Zinc mezo-triphenyltetra-[-4-(п-triphenylmethylphenoxybenzo)] monoazaporphyrinate

FIELD: chemistry.

SUBSTANCE: invention concerns novel compound of zinc mezzo-triphenyltetra-[-(п-triphenylmethylphenoxybenzo)]monoazaporphyrinate.

EFFECT: possible application as fat-soluble green colourant for polymers, as material for thin film microelectronics, as catalyst, and in other scientific and technical fields.

1 cl, 1 ex, 1 dwg


The invention relates to the chemical industry, namely to the new connection - meso-triphenylmethane-[4-(p-triphenylselenonium)]monoisopropylamine zinc, which can be used as a fat-soluble green dye for dyeing plastics, material for thin-film microelectronics, catalysts, as well as in other areas of science and technology.

The level of technology

Known copper complex tetrabenzoporphyrin, a structural analogue [Dent S.E. // J. Am. Chem. Soc. 1938. Part. I. P.1-6].

It is insoluble in nonpolar organic solvents and cannot be used as a fat-soluble dye.

The closest structural analogue of the claimed compound is a zinc complex of meso-triphenyltetrazolium [Galanin N.E., Kudrik E.V., Shaposhnikov G.P. // Joh. 2005. T. No. 4. S-693].

However, this connection cannot be used as a fat-soluble dye due to limited solubility in nonpolar organic solvents.

The invention

Inventive task was to search for new compounds, which are derivatives of the zinc complex of meso-triphenyltetrazolium, which would have increased dissolve the awn in nonpolar organic solvents, that would give the opportunity to use it as a fat-soluble dye green.

The problem is solved meso-triphenylmethane-[4-(p-triphenylselenonium)]monoisopropylamine zinc formula

The structure of this compound proved by data of elemental analysis, electronic, and vibrational spectroscopy, and mass spectrometry.

So, in the electronic absorption spectrum of the inventive meso-triphenylmethane-[4-(p-triphenylselenonium)]monoisopropylamine zinc (see the drawing) in the visible region has a band Sora with a maximum at 470 nm and split into two components close to the intensity of the Q - band with maxima at 645 and 679 nm.

In the IR spectra of the proposed complex has absorption bands characteristic of porphyrin compounds, in particular of the group of bands in the region 1640-1450 cm-1belonging to the stretching vibrations of ties With the-C and C-N. in Addition, it is possible to allocate the absorption bands related to the stretching vibrations of links C-H aromatic fragments (2968 cm-1), relations With-O (1248-1222 cm-1).

The intense band at 696-702 cm-1can be attributed to the deformation vibrations of monosubstituted benzene rings triphenylmethyl group.

In the mass spectrum (MALDI - TOF) of the claimed compounds marked signal of the molecular ion with m/z 2138.

Information confirming the possibility of carrying out the invention

To implement the method using the following ingredients:

benzene - GOST 5955-75;

carbon tetrachloride - TU 2631-027-44493179-98;

aluminium chloride anhydrous - OST 6-01-300-74;

concentrated sulphuric acid - GOST 4204-77;

4-nitrophthalonitrile imported;

phenylacetic acid - TU 6-09-04-240-83;

zinc acetate dehydrate - GOST 5823-78.

Method implemented in five stages:

Stage 1. Getting triphenylmethanol, according to the scheme:

In a mixture of 100 g of benzene and 20 g of carbon tetrachloride at room temperature in portions of 5 g for one hour add 20 g of anhydrous aluminum chloride, heated to boiling and incubated for another 6 h, then add 100 ml of 10% hydrochloric acid and stirred at the boil for 1 hour the Organic layer is separated and distilled from it is not included in the reaction of benzene and carbon tetrachloride, the residue is recrystallized from hexane.

The resulting triphenylmethanol.

A yield of 20 g (58%). Found, %: C 87.22; H 5.88; N, 6.02. With19H16O. Calculated, %: C 87.66; N, 6.19; 6.15.

Stage 2. Getting 4-triphenylmethanol, according to the scheme:

A mixture of 16 g of triphenylmethanol and 7 g of phenol dissolved in 30 ml of acetic acid, add 3 ml of concentrated sulfuric acid, heated and maintained at the boiling temperature of 10 o'clock Rea the traditional mass is then cooled, diluted with 100 ml of water, precipitated precipitate is filtered and washed successively with 100 ml of 10%sodium hydroxide solution, 200 ml of water, 10 ml of acetone and dried.

