3,4-dihydro-2H-pyran → diethyl 3-bromo-2-(tetrahydro-2H-pyran-2-yloxy)propylphosphonate

HRID 2309152Notes

Reaction equation

HRID 2309152 reaction equation
[Br:1][CH2:2][CH:3]([OH:13])[CH2:4][P:5](=[O:12])([O:9][CH2:10][CH3:11])[O:6][CH2:7][CH3:8].[O:14]1[CH:19]=[CH:18][CH2:17][CH2:16][CH2:15]1>C(OCC)(=O)C.C1(C)C=CC(S(O)(=O)=O)=CC=1>[Br:1][CH2:2][CH:3]([O:13][CH:15]1[CH2:16][CH2:17][CH2:18][CH2:19][O:14]1)[CH2:4][P:5](=[O:12])([O:6][CH2:7][CH3:8])[O:9][CH2:10][CH3:11]

Participants

5

Reactant 2

HCID 80803,4-dihydro-2H-pyranHCID 10934659Phosphonic acid, (3-bromo-2-hydroxypropyl)-, diethyl ester

Product 1

HCID 13961617diethyl 3-bromo-2-(tetrahydro-2H-pyran-2-yloxy)propylphosphonateYield 128.1%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of diethyl 3-bromo-2-hydroxypropylphosphonate (82.5 g) and p-toluenesulfonic acid (1.03 g) was added dropwise 3,4-dihydro-2H-pyrane (250 g) under ice-cooling and with stirring. After the reaction mixture was stirred at the same temperature for 10 minutes and at ambient temperature for 1.5 hours, the dihydropyrane was removed off by evaporation under reduced pressure to give a residue, which was dissolved in ethyl acetate (500 ml). The ethyl acetate solution was washed with saturated aqueous sodium bicarbonate solution (100 ml) and with saturated aqueous sodium chloride solution (100 ml) dried over magnesium sulfate and evaporated to dryness under reduced pressure to give oily diethyl 3-bromo-2-(tetrahydro-2H-pyran-2-yloxy)propylphosphonate (138 g).

Workup

  1. temperaturecooling
  2. stirringAfter the reaction mixture was stirred at the same temperature for 10 minutes and at ambient temperature for 1.5 hours
  3. customthe dihydropyrane was removed off by evaporation under reduced pressure
  4. customto give a residue, which
  5. washThe ethyl acetate solution was washed with saturated aqueous sodium bicarbonate solution (100 ml) and with saturated aqueous sodium chloride solution (100 ml)
  6. dry with materialdried over magnesium sulfate
  7. customevaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-429de19040524217a63a5e7369ad3c0e
Source dataset
uspto-grants-1987_09
Patent number
US04693742

Reaction notes

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