SU1065415A1 - Process for purifying crown esters derivatives of crown-6 - Google Patents

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4 The invention relates to a method for the purification of crown ethers derived from kraui-6 from organic impurities. Crown ethers are used as extractants for the extraction of metals and as catalysts for phase transfer in organic synthesis. A known method of purification of crown-ethers - derivatives of crown-6 by column chromatography on alumina or other solid carriers using organic solvents, such as hexane, heptane or acetone, as the customer. The disadvantages of the method are complexity, laboriousness, low productivity, especially with an increase in the scale of the process , and the need to use a large amount of easily volatile and flammable solvents. In addition, with this method of purification significant losses are possible, causing a decrease in the yield of the final product. So, to isolate DXG18K6 in pure form, 130 g of the product obtained after reduction of dibenzo-18kra. U-6 is dissolved in 400 ml of heptane, placed in a column with washed acid alumina and eluted with 700 ml of heptane, until it appears in IR the spectra of the eluate, the bands relating to the vibrations of the OH groups. The solvent is distilled off and the residue is recrystallized from ishexane. The yield of the final product in this case does not exceed 50. The aim of the invention is to simplify the process, as well as to increase the yield and the target product. This goal is achieved in that according to the method of purification of crown ethers - derivatives of crown-6 using an organic solvent solution of crown ether - derivative of crown-b, containing organic impurities, in a nonpolar organic solvent, such as a chlorinated hydrocarbon or aromatic hydrocarbon. hydrocarbon, is treated with 4.5-6.0 M aqueous solution of perchloric acid at -1020 C with subsequent decomposition of the resulting complex with water, washing it with a non-polar organic solvent, dissolving it in chloroform yoke, washing with water and drying by azeotropic distillation of water with IOM chlorophyll. as a non-polar organic solvent, tetrachloride carbon, hexane or benzene is used. Treatment with perchloric acid is carried out at a temperature of from -10 to. The purification method is based on the reaction of the interaction of crown ethers with perchloric acid to obtain solid stable complexes that are insoluble in water and non-polar organic solvents. The resulting complex has a composition of 1: 1 and its structure also includes a water molecule, which suggests that crown ethers form inclusion compounds with hydroxonium perchlorate. At the same time, all organic impurities of non-cyclic nature remain in the organic solvent and can be separated by filtration or decantation. The precipitated crown ether / perchlorate hydroxy complex is filtered or centrifuged and washed on the filter with non-polar organic solvents for further purification. The decomposition of the complex is carried out with water by treating it in a solution of chloroform or another suitable solvent until the waste water is neutral. Removal of chloroform gives crown ethers with a content of the main substance of 97-99%. When the cleaning operation is repeated, the content of the basic substance can be increased to 99-99.5%. The complex is precipitated already at room temperature, but most fully with the highest yield at low temperatures of -10-10 ° C, since below -10 ° C, due to the increased viscosity of the solution, the K separation (9plex is difficult. Increasing the temperature above 20 ° C increases the solubility of the complex. A significant role in the purification process of crown ethers is played by the concentration of perchloric acid. It has been established that using aqueous aqueous solution of perchloric acid with a concentration of 4.5-6.0 mol / l, the crown ether completely separates from the organic Solution in the form of a complex with hydroxy perchlorate. When using perchloric acid with a concentration below 4.5 mol / l, the crown ether may not be completely separated, while an increase in the acid concentration above 6.0 mol / l may lead to a decrease in the purity of the final product. Example 1. 