Water → HCID 86745919, compound

HRID 893037Notes

Reaction equation

HRID 893037 reaction equation
[C:1]([OH:4])(=[O:3])[CH3:2].O1[C:7]23[C@:23]([CH3:28])([CH2:24][CH2:25][C:26](=[O:27])[CH:6]12)[C@@H:22]1[C@H:10]([C@H:11]2[C@:19]([CH3:29])([CH2:20][CH2:21]1)[C@@H:14]([C@H:15]([CH3:18])[CH2:16][OH:17])[CH2:13][CH2:12]2)[CH2:9][CH2:8]3.[N-:30]=[N+:31]=[N-:32].[Na+].S(=O)(=O)(O)O.O>CS(C)=O>[C:1]([OH:4])(=[O:3])[CH3:2].[N:30]([C:6]1[C:26](=[O:27])[CH2:25][CH2:24][C@@:23]2([CH3:28])[C:7]=1[CH2:8][CH2:9][C@@H:10]1[C@@H:22]2[CH2:21][CH2:20][C@@:19]2([CH3:29])[C@H:11]1[CH2:12][CH2:13][C@@H:14]2[C@H:15]([CH3:18])[CH2:16][OH:17])=[N+:31]=[N-:32]

Participants

6

Reactant 4

HCID 962WaterHCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 86745917HCID 86745917, compound

Product 1

HCID 86745919HCID 86745919, compoundYield 50.1%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
60 °C

Procedure

To a vigorously stirred solution of the (20S)-4,5-epoxy21-hydroxy-20-methylpregnan-3-one acetate (3.0 g, 7.72 mmole) obtained in the preceding example, in dimethyl sulfoxide (100 mL), there was added sodium azide (8.2 g) and then concentrated sulfuric acid (0.55 mL). The mixture was heated at 60° C. for 1.5 hours and the cooled mixture was poured into cold water (700 mL). After stirring for 30 minutes, the solids were collected by filtration, washed with water and dried by suction. The resulting solid was purified by flash chromatography on silica gel to give (20S)-4-azido-21-hydroxy-20-methylpregn-4-en-3-one acetate as a white solid (1.6 g, 50.1%), melting at 137°-138° C., with decomposition, after recrystallization from aqueous acetone. IR 2110, 1736, 1670, 1588 (m), 1254 cm-1 ; MS (CI) 386 (3%, M +1 -N2), 326 (100%, M+1 -N2 -AcOH); 1H NMR (CDCl3) δ 0.72 (3H, s, C18 -Me), 1.01 (d, C22 -Me), 1.14 (s, C19 -Me), 2.06 (s, Ac-Me), 3.02 (1H, dq, C6 -H), 3.77 (1H, dd, 1/2 C21 -CH2), 4.08 (1H, dd, 1/2 C21 -CH2).

Workup

  1. filtrationthe solids were collected by filtration
  2. washwashed with water
  3. customdried by suction
  4. customThe resulting solid was purified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-b37e598a8aeb49629e8e30879bbfeb87
Source dataset
uspto-grants-1992_06
Patent number
US05120840

Reaction notes

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