Zinc dimeric complexes of crown-containing styryl phenanthrolines as optical sensors on cations of alkali-earth and heavy metals and method of their obtaining

FIELD: chemistry.

SUBSTANCE: described are 15-crown-5- and dithia-18-crown-6-containig 2-methyl-9-styryl phenanthrolines of formula: where as optical sensors on cations of calcium, barium and lead. Claimed compounds are obtained by interaction of ligand of 15-crown-5 or dithia-18-crown-6-containing 2-methyl-9-styryl phenanthroline with zinc perchlorate in acetonitrile with irradiation with red light.

EFFECT: complexes possess properties of highly efficient fluorescent sensors on cations of calcium, barium and lead, which make it possible to visually determine metal cation.

2 cl, 2 tbl, 2 ex

 

The invention relates to analytical chemistry, namely to new compounds for optical sensors, specifically, to new zinc complexes stirilovyh dyes - 15-crown-5 and dithia-18-crown-6 containing 2-methyl-9-sterilisations formula I:

where:;

The invention may be more successfully used to create optical sensors and spectrophotometric sensors used for operational monitoring of the concentrations of impurities in liquids in laboratory and field conditions.

The inventive compounds of General formula I and their properties are not described in literature.

The claimed compounds contain interconnected zinc ions two molecules kraunsoderzhashchego 2-methyl-9-sterilisation, the chromophore system which includes two aromatic systems (fragment phenanthroline and phenyl nucleus) and the double C=C-valence, paired with iodoform fragment - crown-ether. The combination of these types of relationships can be attributed to these complexes to the class of sensors for cations of alkali and alkaline earth metals (Ia) or heavy metal cations (Ib).

Known thiacrown and Asociacion-compounds of different structure, for example:

[Hiraoka, crown compounds: properties and applications, M. Mir, 1986, 363 S.], which found the ability to bind cations of heavy metals, however, there is no absorption in the visible region of the spectrum.

Known cationic 18(15)-crown-6(5)-containing stillove dyes of the General formula:

where R1, R2, R3represent hydrogen, alkyl-, alkoxy-, aryl - or (R3and R4)-C4H4-anthropo;

R5= alkyl-;

Y=S, O, Se, group C(CH3)2or CH=CH;

X=I-or ClO4-;

n=1 or 2

applicable as selective reagents for cations of ammonium, alkali or alkaline earth metals (Spheromak, Oagadogou, Mvena, Mwilima, RF Patent 2012574, bull. image., 1994, No. 9). These dyes are characterized by the presence of absorption in the visible region of the spectrum and capacity for complexing with cations of alkaline or alkaline earth metals, determined by the size of the crown ether cavity. However, these dyes do not form complexes with heavy metal cations in the absence of oxygen affinity of crown ethers such cations.

Known cationic teatronosotras stillove dyes of the General formula:

where R1, R2, R3and R4= a hydrogen atom, lower alkyl, aryl-, or R3and R4together form4H4-anthropo, CNS group, dialkylamino, alluminare, halogen atom;

R5= lower alkyl, sulfoalkyl, carboxialkilnuyu, postnatally, thiocyanatomethylthio, cyanoaniline group;

X=S, Se, O, group C(CH3)2the group CH=CH;

Y and Z = O, S, provided that the composition of the macrocycle contains sulfur atoms in various combinations with oxygen atoms;

n=0-3;

A=Cl-, Br-I-, ClO4-BF4-TsO-,

which are selective sensors for cations of heavy or transition metals (Spheromak, Oagadogou, Auidence, Avesolana, Wavedrum, Mwilima, RF Patent №2176256, bull. Fig., 2001, No. 33). However, due to the positive charge on the molecule of the complexing agents, the stability of the complexes of these dyes with cations of heavy or transition metals is significantly lower than the stability of the complexes of crown ethers similar patterns.

