RU2649400C1 - 8-amino-5-[[(4-amino-5-sulfo-1-naphthylenyl)imino]-2,3-dihydro-2-phenyl-1h-inden-1-ylidene]amino]-1-naphthylensulfoxy acid, having property of acid dye for silk, wool and capron - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a new heterocyclic compound formula:

.

EFFECT: compound can be used as an acid dye for silk, wool, capron.

1 cl, 3 dwg, 4 ex

Description

The invention relates to the chemical industry, namely, to compounds that can be used as acid dyes for silk, wool, nylon.

The compound is known [G. Synthesis and Properties of Macroheterocyclic Compounds with Substituents of Substituted Benzidine / Journal of General Chemistry, 2006. V. 76, no. 8, p. 1369-1374].

However, it does not have the property of a dye.

Also known are compounds that are structural analogues of the claimed compounds [Berezina G.R., Fomina I.S. Synthesis of Macrocyclic Compounds Based on Indandion-1,3 / International Research Journal, Ekaterinburg, 2013. Part I. No. 10 (17), p. 34-36].

However, they do not have coloring properties and therefore cannot be used for dyeing in solutions, but can be used for the synthesis of macrocyclic compounds that do not have the property of an acid dye.

Known azo dyes [Borodkin V.F. Chemistry of dyes. - M .: Chemistry, 1981. S. 95, 97], which stain protein fibers, but do not stain nylon, for example:

For the prototype, we take active copper-containing vinyl sulfone dyes [RF Patent 2068431. IPC С09В 62/51. Filing: 1992-05-19. Publication: 10.27.1996], dye wool, silk, cellulose, natural and synthetic polyamide fibers in blue:

The technical result consists in finding a new compound that can be used as an acid dye that dyes silk, wool and nylon in various shades of brown-red.

The indicated result was solved by the compound 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1 -naphthylene sulfonic acid having the property of an acid dye for silk, wool and nylon formula

The structure of this compound is proved by elemental analysis, IR, electron spectroscopy.

The invention is illustrated by drawings, where in FIG. 1 shows the IR spectrum of 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-index-1-ylidene] amino] -1 naphthylene sulfonic acid, in FIG. 2 - electronic absorption spectrum of 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] - 1-naphthylene sulfonic acid in water, FIG. 3 - colorization of samples, where a is the sample obtained according to example 2, b - according to example 3, c - according to example 4.

In the IR spectra of the claimed compounds (Fig. 1), a number of common absorption bands with an analogue can be distinguished [1. Berezina G.R., Fomina I.S. Synthesis of Macrocyclic Compounds Based on Indandion-1,3 / International Research Journal, Ekaterinburg, 2013. Part I. No. 10 (17), p. 34-36. 2. Berezina G.R., Kuptsova K.D., Berezina N.M. Synthesis and study of the physicochemical properties of macrocyclic compounds with fragments of n, n-diamines of the diaryl series / Journal of Organic Chemistry, 2015. V. 51, no. 2, p. 279-282].

In the electronic spectra of 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1- Naphthylene sulfonic acid exhibits intense absorption at 470 nm (log ε 4.1), recorded in water (Fig. 2). The nature of the spectrum indicates that the compound exists in solution mainly in the form of a monomer.

8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1-naphthylene sulfonic acid is a substance of red-brown color, having solubility in water, ethanol.

The inventive new compound has the property of an acid dye and can be used for dyeing silk, wool and nylon.

To obtain the target product using the following substances:

Phthalic anhydride GOST 7119-77,

Phenylacetic acid GOST 931666,

sodium metal TU 6-09-356-77,

sodium acetate GOST 199-78,

glacial acetic acid GOST 19814-74,

ammonium acetate GOST 3117-78,

GOST 2222-95 methanol,

ethanol GOST R 55878-2013,

hydrochloric acid GOST 857-95,

hydrogen peroxide GOST 177-88,

aniline GOST 5819-78,

alpha-naphthylamine GOST 830-75,

sodium nitrite GOST 4197-74,

zinc dust GOST 12601-76,

GOST 5100-85 soda,

acetic anhydride GOST 5815-77,

concentrated sulfuric acid GOST 2184-2013.

The inventive compound is prepared as follows: first, diimine of 2-phenylindanedione is synthesized by the interaction of phthalic anhydride, phenylacetic acid, sodium acetic acid, sodium metal, methyl alcohol, ammonium acetate and glacial acetic acid, then the obtained compound is reacted with 1,4-diaminonaphthylene sulfonic acid in the ratio of 1: 2.

Example 1. The synthesis of the target product.

Synthesis of Diimine 2-Phenylindanedione

In a three-necked flask equipped with a reflux condenser, 100 g of phthalic anhydride, 110 g of phenylacetic acid and 2.6 g of freshly melted sodium acetate are added with a thermometer. The mixture was heated to 240 ° C and water was distilled off for 2 hours. The product is then cooled to 95 ° C and dissolved in 40 ml of boiling ethyl alcohol. The solution is filtered, cooled, precipitated crystals of benzalphthalide are filtered off and washed with 50 ml of cold alcohol, so pl. 96-98 ° C. Then 22 g of benzalphthalide are dissolved by heating in 150 ml of methyl alcohol and 50 ml of a 6% sodium methylate solution are added to the solution, the solution turns dark red. After distillation of ethanol, needle-shaped red crystals are isolated, which are dissolved in water and acidified with hydrochloric acid. Yield: 2-phenylindanedione 22 g (90%), a cream-white substance with a _mp = 145 ° C. Then 15 g of the product are dissolved in 50 ml of glacial acetic acid and 70 g of ammonium acetate are gradually added. The mixture is boiled for 3 hours, cooled and left for a day, then filtered, the precipitate is washed with water and dried.

The yield of 2-phenylidanedione diimine (75%). The substance is orange in powder with t _PL = 180 ° C.

Found,%: C 78.88; H 5.55; N, 12.56. C ₁₅ H ₁₂ N ₂ . Calculated,%: C 81.82; H 5.45; N, 12.73.

Synthesis of 1,4-naphthylenediamine

In a 150 ml beaker, 50 ml of water, 12 ml of concentrated hydrochloric acid and 4.7 g (0.05 mol) of aniline are successively loaded. Cool the solution to 0-3 ° C. Then, a 30% sodium nitrite solution (approximately 12 ml) was added dropwise over 10-15 minutes. The temperature is maintained at 2-3 ° C. The end of the reaction is determined by Congo, and the excess of nitrous acid by iodine starch.

25 ml of 15% hydrochloric acid and 7.2 g (0.05 mol) of α-naphthylamine are added to a 150 ml beaker. The mixture is heated to 70-80 ° C and incubated for 10-15 minutes. Then 110 ml of water are poured and heated until the amine salt is completely dissolved. It is cooled with shaking under a stream of water and served for azo combination.

75 g of ice is loaded into a glass with a diazo solution, α-naphthylamine is poured for 10-15 minutes, stirred for 1.5 hours, the product is sampled for leakage.

Yield 4 - benzalo - 1 - naphthylamine 6.25 g (46%).

A flask with a capacity of 150 ml is charged with 6.25 g (0.025 mol) of 4 - benzalo - 1 - naphthylamine, a suspension of zinc dust, consisting of: 1.875 g (0.029 mol) of zinc dust and 95 ml of water and boiled until the solution becomes colorless. The bleached solution was filtered and poured into dilute sulfuric acid (1 part H ₂ O + 2 parts H ₂ SO ₄ ). The crystalline diamine sulfate is separated and heated with a soda solution for no more than 5 minutes. The mixture is cooled, the precipitate is filtered off.

The yield of 1,4-naphthylenediamine 1.1 g (17.8%).

Found,%: C 74.98; H 6.06; N 17.2. C ₁₀ H ₁₀ N ₂ . Calculated,%: C 75.95;

H 6.33; N, 17.72.

Synthesis of 1,4 - diaminonaphthylene sulfonic acid

but. Acylation of 1,4 - naphthalenediamine. Into a 50 ml round bottom flask equipped with a reflux condenser and stirrer, 1.1 g (6.9 mmol) of 1,4-naphthylenediamine and 15 ml of acetic anhydride are added. The mixture is boiled for 2 hours. At the end of the exposure, the reaction mass is poured into 22 ml of 1% hydrochloric acid. The crystals precipitated upon cooling are filtered off, washed with water and dried at 50-60 ° C.

Yield: 1.7 g (80.1%). A peach-colored substance in powder with _mp = 123 ° C.

IR spectrum: ν, cm ^-1 : (NH) 3271; (C = O) 1655; (C = C) 1543; (CN) 1279; (C-C) 1179.

b. Sulfonation of the product. In a two-necked flask with a capacity of 150 ml, equipped with a reflux condenser, stirrer and thermometer, 10 ml of concentrated sulfuric acid, 1.33 ml of oleum are placed. Then, with stirring, 1.7 g (6.2 mmol) of the acylated product are charged at such a rate that the temperature in the reaction mass does not exceed 20 ° C. The reaction mass is maintained at 20 ° C for 24 hours. Next, pour the reaction mass into 300 ml of water. Neutralized with 5% hydrochloric acid to remove acyl groups. The precipitate formed is filtered off and dried.

Yield: 1.55 g (96.9%). The substance is lilac in powder.