50g of the mixture obtained after reduction of dibenzo-18-crown-6 and containing according to GLC 44.5 g of dicyclohexyl-18-crown-6 (DCG18K6), 1.8 g of benzocyclohexyl-18crown-6 and 3.7 g organic products of unknown composition, dissolved in 200 ml of carbon tetrachloride. The resulting solution was shaken at 0 ° C for 10 minutes with 100 ml of a 4.5 M aqueous solution of perchloric acid. The precipitate formed is filtered off, washed with 20 ml of carbon tetrachloride, dissolved in 100 ml of chloroform and treated 3 times with 50 ml of distilled water. Azeotrope-water azeotrope is distilled off by heating, then chloroform is then held under a vacuum of 2 mm Hg. for 1 hour to remove traces of solvent. PolyjjaroT44, 4 g DCG18K6, containing more than 10 according to GLC 99, 2% of the basic substance and not more than 0.1% of water, yield 99.0% of the theoretical. When used to precipitate a 4.0 M aqueous solution of the NDRO, 44.4 g of DCG18C6 is obtained, and when using 3.5m perchloric acid, 39.3 g of DCG18C6 is obtained. When used to precipitate a 6.0 M aqueous solution of perchloric acid, 44.4 g of DCG18C6 containing 99.0% of the basic substance are obtained, while using .6.5 M of perchloric acid, 44.5 g of DCG18C6 containing 97.5% of the basic substance are obtained. Example 2.5 g of a mixture formed during the preparation of di-iso-amyldicyclohexyl-18-crown-6 by the interaction of iso-amylcyclohexanediol-1,2 with chlor-yose bis-2-chloroethyl ether: and containing 2.8 g of di- i-amyldicyclohexyl-18crown-6, 0.6 g of the eac-amylcyclohex of diol-1, 2, 0.1 g of chrooxa and 1.5 g of organic compounds of unknown structure, dissolved in 25 ml of hexa and the resulting solution was shaken at 0 ° C for 10 min with 10 ml of a 4.5 M aqueous solution of perchloric acid. The precipitate introduced is filtered off, washed with 10 ml of hexane, dissolved in 10 ml of chloroform and then treated as in Example 1. 2.75 g of di-iso-amyldicylohexyl-18-crown-6 containing are obtained. 98.5% of the basic substance, yield 96.7% of the theoretical. Example 3. South of the mixture formed during the preparation of di-iso-amyldibenzo-18-crown-6 by the interaction of iso-amylpyrocatechin with chlorox and containing according to GLC 8,1di-iso-amyldibenzo-18-crown-6, 0.5 g mm - amylpyrocatechol, 1.0 g of diethyleneglycol diiso-amylpyrocatechol ether and 0.4 g of organically unknown compounds of unknown structure are dissolved in 50 ml of benzene and the resulting solution is shaken with for 10 minutes with 20 ml of 4.5 M aqueous solution perchloric acid. The precipitate formed is filtered off, washed with 10 ml of benzene, dissolved in 20 ml of chloroform and treated further in Example 1. Half of 8.0 g of di-Ie-amyldibenz 18-crown-6, containing according to GLC data 98.0% of the basic substance, yield 96.8% of theoretical. Example 4. 35g DTSG18K6 and 15 g of a mixture of polyethylene glycols НО (СН2СН2О) Н, p 4-12, are dissolved in 200 ml of carbon tetrachloride and precipitated at various temperatures with 4.5 M perchloric acid. Yield DTSG18K6: about 96.0%, with 97.7%, with - 98.4%. Example 5–50r of the mixture formed during the application; crown ethers as phase transfer catalysts in organic syntheses and containing according to GLC 9.1 g DCG18C6 and 40.9 g of organic products of unknown structure, dissolved in 200 ml of hexane and shaken at 0 ° C for 10 min with 50 ml of 4.5m aqueous perchloric acid solution. The precipitated precipitate is filtered off, washed with 3 times 20 ml of hexane, dissolved in 30 ml of chloroform and further treated as in Example 1. 8.9 g of DCG 1866 containing 97.8% of the basic substance are obtained, the yield is 95.7% of theoretical. Example 6. 50 ml of a long-running extractant containing 2.1 g of DTSG18K6 and 2.0 g of organic impurities of unknown structure in octane are shaken at 10 ° C for 10 minutes with 20 ml of 4.5 M perchloric acid. The precipitate formed is filtered off, washed with 10 ml of octane, dissolved in 10 ml of chloroform and further processed as in Example 1. 2.05 g of DCG18C6 is obtained, containing 99.1% of the basic substance, yield 96.7% of theoretical. Example 7 (known). 50 g of technical DTSG18K6 (O grade) obtained by reducing dibenzo18-crown-b and containing 74.0% DTSG18K6 according to GLC are dissolved in 200 ml of hexane and placed in a column with aluminum oxide (diameter 2 cm, height 100 cm). The alumina is prewashed with 5% hydrochloric acid, then with water until neutral, and dried. DKG18K6 is eluted from the column with 1800 ml of hexane, periodically taking samples of the eluate and analyzing them by GLC. The elution is completed when a mixture appears in the sample (according to GLC data), the process lasts 20 hours. Hexane is distilled off from the eluate while heating, and then kept under vacuum to remove traces of solvent. 18.8 g of DCG18K6 are obtained, containing, according to GLC, 98.0% of the basic substance, a yield of 49.8% of the theoretical. The alumina in the column is washed with 500 ml of acetone and 500 ml of hexane to prepare for the next cleaning operation.

