RU2292368C1 - Optical sensor materials for heavy and transient metals based on dithiacrown-containing butadienyl dyes and methods for their preparing - Google Patents

Abstract

FIELD: organic chemistry, polymers, chemical technology.

SUBSTANCE: invention relates to novel polymeric materials - membranes, films and monolayers based on compounds of novel type - dithiacrown-containing dyes of the general formula (I):

wherein R¹-R⁴ mean hydrogen atom, lower alkyl, alkoxyl group, aryl group, or two substitutes R¹ and R², R² and R³, R³ and R⁴ form in common CH₄-benzo-group; R⁵ means alkyl radical CH_2m+1 wherein m = 1-18; X means chlorine (Cl), bromine (Br), iodine (J) atoms, groups -ClO₄, -PF₆, -BF₄, -PhSO₃, -TsO, -ClC₆H₄SO₃, -CHSO₃, -CF₃SO₃, -CH₃OSO₃; Q means sulfur atom, oxygen atom, selenium atom, group -C(CH₃)₂, group -NH, group -NCH₃; n = 0-3. Also, invention describes a method for synthesis of such compounds and composite materials based on thereof possessing ion-selective optical properties. Proposed dyes and composite materials based on thereof possess the high selectivity to heavy and transient metal ions and can be used as components of optical chemosensors, for example, as components of polymeric membranes, ultrafine films and molecular monolayers, for determination of trace amounts of indicated ions in industrial waters and sewages, among them, for monitoring the environment, in biological fluids and others.

EFFECT: improved methods of synthesis, valuable properties of materials.

3 cl, 4 tbl, 5 ex

Description

The invention relates to the field of chemistry of materials and organic chemistry, namely to new polymer membranes, films and monolayers based on a new type of compounds - dithiacrown-containing butadiene dyes of the general formula I:

in which R ¹ -R ⁴ is a hydrogen atom, lower alkyl, alkoxyl group, an aryl group or two substituents R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ together form a C ₄ H ₄ -benzo group;

R ⁵ is an alkyl radical C _m H _{2m + 1} , where m = 1-18;

X = Cl, Br, I, ClO ₄ , PF ₆ , BF ₄ , PhSO ₃ , TsO, ClC ₆ H ₄ SO ₃ , CH ₃ SO ₃ , CF ₃ SO ₃ , CH ₃ OSO ₃ ;

Q is a sulfur atom, an oxygen atom, a selenium atom, a group C (CH ₃ ) ₂ , an NH group, an NCH ₃ group; n = 0-3.

The proposed compounds and composite materials based on them can be used as part of optical chemosensors for cations of heavy and transition metals, for example, as part of polymer membranes, ultrathin films, and molecular monolayers, to determine the microquantities of these ions in industrial waters and drains, including for environmental monitoring, in biological fluids, etc. The invention also relates to methods for producing such compounds and materials.

The proposed compounds and composite materials based on them, their properties and the production method are not described in the literature. The proposed compounds represent a new type of crown-containing unsaturated dyes, since the heterocyclic residue is connected to the benzocrown ether fragment via a butadiene bridge, which determines their spectral properties. The crown ether fragment in the proposed compounds contains oxygen and sulfur atoms in various combinations, which makes it possible to vary the size of the crown ether cavity and increases the affinity for heavy and transition metal cations. Composite materials are obtained by introducing the proposed compounds into the polymer matrix by irrigation. The structure of polymer film materials provides a combination of desired properties to obtain nanocomposite materials with the properties of optical chemosensors.

Butadienyl dyes are known (Hassner A., Birnbaum D., Loew LM, J. Org. Chem., 1984, 49, 2546; Grinvald A., Hildesheim R., Farber IC, Anglister L., Biophys. J., 1982, 39, 301; Frank J., Zouni A., van Hoek A., Visser AJWG, Clarke RJ, Biochim. Biophys. Acta, 1996, 1280, 51; Zouni A., Clarke RJ, Visser AJWG, Visser NV, Holzwarth JF , Biochim. Biophys. Acta, 1993, 1153, 203; Passechnik VI, Sokolov VS, Bioelectrochem., 2002, 55, 47; Lehmann F., Mohr GJ, Czerney P., Grummt U.-W., Dyes Pigm., 1995, 29, 85; Marder SR, Perry JW, Yakymyshyn CP, Chem. Mater., 1994, 6, 1137; Matsui M., Kawamura S., Shibata K., Muramatsu H., Bull. Chem. Soc. Jpn. 1992, 65, 71; Sertova N., Nunzi J.-M., Petkov I., Deligeorgiev T., J. Photochem. Photobiol. A: Chem., 1998, 112, 187; Alain V., Blanchard-Desce M., Ledoux-Rak I., Zyss J., Chem. Commun., 2000, 353; Brooker LGS, Sprague RH, J. Am. Chem. Soc., 1941, 63, 3203; Hebert P., Baldacchino G. , Gustavsson, T., Mialocq J.-C., J. Photochem. Photobiol. A: Chem., 1994, 84, 45; Quina F.H., Whitten D.G., J. Am. Chem. Soc., 1977, 99, 877; Wolfbeis O.S., Sensors & Actuators B, 1995, 29, 140), a structural feature of which is the presence of a quaternary heterocyclic residue linked through two conjugated carbon-carbon double bonds to a substituted benzene ring. These dyes are intensively absorbed in the visible region of the spectrum, but are not capable of binding any metal cations.

