ETHYNYLBENZYL SUBSTITUENTS

TECHNICAL FIELD

The present invention relates to a method for preparing individual compounds and/or mixture of isomers of tertiary amines with two ethenylbenzyl and one alkyl, alkanol, alkylaminodialkyl (aryl) , alkoxyalkyl (aryl) , or alkylsulfanylalkyl (aryl) substituents and to a method for preparing tertiary polyalkyl (aryl) olyamines with one ethenylbenzyl and two alkyl and/or alkanol, and/or alkylaminodialkyl (aryl) , and/or alkoxyalkyl (aryl) , and/or alkylsulfanylalkyl (aryl) , or aryl substituents. The compounds can be used for preparing polymer nanodispersed gels, rubbers, engineering plastics, . thermosetting compositions, and polymers used as ion-exchange resins, flocculants, thickening agents, etc.

BACKGROUND

A reaction of alkyl- or benzyl -halides with primary amines is known to be a common method for synthesizing substituted amines.

Thus, patent JPH 0586123 discloses the preparation of a mixture of disubstituted and trisubstituted amines with alkyl or aryl substituents by reacting aromatic or aliphatic amines with vinylbenzyl chloride in dimethyl sulfoxide (DMSO) at a temperature of 60 °C by using an aqueous solution of potassium hydroxide (KOH) as a base required for the regeneration of a free amine from the hydrochloride formed.

Patent JPH 0558935 discloses the use of a similar method for preparing a mixture of amines; however, the method further comprises aerating the reaction mixture to prepare, along with amines, a bis - (vinylbenzyl ) ether . The prepared mixtures of amines are used as cross -linking agents in thermosetting compositions.

Patent JP 5140049 discloses a method for preparing a mixture of disubstituted and trisubstituted aromatic amines with monovinylbenzyl and divinylbenzyl substituents by reacting a primary aromatic amine with vinylbenzyl chloride in toluene at a temperature of 60 to 80 °C by using an aqueous solution of potassium hydroxide (KOH) as a base, a phase- transfer catalyst being tetrabutylammonium chloride, and sodium iodide. In this method, sodium iodide is used for an in situ bimolecular nucleophilic substitution of a chlorine atom in vinylbenzyl chloride with a iodine atom (Finkelstein reaction) , which is the best leaving group in reactions with amines, thereby increasing the reaction rate and conversion of vinylbenzyl chloride. The prepared mixtures of amines are used as cross- linking agents in thermosetting compositions.

Common drawbacks of the above methods are the use of a strong base, the absence of an inert atmosphere and antioxidants, which . promotes side reactions and reduces the yield of target products, as well as a low amount of tertiary amines in the prepared mixtures. In addition, the described methods do not comprise a step of separation and purification of the final compounds, which does not allow the use thereof in anionic and cationic polymerization since this results in stoppering the process due to existing impurities and an acid proton in a monosubstituted amine .

In addition, a drawback of the method disclosed in patents JPH 0586123 and JPH 0558935 is in the use of a technologically inconvenient and expensive solvent, such as D SO . The method disclosed in patents JPH 0559123 and JP05140049 provides mixtures of disubstituted and trisubstituted amines with aryl substituents rather than individual compounds, i.e. the spectrum of possible products according to these patents is limited to only mixtures of aromatic amines.

A method disclosed in US 4140659 is the closest prior art to the method according to the present invention. Said method relates to the preparation of tertiary amines with two vinylbenzyl substituents by reacting an alkyl- or arylamine with vinylbenzyl chloride in an aqueous solution of sodium hydroxide first at a low temperature (10-20 °C) for several hours and then at ambient temperature for a night. Drawbacks of this method are the following: the duration of the process (more than 10 hours) , purification of final products, which is insufficient for further use thereof in an anionic or cationic polymerization, the use of a strong base, and the absence of inert atmosphere and antioxidants, which promotes side reactions and a reduction of the target product yield (not more than 75%) . In addition, the method is carried out by using only gaseous primary amines .

Thus, methods for preparing mixtures of disubstituted and trisubstituted amines with aryl substituents or tertiary amines with alkyl and aryl substituents are known in the prior art. However, these methods have some drawbacks, and, therefore, there is a need for the development of a method for preparing tertiary amines comprising ethenylbenzene substituents, the method that enables a reduction of the process duration and a high yield (80-90%) of individual products, as well as an expanded applications of substituted tertiary amines, for example, their use in an anionic and cationic polymerization.

DISCLOSURE OF THE INVENTION

An object of the present invention is to develop a method for preparing individual compounds or a mixture of isomers of tertiary amines of general formula (I) or (II) with high yields and a high conversion rate of initial products, without time- and resource consuming methods of separation and purification of target compounds.

These compounds are used for preparing polymer nanodispersed gels, rubbers, engineering plastics, thermosetting compositions and polymers used as ion- exchange resins, flocculants, thickening agents, etc.

The technical result is to increase the yield of tertiary amines of formula (I) or (II) or a mixture of isomers thereof up to 80-90% and the conversion rate of the initial products up to 99-100% and to shorten the time of the process to 2 hours. In addition, the selective substitution of radicals at the nitrogen atom of compounds of formula (IV) or (V) reaches 97%, while providing tertiary amines of general formula (I) or (II) in the form of individual compounds or a mixture of thereof, thereby avoiding time- and resource consuming methods of separating and purifying the final products.

The objective problem and the technical result are achieved by the method for preparing tertiary amines of general formula (I) or (II) or a mixture of isomers thereof, the method comprising reacting a compound of general formula (III) with a compound of general formula (IV) or (V) in a two-phase aqueous -organic system in an alkaline medium in the presence of a catalyst based on ammonium and phosphonium compounds . The present invention relates to a method for preparing a compound of formula (I) or a mixture of isomers thereof

wherein R is -Alk, -AlkN(Alk) ₂ , -AlkN(Ar) ₂ , -AlkNAlkAr,

-AlkOH, -AlkOAlk, -AlkOAr, -AlkSAlk, -AlkSAr, or -Ar;

R ¹ , R ² , R ³ , and R ⁴ are independently -Alk, -Hal, -OH, -

OAlk, -OAr, -SAlk, -SAr, or -NR ₂ , wherein R is -Alk, -

AlkN(Alk) ₂ , -Alk (Ar) ₂ , -AlkNAlkAr, -AlkOH, -AlkOAlk, AlkOAr, -AlkSAlk, -AlkSAr, or -Ar,

wherein Alk is Ci-Ci ₆ alkyl, C ₃ -Ci ₆ cycloalkyl , C ₂ - Ci ₆ alkenyl, C ₂ -Ci ₆ alkynyl ,

Ar is phenyl,

Hal is halogen selected from -CI, -Br, and -I,

comprising reactin a compound of formula (III)

wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above,

Hal is halogen selected from -CI, -Br, and -I,

with a primary amine of formula IV H

\

N—R

/

^H IV,

wherein R is as defined above,

in a two-phase aqueous -organic system in an alkaline medium in the presence of a catalyst based on ammonium and phosphonium salts .

The present invention also relates to a method for preparing a compound of formula (II) or a mixture of isomers thereof

wherein R' and R" are independently Alk, -AlkN(Alk) ₂ ,

-AlkN(Ar) ₂ , -AlkNAlkAr, -AlkOH, -AlkOAlk, -AlkOAr, AlkSAlk, -AlkSAr, or -Ar;

R ¹ , R ² , R ³ , and R ⁴ are independently -Alk, -Hal, -OH, - OAlk, -OAr, -SAlk, -SAr, or -NR ₂ , wherein R is -Alk, AlkN(Alk) ₂ , -Alk (Ar) ₂ , -AlkNAlkAr, -AlkOH, -AlkOAlk, AlkOAr, -AlkSAlk, -AlkSAr, or -Ar,

wherein Alk is Ci - Ci ₆ alkyl, C ₃ -C ₆ cycloalkyl , C ₂ - Ci ₆ alkenyl, C ₂ - Ci ₆ alkynyl ,

Ar is phenyl,

Hal is halogen selected from -CI, -Br, and -I,

comprising reacting a compound of formula (III)

wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above,

Hal is halogen selected from -CI, -Br, and -I,

with a compound of formula (V)

R'

H— N ^N N— H

\ /

R" V,

wherein R' and R" are as defined above,

in two-phase aqueous-organic system in an alkaline medium in the presence of a catalyst based on ammonium and phosphonium salts.

In the method according to the invention, the halogen atom in a compound of formula (III) may be chlorine, bromine, or iodine, wherein the reaction rate and a reached conversion rate increase from chlorine to iodine.

The compound of formula (III) is preferably selected from the group including 2 -vinylbenzyl chloride, 3- vinylbenzyl chloride, 4 -vinylbenzyl chloride, 2 -vinylbenzyl bromide, 3 -vinylbenzyl bromide, -vinylbenzyl bromide, 2- vinylbenzyl iodide, 3 -vinylbenzyl iodide, 4 -vinylbenzyl iodide, , 2-methyl-l- (chloromethyl) -4 -ethenylbenzene , 3- methyl- 1- (chloromethyl) -4 -ethenylbenzene, 2-ethyl-l- (chloromethyl) -4 -ethenylbenzene , 3 -ethyl- 1- (chloromethyl) - 4 -ethenylbenzene, 3-chloro-l- (chloromethyl) -4- ethenylbenzene , 2-methoxy-l- (chloromethyl) -4- ethenylbenzene, 2-phenoxy-l- (chloromethyl) -4- ethenylbenzene, 3-methoxy-l- (chloromethyl) -4- ethenylbenzene, 2- (chloromethyl) -5-ethenyl-N, N- dimethylaniline, 2- (prop-2-enyl-l) -1- (chloromethyl) -4- ethenylbenzene, 2- (prop-2-ynyl-l) -1- (chloromethyl) -4- ethenylbenzene , 2-methylsulfanyl-1- (chloromethyl) -4- ethenylbenzene , 1- (chloromethyl) -4 -ethenyl -phenyl phenyl sulfide, etc.

In the method according to the invention, the compound of formula (IV) is selected from the group including monoamines, such as methylamine, ethylamine, propylamine, isopropylamine , butylamine, isobutylamine , pentylamine, isoamylamine , hexylamine, N,N- (dimethyl) ethane-1, 2-diamine, N-methyl-N-phenylethane-1, 2 -diamine, N,N- (diphenyl) ethane- 1, 2-diamine, N, -dimethylpent-2-ene-l , 5-diamine etc., 2- aminoethanol , 5-aminopenten-2-ol-l, 2 -methoxyethaneamine , 2-ethoxyethaneamine, 2-phenoxyethaneamine, 2-

(methylsulfanyl) ethaneamine, 2- (phenylsulfanyl) ethaneamine ,

5- (methylsulfanyl) pent-3 -en-l-amine , etc . , aniline , o- toluidine, m-toluidine, p-toluidine, o-ethylaniline, m- ethylaniline , p-ethylaniline , o-propylaniline , m- propylaniline , p-propylaniline , o-isopropylaniline , m- isopropylaniline p- isopropylaniline, 2 , 3 -xylidine , 2,4- xylidine, 2 , 5 -xylidine , 2 , 6 -xylidine , 3 , 4 -xylidine , 3,5- xylidine, 2,4 , 5-trimethylaniline, o-aminophenol , m- aminopheno1 , p -aminophenol , N-methyl-p-aminophenol , 3- amino-2-cresol, 4 -amino- 2 -cresol , 5 -amino- 2 -cresol , 6- amino-2-cresol, 2-amino-3-cresol, 4 -amino- 3 -cresol , 9- amino- 2 -eresol , 2 -amino-4 -cresol , 3 -amino-4 -cresol , 3- aminocatechol , 4 -aminocatechol , 3 -aminoguaiacol , 6- aminoguaiacol , 4 -aminoguaiacol , 5 -aminoguaiacol , 4- aminoresorcin, 2 -aminoresorcin, 5 -aminoresorcin, 2- aminohydroquinone , 2 -chloroaniline , 2-

(methylsulfanyl) aniline, etc.

In the method according to the invention, the compound of formula (V) is selected from the group including diamines, such as methylenediamine, ethylenediamine , propylenediamine , trimethylenediamine , tetramethylenediamine , piperazine, N-aminoethylpiperazine, aminoethylethanolamine , dimethylaminopropylamine , isophorone diamine, 1, 3-diaminobutane, 2 , 3 -diaminobutane , pentamethylenediamine, 2 , 4 -diaminopentane, hexamethylenediamine , heptamethylenediamine , octamethylenediamine , N, N ¹ -dimethyl - 1 -

(methylsulfanyl) ethane- 1, 2-diamine, 1-methoxy-N, ¹ - dimethylethane-1, 2 -diamine, 2- (methylsulfanyl ) piperazine , 2- (phenylsulfanyl) piperazine, 2 , -diaminophenol , 2,5- diaminophenol , 4 , 5 -diaminophenol, 3 , 4 -diaminophenol, 3,5- diaminophenol , 4 , 6-diaminoresorcin, o-phenylenediamine , m- phenylenediamine , p-phenylenediamine, N-methyl-p- phenylenediamine , N-phenyl-p-phenylenediamine, N,N- dimethyl-p-phenylenediamine, Ν,Ν' -dimethyl-p- phenylenediamine , 2 , 4 -diamino-3 -chlorophenol , 2,4-diamino- 1- (methylsulfanyl) benzene, 2 , 4-diamino-l-

(phenylsulfanyl) enzene, 4 -aminodiphenylamina, Ν,Ν'- diphenyl -p-phenylenediamine, 2 , 3 -diaminotoluene , 2,4- diaminotoluene, 3 , 4 -diaminotoluene , 2 , 6 -diaminotoluene , 3 , 5 -diaminotoluene, 2 , 5 -diaminotoluene , 4,4'- diaminodiphenylmethane , 4 , 4 ¹ -diaminodiphenylethane , 2,2- bis (4 -aminophenyl) propane, 4 , 4 ' -diaminodiphenyl ether, etc.

