PL215075B1 - 4-benzyl-4-methyl morpholine salts with inorganic anion and the method of manufacturing 4-benzyl-4-methyl morpholine salts with inorganic anion - Google Patents

Description

The present invention relates to 4-benzyl-4-methylmorpholine salts with an inorganic anion and a process for the preparation of 4-benzyl-4-methylmorpholine salts with an inorganic anion.

Ionic liquids are becoming more and more popular due to their many interesting properties, such as low vapor pressure, high ionic conductivity, wide electrochemical window and high thermal stability. The innumerable possibility of combining various cations and anions allows the synthesis of ionic liquids by modifying their properties as expected. The impurities in the final product also have a great influence on the properties of the compounds, so the possibility of obtaining pure compounds is of great importance.

The invention relates to the 4-benzyl-4-methylmorpholine salts of the general formula I, wherein A is tetrafluoroborate or hexafluorophosphate or trifluoromethyl sulfonate or bis (trifluoromethylsulfonyl) imide or nitrate (V) or nitrate (III).

The preparation of 4-benzyl-4-methylmorpholine salts consists in reacting morpholine halides of general formula 2 in which X is chlorine or bromine or iodine with an inorganic salt of general formula 3 in which M is sodium or potassium, A is tetrafluoroborate, or trifluoromethylsulfonate, or nitrate (V) or nitrate (III), with a stoichiometric amount or 5% excess inorganic salt at a temperature of 273 to 373K. preferably 303K in water, then odpa ₃ rowuje water under reduced pressure, followed by addition of 30 cm ³ of anhydrous acetone, and the precipitate is separated by filtration and the acetone is evaporated from the filtrate, hereafter the product is dried under reduced pressure.

The second preparation method is that morpholino halides of general formula 2 in which X is chlorine or bromine are reacted with an inorganic salt of general formula 3 in which M is lithium or sodium, A is hexafluorophosphate or bis (trifluoromethylsulfonyl) imide , with a stoichiometric amount or a 5% excess of inorganic salt at a temperature of 273 to 373K, preferably 298K, in water, then the hydrophobic product is separated, then the product is rinsed with distilled water until the disappearance of halogen ions in the effluent, and after separation of the layers, the product is dried in a vacuum dryer.

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

- new chemical compounds belonging to the group of morpholine ionic liquids were obtained,

- the synthesis mechanism is not complicated and the total reaction time is short,

- the product was obtained with high efficiency and high purity,

- synthesized chemical compounds have an ionic structure, which means that they do not evaporate at moderate temperatures,

- an additional oxygen atom in many cases has a positive effect on the properties of the compounds,

- water-soluble and insoluble ionic liquids were obtained,

- the use of a morpholine cation makes the obtained compounds cheaper than the commonly known and used imidazolium salts.

The invention is 4-benzyl-4-methylmorpholinium salts of general formula I, wherein A is tetrafluoroborate or hexafluorophosphate or trifluoromethyl sulfonate or bis (trifluoromethylsulfonyl) imide or nitrate or nitrate (III), and the method of their preparation the following examples illustrate:

P r z k ł a d I

4-Benzyl-4-methylmorpholine tetrafluoroborate ₃

In a reactor with a capacity of 50 cm ³ provided with a magnetic stirrer provided ₃

0.0187 mole of sodium tetrafluoroborate dissolved in 20 cm ³ of distilled water and added ₃

0.0179 mole of 4-benzyl-4-methylmorpholine chloride dissolved in 15 cm ³ of distilled water. The reaction was carried out for 24 hours at the temperature of 303K. After the water was evaporated, the residue ₃ was dried at 315K under reduced pressure. The product was then dissolved in 25 cm ^{3 of} anhydrous acetone. An inorganic precipitate formed which was filtered off, and the filtrate's solvent was evaporated.

The residue was dried at 323K in a vacuum oven. The product was obtained in the form of a white solid, m.p. 361-364K in a yield of 82%.

