Benzyl Bromide → HCID 14814224, compound

HRID 1089260Notes

Reaction equation

HRID 1089260 reaction equation
[H-].[Na+].[OH:3][CH2:4][C@@H:5]([O:9][CH2:10][O:11][CH3:12])[CH2:6][CH2:7][OH:8].[CH2:13](Br)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>CCCCCC.CN(C)C=O>[CH2:13]([O:3][CH2:4][C@@H:5]([O:9][CH2:10][O:11][CH3:12])[CH2:6][CH2:7][O:8][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 13611238HCID 13611238, compound

Product 1

HCID 14814224HCID 14814224, compoundYield 83.8%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8058HexaneSolvent

Procedure

A 60% suspension of sodium hydride in oil (1.34 g, 33 mmol) was washed with hexane (2×20 ml) under an atmosphere of dry nitrogen. After decanting the hexane the solid was suspended in dry N,N-dimethylformamide (20 ml) and treated with a solution of (S)-1,4-dihydroxy-2-(methoxymethoxy)butane (2 g, 13 mmol) in N,N-dimethylformamide (5 ml). After stirring at room temperature for 6 hours the mixture was treated with a solution of benzyl bromide (3.9 ml, 33 mmol) in N,N-dimethylformamide (5 ml) and the mixture was stirred at room temperature overnight. The solvent was removed under reduced pressure and the residue partitioned between ethyl acetate (100 ml) and water (50 ml). The organic phase was washed with water (2×50 ml), dried with MgSO4 and the solvent removed to give an oil which was chromatographed on silica eluting with ethyl acetate-hexane 1:2 to give (S)-1,4-dibenzyloxy-2-(methoxymethoxy)butane (3.6 g, 82%), [α]D25 -16.0° (c 1.6 in ethanol); IR: υmax (film) 3080, 3060, 3030, 2920, 2890, 2860, 1495, 1450, 1360, 1210, 1155, 1100, 1040, 920, 740, 700 cm-1 ; 1H NMR: δH (CDCl3) 1.90 (2H, m, CH2), 3.35 (3H, s, OCH3), 3.60 (4H, m, 2×CH2), 3.90 (1H, m, CH), 4.50 (4H, m, 2×CH2), 4.68 (1H, d, J=7 Hz, CH of CH2), 4.74 (1H, d, J=7 Hz, CH of CH2), 7.30 (10H, m, 2×C6H5); m/z (NH3CI), MH+ 151, MNH4+ 168.

Workup

  1. customAfter decanting the hexane the solid
  2. stirringthe mixture was stirred at room temperature overnight
  3. customThe solvent was removed under reduced pressure
  4. customthe residue partitioned between ethyl acetate (100 ml) and water (50 ml)
  5. washThe organic phase was washed with water (2×50 ml)
  6. dry with materialdried with MgSO4
  7. customthe solvent removed
  8. customto give an oil which
  9. customwas chromatographed on silica eluting with ethyl acetate-hexane 1:2

Sources & evidence

ORD record
ord-0ec7d136b8584167ac2e6ae7d45eab6f
Source dataset
uspto-grants-1990_10
Patent number
US04965270

Reaction notes

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