In the method according to the invention, it is preferable to use a vinylbenzyl halide in a 10-50 mol . % excess relative to the hydrogen atoms of the amino groups to achieve a more complete reaction. The method for preparing a compound of formula (I) or (II) or a mixture of isomers thereof may be optionally carried out in the presence of an organic solvent, such as an aromatic hydrocarbon, for example, benzene, toluene, etc.; alkane, such as hexane, heptane, etc.; chlorinated alkane, such as tetrachloromethane, trichloromethane , methylene chloride, etc.; or a mixture thereof in any ratio .

The catalyst used in the method according to the invention is selected from phosphonium or ammonium salts comprising a iodine atom, for example, tetraethylammonium iodide, benzyltriethylammonium iodide, tetraphenylphosphonium iodide, etc.

The catalyst based on ammonium and phosphonium salts is used in from 0.01 to 10 mol.%, preferably, from 0.1 to 5 mol.%, more preferably, from 0.5 to 1 mol.% based on the amount of the used compound of formula (III) .Other phosphonium or ammonium salts also can be used, such as, for example, tetrabutylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride, tetraphenylphosphonium chloride, tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium bromide, tetraphenylphosphonium bromide, tetrabutylammonium iodide, etc. It is preferable to use tetrabutylammonium iodide that serves simultaneously as a phase- transfer catalyst and an iodine-ion source that is able to replace a chlorine atom in the used vinylbenzyl chloride, namely promotes an in situ bimolecular nucleophilic substitution of a chlorine atom with an iodide atom (Finkelstein reaction) :

wherein M is a potassium ion or a tetrabutylammonium ion.

The iodide atom in vinylbenzyl iodide is the best leaving group in a reaction with amines, thereby increasing the rate of reaction and conversion of vinylbenzyl chloride .

The alkaline medium in the method according to the present invention is an aqueous solution of an alkali metal or ammonium carbonate. It is preferable to use potassium carbonate that is necessary for amine regeneration from hydrochloride formed in the reaction due to neutralization of hydrochloric acid. In addition, potassium carbonate does not initiate polymerization side reactions resulting in a reduction in the yield of the final product. Potassium chloride formed in the reaction is characterized by lower solubility than potassium carbonate, so the concentration of an aqueous solution of potassium carbonate is adjusted so that when the synthesis is terminated and the reaction mass is cooled to room temperature, the precipitation of potassium chloride does not occur since this results in a complicated separation of the final compounds. The concentration of the aqueous solution of potassium carbonate in the synthesis of all compounds according to the present invention is 25 to 35 wt . % . It is also possible to use sodium or cesium carbonate at the same concentration without chloride precipitation since the solubility of the corresponding sodium and cesium chlorides is higher than in potassium chloride. The use of said carbonates as a base is necessary to minimize side processes arising due to the anionic polymerization initiated by a strong base, for example, such as sodium hydroxide.

According to the method of the present invention, the radical polymerization is suppressed by carrying out the synthesis in an emulsion of an aqueous solution of potassium carbonate and compounds (I) and (II) or (III) and (IV) in the presence of an antioxidant. The antioxidant preferably used is an inhibitor of polymerization of phenolic or thiophenolic compounds, which are insoluble in water and soluble in an organic solvent, such as 4 -methyl - 2 , 6-di- ert-butylphenol (Vulkanox BHT) , 2 , 2 -methylene- bis (4-methyl-6- tert-butylphenol) (Vulkanox BKF) , 4-hydroxy- 3 , 5-di- tert-butoxybenzene, 4 - ert-butylbenz - 1 , 2 -diol , 4,6- bis (octylthiomethyl) -o-cresol, 2,2' -thiobis (4 -methyl- 6- tert-butyl-phenol) , 4,4' -thiobis (6- ert-butyl-m-cresol) , catechines , 1,3, 5-trimethyl-2 , 4 , 6-tris (3 , 5-di- tert-butyl- 4 - hydroxybenzyl) benzene , 2, 5 -dimethyl -4- (4- butylbenzylthio) phenol, 2-dimethylbenzyl- 4 , 4 (hexylthio) phenol , 2 , 4-dibutyl-6- (butylthio) phenol, 2,6- bis (1, 1-dimethylbutyl) -4- (1, 1 -dimethylbutylthio) henol , etc .

It is more preferable to use 2 , 2 -methylene-bis (4 - methyl-6- ert-butylphenol) (Vulkanox BKF) since it is well soluble in an organic solvents and is insoluble in water, which is important for stabilization of the compounds exactly in the organic phase. The antioxidant is added during the synthesis at any time point in an amount of 0.01 to 10 mol.%, preferably from 0.1 to 5 mol.%, most preferably from 0.5 to 1 mol.%, based on the amount of the used compound of formula (III) or (IV) . The method for preparing compounds of formulas (I) and (II) or a mixture of isomers thereof is carried out at a temperature of between 20 and 100 °C under atmospheric pressure. It is preferable to carry out the method for preparing compounds of formulas (I) and (II) at a temperature of between 50 and 100°C, preferably between 80 and 100°C, more preferably at 80°C, under atmospheric pressure. The method according to the present invention may be carried out under an increased pressure and at a temperature of up to 150 °C, whereas the reaction mass must not be heated higher than 150 °C since it may result in a reduction in the yield due to resinification of the reaction mass. The use of an increased pressure is undesirable since it increases the requirements to the used equipment and leads to a non-productive complication of the developed method of synthesis.

The method according to the invention is carried out under an inert atmosphere .

A preferred duration of the method for preparing compounds of formulas (I) and (II) or mixture of isomers thereof is 2 to 4 hours.

Purification by vacuum distillation is not expedient due to a high boiling point and instability of the prepared compounds, so the purification is carried out by flesh- chromatography. In particular, the following conditions for purification can be used: elution is carried out under nitrogen pressure with the drop rate of a solution in a glass column of 5 cm/min; the column diameter is 50 mm; the height of a sorbent layer is 15 cm; the sorbent is silica gel 60 with a 230-400 mesh fraction; eluent is benzene : ethylacetate (70:30% by volume); the eluent volume is 1 L; the fraction volume is 50 ml; and the level of sample loading is 2.5 g. The method according to the claimed invention is used at the first time for preparing compounds of formulas (I) and (II) . In addition, the method according to the invention provides individual tertiary amines or a mixture of isomers thereof with a high yield.

