SU1766900A1 - Method of dyes synthesis - Google Patents

Abstract

The essence of the invention: mixtures containing polycyclic quinones. Output 96.2%, BF S24NuVg202. Reagent 1. quinone - dibenzpyrenquinone, violantron or isovi-olantron. Reagent 2: hydrobromic acid, potassium permanganate. 125-150 ° C, molten mixture of potassium or sodium perchloric acid, molar ratio of perchloric acid and hydrobromic acid, potassium permanganate (0 09-1)

Description

The invention relates to brominated polycyclic quinones, in particular to a process for the preparation of dyes.

A known method for the preparation of a dye by dibenzpyrene-quinone brominated at 150 ° C in an molten salt based on anhydrous aluminum chloride is sodium bromide in the presence of oxidizing agents. Oxygen or sodium nitrate 1 is used as an oxidizing agent. A disadvantage of the method is the relatively low quality of the target dye (see Example 12).

The purpose of the invention is to improve the quality of dyes.

The goal is achieved by the proposed method of obtaining dyes by brominating polycyclic quinones in a melt of mineral salts based on anhydrous aluminum chloride in the presence of an oxidizing agent at elevated temperature, a distinctive feature of which is dibenzprenquinone, viololtron, izoviolantron and bromination as the quinones. t with a mixture of potassium or sodium salts of perchloric, hydrobromic acid and potassium permanganate at

molar ratio equal to (0 09-1 0). (0,66-5,4): (0,017-0,1), respectively, per 1 mol of quinone, at 125-150 ° С.

The invention is illustrated by the following examples.

EXAMPLE 1 A mixture of 35.0 g (0.26 mol) of anhydrous aluminum chloride, 1.6 g (0.0215 mol) of potassium chloride, and 2.0 g (0.034 mol) of sodium chloride melted at 140 ° C. ° C, cooled to 125 ° G, added: 5.0 g (0.0148 mol) of 1,5-dibenzoyl} taline and at 127-132 ° C, 2.5 g are added in portions over 4-5 hours ( 0.012 mol) dinitrochlorobenzene. At the same time, 1,5-dibenzoyl-naphthalene is converted into an equimolar amount of 3,4,8,9-dibenzpyrene-5,10-quinone, the completeness of the formation of which is judged on the basis of chromatography of the sample in comparison with the sample of benzoyl benzantron (the absence of the latter is considered a sign of complete transformation).

Thereafter, a brominating mixture consisting of powdered potassium permanganate in an amount of 0.2 g (0.00126 mol) with 4.6 g (0.0447 mol) of methyl sodium and

SP

with

Vj

oh oh

Yu

Oh oh

, 8 g (0.0065 mol) of potassium chlorate. The temperature during addition of the brominating mixture is kept within 135-145 ° C.

After the addition of the brominating mixture is complete, the melt is stirred for an additional 1 h, 5 is poured into acidified water, filtered, washed and suspended in water. The suspension formed at 80 ± 5 ° C is crushed by periodically adding 85 ml of 1 bd sodium hypochlorite solution 10 with an active chlorine content of at least 100 g / l.

Before filtration, remove the excess sodium hypochlorite with a solution of bisulfite, separate the precipitate on a Buchner funnel, wash until neutral, and dry. 7.23 g (yield 99.18%) of the dye vat golden yellow CXC are obtained by a coloristic assessment: the hue is redder, the purity is close, the intensity is 120%; resistance to soap processing at 100 ° C is good (soap loss is 7% of the initial intensity).

After additional washing with hot dimethylacetamide, the content of halogens is determined in the product.

Found,%: Br 29.05, 29.60; CI 2.88, 2.22.

S24NUVG202v

Calculated,%: Вг32,59. -thirty

Color conclusion: the shade is redder, the purity is close, the concentration is 160%.

EXAMPLE 2 Similar to that described in Example 1, with the difference that the amount of 35 potassium permanganate was reduced to 0.05 g (0.0003 mol), the potassium chlorate to 0.50 g (0.0041 mol) and methyl bromide. sodium to 2.94 g (0.028 mol); 6.29 g (yield: 96.26%) of the dye was obtained. Color conclusion: 40 is greener, 100% dumber; resistance to soap treatments is unsatisfactory (soap loss 25%). After additional purification, found,%: Br25,06,24,88; CI 5.03, 5.68.45

EXAMPLE 3. Similar to that described in Example 1, with the difference that the amount of methyl nitrate was reduced to 2.94 g (0.028 mol), 7.09 g (yield: 97.26%) of dye was obtained. Color conclusion: 50 somewhat dumber, greener, 110%. Found,%: Br 23.27. 22.89; CI 3.67, 3.32.

PRI me R 4. Similar to that described in example 1, with the difference that instead of sodium bromide use 5.35 g of 55 (0.045 mol) of potassium bromide. 7.0 g of dye was obtained (yield 96.02%). Color score: much dumber, much greener. 120%. Found,%: Br 24.17, 24.60; Ci 3.24, 3.61.

EXAMPLE 5 Similar to that described in Example 1, with the difference that, instead of potassium chate, in the brominating mixture, 0.69 g (0.0065 mol) of sodium chlorate (MaSy) was used, mixing it with 3 , 65 g (0.035 mol) of sodium bromide and 0.2 g (0.00126 mol) of potassium permanganate. 7.19 g (98.63% yield) of a dye with a color score were obtained: significantly dumber, greener, 115%. Found,%: Br 27.82, 27.54; CI 2.34; 2.47.

PRI me R 6. As described in example 1, with the difference that the loading of potassium permanganate increased to 0.94 g (0.0059 mol), potassium chlorate to 1.1 g (0.009 mol), sodium bromide 5 84 g (0.057 mol). 7.58 g of dye was obtained. Color score: cleaner, redder, 130%.

Found,%: Br 30.12, 30.72; CI 3.42, 3.15.

PRI1 meper 7. Similarly to that described in Example 1, with the difference that the isoviolantrone in an amount of 4.42 g (0.0097 mol) was subjected to bromination, dinitrochlorobenzene was added in an amount of 0.5 g (0.002 mol) and a mixture of 0.15 g (0.0009 mol) of potassium manganate, 0.92 g (0.0075 mol) of potassium chlorate and 5.43 g (0.0527 mol) of sodium bromide is used as the brominating composition. 6.10 g of dye was obtained (yield 98.2%) based on dibromizoviolantron. After purification with hot dimethylacetamide, the following elemental analysis data were obtained.

Found%: Br 23.25, 23.41, CI 1.37, C 1.25.

C34N14 E2VG2

Calculated,%: Вг26,01.

PRI me R 8. In the same way as described in Example 7, with the difference that 5.76 g (0.0126 mol) of the violantron is subjected to bromination, KMPSM 0.2 g (0, 00126 mol), KSUz 1.2 g (0.0098 mol) and Na6r 7.0 g (0.068 mol). A dye of 8.57 g (yield: 105.9%) was obtained based on dibromviolantron.

Found,%: Br 24.02, 23.80; CI 0.93, 1.15.

C34N1402B G2

Calculated,%: Вг26,01.

EXAMPLE 9. Similar to that described in Example 7, with the difference that instead of an isovolantron, 3.45 g (0.015 mol) of benanthrone was introduced into the flask. 6.06 g are obtained (yield 104% on dibromobenzantron).

Found%: Br 38.77, 39.09 Ci 1.51, 1.89,

S1bN8OVg2.

Calculated,%: Br 42.49.

PRI me R 10. (partial bromirovanii dibenzipyrenequinone).

Out of 5.0 g of 1,5-dibenzoylnaphthalene, as described in Example 1, the difference is that a mixture of 0.04 g (0.00025 mol) of potassium manganate acid, 1.0 g (0.097 g) is used as the brominating composition. mol of sodium bromide and 0.17 g (0.00139 mol) of potassium chlorate. 5.31 g of dye lac gold yellow are obtained. The yield per bromination of one third of the dye molecules was 98.3%.

Color conclusion: shade is greener, purity is cleaner, concentration is 140%.

Found,%: Br 8.07, 7.73.

С24Н9,6б02Вго.З

Calculated,%: Br 7.40.

Example 11: 15.0 g (0.045 mol) of dry 3.4 was dissolved in salts of 106 g of aluminum chloride, 2.0 g of sodium chloride and 4.8 g of potassium chloride at 120 ° C. , 8,9-dibenzpyrene-5,10-quinone, 0.6 g (0.0038 mol) of potassium permanganate is added and then gradually, without allowing heating to exceed 135 ° C, a mixture consisting of 2.4 g is added ( 0,0196 mol) of potassium chlorate and 10.8 g (0.105 mol) of sodium bromide. Isolation and oxidation treatment in an aqueous medium are carried out as described in Example 1. 22.0 g are obtained (the yield based on dibromodibenzpyrenquinone is 100.7%) of dye, which gives a color test when compared to a standard sample of dye dye yellow CX the following results: purity - close, shade - redder, concentration 100%.

Found,%: Br 24.17, 24.70; CI 3.83, 3.31.

Example12 (prototype).

Synthesis of dibenzpyrenquinone is carried out as described in example 1, based on the following loadings: aluminum chloride 22.2 g (0.166

mol), sodium chloride 3.8 g (0.065 mol), 1,5-dibenzoylnaphthalene 3.4 g (0.010 mol), dinitrochlorobenzene 2.0 g (0.0098 mol). Before addition of the brominating mixture, a mixture of 5.0 g of aluminum chloride and 1.0 g of sodium chloride is additionally charged into the flask. In contrast to that described in Example 1, a mixture of 1.06 g of sodium bromide (1.010 mol) and 0.92 g of sodium nitrate (0.010 mol) is used as the brominating agent. The process of isolation and purification is carried out in a known manner. 4.06 g of dye was obtained (yield: 81.9%, for dibromodibenzpyrenquinone). The color conclusion: the shade is significantly greener, the purity is much dumber, the concentration is 100%. Found,%: Br 1.7,16, 16,73.

S24NUVG202

Calculated,%: Вг32,59.

Data on molar ratios are presented in the table.

Thus, the proposed method allows improving the quality of the target product by increasing the bromine content to 39% against 16% in the known method, also due to the intensity of the dye to 160% against 100% in the known method

Claims (1)

Invention Formula A method for producing dyes by broaming polycyclic quinones in an alloyed mineral salt based on anhydrous aluminum chloride in the presence of an oxidizing agent at an elevated temperature, characterized in that dibenzpyrenquinone, viololtron or isovol-olthrone is used as quinone, and the wire is quinone with a mixture of potassium or sodium salts of perchloric and bremistohydric acids, potassium permanganate at a molar ratio of (0.09-1.0): (0.66-5.4): (0.017-0.1), respectively, by 1 mole quinone a, and 125-150 ° C.