Hydroxide → HCID 54007512, compound

HRID 2247792Notes

Reaction equation

HRID 2247792 reaction equation
O.P([O-])([O-])([O-])=O.[CH2:7]([O:9][C:10]([CH:12]1[CH2:17][CH2:16][C:15]2[CH:18]=[CH:19][C:20]([OH:22])=[CH:21][C:14]=2[O:13]1)=[O:11])[CH3:8].[OH-]>O1CCCC1>[CH2:7]([O:9][C:10]([C@H:12]1[CH2:17][CH2:16][C:15]2[CH:18]=[CH:19][C:20]([OH:22])=[CH:21][C:14]=2[O:13]1)=[O:11])[CH3:8]

Participants

6

Reactant 4

HCID 961HydroxideHCID 962WaterHCID 1061PhosphateHCID 11085381Ethyl 7-hydroxychromane-2-carboxylate

Product 1

HCID 54007512HCID 54007512, compoundYield 45.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 250 mL 3-necked, round-bottomed flask equipped with a mechanical stirrer, a pH electrode connected to a pH control unit and an addition tube connected to a peristaltic pump, was charged with 60 mL of deionized water, 15 mL of 0.05M phosphate buffer (pH 7.0) and 2.2 g racemic 3,4-dihydro-7-hydroxy-2H-1-benzopyran-2-carboxylic acid ethyl ester dissolved in 7.5 mL of tetrahydrofuran. The pH was adjusted to 8.0 with 0.1N aqueous hydroxide solution, and 0.4 g of Pseudomonas lipase enzyme (P-30, Amano International Enzyme Co., Inc., Troy, Va.) was added while the mixture was stirred at a fast rate. The reaction flask was stoppered to avoid loss of the co-solvent by evaporation and the stirring was continued at the same rate. The pH was maintained at 8.0 by adding 0.1N aqueous sodium hydroxide solution via the peristaltic pump. The reaction was discontinued when 55 mL of 0.1N aqueous sodium hydroxide had been consumed (at about the 10 hour mark) and the tetrahydrofuran was removed by evaporation at 35° C. under 10 mm Hg of vacuum. The remaining mixture was extracted 3 times with 50 mL (for a total of 150 mL) of ethyl acetate. The combined organic layers were washed with 50 mL of saturated aqueous sodium bicarbonate and dried over anhydrous sodium sulfate. The solution was filtered and concentrated at 40° C. under 10 mm Hg of vacuum, to obtain 1.0 g (45% yield, 100% of theory) of (R)-3,4-dihydro-7-hydroxy-2H-1-benzopyran-2-carboxylic acid ethyl ester as an off-white solid; m.p. 77°-78° C., (α)D25 -20.2° (c 1.0, CHCl3), 99.6% e.e.

Workup

  1. customA 250 mL 3-necked, round-bottomed flask equipped with a mechanical stirrer
  2. additionwas added while the mixture
  3. customby evaporation
  4. temperatureThe pH was maintained at 8.0
  5. additionby adding 0.1N aqueous sodium hydroxide solution via the peristaltic pump
  6. customhad been consumed (at about the 10 hour mark) and the tetrahydrofuran
  7. customwas removed by evaporation at 35° C. under 10 mm Hg of vacuum
  8. extractionThe remaining mixture was extracted 3 times with 50 mL (for a total of 150 mL) of ethyl acetate
  9. washThe combined organic layers were washed with 50 mL of saturated aqueous sodium bicarbonate
  10. dry with materialdried over anhydrous sodium sulfate
  11. filtrationThe solution was filtered
  12. concentrationconcentrated at 40° C. under 10 mm Hg of vacuum

Sources & evidence

ORD record
ord-3efa445bed4b43bd9b4edf4101bf63ed
Source dataset
uspto-grants-1991_08
Patent number
US05037747

Reaction notes

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