Example 8. 50 g of technical DTSG18K6 (Grade 1), obtained by reducing dibene-18-crown-B and containing 74.0% of DCH18K6 according to GLC, are dissolved in 180 ml of carbon tetrachloride, the resulting solution is shaken at room temperature within 10 minutes with 80 m of 4.5m aqueous perchloric acid solution) a. The precipitated white precipitate is filtered off, washed with 2 O ml of carbon tetrachloride, dissolved in 80 ml of chloroform and treated 3 times with 50 ml of distilled water. The azeotrope of chloroform-water is distilled off with heating, then the chloroform is then kept under vacuum to remove traces of the solvent.

36.8 g of DCG18K6 are obtained, containing 98.0% of the basic, according to GLC. substances, yield 97.5% of theoretical

Example 9. 50g of the mixture obtained after reduction of dibenzo-18-crown-b and containing according to GLC 44.5 g of DTSG18K6, 1.8 g of benzocyclohexyl-18-crown-6 and 3.7 g of organic products of unknown structure, dissolved in 200 ml of four carbon chloride. The resulting solution is shaken for 10 minutes with 100 ml of a 6.0 M aqueous solution of perchloric acid. The precipitated white precipitate is filtered, washed with 20 ml of carbon tetrachloride, dissolved in 100 ml of chloroform and treated further by Example. 8.

I get 44.4 g of DTSG18K6 containing 99.0% of the basic substance, according to GLC, 98.8% of the theoretical yield.

. EXAMPLE 10 35 g of DTSG18K6 and 15 g of a mixture of polyethylene glycols HO {CH2CH2O) f, H, n 4-12 are dissolved in 200 ml of carbon tetrachloride and the resulting solution is shaken at -10 ° C for 10 minutes with 80 ml of 4.5 M aqueous perchloric acid solution. The precipitate formed is filtered off, washed with 20 ml of carbon tetrachloride, dissolved in

80 ml of chloroform and treated further in example 8.

Obtain 34.9 g of DTSG18K6 containing 98.7% of the basic substance, according to GLC, yield 98.4% of the theoretical

Similarly, when carrying out the process of example 10, 33.2 g of DTSG18K6 containing 98.2% of the basic substance are obtained, according to GLC data, a yield of 93.1% of theoretical, while precipitating 34.7 g of DCG18K6, containing according to GLC of 98.5% of the basic substance, yield 97.7% of the theoretical.

When conducting precipitation at a temperature below -10 ° C due to an increase in the viscosity of the solution, the separation of the complex is difficult.

This method allows to increase the yield of crown ethers by reducing cleaning losses from 50 to 98-99%, it takes 1-2 hours to clean any number of crown ethers, while using a known method, the cleaning time is 20-30 hours, and with an increase in the number of purified crown ether, the duration increases dramatically.

In this case, the proposed purification method makes it possible to drastically reduce the required amount of solvents from 2-3 to 200-300 ml, eliminate the use of combustible solvents, such as hexane, acetone, and remove crown ethers from bottom residues and Complex organic mixtures, which is difficult application of the known method.

In addition, the equalization of the cost of both processes by reagents (tab, faces shows that the cost of cleaning technical crown ethers (DTSG18K6) when producing 1 kg of pure product (98% purity) when applying the proposed method is 2.3 times lower than when using the known method, and the economic effect in the implementation of the proposed method will be 3584.36 rubles per 1 kg of finished product.

Known method

DTs18K6 technical (O grade)

Hexane TU 6-09-3375 /

Acetone GOST.2603-79

Aluminum oxide TU 6-09-3916-75

2052.00

5458.32 896.88

7.50 6.72

0.32

20.11

0.63

The proposed method

 DTSG18K6 technical (and copt),

Carbon tetrachloride GOST 20288-74

Chloroform GOST 20015-74

Perchloric acid 57% TU 6-09-2878-73

Table continuation

2052.00 2788.67

0.38

29 0.42 1.37

2.51

4.34

Claims (3)

1. METHOD FOR CLEANING CROWNESTERS - DERIVATIVES OF CROWN-6 Using an organic solvent, characterized in that in order to simplify the process and increase the yield of the target product, a solution of crown ether-derivative crown-6 containing organic impurities in a non-polar organic solvent, such as hydrocarbon, chlorinated hydrocarbon or aromatic hydrocarbon is subjected to treatment with 4.5-6 0 M aqueous solution of perchloric acid at a temperature of from -10 to + 2.0 ° C, followed by decomposition of the resulting complex with water, washing it non-polar organic solvent, by dissolving it in chloroform, washing with water and drying by azeotropic distillation of water with chloroform. 2. The method of pop. 1, characterized in that as a non-polar organic solvent using carbon tetrachloride, hexane or benzene. 3. The method according to π. 1, characterized in that in order to increase the yield of the target product, treatment with perchloric acid is carried out at a temperature of from -10 to +10 ⁰ C.