IR spectrum: ν, cm ^-1 : (O-H) 2926; (C-H) 2636; (C = C) 1607; δ (NH) 1514; (CN) 1222; (CS) 1110; (SO) 1055; (C-C) 1019; (SO) 784.

ESP, λ _max , nm: in DMF 341, 478; in water 307, 523.

Found,%: C 49.3; H 4.0; N, 11.4; O 19.9; S 13.3. C ₁₀ H ₁₀ N ₂ O ₃ S. Calculated,%: C 50.42; H 4.20; N, 11.76; O 20.17; S 13.45.

Synthesis of 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1-naphthylene sulfonic acid

0.15 g (0.7 mmol) of 2-phenylindanedione diimine, 0.32 g (1.36 mmol) of 1,4-diaminonaphthylene sulfonic acid are added to a flask equipped with a reflux condenser and a stirrer and boiled in 7 ml of ethyl alcohol for 30 hours. The precipitate formed upon cooling the reaction mass is filtered off and dried at 80 ° C.

Yield: 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1-naphthylene sulfonic acid 0.39 g (87%). The product is a brownish-red powdery substance, soluble in water, ethanol, DMF, acetone, chloroform.

IR spectrum, ν, cm ^-1 : (NH ₂ ) 3480; (NH) 3296; (OH) 3240; (CH) 2923; (C = N) 1588; (C = C) 1616; (S = 0) 1384; (C-C) 1148; (CN) 999; (SO) 619; (CS) 489.

ESP, λ _max , nm: in water 470; in ethanol: 471, 560; in DMF: 469, 560.

Found,%: C 58.73; H 4.85; N, 7.50; S 8.89; About 15.85. C ₃₅ H ₂₆ N ₄ S ₂ O ₆ .

Calculated,%: C 63.44; H 3.93; N, 8.46; S 9.67; About 14.50.

Example 2. The use of 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1 -naphthylene sulfonic acid as an acid dye for silk. Dyeing was carried out according to the methodology [Laboratory workshop on the use of dyes / Ed. Melnikova B.N. M .: Chemistry - 1972. S. 7-14].

A sample of silk fabric weighing 1 g is placed in a dye bath composition (g / l):

8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1-naphthylene sulfonic acid 6 Glauber's salt 40 Bath module fifty

For 15-30 minutes, the bath is heated to 60 ° C and maintained at this temperature for 40 minutes and 20 minutes in a bath cooling to 30 ° C.

The sample is squeezed, washed thoroughly with warm, then cold water and treated with a solution of sulfuric acid composition (ml):

sulphuric acid one water fifty

The sample is squeezed, washed thoroughly with warm, then cold water, and dried. A brownish-red color sample (Fig. 3a is attached).

Example 3. The use of 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1 -naphthylene sulfonic acid as an acid dye for wool. Dyeing was carried out according to the methodology [Laboratory workshop on the use of dyes / Ed. Melnikova B.N. M .: Chemistry - 1972. S. 7-9].

A sample of wool fiber weighing 1 g is placed in a dye bath composition (g / l):

8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1-naphthylene sulfonic acid 6 Glauber's salt 40 Bath module fifty

For 15-30 minutes, the bath is heated to 60 ° C and maintained at this temperature for 40 minutes and 20 minutes in a bath cooling to 30 ° C.

The sample is squeezed, washed thoroughly with warm, then cold water, and treated with a solution of sulfuric acid composition (ml):

sulphuric acid one water fifty

The sample is squeezed, washed thoroughly with warm, then cold water, and dried. A brown color sample (Fig. 3b is attached).

Example 4. Use of 8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1 -naphthylene sulfonic acid as an acid dye for capron. Dyeing was carried out according to the methodology [Laboratory workshop on the use of dyes / Ed. Melnikova B.N. M.: Chemistry - 1972. S. 7-14].

A sample of kapron tissue weighing 1 g is placed in a dye bath composition (g / l):

8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1-naphthylene sulfonic acid 6 Glauber's salt 40 Bath module fifty

For 15-30 minutes, the bath is heated to 60 ° C and maintained at this temperature for 40 minutes and 20 minutes in a bath cooling to 30 ° C.

The sample is squeezed, washed thoroughly with warm, then cold water, and treated with a solution of sulfuric acid composition (ml):

sulphuric acid one water fifty

The sample is squeezed, washed thoroughly with warm, then cold water, and dried. A brown-red color sample (FIG. 3c is attached).

Claims (3)

8-amino-5 - [[(4-amino-5-sulfo-1-naphthylenyl) imino] -2,3-dihydro-2-phenyl-1H-inden-1-ylidene] amino] -1-naphthylene sulfonic acid of the formula

possessing the property of acid dye for silk, wool and nylon.

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