PL215438B1 - Coloured ammonium ionic liquids with 4-[(3-carboxyl-2-hydroxynaphthalene-1-yl)diazenylo]-3-hydroxynaphthalene-1-sulphonic anion and process for the preparation thereof - Google Patents

Description

The subject of the invention are colored ammonium ionic liquids with the 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic anion and a method of their preparation, used as a coloring agent for wood and wood-related materials .

Examples of compounds include:

Didecyldimethylammonium -4 - [(3-carboxyl-2-hydroxynaphthalen-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonate,

Benzalkonium 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonate,

Hexadecyltrimethylammonium -4 - [(3-carboxyl-2-hydroxynaphthalen-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonate.

Chemical compounds that can permanently dye other substances - are called dyes. Most of the dyes contain an aromatic part (benzene, naphthalene or anthracene rings) and a heterocyclic part, which have very mobile π electrons.

Diazo dyes constitute the largest group of dyes synthesized on an industrial scale. A characteristic feature of these chemical compounds is the grouping of the molecule

-N = N Which is responsible for the color formation of these compounds. The presence of other unsaturated bonds allows for deepening or lowering the color.

A representative of the group of diazo dyes is calcon carboxylic acid or otherwise (4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic acid). It is a blue dye with a high affinity to natural fibers and animal skin. Its main application, however, is not the coloring of materials, but the complexation of rare metals. Voltamperometric studies of the stability of systems are underway in which 4 - [(3-carboxyl-2-hydroxynaphthalen-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic acid is a transition metal ligand. Recently, there have been reports in the literature about the increasing use of calconcarboxylic acid as a reagent for the determination of trace amounts of beryllium and zirconium.

4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic acid was used for the synthesis of ionic liquids exhibiting multifunctional properties. Their multi-functionality is due to the properties of the ammonium cation and the 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic anion.

Ionic liquids are chemical compounds with an ionic structure, consisting of an organic cation and an organic or inorganic anion. The total charge on the molecule is zero, because the positive charge of the cation is balanced by the negative charge of the anion. For the 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic anion, a cation containing a quaternary nitrogen atom linked to alkyl substituents was selected as the counterion.

The essence of the invention are colored ammonium ionic liquids with an ammonium cation and an anion of 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic acid of the general formula 3, in which R ¹ , R ² , R ³ , R ⁴ is an alkyl substituent having a chain length of 1 to 20 carbon atoms, or an alkoxymethyl substituent having a chain length of 2 to 20 carbon atoms, and a method for preparing them by having ammonium halides of general formula 1, wherein R ¹ , R ² , R ³ , R ⁴ is an alkyl substituent with a chain length of 1 to 20 carbon atoms, or an alkoxymethyl substituent with a chain length of 2 to 20 carbon atoms, react with an organic salt of general formula 2, where M is lithium or sodium or potassium dissolved in an organic solvent in a molar ratio of ammonium halide to salt from 1: 1 to 1: 5, preferably 1: 1.2, at a temperature of 293-353K, preferably 313K, for at least 10 minutes.

Examples of ionic liquids described by the general formula 3 are shown in Table 1.

Thanks to the solution according to the invention, the following technical and economic effects were obtained:

• a new group of colored ammonium ionic liquids containing the 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic anion was obtained, • the obtained ionic liquids are soluble in acetone, chloroform, alcohols, a insoluble in hydrocarbons, tetrachloromethane, gasoline, petroleum ether and water,

PL 215 438 B1 • ionic liquids, thanks to the presence of a cation with long alkyl chains, have antibacterial and fungicidal properties, • the compounds can be used to color solid wood, wood chips and veneers, • colored ionic liquids are resistant to UV radiation, • the compounds obtained are insoluble in water, so they will not get into the groundwater.

The following examples illustrate the preparation of colored ammonium ionic liquids with the 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic anion cation and anion:

P r z k ł a d I

Preparation method of didecyldimethylammonium 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonate:

2 g of sodium salt of 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxy- ₃ -naphthalene-1-sulfonic acid was dissolved in 200 cm ^{3 of} methanol, and after heating to 303K, 1 g of didecyldimethylammonium chloride was introduced . The mixture was stirred vigorously for 15 minutes to ensure complete reaction. The mixture was cooled to ambient temperature of ₃ present, then the product was extracted with three portions of chloroform and 20 cm ³ each. The chloroform extracts were combined and the solvent was evaporated under reduced pressure. The product was obtained with a yield of 96%. The structure of the compound was confirmed by proton and carbon nuclear magnetic resonance spectra as well as elemental analysis.

¹ H NMR (DMSO-d6) δ ppm = 0.82 (q, J = 4.2 Hz, 6H), 1.17 (m, 28H), 1.51 (s, 4H), 3.13 (m , 10H), 4.61 (s, 2H), 7.19 (m, 5H), 7.39 (m, 3H), 8.53 (m, 3H);

¹³ C NMR (DMSO-d6) δ ppm = 172.8; 157.0; 137.3; 132.8; 132.6; 130.9; 130.3; 129.0; 128.8 128.4; 128.2; 127.9; 127.0; 126.1; 125.8; 125.4; 125.1; 124.5; 123.2; 121.8; 116.9; 112.4; 110.6 77.4; 77.0; 76.5; 63.8; 51.0; 49.7; 31.8; 31.7; 31.4; 29.56; 29.50; 29.3; 29.2; 29.1; 29.0, 28.9, 26.0 22.5; 14.0; 13.9.

Elemental analysis: C43H61N3O7S (764.03):

calculated values (%): C = 67.60; H = 8.05; N = 5.50;

measured values: C = 67.97; H = 8.38; N = 5.12.

