RU2540865C1 - Cyclo-bis[(1z)-1-imino-2-methyl-1h-inden-3-yl-1,2,4-thiadiazole-3,5-diamine], possessing property of acid dye for silk, wool and polyamide 6 - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to novel heterocyclic compound, representing cyclo-bis[(1Z)-1-imino -2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine]

EFFECT: compound as acid dye for silk, wool and polyamide 6.

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Description

Introduction

The invention relates to the chemical industry, namely, to obtain a new heterocyclic compound, which can be used as an acid dye.

State of the art

The compound is known (Berezina G.R., Vorobyov Yu.G., Smirnov R.P. Synthesis and study of heterocyclic compounds based on 1,3-indandion // Zhokh. 1998. V.68. Issue 6. P.1018- 1020), which is a structural analogue of the claimed compounds.

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

Compounds are known (Berezina G.R., Vorobev Yu.G. Synthesis and properties of macroheterocyclic compounds with substituted benzidine fragments // Zhokh. 2006. V.76. Issue 8. P.1369-1374).

They do not have coloring properties and, therefore, cannot be used for dyeing in solutions.

Known azo dyes (Borodkin VF Chemistry of dyes. - M .: Chemistry, 1981. P.95, 97), which dye protein fibers, but do not stain nylon, for example:

Dyes based on 2-amino-5-mercapto-1,3,4-thiadiazoles (1. Shukurov S.Sh., Kukaniev MA A new method for the synthesis of 2-amino-5-alkyl (aralkyl) thio-1,3 , 4-thiadiazoles // ZhORKh. 1993. V.29. Issue 11. P.2327; 2. Hani R., Varadiya. Dispersed dyes based on 2-amino-5-mercapto-1,3,4-thiadiazoles / / HGS. 2009. No. 10. S.1558-1563) dye only polyamide fibers in red-pink shades, for example:

Copper-containing active vinyl sulfone dyes of blue color (RF Patent No. 2047630. Publ. 10.11.1995) dye cellulose, natural and synthetic polyamide fibers:

SUMMARY OF THE INVENTION

The inventive task was to find a new macroheterocyclic compound that can be used as an acid dye for silk, wool and nylon.

The problem is solved by the macroheterocyclic compound cyclobis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] of the formula

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

In the IR spectra of the claimed compound (Fig. 1), a number of common absorption bands with an analogue can be distinguished (Berezina G.R., Vorobev Yu.G., Smirnov R.P. Synthesis and study of heterocyclic compounds based on 1,3-indandion // JOC. 1998. T.68. Issue 6. S.1018-1020).

In the electronic spectra of cyclobis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine], intense absorption is observed at 465 nm (log 4.65 ) and less intense - at 340 nm, recorded in water (figure 2). The nature of the spectrum indicates that the compound exists in solution mainly in the form of a monomer.

In the ¹ H NMR spectra, a singlet is observed in the region of 1.8 ppm. (1: 1), which characterizes the presence of methyl groups and multiplet in the region of 7.6-8 ppm. (1: 1.5), which indicates the presence of phenyl substituents in the coordination cavity of the molecule and the presence of benzene fragments in the compound. Methyl groups leave the plane of the macrocycle and are located above the phenyl rings, so they fall into their ring current, and therefore the peak shifts to the right on a scale (3 → 1.8 ppm) (Fig. 3).

Cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] is a bright red substance with water solubility , DMF, H ₂ SO ₄ , chloroform, ethanol.

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

Information confirming the possibility of carrying out the invention

To obtain the target product using the following substances:

diethyl phthalate GOST 8981-78,

xylene TU 2631-018-781 19972-06,

sodium metal TU 6-09-356-77,

ethyl ester of propionic acid GOST 22300-76,

glacial acetic acid GOST 18870-72,

ammonium acetate GOST 3 1 17-78,

ethanol GOST 18300-72,

hydrochloric acid GOST 14261-77,

hydrogen peroxide GOST 10929-76,

dicyandiamide TU 6-09-16-919-75,

caustic soda GOST 4328-77.

The inventive compound is prepared as follows: first, 2-methylindanedione diimine is synthesized by the interaction of diethyl phthalate, sodium metal, propionic acid ethyl ester, ammonium acetate and glacial acetic acid, then the obtained compound is reacted with 3,5-diamino-1,2,4-thiadiazole in 2: 2 ratio with a short circuit.

Example 1. The synthesis of the target product.

In a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 20 ml of xylene and 10 g of metallic sodium are added, heated with stirring (100 ° C) for 1 hour, a whitish-gray suspension is obtained, then the suspension is cooled to 50 ° C and gradually a mixture of 50 ml of diethyl phthalate and 70 ml of ethyl propionic acid is added. Stirred for 2 hours, a dark red thick mass is formed. The red-colored aqueous solution of the Na compound is decolorized with concentrated hydrochloric acid, the precipitate is filtered off and washed with ethanol. Yield: 78%, _mp = 84-85 ° 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-methylindanedione diimine is 75%. The substance is red in powder, so pl. 178 ° C. Found,%: C 74.5; H 6.37; N 16.8. C ₁₀ H ₁₀ N ₂ . Calculated,%: C 75.95; H 6.33; N, 17.72.