Known crostarosa hetarylphenylethenes, which are structural analogues of the corresponding cationic stirilovyh dyes, but they do not carry a positive charge, for example:

(Yu.V.Fedrov, .A.Fedorova, .N.Andryukhina, S..Gromov, .V.Alfimov, L.G.Kuzmina, A.V.Churakov, J...Howard and J.-J.Aaron. "Ditopic complex formation of the crown-containing 2-styrylbenzothiazole", New J. Chem. 2003, 27, No.2, P.280-288). Such compounds have higher stability constants of the complexes, however, do not absorb in the visible region of the spectrum.

Known optical sensor on the divalent cations of copper (II), containing in its composition remains heterocyclic fragment (acridine) and Aaditya-15-crown-5-ether.

The compound shows high sensitivity to cations of copper (II), however, is not fluorescent sensor and does not show sensitivity to cations of lead. (Fedorova O.A., Tulyakov E.V., Fyodorov Y.V. "Phenyl-Aaditya-15-crown-5 containing 9-sterility as an optical sensor for cations of copper (II) in aqueous solutions and how to obtain it". RF patent №237633)

Known sensor element for determining ions of lead, mercury and uranium, which comprises a solid carrier and photometric organic reagent. As a solid carrier is used, the copolymer of vinylpyrrolidone and methyl acrylate and polyamide srednesrocnye membranes based on poly-ε-caproamide and polysulfonamide. As organic reagents used GAZAH, ditson, Arsene 111 (Aggera, Averyanova, Subseven Sensitive element to determine which ones heavy metals". RF patent №2056628). The disadvantage of sensing elements of this type is their short shelf life (no more than 2 weeks).

Thus, the known sensors for cations of alkaline-earth and heavy metals have a number of common disadvantages, namely:

- do not absorb light in the visible spectrum, so the visual determination of complexation is impossible;

- have a low stability constant of the complexes, it is therefore possible destruction complex, which makes it impossible for the detection of metal cation;

- generally known sensors do not have a fluorescent response to the binding of the detectable cations, i.e. are not fluorescent sensors.

Thus, there is a need for sensors for metal cations, which absorb light in the visible region of light, and would have a fluorescent response to the binding of the detectable metal cations.

A method of obtaining copper complexes of phenanthroline derivatives, including interaction degassed solution of tetrakis(acetonitrile)copper (I) acetonitrile in an inert atmosphere of nitrogen degassed solution phenanthroline derivative in dichloromethane. The mixture was incubated at room temperature with stirring for 30 min, and then separate column chromatography and release of copper to the complex with the release of 91%. (Y.Leydet, D.M.Bassani, G.Jonusauskas, N.D.McClenaghan. Equilibration between three different excited states in a bichromophoric copper (I) polypyridine complex // J. Am. Chem. Soc. - 2007 - 129 - P.8688-8689 ladies leather strap). The disadvantage of this method is its complexity associated with obtaining completely degassed solutions. To obtain zinc salts phenanthroline this method is not used.

A method of obtaining organic zinc salts derived bipyridine, which lies in the interaction of the organic ligand to the zinc perchlorate in acetonitrile at room temperature (Neapel, Oagadogou, Anguelova, Gyanodaya, Wavedrum. Complexation with transition metal cations and photochemical properties crossterrain mono - and bis(styryl)derived bipyridine // Macroheterocycles. - 2010. No. 3(4). - S-209).

However, this method is not used to obtain the zinc salts of derivatives of phenanthroline. The above method was selected as a prototype.

The present invention is the creation of new derivatives crossterrain of sterilisations as optical and fluorescent sensors for cations of lead, barium and calcium and the development of the retrieval method.

This object is achieved by new connection - dimeric zinc complexes about the formula I and a method of production thereof, characterized in that the organic ligand 15-crown-5 or dithia-18-crown-6-containing 2-methyl-9-sterilisation subjected to interaction with zinc perchlorate in acetonitrile upon irradiation with red light".

