Isopropyl nitrate → HCID 9929531, compound

HRID 1604093Notes

Reaction equation

HRID 1604093 reaction equation
CC(C)([O-])C.[K+].[OH:7][CH2:8][C@H:9]([C@@H:11]1[C@:28]2([CH3:29])[C@H:14]([C@H:15]3[C@H:25]([CH2:26][CH2:27]2)[C@:23]2([CH3:24])[C:18](=[CH:19][C:20](=[O:30])[CH2:21][CH2:22]2)[CH2:17][CH2:16]3)[CH2:13][CH2:12]1)[CH3:10].C([O:34][N+:35]([O-])=[O:36])(C)C>C(O)(C)(C)C>[OH:7][CH2:8][C@H:9]([C@@H:11]1[C@:28]2([CH3:29])[C@H:14]([C@H:15]3[C@H:25]([CH2:26][CH2:27]2)[C@:23]2([CH3:24])[C:18](=[C:19]([N+:35]([O-:36])=[O:34])[C:20](=[O:30])[CH2:21][CH2:22]2)[CH2:17][CH2:16]3)[CH2:13][CH2:12]1)[CH3:10]

Participants

5

Reactant 3

HCID 15575Isopropyl nitrateHCID 11142115HCID 11142115, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 9929531HCID 9929531, compound

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

Potassium tert-butoxide (1.70 g, 15 mM) and (20S)-20-hydroxymethylpregn-4-en-3-one (1.65 g, 5 mM) are mixed together in tert-butanol (25 mL), and heated at reflux temperature under argon atmosphere for 75 minutes. Isopropylnitrate (0.51 mL, 5 mM) is then added to the refluxing reaction mixture, resulting in an exothermic reaction. After one minute, the reaction vessel is removed from heat and allowed to cool to room temperature. The cooled mixture is then made acidic by addition of acetic acid (5 mL), and stirred overnight. The mixture is then diluted with dichloromethane so as to form a separate phase sufficient to solubilize the synthesized product. Subsequently, the solids are removed by filtration and washed with dichloromethane. The materials in both the filtrate and wash(es) are combined together and concentrated. The residue is then redissolved in dichloromethane, then purified by flash chromatagraphy on silica gel to give (20S)-20-hydroxymethyl-4-nitropregn-4-en3-one. The crystallization of this material from aqueous acetone gives white needles (m.p. 166-168° C.).

Workup

  1. temperatureheated
  2. temperatureat reflux temperature under argon atmosphere for 75 minutes
  3. customresulting in an exothermic reaction
  4. customthe reaction vessel is removed
  5. temperaturefrom heat
  6. additionmade acidic by addition of acetic acid (5 mL)
  7. additionThe mixture is then diluted with dichloromethane so as
  8. customto form a separate phase sufficient
  9. customSubsequently, the solids are removed by filtration
  10. washwashed with dichloromethane
  11. concentrationconcentrated
  12. dissolutionThe residue is then redissolved in dichloromethane
  13. custompurified by flash chromatagraphy on silica gel

Sources & evidence

ORD record
ord-a4c5613fca38407c84c62dc45ab3dbc9
Source dataset
uspto-grants-1999_11
Patent number
US05990328

Reaction notes

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