Synthesis and characterization by 1H and 13C nuclear magnetic resonance spectroscopy of 17α-cyano, 17α-aminomethyl, and 17α-alkylamidomethyl derivatives of 5α-dihydrotestosterone and testosterone
| Autor: | Elisabeth Mappus, Marc Rolland de Ravel, Christophe Chambon, Claude Yves Cuilleron, C. Grenot |
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| Rok vydání: | 1997 |
| Předmět: |
Magnetic Resonance Spectroscopy
Acylation medicine.medical_treatment Clinical Biochemistry Molecular Conformation Lithium aluminium hydride Methylation Biochemistry Medicinal chemistry Androgen-Binding Protein Chromatography Affinity Steroid chemistry.chemical_compound Endocrinology Sex Hormone-Binding Globulin Acetamides medicine Organic chemistry Testosterone Amines Potassium Cyanide Molecular Biology Ethylenedioxy Pharmacology Molecular Structure Organic Chemistry Acetylation Affinity Labels Dihydrotestosterone Nuclear magnetic resonance spectroscopy Carbon-13 NMR Acetic anhydride chemistry Indicators and Reagents Androstane |
| Zdroj: | Steroids. 62:603-620 |
| ISSN: | 0039-128X |
| DOI: | 10.1016/s0039-128x(97)00046-9 |
| Popis: | 17 alpha-Aminomethyl, 17 alpha-acetamidomethyl, and 17 alpha-hemiglutaramidomethyl derivatives of dihydrotestosterone and testosterone have been prepared by hydrocyanation of 3,3'-(ethylenedioxy)-5 alpha-androstan-17-one and 3,3'-ethylenedioxyandrost-5-en-17-one, reduction of the corresponding acetylated 17 alpha-cyanohydrins with lithium aluminium hydride, and acylation of the resulting 17 alpha-aminomethyl derivatives with either acetic anhydride or the mono acid chloride of glutaric acid mono methyl ester. Saponification of the 17 alpha-hemiglutaramidomethyl methyl esters gave the corresponding hemiglutaramido derivatives, while acid hydrolysis of the 3-ethylene ketal group of 17 alpha-acetamidomethyl and 17 alpha-hemiglutaramidomethyl derivatives regenerated the 3-oxo and 3-oxo-4-ene functions. The 17 alpha-configuration of 17-substituted steroids was determined by 1H and 13C NMR and confirmed by comparing with NMR data for 17 alpha- and 17 beta-cyano-17-hydroxyandrost-4-en-3-one, 17 beta-cyano-3,3'-(ethylenedioxy)androst-5-en-17-ol, 17 alpha-alkynyl, and 17 alpha-hexanoic derivatives of dihydrotestosterone and testosterone, of known 17-configurations. Several ambiguous assignments of 13C NMR signals of 17 alpha-substituted steroids and unsubstituted 17 beta-hydroxy or 17-oxo precursors have been resolved using steroid analogs deuterated at positions C5-7, or C16 for androstane derivatives, and at positions C6-7, or C7 for androstene derivatives. 17 alpha-Aminomethyl and 17 alpha-alkylamidomethyl derivatives of dihydrotestosterone and testosterone are useful intermediates for the access to potential ligands of androgen-binding proteins necessary for affinity chromatography purification or affinity-labeling experiments. |
| Databáze: | OpenAIRE |
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