivatives of benzoylpyridine represented by the formula (I)or their salts have an excellent effect as an active ingredient fungicides.

1. Derived benzoylpyridine represented by the formula (I)or its salt

where X represents a halogen atom, a C1-6alkoxygroup, optionally substituted Deputy selected from halogen, phenyl which, methoxy, methylthio, dimethylamino, vinyl and ethinyl; fenoxaprop; C3-6cycloalkanes; a hydroxyl group; C1-6alkyl group; C2-6alkenylphenol group; a group of CF3;1-6-allylthiourea; cyano; C1-6alkoxycarbonyl group; C1-6dialkylaminoalkyl group; C1-6alkylcarboxylic; C1-6alkylcarboxylic group; an amino group; C1-4alkylamino; or di-C1-4alkylamino; n represents 1, 2, 3 or 4; R1is1-6alkyl group; R2is1-6alkyl group; C1-6alkoxygroup, optionally substituted by phenyl; fenoxaprop; C3-10cycloalkanes or hydroxyl group; and m is 1, 2 or 3, provided that when m is 2, R2may form a ring-och2O- (except when the pyridine ring is substituted bentilee group in 2-position; the pyridine ring substituted With1-6alkoxygroup, a hydroxyl group or benzyloxypropionic in the 3-position; and n is 1, m is 1 or 2)

as the active ingredient of the fungicide.

2. Derived benzoylpyridine or its salt according to claim 1 as an active ingredient of a fungicide, where X represents a halogen atom, a C1-6alkoxygroup, optionally substituted Zam is the Titel, selected from halogen, phenyl, methoxy, methylthio, dimethylamino, vinyl and ethinyl; fenoxaprop; C3-6cycloalkanes; a hydroxyl group; C1-6alkyl group; C3-6alkenylphenol group; a group of CF3;1-6allylthiourea; cyano or amino group; C1-4alkylamino; di-C1-4alkylamino.

3. Derived benzoylpyridine or its salt according to claim 1 as an active ingredient of a fungicide, where m is 2 or 3.

4. Derived benzoylpyridine or its salt according to claim 1 as an active ingredient of a fungicide, where R1is1-6alkyl group, and R2is1-6alkyl group, a C1-6alkoxygroup or hydroxyl group.

5. Derived benzoylpyridine or its salt according to claim 1, represented by formula (I')

where X, n and R1have specified in claim 1 values, R2'is1-6alkyl group, a C1-6alkoxygroup, fenoxaprop,3-10cycloalkanes or hydroxyl group, p is 1 or 2, and R2"is1-6alkoxygroup or hydroxyl group, provided that two of R2’and R2"may form a ring-och2O- (except when (1) a pyridine ring substituted by a benzoyl group at the 2-position the Institute; the pyridine ring is substituted With1-6alkoxygroup, a hydroxyl group or benzyloxypropionic in the 3-position; and n is 1, R is 1; and (2) a pyridine ring substituted by a chlorine atom or a bromine atom in the 2-position and n is 1).

6. Derived benzoylpyridine or its salt according to claim 5, represented by formula (I")

where X represents a halogen atom, a C1-6alkoxygroup, optionally substituted Deputy selected from halogen, phenyl, methoxy, methylthio, dimethylamino, vinyl and ethinyl; fenoxaprop,3-10-cycloalkane group1-6allylthiourea, cyano, C1-6alkoxycarbonyl group1-6dialkylaminoalkyl group1-6alkylcarboxylic group1-6alkylcarboxylic group, amino group, With1-4alkylamino or di-C1-4-alkylamino; n is 1, 2, 3 or 4; R1is1-6alkyl group; R2'is1-6alkoxygroup; p is 1 or 2; and each of R2"and R2"'is1-6alkoxygroup.

7. Derived benzoylpyridine or its salt according to claim 5, represented by formula (I"')

where X represents a halogen atom, a C1-6alkoxygroup,1-6alkyl group, a group of CF3or1- allylthiourea; n is 1, 2, 3 or 4; R1is1-6alkyl group; R2'is1-6alkoxygroup; p is 1 or 2; and each of R2"and R2"'is1-6alkoxygroup.

