RU2806627C1 - 5-[4′-(1′′,3′′-benzothiazol-2′′-yl)phenyl]-10,15,20-tris(4′-sulfophenyl)porphine as color indicator for visual detection of hydrogen chloride - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: compound representing 5-[4′-(N-methyl-1′′,3′′-benzothiazol-2′-yl)phenyl]-10,15,20-tris( 4′-sulfophenyl)porphine, which can be used as a color indicator that allows the detection of hydrogen chloride vapor and is characterized by a high contrast color transition for the visual determination of HCl. The invention can be used in industry to detect hydrogen chloride leaks; in industrial ecology for the detection of HCl in the air of a working area, at natural sites of increased danger, in areas of chemical release.

EFFECT: obtaining a color indicator capable of immobilization on cellulose, viscose and cotton carrier fabrics for visual determination of the presence of hydrogen chloride in a solution, in the air or in the composition of a radiation-sensitive layer.

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Description

The invention relates to the chemical industry, namely to the production of a compound that can be used as a color indicator in solution or immobilized on a flexible substrate, allowing the detection of hydrogen chloride vapors. The compound is characterized by a high contrast color transition and can be used for the visual detection of hydrogen chloride. The invention can be used in various areas of the national economy: in industry, to detect hydrogen chloride leaks; in ecology and industrial ecology for their detection in the air of the working area, at natural objects of increased danger, in areas of chemical release. The invention also relates to the field of human health protection, since it can be used as a color visual indicator of ionizing radiation, and the indicator must contain, along with the resulting compound, a halogen-containing polymer. In the presence of ionizing radiation, hydrogen halide is released from the polymer, which changes the color of the indicator.

Due to the constantly deteriorating environmental situation, the topic of monitoring environmental pollution has become very relevant. No less in demand are sensors and detectors for quickly determining the presence of dangerous volatile chemical compounds in the air that ionize during emissions and accidents at various industrial and other high-risk facilities. The detection of hydrogen chloride in solutions is widely known using analytical chemistry methods and the use of acid-base indicators. Detection of hydrogen chloride in the air is a more complex task, including sampling of the analyzed air, in the case of small doses - concentration of volatile chemicals using gas membranes, sorbents [Patent 2390750 C2 Russian Federation, IPC G01N 1/22 (2006.01). Method for monitoring impurities in the air [Text] / Logvin Leonid Aleksandrovich (RU), Smirnov Andrey Valentinovich (RU), Ivanova Irina Igorevna (RU); applicant Limited Liability Company "UNISIT" (RU), patent holder Limited Liability Company "UNISIT" (RU); application 01/11/2008; publ. 05/27/2010, Bulletin. No. 15], and then carrying out analytical operations.

There is a known method for determining the content of hydrogen chloride in the air [Patent 2213347 C2 Russian Federation, IPC G01N 30/00 (2000.01). Method for determining the content of hydrogen chloride in the air [Text] / Oksengoit-Gruzman E.A. (RU), Soloviev Yu.F. (RU), Borisov B.N. (RU); applicant Open Joint Stock Company "Soyuztsvetmetavtomatika", patent holder Open Joint Stock Company "Soyuztsvetmetavtomatika"; application 04.10.2001; publ. 09/27/2003, Bulletin. No. 27], which includes sampling and pumping air, dividing the air flow into two and throttling them, determining chlorine gas by the first and second sensors, with the first sensor measuring chlorine gas in the first flow. The second sensor measures chlorine gas obtained in the additionally introduced operation of decomposition of hydrogen chloride into chlorine in the second stream. Signals from the first and second chlorine sensors are subtracted, compared and the content of hydrogen chloride in the environment is determined. The disadvantage of the invention is the dependence of the indicators on the location and method of sampling, the complexity of the technique, the impossibility of detecting the location of the leak, the impossibility of visual detection, and the duration.

