Ethyl bromoacetate → HCID 19070279, compound

HRID 1943317Notes

Reaction equation

HRID 1943317 reaction equation
[H-].[Na+].[OH:3][CH2:4][CH:5]1[CH2:10][CH2:9][CH:8]=[CH:7][O:6]1.[H][H].Br[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16]>CCCCC.O1CCCC1.O>[O:6]1[CH:7]=[CH:8][CH2:9][CH2:10][CH:5]1[CH2:4][O:3][CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16]

Participants

8

Reactant 4

HCID 7748Ethyl bromoacetateHCID 24758Sodium hydride2×HCID 955593,4-dihydro-2H-pyran-2-methanolHCID 178418361HCID 178418361, compound

Product 1

HCID 19070279HCID 19070279, compoundYield 62.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

In a dried round bottomed flask under argon atmosphere, 60% sodium hydride (240 mg, 6.0 mmol) was rinsed three times with anhydrous n-pentane. A solution of 2-hydroxymethyl-3,4-dihydro-2H-pyran (570.8 mg, 5 mmol) in tetrahydrofuran (10 ml) was cooled at 0° C. and then added to the NaH. The reaction mixture was stirred at 0° C. until hydrogen evolution ended. A solution of ethyl bromoacetate (1253 mg, 7.5 mmol) in tetrahydrofuran (6 ml) was added to the reaction mixture and the stirring was continued at room temperature until disappearance of the starting alcohol (TLC analysis). After cooling, H2O was added, and the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography (AcOEt:hexane=1:12) on silica gel (230-400 mesh), affording 626 mg (yield 57%) of ethyl (3,4-dihydro-2H-pyran-2-ylmethoxy)acetate as a colorless oil; 1H NMR (401 MHz, DMSO-d6) δ ppm 1.18-1.23 (m, 3H) 3.55-3.59 (m, 2H) 3.93 (m, J=10.08, 5.11, 5.11, 2.38 Hz, 1H) 4.13 (q, J=7.07 Hz, 2H) 4.14 (s, 2H) 4.67 (dddd, J=6.14, 4.83, 2.56, 1.34 Hz, 1H) 6.36 (dt, J=6.13, 1.75 Hz, 1H).

Workup

  1. temperatureAfter cooling
  2. customthe solvent was evaporated under reduced pressure
  3. customThe residue was purified by flash column chromatography (AcOEt:hexane=1:12) on silica gel (230-400 mesh)

Sources & evidence

ORD record
ord-14527305aad84863b907a350ab5a2241
Source dataset
uspto-grants-2013_03
Patent number
US08389697B2

Reaction notes

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