In a round-bottomed three-necked flask with a capacity of 500 ml equipped with a reflux condenser, a nozzle for passing hydrogen sulfide, a solution of dicyandiamide 42 g (0.5 mol) in 200 ml of water was placed and kept at 75 ° C for 12 hours, then hydrogen sulfide was passed through the solution for 30 hours . The resulting yellow liquid is cooled to 45 ° C and add 15 ml of 40% sodium hydroxide solution, filtered, the filtrate is kept at 0 ° C for 24 hours. The prismatic leaflet was filtered off and washed with ice water (60 ml). The yield of amidinothiourea is 35.4 g (60%), i.e. 170-172 ° C. Found,%: C 19.98; H 5.06; N 47.2; S 26.95. C ₂ H ₆ N ₄ S. Calculated,%: C 20.35; H 5.08; N, 47.45; S 27.12. 11.8 g (0.1 mol) of amidinothiourea and 250 ml of ethanol are added to a flask equipped with a reflux condenser and a stirrer, 10 ml (0.1 mol) of concentrated hydrochloric acid are added and brought to a boil, then 170 ml (0.3 mol) of 20% peroxide are added to the solution hydrogen. The precipitated sulfur is filtered off and, with cooling of the filtrate, 3,5-diamino-1,2,4-thiadiazole precipitates. Yield 7.67 g (66%), mp. 169-171 ° C. Found,%: C 21.41; H 3.38; N, 43.47; S 26.41. C ₂ H ₄ N ₄ S. Calculated,%: C 20.69; H 3.45; N 48.28; S 27.58.

0.49 g (3.5 mmol) of 2-methylindanedione diimine, 0.36 g (3.1 mmol) of 3,5-diamino-1,2,4-thiadiazole and 7 ml of glacial acetic acid are added to a flask equipped with a reflux condenser and a stirrer. The mixture is boiled for 3 hours. At the end of the reaction, the solution is cooled, poured into a minimum amount of water and neutralized with a weak alkali solution. The resulting product is filtered off and washed with acetone on the filter. Dried at 100 ° C.

Yield of cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine]: 0.47 g (58%). The substance is bright red in powder, soluble in water, DMF, H ₂ SO ₄ , chloroform, ethanol, the so-called. decomp. 200 ° C.

IR spectrum: ν, cm ^-1 : (C = C) 1609; (CC) 1153; (C = N) 1115; (NH) 3422; (CN) 1271; (CS) 630; δ (CH) 840.

ESP in water, λ _max , nm: 340, 465 nm (Igε 4.65) (Fig. 1). ESP in water, λ _max , nm: 340, 465 nm (log ε 4.65) (Fig. 2). ¹ H NMR spectrum, δ, ppm: 1.8 s; 7.6-8 m (4 protons) (figure 3).

Found,%: C 55.85; H 4.37; N, 22.54; S 11.95. C ₂₄ H ₁₆ N ₈ S ₂ .

Calculated,%: C 60; H 3.34; N, 23.33; S 13.33.

Example 2. The use of cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] as an acid dye for silk. Dyeing was carried out according to the methodology (Laboratory workshop on the use of dyes // Edited by B. Melnikov - M .: Chemistry. 1972. S.7-14).

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

Cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] 6 Glauber's salt 40 Bath module fifty

Within 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.

Then 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.

Example 3. The use of cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] as an acid dye for wool. Dyeing was carried out according to the methodology (Laboratory workshop on the use of dyes // Edited by B. Melnikov - M .: Chemistry. 1972. S. 7-9).

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

Cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] 6 Glauber's salt 40 Bath module fifty

Within 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.

Then 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.

Example 4. The use of cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] 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 fiber weighing 1 g is placed in a dye bath composition (g / l):

Cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] 6 Glauber's salt 40 Bath module fifty

Within 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.

Then 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.

Example 5. The use of cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] as an acid dye for silk, wool and kapron. All samples were dyed from one bath.

Samples of wool, silk and kapron fibers in a ratio of 1: 1: 1 weighing 1 g are placed in a dye bath composition (g / l):

Cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine] 6 Glauber's salt 40 Bath module fifty

Within 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.

Then the samples are squeezed, washed thoroughly with warm, then cold water and treated with a solution of sulfuric acid composition (ml):

sulphuric acid one water fifty

Samples are squeezed, washed thoroughly with warm, then cold water, and dried.

Samples of colorings according to examples 2, 3, 4, 5 are attached.

Claims (1)

Cyclo-bis [(1Z) -1-imino-2-methyl-1H-inden-3-yl-1,2,4-thiadiazole-3,5-diamine]

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

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