According to the present invention a mixture of isomers is prepared in the case of use as starting compounds of isomers of compounds of the general formula (III) , in particular, and 3 -vinylbenzyl halogenide and 4- vinylbenzyl halogenide. By reacting the said isomers with amines, a mixture of isomers of the tertiary amines differing in position of substituents in a benzene ring is prepared. More specifically, the mixture of isomers of the tertiary amines having the following position of substituents in a benzene ring is prepared: 1,3- and 1,3- isomer, 1,3- and 1,4-isomer, 1,4- and 1,4-isomer. So, for example, by reacting N-butylamine with the mixture of isomers of 3 -vinylbenzyl chloride (60%) and 4 -vinylbenzyl chloride (40%) isomeric products is prepared which are provided below:

The prepared product which is the mixture of isomers of tertiary amines can be used without the need for their separation. The method according to the present invention is described but is not limited to the examples provided below and can be extended to the preparation of compounds of the claimed structure.

EXAMPLES

The structure and purity of the prepared compounds were analyzed by methods of IR spectroscopy, ^X H and ¹³ C NMR- spectroscopy, and chromato-mass-spectrometry (GG-SM) .

Since the method according to the invention uses a mixture of vinylbenzyl chloride isomers (meta:para, 60:40 wt.%), chromatograms for all compounds obtained by the CM- SM method show three closely spaced peaks of target compounds, and, in addition, fragmentations in the mass- spectra are identical, which is indicative of the formation of three isomeric compounds in the reaction of an amine and a mixture of two vinylbenzyl chloride isomers, in particular, of the formation of tertiary amines with vinylbenzyl substituents having the following positions of an ethenyl radical: meta and meta, meta and para, and para and para. The conversion rate in all examples was 99 to 100%.

Comparative example 1. Preparation of a mixture of isomers of N-bis (3-ethenylbenzyl) aniline , N-bis (4- ethenylbenzyl) aniline, and N- (3-ethenylbenzyl) -N- (4- ethenylbenzyl) aniline according to the method disclosed in patent JP 05140049

A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 9.13 ml (0.1 mol) of aniline, 1.37 g (0,006 mol) of benzyltriethylammonium chloride, 0.2 g of 2,4- dinitrophenol , 50 ml of toluene, 32 g of a 50 wt ¾ aqueous solution of sodium hydroxide (16 g of sodium hydroxide) , and 0.2 g (0.0013 mol) of sodium iodine, and 30.5 g (0.2 mol) of vinylbenzyl chloride (VBC, meta:para, 60:40 wt.%) was added under stirring. Stirring is continued at 90 °C for 5 hours. Then, the reaction mixture was separated, the organic layer was washed with water (250 ml) 4 times, and toluene was distilled. The resulting yield of a light brown mass was 31.4 g. An liquid chromatography analysis of the obtained mass showed the following ratio of N- bis (vinylbenzyl) aniline, mono (N-vinylbenzyl ) aniline, divenylbenzyl ether and impurities: 42.3%, 37.1%, 14.7%, and 5.1%, and non-reacted vinylbenzyl chloride and aniline of 0.8%. The substitution selectivity of two hydrogen atoms in the amino group was 42.3%. The molar ratio of isomers N- bis (3-ethylbenzyl) aniline, N-bis ( 4-ethenylbenzyl ) aniline and N- (3-ethenylbenzyl) -N- (4-ethenylbenzyl) aniline =

22:21:57. The residue was purified by flesh-chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene). The yield of the final compound with 99% purity was 11.391 g (35% in terms of the theoretic amount) . Example 1. Preparation of a mixture of isomers of N- bis (3-ethenylbenzyl) aniline, N-bis (4-ethenylbenzyl) aniline, and N- (3-ethenylbenzyl) -N- (4-ethenylbenzyl) aniline

The synthesis was performed under nitrogen atmosphere with addition of Vulkanox BKF (0.050 g) . A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 2.2 ml (0.025 mol) of aniline, 30.0 ml of distilled water, 10.366 g (0.075 mol) of potassium carbonate, and 0.185 g (0.0005 mol) of tetrabutylammonium iodide, and was heated to temperature of 80°C, and 7.7 ml (0.055 mol) of vinylbenzyl chloride (VBC) (meta:para, 60:40 wt.%) was added under stirring. Stirring was carried out at 80 °C for 2 hours. After the synthesis, the reaction mass was extracted with benzene (3x10 ml) . The organic phase was dried over potassium carbonate. Further, the solvent was evaporated from the organic phase. The substitution selectivity of two hydrogen atoms in the amino group was 97.1%. The residue was purified by flesh-chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene). The yield of the final compound with 99% purity was 7.486 g (92% in terms of the theoretic amount) . The molar ratio of isomers N-bis ( 3-ethenylbenzyl ) aniline, N-bis (4- ethenylbenzyl) aniline and N- ( 3-ethenylbenzyl ) -N- ( 4- ethenylbenzyl ) aniline = 23:22:55. GC-MS, (M ⁺ _ca ic . =325.45 a.m.u.), m/z (intensity): 325.1 (high), 222.1 (low), 208.1 (high), 117.1 (high), 91.0 (medium), 77.0 (medium ), 51.0 (low) .

IR spectrometry (cm ^"1 ) : C-H (valence vibration) 3085- 2851 (weak) , Ar-CH=CH ₂ (overtone) 1818 (weak) , C=C (valence vibration) 1628 and 1583 (weak) , Ar (pulse vibration of the carbon framework of an aromatic ring) 1597 and 1504 (strong) .

^X H NMR (400 MHz) of the isomer mixture, δ, ppm. , J (Hz), (CDC1 ₃ ) : 4.81 (s,4H, m- , p-St-CH ₂ -), 5.41-5.44 (m, 2H, =CH e to substituent) ; 5.91-5.95 (m, 2H, =CH z to substituent) ; 6.85-7.00 (m, 4H, Ph-CH=, H-An) ; 7.31-7.75 (m, 10H, H-St, H-An) .

1 ³ C NMR (100 MHz) of the isomer mixture, δ, ppm.,

(CDCI ₃ ) : 54.23 (2 ( (CH ₂ ) ₂ -N) ) ; 112.79 (20, 19C) ; 113.76 (8C) 114.30 (25C) ; 117.13 (23C); 124.88 (3C) ; 124.98 (2C) ; 126.40 (4C) ; 126.75 (15, 16C) ; 127.13 (14, 13C) ; 129.09 (6C) ; 129.50 (22, 21C) ; 136.58 (7C); 136.74 (1C); 137.01 (24C) ; 138.16 (17C); 138.48 (5C); 139.21 (12C) 149.34 (18C) .

