RU2659224C1 - Tetra-4-[4-(2,4,5-trichloro-3,6-disulfophenoxy)]phthalocyanines of copper and cobalt - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to tetra-4-[4-(2,4,5-trichloro-3,6-disulfophenoxy)]phthalocyanines of copper and cobalt of general formula:

.

EFFECT: said compounds are water-soluble, and a copper compound has a color strength with respect to wool fibers and cotton, cobalt compound exhibits catalytic activity in the homogeneous liquid-phase oxidation of sulfur-containing organic compounds.

1 cl, 6 dwg, 8 ex

Description

The invention relates to the chemical industry, in particular to the production of new derivatives of phthalocyanine, specifically metal complexes of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanines with copper, which have a coloring ability with respect to wool fibers and cotton, and with cobalt, exhibiting catalytic activity in the reaction of homogeneous liquid-phase oxidation of sulfur-containing organic compounds.

Known tetra-3- (2,4-dichlorophenoxy) phthalocyanine palladium [Hai-Tao Xu, Wen-Wei Xie, Yan-Chuan Guo, Ying Ci, Li-Juan Chen, Bi-Xian Peng. The Synthesis of Tetra-α-phenoxyphthalocyanines and Research of their Physical and Chemical Properties, Journal of the Chinese Chemical Society. 2007, V. 54, pp. 211-217].

However, in the literature there is no information about the manifestation of tetra-3- (2,4-dichlorophenoxy) phthalocyanine palladium dyeing ability with respect to wool fibers, cotton and catalytic activity in the reaction of homogeneous liquid-phase oxidation of sulfur-containing organic compounds.

The inventive task was to search for new compounds that have a coloring ability with respect to wool fibers, cotton and exhibiting catalytic activity in the reaction of homogeneous liquid-phase oxidation of sulfur-containing organic compounds.

The problem is solved by the synthesis of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanines of copper and cobalt of the general formula:

The structure of this compound is proven by elemental analysis, IR, ¹ H NMR and electron spectroscopy.

So, in the IR spectrum of the claimed compounds there are bands characteristic of the stretching vibrations of the corresponding functional groups: 742-750 cm ^-1 (C-Cl), 1042-1052 and 1123-1167 cm ^-1 (S = O), 1069-1082 cm ^-1 (С-S), 1240-1249 (Ar-O-Ar) [Dyer J.R. Application of absorption spectroscopy of organic compounds / Per. from English Ivanova V.T. M .: Chemistry. 1970.16 s.].

Brief Description of the Drawings

In FIG. 1 shows the IR spectrum of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanine copper; in FIG. 2 - ESP tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanine copper in DMF; in FIG. 3 - IR spectrum of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] cobalt phthalocyanine; in FIG. 4 - ESP IR spectrum of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] cobalt phthalocyanine in DMF; in FIG. 5 is a wool sample stained with tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] copper phthalocyanine obtained in Example 6; FIG. 6 is a cotton sample dyed with the ammonium salt of tetra-4- [4- (2,4,5-trichloro) -3,6-disulfophenoxy)] copper phthalocyanine obtained according to Example 7.

The invention allows to obtain the following advantages

Water-soluble metal complexes of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanines with copper, dyeing with respect to wool fibers and cotton, and with cobalt, exhibiting catalytic activity in a homogeneous reaction liquid-phase oxidation of sulfur-containing organic compounds. For the synthesis of the claimed compounds use the following substances:

- cobalt acetate - GOST 5861-79;

- copper acetate - GOST 5852-79;

- oleum 26% - GOST 2184-2013;

- aqueous ammonia - GOST 3760-79;

- 4- (2,4,5-trichlorophenoxy) phthalonitrile, however, since this compound is new and not commercially available, it was obtained in the following way: from 4-nitrophthalodinitrile [31643-49-9 ACROS ORGANICS (China)] by nucleophilic substitution nitro groups on a 2,4,5-trichlorophenoxy group, synthesize the target phthalonitrile.

The synthesis was carried out as follows.

Synthesis of 4- (2,4,5-trichlorophenoxy) phthalonitrile

1.73 g (0.01 mol) of 4-nitrophthalonitrile and 1.97 g (0.01 mol) of 2,4,5-trichlorophenol are dissolved in 30 ml of DMF, a solution of 2.76 g (0.02 mol) of K ₂ CO ₃ in 5 ml of water is added to the solution and stirred at 100 ° C for 3 hours. The resulting precipitate is filtered off, washed with water to pH = 7 and dried in air at 70-80 ° C.

Yield: 2.43 g (75%).

Found,%: C - 51.15, H - 2.00, N - 8.74; C ₁₄ H ₅ Cl ₃ N ₂ O.

Calculated: C - 51.97, H - 1.56, N - 8.66.

Mass spectrum, m / z = 362 [M + K] ⁺ , calculated - 323.

IR spectrum, cm ^-1 : 2231 (C≡N), 1250 (Ar-O-Ar), 772 (C-Cl).