Organic ligands 15-crown-5 and dithia-18-crown-6 containing 2-methyl-9-sterilisation synthesized by the condensation of neocuproine and the corresponding crown-substituted benzaldehyde under the action of potassium tert-butylate in DMF at room temperature (E.N. Kulakova, O.Y Kolosova, O.A. Fedorova. Obtaining new functional derivatives of 1,10-phenanthroline, " Izv. Academy of Sciences, Ser. chem. - 2010. No. 6. - S.1263-1266), presented in the diagram:

Necessary for the reaction source neocuproine (Acros), 2,3,5,6,8,9,11,12-octahedrons[b] [1,4,7,10,13]pentachlorophenolate-15-carbaldehyde, 2,3,5,6,8,9,11,12,14,15-decahydrate[b] [1,4,10,13,7,16]tetraoxalate-cyclooctadiene-18-carbaldehyde, tert-butyl potassium, dimethylformamide (Acros) are commercially available reagents.

The following examples illustrate the claimed invention.

Example 1.

Dimeric zinc complex of 2-methyl-9-[2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzointislattu-15-yl)]-[1,10]-phenanthroline (Ia).

(A) To a solution of 0.65 mmol 2,3,5,6,8,9,11,12-octahedrons[b][1,4,7,10,13]pentachlorophenolate-15-carbaldehyde in anhydrous DMF (4 ml) in t is ke argon, while stirring, slowly add dropwise a suspension of the mixture to 0.72 mmol dried in vacuum at 150°C to constant mass of neocuproine (Acros) and 0.72 mmol of t-BuOK in 4 ml of DMF. The reaction mass was stirred at room temperature for 24 h, then evaporated in vacuo, the residue is dissolved in 30 ml of dist. water and extracted with chloroform (3×40 ml).

The chloroform extracts are combined evaporated in vacuo, the residue chromatographic in column (Al2O3, eluent benzene-ethanol, 100:1). Get 2-methyl-9-[2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzointislattu-15-yl)]-[1,10]-phenanthroline. TPL 75-78°C.; NMR1H (DMSO-d6, δ, ppm, J, Hz): 2.86 (s, 3H, CH3), 3.70 (m, 6N, ON2), 3.85 (m, 4H, 2OCH2), 4.15 (m, 4H, 2ArOCH2), 4.25 (m, 4H, 2ArOCH2), 7.06 (d, 1H, H-5', J=8.4), 7.30 (d, 1H, H-6', J=8.6), 7.50 (d, 1H, H-2'), 7.59 and 7.86 (2D, 2H, H-a, H-b, J=16.3, J=16.8), 7.7 (d, 1H, H-7, J=8.2), 7.92 (s, 2H, H-5, H-6), 8.13 (d, 1H, H-4, J=8.6), 8.4 (d, 1H, H-8, J=8.2), 8.48 (d, 1H, H-3, J=8.4).

(In) To 2.5 ml of a solution of ligand 2-methyl-9-[2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzointislattu-15-yl)]-[1,10]-phenanthroline in MeCN with a concentration of C=3·10-5mol l-1add 70 μl of a solution of Zn(ClO4)2in MeCN with a concentration of 1·10-3mol l-1. In the resulting solution with a quantitative yield of formed complex Ia.

Perchlorate zinc (Zn(ClO4)2) is dried in vacuum at 240°C and the settlement of annoy mass. Preparation of solutions using acetonitrile with a water content of not more than 0.02% (MeCN, "Panreac"). Preparation of solutions and all studies conducted at the red light. Luminous flux generated by the incandescent lamp, with a capacity of 25 Watts. Spectral lines of this lamp, whose wavelength is less than 580 nm, suppress with red glass filters.

