Sulfuric Acid → HCID 67744897, compound

HRID 1885332Notes

Reaction equation

HRID 1885332 reaction equation
O1[C:3]23[C@:19]([CH3:24])([CH2:20][CH2:21][C:22](=[O:23])[CH:2]12)[C@@H:18]1[C@H:6]([C@H:7]2[C@:15]([CH3:25])([CH2:16][CH2:17]1)[C@@H:10]([C@H:11]([CH3:14])[CH2:12][OH:13])[CH2:9][CH2:8]2)[CH2:5][CH2:4]3.[N-:26]=[N+]=[N-].[Na+].[N-]=[N+]=[N-].S(=O)(=O)(O)O>CS(C)=O>[NH2:26][C:2]1[C:22](=[O:23])[CH2:21][CH2:20][C@@:19]2([CH3:24])[C:3]=1[CH:4]=[CH:5][C@@H:6]1[C@@H:18]2[CH2:17][CH2:16][C@@:15]2([CH3:25])[C@H:7]1[CH2:8][CH2:9][C@@H:10]2[C@H:11]([CH3:14])[CH2:12][OH:13]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 33558AzideHCID 54505623HCID 54505623, compound

Product 1

HCID 67744897HCID 67744897, compound

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
60 °C

Procedure

A solution of (20S)-4,5-epoxy-21-hydroxy-20-methylpregnan-3-one (7.7 mmole) in dimethyl sulfoxide (40 mL), under a nitrogen atmosphere, was placed in an oil bath heated at 60° C. The solution was stirred vigorously as sodium azide (8.11 g, 0.338 mole) was slowly added. After the addition of the azide was complete, concentrated sulfuric acid (0.54 mL) was added. The bath temperature was raised to 100° C. and the reaction was stirred at this temperature for 90 minutes. The reaction was removed from the oil bath and cooled to room temperature and the resulting solid mass was broken up and poured into cold water (550 mL). The mixture was stirred for 30 min and the solids were collected by filtration, washed with water and dried to a yellow solid. The crude product was purified by flash chromatography (hexane-30% ethyl acetate) to give (20S)-4-amino-21-hydroxy-20-methylpregna-4,6-dien-3-one. IR 3462, 3390, 3346, 1652, 1616, 1592, 1564 cm-1 ; MS (CI) m/z 344 (100%, M+ +1); (EI) m/z 343 (60%, M+), 150 (100%); 1H NMR (CDCl3) δ 0.76 (3H, s, C18 -Me), 1.04+1.05 (6H, s+d, C19 -Me+C21 -Me) 2.48 (1H, dq), 2.63 (1H, dq), 3.38 (1H, dd, 1/2 C21 -CH2), 3.64(dd+v br, 1/2 C21 -CH2 +NH2), 5.97 (1H, dd) 6.30 (1H, dd); 13C NMR (CDCl3) δ 121.77, 132.08, 132.98, 136.55, 194.40.

Workup

  1. additionwas slowly added
  2. temperatureThe bath temperature was raised to 100° C.
  3. customThe reaction was removed from the oil bath
  4. temperaturecooled to room temperature
  5. additionpoured into cold water (550 mL)
  6. stirringThe mixture was stirred for 30 min
  7. filtrationthe solids were collected by filtration
  8. washwashed with water
  9. customdried to a yellow solid
  10. customThe crude product was purified by flash chromatography (hexane-30% ethyl acetate)

Sources & evidence

ORD record
ord-3de6ce4448154b1bbe68a7a60a3dd54d
Source dataset
uspto-grants-1992_09
Patent number
US05143909

Reaction notes

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