¹ H NMR spectrum, δ, ppm: 7.80 d (1H; H3), 7.69 s (1H; H1), 7.33 s (1H; H2), 7.28 m (1H; H4), 7.24-7.22 m (1H ; H5).

The inventive compound can be obtained as follows.

Example 1. Synthesis of tetra-4- [4- (2,4,5-trichlorophenoxy)] copper phthalocyanine

A thoroughly ground mixture of 0.32 g (1 mmol) of 4- (2,4,5-trichlorophenoxy) phthalonitrile and 0.036 g (0.17 mol) (CH ₃ COO) ₂ Cu⋅2H ₂ O is heated at 190 ° С for 10 hours. At the end of the process, the reaction mass is cooled, triturated in a mortar and dissolved in concentrated sulfuric acid. The resulting solution was poured onto ice, the precipitate formed was filtered off and washed with water to pH 7, and dried in air at 70 ° C. The target product is extracted with chloroform and subjected to column chromatography on silica gel M60, eluting with chloroform. A dark green solid is obtained, insoluble in water, highly soluble in chloroform and DMF.

Yield: 0.29 g (85%).

Found,%: C - 49.10, H - 1.74 N - 8.12; C ₅₆ H ₂₀ Cl ₁₂ C ₁₁ N ₈ O ₄ .

Calculated: C - 49.54, H - 1.48, N - 8.25.

Mass spectrum, m / z = 1358 [M + H] ⁺ , 1374 [M + Na] ⁺ , calculated - 1357

IR spectrum, (KBr) / cm ^-1 : 752 (C-Cl), 1249 (Ar-O-Ar).

ESP in DMF, λ _max , nm, 676; ESP in chloroform, λ _max , nm, 620, 678.

Example 2. Synthesis of tetra-4- [4- (2,4,5-trichlorophenoxy)] cobalt phthalocyanine

A thoroughly ground mixture of 0.32 g (1 mmol) of 4- (2,4,5-trichlorophenoxy) phthalonitrile and 0.033 g (0.17 mol) (CH ₃ COC) ₂ Co⋅2H ₂ O is heated at 190 ° С for 10 hours. At the end of the process, the reaction mass is cooled, triturated in a mortar and dissolved in concentrated sulfuric acid. The resulting solution was poured onto ice, the precipitate formed was filtered off and washed with water to pH 7, and dried in air at 70 ° C. The target product is extracted with chloroform and subjected to column chromatography on silica gel M60, eluting with chloroform. A dark green solid is obtained, insoluble in water, highly soluble in chloroform and DMF.

Yield: 0.26 g (78%).

Found,%: C - 49.41, H - 1.75, N - 8.02; C ₅₆ H ₂₀ Cl ₁₂ CoN ₈ O ₄ .

Calculated: C - 49.71, H - 1.49, N - 8.28.

Mass spectrum, m / z = 1352 [M] ⁺ , calculated - 1353.

IR spectrum, (KBr) / cm ^-1 : 755 (C-Cl), 1249 (Ar-O-Ar).

ESP in DMF, λ _max , nm, 665; ESP in chloroform, λ _max , nm, 668.

Example 3. The use of tetra-4- [4- (2,4,5-trichlorophenoxy)] phthalocyanine copper as a starting compound for the synthesis of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy )] copper phthalocyanine

Tetra-4- [4- (2,4,5-trichlorophenoxy)] copper phthalocyanine (408 mg, 0.3 mmol) was reacted with 10 ml (24 mmol) of 26% oleum at 90 ° C. for 8 hours. After stirring, the reaction mixture was poured onto ice treated with sodium chloride. The precipitate was collected on a Schott filter, washed with concentrated hydrochloric acid to colorless filtrates and dried in a desiccator over sulfuric acid for 3 days. Final purification is carried out by column chromatography: eluent — DMF, sorbent — silica gel M 60. The products obtained are dark green solids soluble in water, ammonia, aqueous alkaline solutions, and DMF.

Yield: 455 mg (76%).

Found,%: C 33.90, H 1.15, N 5.45, S 12.94; C ₅₆ H ₂₀ Cl ₁₂ CuN ₈ O ₂₈ S ₈ .

Calculated: C 33.66, H 1.01, N 5.61, S 12.84.

¹ H NMR spectrum, δ, ppm: 7.23 (s, H3, 4H), 7.13 (s, H1, 4H), 7.03 (s, H2, 4H).

IR spectrum (KBr) / cm ^-1 : 750 (C-Cl), 1123, 1052 (S = O), 1082 (CS). 1249 (Ar-O-Ar) (Fig. 1).

ESP In DMF, λ _max , nm, 678 (Fig. 2).

