PL214257B1 - Quaternary ammonia salts with 5-methylobenzotriazol anion and production method of quaternary ammonia salts with 5-methylobenzotriazol anion - Google Patents

Description

(21) Filing Number: 382020 (13) B1 (51) Int.Cl.

C07D 249/18 (2006.01) C07C 211/63 (2006.01) (22) Date of notification: 20.03.2007

Quaternary ammonium salts with a 5-methylbenzotriazole anion and a method for the preparation of quaternary ammonium salts with a 5-methylbenzotriazole anion

(73) The right holder of the patent: POZNAŃ UNIVERSITY OF TECHNOLOGY, Poznań, PL (43) Application was announced: 29 September 2008 BUP 20/08 (72) Inventor (s): JULIUSZ PERNAK, Poznań, PL FILIP WALKIEWICZ, Poznań, PL (45) The grant of the patent was announced: 31.07.2013 WUP 07/13 (74) Representative: item. stalemate. Barbara Urbańska-Łuczak

PL 214 257 B1

Description of the invention

The present invention relates to quaternary ammonium salts with a 5-methylbenzotriazole anion and a process for the preparation of quaternary ammonium salts with a 5-methylbenzotriazole anion.

Benzotriazole belongs to the group of five-membered azoles containing three nitrogen atoms. The nitrogen ring is directly connected to the benzene ring. The methyl derivative, also called the tolyl derivative, has an alkyl substituent on the benzene ring at the 5 or 4 position. Benzotriazole and 5-methylbenzotriazole are solids, poorly soluble in water. Both of these compounds are weak organic acids. Benzotriazole and its 5-methyl derivative are widely used in chemical synthesis. coolants, hydraulic fluids, are present in lubricants as polymer stabilizers. Benzotriazoles are also used as polishing agents in the metallurgical industry. The weak acidic properties of benzotriazole are related to the mobile hydrogen in the N-H group. Molecule deprotonization occurs under the influence of strong bases. The resulting benzotriazole anion is rapidly N-alkylated. Examples of the occurrence of the benzotriazolate anion as a large fragment which tends to depart easily from the rest of the compound are described in the literature. Quaternary ammonium salts in which the benzotriazolate anion is present are not described in the literature as pure chemical compounds. Although quaternary ammonium salts have been known and widely used for over 100 years, benzotriazolates are a new group of chemical compounds.

Quaternary ammonium halides constitute a rich group of compounds. These are ionic substances that owe their wide range of applications to this structure. Quaternary ion pairs with a chloride anion are used in numerous applications, ranging from surfactants, through impregnations in construction and in the cosmetic and pharmaceutical industries, to the broadly understood organic synthesis.

The subject of the invention is quaternary ammonium benzotriazolates of general formula I in which R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent having from 1 to 18 ₅ carbon atoms, R ⁵ is a methyl group.

The method for the preparation of quaternary ammonium benzotriazolates of the general formula I, in which R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent containing from 1 to 18 ₅ carbon atoms, R ⁵ is a methyl group, consists in the quaternary ammonium halides of general formula 2, in which R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent containing from 1 to 18 carbon atoms, X is bromide or iodide or chloride, are exchanged in a molar ratio of 1: (0, 8-1,5) at a temperature of 293 to 350 K in an aqueous medium with a salt of an organic ₅ of formula 3, wherein R ⁵ is a methyl group, M is a potassium, sodium or ammonium hydroxide, and then the solvent is evaporated under reduced pressure at a temperature of 293 to 343 K, anhydrous acetone is added, then the precipitate is removed, acetone is evaporated off and dried under reduced pressure at a temperature of 313 to 343 K.

The second method for the preparation of quaternary ammonium benzotriazolates of general formula I, where R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent containing from 1 to 18 ₅ carbon atoms, R ⁵ is a methyl group, is that the quaternary halides ammonium compounds of general formula 2, in which R ¹ , R ² , R ³ , R ⁴ represent a straight-chain alkyl substituent containing from 1 to 18 carbon atoms, X is bromide or iodide or chloride, are exchanged in a molar ratio of 1: (0 , 8-1.5), in a methanol medium at a temperature of 277 to 373 K ₅ with an organic salt of the general formula 3, in which R ⁵ is a methyl group, M is a potassium or sodium or ammonium cation, then the precipitate is removed, the solvent is evaporated under reduced pressure at a temperature of 288 to 333 K, then anhydrous acetone is added, and after removing the precipitate, acetone is evaporated and dried under reduced pressure at a temperature of 303 to 358 K.