The compound azo dye - benzoazo-1-amino-4-naphthalene is also known [Patent 2697653 C1 Russian Federation, IPC G01T 1/04 (2006.01). Color visual radiosensitive indicator reagent, indicator of the absorbed dose of ionizing radiation and method of its manufacture [Text] / Antipov Mikhail Vladimirovich (RU), Zubaty Leonid Aleksandrovich (RU), Sadogursky Maxim Naumovich (RU), Soroka Arkady Matveevich (RU); patent holder Mikhail Vladimirovich Antipov (RU); application 01/11/2019; publ. 08/16/2019, Bulletin. No. 23], which can be used as the basis for a color visual radiosensitive indicator reagent. The indicator reagent is obtained by adding in certain proportions to the previously obtained mixture of epoxidized soybean oil with soybean, a solvent - ethyl acetate, a copolymer of vinyl acetate with vinyl chloride, hexachloroethane, benzoazo-1-amino-4-naphthalene, maintaining at a temperature of 55 with stirring. The specified indicator reagent is used as the basis of a radiosensitive layer for the production of a color visual radiosensitive indicator of ionizing radiation by applying white polyurethane-based paint to a flexible or inflexible substrate, drying it, then applying a layer of indicator reagent (radiosensitive layer) on top of the white paint layer, drying it at 65-80°C for 3-6 hours. After drying, the surface of the indicator is covered with a protective film of transparent polymer material using the lamination method. The disadvantage of the invention is the difficulty of obtaining an indicator reagent, high requirements for the indicators of mixtures and the quality of the reagents. Duration of the operation.

The compound n-diethylaminoazobenzene is known [Patent 2 298 811 C1 Russian Federation, IPC G01T 1/04 (2006.01). Film chemical dosimeter of ionizing radiation and method of its manufacture [Text] / Abramov Vladimir Nikolaevich (RU), Generalova Valentina Vasilievna (RU), Gromov Alexander Alexandrovich (RU), Gursky Mikhail Natanovich (RU), Zhanzhora Alexander Parfirievich (RU), Kochukov Alexey Viktorovich (RU), Meshcheryakova Nina Konstantinovna (RU), Yakovlev Vladimir Borisovich (RU); patent holders Abramov Vladimir Nikolaevich (RU), Generalova Valentina Vasilievna (RU), Gromov Alexander Alexandrovich (RU), Gursky Mikhail Natanovich (RU), Zhanzhora Alexander Parfirievich (RU), Kochukov Alexey Viktorovich (RU), Meshcheryakova Nina Konstantinovna (RU), Yakovlev Vladimir Borisovich (RU); application 11/22/2005; publ. 05/10/2007, Bulletin. No. 13], which is part of a film chemical dispenser for ionizing radiation, in which the radiation-sensitive layer consists of a polymer binder, an azo dye, a plasticizer and a halogen-containing sensitizer. The layer is placed between layers of a transparent substrate with an adhesive sublayer. A copolymer of vinyl chloride with vinyl acetate or a product of its partial saponification is used as a polymer binder. n-diethylaminoazobenzene is used as an azo dye; hexachloroethane, as well as compounds of brominated alkanes or arylalkanes, are used as a halogen-containing sensitizer. The film chemical dispenser is characterized by high sensitivity, good visual effect, before irradiation the film is yellow, after irradiation it is red. The disadvantages are the difficulty of obtaining a radiation-sensitive layer, the long response time of the dye due to diffusion post-radiation processes, and the need to use sensitizers.

A chemical indicator is known [Patent 2 4510303 C1 Russian Federation, IPC G01T 1/04 (2006.01). Color visual indicator of the absorbed dose of ionizing radiation [Text] / Abramov Vladimir Nikolaevich (RU), Kochukov Alexey Viktorovich (RU), Meshcheryakova Nina Konstantinovna (RU), Yakovlev Vladimir Borisovich (RU); patent holder Closed joint-stock company for the development and implementation of new information materials and technologies "BIT" (RU); application 10/06/2010; publ. 05/20/2012, Bulletin. No. 14] based on a luminescent dye of the series 1, 3, 5 triarylpyrazoline, which changes its color under the influence of ionizing radiation. The disadvantages of the invention are the complexity of the composition, the need to use sensitizers, plasticizers, adhesive sublayers containing vinyl series copolymers or mixtures thereof, a reflective layer of a polymer binder, a plasticizer and metals (or their salts and/or oxides) of groups I-VIII, a radiation-sensitive layer , also consisting of a polymer binder, phosphor, halogen-containing sensitizer and other components. In addition, the low UV stability of the luminescent dye necessitates the use of a protective layer of a UV absorber.

The closest to the proposed invention is the proposed composition and method for producing indicator tape [Inventor's certificate SU 1767414 A1, IPC G01N 31/22 (2006.01). Composition for processing indicator tape for the determination of hydrogen chloride or ammonia [Text] /Isaev Viktor Mikhailovich Arsenkin Vladimir Pavlovich; State Research and Design Institute of Paint and Varnish Industry; application 06.10.1992; publ. 10/07/1992, Bulletin. No. 37], which uses a composition for detecting hydrogen chloride gas, which contains an indicator - bromophenol blue, nitrostyromal, cellulose acetate as a carrier, acetone or ethyl acetate as an organic solvent, and PET film as a substrate. The resulting indicator polymer tape is used to determine hydrogen chloride vapor. After exposure of the working area of the indicator polymer tape to hydrogen chloride vapor for a fixed time, the optical density increases, the colored spot on the tape is photometered through transmission and the concentration of hydrogen chloride is determined.