Example 4. The use of tetra-4- [4- (2,4,5-trichlorophenoxy)] cobalt phthalocyanine as a starting compound for the synthesis of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy )] cobalt phthalocyanine

Tetra-4- [4- (2,4,5-trichlorophenoxy)] cobalt phthalocyanine (405 mg, 0.3 mmol) was reacted with 10 ml (24 mmol) of 26% oleum at 90 ° C. for 6 hours. After stirring, the reaction mixture was poured onto ice treated with sodium chloride. The precipitate was collected on a Schott filter, washed with concentrated hydrochloric acid to colorless filtrates and dried in a desiccator over sulfuric acid for 3 days. Final purification is carried out by column chromatography: eluent — DMF, sorbent — silica gel M 60. The products obtained are dark green solids soluble in water, ammonia, aqueous alkaline solutions, and DMF.

Yield: 420 mg (70%).

Found,%: C 33.41, H 1.10, N 5.56, S 12.38; C ₅₆ H ₂₀ Cl ₁₂ CoN ₈ O ₂₈ S ₈ .

Calculated: C 33.74, H 1.01, N 5.62, S 12.86.

IR spectrum (KBr) cm ^-1 : 742 (C-Cl), 1167, 1042 (S = O), 1069 (CS), 1240 (Ar-O-Ar) (Fig. 3).

ESP in DMF, λ _max , nm, 678 (Fig. 4).

Example 5. The use of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanine copper to obtain the ammonium salt of tetra-4- [4- (2,4,5-trichloro-3 , 6-disulfophenoxy)] phthalocyanine copper

Tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] copper phthalocyanine (199 mg, 0.1 mmol) is reacted with 10 ml (25 mmol) of 25% ammonia at room temperature. The solution was evaporated.

Yield: 211 mg (99%).

Found,%: C 31.90, H 2.45, N 10.59, S 12.00; C ₅₆ H ₂₀ Cl ₁₂ CuN ₈ O ₂₈ S ₈ ;

Calculated: C 31.41, H 2.08, N 10.50, S 12.02

Example 6. The use of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanine copper as dyes for wool

2 g of glauber's salt are dissolved in 60 ml of water and 1 ml of concentrated sulfuric acid is added, then 0.2 g of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanine copper and 1 g of wool is added . The resulting mixture is heated to boiling and dyeing is carried out for 50-60 minutes. At the end, the sample is washed with warm water and dried.

A sample is attached (Fig. 5).

Example 7. The use of the ammonium salt of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanine copper as a dye of cotton fabrics

0.5 g of sodium chloride is dissolved in 50 ml of water and 0.1 g of the ammonium salt of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanine is added and 1 g of cotton fabric is added. The resulting mixture is heated to boiling and dyeing is carried out for 50-60 minutes. At the end, the sample is washed with warm water and dried.

A sample is attached (FIG. 6).

Example 8. The use of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanine cobalt as a homogeneous catalyst for the oxidation of sulfur compounds

Catalytic activity is estimated by the value of the effective oxidation rate constant of N, N-diethyldithiocarbamate sodium (GOST 8864-71) with atmospheric oxygen at pH 7.6 and a temperature of 30 ° C (k _eff ). The oxidation is carried out at normal pressure in a 650 ml batch metal reactor equipped with a thermometer, a reflux condenser, a sampling tap and a bubbler for supplying air at a speed of 2 l / min, which ensures the process proceeds in a kinetic mode. 600 ml of a solution of 0.1 g / L sodium N, N-diethyldithiocarbamate are loaded into the reactor. To determine the current concentration of sodium diethyldithiocarbamate, a 2 ml sample was transferred to a 25 ml flask and 4 ml of 0.02 N was added. CuSO ₄ . A solution of copper sulfate is prepared using a reagent in accordance with GOST 19347-99. When copper sulfate is added to the sample, a thick dark brown precipitate of the copper complex is formed. The mixture is stirred for one minute. Then, 5 ml of chloroform, 3 drops of 50% acetic acid are added to the resulting solution and shaken for 1.5 minutes. The copper diethyldithiocarbamate complex is extracted into the chloroform layer. The organic layer was transferred to a 25 ml volumetric flask, and the complex was extracted again from the remaining aqueous solution to increase the accuracy of the analysis. The collected copper complex solution was adjusted to the mark with chloroform. From this flask, 2 ml of solution is taken, transferred to another 25 ml volumetric flask and again brought to the mark with chloroform. On a spectrophotometer at a wavelength of 436 nm, the optical density of the solution is determined and the concentration of N, N-diethyldithiocarbamate is calculated based on the calibration line.

The catalytic activity of tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] cobalt phthalocyanine measured at a catalyst concentration of 6 × 10 ^-5 mol / L and a substrate of 0.00203 mol / L can be estimated using the effective oxidation rate constant of sodium diethyldithiocarbamate, measured at pH = 7.6, which is 41.97 × 10 ^-3 L / (mol⋅s).

Claims (2)

Tetra-4- [4- (2,4,5-trichloro-3,6-disulfophenoxy)] phthalocyanines of copper and cobalt of the general formula:

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