P r z x l a d II

Preparation method of benzalkonium 4 - [(3-carboxyl-2-hydroxynaphthalen-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonate:

₃

1.6 g of benzalkonium bromide in 20 cm ^{3 of} isopropanol were introduced into the reaction vessel, followed by the addition of a 10% isopropanol solution of the potassium salt of 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1. -sulfone. The mixture was stirred at room temperature for 10 minutes, then the solvent was evaporated to yield the crude product. The obtained ₃ colored solid was then dissolved in 50 cm ^{3 of} anhydrous chloroform heated to 308K. The solution was filtered and then the solvent was removed, and the residue was dried under reduced pressure at 353K.

To confirm the structure of the compound obtained with the efficiency of 91%, proton and carbon nuclear magnetic resonance tests and elemental analysis were performed.

¹ H NMR (DMSO-d6) δ = 0.86 ppm (m, 3H), 1.18 (m, 20H), 1.57 (s, 2H), 2.16 (s, 1H), 2.96 (s, 6H), 3.13 (t, J = 5.3Hz, 2H), 4.51 (s, 2H), 4.59 (s, 1H), 6.97 (m, 1H), 7 , 27 (m, 8H), 7.64 (m, 2H), 8.56 (d, J = 4.2 Hz, 1H) ¹³ C NMR (DMSO-d6) δ ppm = 157.5; 155.1; 137.0; 132.7; 132.2; 130.5; 130.2; 129.0; 128.9 128.7; 127.7; 126.9; 126.8; 126.1; 125.7; 125.1; 122.8; 112.4; 110.2; 77.4; 77.0; 76.5; 67.7; 66.1 63.7; 49.5; 31.8; 31.7; 29.5; 29.5; 29.4; 29.3; 29.29; 29.25; 29.22; 29.0; 26.1; 22.6; 22.5; 16.1 14.0.

Elemental analysis: C41H49N3O7S (727.91):

calculated values (%): C = 67.65; H = 6.79; N = 5.77;

measured values: C = 67.87; H = 6.49; N = 5.91.

P r x l a d III

Preparation method of hexadecyltrimethylammonium 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonate:

₃

^{250 cm 3} of a 1% methanolic hexadecyltrimethylammonium hydroxide solution was placed in the reactor, and then 1.2 g of 4 - [(3-carboxyl-2-hydroxynaphthalene-1-yl) diazenyl] -3-hydroxynaphthalene acid lithium salt was introduced into the reactor. 1-sulfone. It was heated to the temperature of 313K and vigorously stirred for 30 minutes. After cooling, the solvent 4 was evaporated

After drying the crude product, it was extracted with boiling chloroform. The chloroform was then removed to give a colored ion pair.

The product was obtained with a yield of 98%. Its structure has been confirmed by elementary analysis.

Elemental analysis: C40H55N3O7S (721.95):

calculated values (%): C = 66.55; H = 7.68; N = 5.82;

measured values: C = 66.81; H = 7.33; N = 7.52.

Application example:

The ionic liquid applied to the surface of pine wood turns it into a navy blue color, which is resistant to weather conditions and UV rays. For the preparation of _three of the color solution for coloring wood was dissolved 1 g of the ionic liquid in 100 cm ³ of methanol. Dissolution was carried out by refluxing the ionic liquid and solvent for 30 minutes. The solution was then sprayed onto a wooden surface, followed by evaporation of the solvent

A colorful, decorative wood surface was obtained.

Claims (2)

1. Colored ammonium ionic liquids with the anion of 4 - [(3-carboxy-2-hydroxynaphthalene-1-yl) phenyl diaza _1] -3-hydroxynaphthalene-1-sulfonic acid and the ammonium cation of the formula 3 wherein ^R1, 234 R ^2, R ^3, R ⁴ is an alkyl chain length of from 1 to 20 carbon atoms, or a substituent alkoksymetylowy a chain length of 2 to 20 carbon atoms. 2. A method of obtaining colored ammonium ionic liquids with the 4 - [(3-carboxyl-2-hydroxynaphthalen-1-yl) diazenyl] -3-hydroxynaphthalene-1-sulfonic anion and an ammonium cation of the general formula 3 as defined in claims A process as claimed in claim 1, characterized in that the ammonium halides of the general formula 1, in which R ¹ , R ² , R ³ , R ⁴ are an alkyl substituent with a chain length of 1 to 20 carbon atoms, or an alkoxymethyl substituent with a chain length of 2 to 20 atoms carbon, X is chlorine, bromine, iodine, or a hydroxyl group, in an organic solvent is mixed with a salt of general formula 2, where M is lithium or sodium or potassium, dissolved in an organic solvent in a molar ratio of ammonium halide to salt from 1: 1 to 1: 5, preferably 1: 1.2, at a temperature of 293-353K, preferably 313K, for at least 10 minutes. PL 215 438 B1 Drawings PL 215 438 B1 Table I. Examples of ionic liquids of general formula 3 Ionic liquid R ¹ _R 2 R ³ R ⁴ 1 ch ₃ PhCH ₂ ch ₃ R 2 ch ₃ CH3 ch ₃ Ci $ H ₃₃ 3 C4II9 ch ₃ C4H9 ch ₃ 4 C ₆ H, 3 C ₆ Hi ₃ c, ₂ h ₂₅ 5 c ₈ h ₁₇ ch ₃ C ₈ Hn C4H9 ó PhCH ₂ ch ₃ PhCH ₂ 7 C _{! 0} H _2i ch ₃ CioH _2t ch ₃ 8 W “il3 ch ₃ Μπο ch ₂ oc ₆ h ₁₃ 9 CsHn ch ₃ C ₈ Hn ch ₂ oc ₉ h ₁₉ 10 Ph ch ₃ Ph CH ₂ OCnH ₂₃ Publishing Department of the Polish Patent Office