Carl Monder

Synthesis of steroids containing the α-keto acid side-chain ☆

Abstract A general method for the chemical synthesis of steroidal 20-keto-21-oic acids is described. 21-Dehydrocorticosteroids, in the presence of catalytic amounts of cyanide ion, are oxidized by methylene blue or chromium trioxide at neutral pH to the corresponding keto acids.

Synthesis of 21-3H-corticosteroids

Abstract General methods for the synthesis of (21R-21- 3 H) and (21S-21- 3 H) corticosteroids are described. The mixed isomeric products were synthesized chemically by reduction of 21-dehydrocorticosteroids with sodium borotritiide. The individual enantiomeric forms were synthesized by stereospecific enzyme-catalyzed reactions of appropriately labeled 21-dehydrocorticosteroids and NADH to form the (21R-21- 3 H) isomer and of unlabeled corticosteroids and NAD-4S- 3 H for the 21S-21- 3 H isomer.

Localization and metabolism of 1,2-3H-vitamin D3 and 26,27-3H-25-hydroxycholecalciferol in goldfish (Carassius auratus L.)

Abstract 1. 1. Goldfish ( Carassius auratus L.) was found to contain 50–60 I.U. of vitamin D 3 per 100 g body weight. Concentration in viscera was five to six times greater than in the remainder of the fish. 2. 2. Radioactivity from a dose of 3 H-vitamin D 3 accumulated mainly in intestine and liver. 3. 3. In neither intestine, liver, gallbladder nor blood was there quantitatively significant transformation of 3 H-vitamin D 3 to 25-hydroxycholecalciferol (25HCC) or related metabolites. 4. 4. When 3 H-25HCC was injected into goldfish it rapidly disappeared from all tissues examined and accumulated in the gallbladder in part unmodified and in part as unidentified metabolites. 25HCC could not be retained in the intestine. 5. 5. It was concluded that goldfish can accumulate vitamin D, but cannot metabolize it.

Gas chromatographic and mass spectrometric analysis of urinary acidic metabolites of cortisol

A method is described suitable for the analysis of the urinary acidic metabolites of cortisol which are amongst the major metabolites of this hormone (5-25% of secretion). Following hydrolysis of the urinary glucuronide conjugates and extraction of the freed steroids, methyl ester-trimethylsilyl ethers were prepared for gas chromatographic analysis. This analysis was carried out on open tubular columns coated with Carbowax stationary phase. The polar phase column permitted the complete resolution of the four acidic metabolites: alpha-cortolonic, beta-cortolonic, alpha-cortolic and beta-cortolic acids.

Lack of vitamin D3 synthesis by goldfish (Carassius auratusl)

Abstract 1. 1. Goldfish (Carassius auratus L. ) did not accumulate radioactive vitamin D in their visceral organs after they were injected with cholesterol-4-14C, 7-dehydrocholesterol-4-14C, dl -mevalonic acid-2-14C, sodium acetate-1,2-14C and l -amino acid mixture-U-14C. 2. 2. No conversion of dl -mevalonate-2-14C to vitamin D3 was detected over a 10-day period, whether the fish were maintained in the dark or continuously exposed to a fluorescent light. 3. 3. Almost all the radioactivity retained viscera after injection of 7-dehydrocholesterol-4-14C was sterol; none of the radioactivity which remained unprecipitated with digitonin was vitamin D3.

Enzyme mediated reduction of 21-Dehydrocorticosteroids at C-20: isolation and characterization of derivatives containing the 20β-Hydroxy-21-Aldehyde side chain

Abstract A method for the stereospecific reduction of 21-dehydrocorticosteroids with bacterial 20β-hydroxy-steroid dehydrogenase to form 20β-hydroxy-21-aldehyde derivatives is described. These products have been given the trivial designation “isocorticosteroids”. The isocorticosteroid homologues of 11-deoxy-corticosterone, corticosterone, 11-deoxycortisol and cortisol were prepared in yields of 84–96%. The new compounds have been characterized by physcial and chemical criteria.

Identification of 11β,17α-dihydroxy-3,20-dioxo-4-pregnene-21-al-1,2-3H (21-dehydrocortisol-1,2-3H) and 11β-hydroxy-4-androstene-3,17-dione-1,2-3H as contaminants in preparations of cortisol-1,2-3H

Abstract Cortisol-1,2- 3 H purchased from several sources contained two contaminants. One of these was identified as 21-dehydrocortisol-1,2- 3 H (11β,17α-dihydroxy-3,20-dioxo-4-pregnene-21-al-1,2- 3 H) by chromatographic mobility, ΔR M , enzymatic conversion to cortisol with 21-hydroxysteroid dehydrogenase, and crystallization of derivatives to constant specific activity. The second was shown to be 11β-hydroxy-4-androstene-3,17-dione-1,2- 3 H on the basis of its chromatographic mobility and crystallization to constant specific activity.

The stereochemistry of enzymic reduction of 21-dehydrocortisol to cortisol.

Abstract A 21-hydroxysteroid dehydrogenase of sheep liver that causes reduction of 21-dehydrocortisol to cortisol does so with transfer of hydrogen from the 4-pro-S-position of NADH to the 21-pro-S-position of cortisol.