NMR1N (CD3CN, δ, ppm, J, Hz): 2.60 (s, 6N, 2CH3), 3.50 (m, 4H, OSN2), 3.65 (m, N, 8ArOCH2), 3.85 (m, 8H, 4ArOCH2), 4.10 (m, 4H, 2N2), 6.15 (s, 2H, 2H-2'), 6.25 (d, 2H, 2H-6', J=8.4), 6.60 (d, 2H, 2H-5', J=8.2), 6.75 and 7.40 (2D, 4H, 2H-a 2H-b, J=16.2, J=16.4), 8.00 (d, 2H, 2H-8, J=8.2), 8.25 (s, 4H, 2N-5, 2N-6), 8.30 (d, 2H, 2H-3, J=8.15), 8.9 (d, 4H, 2H-4, 2H-7 J=8.4).

Example 2.

Dimeric zinc complex of 2-[2-(2,3,5,6,8,9,11,12,14,15-decahydro-1,7,10,16,4,13-benzo-tetraoxalate-cyclooctadiene-18-yl)vinyl]-9-methyl-1,10-phenanthroline (Ib).

(A) To a solution of 0.65 mmol 2,3,5,6,8,9,11,12,14,15-decahydrate[b][1,4,10,13,7,16]tetraoctadecylammonium-18-carbaldehyde in anhydrous DMF (4 ml) in a stream of argon, with stirring, slowly add dropwise a suspension of the mixture to 0.72 mmol dried in vacuum at 150°C to constant mass of neocuproine (Acros) and 0.72 mmol of t-BuOK in 4 ml of DMF. The reaction mass was stirred at room temperature for 24 h, then evaporated in vacuo, the residue is dissolved in 30 ml of dist. water and extracted with chloroform (3×40 ml). Chloroform extras the points of unite, evaporated in vacuo, the residue chromatographic in column (Al2O3, eluent benzene-ethanol, 100:1). Get 2-[2-(2,3,5,6,8,9,11,12,14,15-decahydro-1,7,10,16,4,13-benzo-tetraoxalate-cyclooctadiene-18-yl)vinyl]-9-methyl-1,10-phenanthrolin. TPL 72-74°C; NMR1H (DMSO-d6, δ, ppm, J, Hz): 2.86 (s, 3H, CH3), 2.96 and 3.12 (both m, 8H, 4SCH2), 3.56 and 3.68 (both m, 8H, 4OCH2, 4.22 and 4.31 (both m, 4H, 2ArOCH2), 7.06 (d, 1H, H-5', J=8.4), 7.30 (d, 1H, H-6', J=8.6), 7.50 (s, 1H, H-2'), 7.59 and 7.86 (both d, 2H, H-a, H-b, J=16.3, J=16.8), and 7.68 8.02 (both d, 2H, H-4, H-7, J=7.9, J=8.4), 7.92 (s, 2H, H-5, H-6), 8.38 and 8.46 (both d, 2H, H-3, H-8, J=8.2, J=8.6).

(In) To 2.5 ml of a solution of ligand 2-[2-(2,3,5,6,8,9,11,12,14,15-decahydro-1,7,10,16,4,13-benzo-tetraoxalate-cyclooctadiene-18-yl)vinyl]-9-methyl-1,10-phenanthroline in MeCN with a concentration of C=3·10-5mol l-1add 70 μl of a solution of Zn(ClO4)2in MeCN with a concentration of 1·10-3mol l-1. In the resulting solution with a quantitative yield of formed complex Ib.

Perchlorate zinc (Zn(ClO4)2) is dried in vacuum at 240°C to constant weight. Preparation of solutions using acetonitrile with a water content of not more than 0.02% (MeCN, "Panreac"). Preparation of solutions and all studies conducted at the red light. Luminous flux generated by the incandescent lamp, with a capacity of 25 Watts. Spectral lines of this lamp, whose wavelength is less than 580 nm, suppress with red glass St is efiltro.

