Sodium Azide → HCID 57120851, compound

HRID 622340Notes

Reaction equation

HRID 622340 reaction equation
Br[C@H:2]1[C:19]2[C@:14]([CH3:21])([CH:15]=[CH:16][C:17](=[O:20])[CH:18]=2)[C@@H:13]2[C@H:4]([C@H:5]3[C@@:9]([CH2:11][CH2:12]2)([CH3:10])[C:8](=[O:22])[CH2:7][CH2:6]3)[CH2:3]1.[N-:23]=[N+:24]=[N-:25].[Na+]>CN(C)C=O.O>[N:23]([C@@H:2]1[C:19]2[C@:14]([CH3:21])([CH:15]=[CH:16][C:17](=[O:20])[CH:18]=2)[C@@H:13]2[C@H:4]([C@H:5]3[C@@:9]([CH2:11][CH2:12]2)([CH3:10])[C:8](=[O:22])[CH2:7][CH2:6]3)[CH2:3]1)=[N+:24]=[N-:25]

Participants

5

Reactant 2

HCID 33557Sodium AzideHCID 2517057827759-21-3

Product 1

HCID 57120851HCID 57120851, compoundYield 75.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 6β-bromoandrosta-1,4-diene-3,17-dione (5.0 g) in 250 ml of dimethylformamide, 1,15 g of powdered sodium azide dissolved in 14 ml of water are added and the mixture is warmed to 100° C. and maintained with stirring at the same temperature for 120 minutes. The entire mixture is then poured into 1 l of water and extracted with four 200 ml portions of ethyl acetate. The combined extracts are washed with saturated aqueous sodium chloride solution and dried. The solvent is then removed in vacuum to yield a crude product which is purified by chromatography on Al2O3 (neutral activity) with ethyl acetate:n-hexane 40:60 as eluant so obtaining 3.4 g of pure 6α-azido androsta-1,4-diene-3,17-dione. The analytical sample was crystallized from methanol, m.p. 168°-170° C.; [α]D20° +93.2° (c=1, CHCl3); U.V. (95% EtOH) λmax=244; ε=17,420; N.M.R. (CDCl3) δ: 0.98 (3H, s); 1.3 (3H, s); 4.31 (1H, ddd); 6.44 (1H, dd); 6.26 (1H, dd); 7.02 (1H, d). Following analogous procedure the 6β-azido androsta-1,4-diene-3,17-dione can be prepared, starting from 6α-bromo androsta-1,4-diene-3,17-dione.

Workup

  1. additionare added
  2. temperaturemaintained
  3. extractionextracted with four 200 ml portions of ethyl acetate
  4. washThe combined extracts are washed with saturated aqueous sodium chloride solution
  5. customdried
  6. customThe solvent is then removed in vacuum
  7. customto yield a crude product which
  8. customis purified by chromatography on Al2O3 (neutral activity) with ethyl acetate:n-hexane 40:60 as eluant

Sources & evidence

ORD record
ord-cf04f3171f0946eeab85b5d90b1a2abf
Source dataset
uspto-grants-1988_09
Patent number
US04771043

Reaction notes

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