The obtained 4-triphenylmethanol.

Yield 11.6 g (56%). Found, %: C 89.88; N, 6.15. With25H20O. Calculated, %: C 89.25; N, 5.99.

Stage 3. Getting 4-(p-triphenylethylene)phthalodinitrile, according to the scheme:

A mixture of 2.6 g (0.015 mol) of 4-nitrophthalonitrile, 6.9 g of 4-triphenylmethanol, 3.0 g

To2CO3and 50 ml of DMF is stirred for 10 h at 110°C, cooled and poured into 300 ml of water. The precipitate is filtered off, washed with water, dried in air at 80°C and chromatographic aluminum oxide II degree of activity (eluent benzene).

The obtained 4-(p-triphenylethylene)phthalodinitrile.

Yield 4.8 g (69%), powder of light yellow color, TPL 216 -218°C. Rf0.59 (chloroform, Silufol). The IR spectrum v cm-1: 2928, 2232 (C≡N), 1595 (C=C), 1489, 1386, 1223, 1211, 953, 748. Mass spectrum (of the Belarusian library Association), m/z: 462.1 [M]+, 385.1 [M-C6H5]+, 307.2 [M-2C6H5]+. Found, %: C 86.22; N, 5.05; N, 5.88. C33H22N2O. Calculated, %: C 85.68; N, 4.80; N, 6.06.

Stage 4. Getting 4-(p-triphenylethylene)-1,3-diaminoethane scheme:

In 50 ml of ethanol was dissolved 0.5 g of sodium and add 4.0 g of 4-(p-triphenylethylene)phthalodinitrile. The suspension is stirred the 2 h at 20°C, then heated to 60°C. and passed through a solution of dry ammonia for 3 h, then cooled to 10°C. the precipitation is filtered off, washed with 20 ml of acetone and dried.

The obtained 4-(p-triphenylethylene)-1,3-diminishingly.

Yield 2.3 g (55.5%). The IR spectrum v cm-1: 3410 (N-H), 3087, 3055 (C-H), 3028, 1592 (C=C), 1487, 1280, 1250, 1213 (C-O), 1174 (C-O), 834, 750, 702. Mass spectrum (ES)m/z: 476 [M-3]+, 430 [M-NSN-5]+, 283 [M-HCN-NH-2C6H5]+. Found, %: C 83.01; N, 5.10; N, 8.22. With33H25N3O. Calculated, %: C 82.65; N, 5.25; N, 8.71.

Stage 5. Getting meso-triphenylmethane-[4-(p-triphenylselenonium)]monoisopropylamine zinc, according to the scheme:

A mixture of 2.0 g of 4-(p-triphenylethylene)-1,3-diaminoethane, 6.0 g of phenylacetic acid and 1.0 g of zinc oxide are heated for 40 min at 290°C. the Melt is cooled, crushed, boiled for 5 min in 100 ml of 10%KOH solution, filtered off, washed with 100 ml of water and dried. The residue is dissolved in toluene and chromatographic on a column filled with alumina II degree of activity (eluent is a mixture of toluene-acetone, 50:1 by volume), collecting the first green zone.

Received meso-triphenylmethane-[4-(p-triphenylselenonium)]moneysupermarket zinc.

Yield 0.24 g (11%), powder dark green color, soluble in toluene, chloroform, sparingly soluble in acetone. Rf0.84 (olwal, Silufol). Electronic absorption spectrum (toluene), λmaxnm (D/Dmax):679 (0.17), 645 (0.19), 470 (1.00). Mass spectrum (MALDI-TOF), m/z (IRel(%)): 2138 [M]+(100). Found, %: C 86.02; N, 4.99; N, 2.87. C153H103N5O4Zn. Calculated, %: C 85.84; N, 4.85; N, 3.27.

Example 1. The use of meso-triphenylmethane-[4-(p-triphenylselenonium)]monoisopropylamine zinc for dyeing polystyrene. Dyeing is carried out as follows: 2 g of granulated polystyrene dissolved in 5 ml of benzene, add 5 mg of meso-triphenylmethane-[4-(p-triphenylselenonium)]monoisopropylamine zinc, stirred and maintained at 150°C until complete removal of benzene (10 min).

Meso-Triphenylmethane-[4-(p-triphenylselenonium)]moneysupermarket zinc formula


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