RU2266286C1 - Heterocyclic ortho-dicarbonitriles - Google Patents

Abstract

FIELD: organic chemistry, technology of organic compounds.

SUBSTANCE: invention relates to heterocyclic o-dicarbonitriles. Invention describes heterocyclic o-dicarbonitriles of the general formula:

wherein R1 means the following substances:

wherein R2 means the following substances:

. Heterocyclic o-dicarbonitriles can be used for preparing hexazocyclanes-fluorophores as a donor-fragment used for preparing hexazocyclanes-bifluorophores and hexazocyclanes-trifluorophores. Invention provides preparing new compounds possessing useful properties.

EFFECT: valuable properties of compounds.

4 tbl, 4 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 in conjunction with unsubstituted rhodamine to produce hexazocyclan. (Silling S.A., Feofanov B.N., Barashkov N.N. et al. Polyhexazocyclanes based on heterocyclic diamines. // High Molecule. Comp. B. 1988, Vol. 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 with the general formulas are claimed

The claimed compounds include:

11-oxo-10-phenyl-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1a):

10- (2-methylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1b):

10- (2,4-dimethylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1c):

10- (4-methylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1d):

10- (3-chloro-4-methylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1e):

10- (3,4-dimethylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1f):

10- (4-ethylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1g):

10-benzyl-11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1h):

11-oxo-10-phenyl-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2a):

10- (4-methylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2b):

10- (2-methyl-3-chlorophenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2c):

10- (3-chlorophenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2d):

10- (3,4-methylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2e):

10- (4-ethylphenyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2f):

10-benzyl-11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2g):

10- (2-furylmethyl) -11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2h):

10-cyclopentyl-11-oxo-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2i):

The oxazepindicarbonitriles represented by Scheme 1 are obtained by the reaction of sequential aromatic nucleophilic substitution of a bromine atom and nitro group in 4-bromo-5-nitrophthalonitrile with the corresponding bifunctional nucleophiles formed in situ from salicylic acid amides in the presence of potassium carbonate according to scheme 3:

The thiazepindicarbonitriles represented by Scheme 2 are prepared by the intramolecular denitrocyclization reaction in the corresponding 2 - [(4,5-dicyano-2-nitrophenyl) sulfanyl] benzamides in the presence of potassium carbonate according to Scheme 4:

The reaction was carried out in dimethylformamide medium for 2 hours at a temperature of 90 ° C.

The invention is illustrated by the following examples:

Example 1. To 30 ml of DMF, 2.13 g (0.01 mol) of salicylanilide, 2.8 g (0.02 mol) of anhydrous K ₂ CO ₃ and 2.5 g (0.01 mol) of 4-bromo-5-nitrophthalonitrile were successively added to 30 ml of stirring. The resulting mixture was intensively stirred at 20 ° C for 0.5 h, then the temperature was raised to 90 ° C and stirred for another 1.5 h. After cooling to room temperature, the reaction mass was poured into 100 ml of water, the precipitate formed was filtered off and washed with 50 ml of water and isopropyl alcohol dimethylformamide is recrystallized from a mixture.

2.02 g (60% of theory) of 11-oxo-10-phenyl-10,11-dihydrodibenzo [b, ƒ] [1,4] oxazepine-7,8-dicarbonitrile (1a) are obtained. This is a yellow crystalline powder, mp. 210-212 ° C.

Found,% C 74.57; H 3.29; N 12.50

Calculated,% C: 74.79; H: 3.29; N: 12.46 C ₂₁ H ₁₁ N ₃ O ₂

¹ H NMR (DMSO d6) δ, ppm: 8.43 (s, 1H), 7.85 (d, 1H, J = 7.8), 7.72 (t, 1H), 7.57 (t, 2H), 7.45 (m, 5H), 7.35 (s, 1H).

Oxazepindicarbonitriles 1b-h were prepared analogously to 1a except that the corresponding substituted salicylanilides were used as reagents. The conditions and results of the synthesis are presented in table 1.

Example 2. To 30 ml of DMF, 2.00 g (0.005 mol) of 2 - [(4,5-dicyano-2-nitrophenyl) sulfanyl] benzanilide and 0.69 g (0.005 mol) of anhydrous K ₂ CO ₃ are successively added with stirring. The reaction is carried out at 90 ° C for 2 hours. After cooling to room temperature, the reaction mass is poured into 100 ml of water, the precipitate formed is filtered off and washed with 50 ml of water.

Obtain 1.21 g (68.6% of theory) of 11-oxo-10-phenyl-10,11-dihydrodibenzo [b, ƒ] [1,4] thiazepine-7,8-dicarbonitrile (2a). It is a beige crystalline powder.

Thiazepindicarbonitriles 2b-i were prepared analogously to 2a using substituted 2 - [(4,5-dicyano-2-nitrophenyl) sulfanyl] benzanilides. The conditions and results of the synthesis are presented in table.2.

Example 3. Condensation 1a with rhodamine 123. 3.37 g (0.01 mol) of 1a, 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 O ₅ . 12.4 g (93% of theory) of hexazocyclan are obtained.

Found,% C 75.44; H 0.83; N, 8.38

Calculated,% C 75.67; H 0.83; N, 8.40: (C ₈₄ H ₅₂ N ₈ O ₁₀ )

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 1a and rhodamine 123:

The macroheterocycle obtained on the basis of 1a and rhodamine 123 has the following spectral characteristics: maximums of the emission spectrum — 431, 539, 620, 758 nm, and maximums of the absorption spectrum — 209, 350, 455, 515 nm.

Macroheterocycles based on phthalonitriles 1b-h are obtained analogously to the example, except that instead of phthalonitrile 1a, equimolar amounts of phthalonitriles 1b-h are used.

The conditions and results of the synthesis, as well as the spectral characteristics of the obtained macroheterocycles, are given in Table 3.

Example 4. Condensation 2a with rhodamine 123. 3.53 g (0.01 mol) of 2a, 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 O ₅ . 12.28 g (90% of theory) of hexazocyclan are obtained.

Found,% C 73.66; H 3.84; N, 8.24; S, 4.71

Calculated,% C 73.89; H 3.84; N, 8.24 S 4.70: (C ₈₄ H ₅₂ N ₈ O ₈ 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 2a and rhodamine 123:

The macroheterocycle obtained on the basis of 2a and rhodamine 123 has the following spectral characteristics: maximums of the emission spectrum — 437, 535, 630, 750 nm, with maximums of the absorption spectrum — 199, 338, 455, 525 nm.

Phthalonitrile 2b-i-based macroheterocycles are prepared analogously to the example, except that instead of phthalonitrile 2a, equimolar amounts of phthalonitrile 1b-i are used.

The conditions and results of the synthesis, as well as the spectral characteristics of the obtained macroheterocycles, are given in Table 4.

Claims (1)

Heterocyclic o-dicarbonitriles with general formulas: