SU1689377A1 - Method for preparation of macrocyclic chelate compound, which is able to form complexes with alkaline and alkaline-earth metals in the medium of organic solvent - Google Patents

Abstract

The invention relates to the production of macrocyclic complexing agents in CTPI. THE COMPREHENSIVE TREATMENTS complexes of alkali and alkaline earth metals used for the extraction of these metals or as catalysts in organic solvents. The goal is to increase the solubility of campus formers in solvents. To do this, pyrocatechol is treated with 2-ethyl hexanol in the presence of sulfonic embossing in the H-form while boiling in toluene, followed by the addition of /./-dichloroethyl ester in the presence of KOH while boiling in isopropanol or buznolg. Then the solvent is distilled off, the residue is dissolved in the limiting hydrocarbon of Oor 6lt1.33 of a solution of 40-65% -iu.iM under the mouth of igthyohum potassium rhodanide к dcccg. lek g. and decompose it with water. Luchte. Thionite to use n 20-D) 0% about pgmo SME Ґ. PMrOKATRHIN. The resulting K,: - 1Plexer has an unlimited C solubility of e orgaimrs mx pr1st orts l x (СНС1з, SS. Hexane) in durable-. pills known. one . P. f-ly, 4.-i f.

Description

The present invention relates to an improved method for producing a complex-coater based on a macrocyclic oxygen-containing heterocyclic compound capable of forming complexes with alkaline or alkaline-earth-glegally in an organic solvent medium, which can be used to extract alkaline or alkaline-earth megaloids. , and also as catalysts in the environment of an organic solvent.

The purpose of the invention is to increase the solubility of comorbum in organic solutions of gels by using pyrocatechol 2-ethylhexyl alcohol in the preparation of microcrystalline complexing agents

Example 1, To a mixture of 11.0 g (0.1 mol) of pyrocatechin, 4.4 g of macroporous KU-23 sulfo-cagionite KU-23 (in H-forms) and 40 ml of toluene heated to boiling, 13.0 g (0 , 1 mol) of 2-ethylhexyl alcohol in 40 ml of toluene for 4 hours, while collecting iodine in the water separator after the end of the reaction. After drinking the mixture, the reaction mixture is maintained at boiling and stirring for 1-2 hours stop the release of water. Then the sul focation exchanger is filtered, fig'rat from O

with y

: WITH

N Ы

I pour 80 ml of hot water to remove unreacted catechol, the solvent toluene is distilled off. 14.3 g of 0.1 mol) D / -dichloro-diethyl sfirl, 80 ml of isopropyl alcohol ii 11 2 g of 0.2 mol) of potassium hydroxide are added to the residue and the mixture is boiled under stirring under inergcho gas for 13 hours 1 ml of concentrated hydrochloric acid is added to neutralize the reaction mass and the solvent is distilled by isopropyl alcohol. At the end of distillation, 80 ml of feed is added. I and the solvent is distilled off until the temperature of the steam reaches 100 ° C. 100 ml of hexane DPS frgchnuernip product is added. The organic layer is separated, washed with 3-Egem with water (the exane solution is contacted for 3 min with 30 ml of a 60% aqueous solution of potassium rhodanide) and the 1 pei phase that has precipitated is separated, washed with 20 ml (exane and dissolved in 50%). ml of chloroform Chloroform solution is re-extracted 2 times with water, chloroform is distilled off

20.8 g of the finished product are obtained in the form of a viscous liquid. By GLC and mass spectral analysis, the product contains 905% diisooxyl-dibenzo-18-crown-6 (diisoptyl DB18C6) 6iO isomers, output 64%

Example 2 Similar to Example 1, when used as a solvent in the reaction with (J, / 3-dichlorodiethyl ether, n6) hypochanol (instead of isopropyl), 18.1 g of complexoobium-1N are obtained. 56.1% yield . For 8 hours, 1 7 4 g of komplessobresovatel receive, yield 539%

The effect of the type of salt, solvent, concentration of the aqueous solution of salt used in the isolation of the macrocyclic complexing agent is shown in Table 1 (similar to example i)

When carrying out the process analogously to example 1 using different amounts of sulfonic cation exchanger (in May,% relative to pyrocatechin), the yield of the complexing agent, based on diiso-OCTIL-DB18C6, is%. with the use of 50% KU-23 v.Z 55% KU-23 66.0, 30% KU-23 62.0 25% KU-23 49.3, 40% sulfo cation gel KU-2 55 8;

Example 3. To a mixture of 11.0 g of pyrocatechin, 4.4 g of KU-23 sulfonic cation exchanger and 40 ml of toluene by naphtha before boiling, b 0 g (O, I mol) of isopropyl alcohol in 40 ml of toluene is added with stirring over 4 hours at the same time in the water separator collect

water released by the reaction After the addition of the alcohol is completed, the reaction mixture is maintained at reflux and stirring for 1-2 hours until the evolution of water is suppressed. Then the catalyst is filtered off, the filtrate is washed with 80 ml of hot water, the toluene is distilled off. 14.3 g of D-dichlorodiethylether, 80 ml of isopropyl alcohol and

0 11.2 g of potassium hydroxide, the mixture is boiled under stirring in an inert gas atmosphere for 13 hours. 1 ml of concentrated hydrochloric acid is added to neutralize the reaction mass, the solvent is distilled off. The residue is extracted with 300 ml of boiling hexane. After cooling, the hexane solution is washed with water, then contacted for 3 minutes with 30 ml of 60% aqueous

0 solution of potassium rhodanide. The precipitated third phase is separated, washed with 20 ml of hexane and dissolved in 50 ml of chloroform. The chloroform solution is extracted twice with water, and the chloroform is distilled off.

5 Get 7.1 g of the finished product in the form

in a viscous liquid. According to GLC and mass spectral analysis, the product contains 59.3% diisopropyl dibenzo-18-crown-6, 19.6% triisopropyldibenzo-18-crown-6 and

0 10 8% tetraisopropyl dibenzo-18-crown-6, yield 19.0% of the theoretical in terms of diisopropyl dibene-18 crown-6.

Example 4. Analogously to example 3 using pyrocatechin for the treatment

5 7.4 g (0.1 mol) of n-butyl alcohol does not form a macrocyclic complexing agent. When used to treat pyrocatechin 10.2 g (0.1 mol) of n-ethyl alcohol, macrocyclic

0 complexing agents also not received.

Example 5. To a mixture of 11.0 g of pyrocatechol, 4.4 g of KU-23 sulfonic cation exchanger and 40 ml of toluene heated to boiling, 7.4 g (0.1 mol) of tert-bu-5 alcohol in 40 ml were added with stirring. toluene for 4 hours while collecting water from the water separator as a result of the reaction. Next, the process is carried out as in Example 3.

0.8.8 g of the finished product is obtained, which according to GMH and mass spectral analysis contains 87.4% di-tert-butyldibenzo-18-crown-6. yield 32.6% of theoretical per di5 tert-butyldibenzo-18-crown-b.

Example 6. To a mixture of 11.0 g of pyrocatechol, 4.4 g of sulfonic acid KU-23 and 40 ml of toluene heated to boiling, 10.0 g (0.1 mol) of cyclohexitic alcohol 0 ml ( oluola in

for 4 hours, while water separated by the reaction is collected in the water separator. Next, the process is carried out as in Example 3.

Obtain 10.4 g of the finished product, which according to GLC and mass spectral analysis contains 88.6% of dicyclohexyldibenzo-18-crown-b, yield 35.2% of theoretical calculated on dicyclohexyl-dibenzo-18-crown-b .

Data solubility obtained complexing agents are given in table.2.

Example 7. Comparison of the complexing ability of macrocyclic complexing agents.

10 ml of a 3% solution of a macrocyclic complexing agent in chloroform are contacted for 3 minutes with 10 ml of a solution of potassium nitrate (1 g / l K4) in 5 M nitric acid. After separation of the phases, the concentration of potassium in the aqueous phase is determined by flame photometry and the distribution coefficient of Krc + is calculated as the ratio of the concentrations of potassium in the organic and aqueous phases:

. p to

Krrg.

Cki

drive

where SKorg. - Kish.r-ra SKvodn.

10 ml of a saturated solution of a macrocyclic complexing agent in hexane are contacted for 3 minutes with 10 ml of a solution of potassium nitrate (1 g / l K) in 5 M nitric acid. After separation of the phases, the organic phase is separated and reextracted 2 times in 5 ml of water. In the combined extraextrade, the potassium concentration is determined by flame photometry (Skorg) and Cr is calculated.

To compare the complexing ability of macrocyclic complexing agents, potassium distribution coefficients are used. The results are presented in table 3.

To compare the complexing ability of macrocyclic complexing agents, Table 4 presents the distribution coefficients (Kp) for alkali metals (sodium, potassium) and alkaline earth metals (calcium, strontium), which are determined by contacting 3% solutions of macrocyclic complexing.

5 10

15

0 5

0

five

0

c

g p

l in chloroform with solutions of azt sodium nitrite (1 g / l Na +) in 5 M nitric acid, potassium nitrate (1 i / l K4) in 5 M HNOa. calcium nitrate (1 g / l Ca) in 5 M nitric acid and strontium nitrate (1 g / l M NMO.h

The proposed method of obtaining a macrocyclic complexing agent as compared to the known allows increasing the solubility of the macrocyclic complexing agent in organic solvents to an unlimited solubility, including in saturated hydrocarbons, for example, in chloroform from 72 g / l to unlimited solubility in carbon with 1 , 8 g / l to unlimited solubility in hexane from 0.07 g / l to unlimited solubility. in hexane from 0.07 g / l to unlimited solubility and thereby expand the use of this complex-forming agent and reduce its amount

Claims (2)

Claim 1. A method for producing a macrocyclic complexing agent capable of forming complexes with alkali and alkaline earth metals in an organic solvent medium by reacting pyrocatechin with α, ω-cyclidistil ether in the presence of alkali while boiling in alcohol, characterized in that with the aim of increasing the solubility of macrocyclic complex in organic solvents, catechol is treated with 2-ethylhexyl alcohol in the presence of sulfo-cation exchanger in H as catalyst -form at boiling in toluene, followed by IHM interaction with D ft -dichlorodieth / ovol ether - the presence of potassium hydroxide at boiling in isopropyl or butyl alcohol, with further distillation of the solvent, dissolving the residue g of the limiting hydrocarbon, processing solution 40 -65% aqueous solution of potassium rhodanide, separation of the resulting complex of macrocyclic complexing agent with potassium rhodanide and isolation of the complexing agent by decomposition of the complex of the leaves. 2. Method pop, 1, characterized in that the sulfonic cation exchanger is used in an amount of 30-50% by weight relative to pyrocatechin. Table 1  50% solution. table 2 Table 3 Table 4