UA78959C2 - Method for producing phenylsemicarbazones and intermediate - Google Patents

Abstract

The invention relates to a method for producing semicarbazone compounds of formula (I) wherein R1 and R2 independently represent hydrogen, halogen, CN, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy, and R3 represents C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy. According to said method, a hydrazone compound of general formula (II), wherein R represents C1-C4 alkoxy, amino, C1-C4 alkylamino or di-(C1-C4-alkyl)amino, and R1 and R2 have the above-mentioned designations, is reacted with an aniline compound of general formula (III) wherein R3 has the above-mentioned designation.

Description

Description of the invention

This invention relates to a method of obtaining compounds based on semicarbazones of the formula

No, and in which B" and B? independently of each other mean hydrogen, halogen, CM, C-C alkyl, C-C; -alkyl,

C.-C, -haloalkyl or C.-C.sub.-haloalkyl, and BZ stands for C.-C.u- alkoxy, C.sub.4-C.sub.-haloalkyl or C.sub.4-C.sub.-haloalkyl.

From (EP-A 462 456) compounds of formula I are known, which exhibit insecticidal activity. they are obtained starting from benzylphenylketones of formula IM, represented in schemes 1 and 2 by the following methods:

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However, when carrying out the interaction of phenylbenzylketone IM with M-phenylsemicarbazide MI as shown in scheme 1, the compound | with low outputs. In addition, semicarbazide MI must be obtained at a separate stage of the reaction from the corresponding aniline. h . . them - and? The disadvantage of the method depicted in scheme 2, on the one hand, is the use of hydrazine at the first stage of the reaction, which, in order to avoid the formation of by-products, must be used in a large excess. As

It is known that hydrazine refers to a potentially carcinogenic substance, which, moreover, when in contact with metal materials, is prone to spontaneous decomposition with the release of gas. Thus, the use of hydrazine on an industrial scale in view of safety is possible only with large technical costs. In addition, the removal of hydrazine wastes formed during this reaction, in

Gee! on an industrial scale is associated with high costs, since the chemical destruction of highly concentrated solutions based on hydrazine results in the release of a large amount of heat and at the same time a significant amount of gas is released. Thus, the use of hydrazine is the main cost factor in the implementation of this method.

Another disadvantage of the method presented in Scheme 2 is the use of phenylisocyanates of MIA, which, on the one hand, due to their toxicity, requires the use of special safety measures during their use, and, on the other hand, they must be obtained at a separate stage of the reaction from the corresponding anilines.

Thus, the basis of this invention is the task of developing a method for obtaining compounds based on semicarbazones of the general formula I, which contributes to obtaining a high yield of compound I, which is characterized by high purity, and allows overcoming the shortcomings of the state of the art described here. that high yields of compounds based on semicarbazones of the general formula I!, which is characterized by high purity, can be obtained by the interaction of compounds based on hydrazones of the general formula Ii, b5 sa: FI c, i snev c and in which KE means C .-C.alkoxy .

MN; . you are in in "he ate t yar". in which VZ has the above value.

Thus, the object of this invention is a method of obtaining compounds based on semicarbazones of the general formula I, which includes the interaction of a compound based on a hydrazone of the general formula II with an aniline-based compound of the general formula III.

Compounds based on hydrazone of the general formula II, in turn, can be obtained analogously to known methods of the state of the art from benzylphenyl ketones of the formula IM and; school D

LKK dk "B de she Y He") in which B", 22 have the values indicated above, through the interaction of IM with the hydrazide of the formula Muckey

Sk va E no M. in which K has the above value. Therefore, the method according to the invention also includes the preparation of compounds based on hydrazone II by the method described above.

Hydrazone-based compounds of formula II, in which B? - SM, are new and as starting or intermediate products of the method according to the invention, they are also the object of this invention.

