Sodium ethoxide → HCID 53832780, compound

HRID 1415864Notes

Reaction equation

HRID 1415864 reaction equation
[CH2:1]([O:3][CH2:4][CH2:5][O:6][CH:7]([C:13]([O-:15])=[O:14])[C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH3:2].[O-][CH2:17][CH3:18].[Na+].[C:20]([O:39]CCCBr)(C1C=CC=CC=1)(C1C=CC=CC=1)[C:21]1C=CC=C[CH:22]=1>CCO>[OH:39][CH2:20][CH2:21][CH2:22][C:7]([O:6][CH2:5][CH2:4][O:3][CH2:1][CH3:2])([C:13]([O:15][CH2:17][CH3:18])=[O:14])[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

5

Reactant 3

HCID 2723922Sodium ethoxideHCID 10385165HCID 10385165, compoundHCID 86754088HCID 86754088, compound

Product 1

HCID 53832780HCID 53832780, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
50 °C

Procedure

6 g of ethyl 2-(2-ethoxyethyl)oxymalonate (24.65 mmoles) are added to a solution of sodium ethoxide in EtOH (15 ml, prepared by dissolution of 0.65 g, 0.028 moles metal Na) under stirring and nitrogen atmosphere. Stirring is continued for 1 h at room temperature, then a solution of 3-trityloxy-1-propyl-bromide (9.4 g, 24.7 mmoles) in EtOH (20 ml) is added dropwise. The reaction mixture is heated at 50° C. and kept at this temperature overnight. When the reaction is completed, the solvent is evaporated off under vacuum and the residue is partitioned between water and AcOEt. The aqueous phase is re-extracted with AcOEt (2×50 ml), the combined organic phases are washed to neutrality with a 5% NaH2PO4 aqueous solution, then with water, and finally dried over sodium sulfate. After evaporation of solvent, the resulting solution of crude ethyl 5-trityloxy-2-ethoxycarbonyl-2-[(2-ethoxy)ethyloxy]-pentanoate in EtOH is treated with 0.3 g of p-toluenesulfonic.H2O acid and kept for 12 h at room temperature. After evaporation of solvent, the residue is dissolved in dichloromethane (15 ml) and the organic phase is washed with 2×5 of 5% aqueous NaHCO3, then with water to neutrality, dried over Na2SO4, the solvent is evaporated off and the residue is purified on a silica gel column (eluent CHCl3 /MeOH 98:1.5), to obtain 6.42 g of ethyl 5-hydroxy-2-[(2-ethoxy)ethyloxy]-2-ethoxycarbonyl-pentanoate.

Workup

  1. stirringStirring
  2. customkept at this temperature overnight
  3. customthe solvent is evaporated off under vacuum
  4. customthe residue is partitioned between water and AcOEt
  5. extractionThe aqueous phase is re-extracted with AcOEt (2×50 ml)
  6. washthe combined organic phases are washed to neutrality with a 5% NaH2PO4 aqueous solution
  7. dry with materialwith water, and finally dried over sodium sulfate
  8. customAfter evaporation of solvent
  9. additionthe resulting solution of crude ethyl 5-trityloxy-2-ethoxycarbonyl-2-[(2-ethoxy)ethyloxy]-pentanoate in EtOH is treated with 0.3 g of p-toluenesulfonic
  10. waitH2O acid and kept for 12 h at room temperature
  11. customAfter evaporation of solvent
  12. dissolutionthe residue is dissolved in dichloromethane (15 ml)
  13. washthe organic phase is washed with 2×5 of 5% aqueous NaHCO3
  14. dry with materialwith water to neutrality, dried over Na2SO4
  15. customthe solvent is evaporated off
  16. customthe residue is purified on a silica gel column (eluent CHCl3 /MeOH 98:1.5)

Sources & evidence

ORD record
ord-68b20afee4174e2da4ab14e163cbe897
Source dataset
uspto-grants-1999_06
Patent number
US05908863

Reaction notes

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