RU1213723C - Dialkydicyclohexyl-18-crown-6 as extracting agents of potassium, mercury, iron, lead, indium, thallium, gallium and strontium from solutions - Google Patents

Abstract

Dialkalpicyclohexip-18-crown-6 of the general formula, where R is isopropyl n-butia isopentide n-hexide n-octy n-decide n-dodecid as ekagenti capa mercury, iron, lead, indie, tally, gallium and strontium from solutions .

Description

The invention relates to new chemical compounds, namely dialkyldicyclohexyl-18-crown-6, which are used as extractants in metal recovery and separation processes.

An object of the invention is to increase the extraction properties in a series of dicyclohexyl-18-crown-6 derivatives.

Example. I. Preparation of 4-isopropyl-cyclohexanol.

A mixture of 27.2 g (0.2 mol) of 4-isopropylphenol and 3 g of industrial alloy Nt-AI-Ti catalyst in 200 ml of isopropyl alcohol was placed in a 0.5 L steel autoclave and hydrogenated at 170 ° C with stirring and a pressure of 70 atm for 3 hours until the absorption of 0.6 M hydrogen. After cooling, the catalyst was filtered off and isopropyl alcohol was distilled off. The residue is a liquid which, according to GLC, is a final product with a purity of 99.5%. 28.1 g of 4-isopropylcyclohexanol obtained, yield 98.4%; t.kip. Yub-YuV S / ZO mm Hg 1.4660, 0.922.

By catalytic hydrogenation of the corresponding 4-alkylphenol, 4-butylcyclohexanol, 4-isopentylcyclohexanol, 4-hexylcyclohexanol, 4-octylcyclohexanol, 4-decylcyclohexanol, 4-dodecylcyclohexanol are obtained.

II. Preparation of 4-isopropylcyclohexene.

A mixture of 27 g of 4-isopropylcyclohexanol and 15 ml of 85% phosphoric acid was placed in a flask connected to a top-down cooler and a vacuum was created in the system (pressure 30 mm Hg). The mixture was heated to boiling and held until the distillation of water and 4-isopropyl-cyclohexane had ceased. The lower aqueous layer was separated from the obtained distillate, the upper layer was dried with NaCl and distilled.

Received 21.7 g of 4-isopropylcyclohexane, yield 92.1%, bp. 125-127 ° C, iodine number 203 (Theor. 204.7).

Similarly, dehydration of the corresponding 4-alkylcyclohexanol gives 4-butylcyclohexene, 4-isopentylcyclohexene, 4-hexylcyclohexene, 4-octylcyclohexene, 4-decylcyclohexene, 4-dodecylcyclohexene.

III. Preparation of 4-isopropylcyclohexanediol-1,2.

To 18.6 g of 4-isopropylcyclohexene and with stirring and cooling, a mixture consisting of 18.8 g of glacial acetic acid was slowly added. 18.8 g of 30% H202 and 2 g of concentrated sulfuric acid. The infusion rate is controlled as follows. so that

the temperature remained in the range of 20-25 ° C. Then the mixture is heated for 3 hours at 45 ° C, after cooling, it is neutralized with sodium hydroxide solution and the product is extracted

reactions with ether. The solvent was distilled off, the residue was distilled in vacuo.

Received 14.8 g of 4-isopropylcyclohexanediol-1.2, yield 62.4%, bp. 104-106 ° C / 2 mmHg

0 Found,%: C 68.43: H 11.39. CgHieOa.

Calculated,%: C 68.31; H, 11.47. 4-Butylcyclohexanediol-1,2 is taken into account analogously during the hydroxylation of the corresponding 4-alkylcyclohexene pol5;

4-isopentylcyclohexanediol-1.2; 4-hexylcyclohexanediol-1, 2; 4-octylcyclohexanediol-1, 2; 4-dodecylcyclohexanediol-1,2.

A mixture of 22.8 g of 4-isopropylpyrocatechol

0 and 2.5 g of industrial alloyed NI-AI-TI-catalyst in 200 ml of isopropyl alcohol are placed in a 0.5 L steel autoclave and hydrogenated at 160 ° C with stirring and a pressure of 80 atm for 5 hours to a concentration of 0.45 M hydrogen. After cooling, the catalyst was filtered off and isopropyl alcohol was distilled off. The remainder of the GLC data represents the final product with a purity of 99.1%.

0 23.4 g of 4-isopropylcyclohexanediol-1.2 are obtained, yield 97.8%. t.kip. 104-106 ° C / 2 mmHg

IV. Preparation of 4-isopropylcyclohexanediol di (2-hydroxyethyl) ester-1,2.

5 A mixture of 15.8 g of 4-isopropylcyclohexanediol-1.2, 32.2 g of ethylene chlorohydrin, 1.6 g of 18-crown-6 and 100 ml of a 40% aqueous KOH solution are heated with vigorous stirring in a closed vessel at 40 ° WITH

0 for 8 hours. After cooling, 130 ml of water are added to completely dissolve the precipitate, the organic layer is separated, the aqueous phase is extracted twice with 30 ml of ether. The organic solutions are combined, washed with 25 ml of a 3% hydrochloric acid solution and three times with 100 ml of water. Ether was distilled off, the residue was distilled in vacuo.

Obtain 14.9 g of di (2-hydroxyethyl) ether 4-isopropylcyclohe "diol-1,2 (1A),

0 yield 60.6%, bp 131-133 ° C / 0.1 mmHg Found,%: C 63.24; H, 10.71.

S1zN2b04

Calculated,%: C 63.38; H, 10.64.

Similarly, when dicyclohexyl-18-crown-6 (DTSG18K6) was used as catalyst 5, 2.3 g of the target product were obtained with a yield of 65.3%.

Similarly, by reacting the corresponding 4-alkylcyclohexanediol-1,2 with ethylene chlorohydrin in the presence of

alkalis under conditions of phase catalysis with crown ethers give di (2-hydroxyethyl) esters 4-6 butylcyclohexanediol-1,2 (16), 4-isopentylcyclohexanediol-1,2 (1c), 4-hexylcyclohexanediol-1,2 (1g ), 4-octyl-cyclohexanediol-1,2 (1e), 4-decylcyclr-hexanediol-1,2 (1e), 4-dodecylcyclohexanediol-1.2 (1g),

V. Preparation of 4-isopropylcyclohexanediol-1,2 (IIa) di (2-chloroethyl) ether

A mixture of 12.3 g of 4-isopropylcyclohexanediol-1,2-di (2-hydroxyethyl) ether, 5U ml of benzene and 8.7 g of pyridine is heated to boiling and 13.1 ml of thionyl chloride are added dropwise with stirring for 3 hours, then the mixture is boiled within 8 hours. After cooling, a solution of 1.5 ml of concentrated hydrochloric acid in 5 ml of water is added dropwise with stirring. The organic layer was washed with water and benzene was distilled off. The residue is a liquid which, according to GLC, is a final product with a purity of 94.5%.

Received 13.8 g of di (2-chloroethyl) ether 4-isopropylcyclohexanediol-1,2 (II a), yield 92.2%, C123.6% content (theoretical 25.03%). The di (2-chloroethyl) ethers of 4-butylcyclohexanediol-1,2 (II b), 4-pentylcyclohexanediol-1,2 (II c), 4-hexylcyclohexanediol-1,2 (II g), 4-ok - methylcyclohexanediol-1,2 (II e), 4-decylcyclohexanediol-1,2 (II e), 4-dodecylcyclohexanediol-1,2 (II g) .:

VI. Preparation of diisopropyl dicyclohexyl-18-crown-6.

 A mixture of 5.5 g of compound 1a, 6.8 g of compound IIa, 0.4 g of 18-crown-b and 25 ml of a 40% aqueous KOH solution is heated with vigorous stirring at 80 ° C for 7 hours. After 40 ml of water were added during cooling to completely dissolve the precipitate, the organic layer was separated, the aqueous phase was extracted twice with 10 ml of chloroform. The organic solutions are combined, washed with 10 ml of a 3% hydrochloric acid solution and three times with 50 ml of water. Chloroform was distilled off, the reaction product was purified by column chromatography on alumina (eluent hexane-chloroform-acetone 6: 1: 1).

5.5 g of diisopropyl dicyclohexyl-18-crown-6 (compound I) are obtained. yield 53.5%.

Found,%: C 68.25; H, 10.71.

S2bN480b

Calculated,%: C 68.38; H, 10.59.

IR spectrum vc-o-c 1106 cm no stretching vibrations of the hydroxyl group in the region of 3650-3200 cm

Similarly, when 0.6 g of compound I was used as a catalyst, compound I was obtained in a yield of 59.6%.

Similarly, condensation of compound 5 (16) with compound (Mb) gave dibutyl dicyclohexyl-18-crown-6 (Compound H) in 56.2% yield using compound II as a catalyst.

Found,%; C 69.26, H 10.88.

0С28Н5206

Calculated,%: C 69.38: H 10.81.

IR spectrum: Vc-oo 1105 cm there are no stretching vibrations of the hydroxyl group in the region of 3650-3200 cm 5 Similarly, by condensation of the compound (M c) with the compound (II c), diamyldicyclohexyl-18-crown-6 (comp. with a yield of 47.6% when using 18-crown-6 as a catalyst and with a yield of 55.5% 0, when using compound (II) as a catalyst.