8. Derived benzoylpyridine or its salt according to claim 5, represented by formula (I"")

where X represents a halogen atom, a C1-6alkoxygroup,1-6alkyl group, a group of CF3or1-6allylthiourea; n is 1, 2 or 3; R1is1-6alkyl group; R2'is1-6alkoxygroup, p is 1 or 2; and each of R2"and R2"'is1-6alkoxygroup.

9. Derived benzoylpyridine or its salt of claim 8, represented by formula (I"')

where In represents-SH4=if a is-N=; is-N=, if a represents-CH=; each of X1and X2who are independent from each other, represents a halogen atom, a C1-6alkoxygroup,1-6alkyl group, a group of CF3or1-6allylthiourea; X3represents a hydrogen atom, a halogen atom, a C1-6alkoxygroup or1-6alkyl group; X4represents a hydrogen atom, a halogen atom, a C1-6alkoxygroup or16 allylthiourea; R1is1-6alkyl group; R2'is1-6alkoxygroup; p is 1 or 2; and each of R2"and R2"'is1-6alkoxygroup.

10. The fungicide, which contains as an active ingredient derived benzoylpyridine represented by the formula (I')or its salt according to claim 5.

11. The method of obtaining the derived benzoylpyridine represented by the formula (I')or its salt

where X, n and R1have specified in claim 1 values, R2'is1-6alkyl group, a C1-6alkoxygroup, fenoxaprop,3-10cycloalkanes or hydroxyl group; p is 1 or 2, and R2"is1-6alkoxygroup or hydroxyl group, provided that two of R2'and R2"may form a ring-och2Oh, except when the pyridine ring is substituted bentilee group in 2-position; the pyridine ring substituted With1-6alkoxygroup, a hydroxyl group or benzyloxypropionic in the 3-position; and n is 1, p is 1), which includes the interaction of the substituted benzaldehyde represented by the formula (VI-1)

(where R1, R2’, R2"and R are specified in the above values), and salts of substituted pyridine derivative with the metal represented by formula (VII-1)

(where X has the values indicated above, Z represents a metal atom or a mixed salt) to produce phenylenediamine represented by formula (X')

(where X, n, p, R1, R2'and R2"have the above values, under the conditions described for formula (I')), and its oxidation.

12. The method of obtaining the derived benzoylpyridine represented by the formula (I')or its salt

where X, n and R1have specified in claim 1 values; R2'is1-6alkyl group, a C1-6alkoxygroup, fenoxaprop,3-6cycloalkanes or hydroxyl group; p is 1 or 2, and R2"is1-6alkoxygroup or hydroxyl group; provided that two R2'and R2"may form a ring-och2Oh, except when the pyridine ring is substituted bentilee group in 2-position; the pyridine ring substituted With1-6alkoxygroup, a hydroxyl group or - benzyloxypropionic in the 3-position; and n is 1, p is 1), which includes the engagement of salt substituted derivative of benzo is and the metal, represented by formula (VI-2)

(where R1, R2'and R have the above values, and Z represents a metal atom or a mixed salt), and substituted peredelanaya represented by the formula (VII-2)

(where X has the above values), with phenylenediamine represented by formula (X')

(where X, n, p, R1R2'and R2"have the above values, under the conditions described for formula (I')), and its oxidation.

13. Phenylenediamines represented by the formula (X)

where X represents a halogen atom, a C1-6alkoxygroup,1-6alkyl group, a C2-6alkenylphenol group, a group of CF3; or (C1-6alkoxycarbonyl group; n is 1, 2, 3 or 4; R1represents C1-4alkyl group; R2is1-4alkyl group, a C1-6alkoxygroup,3-10cycloalkanes, or two R2located in positions 4 and 5, form a group-och2O-; and m is 1, 2 or 3, except when the pyridine ring is substituted α-hydroxybenzene group in 2-position; the pyridine ring substituted With1-6alcox the group in 3-position; and n is 1, m is 1 or 2).

14. Phenylenediamines indicated in paragraph 13 is represented by formula (X')

where X, n and R1are specified in clause 13 values, R2'is1-4alkyl group, a C1-6alkoxygroup or3-10cycloalkanes; p is 1 or 2, and R2"is1-6alkoxygroup, provided that two R2'and R2"can form a group (-och2O-) (except when the pyridine ring is substituted α-hydroxybenzene group in 2-position; the pyridine ring substituted With1-6alkoxygroup in the 3-position; and n is 1, p is 1).