Example 2. Preparation of a mixture of isomers of N- bis (3-ethenylbenzyl)butane-l-amine, N-bis (4- ethenylbenzyl)butane-l-amine, and N- (3-ethenylbenzyl) -N- (4- ethenylbenzyl) amine

The synthesis was performed under nitrogen atmosphere with addition of Vulkanox BKF (0.050 g) . A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 10.365 g (0.075 mol) of potassium carbonate, 20 ml of distilled water, 7.7 ml (0.055 mol) of vinylbenzyl chloride (VBC, meta:para, 60:40 wt.%), and 0.185 g (0.0005 mol) of tetrabutylammonium iodide, the mixture was heated to 80 °C, and 2.5 ml (0.025 mol) of n-butylamine was added under stirring for 10 minutes. After addition of n-butylamine, the reaction mass was stirred for 2 hours at 70°C. After the synthesis, the reaction mass was extracted with benzene (3x10 ml) . The organic phase was dried over potassium carbonate. Further, the solvent was evaporated from the organic phase. The substitution selectivity of two hydrogen atoms in the amino group was 97.2%. The residue was purified by flesh- chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene) . The yield of the final compound with 99% purity was 6.262 g (82% in terms of the theoretic amount). The molar ratio of isomers N-bis (3- ethenylbenzyl) butane-l-amine, N-bis ( 4 -ethenylbenzyl ) butane- 1-amine, and N- (3 -ethenylbenzyl) -N- (4 -ethenylbenzyl) amine . = 25:23:52. GC-MS, (M ⁺ caic . =305.46 a.m.u.), m/z (intensity): 305.2 (low), 262.2 (medium), 233.1 (low), 188.1 (low), 170.1 (high), 91.0 (medium), 65.0 (low), 39.0 (low).

IR spectrometry (cm ^"1 ) : C-H (valence vibration) 3100- 2700 (moderate) , ArCH=CH ₂ (overtone) 1815 (weak) , C=C (valence vibration) 1629 and 1581 (weak) , Ar (pulse vibration of the carbon framework of an aromatic ring) 1603 and 1510 (weak) .

¹ H NMR (400 MHz) of the isomer mixture, δ, ppm., J (Hz), (CDC1 ₃ ) : 0.73 (m, 3H, CH ₃ ); 1.18 (m, 2H, CH ₂ ) 1.39 (m, 2H, CH ₂ ) 2.30 (m, 2H, N-CH ₂ ); 3.43 (m, 2H, St-CH ₂ -), 5.11 (ddd, 2H, 2J=13.2, 3J=10.9, 5J=1 =CH e to substituent); 5.63 (ddd, 2H, 2J=17.6, 3J=11.8, 5J=1.0 =CH z to substituent); 6.59 (ddd, 2H, 3J=17.6, 3J=10.9, 4J=4.6, Ph- CH=) ; 7.09-7.35 -St)

^1? C NMR (100 MHz) of the isomer mixture, δ, ppm., (CDCI ₃ ) : 14.83 (23C) ; 21.24 (22C); 30.01 (11C); 53.96 (9C); 58.73 (7C) ; 58.94 (IOC); 113.93 (21C) 114.35 (13C); 125.42 (16C); 125,46 (19C); 126.78 (6C, 2C); 127.36 (17C); 129.06 (15C); 129.67 (5C, 1C) ; 136.88 (20C); 137.49 (18C); 137.80 (4C) ; 138.13 (12C); 140.54 (14C); 141.06 (3C).

Example 3. Preparation of a mixture of isomers of N- 1 , 4-bis (3-ethenylbenzyl) piperazine, 1 , 4-bis (4- ethenylbenzyl) piperazine, and 1- (3-ethenylbenzyl) -4- (4- ethenylbenzyl) piperazine

The synthesis was performed under nitrogen atmosphere with addition of Vulkanox BKF (0.050 g) . A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 2.153 g (0.025 mol) of piperazine, 30.0 ml of distilled water, 10.366 g (0.075 mol) of potassium carbonate, and 0.185 g (0.0005 mol) of tetrabutylammonium iodide, and the mixture was heated to 100°C, and 7.7 ml (0.055 mol) of vinylbenzyl chloride (VBC) (meta:para, 60:40 wt.%) was added under stirring. Stirring was continued at 100 °C for 2 hours. After the synthesis, the reaction mass was extracted with benzene (3x10 ml) . The organic phase was dried over potassium carbonate. The solvent was evaporated from the organic phase. The substitution selectivity of two hydrogen atoms in the amino group was 91.0%. The residue was purified by flesh- chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene). The yield of the final compound with 99% purity was 6.682 g (84% in terms of the theoretic amount). The molar ratio of isomers N-l,4-bis(3- ethenylbenzyl) piperazine, N-l, 4 -bis (4- ethenylbenzyl) iperazine, and N-l- (3-ethenylbenzyl) -N-4- (4- ethenylbenzyl ) piperazine = 25:23:52

GC-MS, (M ⁺ caic.=318.21 a.m.u.), m/z (intensity): 318.3 (medium), 201.2 (medium), 172.1 (low), 158.1 (low), 146.1 (medium), 130.1 (low), 117.1 (high), 91.0 (medium) 42.0 (low) .

IR spectrometry (cm ^-1 ): C-H (valence vibration) 3084- 2660 (moderate) , ArCH=CH ₂ (overtone) 1816 (weak) , C=C (valence vibration) 1629 and 1581 (weak) , Ar (pulse vibration of the carbon framework of an aromatic ring) 1602 and 1510 (weak) .

C-H δ 2650-3084 (moderate) , C=C (overtone) 1816 (weak) , C=C δ 1602-1629 (weak) .

¹ H NMR (400 MHz) isomer mixture, δ, ppm. , J (Hz), (CDCI ₃ ) : 2.25 (S,8H, 4CH ₂ ) ; 3.26 (s, 2H, p-St-CH ₂ -), 3.27 (s, 2H, m-St-CH ₂ -), 5.00 (ddd,2H, 2J=10.9, 3J=9.1, 5J=1.0 =CH e to substituent) ; 5.51 (ddd, 2H, 2J=17.6, 3J=11,7, 5J=1 =CH z to substituent); 6.48 (ddd, 2H, 3J=17.6, 3J=10.9, 4J=4.6, Ph-CH=) ; 6.97-7.13 (m, 8H, H-St)

¹³ C NMR (100 MHz) of the mixture of isomers, δ, ppm., (CDCI ₃ ) : 53.89 (2 ( (CH ₂ ) ₂ -N) ) ; 63.57 (14C); 63.80 (7C) 114.23 (24C) 114.59 (22C); 124.48 (16C); 126,85 (6C, 2C) 127.90 (20C) ; 129.17 (19C); 129.54 (17C); 130.15 (5C, 1C) 137.17 (23C) ; 137.43 (18C); 137.68 (4C) ; 138.27 (21C) 138.71 (15C) ; 139.27 (3C) .

