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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
- Source :
- Steroids. 62:603-620
- Publication Year :
- 1997
- Publisher :
- Elsevier BV, 1997.
-
Abstract
- 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.
- Subjects :
- 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
Subjects
Details
- ISSN :
- 0039128X
- Volume :
- 62
- Database :
- OpenAIRE
- Journal :
- Steroids
- Accession number :
- edsair.doi.dedup.....69fd9cf71025a026a9d734caada4662c