By the definitions of the variables EC, В", В? and КЗ specified in the formulas above, we mean collective non) с concepts, which are the general values of the corresponding substituents. The value Со n-Ст reflects the possible number of carbon atoms in the corresponding substituent or component of a substituent In addition, substituents have the following meanings: halogen: fluorine, chlorine, bromine and iodine alkyl and all alkyl residues in alkoxy, alkylamino and dialkylamino: saturated, straight or branched hydrocarbon residues containing from 1 to 4 atoms carbon, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl (tert-butyl); (ee) haloalkyl, as well as haloalkyl residues in haloalkyl: unbranched or branched alkyl groups containing from 1 to 4, in particular 1 or 2 carbon atoms (as indicated above), and in these groups, hydrogen atoms can be partially or completely replaced by halogen atoms, as indicated above, in particular by fluorine sl 250 ( fluoroalkyl), for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, with 1-chloroethyl, 1-bromomethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl , 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl , heptafluoropropyl and 1,1,1-trifluoroprop-2-yl. A preferred haloalkyl is C1-C0-fluoroalkyl, such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, trifluoromethyl and

HF) difluoromethyl.

For the implementation of the method according to the invention, the variant in which K in the formula II, as well as in the formula M means C, -C, - alkoxy, in particular methoxy, turned out to be particularly preferable.

According to another preferred embodiment of the invention, K means MH 5, C-C-alkylamino or 60 di-(Ci-C-C-alkyl)zamino. In this case, K preferably means amino (МНо), methylamino, ethylamino or dimethylamine, in particular МН".

The advantages of the method according to the invention are manifested, in particular, in the preparation of compounds of formula I, in which the variables K1, p? and EZ independently of each other and especially preferably together have the following values: в5 B means C1-C1-haloalkyl, in particular trifluoromethyl, namely trifluoromethyl, which is in the meta-position (position C) of the phenyl ring;

IN? means cyano, namely cyano in the para position (position 4);

BZ stands for C.-C.-halo-alkoxy, in particular trifluoromethoxy, namely trifluoromethoxy, which is in the para-position.

To carry out the interaction of the compound based on aniline ШИ with the hydrazone derivative I, the compounds are preferably used in a molar ratio of PI: in the range from 1:1.5 to 1.5:1, in particular from 1:1 to 1.3:1, especially preferably from 1.02:1 to 1.2:1.

The interaction of the aniline-based compound PSh with the hydrazone-based compound II is preferably carried out at a temperature above room temperature, for example, from 30 to 2002С, in particular from 50 to 1802С, especially preferably from 70 to 70 1509Сb. For the successful implementation of the method, the reaction pressure plays a secondary role, it can be, for example, from 500mbar to 10bar. The reaction is preferably carried out at normal pressure, that is, at a pressure of 0.9 to 1.2 bar. The reaction time required for the interaction is, as a rule, from 1 hour to 24 hours, in particular from 3 to 12 hours.

The interaction can be carried out without a solvent. However, preferably, the compound based on aniline II is subjected to 75 interaction with the compound based on hydrazone II in an organic solvent. All solvents capable of at least partially, preferably completely, dissolving compounds II and II under reaction conditions are suitable. The preferred solvents are aprotic. In particular, we are talking about such solvents, the boiling point of which at normal pressure is from 60 to 2002С, in particular from 80 to 15022. Particularly preferred solvents are aromatic solvents, in particular alkylbenzenes, such as toluene, xylenes, ethylbenzene, cumene (2-propylbenzene), cymols (isopropyltoluenes) and mesitylene, as well as chlorobenzenes such as chlorobenzene, 1,2-, 1,3- and 1,4-dichlorobenzene, aliphatic nitriles such as acetonitrile and propionitrile, and mixtures of these solvents.

The interaction of the compound based on aniline PP with the compound based on hydrazone I can be carried out in the presence of acid, but the use of acid is optional. Examples of suitable acids are sulfuric acid, organic sulfonic acids, in particular aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, aliphatic sulfonic acids such as methanesulfonic acid and o-trifluoromethanesulfonic acid, aromatic carboxylic acids such as benzoic acid and 4 -trifluoromethylbenzoic acid, as well as aliphatic carboxylic acids containing mainly from 1 to 3 carbon atoms, for example, acetic acid and propionic acid. As a rule, the acid is used in catalytic amounts, that is, in amounts less than 1 mol per mol of compound II or II, in particular less than 0.5 mol/mol, preferably (2) not more than 0.2 mol/mol. In the preferred embodiment of the method according to the invention, the interaction of I! with PI is carried out in the absence of acid.