Example 4. Preparation of Ν,Ν-bis (2-methyl-4- vinylbenzyl) ethaneamine

The synthesis was performed under nitrogen atmosphere in the presence of Vulkanox BKF (0.040 g) . A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 10.365 g (0.075 mol) of potassium carbonate, 20 ml of distilled water, 8.33 g (0.050 mol) of 1 - (chloromethyl ) -4 - ethenyl- 2 -methylbenzene, and 0.185 g (0.0005 mol) of tetrabutylammonium iodide, and the mixture was heated to 70 °C, and 1.635 ml (0.025 mol) of ethylamine was added under stirring for 10 minutes. After addition of ethylamine, the reaction mass was stirred for 2 hours at 70 °C. After the synthesis, the reaction mass was extracted with benzene (3x15 ml) . The organic phase was dried over potassium carbonate. The substitution selectivity of two hydrogen atoms in the amino group was 90.1%. After evaporation of the solvent, the residue was purified by flesh- chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene). The yield of the final compound with 98% purity was 2.77 g (80% in terms of the theoretic amount).

² H NMR (400 MHz), δ, ppm, J (Hz) ₍ (CDC1 ₃ ): 1.02 (t, 3H, C23H3, 3J=8.0 Hz), 2.34 (s, 6H, C17H3, C18H3), 2.64 (k, 2H, C9H2, 3J=8.0 Hz), 3,64 (s, 4H, C7H2 , C10H2), 5.18 (d, 2H, C20Ha, C22Ha, 3J-10.1 Hz), 5.61 (d, 2H, C20Hb, C22Hb, 3J=16.1 Hz), 6.61 (dd, 2H, C19H, C21H, 3J=10.1 Hz, 3J=16.1 Hz), 6.97 (s, 2H, C2H, C13H) , 7.06 (d, 2H, C5H, C16H 3J=7.5 Hz), 7.40 (s, 2H, C6H, C15H 3J=7.5 Hz).

¹³ C NMR (100 MHz) δ, ppm, (CDC1 ₃ ):13.3 (C23), 19.2 (C17, C18), 51.5 (C9) 59.8 (C7, CIO), 114.3 (C20, C22), 125.3 (C6, C15), 128.6 (C5, C16), 131.1 (C2, C13), 135.3 (CI, C14), 136.5 (C3, C12), 136.8 (C4, Cll) .

Example 5. Preparation of N, N-bis ( 2 -methyl -4 - vinybenzyl) etheneamine .

A three-neck flask equipped with a water-cooled .reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 10 g (0.23 mol) of etheneamine, 1.37 g (0.006 mol) of benzyltriethylammonium chloride, 0.2 g of 2,4- dinitrophenol , 50 ml of toluene, 32 g of a 50 wt% (wt) aqueous solution of sodium hydroxide (16 g of sodium hydroxide), and 0.2 g (0,0013 mol) of sodium iodine, and 106.5 g (0.46 mol) of 1 -bromo- 2 - (chloromethyl ) - 4 - ethenylbenzene was added under stirring. Stirring was continued for 2 hours at 80 °C. After this process, the reaction mixture was separated, the organic layer was washed with water (250 ml) 4 times, and toluene was distilled. The yield of the product was 98 g. The substitution selectivity of two hydrogen atoms in the amino group was 70.2%. The residue was purified by flesh- chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene) . The yield of the final compound with 99% purity was 54.88 g (5 unt) .

^X H NMR (400 NHz) , δ, ppm, J (Hz), (CDCl ₃ ) : 4.26 (s, 4H, C7H2, C8H2), 4.99 (s, 1H C12Ha, ) , 5.17 (d, 2H, C15Ha, C23Ha, 3J=10.1 Hz), 5.58-5.62 (m, 3H C12Hb, C15Ha, C23Ha) , 6.05 (dd, 1H, C11H, 3J=9.8 Hz, 3J=16.3 Hz), 6.63 (dd, 2H, C13H, C22H, 3J=9.8 Hz, 3J=16.3 Hz), 6.98 (s 2H, C5H, C16H) , 7.40-7.45 (m, 4H, C1H, C2H, C18H, C19H) .

¹³ C NMR (100 MHz) δ, ppm, (CDC1 ₃ ) : 54.6 (C7, C9), 95.1 (C12) , 114.3 (C15, C23) 122.1 (C3, C17), 126.9 (CI, C18), 127.7 (C5, C16), 131.3 (C2, C19) , 135.7 (C6, C17), 136.1 (C13, C22) , 140.6 (C4, CIO), 147.3 (Cll).

Example 6. Preparation of N,N-dimethyl-N,N- bis (vinylbenzyl)methanediamine

The synthesis was performed under nitrogen atmosphere in the presence of Vulkanox BKF (0.040 g) . A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 10.365 g (0.075 mol) of potassium carbonate, 20 ml of distilled water, 7.63 g (0.050 mol) of vinylbenzyl chloride (meta:para isomers, 60:40 wt.%) and 0.185 g (0.0005 mol) of tetrabutylammonium iodide, and the mixture was heated to 70 °C, and 2.7 ml (0.025) mol of N, N-dimethylmethanediamine was added under stirring for 10 minutes. After addition of N, N-dimethylmethanediamine, the reaction mass was stirred for 2 hours at 70°C. After the synthesis, the reaction mass was extracted with benzene (3x80 ml) . The substitution selectivity of two hydrogen atoms in the amino group was 85.7%. The organic phase was dried over potassium carbonate. After evaporation of the solvent, the residue was purified by flesh-chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene). The yield of the final compound with 99% purity was 5.38 g (70% in terms of the theoretic amount) .

H NMR (400 MHz) , δ, ppm, J (Hz) , (CDC1 ₃ ) : 2.26 (s, 6H, C22H3, C23H3) , 3.43 (s, 2H, C20H2) , 3.66 (s, 4H, C9H2 , C11H2) , 5.18 (d, 2H, C8Ha, C19Ha, 3J=10.2 Hz) , 5.61 (d, 2H C8Hb, C19Hb, 3J=16.7 Hz) , 6.60 (dd, 2H, C7H, C18H 3J=10.2 Hz, 3J=16.7 Hz) , 6.63 (dd, 2H, C13H, C22H, 3J=9.8 Hz, 3J=16.3 Hz) , 7.18 (d, 4H, C2H, C4H, C13H, C17H, 3J=7.8 Hz) , 7.59 (d, 4H, C1H, C5H, C14H, C16H, 3J=7.8 Hz) .