15. Phenylenediamines on 14 represented by the formula (X")

where X represents a halogen atom, a C1-6alkoxygroup,1-4alkyl group, a C2-6alkenylphenol group, a group of CF3;1-6alkoxycarbonyl group, n is 1, 2, 3 or 4; R1is1-4alkyl group; R2'is1-6alkoxygroup, p is 1 or 2, and each of R2"and R2"'is1-6alkoxygroup.

16. Phenylenediamines on 14 represented by the formula (X"')

where X represents a halogen atom, a C1-6alkoxyl the PPU, With1-4alkyl group or a group of CF3; n is 1, 2, 3 or 4; R1represents C1-4alkyl group; R2'is1-6alkoxygroup; p is 1 or 2; and each of R2"and R2"'is1-6alkoxygroup.

17. Phenylenediamines on P16, represented by formula (X'"')

where In represents-SH4=if a is-N=; is-N=, if a represents-CH=; each of X1and X2who are independent from each other, represents a halogen atom, a C1-6alkoxygroup, C1-4alkyl group or a group of CF3; X3represents a halogen atom or a group of CF3; X4represents a hydrogen atom or halogen atom; R1represents C1-4alkyl group; R2'is1-6alkoxygroup; p is 1 or 2; and each of R2"and R2"'is1-6alkoxygroup.



 

Same patents:

FIELD: organic chemistry, chemical technology.

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

EFFECT: improved method for preparing.

8 cl, 3 ex

FIELD: chemistry of metalloorganic compounds, medicine, oncology.

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

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

2 cl, 3 ex

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

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

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

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

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

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

R3-

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

The invention relates to new salts of pyridinium General formula (I) or their pharmaceutically acceptable salts, where R1is-R4- R5or-N(R7)N(R7R9, R4choose from the group of-N(R7R6O-, N(R7R6N(R7), -OR6O-,

-OR SIG6N(R7)-, where R6- alkyl, R5choose from the group of alkyl, aryl, including heteroaryl, -COR7, -SO2R7and-COR10where R7Is H, alkyl or aryl, including heteroaryl, R2Is F, Cl, Br, J, alkyl, aryl, including heteroaryl, formyl, acyl, C(O)NR7R10or C(O)or SIG7, m = 0, 1, or 2, R3selected from the group comprising R7OR7N(R7)(R10) and CH(R7)C(O)R8, R8is R7OR7and NR7R10, R9is hydrogen, alkyl, aryl, including heteroaryl, -C(O)R10, -SO2R10, -C(S)OTHER10, -C(NH)NH(R10), -C(O)OTHER10, R10- H, alkyl, or aryl, including heteroaryl, and in each case, it is not necessarily different from R7X represents an ion halogen provided that 1) when two alkyl groups are the same carbon or nitrogen, they are not necessarily linked together with the formation of a cyclic structure, and (2) nitrogen heteroaryl ring R1

The invention relates to the field of organic chemistry

The invention relates to new compounds of the formula (I)

< / BR>
where AG represents a radical selected from formulas (a) and (b) below:

< / BR>
R1represents a halogen atom, -CH3CH2OR SIG7, -OR SIG7, СОR8, R2and R3taken together form a 5 - or 6-membered ring, R4and R5represent H, a halogen atom, a C1-C10-alkyl, R7represents H, R8represents H orX represents the radical-Y-C-, r' and r" is H, C1-C10alkyl, phenyl, Y represents S(O)nor SE, n = 0, 1, or 2, and salts of compounds of formula (I)

The invention relates to new Bermatingen compounds, the United propylenebis communication, General formula I where Ar represents a radical of formula (a) or (b), R1is-OR6or-COR7, R2represents a polyether radical, comprising 1 to 6 carbon atoms and 1 to 3 atoms of oxygen or sulfur, and if in the latter case, R4represents a linear or branched C1-C20alkyl, he is in ortho - or meta-position relative to X-Ar connection, R3represents lower alkyl, or R2or R3taken together form a 6-membered ring, optionally substituted by at least one of the stands and/or optional split the atom of oxygen or sulfur, R4represents H, linear or branched C1-C20alkyl or aryl, R5represents H or-OR8, R6represents H, R7represents H, -OR10or-N(r)r (r) r are H, lower alkyl or taken together with the nitrogen atom form a ring of morpholino, R8represents H or lower alkyl, R10represents H, linear or branched C1-C20alkyl, X represents a divalent radical, which is from right to left or Vice versa has the formula (d), R11Fri carboxylic acid and the optical and geometrical isomers of the above compounds of formula (I)

The invention relates to new compounds of the formula (I)

in which Ar1means pyrazole which may be substituted by one or more groups R1, R2or R3; Ar2means naphthyl, tetrahydronaphthyl, each of which is optionally substituted by 0-1 groups R2; X means5-C8cycloalkenyl, phenyl, optionally substituted by a hydroxy-group or1-C4alkoxygroup, furan, pyridinoyl, pyrazolyl, pyridinyl, optionally substituted by a hydroxy-group or1-C4alkoxygroup, piperidinyl; Y represents a bond or a saturated branched or unbranched1-C4the carbon chain, with one methylene group is optionally replaced with NH, or and Y is optionally independently substituted by oxopropoxy; Z means morpholine, group, pyridinyl, furanyl, tetrahydrofuranyl, thiomorpholine, pentamethylbenzene, pentamethylbenzene, secondary or tertiary amine, the nitrogen atom of the amino group covalently linked to the following groups selected from a range that includes the C1-C3alkyl and C1-C5alkoxyalkyl; R1means31-C6alkyl which is optionally partially or fully galogenidov, halogen; R3means phenyl, pyrimidinyl, pyrazolyl, which is substituted by one branched or unbranched1-C6the alkyl, and pyridinyl, optionally substituted C1-C3alkoxygroup or amino group, W denotes O and its pharmaceutically acceptable salts

The invention relates to new derivatives of 1,3-diaryl-2-pyridin-2-yl-3-(pyridine-2-ylamino)propanol of the formula (I)

where Z denotes-NH-(C1-C16-alkyl)-(C=O)-; -(C=O)-(C1-C16-alkyl)-(C=O)-;

-(C=O)-phenyl-(C=O)-; AND1AND2AND3AND4denote independently of each amino-acid residue, E represents-SO2-R4and-CO-R4; R1- phenyl, thiazolyl, oxazolyl, thienyl, thiophenyl and others, R2- N., HE, CH2HE, OMe; R3Is h, F, methyl, OMe; R4denotes -(C5-C16-alkyl), -(C0-C16-alkylen)-R5, -(C=O)-(C0-C16-alkylen)-R5, -(C=O)-(C0-C16-alkylene)-NH-R5and others, R5denotes-COO-R6, -(C=O)-R6-(C1-C6-alkylen)-R7, phenyl, naphthyl and others, R6denotes H, -(C1-C6) alkyl; R7denotes H, -(C1-C7-cycloalkyl, phenyl, naphthyl and others, l, q, m, n, o, p denote 0 or 1, and l+q+m+n+o+p is greater than or equal to 1, and their pharmaceutically acceptable salts

The invention relates to arylpiperazines General formula I

< / BR>
where is phenyl, pyridyl or pyrimidyl; each R3- H, halogen, NO2, СООR, where R is H, C1-6alkyl, CN, CF3WITH1-6alkyl, -S - C1-6alkyl, -SO-Cl - C1-6alkyl, -SO2-Cl-C1-6alkyl, C1-6alkoxy and up to10aryloxy, n= 1, 2, or 3; R is a direct bond; And - piperazinil, X1and X2IS N; Y IS-SO2-; Z IS - N(OH)-CHO; Q - CH2-; R1- H, C1-6alkyl, C5-7cycloalkyl until10aryl, until10heteroaryl until1-2aralkyl or until12heteroallyl, R4- H, C1-6alkyl, and others; R2- H, C1-6alkyl, or together with R1- carbocyclic or heterocyclic Spiro 5-, 6 - or 7-membered ring containing at least one heteroatom selected from N, O or S, and the group Q can be associated either with R1or R2with the formation of 5,- 6 - or 7-membered alkyl or heteroalkyl ring that includes one or more O, S or N

The invention relates to amino acid derivatives of the formula I

< / BR>
or its non-toxic salt or its hydrate, the pharmaceutical composition having inhibitory effect on calcium channel iv-type; the inhibitor calcium channel N-type; a pharmaceutical composition for prevention and/or treatment of cerebral infarction and pharmaceutical compositions for the treatment of pain