Styryl dyes are described in the literature in which a heterocyclic residue is connected via a single carbon-carbon double bond to a crown ether or thiacrown ether fragment (Gromov S.P., Alfimov M.V., Izv. AN Ser. Chem., 1997 , 641; Gromov S.P., Fedorova O.A., Vedernikov A.I., D stillulova O.V., Fedorov Yu.V., Alfimov M.V., RF Patent 2176256, Bull. No. 33; Gromov S.P., Fedorova O.A., Fomina M.V., Alfimov M.V., Patent 2012574 RF, Bull. Izob., 1994, No. 9; Gromov SP, Ushakov EN, Fedorova OA, Baskin II, Buevich AV, Andryukhina EN, Alfimov MV, Johnels D., Ediund UG, Whitesell JK, Fox MA, J. Org. Chem., 2003, 68, 6115). Such dyes are characterized by a pronounced ability to complex with metal cations, however, their absorption and fluorescence are shifted to the short-wavelength region of the spectrum, and the intensity of molar absorption and fluorescence is significantly reduced in comparison with butadiene dyes.

Butadienyl dyes containing crown ether or azacrown ether fragments are also known, which have a pronounced ability to bind cations of alkali and alkaline earth metals in an aprotic medium, which is accompanied by a significant change in the spectral properties of the dyes (Gromov S.P., Sergeev S.A., Druzhinin S.I., Rusalov M.V., Uzhinov B.M., Kuzmina L.G., Churakov A.V., Howard J.A.K., Alfimov M.V., Izv. Chem., 1999, 530; Gromov SP, Vedemikov AI, Ushakov EN, Kuz'mina LG, Feofanov AV, Avakyan VG, Churakov AV, Alaverdyan Yu. S., Malysheva EV, Alfimov MV, Howard JAK, Eliasson B., Ediund UG, Helv. Ch im. Acta, 2002, 85, 60; Ushakov E.N., Gromov S.P., Kuzmina L.G., Vedernikov A.I., Avakyan V.G., Howard J.A.K., Alfimov M .V., Izv. AN Ser. Chem., 2004, 1491). Dyes of this structure are not able to form strong complexes with cations of heavy and transition metals, and also do not show ligand properties in the aquatic environment, so their use in composite materials will not lead to the creation of selective optical sensors for these metals that can work in aqueous solutions.

Composite materials are obtained by introducing compounds, including unsaturated dyes, into the polymer matrix using one of the known methods, mainly by irrigation (Gul V.E., Dyakonova V.P., Physicochemical principles for the production of polymer films. - M.: Science 1978, 279 pp .; Polymer handbook, Ed. Bloch DR, V. 2, John Wiley & Sons, 2003, 897 pp .; Composite materials handbook. Polymer matrix composites guidelines for characterization of structural materials. MIL-HDBK-17- 1F, V.1, 2002, 734 pp .; Industrial Polymers Handbook, Ed. Wilks ES, Ausgabe, 2000, Wiley-VCH, 657 pp.). The irrigation method is technologically simple and available both in laboratory practice and in the production process and is optimal for the purposes specified in this invention. An important advantage of the method of obtaining films from a solution is that the films are cast at a relatively low temperature, non-heat-resistant additives, for example, dyes, which determine the further use of the film, can be introduced. However, crown-containing butadienyl dyes have not previously been introduced into polymer films or composite materials in this or another way.