PL 215 075 B1

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

¹ H NMR (DMSO) δ ppm = 3.06 (s, 3H); 3.32 (t, J = 9.74 Hz, 2H); 3.53 (t, J = 3.15 Hz, 2H); 3.98 (t, J = 6.77 Hz, 4H); 4.68 (s. 2H); 7.54 (m, 5H);

¹³ C NMR (DMSO) δ ppm = 44.9; 58.6; 59.8; 67.7; 127.1; 129.0; 130.4; 133.2.

The purity of the obtained compound was confirmed by the elemental CHN analysis performed.

For C12H18NOBF4 (M = 279.08), the values calculated in% are C = 51.64; H = 6.50; N = 5.02 and the values found in% C = 51.93; H = 6.12; N = 5.49.

P r z x l a d II

4-Benzyl-4-methylmorpholine trifluoromethylsulfonate

To the reactor was charged with 0.0153 mol of sodium triflate dissolved head of 20 cm of distilled water were added 0.0146 mol of 4-benzyl-4-methylmorpholinium puszczonego a size ₃ in 20 cm ³ of distilled water. The reaction was carried out for 24 hours at temperature

303K. After the water was evaporated, the residue was dried at 323K under reduced pressure. ₃

The product was then dissolved in 30 cm ^{3 of} anhydrous acetone. An inorganic precipitate formed which was filtered off, and the filtrate's solvent was evaporated. The residue was dried at 318K under reduced pressure.

The product was obtained in the form of a slightly yellow liquid with a high viscosity, with a yield of 94.5%. The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

¹ H NMR (DMSO) δ ppm = 3.06 (s, 3H); 3.33 (t, J = 4.26 Hz, 2H); 3.53 (t, J = 2.74 Hz, 2H); 3.98 (t, J = 2.91 Hz, 4H); 4.68 (s. 2H); 7.54 (m, 5H);

¹³ C NMR (DMSO) δ ppm = 45.0; 58.6; 59.8; 67.7; 114.3; 118.5; 122.8; 127.1; 128.9; 130.4;

133.2.

P r x l a d III

4-Benzyl-4-methylmorpholine nitrate ₃

_{0.0206 3} mol of potassium nitrate salt dissolved in 20 cm ³ of distilled water were placed in a 50 cm ³ flask equipped with a magnetic stirrer _{and 0.0194 mol 3} of 4-benzyl-4-methylmorpholine bromide dissolved in 10 cm ^{3 was added.} distilled water. The reaction was carried out for 8 hours at the reflux temperature of the solvent. After the water was evaporated, the product _{3 was} dissolved in 30 cm ^{3 of} anhydrous acetone. An inorganic precipitate formed which was filtered off. The filtrate's solvent was evaporated under reduced pressure and the residue was dried at 323K under reduced pressure.

The product was obtained in the form of a liquid with a yield of 98%.

Compound purity was confirmed by elemental CHN analysis.

For C12H18N2O4 (M = 254.28) the following values were established:

calculated C = 56.68; H = 7.13; N = 11.02 and found C = 57.03; H = 6.85; N = 11.46 percent.

P r x l a d IV

4-Benzyl-4-methylmorpholine nitrate (III)

To a round bottom flask equipped with a magnetic stirrer, were introduced 0.022 mol salt ₃ nitrate (III) of sodium dissolved in 20 cm ³ of distilled water and to the solution was added 0.021 ₃ mol of iodide 4-benzyl-4-methylmorpholinium dissolved in 20 cm ³ of distilled water . The reaction was carried out for 8 hours at the reflux temperature of the solvent. Then, evaporated water and the product ₃ is dissolved in 25 cm ³ of anhydrous acetone. A white crystalline solid precipitated. The precipitate was filtered off and the filtrate was evaporated off acetone. The residue was dried in vacuum drying.

The product was obtained in 91% yield as a liquid.

The results of the CHN elemental analysis for C12H18N2O3 (M = 238.28) are as follows: values calculated in%: C = 68.09; H = 7.07; N = 7.56;

values obtained in%: C = 67.94; H = 6.98; N = 7.69.

P r z k ł a d V

4-Benzyl-4-methylmorpholine hexafluorophosphate ₃

0.0155 mol of potassium hexafluorophosphate dissolved in 20 cm ³ of distilled water was introduced into the reactor. To the solution was added 0.0148 mol of 4-benzyl-4-methylmorpholinium puszczonego a size ₃ in 20 cm ^{3 of} distilled water. The reaction was carried out for 24 hours at the temperature of 298K. A second layer formed in the reactor and was washed several times after the water had been separated off

With water to completely remove the inorganic salt. The presence of chlorides in the effluent was checked with an aqueous solution of silver nitrate. After the layers were separated, the product was dried at 323K in a vacuum dryer.

The product was obtained in 89.5% yield in the form of a white solid, m.p. 397-399K.

Compound purity was confirmed by elemental CHN analysis. For C12H18NOPF6 (M = 337.24) the following values were found: calculated C = 42.74; H = 5.38; N = 4.15 and found C = 42.65; H = 5.47; N = 4.23 percent.

P r x l a d VI

4-Benzyl-4-methylmorpholine bis (trifluoromethylsulfonyl) imide ₃

In a flask with a capacity of 50 cm ³ provided with magnetic agitation provided ₃

0.0111 mole of bis (trifluoromethylsulfonyl) imidku lithium dissolved in 20 cm ³ of distilled water, ₃ then 0.0105 mol of 4-benzyl-4-methylmorpholinium dissolved in 10 cm ³ of distilled water. The reaction was carried out for 24 hours at the temperature of 298K. A second layer had formed in the flask, which was washed several times with water after separating the water to completely remove the inorganic salt. The presence of chlorides in the effluent was checked with an aqueous solution of silver nitrate. After the layers were separated, the product was dried at 323K under reduced pressure.

The product was obtained in the form of a colorless liquid with a yield of 83%.

The purity of the obtained morpholine salt is confirmed by the elemental CHN analysis performed for

C14H18N2O5F6S2 (M = 472.42): calculated values in%: C = 35.59; H = 3.84; N = 5.93; values found in%: C = 35.47; H = 3.92; N = 5.87.

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

¹ H NMR (DMSO) δ ppm = 3.06 (s, 3H); 3.33 (t, J = 4.26 Hz, 2H); 3.54 (t, J = 2.74 Hz, 2H); 3.98 (t, J = 2.88 Hz, 4H); 4.68 (s. 2H); 7.55 (m, 5H);

¹³ C NMR (DMSO) δ ppm = 45.0; 58.6; 59.9; 67.8; 113.1; 117.4; 121.6; 125.9; 127.1; 128.9;

130.4; 133.2.

Claims (3)

CLAIMS 1. 4-benzyl-4-methylmorpholinium salts with an inorganic anion of the general formula wherein A is tetrafluoroborate, or hexafluorophosphate, or trifluoromethylsulfonate, or bis (trifluoromethylsulfonyl) imide, or nitrate (V), or nitrate (III). 2. A process for the preparation of 4-benzyl-4-methylmorpholine salts according to claim 1 The process of claim 1, wherein the morpholine halides of the general formula in which X is chlorine or bromine or iodine are reacted with an inorganic salt of the general formula Wherein M is sodium or potassium, A is tetrafluoroborate, or trifluoromethylsulfonate, or nitrate (V) or nitrate (III), with a stoichiometric amount or 5% excess of an inorganic salt at a temperature of 273 to 373K, preferably 303K, in water, then the water is evaporated under reduced pressure _3, and then added to ³ cm of anhydrous acetone, and the precipitate is separated by filtration and the acetone is evaporated from the filtrate, the product further dried under reduced pressure. 3. A process for the preparation of 4-benzyl-4-methylmorpholine salts according to claim 1 A process as claimed in claim 1, characterized in that the morpholine halides of the general formula in which X is chlorine or bromine are reacted with an inorganic salt of the general formula in which M is lithium or sodium, A is hexafluorophosphate or bis (trifluoromethylsulfonyl) imide, with a stoichiometric amount or % excess of inorganic salt at a temperature of 273 to 373K, preferably 298K, in water, then the hydrophobic product is separated, then the product is rinsed with distilled water until the disappearance of halogen ions in the effluent, and after separation of the layers, the product is dried in a vacuum dryer.