RU2532903C1 - Method of synthesising 2-dodecyl-5-(2,3,7,8-bis-(9h, 10h-anthracene-9,10-diyl)pyren-1-yl)thiophene - monomolecular optic sensor for detection of nitroaromatic compounds - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining 2-dodecyl-5-(2,3,7,8-bis-(9H, 10H-anthracene-9,10-diyl)pyren-1-yl)thiophene, which consists in the interaction of 1-bromopyrene with 2-dodecyl-5-tributylstannylthiophene by the Stille reaction with obtaining the first half-product 5-(pyren-1-yl)-2-dodecylthiophene, with the following bromination of the latter with obtaining the second half-product 2-dodecyl-5-(3,6,8-tribromopyren-1-yl)thiophene, its following heating with anthracene and sodium amine in the argon atmosphere.

EFFECT: developed is the novel method of synthesising a derivative of pentasubstituted pyrene with the application of a cross-combination by Stille and highly reactive arine intermediates, which in a result leads to the synthetic availability of pentasubstituted pyrene derivatives, which can be applied for distant detection of nitroaromatic compounds present on surfaces, in solutions of nonpolar solvents, water and in air.

2 dwg, 1 tbl

Description

The invention relates to the field of organic synthesis of sensory materials and relates to pentasubstituted pyrene having sensory properties, and intended for remote detection of the presence of nitroaromatic compounds on surfaces, in solutions of non-polar solvents, water and in air, in ultra-low concentrations based on changes in optical properties - quenching of photoluminescence designated sensor in contact with molecules of nitroaromatic compounds. The invention can be used to synthesize sensory substituted pyrenes, which can be used in customs services, law enforcement agencies (army, police, etc.), research laboratories, as well as in everyday life and agriculture.

Pyrene itself is quite well known as a monomolecular sensor for π-deficient aromatic compounds, including nitroaromatic derivatives. Although Stern-Volmer’s quenching photoluminescence quenching constants are satisfactory, he has found limited use as an explosive sensor. For example, in a dissolved state, in polystyrene nanofibers (Ying Wang, Anthony La, Yu Ding, Yixin Liu, and Yu Lei Adv. Func. Mat. 2012 1, 1), the membrane of which was used to visually detect explosives hidden in the soil and their fumes. Pyrene was used as a sensor for the indirect detection of explosives and their decomposition products in high performance liquid chromatography (John V. Goodpaster and Victoria L. McGuffin Anal. Chem. 2001, 73, 2004-2011). In the case of 2,4-dinitrotoluene, the Stern-Volmer photoluminescence quenching constant was (Ksν = 386 M ^-1 ). The use of pyrene-1-ylthiophene fluorophore derivatives as the working medium of solar cells (M. Hemgesberg, DM Ohlmann, Y. Schmitt, MR Wolfe, MK Müller, B. Erb, Y. Sun, LJ Gooßen, M. Gerhards, and WR Thiel Eur. J. Org. Chem. 2012 pp. 2142-2151; A. Baheti, C.-P. Lee, KR Justin Thomas and K.-C. Ho Phys. Chem. Chem. Phys., 2011, 13, pp.17210-17221). Monomolecular sensors for nitroaromatic derivatives based on pyrenylthiophene were not found in the world literature.

Currently, methods for producing 2-dodecyl-5- (2,3,7,8-bis- (9H, 10H-anthracene-9,10-diyl) pyren-1-yl) thiophene 1 (hereinafter bisipticenopyrenylthiophene) in the world literature not described. See appendix 1.

There is evidence of the use of mixed polymers including pentipticene-acetylene units for the visual determination of 2,4,6-trinitrotoluene (TNT) in air (Thomas, SW, III; Joly, GD; Swager, TM Chem. Rev. 2007, 107, 1339-1386; Yang, J.-S .; Swager, T.MJ Am. Chem. Soc. 1998, 120, 5321-5322; Yang, J.-S .; Swager, T.MJ Am. Chem. Soc. 1998, 120, 11864-11873). Also known is a method for producing 1,4-diethyl derivatives of pentipticene 2, appendix 1 (Thomas, SW, III; Joly, GD; Swager, T. M. Chem. Rev. 2007, 107, 1339-1386; Yang, J.-S. ; Swager, TMJ Am. Chem. Soc. 1998, 120, 5321-5322; Yang, J.-S .; Swager, T. MJ Am. Chem. Soc. 1998, 120, 11864-11873), which are distant structural analogues 1.

The essence of the invention is a method for producing bisipticenopirenylthiophene 1 - optical sensor for π-deficient (hetero) aromatic compounds, including the interaction of 1-bromopyrene with 2-dodecyl-5-tributylstannylthiophene according to the Stille reaction to obtain the first intermediate 5- (pyrene-1-yl) - 2-dodecylthiophene, bromination of the latter to obtain a second intermediate of 2-dodecyl-5- (3,6,8-tribromopyren-1-yl) thiophene, its subsequent heating with anthracene and sodium amide in argon atmosphere. When calculating the practical yield, counting on the readily available bromopyrene, yield 1 is 16%.