The objective of the present invention is to provide a new type of compounds - crown-containing butadienyl dyes, incorporating an alkyl substituent on the nitrogen atom of the heterocyclic residue and a fragment of the dithiacrown compound with a different combination of oxygen and sulfur atoms, capable of binding heavy and transition metal cations, including in the aquatic environment, and their use as part of new optical sensor composite materials. The objective of the invention is the development of methods for producing target compounds with high yield and to obtain sensor composite materials based on them.

The solution to this problem is achieved by the structure of the proposed new type of butadienyl dyes of the general formula I and the method for their preparation, namely, that the quaternary salt of the heterocyclic base of the general formula II:

in which R ¹ -R ⁵ , Q and X are as defined above,

subjected to interaction with dithiacrown cinnamaldehyde of the General formula III:

where n is as defined above in an organic solvent environment.

The condensation of these quaternary salts of heterocyclic bases II with dithiacrown-containing cinnamaldehydes III has not yet been known. According to the proposed method, the synthesis of the inventive butadienyl dyes of the general formula I is carried out by condensing the methyl group II heterocyclic bases activated in the quaternary salts with the carbonyl group of the dithiacrown-containing cinnamaldehydes III to form a carbon-carbon double bond. The reaction is carried out in an organic solvent, for example, alcohol, at temperatures of 20-140 ° C.

Anion X in I and II can be the same, or replaced in dye I by treatment with acid HX or its salts, where X is as defined above.

The structure of the obtained compounds I was proved using ¹ H NMR spectroscopy, electron spectroscopy, and confirmed by elemental analysis (examples 1-4).

Example 1. 3-Ethyl-2 Perchlorate - [(1E, 3E) -4- (2,3,5,6,8,9,11,12-octahydro-1,7,13,4,10-benzotrioxadithiacyclopentadecene- 15-yl) -1,3-butadienyl] -1,3-benzothiazol-3-yl.

82 mg (0.30 mmol) of 2-methyl-3-ethyl-1,3-benzothiazol-3-yl perchlorate, 115 mg (0.33 mmol) (E) -3- (2,3,5, 6,8,9,11,12-octahydro-1,7,13,4,10-benzotrioxadithiacyclopentadecene-15-yl) propen-2-al and 10 ml abs. ethanol. The reaction mixture is boiled for 100 hours in an oil bath and cooled to 5 ° C. The precipitate is filtered off, washed with cold abs. ethanol (2 × 3 ml), benzene (3 ml) and dried in air. Receive 100 mg (55%) of the dye in the form of red-brown crystals, so pl. 201-203 ° C.

¹ H NMR spectrum (500 MHz, in DMSO-d ₆ , 30 ° C): 1.47 (t, 3H, Me, J = 7.2 Hz); 2.89 (t, 4H, γ-CH ₂ S, γ'-CH ₂ S, J = 6.6 Hz); 3.05 and 3.07 (2 t, 4H, β-CH ₂ S, β'-CH ₂ S, J = 5.2 Hz, J = 5.1 Hz); 3.71 and 3.72 (2 t, 4H, δ-CH ₂ O, δ'-CH ₂ O, J = 6.6 Hz, J = 6.6 Hz); 4.27 and 4.28 (2 t, 4H, α-CH ₂ O, α'-CH ₂ O, J = 5.1 Hz, J = 5.2 Hz); 4.79 (q, 2H, CH ₂ N, J = 7.2 Hz); 7.08 (d, 1H, H (5 '), J = 8.4 Hz); 7.24 (dd, 1H, H (6 '), J = 8.4 Hz, J = 1.7 Hz); 7.32 (d, 1H, H (2 '), J = 1.7 Hz); 7.37 (dd, 1H, H (s), ³ J _trans = 15.3 Hz, J = 10.3 Hz); 7.45 (d, 1H, H (d), ³ J _trans = 15.3 Hz); 7.49 (d, 1H, H (a), ³ J _trans = 14.8 Hz); 7.77 (m, 1H, H (6)); 7.86 (m, 1H, H (5)); 8.04 (dd, 1H, H (b), ³ J _trans = 14.8 Hz, J = 10.3 Hz); 8.27 (d, 1H, H (4), J = 8.5 Hz); 8.40 (d, 1H, H (7), J = 7.9 Hz).

UV spectrum (C = 1 × 10 ^-5 mol · L ^-1 , acetonitrile), nm: 457 (ε = 54000).

Found,%: C 52.68; H 5.31; N, 2.34.

C ₂₇ H ₃₂ ClNO ₇ S ₃ .

Calculated,%: C 52.80; H 5.25; N, 2.28.

Example 2. Perchlorate 2 - [(1E, 3E) -4- (2,3,5,6,8,9,11,12,14,15-decahydro-1,7,10,16,4,13- benzotetraoxadithiacyclooctadecen-18-yl) -1,3-butadienyl] -3-ethyl-1,3-benzothiazol-3-ya.

In a flask with a reflux condenser, 50 mg (0.18 mmol) of 2-methyl-3-ethyl-1,3-benzothiazol-3-yl perchlorate, 79 mg (0.20 mmol) (E) -3- (2,3,5, 6,8,9,11,12,14,15-decahydro-1,7,10,16,4,13-benzotetraoxadithiacyclooctadecen-18-yl) propen-2-al and 10 ml abs. ethanol. The reaction mixture is boiled for 100 hours in an oil bath and cooled to 5 ° C. The precipitate is filtered off, washed with cold abs. ethanol (2 × 3 ml), benzene (3 ml) and dried in air. Receive 68 mg (58%) of the dye in the form of red-brown crystals, so pl. 202-204 ° C.

¹ H NMR spectrum (500 MHz, in DMSO-d ₆ , 30 ° C): 1.47 (t, 3H, Me, J = 7.2 Hz); 2.90 and 2.92 (2 t, 4H, γ-CH ₂ S, γ'-CH ₂ S, J = 6.3 Hz, J = 6.6 Hz); 3.05 (t, 2H, β'-CH ₂ S, J = 6.3 Hz); 3.10 (t, 2H, β-CH ₂ S, J = 6.7 Hz); 3.54 (m, 4 H, 2 ε-CH ₂ O); 3.63 and 3.66 (2 t, 4H, δ-CH ₂ O, δ'-CH ₂ O, J = 6.6 Hz, J = 6.3 Hz); 4.21 (br t, 4H, α-CH ₂ O, α'-CH ₂ O, J = 6.5 Hz); 4.79 (q, 2H, CH ₂ N, J = 7.2 Hz); 7.06 (d, 1H, H (5 '), J = 8.4 Hz); 7.21 (dd, 1H, H (6 '), J = 8.4 Hz, J = 1.5 Hz); 7.30 (d, 1H, H (2 '), J = 1.5 Hz); 7.37 (dd, 1H, H (s), ³ J _trans = 15.3 Hz, J = 10.3 Hz); 7.45 (d, 1H, H (d), ³ J _trans = 15.3 Hz); 7.51 (d, 1H, H (a), ³ J _trans = 14.8 Hz); 7.76 (m, 1H, H (6)); 7.85 (m, 1H, H (5)); 8.04 (dd, 1H, H (b), ³ J _trans = 14.8 Hz, J = 10.3 Hz); 8.26 (d, 1H, H (4), J = 8.5 Hz); 8.39 (d, 1H, H (7), J = 7.9 Hz).

UV spectrum (C = 1 × 10 ^-5 mol · L ^-1 , acetonitrile), nm: 461 (ε = 54000).

Found,%: C 52.99; H 5.61; N, 2.14.

C ₂₉ H ₃₆ ClNO ₈ S ₃ .

Calculated,%: C 52.91; H 5.51; N 2.13.

Example 3. Perchlorate 3-octadecyl-2 - [(1E, 3E) -4- (2,3,5,6,8,9,9,11,12-octahydro-1,7,13,4,10-benzotrioxadithiacyclopentadecene- 15-yl) -1,3-butadienyl] -1,3-benzothiazol-3-yl.

56 mg (0.11 mmol) of 2-methyl-3-octadecyl-1,3-benzothiazol-3-yl perchlorate, 47 mg (0.13 mmol) (E) -3- (2,3,5, 6,8,9,11,12-octahydro-1,7,13,4,10-benzotrioxadithiacyclopentadecene-15-yl) propen-2-al and 7 ml abs. ethanol. The reaction mixture is boiled for 100 hours in an oil bath and cooled to 5 ° C. The precipitate is filtered off, washed with cold abs. ethanol (2 × 3 ml) and recrystallized from abs. ethanol (15 ml). Obtain 29 mg (31%) of the dye in the form of a red-brown powder, so pl. 141-143 ° C.

¹ H NMR spectrum (500 MHz, in CDCl ₃ , 30 ° C): 0.89 (t, 3H, Me, J = 6.8 Hz); 1.19-1.37 (m, 28H, 14 CH ₂ ); 1.49 (m, 2H, CH ₂ CH ₂ CH ₂ N); 1.87 (m, 2 N, CH ₂ CH ₂ N); 2.98 and 3.02 (2 t, 4H, γ- and γ'-CH ₂ S, J = 6.5 Hz, J = 6.9 Hz); 3.11 (br t, 4 N, β- and β'-CH ₂ S); 3.84 and 3.86 (2 t, 4H, δ- and δ'-CH ₂ O, J = 6.9 Hz, J = 6.5 Hz); 4.12 (m, 2 N, α-CH ₂ O); 4.32 (m, 2 N, α'-CH ₂ O); 4.60 (m, 2 N, CH ₂ N); 6.52 (d, 1H, H (5 '), J = 8.3 Hz); 6.95 (brd, 1H, H (6 '), J = 8.3 Hz); 7.17 (br s, 1H, H (2 ')); 7.26 (d, 1H, H (d), ³ J _trans = 15.3 Hz); 7.48 (dd, 1H, H (s), ³ J _trans = 15.3 Hz, J = 11.1 Hz); 7.50 (d, 1H, H (a), ³ J _trans = 14.4 Hz); 7.61 (d, 1H, H (4), J = 8.4 Hz); 7.64 (m, 1H, H (6)); 7.72 (m, 1H, H (5)); 7.89 (dd, 1H, H (b), ³ J _trans = 14.4 Hz, J = 11.1 Hz); 7.95 (d, 1H, H (7), J = 8.0 Hz).

Found,%: C 62.13; H, 7.70; N 1.65.

C ₄₃ H ₆₄ ClNO ₇ S ₃ .

Calculated,%: C 61.58; H, 7.69; N 1.67.

Example 4. Perchlorate 2 - [(1E, 3E) -4- (2,3,5,6,8,9,11,12,14,15-decahydro-1,7,10,16,4,13- benzotetraoxadithiacyclooctadecen-18-yl) -1,3-butadienyl] -3-octadecyl-1,3-benzothiazol-3-yl.

In a reflux flask, 33 mg (0.07 mmol) of 2-methyl-3-octadecyl-1,3-benzothiazol-3-yl perchlorate, 31 mg (0.08 mmol) (E) -3- (2,3,5, 6,8,9,11,12,14,15-decahydro-1,7,10,16,4,13-benzotetraoxadithiacyclooctadecen-18-yl) propen-2-al and 6 ml abs. ethanol. The reaction mixture is boiled for 100 hours in an oil bath and cooled to 5 ° C. The precipitate is filtered off, washed with cold abs. ethanol (2 × 2 ml) and dried in air. Obtain 26 mg (45%) of the dye in the form of a brownish-black powder, so pl. 179-181 ° C.

¹ H NMR spectrum (500 MHz, in CDCl ₃ , 25 ° C): 0.88 (t, 3H, Me, J = 6.9 Hz); 1.19-1.37 (m, 28H, 14 CH ₂ N); 1.48 (m, 2H, CH ₂ CH ₂ CH ₂ N); 1.87 (m, 2H, CH ₂ CH ₂ N); 2.91 (t, 2H, γ-CH ₂ S, J = 5.8 Hz); 3.09 (m, 4H, β'-CH ₂ S, γ'-CH ₂ S); 3.20 (t, 2H, β-CH ₂ S, J = 7.2 Hz); 3.65 (s, 4H, 2 ε-CH ₂ O); 3.73 (t, 2H, δ'-CH ₂ O, J = 7.1 Hz); 3.82 (t, 2H, δ-CH ₂ O, J = 5.8 Hz); 4.02 (t, 2H, α-CH ₂ O, J = 7.2 Hz); 4.30 (t, 2H, α'-CH ₂ O, J = 5.7 Hz); 4.60 (m, 2H, CH ₂ N); 6.52 (d, 1H, H (5 '), J = 8.3 Hz); 6.95 (brd, 1H, H (6 '), J = 8.3 Hz); 7.14 (br.s, 1H, H (2 ')); 7.23 (d, 1H, H (d), ³ J _trans = 15.3 Hz); 7.45 (dd, 1H, H (s), ³ J _trans = 15.3 Hz, J = 11.1 Hz); 7.47 (d, 1H, H (a), ³ J _trans = 14.5 Hz); 7.60 (d, 1H, H (4), J = 8.4 Hz); 7.63 (m, 1H, H (6)); 7.70 (m, 1H, H (5)); 7.89 (dd, 1H, H (b), ³ J _trans = 14.5 Hz, J = 11.1 Hz); 7.95 (d, 1H, H (7), J = 7.9 Hz).

Found,%: C 61.46; H 7.84; N, 1.58.