The invention relates to derivatives of N-(4-carbamimidoyl) glycinamide formula (I), where E denotes hydrogen or HE, Q denotes hydrogen or alkyl, R is aryl, cycloalkyl or alkyl substituted radicals R1, R2, R3, R1denotes hydrogen, COOH, COO-alkyl or aryl, R2denotes hydrogen, aryl, cycloalkyl or heteroaryl, R3denotes hydrogen, aryl or HE (in any position other thanposition relative to the nitrogen atom is attached to an alkyl group R) or optional substituted by an amino group, three of the radicals X1-X4denote the group of C(Ra), C(Rb) or C(Rc), and the fourth represents C(Rd), Ra-Rddenote H, HE, NO2dialkylamino, halogen, alkyl, alkoxy, aryloxy, aralkylated, heteroarylboronic, geterotsiklicheskikh, COOH, COO-alkyl, NH-SO2-alkyl, NH-SO2-aryl, two adjacent groups Ra-Rbdenote alkylenedioxy, G1and G2denote hydrogen, HE, the invention relates to intermediate compounds of the formula (IV), (V), (VI) used in the methods of making compounds of formula (I), and are in взаимодействCN, the nitrile of formula (IV) is transformed into amidinopropane C(N-G1)NH-G2

The invention relates to benzosulfimide derivative of the formula I, where R1denotes hydrogen, R2denotes hydrogen, trifluoromethyl or (ness.)alkyl, R3denotes hydrogen or amino, or R1and R2or R3and R2together represent a group-CH= CH-CH= CH-, Z denotes pyrimidine-4-yl, pyridine-4-yl, pyridine-2-yl or phenyl, R4, R5each independently of one another denotes hydrogen, (ness.)alkyl, trifluoromethyl, halogen, (ness.)alkoxy, nitrile, amino, (ness.)alkylamino-, di(ness.)alkylamino, piperazinil, morpholinyl, pyrrolidinyl, vinyl, WITH3-C6cycloalkyl,3-C6cycloalkenyl, tert-butylamine, hydroxyalkylated, phenylethyl, naphthyl, thiophenyl or phenyl which may be substituted with halogen, (ness.)alkoxyl, (ness.)the alkyl, trifluoromethyl or nitro-group, or a group-NH(CH2)nNR6R7, -N(CH3)(CH2)nNR6R7, -NH(CH2)n-morpholine-4-yl or-NH(CH2)nOH, n denotes the number of 2-4, R6and R7each independently of one another denotes hydrogen or (ness.)alkyl, and their pharmaceutically acceptable salts

The invention relates to the derivatives of propanolamine formula (I) and their pharmaceutically acceptable salts, where R1and R2means phenyl, naphthyl, pyridyl, thienyl, pyrimidyl, thiazolyl, hinely, piperazinil, oxazolyl, which may be substituted with halogen, HE, NO2, NH2, COOH, etc., R3-R8mean hydrogen, hydroxyl, (C1-C8-alkoxy, NH2-THE OTHER9, -N(R9R10, R9-R10mean hydrogen or (C1-C8)alkyl, X is CH or N, Y represents CH or N, provided that the residues R1, R2X and Y are not simultaneously mean R1- phenyl, R2is phenyl, X is CH, Y is CH

FIELD: organic chemistry, biochemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new sulfur-containing compounds of the formula (I):

their pharmaceutically acceptable salts or solvates, or salt solvates wherein R1 represents (C1-C6)-alkyl, cycloalkyl, aryl, aliphatic or aromatic heterocyclyl substituted with one more basic group, such as amino-, amidino- and/or guanidine-group; R2 represents hydrogen atom (H), alkyl, alkylthio-, alkoxy- or cycloalkyl group; R3 represents COOR5, SO(OR5), SOR5 and others; R4 represents hydrogen atom (H) or (C1-C6)-alkyl; R6 represents hydrogen atom (H); X represents C(Z)2 or NR6CO; Y represents C(Z)2; Z represents hydrogen atom (H), (C1-C6)-alkyl, aryl or cycloalkyl. Indicated compounds inhibit activity of carboxypeptidase U and can be used for prophylaxis and treatment of diseases associated with carboxypeptidase U.

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

14 cl, 36 ex

Up!