NMR1H (CD3CN, δ, ppm, J, Hz): 3.00 (s, 6N, 2CH3), 3.15 (m, 8H, 4SCH2), 3.65 and 3.86 (both m, 16 H, 8OCH2), 4.31 and 4.44 (both m, 8H, 2ArOCH2), 4.55 (m, 8H, 4SCH2), 6.10 (s, 2H, 2H-2'), 6.40 (d, 2H, 2H-6', J=8.2), 6.55 (d, 2H, 2H-5', J=8.1), 6.80 and 7.30 (2D, 4H, 2H, 2H-b, J=16.1, J=16.3), 8.05 (d, 2H, 2H-8, J=8.2), 8.3 (s, 4H, 2N-5, 2N-6), 8.41 (d, 2H, 2H-3, J=8.1), 9.0 (d, 4H, 2N-4, 2H-7 J=8.3).

Received dimeric zinc complexes of derivatives of 2-sterilisation General formula I have a high long-wave absorption band (DPP) in the visible region (absorption spectra were recorded on spectrophotometer Cary 100) and practically does not fluoresce.

Measured using the method of spectrophotometric titration constants of stability of dimeric zinc complexes of derivatives of 2-sterilisation General formula I at 293 K indicate their greater strength:

Complexλwill.(nm)log KFfluo(%)ε·10-4, l/mol·cm
Ia40615.2±0.60.424.76
Ib40315±10.36 3.92

The presence of crown ether fragments in the resulting dimeric zinc complexes of General formula I allows you to form inclusion complexes with metal cations. The selectivity to cations of metals depends on the composition of the heteroatoms in the crown-ether fragments. So, it is known that oxygen-containing crown ethers form complexes with alkali and alkaline earth metals, while sulfur-containing crown ethers form complexes with heavy metal cations. In both cases there is hypsochromic shift of the maximum of the DPP with respect to the initial zinc complexes of General formula I, indicating that binding of macrocyclic fragments cations CA2+BA2+in the case of Ia and Pb2+in the case of Ib. In addition, the introduction into the solution of the zinc complexes of the General formula I, salts of calcium, barium or lead is accompanied by the effect of the rise of fluorescence in 3, 5 and 10 times, respectively. Thus, applying the approach of "metal complexes as ligands", demonstrated the possibility of using new dimeric zinc complexes of General formula I as fluorescent sensors for the corresponding cations of metals.

tr>
λwill.(nm)log Kε·10-4, l/mol·cm
Ia40615.2±0.60.424.76
Ia·VA2+3355.36
19.29±0.044.00
3685.21
Ia·(Ba2+)23364.53
22.10±0.34.40
3784.55
Ia·CA2+3335.48
18.62±0.072.00
3724.82
Ia·(Ca2+)23335.11
21.60±0.21.12
3794.72
Ib40315±10.363.92
Ib·Pb2+3374.00
19.65±0.071.80
380 4.59
Ib·(Pb2+)23364.20
23.90±0.151.60
3644.14

The detected properties of the metal complexes of General formula I given the possibility of their use, for example, in the development of optical sensors for cations of barium, calcium or lead, respectively. To date, there are several commercially available optical reagents for cations barium based crossterrain of hetarylphenylethenes and cations of lead-based polycaproamide and polysulfonamide.

This patent new optical chelating agents have a higher selectivity than known, due to the presence of macrocyclic cation binding centre, well suitable to bind to the cation of the metal as the size and nature of the coordinating heteroatoms.

Another advantage of the proposed new chelating agents are the two which is a significant color and fluorescent contrast in the visible spectrum, arising in the process of complexation. This circumstance facilitates visual way of determining the cation of the metal and makes quantitative analytical determination of the metal cation to be more precise.

The inventive method of obtaining zinc complexes crossterrain of sterilisations quite simple in execution. The output of zinc complexes in this method is quantitative.

The technical result of the present invention are fluorescent sensors for cations of calcium, barium and lead, allowing a visual way of determining the cation of the metal.

1. Dimeric zinc complexes of 15-crown-5 or dithia-18-crown-6 containing 2-methyl-9-sterilisations General formula:

where
as optical sensors for cations of calcium, barium and lead.

