RU2756161C1 - Dimeric quaternary pyridinium salts containing a dioxynaphthalene fragment with a biocidal effect - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: invention relates to new dimeric quaternary pyridinium salts of general formula (I), which have a biocidal effect and can be used as an active biocidal ingredient for the production of antiseptic and disinfectants. In the formula (I), R is a linear or branched alkyl or alkenyl, or alkyne group containing from 8 to 18 carbon atoms, X is a halogen atom - chlorine, bromine or iodine. The invention also relates to the use of these salts as an active biocidal ingredient for the production of antiseptics and disinfectants and a method for their production.

EFFECT: extension of the range of antiseptic and disinfecting substances.

4 cl, 5 tbl, 62 ex

Description

The present invention relates to a new type of dimeric quaternary pyridinium salts containing a diosconaphthalene moiety as a spacer and having a biocidal effect, as well as to a method for their preparation. The proposed compounds can be used as antiseptics and disinfectants.

The spread of microbes and their increasing resistance to many known antimicrobial drugs is a potentially high threat to humanity around the world. Therefore, the search for new chemicals with biocidal properties against a wide range of opportunistic and pathogenic microorganisms is very important. Nowadays, the task of creating a new generation of highly effective antiseptics with a wide spectrum of antibacterial action with low toxicity and efficiency is extremely urgent. These new biocides will increase the number of available starting materials for the creation of various antiseptic and disinfecting agents. Quaternary ammonium salts (QAS) are one of the most commonly used classes of disinfectants, which are used in hospitals, water treatment, textile, paint and varnish and food industries due to their relatively low toxicity to humans and animals and their broad specificity of antimicrobial action [Block, SS Disinfection, Sterilization and Preservation, 5th ed. Lippincott, Williams & Wilkins, Philadelphia, U.S.A. 2001, p. 283-319]. Among them, the quaternary salts of pyridinium and bis-pyridinium represent an important group of chemicals widely used as biocides, due to their strong antimicrobial action, even at very low concentrations, on a wide range of gram-positive and gram-negative bacteria, fungi and some viruses [Chanawanno, K., Chantrapromma, S., Anantapong, T., Kanjana-Opas, Α., Fun, H.-K. Synthesis, structure and in vitro antibacterial activities of new hybrid disinfectants quaternary ammonium compounds: Pyridinium and quinolinium stilbene benzenesulfonates. European Journal of Medicinal Chemistry, 45, 4199-4208 (2010); Kourai, H., Yabuhara, T., Shirai, Α., Maeda, T., Nagamune, H. Syntheses and antimicrobial activities of a series of new bis-quaternary ammonium compounds. European Journal of Medicinal Chemistry, 41 (4), 437-444 (2006); Perles, C.E., Matheus, Α., Volpe, P.L.O. The effect of quaternary ammonium surfactants on the inhibition of the aerobic metabolism of Sacharomyce cerevisiae - A calorimetric study. Thermochimica Acta 479 (1-2), 28-31 (2008); Ng, C. L. L., Singhal, V., Widmer F., Wright, L. C., Sorell, T. C., Jolliffe, K. A. Synthesis, antifungal and hemolytic activity of a series of bis (pyridinium) alkanes. Bioorganic & Medicinal Chemistry, 15 (10), 3422-3429 (2007)].

Given the recent results regarding the low cytotoxic effect of some antimicrobial agents from the group of bis-quaternary pyridinium salts on human cells, it is expected that pyridinium and bis-pyridinium salts are potential agents recommended for use in hygiene product compositions, in the food industry (industrial environment, equipment, various surfaces) and in restaurants, hospitals, etc. [Nagamune, Η., Maeda, T., Ohkura, K., Yamamoto, K., Nakajima, Μ., Kourai, Η. Evaluation of cytotoxic effects of bisquaternary ammonium antimicrobial reagents on human cells. Toxicology in Vitro, 14 (2), 139-147 (2000)].

In patents and scientific literature, you can find some salts of bis-quaternary pyridinium, which have antimicrobial and antifungal effects [US 4206215 A, 03.06.1980; WO 2007128059 A1, 15.10.2007; US 7612097 B2, 03.11.2009]. The molecular structure of these compounds can be represented by A, B and C types, as shown below.

Here, in structures A and B, spacer Ζ is a long aliphatic chain containing from 6 to 18 carbon atoms or containing a similar chain with double and triple bonds inside, or embedded oxygen, nitrogen and sulfur atoms, or ester groups attached to the nitrogen atom of pyridine rings [structure A - US 4206215 A, 03.06.1980; Bailey D.M., DeGrazia C.G., Hoff S.J., Schulenberg P.L., O'Connor J.R., Paris D.A., Slee A.M., Bispyridinamines: a new class of topical antimicrobial agents as inhibitors of dental plaque, J. Med. Chem. 27, p. 1457-1464 (1984); structure B - WO 2007128059 A1, 15.10.2007]. In structure C, the spacer Ζ is either a long aliphatic chain containing from 6 to 18 carbon atoms or containing a similar chain with double and triple bonds inside, or embedded oxygen, nitrogen and sulfur atoms, or ester groups [structure C - US 7612097 B2, 03.11.2009] and a cyclic oxygen-containing divalent structure based on pentaerythritol, dipentaerythritol or hydroquinone [EA 26416 B1, 28.04.2017], and 4,4'-biphenyl or 4,4'-oxybiphenyl [RU 2689419 C1, 28.05.2019 ].

However, there is an important difference between structure C and structures A and B, namely, in structure C, the spacer Ζ is connected to the carbon atoms of the pyridine ring [US 7612097 B2, 03.11.2009].

One of the compounds of structure A - "octenidine dihydrochloride" is widely used as an active antibacterial agent in the creation of compositions of antiseptic and disinfectants, and it is commercially available [US 20010036963 A1, 01.10.2011; US 20110217360 No. 1, 09/08/2011; EP 2401914 No. 1, 04.01.2012].

Known dimeric quaternary pyridinium salts of structure C with a spacer Ζ hydroquinone [EA 26416 B1, 28.04.2017]. The main disadvantages of these bis-quaternary pyridiniums are weak biocidal effect on gram-negative bacteria, high toxicity and skin irritation.

The closest analogs in terms of structure and properties are salts of structure C with a 4,4'-biphenyl or 4,4'-oxybiphenyl spacer [RU 2689419 C1, 28.05.2019]. These compounds show a stronger biocidal effect compared to the above-mentioned compounds, but still insufficient against certain strains of bacteria. The technical objective of the present invention is to expand the range of compounds with increased biocidal activity and low toxicity at the same time, and to develop a method for their production.

The technical problem posed is achieved by a new type of dimeric quaternary pyridinium salts of the general formula:

where R is a linear or branched alkyl or alkenylene or alkyne group containing from 8 to 18 carbon atoms; X is a halogen atom: chlorine, bromine or iodine.

The proposed new compounds of general formula I have a biocidal effect and can be used as an active biocidal ingredient for the preparation of antiseptic and disinfectants. Compounds of general formula I, where the 2,7-1,6 or 1,5-dioxynaphthalene moiety is connected directly to the carbon of the pyridinium ring in position 2, 3 or 4, exhibit similar biocidal properties in comparison with bis-quaternary pyridinium salts used in modern antiseptics and disinfectant compositions. However, unlike the known antiseptics, in particular the type C compounds described above, the new compounds have a higher biocidal effect and lower toxicity at the same time. Therefore, the use of these compounds can be extended to active compounds for skin antiseptics as well as other disinfectant compositions. Compounds of general formula I can be used as antimicrobial agents. They are biocidal, i.e. bacteriostatic and bactericidal action with low toxicity. The proposed new type of dimeric pyridinium quaternary salts derived from pyridine, dioxynaphthalenes and alkyl halides have excellent biocidal action and can be used as active compounds in antiseptic and disinfectant compositions. The compounds of general formula I in accordance with this invention have a higher biocidal action and lower toxicity compared to existing quaternary ammonium salts.

According to Directive 98/8 / EC of the European Parliament and of the Council of the European Union of 16 February 1998, the following definitions of terms apply in this invention:

antibacterial - a chemical that kills or slows down the growth of bacteria;

antimicrobial - a chemical that, in low concentrations, acts against microorganisms and destroys them or inhibits their growth;

antiseptic - an antimicrobial substance that is used on living tissues / skin to reduce the likelihood of infection, sepsis, or putrefactive decomposition;

antifungal - a chemical that destroys or inhibits the growth of fungi

bacteriostatic - a chemical that stops bacteria from reproducing without necessarily damaging them in another way; biocide (biocidal products) - a chemical agent designed to destroy, neutralize, prevent the action or other control action on any harmful organism by chemical or biological agents. Examples include disinfectants, preservatives, antiseptics, pesticides, herbicides, fungicides, and insecticides.

disinfectant - a chemical that is used on non-living objects to destroy microorganisms that live on objects. Currently, the resistance of bacteria to modern antibacterial agents stimulates research and the creation of works to find new improved biocidal materials.

This invention presents the fact that dimeric quaternary pyridinium salts having the general formula I and which are derivatives of dioxynaphthalenes combine the biocidal action of a broad antimicrobial spectrum together with low toxicity, and can be used as an active ingredient to create a new generation of antiseptics and disinfectants. having low toxicity in comparison with known agents used in practice, i. e. for medical purposes and household use. According to modern scientific views on the principles of antiseptic action, the biocidal action of the compounds of general formula I can be determined, but not limited to, their ability to adhere to the cell walls and membrane of bacteria, as well as penetrate into the core of the cell with subsequent inhibition of the cell.

The sequence of destruction of a cell by a biocide can be described as follows.

1. Absorption of the biocide on the cell surface.

2. Diffusion of the biocide molecule through the cell wall into the cell.

3. Attachment of a diffuse biocide molecule to the cytoplasmic membrane.

4. Destabilization and destruction of the cytoplasmic membrane.

5. Isolation of cytoplasmic compounds from the cell.

6. Destruction of the cell.

The ability to bind to membranes is mainly determined, on the one hand, by the presence of positively charged groups in the compounds represented by general formula I, in particular two quaternary pyridinium groups, and, on the other hand, by the presence of a negative charge on the cell surface, which is usual for phosphate groups. lipids and acids.

The mechanism of interaction of compounds of general formula I with membranes of microorganisms can be described as follows. After contact between the cell and the biocide molecule, an electrostatic interaction of negatively charged groups on the cell surface and the biocide molecule occurs. This leads to a reorientation of the biocide molecule and the introduction of its charged fragments into the lipid monolayer (membrane). The compound of general formula I together can bind with a large amount of phospholipids in the membrane and cause neutralization of its negative charge. The created complex is stabilized by a strong hydrophobic interaction with the alkyl chains of fatty acids of phospholipids. This leads to a strong imbalance in electrostatic and hydrophobic interactions and decreases lipid-lipid interactions. At the same time, another aspect of the adsorption of the biocide on the cell surface is the inhibition of the barrier and transport functions of the membrane. Further introduction of the hydrophobic fragment of the biocide molecule into the non-polar part of the cell membrane leads to its expansion and a decrease in the van der Waals forces between lipid molecules. As a consequence, firstly, the electrical permeability of the membrane changes, secondly, the integrity of the membrane is disrupted, and finally, the membrane is fragmented and destroyed.

A spacer can make a positive contribution to the high antibacterial effect in combination with the low toxicity level of the compounds of general formula I. The presence of oxygen atoms within the spacer structure undoubtedly perpetuates a good balance between the hydrophobic and hydrophilic components of the molecule. This gives a high antibacterial effect and low toxicity.

In general formula I, R is a linear or branched alkyl or alkenylene or alkyne group containing from 8 to 18 carbon atoms.

The terms "alkyl" in the compounds of this invention generally include C8-18, preferably C8-16, more preferably C8-12. Examples of such alkyl groups include n-octyl, tert-octyl, 2-ethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, etc. Preferred groups are C8-18 linear alkyl groups such as n-octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl; more preferred are n-octyl, nonyl, decyl, undecyl, dodecyl.

The terms "alkenylene" in the compounds of this invention generally include C8-18, preferably C8-16, more preferably C8-12, and at least one double bond. Examples of such alkenylene groups include octenyl, nonenyl, decenyl, isodecenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl and octadecenyl, etc., preferred groups include C8-18 linear alkenylene groups such as octenyl, decenyl, dodecenyl tetradecenyl, hexadecenyl and octadecenyl; more preferred are octenyl, nonenyl, decenyl, undecenyl, dodecenyl. The terms "alkyne" in the compound of this invention generally include C8-18, preferably C8-16, more preferably C8-12, and at least one triple bond. Examples of such alkyne groups include octynyl, noninyl, decynyl, isodecynyl, undecynyl, dodecynyl, tridecenyl, tetradecinyl, pentadecinyl, hexadecinyl, and octadecinyl, etc. Preferred groups include C8-18 linear alkyne groups such as octynyl, decynyl, dodecinyl, tetradecinyl, hexadecinyl, and octadecinyl; more preferred are octynyl, noninyl, decinyl, undecinyl, dodecinyl.

