RU2238276C1 - Heterocyclic ortho-dicarbonitriles - Google Patents

Abstract

FIELD: chemistry of heterocyclic compounds.

SUBSTANCE: invention relates to preparing new heterocyclic o-dicarbonitriles of the general formula:

wherein Ph means

.

Ortho-dicarbonitriles can be used for preparing hexazocyclanes-fluorophores, as a donor-fragment for preparing hexazocyclanes-bifluorophores and hexazocyclanes-trifluorophores that are used as active media for liquid and solid lasers, scintillators, for transformation of short-wave radiation to long-wave radiation, in the information transfer by fiber-optics communication lines, for enhancing solar batteries power, for securities protection, for making billboards and so on.

EFFECT: valuable properties of compounds.

2 tbl, 6 ex

Description

The invention relates to the field of producing new heterocyclic o-dicarbonitriles. o-Dicarbonitriles can be used to produce hexazocyclanes-fluorophores, as a donor fragment for producing hexazocyclanes-bifluorophores and hexazocyclanes-trifluorophores. Such hexazocyclanes are promising for use as active media in liquid and solid lasers, scintillators, especially for indicating hard radiation, for transforming short-wave radiation into long-wave radiation when transmitting information via fiber-optic communication lines, to increase the power of solar panels, to protect securities, for making billboards, etc.

It is known to use phthalonitrile together with unsubstituted rhodamine to produce hexazocyclan (Seeling S.A., Feofanov B.N., Barashkov N.N. et al. Polyhexazocyclanes based on heterocyclic diamines. // Vysokomolek. Soed. B., 1988. T. 30, No. 4, p. 286-291).

This hexazocyclan has the following spectral characteristics: a 540 nm emission band when excited to a 312 nm band.

The problem solved by the present invention is to obtain new heterocyclic o-dicarbonitriles.

Heterocyclic o-dicarbonitriles of the general formula

Where

The claimed compounds include

3-phenyl [1,2,4] triazolo [3,4, -b] [1,3] benzothiazole-6,7-dicarbonyl (I):

3- [3,5-di (tert-butyl) phenyl] [1,2,4] triazolo [3,4-b] [1,3] benzothiazole-6,7-dicarbonitrile (II):

3- (4-bromophenyl) [1,2,4] triazolo [3,4-b] [1,3] benzothiazole-6,7-dicarbonitrile (III):

These compounds are prepared by aromatic nucleophilic substitution of a bromine atom and a nitro group in 4-bromo-5-nitrophthalonitrile with the corresponding bifunctional nucleophile formed in situ from 5-aryl-4H-1,2,4-triazole-3-thiols in the presence of potassium carbonate scheme:

This reaction is carried out in DMF in the presence of potassium carbonate at a temperature of 130 ... 140 ° C for 2 hours.

The invention is illustrated by the following examples.

Example 1. To 20 ml of DMF, 2.52 g (0.01 mol) of BNFN and 1.77 g (0.01 mol) of 5-phenyl-4H-1,2,4-triazole-3-thiol were added with stirring. After the reagents were dissolved, 4.14 g (0.03 mol) of K ₂ CO _{3 was} added to the reaction mixture at 130 ° C with vigorous stirring. The resulting mixture was stirred for 120 minutes. Next, the reaction mass was poured into 50 ml of water. The precipitate was filtered off, washed with 50 ml of water and recrystallized from a mixture of 2-propanol with DMF.

2.25 g (75% of theory) of 3-phenyl [1,2,4] triazolo [3,4-b] [1,3] benzothiazole-6,7-dicarbo-nitrile (I) are obtained. It is a yellow crystalline powder, mp> 300 ° C.

Found,%: C 63.59; H 2.33; N, 23.30; S 10.66.

Calculated,%: C 63.78; H 2.34; N, 23.34; S 10.64.

C ₁₆ H ₇ N ₅ S

1 H NMR ([2H6] DMSO): δ, ppm: 9.00 (s, 2H), 8.65 (s, 1H), 8.10 (d, 2H, J = 8), 7.60 (m, 3H).

Example 2-3. The reaction is carried out analogously to example 1, except that 5- [3,5-di (tert-butyl) phenyl] -4H-1, respectively, are used as the reagent 5-phenyl-4H-1,2,4-triazole-3-thiol , 2,4-triazole-3-thiol and 5- (4-bromophenyl) -4H-1,2,4-triazole-3-thiol. The conditions and results of the synthesis are presented in table. 1.

Example 4. Condensation of I with rhodamine 123. 3.01 g (0.01 mol) of I, 3.8 g (0.01 mol) of rhodamine 123 and 10 g of phenol are charged into a flask equipped with a stirrer, thermometer, reflux condenser and capillary for introducing argon. The resulting mixture is slowly heated with stirring to 175 ... 185 ° C. The resulting melt is kept under stirring in a stream of argon until the evolution of ammonia ceases. After completion of the reaction, the reaction mixture was poured into 20 ml of ethanol, the precipitated precipitate was filtered off, washed with 3 ml of ethanol and dried at T = 60 ° C for 2 hours, then in vacuum over P ₂ 0 ₅ . 5.99 g (95% of theory) of hexazocyclan are obtained.

Found,%: C 70.25; H 3.52; N 13.30; S 5.09.

Calculated,%: C 70.46; H 3.52; N 13.33; S 5.08.

(C ₇₄ H ₄₄ N ₁₂ S ₂ )

In the IR spectrum of hexazocyclan there is no band 2220 cm ^-1 - C = N, there is a band 680 cm ^-1 - C = N-.

The structural formula of hexazocyclan obtained on the basis of I and rhodamine 123

The macroheterocycle obtained on the basis of I and rhodamine 123 has the following spectral characteristics: the maximums of the emission spectrum are 526, 567, 610 nm and the maximums of the absorption spectrum are 340, 465, 534 nm.

Example 5-6. The reaction is carried out analogously to example 4, except that instead of phthalonitrile I, equimolar amounts of phthalonitriles II-III are used.

The conditions and results of the synthesis, as well as the spectral characteristics of the obtained macroheterocycles, are given in Table 2.

Claims (1)

Heterocyclic o-dicarbonitriles of the general formula

where ph is