A significant disadvantage of the prototype is the complexity, labor-intensive and time-consuming transfer of bromophenol blue to the carrier. This operation includes dissolving polymers (nitrostyromal, cellulose acetate) in organic solvents, filtering, and preparing a solution of bromophenol blue in organic solvents. Another significant drawback is the low sensitivity of the tape for hydrogen chloride (0.005 mg/dm ³⁾ and low resistance to UV light. In addition, detection requires transmission photometric equipment.

The objective of the invention is to obtain a color indicator capable of immobilization on cellulose, viscose and cotton carrier fabrics for visual determination of the presence of hydrogen chloride in a solution, in the air or in the composition of a radiation-sensitive layer.

The problem was solved by a new chemical compound of the formula:

The problem was solved due to the fact that a new porphyrin compound was obtained containing three sulfo groups and a benzothiazole residue, the structure of which was confirmed by physicochemical methods of analysis. The choice of porphyrin is due to the following reasons: three sulfo groups ensure the solubility of the compound in aqueous and physiological media, as well as the ability of the compound to participate in acid-base equilibria due to protonation or deprotonation of the sulfo groups of the porphyrin, the heteryl (benzothiazole) substituent gives the compound the required hydrophobic-hydrophilic balance, which is necessary for immobilization, uniform dyeing of cellulose, viscose and cotton carrier fabrics. In addition, three sulfo groups and a heteryl substituent act as electron-withdrawing substituents that have a negative inductive effect, which leads to a change in the proton-accepting ability of the pyridine nitrogen atoms of the porphyrin reaction center. Thus, the new porphyrin compound is capable of participating in a reaction with hydrogen chloride, which is accompanied by a contrasting and sharp change in the color of the compound from brown-red to fluorescent yellow-green. The proposed compound is a two-color indicator of hydrogen chloride in air or hydrochloric acid in solution. The resulting compound is highly soluble in aqueous media and is easily and evenly applied to cellulose, viscose and cotton fabrics by any known method (dipping, painting, spraying).

To obtain this compound, the following substances are used:

- petroleum paraxylene TU 38.101255-87;

- benzaldehyde - commercial product TCI EUROPE N.V.;

- trifluoroacetic acid TU 6-09-3877-80;

- pyrrole - TU 6-09-07-242-84;

- zinc acetate - GOST 5852-78;

- aluminum oxide - TU 6-09-426-75;

- chloroform - TU 263-44493179-01 as amended. No. 1, 2;

- methanol - GOST 2222-95;

- triphenylphosphine - commercial product TCI EUROPE N.V.;

- potash (potassium carbonate) - GOST 4221-76;

- copper acetate - GOST 5852-79;

- palladium acetate - TU 2625-024-00205067-2003;

- benzothiazole - commercial product TCI EUROPE N.V.;

- methylene chloride - TU 2631-44493179-98 as amended. No. 1, 2, 3;

- hexane - TU 6-09-06-4521-77;

- benzene - GOST 5955-75 as amended. No. 1, 2;

-toluene TU 2414-006-72021999-2009.

The invention is illustrated by drawings, where in Fig. Figure 1 shows the result of changes in the electronic absorption spectra of a solution of 5-[4′-(1′′,3′′-benzothiazol-2′′-yl)phenyl]-10,15,20-tris(4′-sulfophenyl)porphine (4 ,1⋅10 ^-6 M) in phosphate buffer 2 ml with the addition of 24 μl of hydrochloric acid (1N). The initial electronic absorption spectrum of the porphyrin compound is classical and contains a Soret band (419 nm) and four absorption bands in the far-wave part of the spectrum (520, 558, 594, 651 nm), which corresponds to the symmetry of the porphyrin compound D2h. Protonation of the reaction center upon interaction with HCl leads to a bathochromic shift of the Soret band to 439 nm. The disappearance of absorption in the region of 520, 558, 594 nm and the appearance of two relatively intense absorption bands at 489 and 657 nm. These spectral changes indicate an increase in the symmetry of the porphyrin compound to D4h due to protonation of the porphyrin reaction center. In fig. Figure 2 shows the potentiometric titration curve of 5-[4′-(1′′,3′′-benzothiazol-2′′-yl)phenyl]-10,15,20-tris(4′-sulfophenyl)porphine (4.1⋅ 10 ^-6 M) in phosphate buffer 2 ml titrated with hydrochloric acid (1N). In fig. 3 - photograph of cotton fabric with a solution of a porphyrin compound applied to it, before and after introducing the fabric into an air environment containing 1.5 mg/l HCl.

