Extraction of steroidal glucosiduronic acids from aqueous solutions by anionic liquid ion-exchangers

Abstract

A pilot study on the extraction of three steroidal glucosiduronic acids from water into organic solutions of liquid ion-exchangers is reported. A single extraction of a 0.5mm aqueous solution of either 11-deoxycorticosterone 21-glucosiduronic acid or cortisone 21-glucosiduronic acid with 0.1m-tetraheptylammonium chloride in chloroform took more than 99% of the conjugate into the organic phase; under the same conditions, the very polar conjugate, beta-cortol 3-glucosiduronic acid, was extracted to the extent of 43%. The presence of a small amount of chloride, acetate, or sulphate ion in the aqueous phase inhibited extraction, but making the aqueous phase 4.0m with ammonium sulphate promoted extraction strongly. An increase in the concentration of ion-exchanger in the organic phase also promoted extraction. The amount of cortisone 21-glucosiduronic acid extracted by tetraheptylammonium chloride over the pH range of 3.9 to 10.7 was essentially constant. Chloroform solutions of a tertiary, a secondary, or a primary amine hydrochloride also will extract cortisone 21-glucosiduronic acid from water. The various liquid ion exchangers will extract steroidal glucosiduronic acid methyl esters from water into chloroform, although less completely than the corresponding free acids. The extraction of the glucosiduronic acids from water by tetraheptylammonium chloride occurs by an ion-exchange process; extraction of the esters does not involve ion exchange.

Recovery of steroidal glucosiduronic acids from organic solvents containing anionic liquid ion-exchangers

“…NaHCO3. The ionexchanger Aliquat 336, a technical grade of tricaprylylmethylammonium chloride, is very similar to tetraheptylammonium chloride in its ability to promote extraction (Mattox et al, 1972) of glucosiduronic acids. We have separated a mixture of 11-deoxycorticosterone 21-glucosiduronic acid, 11deoxycortisol 21-glucosiduronic acid and cortisone 21-glucosiduronic acid on a column by using Aliquat 336 in chloroform as the mobile phase and KCI in formamide as the stationary phase (V. R. Mattox & J. E. Goodrich, unpublished work).…”

“…The techniques and reagents have been described by Mattox et al (1972). Myristic acid was obtained from Eastman Organic Chemicals, Rochester, N.Y., U.S.A. Partitions were done in duplicate in glassstoppered centrifuge tubes.…”

“…The extraction of a steroidal glucosiduronic acid and its methyl ester by Aliquat 336 (methyltricaprylylammonium chloride) has been reported by Mattox et al (1972); a solution of this quaternary ammonium chloride in chloroform removed about the same percentage of steroidal conjugates from aqueous solutions as was extracted by a comparable concentration of tetraheptylammonium chloride. Fig.…”

“…Studies by Mattox et al (1972) have shown that the partition of cortisone 21-glucosiduronic acid between water and a solution of tetraheptylammonium 0 547 +1.o Table 2. Effect ofpH on partition ofchloride and glucosiduronates The phases consisted of equal volumes of carbon tetrachloride (containing 0.05 M-tetraheptylammonium chloride and 0.0625M-myristic acid) and aqueous solutions; the concentrations of 11-deoxycorticosterone 21 -glucosiduronic acid (Q-GA) and cortisone 21-glucosiduronic acid (E-GA) were equivalent to 0.25,umol/ml of organic phase.…”

“…In the preceding paper (Mattox et al, 1972) we reported that certain steroidal glucosiduronic acids can be extracted almost quantitatively from aqueous solutions into organic solutions of liquid ion-exchanger. In other studies, liquid ion-exchangers have been used for chromatography of glucosiduronic acids on micro (Mattox & Goodrich, 1968;Mattox et al, 1970) and preparative scales (V. R. Mattox & J. E. Goodrich, unpublished work).…”