Sodium Bicarbonate → HCID 2723959, compound

HRID 2408168Notes

Reaction equation

HRID 2408168 reaction equation
C([O:4][C@@H:5]1[C@H:14]([O:15]CC2C=CC=CC=2)[C@@H:13]([O:23]CC2C=CC=CC=2)[C@H:12]([CH3:31])[O:11][C@H:6]1[O:7]CC=C)(=[O:3])C.C([O-])(O)=O.[Na+]>CCOC(C)=O>[CH3:31][C@@H:12]1[O:11][CH:6]([OH:7])[C@H:5]([OH:4])[C@H:14]([OH:15])[C@H:13]1[OH:23].[OH2:3]

Participants

4

Reactant 2

HCID 516892Sodium BicarbonateHCID 67541659HCID 67541659, compound2×

Product 1

HCID 2723959HCID 2723959, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

The raw product from 76 (65.2 g, 200.0 mmol) is taken up in EtOAc (300 mL). The organic phase is washed with 10% HCl solution (3×50 mL), NaClsat solution (3×50 mL), and a solution of H2O (3×50 mL) and then dried over Na2SO4 and concentrated in a rotary evaporator. Acetyl chloride is added (35.5 mL, 500.0 mmol, 2.5 eq.) in portions to allyl alcohol (300 mL) at 0° C. for 15 min, then the previous raw product is added to the reaction mixture. The reaction mixture is then heated at 70° C. for 2.5 h and then at 40° C. overnight. Monitoring of the reaction by TLC (Chex/EtOAc, 7/3) shows the disappearance of 76 (Rf=0.25) and the presence of a less polar main product (Rf=0.35). The reaction mixture is cooled to 0° C., neutralized by adding NaHCO3 and then filtered on Celite and finally concentrated in a rotary evaporator. The volatile substances are coevaporated with Tol (2×100 mL) to give a yellow oil. The yellow oil is purified by silica gel chromatography (Chex/EtOAc, 8/2→1/1) to give the alcohol 58 in the form of a colorless oil (55 g, 72% starting from commercial L-rhamnose 27).

Workup

  1. washThe organic phase is washed with 10% HCl solution (3×50 mL), NaClsat solution (3×50 mL)
  2. dry with materiala solution of H2O (3×50 mL) and then dried over Na2SO4
  3. concentrationconcentrated in a rotary evaporator
  4. additionAcetyl chloride is added (35.5 mL, 500.0 mmol, 2.5 eq.) in portions to allyl alcohol (300 mL) at 0° C. for 15 min
  5. additionthe previous raw product is added to the reaction mixture
  6. customat 40° C.
  7. customovernight
  8. customMonitoring of the reaction by TLC (Chex/EtOAc, 7/3)
  9. temperatureThe reaction mixture is cooled to 0° C.
  10. filtrationfiltered on Celite
  11. concentrationfinally concentrated in a rotary evaporator
  12. customto give a yellow oil
  13. customThe yellow oil is purified by silica gel chromatography (Chex/EtOAc, 8/2→1/1)

Sources & evidence

ORD record
ord-a83ea0969db5480babd1dd85edeba369
Source dataset
uspto-grants-2014_08
Patent number
US08815239B2

Reaction notes

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