The claimed compound is prepared as follows:

First, 5-(4′-bromophenyl)-10,15,20-triphenylporphine is prepared as follows:

To a boiling solution of 2 ml of trifluoroacetic acid in 250 ml of para -xylene, under a stream of nitrogen, a solution of 5 ml (72 mmol) of pyrrole, 3.3 g (18 mmol) of 4-bromobenzaldehyde and 5.5 ml of ( 54 mmol) benzaldehyde in 50 ml para -xylene. The mixture is boiled for 40 minutes in a stream of nitrogen and then for 1 hour in a stream of air. The solution is cooled and neutralized with 20 ml of 25% ammonia solution. Xylene is distilled off with steam, the residue in the flask is filtered, dried at room temperature, dissolved in 200 ml of chloroform and chromatographed on a column with Al ₂ O ₃ (II degree of activity according to Brockman), eluting with a mixture of chloroform-hexane (1: 1). The first dark red zone of 5-(4'-bromophenyl)-10,15,20-triphenylporphine, containing the co-formed tetraphenylporphine as an impurity, is collected. The eluate is evaporated to 5 ml, monobromoporphyrin is precipitated with 50 ml of methanol and dried at room temperature to constant weight. Yield 1.14 g (23%). R f 0.67 (silufol, chlorofom). ESP (chloroform), λmax, nm (logε): 648 (3.63), 590 (3.77), 551 (3.91), 515 (4.26), 491 (5.64). Mass spectrum (MALDI-TOF), m/z : calculated: 693.63 C ₄₄ H ₂₉ BrN ₄ : Found: 694.42 [M+H] ⁺ .

Next, zinc 5-(4′-bromophenyl)-10,15,20-triphenylporphynate is obtained:

Dissolve 3 g (4.3 mmol) 5-(4′-bromophenyl)-10,15,20-triphenylporphyrin and 4.7 g (0.021 mol) anhydrous zinc acetate in a mixture of 200 ml methanol and 100 ml chloroform. The mixture is boiled for 1.5 hours, monitoring the progress of the reaction using ESP. The mixture is cooled, the excess solvent is distilled off, the residue is chromatographed on a column with Al ₂ O ₃ (III degree of activity according to Brockmann), eluting with chlorophore. The solvent is distilled off, the residue is washed with water, filtered and dried at room temperature to constant weight. Yield 3.3 g (98%).

¹ H NMR δ, ppm: 9.02-8.99m (2H, H ^8.12 ), 8.97-8.96m (2H, H ^2.18 ), 8.27-8.24m ( 4H, H ^3,7,13,17 ), 8.14-8.12m (1H, H ^4-HPh ), 7.78-7.73m (10H; 8H, H ^2,6-HPh ; 2H, H ^4-HPh ), 7.59–7.51m (8H, H3.5 ^-HPh ) ( _CDCl3 ). ESP: λ _max , nm (logε): 595(3.70), 551(4.14), 424(5.51) (CHCl ₃ ). MALDI-TOF MS: m / z Calculated: C ₄₄ H ₂₇ BrN ₄ Zn, 757.0156; Found: 757.5608.

Zinc 5-[4′-(1′′,3′′-benzothiazol-2′′-yl)phenyl]-10,15,20-triphenylporphynate is then obtained:

In a 100 ml flask equipped with a magnetic stirrer and reflux condenser, boil with stirring for 52 hours a mixture of 1 g (0.132 mmol) 5-(4′-bromophenyl)-10,15,20-triphenyl zinc porphynate, 0.0592 g ( 0.264 mmol) Pd(OAc) ₂ , 0.0575 g (0.264 mmol) Cu(OAc) ₂ H ₂ O, 0.34 g (0.132 mmol) triphenylphosphine, 0.364 g (1.342 mmol) potassium carbonate, and 290 μl (0.264 mmol) benzothiazole in 45 ml of toluene. Next, the mixture is cooled to room temperature and 50 ml of methylene chloride is added and filtered. The precipitate is washed with 10 ml of methylene chloride, the combined organic fractions are evaporated in vacuum. The residue is dissolved in 30 ml of methylene chloride and chromatographed on a silica gel column, eluting initially with a mixture of hexane and methylene chloride (1:1) (the zone of tetraphenylporphine impurities disappears), then with methylene chloride, collecting the dark red zone of monoheterylporphyrin. The solvent is evaporated to dryness. Yield 0.152 g (75%). R f 0.61 (silufol, chlorofom).