Found,%: C 70.33: H 11.08.

SzoNBbOa

Calculated.%: C 70.27: H 11.01. 5 IR spectrum: vc-o-o 1108 cm there are no stretching vibrations of the hydroxyl group in the region of 3650-3200 cm

Similarly, by condensing compound (I g) with compound (11 g), dihexyl-0 dIcyclohexyl-18-crown-6 (compound) is obtained with a yield of 46.5% when using 18-crown-6 as a catalyst and with a yield of 54.9% when using compound IV as a catalyst. 5 Found,%: C 71.01: H 11.28.

S21NboOb

Calculated,%: C71.07; H, 1.18.

IR spectrum: vc-o-c 1107 cm there are no stretching vibrations of the hydroxyl group in the region of 3650-3200 cm

Similarly, upon the condensation of compound (I d) with compound (Id), dioctyldicyclohexyl-18-crown-6 (Compound V) was obtained in 51.2% yield using compound V as catalyst 5.

Found,%: C 72.31; H, 11.40.

SzbNbvOb

Calculated,%: c 72.44; H, 11.48.

IR spectrum vc-o-c 11.06 cm; there are no stretching vibrations of the hydroxyl group in the region of 3650-3200 cm.

Similarly, condensation of the compound

(I e) with compound (II e), didecyldicyclohexyl-18-crown-6 (compound VI) is obtained with a yield of 44.2% (catalyst 18-crown-6) and

52.4% yield (Compound VI catalyst).

Found,%: C 73.49; H, 11.81.

S40N7bOb

Calculated,%: C 73.57; H, 11.73.

IR spectrum: vc-o-c 1110 cm, there are no stretching vibrations of the hydroxyl group in the region of 3650-3200 cm. Upon condensation of compound (I g) with compound (I g), didodecyldicyclobxyl-18-Kpia-un-6 (compound VII) was obtained in 46.4% yield (18-crown-6 catalyst) and 50.8% yield ( catalyst compound VII).

Found,%: C 74.73; H, 11.82.

Sdddad

Calculated.%: C 74.52; H, 11.94.

IR spectrum: vc-o-c 1109 cm there are no stretching vibrations of the OH group in the region of 3650-3200 cm

Extraction properties of dialkyl dicyclohexyl-18-crown-6 (l-Vli compounds).

The results of comparing the extra-structural properties of l-Vll compounds with dicyclohexyl-18-crown-6 are presented in Table 1.

From the presented tabular data it follows that crown ethers with alkyl substituents in the cyclohexyl ring have a higher extraction ability compared to Unsubstituted dicyclohexyl-18-crown-6.

Table 2 shows the concentration distribution of metals

Comparison of the extraction of metal cations from 1.5 M nitric acid with 0.05 M solutions of derivatives 18-1crown-6 in chloroform. The initial aq "p1 solution contains 0.01 M each of the cations

nitric acid during extraction with 0.05 M solutions of crown ethers in chloroform.

Thus, the dependences of the distribution coefficients on the concentration of nitric acid are extreme in nature with a maximum extraction at 1.5 M nitric acid.

Table L.3 compares the solubility of crown ethers in water and nitric acid solutions of various concentrations.

The data presented in Table 3 indicate that the introduction into the cyclohexyl ring of alkyl radicals with

chain length from СЗН to Ci2H25 causes a decrease (more than 10,000 times) in the solubility of crown ethers in aqueous solutions compared to dicyclohexyl-18-crown-6. This means that the loss of extractants in

metal recovery processes are reduced from 10 kg per 1 m of the processed solution to 2-3 g / m. This is an advantage of dialkyl dicyclohexyl-18-crown-6 over an unsubstituted analog.

dicyclohexyl-18-crown-6.

(56) Copyright certificate of the USSR M: 931778, cl. C 22 V 26 L O, 1981.

Table 1

Table 2

Comparison of the dependence of the distribution coefficients of metals on the concentration

nitric acid upon extraction with 0.05 M solutions of crown ethers in chloroform for dicyclohexyl-18-crown-6 and compounds V and VI. The initial model solution contains 0.01 M

each cation

Table 3

Formula hierbrett and

Dialkyl dicyclohexyl-18-crown-b of the general formula

Yv

Cui; I yvp I viin

Tehred M; Morgenthal

Corre

Circulation of NGOs Search for Rospatent 113035, Moscow, Zh-35. Rauska nab., 4/5

Sub

Production and Publishing Plant Patent, Uzhhorod, 101 Gagarin St.

where R is iso-propyl, n-butyl, iso-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl. as extractants of potassium, mercury, iron, lead, indie, tally, gallium and strontium from solutions.

Corrector s. Patrusheva

., 4/5

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