¹³ C NMR (100 MHz) δ, ppm, (CDC1 ₃ ) : 44.7 (C22, C23) , 60.6 (C9, Cll) , 94.3 (C20) 116.1 (C8, C19) , 128.3 (CI, C5, C14, C16) , 128.7 (C2, C4 , C13 , C17) , 136.0 (C7, C18) , 136.4 (C6, C15) , 137.4 (C3, C12) .

Example 7^ Preparation of 2-methoxy-N,N- bis (vinylbenzyl) ethaneamine

A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 37.5 g (0.50 mol) of 2 -methoxyethaneamine , 2.37 g (6 mmol) of benzyltriethylammonium chloride, 0.2 g of 2 , 4 -dinitrophenol , 50 ml of toluene, 50 g of a 50 wt % aqueous solution of sodium hydroxide (16 g of sodium hydroxide), and 0.3 g (0,0013 mol) of sodium iodine, and 152.7 g (1.0 mol) of vinylbenzyl chloride was added under stirring. Stirring was continued for 4 hours at 75°C. After this process, the reaction mixture was separated, the organic layer was washed with water (300 ml) 4 times, and toluene was distilled. The organic phase was dried over potassium carbonate. The yield of the product was 156 g. The substitution selectivity of two hydrogen atoms in the amino group was 95.1%. The residue was purified by flesh- chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene) . The yield of the final compound of 99% purity was 80.99 g (52% in terms of the theoretic amount) .

^X H NMR (400 MHz), δ, ppm, J (Hz), (CDC1 ₃ ) : 2.51 (t, 2H, C20H2, 3J=7.1 Hz), 3.30 (s, 3H, C23H3), 3.60 (t, 2H, C21H2,

3J=7.1 Hz), 3.61 (s, 4H, C9H2 , C11H2), 5.19 (d, 2H, C8Ha, C19Ha, 3J=10.1 Hz), 5.58 (d, 2H C8Hb, C19Hb, 3J=16.9 Hz), 6.63 (dd, 2H, C7H, C18H 3J=10.1 Hz, 3J=16.9 Hz), 6.63 (dd, 2H, C13H, C22H, 3J=10.1 Hz, 3J=16.9 Hz), 7.16 (d, 4H, C2H , C4H, C13H, C17H, 3J=7.7 Hz), 7.54 (d, 4H, C1H, C5H, C14H, C16H 3J=7.7 Hz) .

¹³ C MR (100 MHz) δ, ppm, (CDC1 ₃ ) : 56.7 (C20) , 59.2 (C23), 61.1 (C9, Cll) 70.7 (C21) , 115.3 (C8, C19), 128.4 (CI, C5, C14, C16), 128.7 (C2, C4 , C13, C17), 136.1 (C7, C18), 136.4 (C6, C15), 137.8 (C3, C12).

Example 8^ Preparation of

(vinylbenzyl) amino) methanol

A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 24.43 g (0.40 mol) of 1-methoxymethaneamine , 2.37; g ( 0 , 006 mol). of benzyltriethylammonium chloride, 0.2 g of 2 , 4 -dinitrophenol , 100 ml of toluene, 60 g of a 50 wt % aqueous solution of sodium hydroxide (16 g of sodium hydroxide) , and 0.3 g (0,0013 mol) of sodium iodine, and 122.12 g (0.8 mol) of vinylbenzyl chloride was added under stirring. Stirring was continued for 4 hours at 80°C. After this process, the reaction mixture was separated, the organic layer was washed with water (300 ml) 4 times, and toluene was distilled. The organic phase was dried over potassium carbonate. The yield of the product was 308.41 g. The substitution selectivity of two hydrogen atoms in the amino group was 77.5%. The residue was purified by flesh-chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene) . The yield of the final compound with 99 ^s purity was 132,39 g (85% in terms of the theoretic amount).

¾ NMR (400 MHz) , δ , ppm, J (Hz), (CDC1 ₃ ) : 2.53 (t, _. 2H, C20H2, 3J=7.0 Hz), 3.45 (t, 2H, C21H2, 3J=7.0 Hz), 3.65 (,1H, C22H1) , 3.67 (s, 4H, C9H2 , C11H2), 5.18 (d, 2H, C8Ha, C19Ha, 3J=10.0 Hz), 5.58 (d, 2H C8Hb, C19Hb, 3J=16.7 Hz), 6.62 (dd, 2H, C7H, C18H 3J=10,0 Hz, 3J=16,7 Hz), 6,63 (dd, 2H, C13H, 3J=10.0 Hz, 3J=16.7 Hz), 7.16 (d, 4H, C2H, C4H, C13H, C17H, 3J=7.8 Hz), 7.54 (d, 4H, C1H, C5H, C14H, C16H 3J=7.8 Hz) .

¹³ C NMR (100 MHz) δ , ppm, (CDC1 ₃ ): 58.7 (C20), 61.3 (C9, Cll) , 115.3 (C8, C19) , 127.4 (CI, C5 , C1 , C16) , 127.7 (C2, C4, C13, C17) , 134.1 (C7, C18), 136.2 (C6, C15), 136.8 (C3 , C12) .

Example 9. Preparation of 2 , 5-dimethyl-l , 4- bis (vinylbenzyl) piperazine

The synthesis was performed under nitrogen atmosphere in the presence of Vulkanox BKF (0.040 g) . A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 10.365 g (0.075 mol) of potassium carbonate, 20 ml of distilled water, 7.63 ml (0.050 mol) of vinylbenzyl chloride (meta:para isomers, 60:40 wt.%), and 0.185 g (0.0005 mol) of tetrabutylammonium iodide, and the mixture was heated to 70 °C, and 0.025 ml of 2,5 dimethylpiperazine was added under stirring for 10 minutes. After addition of N, -dimethylmethanediamine, the reaction mass was stirred for 3 hours at 80 °C. After the synthesis, the reaction mass was extracted with benzene (3x150 ml) . The organic phase was dried over potassium carbonate. After evaporation of the solvent, the residue was purified by flesh- chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene) . The substitution selectivity of two hydrogen atoms in the amino group was 79.8%. The yield of the final compound with 99% purity was 6.95 g (60% in terms of the theoretic amount) .

^X H NMR (400 MHz), δ, ppm., J(Hz), (CDCl ₃ ) : 1.12 (d, 6H, C7H3, C8H3, 3J=6.8 Hz), 2.42 (m, 4H, C3H2, C6H2 , 3J=7.0 Hz), 3.03 (m, 2H, C1H, C4H, 3J=7.0 Hz), 3.62 (s, 4H, C9H2 , C10H2) , 5.18 (dd, 2H, C24HA, C26HA, 2J=2.1 Hz, 3J=10.0 Hz), 5.61 (dd, 2H, C24Hb, C26Hb, 2J=2.1 Hz, 3J=16.8 Hz), 6.63 (m, 2H, C23H, C25H, 3J _A =16.8 Hz, 3J _B =10.0 Hz), 7.09-7.41 (m, 8H, Ar, 3J=1.5 Hz) .

