RU2708399C1 - 4,4'-(((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(oxy))diphtalonitrile - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemical industry, namely, to 4,4'-(((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(oxy))diphthalonitrile of the formula given below, which can be used as a starting compound for synthesis of octacyanosubstituted phthalocyanine and its metal complexes, as well as polyphthalocyanine structures exhibiting electrochemical, electrocatalytic and sensory properties.

EFFECT: disclosed is 4,4'-(((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(oxy))diphtalonitrile.

1 cl, 3 dwg, 2 ex

Description

The invention relates to the chemical industry, in particular, to the production of a phthalonitrile derivative, specifically, 4.4 '- (((1,4-phenylenebis (hydroxy)) bis (4,1-phenylene)) bis (hydroxy)) diphthalonitrile the starting compound for the synthesis of octacyanubstituted phthalocyanine and its metal complexes, polyphthalocyanine or specific, closed in one or more positions by cyano groups of various "decks", structures exhibiting valuable electrochemical, electrocatalytic, semiconductor and sensory properties.

Salan, A. Altindal, A. R.

В. Salihc,

// DaltonTrans., 2012, 41, p. 5177-5187], формулы:Known 4,4 '- ((methylenebis (2-oxo-2H-chromene-3,4-diyl)) bis (hydroxy)) diphthalonitrile [

Salan, A. Altindal, AR

B. Salihc,

// DaltonTrans., 2012, 41, p. 5177-5187], the formula:

The main disadvantage of this compound is the need to use 3,3'-methylenebis (4-hydroxy-2H-chromen-2-one) at a cost of 11221.78 euros per 10 grams [https: //www.sigmaaldrich.com/catalog/product / aldrich / r782262? lang = en & region = RU].

, B. Salih,

Bekaroglu // SyntheticMetals. 2010. 160. p. 967-977], формулы:4.4 '- ((7a, 14c-dihydronaphtho [2,1-b] naphtho [1', 2 ': 4,5] furo [3,2-d] furan-2,13-diyl) is also known bis (hydroxy)) diphthalonitrile [Z Odabas, I. Koc, A. Altindal, AR

, B. Salih,

Bekaroglu // SyntheticMetals. 2010.160.p. 967-977], the formula:

The main disadvantage of this compound is the need to use 1a, 8b-dihydronaphtho [b] naphthofuro [3,2-d] furan-7,10-diol, which is not commercially available, in its preparation.

, A. Altindal, В. Salih,

Bekaroglu // InorganicaChimicaActa. 2015. 428. P. 83-92], формулы:The closest structural analogue of the claimed compounds found in the literature is 4,4 - ((((1Z, 1'Z) - (1,2-phenylenebis (azanylylidene)) bis (2,1-phenylene)) bis (oxy)) diphthalonitrile [A. Yazici, B.

, A. Altindal, B. Salih,

Bekaroglu // InorganicaChimicaActa. 2015. 428. P. 83-92], the formula:

The main disadvantage of the prototype is the need to use in the process of its production of toxic, irritating skin, eyes and respiratory tract N, N'-bis (salicylidene) -1,2-phenylenediamine, worth $ 86 per 5 grams [https: //www.chemicalbook .com / ChemicalProductProperty_EN_CB1699076.htm].

An inventive task is to obtain a phthalonitrile derivative containing 4 terminal cyano groups, which is of interest as a starting compound for the synthesis of octacyano-substituted phthalocyanine and its metal complexes, polyphthalocyanine or specific, closed in one or more positions on cyano groups of various "decks", structures using a simpler , a cheap and affordable synthetic precursor.

The specified result is achieved 4.4 '- (((1,4-phenylenebis (hydroxy)) bis (4,1-phenylene)) bis (hydroxy)) diphthalonitrile of the formula:

The structure of this compound is proved by the data of elemental analysis, IR and ¹ H NMR spectroscopy, MALDI-TOF spectrometry.

So, in the IR spectra of the claimed compounds there are bands characteristic of the stretching vibrations of the corresponding functional groups: C (Ar) -H (3075, 2922, 2846), 2233 (C≡N), C (Ar) -C (Ar) ( 1584, 1514, 1484), 1214 (Ar-O-Ar). [Dyer J. R. Application of absorption spectroscopy of organic compounds / Per. from English Ivanova V.T. M: Chemistry. 1970.16 s]. A signal of the target molecular ion with m / z = 569.80 was detected in the mass spectrum of the synthesized 4,4 '- (((1,4-phenylenebis (oxy)) bis (4,1-phenylene)) bis (oxy)) diphthalonitrile.