C ₄₅ H ₆₈ ClNO ₈ S ₃ .

Calculated,%: C 61.23; H 7.77; N, 1.59.

The remaining compounds were obtained by a method analogous to example 1.

To obtain compounds of formula I, in which R ¹ -R ⁴ lower alkyl, iodides or perchlorates of 2-methylpolyalkylindoleninium were used; to obtain compounds of formula I, in which one of the substituents R ¹ -R ⁴ alkoxyl group, 2-methylalkoxybenzothiazolium iodides were used; to obtain compounds of formula I, in which one of the substituents R ¹ -R ⁴ aryl group, 2-methylarylbenzothiazolium iodides were used; to obtain compounds of formula I, in which two substituents R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ together form a C ₄ H ₄ -benzo group, 2-methylnaphthothiazolium iodides were used. For the preparation of compounds of formula I in which Q = an oxygen atom, a selenium atom, an NH group or an NCH ₃ group, iodides or perchlorates of 2-methylbenzoxazolium, 2-methylbenzo-selenosolium, 2-methylbenzimidazolium were used. To transfer the iodides of the compounds of formula I into salts with other counterions, we used the addition of perchloric acid or a sodium salt containing X = Cl, Br, I, ClO ₄ , PF ₆ , BF ₄ , PhSO ₃ , TsO, ClC ₆ H ₄ SO as counterions ₃ , CH ₃ SO ₃ , CF ₃ SO ₃ , CH ₃ OSO ₃ to the alcohol solution of compound I.

The obtained butadienyl dyes were investigated as chromoionophore compounds.

Compounds of a new type of the indicated structure I have a deep and intense color in the region of 460 nm, which is associated with the ability of the electron pair of the oxygen atom of the fragment of the dithiacrown compound in the para position to the butadiene fragment to participate in conjugation with a quaternized heterocyclic residue.

In the study of the properties of the obtained compounds, their pronounced ability to complex with heavy metal cations was found due to the formation of high-strength coordination bonds with two sulfur atoms of the dithiacrown ether dye fragment. For example, the complexation of the dye Ia obtained in Example 1 was studied (Q = S, R ¹ = R ² = R ³ = R ⁴ = H, R ⁵ = C ₂ H ₅ , X = ClO ₄ , n = 1), and dye Ib obtained in example 2 (Q = S, R ¹ = R ² = R ³ = R ⁴ = H, R ⁵ = C ₂ H ₅ , X = ClO ₄ , n = 2), (C _{Ia, b} = 10 ^-5 mol / L) with Hg (II), Ag (I), Pb (II), Cd (II), Zn (II) perchlorates, as well as with alkaline earth metal perchlorates in acetonitrile, water-acetonitrile mixtures, and water. During the formation of complexes, the spectral characteristics of the dyes change significantly (Table 1). As a result of coordination of the metal cation over the fragment of the dithiacrown compound, the lone electron pair of the oxygen atom in the pore position is switched to the butadiene fragment from participating in effective conjugation with the chromophore dye fragment to form a coordination bond with the metal cation. In this case, a hypsochromic shift of the long-wavelength absorption band of the dye to 21 nm is observed. In acetonitrile, relatively stable complexes are formed only with heavy metal ions (Hg ²⁺ , Ag ⁺ and Pb ²⁺ ). The presence of perchlorates Zn (II), Cd (II), Pb (II) or alkaline earth metals with C _M = 10 ^-3 mol / L practically does not affect the spectral characteristics of dyes Ia and Ib, which confirms the absence of complexation with cations of these metals. The presence of Hg (II) or Ag (I) perchlorates also causes significant spectral changes for solutions of dyes Ia and Ib in water and water-acetonitrile mixtures, which indicates the effective complexation with Hg ²⁺ and Ag ⁺ ions under these conditions.

Table 1.
Spectral characteristics of dyes Ia, Ib and their complexes with Ag ⁺ , Hg ²⁺ and Pb ^{2+ ions} in acetonitrile, water-acetonitrile (1: 1) solution and water. Compound Δλ _max (λ _max ) / nm Mecn MeCN / water water Ia (457) (453) (440) Ia Ag ⁺ 10.5 8 3.5 Ia Hg ²⁺ 23 17 10 Ib (460.5) (455) (440.5) IB Ag ⁺ 10 6.5 1.5 IB · Hg ²⁺ twenty 13.5 5 IbPb ²⁺ 20.5 Δλ _max = (λ _max ) (dye) -λ _max (complex)

The stability constants of the complexes of dyes Ia, Ib with heavy metal cations, measured using UV and ¹ H NMR ¹ -titration methods, indicate their high strength. For example, in aqueous acetonitrile solutions, the stability constants of complexes with Ag ⁺ varied within logK = 4.8–6.5, significantly increasing with increasing water content in the solution. At the same time, the stability constants of complexes with Pb ²⁺ decrease by more than four orders of magnitude with increasing water content (Table 2). Thus, a change in the medium leads to a change in the selectivity of dyes Ia, b - in an aqueous-acetonitrile (1: 1) solution, the dyes exhibit high selectivity for Ag ⁺ relative to Pb ²⁺ , and, on the contrary, preferably bind Pb ²⁺ ions in anhydrous acetonitrile. The values of the stability constants of complexes with Hg ^{2+ ions} have a value of LogK≥11 for any water content in the mixture. Thus, the high selectivity of dithiacrown-containing butadienyl dyes to Hg ²⁺ relative to Ag ⁺ (as well as any other of the studied metal cations) remains high at any water / acetonitrile ratios.

Table 2.
The stability constants of complexes of dyes Ia, Ib in aqueous acetonitrile solutions with different water contents, determined by spectrophotometric titration, 22 ° С. Content
water / volume% lgK Ia Ag ⁺ IB Ag ⁺ IbPb ²⁺ 0
10
fifty
75 4.77
4.94
5.68
6.46 5.35
5.51
6.33
- 6.43
2.1
<2
-

The stability constants of the dye complexes Ia, Ib with perchlorates Ag (I), Pb (II), and Hg (II), measured by ¹ H NMR ¹ -titration method, indicate their high strength in acetonitrile (Table 3). For example, in a solution with a dye concentration of 10 ^-3 mol / L, complexes with Hg ^{2+ ions are} characterized by very high stability (logK = 18.3-19.0), more than 10 orders of magnitude higher than the stability of complexes of these dyes with other studied heavy metal cations. The found constants also demonstrate a high selectivity of the dyes Ia, Ib to the Ag ⁺ and Pb ^{2+ ions} relative to Cd ²⁺ .

Table 3.
The stability constants of complexes of dyes Ia, Ib with heavy metal perchlorates, as determined by NMR ¹ H-titration in acetonitrile-d ₃ , 30 ° C. Dye Lgk Ag ⁺ Cd ²⁺ Pb ²⁺ Hg ²⁺ Ia 4.9 1.6 4.6 18.3 Ib 5.1 2.8 7.4 19.0

The claimed dithiacrown-containing butadienyl dyes were introduced into polymer film materials and their chemosensory properties were investigated. For example, dyes Ia, Ib are introduced into the composition of polymer matrices obtained by irrigation by the following method. Solutions of polymers in chloroform, dichloroethane or acetonitrile with a concentration of 2-8 mass% are poured onto silica or glass slides. 1 mass% of dye Ia, Ib, based on the weight of the polymer, is preliminarily introduced into the polymer carrier solution. The dye is administered as a solution in chloroform, dichloroethane or acetonitrile (C _{Ia, b} = 10 mmol / L). Evaporation of the solvent leads to the formation of a film, which is dried at room temperature for 24 hours. Mowital B30H polyvinyl butyral (Germany, content of aldehyde units of about 40%) and a copolymer of methyl methacrylate and ethyl acrylate (Mn = 39500, Mw = 101000 (GPC) are used as polymers , Sigma-Aldrich Chemie GmbH). The resulting polymer matrices are colored transparent films with a thickness of 10-40 microns.

The obtained polymer matrices containing dyes Ia, Ib were investigated as ion-selective optical materials for the presence of heavy metal cations in water. For this, the films were kept for 1.5 h in aqueous solutions of silver or mercury (II) perchlorates (С _M = 1 mmol / L) and then the absorption spectra of the composites were measured (Table 4). The observed spectral changes — the hypochromic shifts of the long-wavelength absorption band up to 15 nm — confirm the formation of complexes Ia, Ib with Ag ⁺ and Hg ^{2+ ions} in the polymer matrix, which can be used to optically determine these heavy metal ions in an aqueous medium.