The vast majority of compounds represented by the general formula I were evaluated and tested for antibacterial and antifungal action against microorganisms Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, A. Kirby W.M .; Sherris J. C .; Turck M. Antibiotic Susceptibility Testing by a Standardized Single Disk Method. Am. J. Clinic. Pathol., 45, 493-496 (1966)]. These strains are recommended for testing the bacterial action of disinfectants [European Committee for Standardization. EN 1040, Chemical disinfectants and antiseptics - Quantitative suspension test for the evaluation of basic bactericidal activity of chemical disinfectants and antiseptics - Test method and requirements. (Phase 1) Brussels, Belgium, (2005)].

Some compounds represented by the general formula I, as shown in the examples below, were superior to the control compounds - benzalkonium chloride, 3,3 '- [1,4-phenylene-bis (oxy)] - bis- (1-dodecylpyridinium) dibromide, as well as the closest analogs - dimeric quaternary pyridinium salts 3,3 '- [biphenyl-4,4'-diylbis (oxy)] bis (1-decylpyridinium) dibromide, 3,3' - [oxybis (4,1-phenylene)] bis (1-decylpyridinium) dibromide [RU 2689419 C1, 28.05.2019], demonstrating high antibacterial and antifungal action against all of the above microorganisms.

Benzalkonium chloride (CBA) is used as a reference drug for control. Although CBA is a benzylammonium compound that does not have bis-quaternary ammonium groups, it was chosen as the standard because it is now widely used as a bactericidal agent [Murguia M.S., Vaillard VA, Sanchez VG, Conza JD, Grau RJ Synthesis, surfaceactive properties, and antimicrobial activities of new double-chain gemini surfactants. J. Oleo Sci. 57 (5), 301-308 (2008); US 7612097 B2, 03.11.2009)].

Most of the compounds represented by the general formula I, as shown in the examples below, have low toxicity and lower cytotoxicity than benzalkonium chloride and other bis-quaternary pyridinium salts - 3,3 '- [biphenyl-4,4'-diylbis ( hydroxy)] bis (1-decylpyridinium) dibromide, 3,3 '- [oxybis (4,1-phenylene)] bis (1-decylpyridinium) dibromide [RU 2689419 C1, 28.05.2019] and commercially available bis-quaternary pyridinium salt - "octenidine dihydrochloride" [Muller G., Kramer A. Biocompatibility index of antiseptic agents byparallel assessment of antimicrobial activity and cellular cytotoxicity. J. Antimicrob Chemother 61, p. 1281-7 (2008)].

Compounds of general formula I can be used as antiseptics or disinfectants. They can be dissolved, suspended or emulsified. Connections can be applied by spraying, wiping, etc. The dimeric quaternary pyridinium compounds described herein can be combined with one or more suitable adjuvants and / or carriers to provide a composition. A method for obtaining a new type of dimeric quaternary pyridinium salts of the general formula is also proposed:

where R is a linear or branched alkyl or alkenylene or alkyne group containing from 8 to 18 carbon atoms; X is a halogen atom: chlorine, bromine or iodine, which means that the corresponding bipyridyl derivatives of the general formula:

is reacted with a compound of general formula RX, where R is a linear or branched alkyl or alkenylene or alkyne group containing from 8 to 18 carbon atoms, and X is a halogen atom: chlorine, bromine or iodine, at reflux.

The process can be carried out in an organic solvent or without it.

As the organic solvent, for example, acetonitrile, alcohols, 4-methylpentan-2-one, DMSO, DMF, DMA can be used.

Moreover, new bipyridyl derivatives of general formula II are easily obtained at low cost from the available pyridine compounds and dihydroxynaphthalenes.

The compound of formula IIa can be obtained by condensation of 2,7-dihydroxynaphthalene with 2-bromopyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 72% yield; The quaternization of compound IIa with an excess of alkyl bromide is carried out by refluxing in acetonitrile to obtain compound Ia _1-5 in 70-85% yield. The process proceeds according to the following scheme:

The dipyridyl derivative IIb is obtained by condensation of 2,7-dihydroxynaphthalene with 3-bromopyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 61% yield; the quaternization of compound IIb with alkyl bromide is carried out by boiling under reflux in acetonitrile to obtain compound IIb _1-6 in 65-94% yield. The process proceeds according to the following scheme:

The dipyridyl derivative IIc is obtained by condensation of 2,7-dihydroxynaphthalene with 4-chloropyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 85% yield; the quaternization of compound IIc with alkyl bromide is carried out by boiling under reflux in acetonitrile to obtain compound Ic _1-6 in 68-90% yield. The process proceeds according to the following scheme:

The dipyridyl derivative IId is obtained by condensation of 1,6-dihydroxynaphthalene with 2-bromopyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 77% yield; the quaternization of compound IId with alkyl bromide is carried out by boiling under reflux in acetonitrile to obtain compound Id _1-5 in 42-60% yield. The process proceeds according to the following scheme:

The dipyridyl derivative IIe is obtained by condensation of 1,6-dihydroxynaphthalene with 3-bromopyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 57% yield; The quaternization of compound IIe with alkyl bromide is carried out by refluxing in acetonitrile to obtain compound Ie _1-5 in 80-89% yield.

The dipyridyl derivative IIf is obtained by condensation of 1,6-dihydroxynaphthalene with 4-chloropyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 63% yield; the quaternization of compound IIf with alkyl bromide is carried out under reflux in acetonitrile to obtain compound If _1-5 in 68-93% yield. The process proceeds according to the following scheme:

The compound of formula IIg can be obtained by condensation of 1,5-dihydroxynaphthalene with 2-bromopyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 74% yield; the quaternization of compound IIa with alkyl bromide is carried out by boiling under reflux in acetonitrile to obtain compound Ig _1-5 in 35-54% yield. The process proceeds according to the following scheme:

The dipyridyl derivative IIh is obtained by condensation of 1,5-dihydroxynaphthalene with 3-bromopyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 60% yield; the quaternization of compound IIb with alkyl bromide is carried out under reflux in acetonitrile to obtain compound Ih _1-5 in 74-90% yield. The process proceeds according to the following scheme:

The dipyridyl derivative IIi is obtained by condensation of 1,5-dihydroxynaphthalene with 4-chloropyridine using the known method [Y. Liu, W. Zhang, J. Zhang, CN 104262159 A, 07.01.2015] with 75% yield; the quaternization of compound IIc with alkyl bromide is carried out under reflux in acetonitrile to obtain compound Ii _1-5 in 80-95% yield. The process proceeds according to the following scheme:

Other objects and advantages of the present invention will become apparent from the detailed description of the examples and claims presented below.

For an easier understanding of the invention, reference is made to the following examples, which are only illustrative of the invention and do not limit its scope.

Melting points are determined using a Stuart ESTSMP3 melting point apparatus and are not corrected. 1H nuclear magnetic resonance spectrum is recorded with a Bruker Avance II 300 spectrometer at 300.13 MHz and chemical shifts are recorded in parts per million (ppm) with deuterochloroform (CDCl ₃ ; δ _n 7.26), deuteromethanol (CD3OD-d4; δ _n 3.31) or deuterodimethyl sulfoxide (DMSO-d ₆ ; δ _n 2.50) as a solvent. Data are recorded as chemical shift (δ), multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet), binding constant (J Hz), relative integral location. Analytical thin layer chromatography (TLC) is performed using silica gel-coated plates (Merck Kieselgel 60 F254) and visualized using a UV apparatus with a wavelength of λ = 254 nm. Preparative column chromatography was carried out using Merck Kieselgel 60 silica gel (SiO ₂ , 0.04-0.065 mm) with the indicated solvent system. Solvent ratios for TLC and column chromatography are shown in (v / v) as indicated. All solvents are distilled before use and distilled, the mass spectrum is obtained directly using a Finningan MAT INCOS 50 spectrometer (EI, 70 eV).

Examples 1-5 [scheme 1]. General method for the synthesis of dimeric compounds (Ia _1-5 )

To a solution of 2,2 '- [naphthalene-2,7-diylbis (oxy)] dipyridine IIa (0.34 g, 1 mmol) in acetonitrile (10 ml) was added alkyl bromide (8 mmol). The mixture was boiled under reflux for 7 days, then cooled and the solvent was evaporated in a water-jet vacuum. The residue was boiled in 10 ml of acetone, cooled and filtered to give 2,2 '- [naphthalene-2,7-diylbis (oxy)] bis (1-alkylpyridinium) dibromide as a white solid.

2,2 '- [naphthalene-2,7-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 75-78 ° C; ¹ Ή NMR (300 MHz, DMSO-d _6): δ 0.83 (t, J = 6.4 Hz, 6H, 2CH3), 1.14-1.51 (m, 20H, 10SN2), 1.91-2.07 (m, 4H, 2CH ₂₎ , 4.68 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.32 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.72-7.84 (m, 4H), 8.14 (d, J = 1.7 Hz , 2Н, 2CH _Ar ), 8.37 (d, J = 9.0 Hz, 2Н, CH _Ar ), 8.47 (t, J = 7.6 Hz, 2Н, 2СН _РУ ), 8.99 (d, J = 5.6 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 22.0, 25.7, 28.4, 28.5, 28.7, 31.1, 54.8, 113.7, 118.4,120.6, 120.8, 130.6, 131.7, 134.5, 143.8, 148.5, 150.2, 158.7 ppm;

2,2 '- [naphthalene-2,7-diylbis (oxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H ₅₂ Br ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 115-118 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.83 (t, J = 6.4 Hz, 6H, 2CH3), 1.12-1.49 (m, 24H, 12SN2), 1.96-2.08 (m, 4H, 2CH ₂₎ , 4.67 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.32 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.72-7.84 (m, 4H), 8.14 (d, J - 1.7 Hz , 2H, 2CH _Ar ), 8.36 (d, J = 9.0 Hz, 2H, CH _Ar ), 8.47 (t, J - 7.6 Hz, 2H, 2CH _RU ), 8.99 (d, J = 5.6 Hz, 2H, 2CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 22.1, 25.6, 28.4, 28.5, 28.8, 28.9, 31.1, 55.0, 113.6, 118.4, 120.5, 120.6, 130.5, 131.7, 134.3, 143.7, 148.4, 150.2, 158.6 ppm;

2,2 [naphthal in-2,7-diylbis (oxy)] bis (1-decyl pyridinium) dibromide of the formula:

C ₄₀ H ₅₆ Br ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 139-142 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.81 (t, J = 6.4 Hz, 6H, 2CH3), 1.09-1.52 (m, 28H, 14SN2), 1.91-2.09 (m, 4H, 2CH ₂₎ , 4.67 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.31 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.72-7.84 (m, 4H), 8.14 (d, J = 1.7 Hz , 2H, 2CH _Ar ), 8.37 (d, J = 9.0 Hz, 2H, CH _Ar ), 8.46 (t, J = 7.6 Hz, 2H, 2CH _RU ), 8.97 (d, J = 5.6 Hz, 2H, 2CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 22.0, 25.6, 28.3, 28.6, 28.7, 28.8, 31.2, 54.8, 113.6, 118.4, 120.5, 120.8, 130.5, 131.7, 134.5, 143.7, 148.4, 150.2, 158.6 ppm;

2,2 '- [naphthalene-2,7-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H ₆₀ Br ₂ N ₂ O ₂ ; Μ = 784.8; White powder; T. pl. 92-95 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.82 (t, J = 6.4 Hz, 6H, 2CH3), 1.08-1.52 (m, 32H, 16CH2), 1.91-2.07 (m, 4Η, 2CH ₂ ) , 4.68 (t, J = 6.8 Hz, 4Η, 2CH ₂ N ⁺ ), 7.31 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.72-7.84 (m, 4H), 8.13 (d, J = 1.7 Hz , 2H, 2CH _Ar ), 8.36 (d, J = 9.0 Hz, 2H, CH _Ar ), 8.47 (t, J - 7.6 Hz, 2H, 2CH _RU ), 8.98 (d, J = 5.6 Hz, 2H, 2CH _RU ) ppm; ¹³ С NMR (75 MHz, OMSO-d ₆ ): δ 14.1, 22.2, 25.8, 26.1, 28.5, 28.8, 28.9, 29.1, 31.4, 55.1, 113.8, 118.6, 120.7, 121.1, 130.8, 132.0, 134.7, 143.9, 148.7, 150.4, 158.9 ppm;

2,2 '- [naphthalene-2,7-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ = 812.8; White powder; T. pl. 105-108 ° C; ¹ Ή NMR (300 MHz, DMSO-d _6): δ 0.83 (t, J = 6.4 Hz, 6H, 2CH3), 1.14-1.51 (m, 36H, 18SN2), 1.91-2.07 (m, 4H, 2CH ₂₎ , 4.67 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.30 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.72-7.84 (m, 4H), 8.12 (d, J = 1.7 Hz , 2Н, 2CH _Ar ), 8.36 (d, J = 9.0 Hz, 2Н, CH _Ar ), 8.46 (t, J - 7.6 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.6 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.5, 28.3, 28.5, 28.6, 28.7, 28.8, 28.9, 31.1, 54.7, 113.6, 118.3, 120.5, 120.7, 130.5, 131.6, 134.4, 143.7, 148.4, 150.1, 158.6 ppm;

Examples 6-11 [Scheme 2]. General method for the synthesis of dimeric compounds (Ib _1-6)

To a solution of 3,3 '- [naphthalene-2,7-diylbis (oxy)] dipyridine IIb (0.34 g, 1 mmol) in acetonitrile (3 ml) was added alkyl bromide (4 mmol). The mixture was boiled under reflux for 24 hours, then the solvent was evaporated in a water-jet vacuum pump. The residue was boiled in 10 ml of acetone, cooled and filtered to give 3,3 '- [naphthalene-2,7-diylbis (oxy)] bis (1-alkylpyridinium) dibromide as a white solid.