Preferably, the K-H compound formed during the reaction of aniline II with hydrazone IS is, at least partially, Me) preferably not less than 5095, in particular not less than 80 95 during the reaction, is removed from the reaction mixture, so especially if under the compound K-H refers to a C,-C,-alkanol such as methanol or ethanol. For this purpose

The reaction is carried out at such a temperature and pressure, at which the VB-H compound, if necessary, is distilled off from the reaction mixture as an azeotrope with a solvent. If necessary, for compensation, a fresh solvent is introduced into the reaction or a solvent that is distilled off together with the K-H compound, if necessary, after removing the compound

VK-N is returned to the reaction. For this reason, the variant in which the boiling temperature of the solvent used is at least 10 K, in particular at least 30 K higher than the boiling temperature of the K-H compound formed during the reaction (respectively at normal pressure). The interaction of compound II with compound ІІ c) c) is expedient to be carried out in a device equipped with at least one distillation and rectification apparatus, for example, a distillation column that allows driving off compound K-H, if necessary, together with a solvent, and in the same time to isolate and return to the reaction the solvent, which, if necessary, was driven off together with the K-H compound.

For interaction, compounds II and I can be brought into contact with each other in any way. So, for example, compounds II and I, if necessary, together with the desired solvent, are placed in a reaction vessel, and then the necessary reaction conditions are created. In addition, the main or total amount of compounds II and I can also be placed in the reaction vessel, if necessary, in a solvent, under appropriate reaction conditions. According to the preferred form of implementation of the invention, take the main amount, in particular less than 20 8095, especially preferably the total amount or close to the total amount (» 95 95) of the compound based on hydrazone II, if necessary, in the desired solvent, and during the reaction, for example, in the time interval from

Me) 0.5 to 20 hours, in particular from 1 to 10 hours, under the reaction conditions add the main amount, in particular less than 80 to, especially preferably the total amount or close to the total amount (? 95 90) of the compound based on aniline. For this purpose, the compound based on aniline is preferably dissolved in a solvent. If necessary, after completion of the addition of the aniline-based compound, the mixture is left for some time, for example, from 10

F! minutes to 10 hours, in particular from 20 minutes to 5 hours.

Isolation of the compound | from the reaction mixture can also be carried out by known methods. If the interaction is carried out in a solvent, then, as a rule, the reaction mixture is concentrated and/or cooled and/or a precipitating agent is added. Solvents in which the compound | at a temperature of 60 below 252C, it does not dissolve or dissolves in a very small amount. This includes, in particular, aliphatic and cycloaliphatic hydrocarbons, such as pentane, hexane, cyclohexane, heptane, petroleum ether, etc. After precipitation/crystallization, other methods of purification can be carried out.

When carrying out the method according to the invention, high yields of compounds I are obtained, as a rule, not less than 8095, more often not less than 9095, in terms of compound II, which are characterized by high purity, even in b5 crude form, as a rule, not less than 9095, without the need to carry out expensive methods of crystallization or other methods of purification. Of course, various purification methods, such as crystallization, can be carried out by known methods. Unexpectedly, it was found that when carrying out the method according to the invention, a compound is obtained with a high ratio of isomers E/7, which is E:2 24, which is very advantageous when using compounds | as insecticides. An increase in the E/7 ratio can be achieved in a known manner by isomerization with iodine. The method of isomerization of the 2-isomer of compound I into the E-isomer in the presence of iodine is described in the publication |PCT/ЕР2004/012872 dated November 12, 2004), to which there are references in this text.

Used in the method according to the invention, compounds based on the hydrazone of the general formula II can be obtained analogously to methods known from the state of the art for obtaining semicarbazones by reacting 70 phenylbenzyl ketone of the formula IM with a hydrazide of the formula U, for example, analogously to the methods described in |). At.

Spent Zos. 75, 1953, 5. 2259-2261, 3. Ogd. Spent 55, 1990, 5. 1070-1076 and Zupipevziv, 1985, 5. 1048-10511.

