Diethyl Carbonate → HCID 86734293, compound

HRID 1973723Notes

Reaction equation

HRID 1973723 reaction equation
O1CCCCC1[O:7][C@@H:8]1[CH2:27][CH2:26][C@@:25]2([CH3:28])[C@@H:10]([CH2:11][CH2:12][C@@H:13]3[C@@H:24]2[C:23](=[O:29])[CH2:22][C@@:21]2([CH3:30])[C@H:14]3[CH2:15][CH2:16][C@@H:17]2[C:18](=[O:20])[CH3:19])[CH2:9]1.[C:31](=[O:38])([O:35][CH2:36][CH3:37])OCC.[OH-].[Na+]>C(O)C>[CH2:36]([O:35][C:31]([CH2:19][C:18](=[O:20])[C@@H:17]1[C@:21]2([CH3:30])[C@H:14]([C@H:13]3[C@H:24]([C:23](=[O:29])[CH2:22]2)[C@:25]2([CH3:28])[C@H:10]([CH2:9][C@H:8]([OH:7])[CH2:27][CH2:26]2)[CH2:11][CH2:12]3)[CH2:15][CH2:16]1)=[O:38])[CH3:37]

Participants

5

Reactant 3

HCID 7766Diethyl CarbonateHCID 14798Sodium HydroxideHCID 131710577HCID 131710577, compound

Product 1

HCID 86734293HCID 86734293, compound

Reagents, catalysts & solvents 1

HCID 702EthanolCatalyst

Procedure

3α-(Tetrahydropyran-2ξ- yloxy)-5α-pregnane-11,20-dione (0.9 g) in boiling diethyl carbonate (12 ml) under nitrogen was treated with 1 drop of ethanol and then sodium hydroxide (0.17 g). The mixture was refluxed for 20 minutes, then cooled and the excess sodium hydride was destroyed with ethanol. The reaction mixture was partitioned between water and ether. The organic layer was washed with water, dried (MgSO4) and evaporated. The residue (1.0 g) was purified by preparative t.l.c. to give the ester (0.59 g) This ester in ethanol (5 ml) was treated with 2N hydrochloric acid (0.5 ml) and after ca 6 hours the reaction mixture was partitioned between water and ether. The organic layer was washed with water, dried (MgS04) and evaporated. The residue (0.6 g) was subjected to preparative t.l.c. (ethyl acetate/petrol 1:2). The more polar fraction (0.29 g) gave after crystallisation from ispropyl ether the title compound (0.08 g), m.p. 120-121°, [α]D + 120.5°, λmax. 249 nm. (ε 4,250).

Workup

  1. temperatureThe mixture was refluxed for 20 minutes
  2. temperaturecooled
  3. customthe excess sodium hydride was destroyed with ethanol
  4. customThe reaction mixture was partitioned between water and ether
  5. washThe organic layer was washed with water
  6. dry with materialdried (MgSO4)
  7. customevaporated
  8. customThe residue (1.0 g) was purified by preparative t.l.c

Sources & evidence

ORD record
ord-ab6afcb1db6c4615bb71d3a50eba47f3
Source dataset
uspto-grants-1976_12
Patent number
US03998829

Reaction notes

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