3,3 '- [naphthalene-2,7-diylbis (oxy)] bis (1-heptylpyridinium) dibromide of the formula:

C ₃₄ H ₄₄ Br ₂ N ₂ O ₂ ; Μ = 726.6; White powder; T. pl. 180-182 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ,): δ 0.85 (t, J - 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 16H, 8CH2), 1.87-2.00 (m, 4H, 2CH ₂ ), 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.50 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.76 (d, J = 2.4 Hz, 2H, 2CH _Ar ) , 8.17 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.19 (d, J = 8.9 Hz, 2Н, 2CH _Ar ), 8.30 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2H, 2СН _РУ ), 9.23 (d, J = 2.0 Hz, 2Н, 2СН _РУ ); ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 28.3, 30.7, 31.1, 60.9, 115.4, 119.0, 128.5, 129.1, 131.0, 133.9, 134.9, 136.4, 139.8, 153.1, 155.7;

3,3 '[naphthalene-2,7-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 170-173 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 20H, 10SN2), 1.87-2.00 (m, 4H, 2CH ₂₎ , 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.50 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.76 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.17 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.19 (d, J = 8.9 Hz, 2Н, 2CH _Ar ), 8.30 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2H, 2СН _РУ ), 9.23 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 28.3, 28.4, 30.7, 31.1, 60.9, 115.4, 119.0, 128.5,129.1, 131.0, 133.9, 134.9, 136.4, 139.8, 153.1, 155.7 ppm;

3,3 '- [naphthalene-2,7-diylbis (oxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H ₅₂ Br ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 101-104 ° C; ¹ H NMR (300 MHz, OMSO-d _6): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 24H, 12SN2), 1.87-2.00 (m, 4Η, 2CH ₂₎ , 4.63 (t, J = 7.4 Hz, 4Η, 2CH ₂ N ⁺ ), 7.50 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.76 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.17 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.19 (d, J = 8.9 Hz, 2Н, 2CH _Ar ), 8.30 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2H, 2СН _РУ ), 9.23 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 28.3, 28.4, 28.6, 30.7, 31.1, 60.9, 115.4, 119.0, 128.5, 129.1, 131.0, 133.9, 134.9, 136.4, 139.8, 153.1, 155.7 ppm;

3,3 '- [naphthalene-2,7-diylbis (oxy)] bis (1-decylpyridinium) dibromide of the formula:

C ₄₀ H ₅₆ Br ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 141-144 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 28H, 14SN2), 1.87-2.00 (m, 4H, 2CH ₂₎ , 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.50 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.76 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.17 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.19 (d, J = 8.9 Hz, 2Н, 2CH _Ar ), 8.30 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2H, 2СН _РУ ), 9.23 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 27.9, 28.3, 28.4, 28.5, 30.7, 31.1, 60.9, 115.4, 119.0,128.5, 129.1, 131.0, 133.9, 134.9, 136.4, 139.8, 153.1, 155.7 ppm;

3,3 '- [naphthalene-2,7-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H ₆₀ Br ₂ N ₂ O ₂ ; Μ - 784.8; White powder; T. pl. 150-153 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 32H, 16SN2), 1.87-2.00 (m, 4H, 2CH ₂₎ , 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.50 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.76 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.17 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.19 (d, J = 8.9 Hz, 2Н, 2CH _Ar ), 8.30 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2H, 2СН _РУ ), 9.23 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.1, 25.3, 28.3, 28.4, 28.5, 28.7, 30.7, 31.1, 60.9, 115.4, 119.0, 128.5, 129.1, 131.0, 133.9, 134.9, 136.4, 139.8, 153.1, 155.7 ppm;

3,3 '- [naphthalene-2,7-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ = 812.8; White powder; T. pl. 133-136 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 36H, 18CH2), 1.87-2.00 (m, 4H, 2CH ₂ ) , 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.50 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.76 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.17 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.19 (d, J = 8.9 Hz, 2Н, 2CH _Ar ), 8.30 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2H, 2СН _РУ ), 9.23 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 28.1, 28.3, 28.4, 28.5, 28.6, 28.7, 30.7, 31.1, 60.9, 115.4, 119.0, 128.5, 129.1, 131.0, 133.9, 134.9, 136.4, 139.8, 153.1, 155.7 ppm;

Examples 12-17 [Scheme 3]. General method for the synthesis of dimeric compounds (Ic _1-6 )

To a solution of 4,4 '- [naphthalene-2,7-diylbis (oxy)] dipyridine (0.34 g, 1 mmol) in acetonitrile (10 ml) was added alkyl bromide (4 mmol). The mixture was boiled under reflux for 3 days, then cooled and the solvent was evaporated in a water-jet vacuum. The residue was boiled in 10 ml of acetone, cooled and filtered to give 4,4 '- [naphthalene-2,7-diylbis (oxy)] bis (1-alkylpyridinium) dibromide.

4,4 '- [naphthalene-2,7-diylbis (oxy)] bis (1-heptyl pyridinium) dibromide of the formula:

C ₃₈ H ₅₀ Br ₂ N ₂ O ₂ ; Μ = 726.6; White powder; T. pl. 138-140 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.16-1.38 (m, 20H, 10SN2), 1.79-1.94 (m, 4H, 2CH ₂₎ , 4.51 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.66 (d, J = 7.3 Hz, 4H, 4CH _RU ), 8.00 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.32 (d, J - 8.9 Hz, 2H, 2CH _Ar ), 9.00 (d, J = 7.3 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.3, 28.4, 30.5, 31.0, 59.1, 114.8, 118.1, 120.4, 130.1, 131.5, 134.8, 146.9, 150.6, 168.9 ppm;

4,4 '- [naphthalene-2,7-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 150-152 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.16-1.38 (m, 20H, 10SN2), 1.79-1.94 (m, 4H, 2CH ₂₎ , 4.51 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.66 (d, J = 7.3 Hz, 4H, 4CH _RU ), 8.00 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.32 (d, J = 8.9 Hz, 2H, 2CH _Ar ), 9.00 (d, J = 7.3 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.3, 28.4, 30.5, 31.0, 59.1, 114.8, 118.1, 120.4, 130.1, 131.5, 134.8, 146.9, 150.6, 168.9 ppm;

4,4 '- [naphthalene-2,7-diylbis (oxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H ₅₂ Br ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 184-186 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.4 Hz, 6H, 2CH3), 1.14-1.34 (m, 24H, 12CH2), 1.79-1.94 (m, 4H, 2CH ₂ ) , 4.51 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.66 (d, J = 7.3 Hz, 4H, 4CH _RU ), 8.00 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.32 (d, J = 8.9 Hz, 2H, 2CH _Ar ), 9.00 (d, J = 7.3 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 22.0, 25.2, 28.3, 28.5, 28.7, 30.5, 31.1, 59.1, 114.8, 118.1, 120.4, 130.1, 131.5, 134.8, 146.9, 150.6, 168.9 ppm ;

4,4 '- [naphthalene-2,7-diylbis (oxy)] bis (1-decylpyridinium) dibromide of the formula:

C ₄₀ H _{56 B} r ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 197-198 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.86 (t, J = 6.4 Hz, 6H, 2CH3), 1.14-1.51 (m, 28H, 14SN2), 1.79-1.94 (m, 4H, 2CH ₂₎ , 4.51 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.66 (d, J = 7.3 Hz, 4H, 4CH _RU ), 8.00 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.32 (d, J = 8.9 Hz, 2H, 2CH _Ar ), 9.00 (d, J = 7.3 Hz, 4H, 4CH _RU ) ppm; ^{! 3} С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 22.0, 25.2, 28.3, 28.5, 28.7, 28.8, 30.5, 31.1, 59.1, 114.8, 118.1, 120.4, 130.1, 131.5, 134.8, 146.9, 150.6 , 168.9 ppm;

4,4 '- [naphthalene-2,7-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H ₆₀ Br ₂ N ₂ O ₂ ; Μ = 784.8; White powder; T. pl. 200-204 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.4 Hz, 6H, 2CH3), 1.14-1.51 (m, 32H, 16CH2), 1.79-1.94 (m, 4H, 2CH ₂ ) , 4.51 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.66 (d, J = 7.3 Hz, 4H, 4CH _RU ), 8.00 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.32 (d, J = 8.9 Hz, 2H, 2CH _Ar ), 9.00 (d, J = 7.3 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 22.0, 25.2, 28.3, 28.6, 28.7, 28.8, 30.5, 31.2, 59.1, 114.8,118.1, 120.4, 130.1, 131.5, 134.8, 146.9, 150.6, 168.9 ppm;

4,4 '- [naphthalene-2,7-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ = 812.8; White powder; T. pl. 213-216 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.4 Hz, 6H, 2CH3), 1.14-1.51 (m, 36H, 18CH2), 1.79-1.94 (m, 4Η, 2CH ₂ ) , 4.51 (t, J = 6.8 Hz, 4Η, 2CH ₂ N ⁺ ), 7.60 (dd, J = 8.9, 2.4 Hz, 2H, 2CH _Ar ), 7.66 (d, J = 7.3 Hz, 4H, 4CH _RU ), 7.99 (d, J = 2.4 Hz, 2H, 2CH _Ar ), 8.32 (d, J = 8.9 Hz, 2H, 2CH _Ar ), 8.99 (d, J = 7.3 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, OMSO-d ₆ ): δ 13.8, 22.0, 25.2, 28.3, 28.6, 28.7, 28.8, 28.9, 30.5, 31.2, 59.1, 114.8, 118.1, 120.4, 130.1, 131.5, 134.8, 146.9, 150.6, 168.9 ppm;

Examples 18-22 [Scheme 4]. General method for the synthesis of dimeric compounds (Id _1-s )

To a solution of 2,2 '- [naphthalene-1,6-diylbis (oxy)] dipyridine (0.36 g, 1 mmol) in acetonitrile (10 ml) was added alkyl bromide (8 mmol). The mixture was boiled under reflux for 7 days, then cooled and the solvent was evaporated in a water-jet vacuum. The residue was boiled in 10 ml of acetone, cooled and filtered to give 2,2 '- [naphthalene-1,6-diylbis (oxy)] bis (1-alkylpyridinium) dibromide.

2,2 '- [naphthalene-1,6-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 50-52 ° C; ¹ H NMR (300 MHz, OMSO-d ₆ ): 0.78-0.87 (m, 6H, 2CH3), 1.15-1.54 (m, 20H, 10CH2), 1.92-2.15 (m, 4H, 2CH ₂ ), 4.68 (t , J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 4.78 (t, J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 7.17 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.34 (d, J = 8.7 Hz, 2H, 2CH _RC), 7.72-7.87 (m, 5H, 3CH _Ar, 2CH _RC), 8.13-8.19 (m, 1H, CH _Ar), 8.31 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.34 (d, J = 9.2 Hz, 1H, CH _Ar ), 8.39-8.51 (m, 2H, 2CH _RU ), 8.94-9.06 (m, 2H, 2CH _RU ); ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.2, 28.3, 28.8, 28.9, 30.5, 31.0, 55.0, 55.3 113.5, 113.9, 118.5, 119.1, 121.0, 121.6, 124.3, 124.7 , 128.0, 128.3, 135.1, 135.7, 143.8, 143.9, 147.5, 148.5, 148.7, 150.4,158.8, 159.0 ppm.

2,2 '- [naphthalene-1,6-diylbifxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H ₅₂ Br ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 71-73 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): 0.78-0.87 (m, 6H, 2CH3), 1.18-1.57 (m, 24H, 12CH2), 1.92-2.13 (m, 4H, 2CH ₂ ), 4.68 (t , J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 4.78 (t, J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 7.17 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.34 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.73-7.84 (m, 5H, 3CH _Ar , 2CH _py ), 8.12-8.21 (m, 1H, CH _Ar ), 8.31 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.34 (d, J = 9.2 Hz, 1H, CH _Ar ), 8.42-8.54 (m, 2H, 2CH _RU ), 8.93-9.04 (m, 2H, 2CH _RU ); ¹³ С NMR (75 MHz, OMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.2, 28.3, 28.4, 28.8, 28.9, 30.5, 31.0, 55.0, 55.3 113.5, 113.9, 118.5, 119.1, 121.0, 121.6, 124.3 , 124.7, 128.0, 128.3, 135.1, 135.7, 143.8, 143.9, 147.5, 148.5, 148.7, 150.4, 158.8, 159.0 ppm.