At the same time, the interaction of benzylphenylketone IM with hydrazide M in the presence of acid turned out to be preferable. Examples of suitable acids are sulfuric acid, organic acids, in particular aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, aliphatic sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, aromatic carboxylic acids such as benzoic acid and substituted benzoic acids acids, such as 4-trifluoromethylbenzoic acid, as well as aliphatic carboxylic acids containing preferably from 1 to 4 carbon atoms, for example, acetic acid and propionic acid. Preferred acids are carboxylic acids, in particular aliphatic carboxylic acids containing mainly from 1 to 4 carbon atoms, as well as acetic acid. As a rule, the acid is used in an amount from 0.01 to 2 mol per mol of compound IM, in particular in an amount from 0.05 to 1.5 mol/mol of compound IM. In the case of sulfonic acids, catalytic amounts are preferable, i.e. amounts less than 1 mol per mol of compound M, in particular from 0.01 to 0.5 mol/mol, preferably from 0.05 to 0.2 mol/mol. In the case of carboxylic acids, large amounts of acid can be used, for example from 0.1 to 2 mol, preferably from 0.5 to 1.5 mol per mol of compound IM. high school

To carry out the interaction of ketone IM with hydrazine M, the compounds are preferably used in a molar ratio of IM:M in the range from 1:2 to 1.1:1, in particular from 1:1.5 to 1:11, especially preferably from 1:1.3 to 1:1.05. (8)

According to the preferred form of implementation of the invention, a hydrazide of the formula U is used, in which K means

C.-C.Alkoxy, in particular methoxy. Such hydrazides M are called carbazate M below.

The interaction of ketone IM with hydrazide M is carried out mainly at a temperature from 10 to 1002C, in particular from 20 Ge! from to 802C. For the successful implementation of the method, the reaction pressure plays a secondary role, it can be, for example, from 500mbar to 10bar. Preferably, the reaction is carried out at normal pressure, that is, at a pressure from 0.9 to 1.2 bar. The reaction time required for the interaction is, as a rule, from 4 to 72 hours, Ge») in particular from 8 to 60 hours.

The interaction can be carried out without a solvent. However, preferably the hydrazide of formula M is subjected to interaction with so

Ketone IM in an organic solvent. Suitable organic solvents are C1-Cdanols, including methanol, ethanol, and aromatic solvents, including alkylbenzenes, such as toluene, xylenes, ethylbenzene, cumene (2-propylbenzene), cymols (isopropyltoluenes), and mesitylene, as well as chlorobenzene. , 1,2-, 1,3- and 1,4-dichlorobenzene and mixtures of these solvents. "

Water formed during the reaction of ketone IM with hydrazide M can be removed from the reaction mixture in the process of interaction by known methods, for example, an azeotope with a solvent used in the reaction. However, the reaction water can be left in the reaction mixture. To carry out the interaction, ketone IM and hydrazide M can be brought into contact with each other in any way. So, for example, ketone IM and hydrazide B, if necessary, together with the desired solvent, are placed in a reaction vessel, and then create necessary reaction conditions. In addition, the bulk or total amount of ketone IM and hydrazide M can also be placed in the reaction vessel, if necessary, in a solvent under -I appropriate reaction conditions, or take one of the components of IM or M and add the bulk amount during the reaction of another component. Compound II can be isolated from the reaction mixture by known methods. If the reaction is carried out in a solvent, then, as a rule, the reaction mixture is concentrated and/or cooled and/or a precipitating agent is added. Suitable precipitating agents are solvents in which the compound II does not dissolve or dissolves in a very small amount at a temperature below 259202. These include, in particular, aliphatic and iChe)cyclic aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, petroleum ether, methanol, ethanol, alkylbenzenes, etc. After precipitation/crystallization, other methods of purification can be carried out. If the interaction according to the preferred option is carried out in an alcohol, in particular in methanol or ethanol, or in alkylbenzene, then the addition of a precipitating agent, as a rule, is optional.