EFFECT: invention enables to obtain a phthalonitrile derivative containing 4 terminal cyano groups, which is of interest as a starting compound for the synthesis of octacyanosubstituted phthalocyanine and its metal complexes, polyphthalocyanine or specific, closed in one or several positions on cyano groups of various "decks", structures using simpler , cheap and affordable synthetic precursors, which is hydroquinone costing 630 rubles per kilogram, despite the fact that the cost of N, N'-bis (sa lycylidene) -1,2-phenylenediamine in the prototype is $ 86 per 5 grams.

Brief Description of the Drawings:

In FIG. 1 depicts the MALDI-TOF mass spectrum 4.4 '- (((1,4-phenylenebis (hydroxy)) bis (4,1-phenylene)) bis (hydroxy)) diphthalonitrile; in FIG. 2 - ¹ H NMR spectrum 4,4 '- (((1,4-phenylenebis (hydroxy)) bis (4,1-phenylene)) bis (hydroxy)) diphthalonitrile; in FIG. 3 - IR spectrum of 4,4 '- (((1,4-phenylenebis (hydroxy)) bis (4,1-phenylene)) bis (hydroxy)) diphthalonitrile.

For the synthesis of the claimed compounds use the following substances:

- 4-nitrophthalonitrile - Sigma Aldrich CAS Number 31643-49-9;

- 4-nitrophenol - Sigma Aldrich CAS Number 100-02-7;

- potassium carbonate - GOST 10690-73;

- hydroquinone - GOST 19627-74.

The synthesis was carried out in the following way:

Example 1. Synthesis of 4- (4-nitrophenoxy) phthalonitrile.

1.73 g (0.01 mol) of 4-nitrophthalonitrile, 1.39 g (0.01 mol) of 4-nitrophenol and 30 ml of DMF were charged into a flask equipped with a stirrer, reflux condenser and thermometer. After dissolving the reagents with vigorous stirring, a solution of 1.56 g (0.01 mol) of K ₂ CO ₃ in 10 cm ^{3 of} water was added to the reaction mixture. The reaction mass was stirred at 70-75 ° C for 1-1.5 hours and cooled to 5-10 ° C. The precipitate was filtered off, washed with 50 ml of 2-propanol, water (3 × 50 ml) and dried at 70 ° C.

Yield: 2.23 g (84%).

Found: C, 63.24; H, 2.62; N, 15.80% (C ₁₄ H ₇ N ₃ O ₃ );

Calculated: C, 63.40; H, 2.66; N, 15.84.

Example 2. Synthesis of 4.4 '- (((1,4-phenylenebis (hydroxy)) bis (4,1-phenylene)) bis (hydroxy)) diphthalonitrile.

Into a three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux condenser were placed 0.10 g (0.01 mol) of hydroquinone, 0.53 g (0.02 mol) of 4- (4-nitrophenoxy) phthalonitrile and 50 ml of DMF. The solution was stirred until completely dissolved, after which 0.35 g (0.025 mol) of potassium carbonate was added in portions. The reaction mixture was stirred for 72 hours at room temperature, after which the reaction mixture was poured into 150 ml of 0.1 M aqueous NaOH solution cooled to 5 ° C. The precipitate was filtered off, washed with a 10% alkali solution, and water to neutral pH values. Then, the resulting material was recrystallized from ethanol. Yield: 0.11 g (20%).

¹ H NMR (500 MHz, CDCl ₃ ): δ 7.79 (d, J = 6.4 Hz, 2H, H (4)), 7.31 (d, J = 2.1 Hz, 2H, H (3)), 7.11 (dd, J = 6.5.2.1 Hz, 2H, H (2)), 6.95-6.92 (m, 12H, H (1)).

IR spectrum: C (Ar) -H (3075, 2922, 2846), 2233 (C≡N), C (Ar) -C (Ar) (1584, 1514, 1484), 1214 (Ar-O-Ar).

Claims (2)

4,4 '- (((1,4-Phenylenebis (hydroxy)) bis (4,1-phenylene)) bis (hydroxy)) diphthalonitrile of the formula:

.

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