2,2 '- [naphthalene-1,6-diylbis (oxy)] bis (1-decylpyridinium) dibromide of the formula:

C ₄₀ H ₅₆ Br ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 75-78 ° C; ¹ H NMR (300 MHz, DMSO-d _6): 0.78-0.87 (m, 6H, 2CH3), 1.15-1.53 (m, 28H, 14SN2), 1.98-2.21 (m, 4H, 2CH _2), 4.68 (t , J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 4.78 (t, J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 7.17 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.34 (d, J = 8.7 Hz, 2H, 2CH _RC), 7.75-7.87 (m, 5H, 3CH _Ar, 2CH _RC), 8.17-8.25 (m, 1H, CH _Ar), 8.31 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.34 (d, J = 9.2 Hz, 1H, CH _Ar ), 8.39-8.51 (m, 2H, 2CH _RU ), 8.92-9.06 (m, 2H, 2CH _RU ); ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 25.3, 28.1, 28.2, 28.3, 28.8, 28.9, 30.5.31.0, 55.0, 55.3 113.5, 113.9, 118.5, 119.1, 121.0, 121.6 , 124.3, 124.7, 128.0, 128.3,135.1, 135.7, 143.8, 143.9, 147.5, 148.5, 148.7, 150.4, 158.8, 159.0 ppm.

2,2 '- [naphthalene-1,6-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H ₆₀ Br ₂ N ₂ O ₂ ; Μ = 784.8; White powder; T. pl. 85-88 ° C; ¹ H NMR (300 MHz, DMSO-d _6): 0.78-0.87 (m, 6H, 2CH3), 1.10-1.51 (m, 32H, 16SN2), 1.92-2.15 (m, 4H, 2CH _2), 4.68 (t , J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 4.78 (t, J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 7.17 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.34 (d, J - 8.7 Hz, 2H, 2CH _RC), 7.72-7.87 (m, 5H, 3CH _Ar, 2CH _RC), 8.13-8.19 (m, 1H, CH _Ar), 8.31 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.34 (d, J = 9.2 Hz, 1H, CH _Ar ), 8.40-8.53 (m, 2H, 2CH _RU ), 8.94-9.05 (m, 2H, 2CH _RU ); ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.1, 25.2, 25.4, 28.2, 28.3, 28.7, 28.8, 28.9, 30.5, 31.0, 55.0, 55.3 113.5, 113.9, 118.5, 119.1, 121.0 , 121.6, 124.3, 124.7, 128.0, 128.3, 135.1, 135.7, 143.8, 143.9, 147.5, 148.5, 148.7, 150.4, 158.8, 159.0 ppm.

2,2 '- [naphthalene-1,6-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ = 812.8; White powder; T. pl. 103-105 ° C; ¹ H NMR (300 MHz, DMSO-d _6): 0.78-0.87 (m, 6H, 2CH3), 1.15-1.54 (m, 36H, 18SN2), 1.92-2.15 (m, 4H, 2CH _2), 4.68 (t , J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 4.78 (t, J = 7.5 Hz, 2H, CH ₂ N ⁺ ), 7.17 (d, J = 8.7 Hz, 2H, 2CH _RU ), 7.34 (d, J = 8.7 Hz, 2H, 2CH _RC), 7.72-7.87 (m, 5H, 3CH _Ar, 2CH _RC), 8.13-8.19 _{(m, 1H, CH Ar), 8.31} ( d, J = 2.3 Hz, 1H, CH _Ar ), 8.34 (d, J = 9.2 Hz, 1H, CH _Ar ), 8.39-8.51 (m, 2H, 2CH _RU ), 8.94-9.07 (m, 2H, 2CH _RU ); ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.1, 25.2, 25.4, 28.2, 28.3, 28.7, 28.8, 28.9, 30.0, 30.5, 31.0, 55.0, 55.3 113.5, 113.9, 118.5, 119.1 , 121.0, 121.6, 124.3, 124.7, 128.0, 128.3, 135.1, 135.7, 143.8, 143.9, 147.5, 148.5, 148.7, 150.4, 158.8, 159.0 ppm.

Examples 23-27 [scheme 5]. General method for the synthesis of dimeric compounds (Ie _1-5 )

To a solution of 3,3 '- [naphthalene-1,6-diylbis (oxy)] dipyridine I (0.36 g, 1 mmol) in acetonitrile (3 ml) was added alkyl bromide (4 mmol). The mixture was boiled under reflux for 24 hours, then the solvent was evaporated in a water-jet vacuum pump. The residue was boiled in 10 ml of acetone, cooled and filtered to give 3,3 '- [naphthalene-1,6-diylbis (oxy)] bis (1-alkylpyridinium) dibromide.

3,3 '- [naphthalene-1,6-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 102-105 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.25-1.50 (m, 20H, 10SN2), 1.84-2.01 (m, 4H, 2CH ₂₎ , 4.62 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.25 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.53 (d, J = 7.9 Hz, 1H, CH _Ar ) 7.78 (t, J = 7.9 Hz, 1H, CH _Ar ), 7.96 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.05 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.11 (d, J = 2.3 Hz, 1Н, CH _Ar ), 8.27 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.35 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2Н, 2СН _РУ ), 9.33 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.2, 28.3, 30.5, 31.0, 59.1, 107.0, 109.6, 118.6, 119.3, 121.5, 123.5, 126.7, 128.6, 128.8, 129.7, 129.9, 132.1, 132.3, 137.4, 137.6, 149.4, 153.7, 160.3, 160.6.

3,3 '- [naphthalene-1,6-diylbis (oxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H ₅₂ Br ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 120-123 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.27-1.48 (m, 24H, 12CH2), 1.81-2.02 (m, 4H, 2CH ₂ ) , 4.62 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.25 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.53 (d, J = 7.9 Hz, 1H, CH _Ar ) 7.78 (t, J = 7.9 Hz, 1H, CH _Ar ), 7.96 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.04 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.11 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.27 (dd, J = 8.7, 5.8 Hz, 2H, 2СН _РУ ), 8.35 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2Н, 2СН _РУ ), 9.33 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.1, 28.2, 28.3, 30.5, 31.0, 59.1, 107.0, 109.6, 118.6, 119.3, 121.5, 123.5, 126.7, 128.6, 128.8, 129.7, 129.9, 132.1, 132.3, 137.4, 137.6, 149.4, 153.7, 160.3, 160.6.

3,3 '- [naphthalene-1,6-diylbis (oxy)] bis (1-decylpyridinium) dibromide of the formula:

C ₄₀ H _{56 B} r ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 138-141 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.24-1.50 (m, 28H, 14CH2), 1.84-2.01 (m, 4H, 2CH ₂ ) , 4.62 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.25 (dd, J = 9.1, 2.3 Hz, B, CH _Ar ), 7.53 (d, J = 7.9 Hz, 1H, CH _Ar ) 7.79 (t, J = 7.9 Hz, 1H, CH _Ar ), 7.96 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.05 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.11 (d, J = 2.3 Hz, 1Н, CH _Ar ), 8.25 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.35 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2Н, 2СН _РУ ), 9.31 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.1, 28.2, 28.3, 28.6, 30.5, 31.0, 59.1, 107.0, 109.6, 118.6, 119.3, 121.5, 123.5, 126.7, 128.6, 128.8, 129.7, 129.9, 132.1, 132.3, 137.4, 137.6, 149.4, 153.7, 160.3, 160.6.

3,3 '- [naphthalene-1,6-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H _{60 B} r ₂ N ₂ O ₂ ; Μ = 784.8; White powder; T. pl. 152-155 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.27-1.54 (m, 32H, 16CH2), 1.84-2.01 (m, 4H, 2CH ₂ ) , 4.62 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.26 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.53 (d, J = 7.9 Hz, 1H, CH _Ar ) 7.78 (t, J = 7.9 Hz, 1H, CH _Ar ), 7.96 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.05 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.11 (d, J = 2.3 Hz, 1Н, CH _Ar ), 8.27 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.34 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2Н, 2СН _РУ ), 9.33 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.1, 28.2, 28.3, 28.6, 28.8, 30.5, 31.0, 59.1, 107.0, 109.6, 118.6, 119.3, 121.5, 123.5, 126.7, 128.6, 128.8, 129.7, 129.9, 132.1, 132.3, 137.4, 137.6, 149.4, 153.7, 160.3, 160.6.

3,3 '- [naphthalene-1,6-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ - 812.8; White powder; T. pl. 173-176 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J - 6.6 Hz, 6H, 2CH3), 1.25-1.52 (m, 36H, 18CH2), 1.87-2.03 (m, 4H, 2CH ₂ ) , 4.62 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.25 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.53 (d, J = 7.9 Hz, 1H, CH _Ar ) 7.78 (t, J = 7.9 Hz, 1H, CH _Ar ), 7.96 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.06 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.11 (d, J = 2.3 Hz, 1Н, CH _Ar ), 8.27 (dd, J = 8.7, 5.8 Hz, 2Н, 2СН _РУ ), 8.35 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.96 (d, J = 5.8 Hz, 2Н, 2СН _РУ ), 9.31 (d, J = 2.0 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.0, 28.2, 28.4, 28.5, 28.6, 28.8, 30.5, 31.0, 59.1, 107.0, 109.6, 118.6, 119.3, 121.5, 123.5, 126.7, 128.6, 128.8, 129.7, 129.9, 132.1, 132.3, 137.4, 137.6, 149.4, 153.7, 160.3, 160.6.

Examples 28-33 [Scheme 6]. General method for the synthesis of dimeric compounds (If _1-6 )

To a solution of 4,4 '- [naphthalene-1,6-diylbis (oxy)] dipyridine I (0.36 g, 1 mmol) in acetonitrile (3 ml) was added alkyl bromide (4 mmol). The mixture was boiled under reflux for 72 hours, then the solvent was evaporated in a water-jet vacuum pump. The residue was boiled in 10 ml of acetone, cooled and filtered to give 4,4 '- [naphthalene-1,6-diylbis (oxy)] bis (1-alkylpyridinium) dibromide.

4,4 '- [naphthalene-1,6-diylbis (oxy)] bis (1-heptylpyridinium) dibromide of the formula:

C ₃₈ H ₅₀ Br ₂ N ₂ O ₃ ; Μ = 742.6; White powder; T. pl. 196-199 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.13-1.44 (m, 16H, 8SN2), 1.79-1.94 (m, 4H, 2CH ₂₎ , 4.52 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.64-7.72 (m, 5H, CH _Ar , 4CH _py ) 7.80 (t, J = 7.9 Hz, 1H, CH _Ar ), 8.08 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.11 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.17 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.99 (d, J = 6.8 Hz, 4H, 4CH _RU ); ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.3, 30.5, 31.0, 59.1, 114.7, 114.9, 118.2, 118.8, 121.4, 124.0, 124.3, 127.2, 127.9, 135.8, 146.9, 147.0, 147.8, 150.7, 168.9, 169.2 ppm;

4,4 '- [naphthalene-1,6-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 217-220 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.85 (t, J = 6.6 Hz, 6H, 2CH3), 1.10-1.45 (m, 20H, 10CH2), 1.79-1.94 (m, 4H, 2CH ₂ ) , 4.51 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.62-7.71 (m, 5H, CH _Ar , 4CH _RU ) 7.80 (t, J = 7.9 Hz, 1H, CH _Ar ), 8.08 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.11 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.17 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.99 (d, J = 6.8 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, OMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.2, 28.3, 30.5, 31.0, 59.1, 114.7, 114.9, 118.2, 118.8, 121.4, 124.0, 124.3, 127.2, 127.9, 135.8, 146.9, 147.0, 147.8, 150.7, 168.9, 169.2 ppm;

4,4 '- [naphthalene-1,6-diylbis (oxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H _{52 B} r ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 227-230 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.84 (t, J = 6.6 Hz, 6H, 2CH3), 1.12-1.48 (m, 24H, 12CH2), 1.79-1.94 (m, 4H, 2CH ₂ ) , 4.51 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.62-7.70 (m, 5H, CH _Ar , 4CH _RU ) 7.80 (t, J = 7.9 Hz, 1H, CH _Ar ), 8.08 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.11 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.17 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.99 (d, J = 6.8 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.2, 28.3, 28.5, 30.5, 31.0, 59.1, 114.7, 114.9, 118.2, 118.8, 121.4, 124.0, 124.3, 127.2, 127.9, 135.8, 146.9, 147.0, 147.8, 150.7, 168.9, 169.2 ppm;

4,4 '- [naphthalene-1,6-diylbis (oxy)] bis (1-decylpyridinium) dibromide of the formula:

C ₄₀ H ₅₆ Br ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 236-239 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.85 (t, J = 6.6 Hz, 6H, 2CH3), 1.12-1.45 (m, 28H, 14CH2), 1.79-1.94 (m, 4H, 2CH ₂ ) , 4.51 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.67-7.73 (m, 5H, CH _Ar , 4CH _py ) 7.80 (t, J = 7.9 Hz, 1H, CH _Ar ), 8.08 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.11 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.17 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.99 (d, J = 6.8 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, OMSO-d ₆ ): δ 13.8,21.9, 25.2, 28.2, 28.3,28.5, 28.7, 30.5.31.0, 59.1, 114.7, 114.9, 118.2, 118.8, 121.4, 124.0, 124.3, 127.2, 127.9, 135.8, 146.9, 147.0, 147.8, 150.7, 168.9, 169.2 ppm;

4,4 '- [naphthalene-1,6-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H ₆₀ Br ₂ N ₂ O ₂ ; Μ = 784.8; White powder; T. pl. 225-228 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.85 (t, J = 6.6 Hz, 6H, 2CH3), 1.12-1.45 (m, 32H, 16CH2), 1.79-1.94 (m, 4H, 2CH ₂ ) , 4.51 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.62-7.70 (m, 5H, CH _Ar , 4CH _RU ) 7.80 (t, J = 7.9 Hz, 1H, CH _Ar ), 8.08 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.11 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.17 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.99 (d, J = 6.8 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.1, 28.2, 28.3, 28.4, 28.6, 30.5, 31.0, 59.1, 114.7, 114.9, 118.2, 118.8, 121.4, 124.0, 124.3, 127.2, 127.9, 135.8, 146.9, 147.0, 147.8, 150.7, 168.9, 169.2 ppm;

4,4 '- [naphthalene-1,6-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ = 812.8; White powder; T. pl. 230-233 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.85 (t, J = 6.6 Hz, 6H, 2CH3), 1.12-1.45 (m, 36H, 18SN2), 1.79-1.94 (m, 4H, 2CH ₂₎ , 4.51 (t, J = 7.2 Hz, 4H, 2CH ₂ N ⁺ ), 7.60 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.62-7.70 (m, 5H, CH _Ar , 4CH _RU ) 7.80 (t, J = 7.9 Hz, 1H, CH _Ar ), 8.08 (d, J = 9.1 Hz, 1H, CH _Ar ), 8.11 (d, J = 7.9 Hz, 1H, CH _Ar ), 8.17 (d, J = 2.3 Hz, 1H, CH _Ar ), 8.99 (d, J = 6.8 Hz, 4H, 4CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.0, 28.1, 28.2, 28.3, 28.4, 28.6, 30.5, 31.0, 59.1, 114.7, 114.9, 118.2, 118.8, 121.4, 124.0, 124.3, 127.2, 127.9, 135.8, 146.9, 147.0, 147.8, 150.7, 168.9, 169.2 ppm;

Examples 34-38 [Scheme 7]. General method for the synthesis of dimeric compounds (Ig _l-5 )

To a solution of 2,2 '- [naphthalene-1,5-diylbis (oxy)] dipyridine (0.36 g, 1 mmol) in acetonitrile (10 ml) was added alkyl bromide (8 mmol). The mixture was boiled under reflux for 7 days, then cooled and the solvent was evaporated in a water-jet vacuum. The residue was boiled in 10 ml of acetone, cooled and filtered to give 2,2 '- [naphthalene-1,5-diylbis (oxy)] bis (1-alkylpyridinium) dibromide.

2,2 '- [naphthalene-1,5-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 192-195 ° C; ¹ H NMR (300 MHz, OMSO-d _6): δ 0.83 (t, J - 6.4 Hz, 6H, 2CH3), 1.09-1.57 (m, 20H, 10SN2), 2.02-2.18 (m, 4H, 2CH ₂₎ , 4.77 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.21 (d, J = 7.7 Hz, 2H, 2CH _RU ), 7.74-7.95 (m, 6H), 8.19 (d, J = 8.3 Hz , 2Н, CH _Ar ), 8.42 (t, J = 7.7 Hz, 2Н, 2СН _РУ ), 9.00 (d, J = 6.1 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 28.3, 28.4, 30.7, 31.1, 57.9, 113.1, 120.3, 120.5, 123.0, 130.4, 131.7, 140.3, 140.5, 147.8, 158.8 ppm ;

2,2 '- [naphthalene-1,5-diylbis (oxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H ₅₂ Br ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 200-202 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.83 (t, J = 6.4 Hz, 6H, 2CH), 1.09-1.57 (m, 24H, 12CH2), 2.02-2.18 (m, 4H, 2CH ₂ ) , 4.77 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.21 (d, J = 7.7 Hz, 2H, 2CH _RU ), 7.74-7.95 (m, 6H), 8.19 (d, J = 8.3 Hz , 2Н, CH _Ar ), 8.42 (t, J - 7.7 Hz, 2Н, 2СН _РУ ), 9.00 (d, J = 6.1 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, OMSO-d ₆ ): δ 13.9, 21.9, 25.3, 28.3, 28.4, 28.5, 30.7, 31.1, 57.9, 113.1, 120.3, 120.5, 123.0, 130.4, 131.7, 140.3, 140.5, 147.8, 158.8 ppm;

2,2 '- [naphthalene-1,5-diylbis (oxy)] bis (1-decylpyridinium) dibromide of the formula:

C ₄₀ H ₅₆ Br ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 210-211 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.83 (t, J = 6.4 Hz, 6H, 2CH3), 1.09-1.57 (m, 28H, 14CH2), 2.02-2.18 (m, 4H, 2CH ₂ ) , 4.77 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.21 (d, J = 7.7 Hz, 2H, 2CH _RU ), 7.74-7.95 (m, 6H), 8.19 (d, J = 8.3 Hz , 2Н, CH _Ar ), 8.42 (t, J = 7.7 Hz, 2Н, 2СН _РУ ), 9.00 (d, J = 6.1 Hz, 2Н, 2СН _РУ ) ppm; ^I3 C NMR (75 MHz, DMSO-d ₆ ): δ 13.9,21.9, 25.2, 25.3, 28.3,28.6, 28.4, 30.7,31.1,57.9, 113.1, 120.3, 120.5, 123.0, 130.4, 131.7, 140.3, 140.5, 147.8, 158.8 ppm;

2,2 '- [naphthalene-1,5-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H ₆₀ Br ₂ N ₂ O ₂ ; Μ = 784.8; White powder; T. pl. 226-227 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.83 (t, J - 6.4 Hz, 6H, 2CH3), 1.09-1.57 (m, 32H, 16SN2), 2.02-2.18 (m, 4H, 2CH ₂₎ , 4.77 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.21 (d, J = 7.7 Hz, 2H, 2CH _RU ), 7.74-7.95 (m, 6H), 8.19 (d, J = 8.3 Hz , 2Н, CH _Ar ), 8.42 (t, J = 7.7 Hz, 2Н, 2СН _РУ ), 9.00 (d, J - 6.1 Hz, 2Н, 2СН _РУ ) ppm; ^l3 C NMR (75 MHz, OMSO-d ₆ ): δ 13.9, 21.9, 25.1, 25.3, 28.2, 28.3, 28.4, 28.7, 30.7, 31.1, 57.9, 113.1, 120.3, 120.5, 123.0, 130.4, 131.7, 140.3, 140.5, 147.8, 158.8 ppm;

2,2 '- [naphthalene-1,5-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ = 812.8; White powder; T. pl. 245-248 ° C; ¹ H NMR (300 MHz, OMSO-d _6): δ 0.83 (t, J = 6.4 Hz, 6H, 2CH3), 1.09-1.57 (m, 36H, 18SN2), 2.02-2.18 (m, 4H, 2CH ₂₎ , 4.77 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.21 (d, J = 7.7 Hz, 2H, 2CH _RU ), 7.74-7.95 (m, 6H), 8.19 (d, J = 8.3 Hz , 2Н, CH _Ar ), 8.42 (t, J = 7.7 Hz, 2Н, 2СН _РУ ), 9.00 (d, J = 6.1 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.1, 25.3, 28.1, 28.2, 28.3, 28.4, 28.7, 30.7, 31.1, 57.9, 113.1, 120.3, 120.5, 123.0, 130.4, 131.7, 140.3, 140.5, 147.8, 158.8 ppm;

Examples 39-43 [Scheme 8]. General method for the synthesis of dimeric compounds (Ih _1-5 )

To a solution of 3,3 '- [naphthalene-1,5-diylbis (oxy)] dipyridine (0.36 g, 1 mmol) in acetonitrile (10 ml) was added alkyl bromide (4 mmol). The mixture was boiled under reflux for 24 hours, then cooled and the solvent was evaporated in a water-jet vacuum. The residue was boiled in 10 ml of acetone, cooled and filtered off to give 3,3 '- [naphthalene-1,5-diylbis (oxy)] bis (1-alkylpyridinium) dibromide.

3,3 '- [naphthalene-1,5-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 151-154 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.86 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 20H, 10SN2), 1.87-2.00 (m, 4H, 2CH ₂₎ , 4.64 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.43 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.75 (t, J = 8.3 Hz, 2H, 2CH _Ar ), 7.98 ( dd, J = 8.4, 4.5 Hz, 2Н, 2СН _РУ ), 8.11 (d, J = 8.3 Hz, 2Н, 2CH _Ar ), 8.25 (dd, J = 8.4, 1.9 Hz, 2Н, 2СН _РУ ), 8.47 (d , J = 4.5 Hz, 2Н, 2СН _РУ ), 9.01 (d, J = 1.9 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 28.3, 28.4, 30.7, 31.1, 60.9, 113.1, 120.3, 120.5, 121.0, 128.5, 129.8, 140.3, 145.7, 149.8, 155.1 ppm ...

3,3 '- (naphthalene-1,5-diylbis (oxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H ₅₂ Br ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 170-173 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 24H, 12CH2), 1.87-2.00 (m, 4H, 2CH ₂ ) , 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.43 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.75 (t, J = 8.3 Hz, 2H, 2CH _Ar ), 7.98 ( dd, J = 8.4, 4.5 Hz, 2Н, 2СН _РУ ), 8.11 (d, J = 8.3 Hz, 2Н, 2CH _Ar ), 8.25 (dd, J = 8.4, 1.9 Hz, 2Н, 2СН _РУ ), 8.47 (d , J = 4.5 Hz, 2Н, 2СН _РУ ), 9.01 (d, J = 1.9 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 25.4, 28.3, 28.4, 30.7, 31.1, 60.9, 113.1, 120.3, 120.5, 121.0, 128.5, 129.8, 140.3, 145.7, 149.8, 155.1 ppm.

3,3 '- [naphthalene-1,5-diylbis (oxy)] bis (1-decylpyridinium) dibromide of the formula:

C ₄₀ H ₅₆ Br ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 175-178 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 28H, 14SN2), 1.87-2.00 (m, 4H, 2CH ₂₎ , 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.43 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.75 (t, J = 8.3 Hz, 2H, 2CH _Ar ), 7.98 ( dd, J - 8.4, 4.5 Hz, 2Н, 2СН _РУ ), 8.11 (d, J = 8.3 Hz, 2Н, 2CH _Ar ), 8.25 (dd, J = 8.4, 1.9 Hz, 2Н, 2СН _РУ ), 8.47 (d , J = 4.5 Hz, 2H, 2CH _RU ), 9.01 (d, J = 1.9 Hz, 2H, 2CH _ru ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 25.4, 28.3, 28.4, 28.5, 30.7, 31.1, 60.9, 113.1, 120.3, 120.5, 121.0, 128.5, 129.8, 140.3, 145.7, 149.8, 155.1 ppm.

3,3 [naphthalene-1,5-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H ₆₀ Br ₂ N ₂ O ₂ ; Μ = 784.8; White powder; T. pl. 181-184 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3), 1.17-1.35 (m, 32H, 16SN2), 1.87-2.00 (m, 4H, 2CH ₂₎ , 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.43 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.75 (t, J = 8.3 Hz, 2H, 2CH _Ar ), 7.98 ( dd, J = 8.4, 4.5 Hz, 2Н, 2СН _РУ ), 8.11 (d, J = 8.3 Hz, 2Н, 2CH _Ar ), 8.25 (dd, J = 8.4, 1.9 Hz, 2Н, 2СН _РУ ), 8.47 (d , J = 4.5 Hz, 2Н, 2СН _РУ ), 9.01 (d, J = 1.9 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.3, 25.4, 28.3, 28.4, 28.5, 28.6, 30.7, 31.1, 60.9, 113.1, 120.3, 120.5, 121.0, 128.5, 129.8, 140.3, 145.7, 149.8, 155.1 ppm.

3,3 '- [naphthalene-1,5-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ = 812.8; White powder; T. pl. 195-196 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.85 (t, J = 6.5 Hz, 6H, 2CH3, 1.17-1.35 (m, 36H, 18CH2), 1.87-2.00 (m, 4H, 2CH ₂ ), 4.63 (t, J = 7.4 Hz, 4H, 2CH ₂ N ⁺ ), 7.43 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.75 (t, J = 8.3 Hz, 2H, 2CH _Ar ), 7.98 (dd , J = 8.4, 4.5 Hz, 2Н, 2СН _РУ ), 8.11 (d, J = 8.3 Hz, 2Н, 2CH _Ar ), 8.25 (dd, J = 8.4, 1.9 Hz, 2Н, 2СН _РУ ), 8.47 (d, J = 4.5 Hz, 2Н, 2СН _РУ ), 9.01 (d, J = 1.9 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.9, 21.9, 25.1, 25.3, 25.4 , 28.3, 28.4, 28.5, 28.6, 30.7, 31.1, 60.9, 113.1, 120.3, 120.5, 121.0, 128.5, 129.8, 140.3, 145.7, 149.8, 155.1 ppm.

Examples 44-48 [Scheme 9]. General method for the synthesis of dimeric compounds (Ii _1-5 )

To a solution of 4,4 '- [naphthalene-1,5-diylbis (oxy)] dipyridine (0.36 g, 1 mmol) in acetonitrile (10 ml) was added alkyl bromide (8 mmol). The mixture was boiled under reflux for 72 hours, then cooled and the solvent was evaporated in a water-jet vacuum. The residue was boiled in 10 ml of acetone, cooled and filtered to give 4,4 '- [naphthalene-1,5-diylbis (oxy)] bis (1-alkylpyridinium) dibromide.

4,4 '- [naphthalene-1,5-diylbis (oxy)] bis (1-octylpyridinium) dibromide of the formula:

C ₃₆ H ₄₈ Br ₂ N ₂ O ₂ ; Μ = 700.6; White powder; T. pl. 210-213 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.25-1.41 (m, 20H, 10CH2), 1.91-2.06 (m, 4H, 2CH ₂ ) , 4.81 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.65 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.84 (d, J = 5.3 Hz, 2H, 2CH _RU ), 8.02 ( t, J = 8.3 Hz, 2H, 2CH _Ar ), 8.45 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 9.01 (d, J = 5.3 Hz, 2H, 2CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.2, 28.3, 30.5, 31.0, 60.1, 113.9, 118.5, 117.8, 126.4, 128.7, 149.8, 149.4, 160.6 ppm.

4,4 '- [naphthalene-1,5-diylbis (oxy)] bis (1-nonylpyridinium) dibromide of the formula:

C ₃₈ H ₅₂ Br ₂ N ₂ O ₂ ; Μ = 728.7; White powder; T. pl. 221-223 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.25-1.41 (m, 24H, 12CH2), 1.91-2.06 (m, 4H, 2CH ₂ ) , 4.81 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.65 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.84 (d, J = 5.3 Hz, 2H, 2CH _RU ), 8.02 ( t, J = 8.3 Hz, 2H, 2CH _Ar ), 8.45 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 9.01 (d, J = 5.3 Hz, 2H, 2CH _RU ) ppm; ^I3 C NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 28.2, 28.3, 28.5, 30.5, 31.0, 60.1, 113.9, 118.5, 117.8, 126.4, 128.7, 149.8, 149.4, 160.6 ppm.

4,4 '- [naphthalene-1,5-diylbis (oxy)] bis (1-decylpyridinium) dibromide of the formula:

C ₄₀ H ₅₆ Br ₂ N ₂ O ₂ ; Μ = 756.7; White powder; T. pl. 235-238 ° C; ¹ H NMR (300 MHz, DMSO-d _6): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.25-1.41 (m, 28H, 14SN2), 1.91-2.06 (m, 4H, 2CH ₂₎ , 4.81 (t, J - 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.65 (d, J - 8.3 Hz, 2H, 2CH _Ar ), 7.84 (d, J = 5.3 Hz, 2H, 2CH _RU ), 8.02 ( t, J = 8.3 Hz, 2H, 2CH _Ar ), 8.45 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 9.01 (d, J = 5.3 Hz, 2H, 2CH _RU ) ppm; ^I3 C NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.2, 25.3,28.2, 28.3, 28.5, 30.5, 31.0, 60.1, 113.9, 118.5, 117.8, 126.4, 128.7, 149.8, 149.4, 160.6 ppm ...

4,4 '- [naphthalene-1,5-diylbis (oxy)] bis (1-undecylpyridinium) dibromide of the formula:

C ₄₂ H ₆₀ Br ₂ N ₂ O ₂ ; Μ = 784.8; White powder; T. pl. 256-257 ° C; ¹ H NMR (300 MHz, OMSO-d _6): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.25-1.41 (m, 32H, 16SN2), 1.91-2.06 (m, 4H, 2CH ₂₎ , 4.81 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.65 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.84 (d, J = 5.3 Hz, 2H, 2CH _RU ), 8.02 ( t, J = 8.3 Hz, 2H, 2CH _Ar ), 8.45 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 9.01 (d, J = 5.3 Hz, 2H, 2CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.1, 25.2, 28.2, 28.3, 28.4, 28.6, 30.5, 31.0, 60.1, 113.9, 118.5, 117.8, 126.4, 128.7, 149.8, 149.4, 160.6 ppm.

4,4 '- [naphthalene-1,5-diylbis (oxy)] bis (1-dodecylpyridinium) dibromide of the formula:

C ₄₄ H ₆₄ Br ₂ N ₂ O ₂ ; Μ = 812.8; White powder; T. pl. 280-283 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 0.86 (t, J = 6.6 Hz, 6H, 2CH3), 1.25-1.41 (m, 36H, 18CH2), 1.91-2.06 (m, 4H, 2CH ₂ ) , 4.81 (t, J = 6.8 Hz, 4H, 2CH ₂ N ⁺ ), 7.65 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.84 (d, J = 5.3 Hz, 2H, 2CH _RU ), 8.02 ( t, J = 8.3 Hz, 2H, 2CH _Ar ), 8.45 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 9.01 (d, J = 5.3 Hz, 2H, 2CH _RU ) ppm; ¹³ С NMR (75 MHz, DMSO-d ₆ ): δ 13.8, 21.9, 25.0, 25.2, 25.4, 28.1, 28.3, 28.5, 28.6, 30.5, 31.0, 60.1, 113.9, 118.5, 117.8, 126.4, 128.7, 149.8, 149.4, 160.6 ppm.

Examples of obtaining source materials.

The starting materials used in the above examples include compounds prepared using standard methods from known materials. Some of the starting materials fall within the scope of this invention.

Examples 27-32 are shown for illustration only and do not limit the methods for synthesizing these starting materials.

Example 49 (Scheme 1).

The method of obtaining 2,2 '- [naphthalene-2,7-diylbis (oxy)] dipyridine of the formula:

A flask in an argon atmosphere was sequentially loaded with 2,7-dihydroxynaphthalene (1.6 g, 10 mmol), 2-bromopyridine (3.16 g 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 90 ° C for 24 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. 2,2- [naphthalene-2,7-diylbis (oxy)] dipyridine (2.26 g 7.2 mmol) was obtained, yield 72%. C ₂₂ H ₁₆ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 103-106 ° C; ¹ H NMR (500 MHz, CDCl ₃ ): δ 6.98 (d, J = 8.3 Hz, 2H, 2СН _РУ ), 7.05 (dd, J = 7.1, 5.1 Hz, 2Н, 2СН _РУ ), 7.29 (dd, J = 8.8, 2.1 Hz, 2H, 2CH _Ar ), 7.53 (d, J = 2.1 Hz, 2H, 2CH _Ar ), 7.74 (ddd, J = 8.3, 7.1, 1.6 Hz, 2H, 2CH _RU ), 7.90 (d, J = 8.8 Hz, 2H, 2CH _Ar ), 8.25 (dd, J = 5.1, 1.6 Hz, 2H, 2CH _RU ) ppm; ¹³ С NMR (150 MHz, CDCl ₃ ): δ 111.6, 116.7, 119.1, 120.7, 127.7, 129.4, 134.8, 140.2, 147.5, 152.2, 163.0 ppm. Mass spectrum (EI, 70 eV): m / z = 314 [M ⁺ ].

Example 50 (Scheme 2).

The method of obtaining 3,3 '- [naphthalene-2,7-diylbis (oxy)] dipyridine of the formula:

In a flask in an argon atmosphere, 2,7-dihydroxynaphthalene (1.6 g, 10 mmol), 3-bromopyridine (3.16 g 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 120 ° C for 72 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. Received 3,3 '- [naphthalene-2,7-diylbis (oxy)] dipyridine (1.92 g 6.1 mmol), yield 61%. C ₂₀ H ₁₄ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 71-73; ¹ H NMR (300 MHz, CDCl ₃ ): δ 7.28 (dd, J = 8.9, 2.2 Hz, 2H, 2CH _Ar ), 7.40 (d, J = 2.2 Hz, 2H, 2CH _Ar ), 7.45 (dd, J = 8.4, 4.5 Hz, 2Н, 2СН _РУ ), 7.53 (dd, J = 8.4, 1.9 Hz, 2Н, 2СН _РУ ), 8.01 (d, J = 8.9 Hz, 2Н, 2CH _Ar ), 8.41 (d, J - 4.5 Hz, 2Н, 2СН _РУ ), 8.45 (d, J - 1.9 Hz, 2Н, 2СН _РУ ) ppm; ¹³ C NMR (75 MHz, DMSO-d ₆ ): δ 113.5, 118.6, 124.3, 126.2, 127.3, 130.2,135.3,141.7,144.7,155.3 ppm; Mass spectrum (EI, 70 eV): mix = 314 [M ⁺ ].

Example 51 (Scheme 3).

The method of obtaining 4,4 '- [naphthalene-2,7-diylbis (oxy)] dipyridine of the formula:

A flask in an argon atmosphere was sequentially loaded with 2,7-dihydroxynaphthalene (1.6 g, 10 mmol), 4-chloropyridine hydrochloride (3.00 g, 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 140 ° C for 72 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. Received 4,4 '- [naphthalene-2,7-diylbis (oxy)] dipyridine (2.67 g 8.5 mmol), yield 85%.

C ₂₀ H ₁₄ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 96-98 ° C; ¹ H NMR (300 MHz, CDCl ₃ ): δ 6.95 (d, J = 5.3 Hz, 2H, 2CH _RU ), 7.27 (dd, J = 8.6, 2.1 Hz, 2H, 2CH _Ar ), 7.48 (d, J - 2.1 Hz, 2H, 2CH _Ar ), 7.96 (d, J = 8.6 Hz, 2H, 2CH _Ar ), 8.53 (d, J = 5.3 Hz, 2H, 2CH _RU ) ppm; ¹³ C NMR (75 MHz, OMSO-d ₆ ): δ 112.6, 116.7, 120.2, 128.8, 130.5, 135.3, 151.4, 152.8, 164.6 ppm; Mass spectrum (EI, 70 eV): m / z = 314 [M ⁺ ].

Example 52 (Scheme 4).

The method of obtaining 2,2 '- [naphthalene-1,6-diylbis (oxy)] dipyridine of the formula:

1,6-dihydroxynaphthalene (1.6 g, 10 mmol), 2-bromopyridine (3.16 g 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 90 ° C for 24 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. 2,2- [naphthalene-1,6-diylbis (oxy)] dipyridine (2.42 g 7.7 mmol) was obtained in 77% yield. C ₂₀ H ₁₄ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 98-101 ° C; ¹ H NMR (500 MHz, CDCl ₃ ): δ 6.94-7.00 (m, 2H, 2CH _RU ), 7.02-7.07 (m, 2H, 2CH _RU ), 7.21 (d, J = 7.9 Hz, 1H, CH _Ar ) , 7.29 (dd, J = 9.1, 2.2 Hz, 1H, CH _Ar ), 7.50 (t, J = 7.9 Hz, 1H, CH _Ar ), 7.63 (d, J = 2.2 Hz, 1H, CH _Ar ), 7.68 ( d, J = 7.9 Hz, 1H, CH _Ar ), 7.70-7.76 (m, 2H, 2CH _RU ), 8.07 (d, J - 9.1 Hz, 1H, CH _Ar ), 8.20-8.25 (m, 2H, 2CH _RU ) ppm; ¹³ С NMR (150 MHz, CDCl3): δ 111.0, 111.7, 116.4, 117.4, 118.6, 118.7, 121.5, 124.0, 124.5, 125.0, 126.6, 136.0, 139.6, 147.7, 147.9, 150.3, 152.5, 163.6, 164.2 ppm. Mass spectrum (EI, 70 eV): m / z = 314 [M ⁺ ].

Example 53 (Scheme 5).

