Water → Ethyl hydroxy-(2-isopropoxytetrahydro-3-furanyl)acetate

HRID 1692154Notes

Reaction equation

HRID 1692154 reaction equation
ClCCl.[C:4]([O:8][CH2:9][CH3:10])(=[O:7])[CH:5]=[O:6].[O:11]1[CH:15]=[CH:14][CH2:13][CH2:12]1.[CH:16]([OH:19])([CH3:18])[CH3:17].C(=O)([O-])[O-].[K+].[K+].N(CCO)CCO.O>[Ti](Cl)(Cl)(Cl)Cl.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4].C1(C)C=CC=CC=1>[OH:6][CH:5]([CH:14]1[CH2:13][CH2:12][O:11][CH:15]1[O:19][CH:16]([CH3:18])[CH3:17])[C:4]([O:8][CH2:9][CH3:10])=[O:7]

Participants

11

Reactant 7

HCID 962Water2×HCID 3776IsopropanolHCID 6344Dichloromethane4×HCID 8113DiethanolamineHCID 11430Potassium CarbonateHCID 70211Ethyl oxoacetateHCID 709342,3-Dihydrofuran

Product 1

HCID 25242000Ethyl hydroxy-(2-isopropoxytetrahydro-3-furanyl)acetateYield 84.5%

Reagents, catalysts & solvents 3

HCID 11026Titanium isopropoxideCatalystHCID 24193Titanium TetrachlorideCatalystHCID 1140TolueneSolvent

Procedure

In a 1 L round button flask, titanium tetrachloride (17.83 mmoles; 1.96 mL; 3.38 g) was dissolved in dichloromethane (70 mL; 1.092 moles; 92.75 g) at room temperature. Then titanium tetra(isopropoxide) (17.83 mmoles; 5.28 mL; 5.07 g) dissolved in dichloromethane (70 mL; 1.092 moles; 92.75 g) was added dropwise at room temperature. After a 1 hour stirring period, ethyl glyoxalate (1.1 equiv; 39.24 mmoles; 3.55 mL; 4.0 g) free of toluene, dissolved in dichloromethane (8.75 mL; 136.5 mmoles; 11.59 g) was added dropwise over 30 min at room temperature. After 15 min., 2,3-dihydrofuran (2.5 g; 1.000 equiv; 35.67 mmoles; 2.70 mL) dissolved in dichloromethane (17.5 mL; 273.0 mmoles; 23.19 g) was added over 30 min. at room temperature. After a 3 hours stirring period, isopropyl alcohol (10 equiv; 356.7 mmoles; 27.26 mL; 21.44 g) was added dropwise. After 3 hours, the mixture of potassium carbonate (1.75 g; 12.66 mmoles) and diethanolamine (9.5 g; 90.6 mmoles) dissolved in water (175 mL; 9.72 moles; 175 g) was added to the reaction mixture. After stirring over a weekend, the two layers were separated and the organic layer was washed with (2×100 mL) of water (200 mL; 11.10 moles; 200.0 g). The organic solvent was evaporated over reduced pressure to afford the desired product (7.0 g; GC: 96 area %).

Workup

  1. additionwas added dropwise at room temperature
  2. additionwas added dropwise over 30 min at room temperature
  3. waitAfter 15 min.
  4. additionwas added over 30 min. at room temperature
  5. stirringAfter a 3 hours stirring period
  6. waitAfter 3 hours
  7. additionwas added to the reaction mixture
  8. stirringAfter stirring over a weekend
  9. customthe two layers were separated
  10. customThe organic solvent was evaporated over reduced pressure

Sources & evidence

ORD record
ord-6c33dff4981246e4af435bd49e709da0
Source dataset
uspto-grants-2012_04
Patent number
US08153829B2

Reaction notes

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