2. The method of obtaining complexes of the formula (I) according to claim 1, characterized in that the organic ligand 15-crown-5 or dithia-18-crown-6 containing 2-methyl-9-sterilisation subjected to interaction with zinc perchlorate in acetonitrile upon irradiation with red light.



 

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SUBSTANCE: invention relates to acridine styryl dyes, and more specifically to phenylazadithia-15-crown-5-containing 9-styrylacridine of the following formula: I, as well as to a method of producing the said compound.

EFFECT: new compound is useful as an optical sensor of copper cations.

2 cl, 1 ex

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 CH2m+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

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to new type of compounds representing crown-containing styryl dyes with ammonium group at N-substitute of heterocyclic residue that can be used as photo- and thermosensitive compounds. Invention describes new crown-containing styryl dyes with ammonium group at N-substitute of a heterocyclic residue. Also, invention describes two variants of the method for their preparing. The first method is based on the interaction of a heterocyclic base quaternary salt with formyl derivative of the corresponding crown-compound, and the second method involves quaternization reaction of crown-containing heteroarylphenylethylene at heterocycle nitrogen atom. Proposed crown-containing styryl dyes are prepared from available raw with high yield and represent compounds of the new type able to stereospecific reactions [2 + 2], i. e. photocyclo-addition and possessing thermochromism properties.

EFFECT: improved preparing methods, valuable properties of dyes.

4 cl, 4 dwg, 16 ex

The invention relates to organic chemistry, a new class of compounds - crusaderism Stillavin dyes and method of production thereof

FIELD: chemistry.

SUBSTANCE: invention relates to acridine styryl dyes, and more specifically to phenylazadithia-15-crown-5-containing 9-styrylacridine of the following formula: I, as well as to a method of producing the said compound.

EFFECT: new compound is useful as an optical sensor of copper cations.

2 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to zinc complex of asymmetric ethylenediamine-N,N-dipropyonic acid dichloride of formula Also claimed is method of its obtaining. Complex can be applied for solution of problems, associated with the necessity to introduce Zn2+ in chelate form instead of its mineral salts, as well as to serve as initial product for synthesis of other chemical compounds of series of polydentate ligands, in particular asymmetric ethylenediamine-N,N-dipropyonic acid.

EFFECT: obtaining zinc complex of asymmetric ethylenediamine-N,N-dipropyonic acid dichloride.

4 cl, 4 dwg, 3 ex

FIELD: biotechnologies.

SUBSTANCE: invention refers to a compound having general formula (I),

where: m and n are independent integer numbers of 1 to 6; each of X1-X3 and Y1-Y3 is O; each of R1-R3 is independently chosen from a group consisting of hydrogen or alkyl; and R is O-(CH2)x-C(-O)NR'-(CH2)y-NHR'. Besides, x and y are independent integer numbers of 1 to 6; and R' is chosen from the group consisting of hydrogen and alkyl. In addition, an antibody containing an antigen recognition area, use of the compound, pharmaceutical composition, use of the antibody, method for MMP-2 or MMP-9 activity inhibition in a sample and a composition for determining MMP-2 or MMP-9 are proposed.

EFFECT: invention allows obtaining compounds that are able to inhibit MMP-2 or MMP-9 activity.

11 cl, 16 dwg, 4 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to molecular complexes of zinc and cadmium bis(1-phenyl-3-methyl-4-formyl-5-pyrazolonate) with amino-derivatives of nitric heterocycles of general formula (I) (NH2-Het)n, where NH2-Het is 1-aminoisoquinoline, 3-aminoquinoline, 6-aminoquinoline, 5-amino-4,6-dimethylquinoline, 2-aminopyridine, 2-amino-5-bromopyridine, 3-amino-5-methylisoxazole, 2-amino-1-ethylbenzimidazole, M is Zn, Cd, n=1, 2.

EFFECT: molecular complexes of formula (I) exhibit luminescent properties in the blue region of the spectrum and can be used as phosphors for making organic light-emitting diodes of white and visible light.

14 ex

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