Acetic Acid → HCID 66902687, compound

HRID 2222744Notes

Reaction equation

HRID 2222744 reaction equation
CC[CH:3]([C:8]([O-:10])=O)[CH2:4][CH2:5][CH2:6]C.[C:11]([O-:14])(=[O:13])[CH3:12].[Na+].[I-].[Na+].[C:18](O)(=O)[CH3:19].CC(C)=[O:24]>>[OH:24][C@@H:5]1[CH:4]2[CH:3]([C@H:12]2[C:11]([O:14][CH2:18][CH3:19])=[O:13])[C:8](=[O:10])[CH2:6]1

Participants

6

Reactant 5

HCID 176Acetic AcidHCID 180Acetone2×HCID 5238Sodium IodideHCID 517045Sodium AcetateHCID 40723562-Ethylhexanoate

Product 1

HCID 66902687HCID 66902687, compoundYield 114%

Procedure

A stirred solution of ethyl (3S,1R,6R)-7-oxa-5-oxotricyclo[4.1.0.0<2,4>]heptane-3-carboxylate (36.3 g, 0.20 mol) in 667 mL of acetone is treated sequentially with sodium acetate (36.1 g, 0.44 mol), sodium iodide (65.8 g, 0.44 mol), and acetic acid (27.5 mL, 0.48 mol). The mixture is allowed to stir at 30° C. for 15 hours before the acetone is removed in vacuo leaving behind a brown solid that is partitioned between ethyl acetate (323 mL) and H2O (323 mL). The layers are separated and the aqueous layer is washed with ethyl acetate (3×323 mL). The combined organics are washed sequentially with aqueous saturated Na2S2O3 (364 mL) and aqueous saturated NaHCO3 (364 mL). Each aqueous wash is back-extracted with ethyl acetate (323 mL). The combined organics are dried (Na2SO4), filtered, and concentrated to a red-brown oil which was dissolved in 300 mL of ethanol. Evaporation of the volatiles affords the title product as a red-brown oil (41.8 g, 114%). Column chromatography on silica gel using ethyl acetate/hexanes (1:2 to 2:1) followed by crystallization from hot MTBE provides an analytically pure sample of the title compound as a white solid.

Workup

  1. customis removed in vacuo
  2. customleaving behind a brown solid that
  3. customis partitioned between ethyl acetate (323 mL) and H2O (323 mL)
  4. customThe layers are separated
  5. washthe aqueous layer is washed with ethyl acetate (3×323 mL)
  6. washThe combined organics are washed sequentially with aqueous saturated Na2S2O3 (364 mL) and aqueous saturated NaHCO3 (364 mL)
  7. washEach aqueous wash
  8. extractionis back-extracted with ethyl acetate (323 mL)
  9. dry with materialThe combined organics are dried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated to a red-brown oil which
  12. dissolutionwas dissolved in 300 mL of ethanol
  13. customEvaporation of the volatiles

Sources & evidence

ORD record
ord-01d1cb0097864bbab92b00a0a5185324
Source dataset
uspto-grants-2008_05
Patent number
US07371872B2

Reaction notes

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