A third method for the preparation of quaternary ammonium benzotriazolates of general formula I, where R ¹ , R ² , R ³ , R ⁴ are a straight chain alkyl substituent containing from 1 to ₅ carbon atoms, R ⁵ is a methyl group, is that the quaternary ammonium halides of general formula 2, in which R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent containing from 1 to 18 carbon atoms, X is bromide or iodide, or chloride, are exchanged in a molar ratio of 1: (0 , 8-1.5) in a water-isopropanol environment at a temperature of ₅

288 to 373 K with an organic salt of general formula 3 in which R ⁵ is a methyl group, M is

Potassium or sodium or ammonium cation, then the organic layer containing the product is separated and washed with distilled water, then the solvent of the organic phase is evaporated under reduced pressure at a temperature of 293 to 353 K, then anhydrous acetone is added and after separating the precipitate, acetone was evaporated and dried under reduced pressure at a temperature of 293 to 373 K.

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

- new compounds belonging to the group of quaternary ammonium salts were obtained,

- compounds have an ionic structure where the anion is the benzotriazolate anion,

- ion pairs were obtained, including ionic liquids,

- liquid synthesis, ammonium benzotriazolates can be used as solvents,

- the obtained benzothyrizolates can be used as intermediates in organic synthesis,

- quaternary ammonium benzotriazolates show surface activity.

Summing up, the obtained compounds show both universal and multifunctional character.

The invention relates to quaternary ammonium 5-methylbenzotriazolates of the general formula 1, wherein R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent having from 1 to 18 ₅ carbon atoms, R ⁵ is a methyl group. The following examples illustrate the preparation of the above compounds:

P r z k ł a d I

Didecyldimethylammonium 5-Methylbenzotriazolate ₃

0.01 moles of the didecyldimethylammonium chloride in 10 cm ^{3 of} a mixture of water and isopropanol, Queen ₃ was added 0.0115 mol of potassium 5-metylobenzotriazolanu in 10 cm ³ of distilled water. The mixture was vigorously stirred for one hour at ambient temperature. The organic phase was then separated from the aqueous phase and washed with distilled water until the chloride was completely removed, the presence of which was monitored with an aqueous solution of silver nitrate. After removing the solvent from the organic phase, the residue was dried at 363 K under reduced pressure. The product in the form of a cream wax was obtained with a yield of 74%.

The structure of the obtained compound was confirmed by proton and carbon nuclear magnetic resonance:

¹ H NMR (DMSO-d6) 0.85 (t, J = 6.0Hz, 3H); 1.26 (m, 28H); 1.58 (m, 4H); 2.39 (s. 3H); 2.96 (s, 6H): 3.14 (t, J = 8.4 Hz, 4H); 6.8 (d. 1H); 7.43 (s. 1H); 7.54 (d, 1H) ¹³ C NMR (DMSO-d6) 14.0; 21.4; 22.1; 25.7; 28.5; 28.7; 28.8; 28.9; 31.3; 52.0; 62.7; 114.4; 115.2; 128.6; 142.8; 144.2;

The purity of the benzotriazolane was confirmed by elemental CHN analysis. For the salt with the general formula C29H54N4 (M = 458.77) the calculated% values: C = 75.92; H = 11.86; N = 12.21; values found in%: C = 76.28; H = 11.52; N = 12.04.

P r z x l a d II

Hexadecylthimethylammonium 5-Methylbenzotriazolate ₃

In a 100 cm ³ reactor equipped with a magnetic stirrer, 0.01 ₃ mol of hexadecyltrimethylammonium bromide in 10 cm ^{3 of} methanol was introduced and 0.008 mol of _{sodium 5-methyl 3-} benzotriazolate in 10 cm ^{3 of} methanol was added. The mixture was vigorously stirred for an hour at 323 K. After some of the inorganic salt was filtered hot, then the solvent was evaporated, and the residue was dissolved while hot in anhydrous acetone. After the inorganic salt was filtered off hot, the residue was recrystallized from anhydrous acetone. The product in the form of a white solid, m.p. 457-460 K, is obtained in 88% yield.

