RU2501780C1 - Method for synthesis of 1,2,6,7-bis-(9h, 10h-anthracene-9,10-diiyl)pyrene - monomolecular optical sensor for detecting nitroaromatic compounds - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of 1,2,6,7-bis-(9H, 10H-anthracene-9,10-diiyl)pyrene 1 by reacting an in situ generated aryne derivative of pyrene with anthracene in an argon atmosphere

.

The present invention provides a method for synthesis of said compound, which can be used as a monomolecular optical sensor for detecting nitroaromatic compounds.

EFFECT: improved method.

1 ex, 1 tbl

Description

The technical field to which the invention relates.

The invention relates to the field of organic synthesis of sensory materials and relates to a tetra-substituted pyrene having sensory properties and designed to remotely detect the presence of nitroaromatic compounds on surfaces, in solutions of non-polar solvents, water and in air at very low concentrations based on changes in optical properties - quenching of photoluminescence - a 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.

The level of technology.

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 under high performance liquid chromatography (John V. Goodpaster and Victoria L. McGuffin Anal. Chem. 2001, 73, 2004-2011). In the case of 2,4-dipitrotoluene, the Stern-Volmer photoluminescence quenching constant was (Ksv = 386 M ^-1 ).

Currently, methods for producing 1,2,6,7-bis- (9H, 10H-anthracene-9,10-diyl) pyrene 1 (hereinafter bisipticenopyrene) are not described in the world literature.

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

SUMMARY OF THE INVENTION

The essence of the invention is a method for producing 1,2,6,7-bis- (9H, 10H-anthracene-9,10-diyl) pyrene ("bisiptitsenopiren") 1 - optical sensor for π-deficient (hetero) aromatic compounds, including interaction an in situ generated arine pyrene derivative with anthracene in an argon atmosphere. When calculating the practical yield, counting on the easily available tetrabromopyrene, yield 1 is 40%.

Information confirming the possibility of carrying out the invention.

4.1. Synthesis of 1,2,6,7-bis- (9H, 10H-anthracene-9,10-diyl) pyrene (1)

A mixture of tetrabromopyrene ¹ ( ¹ Venkataramana, G .; Sankararaman, S. Eur. J. Org. Chem. 2005, 4162.) (1 g, 1.93 mmol), anthracene (1.78 g, 9.66 mmol) and potassium tert-butylate (1.34 g, 12 mmol) are suspended in 60 ml of dry freshly distilled toluene and the resulting mixture is stirred at 140 ° C for 15 hours. The precipitate formed is filtered off, the filtrate is evaporated under reduced pressure. The residue was recrystallized from toluene, washed with methanol, and dried in air.

1,2,6,7-bis- (9H, 10H-anthracene-9,10-diyl) pyrene ("bisipticenopyrene"). Mp> 250 ° C; Yield 0.43 g (0.77 mmol, 40%). ¹ H NMR (CDCl ₃ ): 5.78 (s, 2H, HC (sp ³ )), 6.38 (s, 2H, HC (sp ³ )), 6.99 (m, 8H, anthranyl), 7.50 (m, 4H, anthranyl ), 7.95 (d, 2H, ³ J 9.2 Hz, pyrene), 8.12 (s, 2H, pyrene), 8.46 (d, 2H, ³ J 9.2 Hz, pyrene). ¹³ C NMR (CDCl ₃ ): 49.88, 54.97, 120.17, 121.44, 121.13, 123.77, 123.93, 125.20, 125.28, 125.87, 127.54, 128.13, 139.02, 142.37, 145.38, 146.28. EI-MS (m / z): 554 (100). Calculated for C ₄₄ H ₂₆ * H ₂ O,%: C 92.28, H 4.93. Found,%: C 92.11, H 4.87.

The claimed compound is a colorless crystalline substance, soluble in nitrobenzene, benzene, chloroform, insoluble in methanol and water.

4.2. Visual detection of aromatic compounds using the claimed compounds (1-2)

Example 1

The interaction of 1 with nitroaromatic compounds was studied 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

I ^o / I = 1 + K _sv * [Q],

where I ^o , I is the 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)^-1 The values of the fluorescence quenching constants of the claimed compound 1 and the prototype compound (pyrene) in a linear approximation,

(mol / l) ^-1

, M ^-1 1

, M ^-1 pyrene 2,4-DNT 14.3210 ³ 0.9310 ³

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

The proposed synthesis method is unique in the series of pyrene.

Claims (1)

Method for the synthesis of 1,2,6,7-bis- (9H, 10H-anthracene-9,10-diyl) pyrene of a 1-monomolecular optical sensor for detecting nitroaromatic compounds by reacting an in situ generated aromatic derivative of pyrene with anthracene in an argon atmosphere