Stickstoffhaltige Steroide. XXIV. Darstellung von 6‐Azido‐ und 6‐Amino‐progesteron‐Derivaten

Abstract

InhaltsubersichtReaktion von 6,7x-Epoxy-17n-acetoxy-progesteron 1 rnit Natriumazid in Athylenglykolmonomethyliither fiihrt zu 6~-Azido-7a-hydroxy-l7a-acetoxy-progesteron 2a, das durch Sauren zu 6-A~ido-l7a-acetoxy-A~~~-pregnadien-dion-(3,20) 3 dehydratisiert wird.Durch Reduktion des Azidoalkohols 2 a werden 6-Amino-Derivate des l7n-Acetoxy-progesterons erhalten.

Synthesis of steroidal azides. Part 1. Stereospecific vicinal azidohydroxylation of steroidal olefins

“…The residue, after evaporation of the solvent, was chromatographed on a silica gel column and eluted (gradient) with light petroleum-ether to afford 7a-azido-3,6,11,20-tetruoxopregn-4ene-17a,21-dioZ 21-acetate (18) as an unstable oil (164 mg, 12%), [aID f15"; hmX. 232 nm (E 11 OOO); 6 6.07 (1 H, s, 4-H), 5.90 (1 H, S, 17-OH), 4.87 (2 H, 9, J,,, 18 Hz, 21-H2), 4 C23H29N307 requires C, 60.12; H, 6.36; N, 9.15%; M, 459).…”

“…6P-A Ado-20-oxupregnane-3 P, 5 a-did 3-Acetate (4) .-( i) From 20-oxopregn-5-en-3P-y/, acetate (3). Sodium azide (2.6 g, 40 mmol) and then chromium trioxide (200 mg, 2.0 mmol) were added to a magnetically stirred solution of 20-oxopregn-5-en-3P-yl acetate (3) (716 mg, 2.0 mmol) in glacial acetic acid (15 ml) and the mixture was stirred for 30 min at room ternperature.…”

Synthesis of steroidal azides. Part 2. Reaction of 4,6-dien-3-ones with lead tetra-acetate and trimethylsilyl azide

“…Treatment of 1,2 :6,7-didehydro-l7a-hydroxyprogesterone (3) with lead tetra-acetate-trimethylsilyl azide under the same conditions led only to products resulting from reaction in obtained the analogous 6B-chloro-7a-azide (7) together with smaller amounts of the previously isolated 7a-azido-6-ketone (5). The chloro azide adduct (7) could be converted into the previously described l 4 17a-acetoxy-6-chloro-6,7-dehydroprogesterone (15) with tetramethylammonium fluoride in acetonitrile.…”