When carrying out the described interaction of ketone IM with hydrazide M according to the invention, high yields of compounds II are obtained, as a rule, not less than 8095, more often not less than 95905, in terms of compound II, characterized by high purity, as a rule, not less than 9095, especially preferably at least 9595, without the need for expensive crystallization methods or other purification methods. Therefore, it is possible to abandon the isolation of compound II from the reaction mixture.

Thus, the preferred form of implementation of the invention relates to the method in which, in the first stage, the hydrazone derivative of the formula II is obtained by the interaction of ketone IM with hydrazide Y, after which compound II is subjected to interaction with an aniline-based compound SH without prior isolation. In this case, it may be advantageous to remove part or the total amount of solvent used to obtain hydrazone II, 65 and replacing it with another solvent. However, more often the interaction of hydrazone I with aniline SHS is carried out in the solvent used to obtain hydrazone IH.

IM ketones, used for obtaining hydrazone II, and the method of their preparation are known from the state of the art, for example, from ZIMMO 00/18714, UR 4168826 and UMO 03/0912031.

The following examples illustrate the invention without limiting the scope of its protection.

The purity and ratio of isomers are determined by high-performance liquid chromatography (HPLC) based on the ratio of the areas of the corresponding peaks.

In NMR spectra, c stands for singlet, d stands for doublet, and t stands for triplet. MS stands for mass spectrum and 14 stands for IR spectrum.

Example 1: preparation of hydrazone of formula II, in which KE means methoxy, KE! means 3-SEz and KE? means 4-CM 70 Option A: 18.8 g (0.21 mol) of methylcarbazate (НЯ-МН-С(0)-ОСН») and 57.8 g (0.20 mol)

3-trifluoromethylphenyl-4-cyanobenzyl ketone (compound IM, where B! means 3-SEz, and B? means 4-CM) is dissolved in 700 ml of methanol at 2020. Then 2 ml of concentrated sulfuric acid is added, stirred for 2 days at 202C, and the solid the substance formed is isolated. It is washed with 100 ml of methanol and dried in a 72 oven at 5092/1Ombar. In this way, 62.bg (corresponding to the theoretical yield of 86.795) of hydrazone II "B" are obtained. means 3-SEz, V? means 4-CM), the purity of which (HPLC) is 99.6965.

Temporaturya plavleknyah yati di v: ee "neyaMehDMOO acts ZV ZNYuv S Nr TYA (dgaNKt v (tu Nu; hachid, YAN Ta

What yidsaNnk Vod Well VYBTo NOT 10:95 (b, 1) with YMR IDS bnatst. ZHT I BaLOy TO0, Zo: TVA S am (dk ay

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Option B: 7.3 g (0.025 mol) of 3-trifluoromethylphenyl-4-cyanobenzyl ketone and 2.4 g (0.025 mol) of methyl carbazate (97965) are reacted in the presence of 2.0 g of acetic acid in 50 g of xylene for 24 hours at 5020. After After cooling to 202C, the resulting solid is isolated, washed with 10 g of xylene and dried in an oven at 502C/1Ombar. In this way, 8.0 g (corresponding to the theoretical yield of 88.195 g) of II B hydrazone are obtained! yuyu means 3-SE»z, V? means 4-CM), the purity of which (HPLC) is 99.9905. b

Example 2: preparation of compound I, in which БЕ" means З-СЕзв, 22 means 4-СМ and ЕЗ means 4-OSГЕз со

Option A:

7.2 g (0.02 mol) of hydrazone from example 1 and 3.9 g (0.022 mmol) of of 4-trifluoromethoxyaniline in 100 g of xylene, the mixture is boiled under reflux. 80 g of a mixture of methanol and xylene are distilled for 7 hours with a high phlegm number. The reaction mixture is slowly cooled to 602C and at this temperature 5 g of cyclohexane is added. Then the mixture is cooled again to 109C. The solid substance that precipitates is isolated, washed with 10 g of cyclohexane and dried in an oven at 802 0 p Ombar. In this way, 9.4 g of the title compound (corresponding to a theoretical yield of 92.290) are obtained in the 8s form of a mixture of isomers, the purity of which is 98.190 (81.29 of the E-isomer and 16.9952 of the 2-isomer).