^1H NMR δ, ppm: 8.99-8.95m (4H, H ^3.7,13.17 ), 8.49-8.47d (2H, H ^8.12 , J = 7.85 ), 8.37-8.35d (2H, H ^2.18 , J = 7.83), 8.23-8.21m (2H, H ^4-HPh ), 8.12-8.09t (1H, H ^4-HPh , J = 7.14; J = 5.28), 8.05-8.03d (2H, H ^2,6-HPh , J = 8.1), 7.80-7.74m ( 6H; 4H, H ^3,5-HPh ; 2H, H ^2,6-HPh ), 7.23-7.21m (4H, H ^2,6-HPh ), 7.65-7.63m (1H, from benzothiazole), 7.62-7.59t (1H, from benzothiazole J = 7.72; J = 7.60), 7.57-7.55d (1H, from benzothiazole J = 7.57), 7.51-7.48t (1H, from benzothiazole J = 7 .72; J = 7.59) 7.21-7.20m (4H=3.5-Ph) (CDCl ₃ ). ESP: λ _max , nm (logε): 596(3.75), 551(4.16), 424(5.52) (CHCl ₃ ). MALDI _- TOF MS: m / z _Calculated : _C51H31N5SZn , 811.28; Found: 811.61.

Preparation of the claimed compound - 5-[4′-(1′′,3′′-benzothiazol-2′′-yl)phenyl]-10,15,20-tris(4′-sulfophenyl)porphine:

In a 50 ml flask equipped with an air cooler, 100 mg of 5-[4′-(1′′,3′′-benzothiazol-2′′-yl)phenyl]-10,15,20 is heated with stirring to 70°C -zinc triphenylporphynate, add 10 ml of sulfuric acid (98%). The mixture is stirred at 70°C for 48 hours, then cooled to room temperature and stirred for another 72 hours. Then pour it onto ice. The dark green suspension is filtered, washed with cold water until the barium chloride solution becomes cloudy, then with acetone. The sulfonated porphyrin is dried at room temperature to constant weight.

Yield 0.113 g (93%). R _f = 0.54 (EtOH - 25% ammonia solution (20:1). ¹ H NMR δ, ppm: 8.96-8.87m (4H, H ^3.7,13,17 ) , 8.58-8.59m (2H, H ^8.12 ), 8.48-8.47m (2H, H ^2.18 ), 8.22-8.21m (8H, H ^2.6-HPh ) , 8.07-8.06m (8H, H ^3.5-HPh ), 7.66-7.57m (4H, from benzothiazole); -0.81 bs (2H, NH) (DMSO-d ₆ ). ESP: λ _max , nm (logε): 646 (3.59), 590 (3.73), 558 (3.88), 520 (4.11), 418 (5.25) (H ₂ O). MALDI-TOF MS _: m / z _{Calculated: C51H33N5O9S4 , 988.1} ; Found: _988.43 .

Example of application of the claimed compound

Prepare a concentrated solution of 5-[4′-(1′′,3′′-benzoxazol-2′′-yl)phenyl]-10,15,20-tris(4′-sulfophenyl)porphin in water by weighing the compound weighing 0.00163 g is dissolved in 5 ml of phosphate buffer (pH = 7.4). The resulting indicator solution with a concentration of 4.1⋅10 ^-4 mol/l is stored in an airtight container in a light-protected place.

Example 1. Detection of hydrochloric acid in solution. To detect acid in the analyzed solution, the resulting indicator solution is added in an amount of 20 μl for every 1 ml of the analyzed solution. In the presence of acid in the solution at a concentration of 1.86⋅10 ^-5 mol/l and higher, the solution changes color to fluorescent yellow-green.

Example 2: Detection of hydrogen chloride in air. To detect hydrogen chloride in the air, a solution of a porphyrin compound with a concentration of 4.1⋅10 ^-4 mol/l in a buffer is applied to a carrier (cellulose, viscose, cotton fabric) by any method. The indicator on a flexible carrier is introduced into the analyzed air environment. In the presence of hydrogen chloride in the analyzed atmosphere, the indicator changes color from red-brown to fluorescent yellow-green (Fig. 3). The indicator on a flexible carrier can be combined with a polyvinyl chloride polymer and can act as a radiation-sensitive layer in visual radiation detection systems.

Claims (3)

5-[4′-(1′′,3′′-benzothiazol-2′′-yl)phenyl]-10,15,20-tris(4′-sulfophenyl)porphine formula: as a color indicator for the visual detection of hydrogen chloride.