The method of obtaining 3,3 '- [naphthalene-1,6-diylbis (oxy)] dipyridine of the formula:

1,6-dihydroxynaphthalene (1.6 g, 10 mmol), 3-bromopyridine (3.16 g 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 120 ° C for 72 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. Received 3,3 '- [naphthalene-1,6-diylbis (oxy)] dipyridine (1.79 g 5.7 mmol), yield 57%. C ₂₀ H ₁₄ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 93-96 ° C; ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 7.03 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.25 (d, J = 7.9 Hz, 1H, CH _Ar ) 7.54 (t, J = 7.9 Hz, 1H, CH _Ar ), 7.68 (dd, J = 8.7, 5.8 Hz, 2H, 2CH _RU ), 7.77 (d, J = 9.1 Hz, 1H, CH _Ar ), 7.90 (d, J = 7.9 Hz , 1Н, CH _Ar ), 8.02 (d, J = 2.3 Hz, 1Н, CH _Ar ), 8.11 (dd, J = 8.7, 2.0 Hz, 2Н, 2СН _РУ ), 8.25 (d, J = 5.8 Hz, 2Н, 2CH _RC), 8.87 (d, J = 2.0 Hz, 2H, 2CH _RC) ppm; ¹³ С NMR (75 MHz, OMSO-d ₆ ): δ 106.5, 108.6, 115.6, 118.3, 120.5, 120.6, 124.7, 125.6, 125.8, 127.7, 128.1, 132.1, 132.3, 137.4, 137.6, 149.4,153.7, 160.3, 160.6. Mass spectrum (EI, 70 eV): m / z = 314 [M ⁺ ].

Example 54 (Scheme 6).

The method of obtaining 4,4 '- [naphthalene-1,6-diylbis (oxy)] dipyridine of the formula:

1,6-dihydroxynaphthalene (1.6 g, 10 mmol), 4-chloropyridine hydrochloride (3.00 g, 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 140 ° C for 72 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. There was obtained 4,4 '- [naphthalene-1,6-diylbis (oxy)] dipyridine (1.98 g 6.3 mmol), yield 63%. C ₂₀ H ₁₄ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 92-95 ° C; ¹ H NMR (300 MHz, CDCl3): δ 6.97 (d, J = 5.0 Hz, 2H, 2CH _py ), 7.03 (d, J = 5.0 Hz, 2H, 2CH _py ), 7.33 (d, J = 7.9 Hz, 1H, CH _Ar ), 7.53 (dd, J = 9.1, 2.3 Hz, 1H, CH _Ar ), 7.62 (t, J = 7.9 Hz, 1H, CH _Ar ), 7.84 (d, J = 2.3 Hz, 1H, CH _Ar ), 7.90 (d, J = 7.9Hz, 1H, CH _Ar ), 7.97 (d, J = 9.1Hz, 1H, CH _Ar ), 8.35-8.64 (μ, 4H, 4CH _py ) ppm; ¹³ C NMR (75 MHz, CDC1 ₃ ): δ 111.8, 112.5, 116.6, 117.1, 121.2, 123.9, 124.0, 125.3, 127.4, 135.9, 149.3, 151.6, 152.3, 163.6, 164.4 ppm. Mass spectrum (EI, 70 eV): m / z = 314 [M ⁺ ].

Example 55 (Scheme 7).

The method of obtaining 2,2 '- [naphthalene-1,5-diylbis (oxy)] dipyridine of the formula:

A flask in an argon atmosphere was sequentially loaded with 1,5-dihydroxynaphthalene (1.6 g, 10 mmol), 2-bromopyridine (3.16 g 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 90 ° C for 24 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. There was obtained 2,2 '- [naphthalene-1,5-diylbis (oxy)] dipyridine (2.32 g, 7.4 mmol), 74% yield. C ₂₀ H ₁₄ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 188-191 ° C; ¹ H NMR (300 MHz, CDCl ₃ ): δ 7.15 (t, J = 6.14 Hz, 2H, 2CH _RU ), 7.22 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.31 (d, J = 7.7 Hz , 2H, 2CH _py ), 7.52 (t, J = 8.3 Hz, 2H, 2CH _Ar ), 7.74 (d, J = 8.3 Hz, 2H, 2CH _Ar , 7.92 (t, J = 7/7 Hz, 2H , 2CH _RC), 8.09 (dd, J = 6.14 Hz, 2H, 2CH _RC) ppm; ¹³ C NMR (75 MHz, CDC1 _3): δ 111.1, 118.3, 118.5, 119.0, 126.4, 128.7, 140.3, 147.4, 149.8 , 163.6 ppm MS (EI, 70 eV): m / z = 314 [M ⁺ ].

Example 56 (Scheme 8).

The method of obtaining 3,3 '- [naphthalene-1,5-diylbis (oxy)] dipyridine of the formula:

1,5-dihydroxynaphthalene (1.6 g, 10 mmol), 3-bromopyridine (3.16 g 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 120 ° C for 72 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. Received 3,3 '- [naphthalene-1,5-diylbis (oxy)] dipyridine (1.88 g, 6.0 mmol), yield 60%. C ₂₀ H ₁₄ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 140-143 ° C; ¹ H NMR (300 MHz, CDCl ₃ ): δ 7.26 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.34 (dd, J = 8.4, 4.5 Hz, 2H, 2CH _RU ), 7.42 (dd, J = 8.4, 1.9 Hz, 2H, 2CH _RU ), 7.68 (t, J = 8.3 Hz, 2H, 2CH _Ar ), 7.96 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 8.18 (d, J = 4.5 Hz, 2Н, 2СН _РУ ), 8.29 (d, J = 1.9 Hz, 2Н, 2СН _РУ ) ppm; ¹³ С NMR (75 MHz, CDCl ₃ ): δ 111.1, 118.3, 118.5, 119.0, 126.4, 128.7, 140.3, 147.4, 149.8, 163.6 ppm. Mass spectrum (EI, 70 eV): m / z = 314 [M ⁺ ].

Example 57 (Scheme 9).

The method of obtaining 4,4 '- [naphthalene-1,5-diylbis (oxy)] dipyridine of the formula:

A flask in an argon atmosphere was sequentially loaded with 1,5-dihydroxynaphthalene (1.6 g, 10 mmol), 4-chloropyridine hydrochloride (3.00 g, 20 mmol), potassium phosphate (8.48 g 40 mol), copper iodide (1.90 g 10 mmol), picolinic acid (0.25 g, 2 mmol) and dimethyl sulfoxide (50 ml). The mixture was stirred at a temperature of 140 ° C for 72 h. Then it was cooled and the solvent was evaporated in a water-jet vacuum pump. Ethyl acetate (50 ml) was added to the dry residue and the mixture was boiled with stirring for 1 hour. The precipitate was filtered off through a paper filter. The filtrate was evaporated in a water-jet vacuum pump. The residue was crystallized from heptane. Received 4,4 '- [naphthalene-1,5-diylbis (oxy)] dipyridine (2.35 g 7.5 mmol), yield 75%. C ₂₀ H ₁₄ N ₂ O ₂ ; Μ = 314.34; White powder; T. pl. 200-203 ° C; ¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01 (d, J = 5.3 Hz, 2H, 2CH _RU ), 7.43 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 7.62 (t, J = 8, 3 Hz, 2H, 2CH _Ar ), 7.83 (d, J = 8.3 Hz, 2H, 2CH _Ar ), 8.50 (d, J = 5.3 Hz, 2H, 2CH _py ) ppm; ¹³ C NMR (75 MHz, DMSO-d ₆ ): δ 112.8, 117.3, 117.5, 125.4, 128.7, 149.8, 151.4,164.6 ppm; Mass spectrum (EI, 70 eV): m / z = 314 [M ⁺ ].

Examples 58-62.

The new compounds of general formula I have useful antibacterial and antifungal effects and are effective against gram-positive and gram-negative bacteria and several types of fungi. Thus, these compounds are indeed broad spectrum biocidal agents. Moreover, these compounds are of low toxicity.

The tested bacterial strains (Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa) used in the examples below are the most resistant forms of bacteria. The resistance of these bacteria to disinfectants or antiseptic treatments is the highest among the large number of different classes of protozoa. The action of the chemical against these bacteria is a criterion for the biocidal action of the chemical in the test. For example, if Escherichia coli bacteria are effectively killed after a biocidal treatment, other members of the E. coli class will die as well, or even more effectively, from the same biocidal agent. The compound of benzalkonium chloride (CBA) is often used as a reference for a quantitative comparison of various antiseptics and disinfectants [US 7612097 B2, 03.11.2009]. Thus, the tests presented below are given in comparison with CBA to demonstrate the high biocidal efficacy of the new compounds when tested, as well as their low toxicity.

For a comparative test for typical dimeric pyridinium quaternary salts obtained according to general formula I and commercially available benzalkonium chloride (CBA), bis-quaternary ammonium salts were used: 1,4-bis- (3,3 '- (1-decylpyridinium) methyloxy) butanedibromide (type C), known as "Hygenia" (from Tama Kagaku Kogyo Co, Ltd.) [JP 2008179571, 07.08.2008], dibromide 3,3 '- [1,4-phenylene-bis- (oxy)] - bis- ( 1-dodecylpyridinium) (type C) [EA 26416 B1, 04/28/2017], "Octenidine dihydrochloride" (from the Dishman Group, type A) [US 4206215 A, 06/03/1980], as well as the closest analogs - 3,3'- [biphenyl-4,4'-diylbis (oxy)] bis (1-decylpyridinium) dibromide and 3,3 '- [oxybis (4,1-phenylene)] bis (1-decylpyridinium) dibromide (type C) [RU 2689419 C1, 28.05.2019].

Biological testing

The biocidal efficacy of samples of new compounds of general formula I, obtained according to the recommendations of the Clinical and Laboratory Standards Institute (CLSI), is determined by the minimum inhibitory concentration (MIC), the minimum bactericidal concentration (MBC) and cytotoxicity against human embryonic kidney cells. Materials and methods

Testing of the biocidal action of the new compounds of general formula I is carried out according to the usual method of dilution in a liquid nutrient medium.

Test compounds: Ia ₁ (prepared according to example 1), Ia ₂ (prepared according to example 2), Ia ₃ (prepared according to example 3), Ia ₄ (prepared according to example 4), Ia ₅ (prepared according to example 5), Ib ₂ (obtained according to example 7), Ib ₃ (obtained according to example 8), Ib ₄ (obtained according to example 9), Ib ₅ (obtained according to example 10), Ib ₆ (obtained according to example 11), Ic ₂ (obtained according to example 13 ), Ic ₃ (obtained according to example 14), Ic ₄ (obtained according to example 15), Ic ₅ (obtained according to example 16), Ic ₆ (obtained according to example 17), Id ₁ (obtained according to example 18), Id ₂ ( obtained according to example 19), Id ₃ (obtained according to example 20), Id ₄ (obtained according to example 21), Id ₅ (obtained according to example 22), If ₃ (obtained according to example 28), If ₂ (obtained according to example 29) , If ₃ (obtained according to example 30), If ₄ (obtained according to example 31), If ₅ (obtained according to example 32), If ₆ (obtained according to example 33).

Reference compounds: benzalkonium chloride (CBA), bis-quaternary ammonium salts: 1,4-bis (3,3 '- (1-decylpyridinium) methyloxy) butanedibromide (Bis-CHAS-1) [JP 2008179571, 07.08.2008], dibromide 3,3 '- [1,4-phenylene-bis- (oxy)] - bis- (1-dodecylpyridinium) (Bis-CHAS-2) [ЕА 26416 В1, 28.04.2017], "Octenidine dihydrochloride" (Bis -CHAS-3) [US 4206215 A, 03.06.1980], the closest structural analogs are 3,3 '- [biphenyl-4,4'-diylbis (oxy)] bis (1-decylpyridinium) dibromide (Bis-CHAS-4 ) and 3,3 '- [oxybis (4,1-phenylene)] bis (1-decylpyridinium) dibromide (Bis-CHAS-5) [RU 2689419 C1, 28.05.2019].

Standard test organisms:

Bacteria:

Staphylococcus aureus ATCC 43300,

Escherichia coli ATCC 25922,

Klebsiella pneumoniae ATCC 700603,

Acinetobacter baumannii ATCC 19606

Pseudomonas aeruginosa ATCC 27853 MIC test (method 1):

The test samples are prepared in a mixture of DMSO and water to a final test concentration of 32 μg / ml and serially diluted with sterilized water by half 7 times, obtaining sample concentrations of 16, 8, 4, 2, 1, 0.5 and 0.25 μg / ml. The final concentration of DMSO does not exceed 0.5%. A sample of each concentration was placed in a 384-well Corning 3640 plate. All bacteria were cultured in Cation-adjusted Mueller Hinton broth (CAMHB) at 37 ° C for 12 hours. Then, a sample of each culture was diluted 40-fold with saline and incubated at 37 ° C for 1.5-3 hours, obtaining 5 × 10 ⁵ CFU / ml. All samples in the plate were incubated at 37 ° C for 18 hours without shaking.

The inhibition of bacterial growth was determined by measuring the optical density at 600 nm (OD600). MIC was defined as the lowest concentration at which bacterial growth was completely inhibited. MIC and MBK test (method 2):

The MIC was determined by the micromethod of serial dilutions in broth in the presence of various stepwise concentrations of antibacterial drugs in sterile 96-well plates. Müller-Hinton broth, Müller-Hinton agar were used as a nutrient medium.