From" Variant B: 21.bg (0.0 bmol) of hydrazone from example 1 and 11.7 g (0.6 bmol) of 4-trifluoromethoxyaniline in 300 g of xylene are loaded into a reactor with a distillation column, the mixture is refluxed. 12 g of a mixture of methanol and xylene are distilled for 7 hours with a high phlegm number. For crystallization of the product, another 234 g of xylene is distilled off. The reaction mixture is slowly cooled to 602С, at this temperature 75 g (o) of cyclohexane are added and cooled again to 102С. The solid that precipitates is isolated, washed with Zog and cyclohexane and dried in an oven at 1002C/1Ombar. In this way, 28.0 g of the title compound (corresponding to a theoretical yield of 84.69 g) are obtained in the form of a mixture of isomers, the purity of which is 1 91.5905 (77.4 to the E-isomer and 14.1 to the Fo 2-isomer) . 3e)

Claims (14)

The formula of the invention 59 1. The method of obtaining phenylsemicarbazone of the formula I Ф) име) 60 b5 Н Н (), M ee v - o r E" E- What and in which BK! and B? independently of each other mean hydrogen, halogen, SM, C.i-C.-alkyl, C.-C, -Alkoxy, C.-C.-haloalkyl or C.-C.-haloalkyl, and BZ stands for C.-C.-alkyl, C.-C.-haloalkyl or C.-C.-haloalkyl, which includes the interaction of a hydrazone compound of the general formula II, in which K means C and -C,.-Alkoxy, amino, C.-C.-alkylamino or di-(C.4-C.-alkyl)amino, and 2", 82 have the values indicated above, (I); (1) n МН. и п щ щи о 6) E "-D vi 2 yu oo Fo . . . go tsk C (ee) with an aniline compound of the general formula I, in which K" has the above value. 2. The method according to item 1, which is characterized by the fact that K means C.-C.-Alkoxy. - 3. The method according to claim 2, characterized in that K is methoxy. 4. The method according to item 1, which differs in that K means amino, methylamino, ethylamino or dimethylamino. 5. The method according to one of the previous points, which differs in that the aniline compound of the general formula "Ш" and the hydrazone compound of the general formula III are used in a molar ratio of III from 1:1.5 to 1.5:1. 6. The method according to any of the previous clauses, which differs in that the hydrazone compound of the general formula II is obtained by the interaction of the benzyl phenylketone of the formula IM xz» o (M) She I iv. 1 k (ee) ryy yad se) 2 s po iChe) in which B", 22 have the values indicated above, with the hydrazide of the formula M H (M, O nm -M. yu and SHI 60 Che in which K has the above value . 7. The method according to item 6, which differs in that K in the formula M means C.-C.-Alkoxy. 8. The method according to item 7, which is characterized by the fact that the interaction of benzylphenylketone of formula IM with hydrazide of formula M is carried out in the presence of an acid. 65 9. The method according to any of items 6-8, which is characterized by the fact that the hydrazone compound of the general formula II is subjected to interaction with the aniline compound of the general formula II without prior isolation. 10. The method according to any of the previous items, which differs in that B " in the formulas I, II and IM means meta-trifluoromethyl, B? in the formulas !, PP and IM means para-CM and BZ in the formulas | and Ш means para-trifluoromethoxy. 11. The hydrazone compound of the general formula ИЙ Н (1), M o She E! 5 od what E- oh in which B! means hydrogen, halogen, CM, C4-C6-alkyl C4-C6-alkoxy, C.-C.-haloalkyl or C.i.-C.-haloalkyl, B? means CM and K means C 1 -C 6 -alkoxy, amino or C 1 -C 6 -alkylamino, or di-(C 1 -C 6 -alkyl)amino. 12. A hydrazone compound of the general formula II according to item 171, which differs in that K means C.i-C,-Alkoxy. 13. The hydrazone compound of the general formula I! according to claim 12, characterized in that K is methoxy. with 14. The hydrazone compound of the general formula I! according to any of items 11-13, which differs in that B! o means meta-trifluoromethyl and B? stands for para-CM. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2007, M 5 04/25/2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. you (22) with m. - with . and? -I (ee) se) c 50 3e) F) ime) 60 b5