Table 4.
Spectral characteristics of dyes Ia, Ib and their complexes with Ag ⁺ and Hg ^{2+ ions} in a polymer matrix based on polyvinyl butyral (PVB) and methyl methacrylate-ethyl acrylate copolymer (SPMMAEA). The film thickness is 10 μm, C _{Ia, b} = 1 mass% calculated on the polymer. Compound Δλ _max (λ _max ) / nm PVB SPMMAEA Ia (456) (455) Ia Ag ⁺ 7 6 Ia Hg ²⁺ fifteen fourteen Ib (458) (457.5) IB Ag ⁺ four 4.5 IB · Hg ²⁺ 7.5 7 Δλ _max = (λ _max ) (dye) -λ _max (complex)

We studied the spectral and ion-selective properties of monolayers of amphiphilic butadiene dye Ib obtained in Example 3 (Q = S, R ¹ = R ² = R ³ = R ⁴ = H, R ⁵ = n-C ₁₈ H ₃₇ , X = ClO ₄ , n = 1) and the dye I g obtained in Example 4 (Q = S, R ¹ = R ² = R ³ = R ⁴ = H, R ⁵ = n-C ₁₈ H ₃₇ , X = ClO ₄ , n = 2). Monolayers are obtained on Film Balance plants (Lauda, Germany and NIMA-NFT, England-Germany) in the following way: on a thoroughly cleaned surface of bidistilled water (or solutions of alkaline earth or heavy metal salts) 10 μl of IV solution are applied with a microsyringe between the movable and measuring barriers , Ig in chloroform (С _{Iв, g} = 1 mmol / l). The monolayer was incubated for about 5 minutes until the solvent was completely evaporated, and then compressed at a constant speed of 1 cm / min with a moving barrier. The resulting monolayers are transferred by the Langmuir-Schaeffer or Langmuir-Blodgett method from the water / air interface to various solid substrates (quartz, graphite, mica) at a constant surface pressure (10-30 mN / m). These monolayers exhibit a strong optical response to the presence of Ag (I) and Hg (II) cations in the aqueous phase as a result of strong and specific complexation along the crown ether fragment of the dye. For example, when recording the reflection spectra of a 1 g monolayer on the water surface, an intense absorption band is observed in the region of 442 nm. Among the studied metal salts, only in the presence of Ag ⁺ or Hg ²⁺ ions in the aqueous subphase (С _M = 1 mmol / L) is a narrow intense reflection band of a 1 g monolayer with a maximum at 470-474 nm. Only in the presence of Hg ²⁺ ions in the aqueous subphase does the reflection maximum shift when the monolayer is compressed (for example, at π = 30 mN / m, maximum at 442 nm) and a small shoulder is observed at 420 nm.

The remaining compounds have similar compounds obtained in examples 1-4, properties in solutions, films and monolayers.

Thus, a new type of butadienyl dyes having a dithiacrown ether fragment and containing an alkyl N-substituent in a heterocyclic residue was obtained, and their pronounced ability to selectively bind heavy metal cations in both an aprotic and in an aqueous medium, including the composition of polymer matrices and in monolayers, characterized by significant spectral changes. The detected ionophore effects allow the use of the claimed compounds in optical sensory materials, for example, for the determination of heavy metal ions in industrial waters, biological fluids, and for environmental monitoring. A method has also been developed to obtain the claimed compounds of high purity and with good yields (up to 58%) from available substances.

Claims (3)

1. Dithiacrown-containing butadiene dyes of the general formula I:

in which R ¹ -R ⁴ is a hydrogen atom, lower alkyl, alkoxyl group, an aryl group or two substituents R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ together form a C ₄ H ₄ -benzo group; R ⁵ is an alkyl radical C _m H _{2m + 1} , where m = 1-18; X = Cl, Br, I, ClO ₄ , PF ₆ , BF ₄ , PhSO ₃ , TsO, ClC ₆ H ₄ SO ₃ , CH ₃ SO ₃ , CF ₃ SO ₃ , CH ₃ OSO ₃ ; Q is a sulfur atom, an oxygen atom, a selenium atom, a group C (CH ₃ ) ₂ , an NH group, an NCH ₃ group; n = 0-3. 2. The method of obtaining dithiacrown-containing butadiene dyes of the formula I according to claim 1, characterized in that the quaternary salt of the heterocyclic base of the general formula II:

in which R ¹ -R ⁵ , Q and X are as defined in claim 1, subjected to interaction with dithiacrown cinnamaldehyde of the General formula III:

where n is as defined in claim 1, in an organic solvent environment. 3. A composite film material exhibiting ion-selective optical properties for the presence of heavy and transition metal cations, characterized in that it contains a dithiacrown-containing butadiene dye of formula I in accordance with claim 1 in a polymer matrix based on polyvinyl butyral or a copolymer of methyl methacrylate and ethyl acrylate.