The synthesis of 2-dodecyl-5- (2,3,7,8-bis- (9H, 10H-anthracene-9,10-diyl) pyrene-1-yl) thiophene (1) is given as evidence of the possibility of carrying out the invention. :

A mixture of 1-bromopyrene ¹ ( ¹ Mitchell RH, Chen Y., Zhang J. Organic Preparations and Procedures International, 1997, 29 (6), 715-719.) (500 mg, 1.78 mmol), 5-dodecyl-2-tributylstannylthiophene (1.13 g, 2.09 mmol), PdCl ₂ * 2tpp (49 mg, 0.07 mmol), triphenylphosphine (37 mg, 0.14 mmol) and anhydrous toluene (20 ml) are boiled under argon for 60 hours. The solvent is distilled off under reduced pressure, the residue was purified by column chromatography (eluent was a mixture of petroleum ether (40-70) and methylene chloride (20: 1), Rf = 0.7. EI MS, m / z (I): 452 (100). Yield 460 mg (1.01 mmol, 57%). The intermediate product without further purification is sent to the next Dieu.

The intermediate product (460 mg, 1.01 mmol) was dissolved in nitrobenzene (25 ml), bromine (1.53 ml, 3.13 mmol) was added and the resulting mixture was stirred for 10 hours at 70 ° C. The reaction mixture was cooled to room temperature, the precipitate formed was filtered off, washed with ethanol, and dried. EI MS, m / z (I): 689 (100). Yield 560 mg (0.81 mmol, 80%). The intermediate product is sent to the next step without further purification.

A mixture of tribromo derivative (560 mg, 0.81 mmol), anthracene (1.44 g, 8.1 mmol), sodium amide (90 mg, 2.27 mmol) and toluene (50 ml) was stirred at 110 ° C for 10 h. The precipitate was filtered off, the solvent was the filtrate is distilled off under reduced pressure, the residue is purified by column chromatography (mixture of petroleum ether (40-70) and methylene chloride (10: 1), Rf = 0.3.

2-dodecyl-5- (2,3,7,8-bis- (9H, 10H-anthracene-9,10-diyl) pyrene-1-yl) thiophene ("bisipticenopyrenylthiophene"). Light yellow oil; Yield 0.26 g (0.32 mmol, 40%). ¹ H NMR (CDCl ₃ ): 0.88 (t, 3H, ³ J 7.2 Hz, CH ₃ ), 1.20-1.50 (m, 18H, thiophene-CH ₂ CH ₂ (C H ₂ ) ₉ ), 1.89 (m, 2H , thiophene-CH ₂ C H ₂ ), 3.04 (t, 2H, ³ J 7.2 Hz, thiophene-C H ₂ ), 5.78 (s, 1H, HC (sp ³ )), 5.85 (s, 1H, HC (sp ³ )), 6.34 (s, 1H, HC (sp ³ )), 6.44 (s, 1H, HC (sp ³ )), 6.97 (m, 9H, anthracenediyl, H-4 (thiophene)), 7.04 (d, 1H, ³ J 3.2 Hz, H-3 (thiophene)), 7.36 (m, 2H, anthracendiyl), 7.46 (m, 4H, anthracendiyl), 7.52 (m, 2H, anthracendiyl), 7.99 (d, 1H, ³ J 9.6 Hz, pyrene), 8.00 (d, 1H, ³ J 9.6 Hz, pyrene), 8.17 (s, 1H, H-6 (pyrene)), 8.42 (d, 1H, ³ J 9.6 Hz, pyrene), 8.50 ( d, 1H, ³ J, 9.6 Hz, pyrene). EI MS, m / z (I): 804 (100). Calculated,%: C 89.51, H 6.51. C ₆₀ H ₅₂ S. Found,%: C 89.33, H 6.34. The compound is a light yellow oil soluble in nitrobenzene, benzene, chloroform, insoluble in methanol and water.

As an example of the visual detection of nitroaromatic compounds using a compound, we study the interaction of 1 with nitroaromatic compounds, which was carried out in solutions of dry tetrahydrofuran at sensor concentrations of (5-10) · 10 ^-6 M, depending on the value of the absorption coefficient according to UV data (A≤0.1 )

Fluorescence titration was carried out using a solution of a nitroaromatic compound: 2,4-dinitrotoluene (DNT), 5 · 10 ^-3 M. The criterion for evaluating the effectiveness of the claimed compounds and prototype was the value of the Stern-Volmer constant (quenching constant, it is association constant of the obtained complex of the claimed compound of nitroaromatic compounds and expressed by the equation

,

,

where I °, I - fluorescence intensity before and after the addition of nitroaromatic compounds (quencher); Q is the concentration of nitroaromatic compounds, mol / l; K _SV - constant value, (mol / l) ^-1

Table 1

(моль/л)-1The values of the fluorescence quenching constants of the claimed compound 1 and pyrene in a linear approximation,

(mol / l) -1

, M ^-1

, M ^-1 one pyrene 2,4-DNT 1.26310 ³ 0.38610 ³

The experimental results showed the high efficiency of the claimed compounds for the visual detection of nitroaromatic compounds. Pyrene is less effective in similar conditions.

Claims (1)

The method of obtaining 2-dodecyl-5- (2,3,7,8-bis- (9H, 10H-anthracene-9,10-diyl) pyrene-1-yl) thiophene - a monomolecular optical sensor for the detection of nitroaromatic compounds, including interaction 1-bromopyrene with 2-dodecyl-5-tributylstannylthiophene according to the Stille reaction to obtain the first intermediate of 5- (pyren-1-yl) -2-dodecylthiophene, bromination of the latter to obtain the second intermediate of 2-dodecyl-5- (3,6,8 tribrompiren-1-yl) thiophene, its subsequent heating with anthracene and sodium amide in an argon atmosphere.

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