In the course of the study, two-fold serial dilutions of the studied drugs were used. The mother liquor was prepared in 10% DMSO. Working solutions of the drug and its two-fold dilutions (500-1 mg / ml) were prepared from the stock solution with the addition of the GRM broth.

Nutrient broth with the appropriate concentration of the test drug was introduced into 10 wells in 10 holes in horizontal rows of the studied bacterial strains. Broth was added to separate rows without a drug to control the growth of cultures.

From single colonies grown on the GRM medium at 37 ° C for 18 hours, a suspension was prepared with an optical density of 0.5 according to the McFarland standard in sterile saline, which corresponds to approximately 1-2 × 10 ⁸ CFU / ml. Then the suspension was diluted 1: 100 by adding 0.2 ml of the suspension to a flask containing 19.8 ml of MCB. The concentration of microorganisms in this case was 10 ⁶ CFU / ml. 0.1 ml of the original suspension was introduced into the wells with the test drug and control wells with broth. The final concentration of the microorganism in each well was 5 × 10 ⁵ CFU / ml. The plates were covered with lids and placed in a thermostat (37 ° C) for 20 hours. The presence of bacterial growth was taken into account visually (by the presence of turbidity in the well). The minimum inhibitory concentration (MIC) was taken as the minimum concentration of the preparation, at which the growth of bacteria was absent after 20 h of incubation. The minimum bactericidal concentration (MBC) was determined by the results of seeding on solid nutrient media. For this, from all the wells in which there was no visible growth (by the presence of turbidity), 10 μl were inoculated on Mueller-Hinton nutrient agar. The results were taken into account by the presence of culture growth at the site of application after 24 h of incubation at 37 ° C. If there was no growth in the well, but at the same time the growth of the studied culture was observed when sowing from this well on a solid nutrient medium, then this concentration was taken as bacteriostatic. The MBC was taken as the lowest concentration at which the cell growth was completely inhibited when plated on a solid nutrient medium.

Example 58.

Testing the bacteriostatic action of the new compounds described above (Ia ₁ , Ia ₂ , Ia ₃ , Ia ₄ , Ia ₅ ) against various bacteria according to method 1.With the use of benzalkonium chloride (CBA), 1,4-bis (3,3 '- ( 1-decylpyridinium) methyloxy) butanedibromide (Bis-QAS-1), dibromide 3,3 '- [1,4-phenylene-bis- (oxy)] - bis- (1-dodecylpyridinium) (Bis-QAS-2), closest structural analogs - 3,3 '- [biphenyl-4,4 * -diylbis (oxy)] bis (1-decylpyridinium) dibromide (Bis-CHAS-4), 3,3' - [oxybis (4,1-phenylene )] bis (1-decylpyridinium) dibromide (Bis-QAC-5) as reference compounds. Determine the minimum inhibitory concentration (MIC). The results are shown in Table 1.

Conclusion: compounds Ia ₂ , Ia ₃ , Ia ₄ , Ia ₅ in comparison with reference compounds - HBA, Bis-CHAS-1, Bis-CHAS-2 and the closest structural analogs - Bis-CHAS-4, Bis-CHAS-5 demonstrate comparable or higher bacteriostatic effect against all tested bacterial strains.

Example 59.

Testing the bacteriostatic action of the new compounds described above (Ib ₂ , Ib ₃ , Ib ₄ , Ib ₅ , Ib ₆ , Ic ₂ , Ic ₃ , Ic ₄ , Ic ₅ , Ic ₆ , Id ₁ Id ₂ , Id ₃ , Ιd ₄ , Id ₅ , If ₁ , If ₂ , If ₃ , If ₄ , If ₅ , If ₆ ) against various bacteria according to method 2. Using benzalkonium chloride (CBA), dibromide 3,3 '- [1,4-phenylene-bis- (oxy)] - bis- (1-dodecylpyridinium) (Bis-CHAS-2), the closest structural analogs are 3,3 '- [biphenyl-4,4'-diylbis (oxy)] bis (1-decylpyridinium) dibromide ( Bis-QAC-4), 3,3 '- [oxybis (4,1-phenylene)] bis (1-decylpyridinium) dibromide (Bis-QAC-5) as reference compounds. Determine the minimum inhibitory concentration (MIC). The results are shown in Table 1.

Conclusion: compounds Ib ₂ , Ib ₃ , Ib ₄ , Ib ₅ , Ib ₆ , Ic ₂ , Ic ₃ , Ic ₄ , Ic ₅ , Ic ₆ , Id ₁ Id ₂ , Id ₃ , Id ₄ , Id ₅ , If ₁ , If ₂ , If ₃ , If ₄ , If ₅ , If ₆ in comparison with reference compounds - HBA, Bis-CHAS-2 and the closest structural analogs - Bis-CHAS-4, Bis-CHAS-5 demonstrate a comparable or higher bacteriostatic effect against all tested bacterial strains.

Example 60.

Testing the bactericidal action of the new compounds described above (Ib ₂ , Ib ₃ , Ib ₄ , Ib ₅ , Ib ₆ , Ic ₂ , Ic ₃ , Ic ₄ , Ic ₅ , Ic ₆ , Id ₁ , Id ₂ , Id ₃ , Id ₄ , Id ₅ , If ₁ , If ₂ , If ₃ , If ₄ , If ₅ , If ₆ ) against various bacteria according to method 2. Using benzalkonium chloride (CBA), dibromide 3,3 '- [1,4-phenylene bis - (oxy)] - bis- (1-dodecylpyridinium) (Bis-CHAS-2), the closest structural analogs are 3,3 '- [biphenyl-4,4'-diylbis (oxy)] bis (1-decylpyridinium) dibromide (Bis-QAC-4), 3,3 '- [oxybis (4,1-phenylene)] bis (1-decylpyridinium) dibromide (Bis-QAC-5) as reference compounds. Determine the minimum bactericidal concentration (MBC). The results are shown in Table 3.

Conclusion: compounds Ib ₂ , Ib ₃ , Ib ₄ , Ib ₅ , Ib ₆ , Ic ₂ , Ic ₃ , Ic ₄ , Ic ₅ , Ic ₆ , Id ₁ Id ₂ , Id ₃ , Id ₄ , Id ₅ , If ₁ , If ₂ , If ₃ , If ₄ , If ₅ , If ₆ in comparison with the reference compounds -CBA, Bis-CHAS-2 and the closest structural analogs - Bis-CHAS-4, Bis-CHAS-5 demonstrate a comparable or higher bactericidal effect against all tested bacterial strains.

Example 61

Testing the antifungal action of the compounds described above in accordance with the present invention (Ia ₁ , Ia ₂ , Ia ₃ , Ia ₄ , Ia ₅ ) against the fungi Candida albicans and Cryptococcus neoformans. Test mushrooms:

Candida albicans ATCC 90028

Cryptococcus neoformans ATCC 208821 Test Method:

The test samples are prepared in a mixture of DMSO and water to a final test concentration of 32 μg / ml and serially diluted with sterilized water by half 7 times, obtaining sample concentrations of 16, 8, 4, 2, 1, 0.5 and 0.25 μg / ml. The final concentration of DMSO does not exceed 0.5%. The fungal strains were cultured for 3 days on yeast extract-Peptone Dextrose agar (YPD) at 30 ° C. A yeast suspension from 1 × 10 ⁶ to 5 × 10 ⁶ CFU / ml (as determined by OD530) was prepared from five colonies. The suspension was then diluted and added to the well for each test compound. Final cell density of fungi 2.5 × 10 ³ CFU / ml, total volume 50 μl. All samples were incubated at 35 ° C for 36 h without shaking.

Growth inhibition of C. albicans was determined by measuring absorbance at 630 nm (OD600), while growth inhibition of C. neoformans was determined by measuring the difference in optical density from 600 to 570 nm (OD 600-570) after addition of resazurin (0.001% final concentration ) and incubation at 35 ° C for 2 hours. MIC was defined as the lowest concentration at which bacterial growth was completely inhibited. With the use of benzalkonium chloride (CBA), 1,4-bis (3,3 '- (1-decylpyridinium) methyloxy) butanedibromide (Bis-CHAS-1), dibromide 3,3' - [1,4-phenylene-bis- (oxy)] - bis- (1-dodecylpyridinium) (Bis-CHAS-2), the closest structural analogs are 3,3 '- [biphenyl-4,4'-diylbis (oxy)] bis (1-decylpyridinium) dibromide ( Bis-QAC-4), 3,3 '- [oxybis (4,1-phenylene)] bis (1-decylpyridinium) dibromide (Bis-QAC-5) as reference compounds. Determine the minimum inhibitory concentration (MIC). The results are shown in Table 4.

Conclusion: compounds Ia ₂ , Ia ₃ , Ia ₄ , ia ₅ in comparison with reference compounds - HBA, Bis-CHAS-1, Bis-CHAS-2 and the closest structural analogs - Bis-CHAS-4, Bis-CHAS-5 demonstrate comparable or higher bacteriostatic action against all tested fungi.

Example 62

Testing the cytotoxicity of the above described new compounds Ia ₂ , Ia ₃ , Ia ₄ , Ia ₅ on human embryonic kidney cells.

HEK293 cells: human embryonic kidney cells.

Growth medium: Dulbecco's Modified Eagle Medium (Dulbecco's Modified Eagle Medium) supplemented with 10% FBS (Fetal Bovine Serum).

HEK293 cells were counted manually using a Neubauer hemocytometer and then plated into 384-well plates containing test compounds in medium to obtain a density of 5000 cells / well and a solution volume of 50 μl. HEK293 cells were incubated with compounds for 20 h at 37 ° C in 5% CO ₂ . Then 5 μl of 25 μg / ml resazurin (final concentration 2.3 μg / ml) was added and incubated for an additional 3 h at 37 ° C in 5% CO ₂ .

The absorbance of each well is then measured using an automated plate reader (Tesan # 1000 Pro) at 560 nm. Cytotoxicity (or cell viability) is expressed as a percentage of the control (treated with purified water). With the use of benzalkonium chloride (CBA), 1,4-bis (3,3 '- (1-decylpyridinium) methyloxy) butanedibromide (Bis-CHAS-1), dibromide 3,3- [1,4-phenylene-bis- ( oxy)] - bis- (1-dodecylpyridinium) (Bis-CHAS-2), "Octenidine dihydrochloride" (Bis-CHAS-3), the closest structural analogs are 3,3 '- [biphenyl-4,4'-diylbis ( hydroxy)] bis (1-decylpyridinium) dibromide (Bis-CHAS-4), 3,3 '- [oxybis (4,1-phenylene)] bis (1-decylpyridinium) dibromide (Bis-CHAS-5) as reference connections. Determine cytotoxicity data. The results are shown in Table 5.

Conclusion: compounds Ia ₂ , Ia ₃ , Ia ₄ , Ia ₅ have comparative or lower toxicity compared to control compounds - KhBA, Bis-CHAS-1, Bis-CHAS-2, the closest structural analogs - Bis-CHAS-3, Bis -CHAS-4 and "Octenidine dihydrochloride" Bis-CHAS-5. Based on the above results, it can be concluded that many compounds of formula (I) exhibit high antibacterial and antifungal effects in combination with low cytotoxicity compared to control compounds - benzalkonium chloride (CBA), dimeric pyridinium salts: Bis-CHAS-1, Bis -CHAS-2, Bis-CHAS-3, the closest structural analogs of Bis-CHAS-4 and Bis-CHAS-5 - and can be used as effective bactericidal ingredients in disinfectants or antiseptic compositions that have low toxicity.

Although this invention has been described in detail with reference to specific preferred embodiments, one skilled in the art to which this invention belongs will understand that various modifications and improvements may be made without departing from the spirit and scope of the claims presented.

The technical result of this invention is the expansion of the range of dimeric pyridinium quaternary salts, the creation of a new type of dimeric pyridinium quaternary salts of general formula I, which have a higher biocidal activity in comparison with the common CBA antiseptic, low cellular toxicity in comparison with the well-known antiseptic "Octenidine dihydrochloride" and activity and low cellular toxicity at the same time in comparison with the prototype, suitable for the production of antiseptic or disinfectants, as well as the development of a method for their production.

Claims (8)

1. Dimeric quaternary pyridinium salts of the general formula

where R is a linear or branched alkyl or alkenylene, or alkyne group containing from 8 to 18 carbon atoms; X is a halogen atom - chlorine, bromine or iodine. 2. Compounds according to claim 1 with biocidal action. 3. Application of the connection according to PP. 1, 2 as an active biocidal ingredient for the production of antiseptic and disinfectants. 4. A method of obtaining a compound according to PP. 1, 2, which consists in the fact that the corresponding dipyridyl derivatives of the general formula

is reacted with a compound of general formula RX, where R is a linear or branched alkyl or alkenylene, or alkyne group containing from 8 to 18 carbon atoms, and X is a halogen atom - chlorine, bromine or iodine, at reflux.