¹³ C NMR (100 MHz), δ, ppm, (CDC1 ₃ ) : 16.7 (C7, C8), 60.6 (C9, CIO), 62.1 (C3, C6), 63.6 (CI, C4), 114.3 (C24, C26), 124.2 (C15, C20) , 126.4 (C17, C18), 128.0-128.3 (C13, C14 , C21, C22), 135.4 (Cll, C12), 136.1 (C23, C25), 136.6 (C16, C19) .

Example 10. Preparation of 2 , 11-bis (2-methoxy-5- vinyl) diaza [3.3] meta-cyclophane

The synthesis was carried out under nitrogen in the presence of Vulkanox BKF (0.040 g) . A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 10.365 g (0.075 mol) of potassium carbonate, 20 ml of distilled water, 9.13 ml (0.050 mol) of 2 -chloromethyl-4 - ethenyl-l-methoxybenzene, and 0.185 g (0.0005 mol) of tetrabutylammonium iodide, and the mixture was heated to 70°C, and 5.96 ml (0.025 mol) of 2 , 11-diaza [3.3] meta- cyclophane was added under stirring for 10 minutes. After addition of 2 , 11-diaza [3.3] meta-cyclophane , the reaction mass was stirred for 4 hours at temperature of 70°C. After the synthesis, the reaction mass was extracted with benzene (3x200 ml) . The organic phase was dried over potassium carbonate. After evaporation of the solvent, the residue was purified by flesh- chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene) . The substitution selectivity of two hydrogen atoms in the amino group was 88.7%. The yield of the final compound with 99% purity was 9.31 g (70% in terms of the theoretic amount) .

H NMR (400 MHz), δ, ppm, J (Hz), (CDC1 ₃ ) : 3.62 (s, 8H,

C13H2, C14H2, C15H2, C17H2), 3.66 (s, 4H, C19H2, C20H2), 3.83 (s, 6H, C38H3, C40H3), 5.18 (dd, 2H, C34Ha, C36Ha, 2J=2.1 Hz, 3J=10.0 Hz), 5.61 (dd, 2H, C34Hb, C36Hb, 2J=2.1 Hz, 3J=16.8 Hz), 6.63 (m, 2H, C33H, C35H, 3JA=16.8 Hz, 3JB=10.0 Hz), 6.82 (d, 2H, C24H, C31H, 3J=7.5 Hz), 6.98 (s, 2H, C27H, C28H) , 7.11 (d, 8H, C1H, C3H, C4H, C6H, C7H, C9H, CIOH, C12H, 3J=7.5 Hz), 7.43 (d, 2H, C25H, C30H, 3J=7.5 Hz) .

¹³ C NMR (100 MHz), δ, ppm, (CDC1 ₃ ): 56.1 (C38, C40) , 56.7 (C19, C20) , 61.4 (C13, C14 , C15, C17), 113.9 (C24, C31) , 114.3 (C34, C36), 121.1 (C21, C22), 127.4 (C27, C28), 128.7 (C25, C30) , 128.9 (C26, C29), 129.8 (CI, C3 , C4 , C6 , C7, C9, CIO, C12) , 136.1 (C33, C35), 137.1 (C2, C5 , C8 , Cll) , 157.6 (C23, C32) .

Example 11. Preparation of a mixture of isomers of

2 , 6-bis (ethenylbenzyl) tetrahydro-dithiadiazocyne

The synthesis was performed under nitrogen atmosphere with addition of Vulkanox BKF (0.040 g) . A three-neck flask equipped with a water-cooled reflux condenser, a thermometer, a septa, and a magnetic mixer was filled with 10.365 g (0.075 mol) of potassium carbonate, 20 ml of distilled water, 7.63 g (0.050 mol) of vinylbenzyl chloride (metarpara isomers, 60:40 wt.%), and 0.185 g (0.0005 mol) of tetrabutylammonium iodide, and the mixture was heated to 85°C, and 3.76 g (0.025 mol) of tetrahydro- 2H, 6H-1 , 5 , 3 , 7-dithiadiazocyne was added under stirring for 10 minutes. After addition of tetrahydro-2H, 6H- 1 , 5 , 3 , 7 - dithiadiazocyne , the reaction mass was stirred for 5 hours at 90 °C. After the synthesis, the reaction mass was extracted with benzene (3x200 ml) . The organic phase was dried over potassium carbonate. After evaporation of the solvent, the residue was purified by flesh-chromatography (sorbent: 230-400 mesh silica gel, eluent: benzene). The substitution selectivity of two hydrogen atoms in the amino group was 82.9%. The yield of the final compound of 99% purity was 6.71 (70% in terms of the theoretic amount).

^X H NMR (400 MHz), δ, ppm, J (Hz), (CDC1 ₃ ): 3.51 (s, 8H, C2H2, C3H2, C6H2, C8H2), 3.66 (s, 4H, C9H2, C10H2), 5.18 (dd, 2H, C24Ha, C26Ha, 2J=2.1 Hz, 3J=10.0 Hz), 5.61 (dd, 2H, C24Hb, C26Hb, 2J=2.1 Hz, 3J=16.8 Hz), 6.63 (m, 2H, C23H, C25H, 3JA=16.8 Hz, 3JB=10.0 Hz), 7.14-7.41 (m, 8H, Ar, 3J=7.5 Hz) . "C N R (100 MHz) , δ, ppm, (CDC1 ₃ ): 55.4 (C2, C3 , C6 , C8) , 61.2 (C9, CIO), 114.3 (C24, C26), 124.2 (C15, C20), 126.4 (C13, C22), 128.0 (C17, C18), 128.3 (C16, C19), 135.4 (Cll, C12), 136.1 (C23, C25), 136.6 (C14, C21) .

The resulting experimental data show that the method disclosed in JP05140049 (comparative example 1) results in the formation of a mixture consisting of bis (N- vinylbenzyl) aniline, mono (N-vinylbenzyl) aniline, divinylbenzene ether, impurities, and non- reacted vinylbenzyl chloride and aniline (42.3%, 37.1%, 14.7%, 5.1%, and 0.8%, respectively), which is evidence that the formation, mainly, of a secondary or tertiary aromatic amine does not occur. The method according to the present invention, on the contrary, provides the formation, mainly, of a tertiary aromatic amine. So, in example 1, the mixture of isomers of tertiary aromatic amines is prepared: the molar ratio of isomers N-bis ( 3-ethenylbenzyl ) aniline, N- bis (4-ethenylbenzyl) aniline and -N- ( 3-ethenylbenzyl) -N- ( 4- ethenylbenzyl) aniline is 23:22:55. The substitution selectivity of two hydrogen atoms in the amino group was 97.1%.