The structure of the obtained compound was confirmed by proton and carbon nuclear magnetic resonance:

¹ H NMR (CD 3 OD) 0.89 (t, 3H, J = 6.7Hz); 1.28 (m, 28H); 1.65 (m, 2H); 2.44 (s, 3H); 3.02 (s, 9H); 3.16 (t, 2H, J = 8.7Hz); 6.98 (d, 1H, J = 10Hz); 7.51 (s. 1H); 7.62 (d, 1H, J = 8.5Hz) ¹³ C NMR (CD3OD) 14.6; 22.0; 23.8; 24.0; 27.4; 30.3; 30.55; 30.6; 30.7; 30.8; 30.86; 33.15; 53.4; 67.8; 115.7; 116.5; 125.6; 133.0; 143.9; 145.6

The purity of the benzotriazolane was confirmed by elemental CHN analysis. For salts with the general formula C26H48N4 (M = 416.69)

Values calculated in%: C = 74.94; H = 11.61; N = 13.45;

Values obtained in%: C = 74.58; H = 11.96; N = 13.72;

PL 214 257 B1

P r z x l a d III

Tetrabutylammonium 5-Methylbenzotriazolate ₃

To 4.2 g of 5-metylobenzotriazolanu sodium in 15 cm ³ of water was added 8.6 g of tetrabutylammonium _three cherry dissolved in 20 cm ³ of water, stirred for one hour at 328K, and the resulting precipitate was removed and the solvent evaporated. The residue was dissolved in anhydrous acetone and the remainder of the inorganic salt was removed. After evaporating off the solvent, the residue was dried under reduced pressure at 358 K. The product was obtained in the form of a straw-colored liquid with a yield of 96%.

The structure of the obtained tetrabutylammonium 5-methylbenzotriazolate was confirmed by proton and carbon nuclear magnetic resonance:

¹ H (CDCl3) 0.82 (t, J = 1 Hz, 12H); 1.02 (m, 16H); 2.35 (m, 11H); 6.85 (d, J = 9.9 Hz, 1H); 7.51 (s. 1H); 7.63 (d, J = 8.8 Hz, 1H);

¹³ C (CDCl 3) 13.2; 18.9; 21.3; 23.0; 57.0; 114.8; 115.5; 122.8; 129.9; 142.9; 144.5.

The purity of the salt obtained was confirmed on the basis of CHN elemental analysis: for values calculated in%: C = 73.74; H = 11.30; N = 14.96; values found in%: C = 73.54; H = 11.03; N = 14.64.

P r x l a d IV

Trioctylmethylammonium 5-Methylbenzotriazolate ₃

To a reactor containing 10 mmol of 5-metylobenzotriazolanu ammonium in 15 cm ³ of methanol and ₃ were given 13 mmol trioktylometyloamoniowego iodide dissolved in 20 cm ³ of methanol. The mixture was stirred for one hour at 328 K. Then, after removing the precipitate, the solvent was evaporated, the residue was dissolved in anhydrous acetone and the remaining inorganic salt was removed. After evaporating off the solvent, the residue was dried under reduced pressure at 358 K. The product was obtained in the form of a straw-colored liquid with a yield of 98%.

The purity of the product obtained was determined on the basis of CHN elemental analysis. For the salt of the summarized formula C32H60N4 (500.85), the following data was obtained, expressed as a percentage, calculated C = 76.74; H = 12.07; N = 11.19; and the values found C = 76.41; H = 11.86; N = 10.93.

P r z k ł a d V

Tetraoctylammonium 5-Methylbenzotriazolate ₃

1.7 g of 5-metylobenzotriazolanu potassium in 15 cm ^{3 of} methanol were added 7.8 g of iodide tetraoktyloamo _three cherry dissolved in 20 cm ³ of methanol. The mixture was stirred for one hour at 338 K. Then, after removing the precipitate, the solvent was evaporated, the residue was dissolved in anhydrous acetone and the remaining inorganic salt was removed. After evaporating off the solvent, the residue was dried under reduced pressure at 358 K. The product was obtained in the form of a straw-colored liquid with a yield of 96%.

The purity of the product obtained was determined on the basis of CHN elemental analysis. For the salt of the summarized formula C39H74N4 (599.03) the following data was obtained, expressed as a percentage, calculated C = 78.20; H = 12.45; N = 9.35; and the values found C = 77.93; H = 12.18; N = 9.06.

P r x l a d VI

Tetramethylammonium 5-Methylbenzotriazolate ₃

In a round-bottomed flask 12 mmol of 5-metylobenzotriazolanu ammonium in 15 cm ³ Me ₃ tanolu and 10 mmol of tetramethylammonium iodide are dissolved in 20 cm ³ of methanol. The mixture was stirred for one hour at 338 K. Then, after removing the precipitate, the solvent was evaporated, the residue was dissolved in anhydrous acetone and the remaining inorganic salt was removed. After evaporating off the solvent, the residue was dried under reduced pressure at 358 K. The product was obtained in the form of a straw-colored liquid with a yield of 95%.

The purity of the product obtained was determined on the basis of CHN elemental analysis. For the salt of the summarized formula C11H18N4 (206.29), the following data was obtained, expressed as a percentage, calculated C = 64.05; H = 8.79; N = 27.16; and the values found C = 63.72; H = 8.44; N = 26.88

P r o x l a d VII

Tributylmethylammonium 5-methylbenzotriazolate ₃

A round bottom flask was placed 10 mmol of 5-metylobenzotriazolanu ammonium in 15 cm ³ and Me ₃ tanolu 12 mmol tributylometyloamoniowego bromide dissolved in 20 cm ³ of methanol. The mixture was stirred for one hour at 338 K. Then, after removing the precipitate, the solvent was evaporated, the residue was dissolved in anhydrous acetone and the remaining inorganic salt was removed.

PL 214 257 B1

After evaporating off the solvent, the residue was dried under reduced pressure at 358 K. The product was obtained in the form of a straw-colored liquid with a yield of 95%.

The purity of the product obtained was determined on the basis of CHN elemental analysis. For the salt of the summarized formula C20H36N4 (332.53) the following data was obtained, expressed as a percentage, calculated C = 72.24; H = 10.91; N = 16.85; and the values found C = 71.94; H = 10.65; N = 16.68.

Claims (4)

Patent claims CLAIMS 1. Quaternary ammonium salts with a 5-methylbenzotriazole anion of the general formula 1, wherein R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent having from 1 to 18 ₅ carbon atoms, R ⁵ is a methyl group. 2. A process for preparing quaternary ammonium salts of 5-metylobenzotriazolowym anion of the general formula 1, wherein R ^1, R ^2, R ^3, R ⁴ represent a straight chain alkyl radical containing from 1 ₅ to 18 carbon atoms, R ⁵ is methyl, characterized in in that the quaternary ammonium halides of general formula 2, wherein R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent containing from 1 to 18 carbon atoms, X is bromide or iodide or chloride, are exchanged in the ratio molar ratio of 1: (0.8-1.5) at a temperature of 293 to 350 K in ₅ Wed aqueous medium with an organic salt of general formula 3 wherein R ⁵ is a methyl group, M is a cation of sodium or potassium, or ammonium, then the solvent is evaporated under reduced pressure at a temperature of 293 to 343 K, anhydrous acetone is added, then the precipitate is removed, acetone is evaporated and dried under reduced pressure at a temperature of 313 to 343 K. 3. A process for preparing quaternary ammonium salts of 5-metylobenzotriazolowym anion of the general formula 1, wherein R ^1, R ^2, R ^3, R ⁴ means a _{straight-five} substituent alkyl ether containing 1 to 18 carbon atoms, R ⁵ is a methyl group, characterized in that the quaternary ammonium halides of the general formula 2 in which R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent containing from 1 to 18 carbon atoms, X is bromide or iodide or chloride, are subjected to an exchange reaction in molar ratio of 1: (0.8-1.5) in methanolic medium ₅ at a temperature of 277 to 373 K with an organic salt of general formula 3 wherein R ⁵ is methyl, M is sodium or potassium cation, or ammonium, then the precipitate is removed, the solvent is evaporated under reduced pressure at a temperature of 288 to 333 K, then anhydrous acetone is added, and after removing the precipitate, acetone is evaporated off and dried under reduced pressure at a temperature of 303 to 358 K . 4. A process for preparing quaternary ammonium salts of 5-metylobenzotriazolowym anion of the general formula 1, wherein R ^1, R ^2, R ^3, R ⁴ represent a straight chain alkyl radical containing from 1 ₅ to 18 carbon atoms, R ⁵ is methyl, characterized in in that the quaternary ammonium halides of general formula 2, wherein R ¹ , R ² , R ³ , R ⁴ represent a straight chain alkyl substituent containing from 1 to 18 carbon atoms, X is bromide or iodide, or chloride, are subjected to an exchange reaction in molar ratio of 1: (0.8-1.5) in an aqueous isopropanol at a temperature of from ₅ 288 to 373 K with an organic salt of general formula 3 wherein R ⁵ is methyl, M is sodium or potassium cation, or ammonium, then the organic layer containing the product is separated and washed with distilled water, then the solvent of the organic phase is evaporated under reduced pressure at a temperature of 293 to 353 K, anhydrous acetone is further added, and after separation After the precipitate is formed, acetone is evaporated and dried under reduced pressure at a temperature of 293 to 373 K.