Benzyl Bromide → HCID 23295265, compound

HRID 546165Notes

Reaction equation

HRID 546165 reaction equation
[H-].[Na+].[CH3:3][C:4]1([CH3:12])[O:9][CH2:8][CH:7]([CH2:10][OH:11])[CH2:6][O:5]1.[CH2:13](Br)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>O1CCCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[CH2:13]([O:11][CH2:10][CH:7]1[CH2:8][O:9][C:4]([CH3:12])([CH3:3])[O:5][CH2:6]1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

7

Reactant 3

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 3584869(2,2-Dimethyl-1,3-dioxan-5-yl)methanol

Product 1

HCID 23295265HCID 23295265, compoundYield 80%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
25 °C

Procedure

To a stirred suspension of sodium hydride (2.0 g, 42.02 mmol, 50% dispersion in oil) in tetrahydrofuran (20.0 ml) was added dropwise a solution of (2,2-dimethyl-[1,3]dioxan-5-yl)-methanol (4.09 g, 28.01 mmol) in tetrahydrofuran (10 ml) at 0° C. it was then stirred at 0° C. for 10 min and at 25° C. for 20 min. After that time, the reaction was cooled back to 0° C. and benzyl bromide (4.7 ml, 39.22 mmol) and tetrabutylammonium iodide (0.1 g, 0.27 mmol) were added. The reaction was stirred overnight at 25° C. After such time, the reaction was diluted with ethyl acetate and washed with water. The organic layer was dried over magnesium sulfate, filtered and then concentrated in vacuo. Purification on an AnaLogix Intelliflash system (120 g column, 15% ethyl acetate/hexanes to 25% ethyl acetate/hexanes) afforded 5-benzyloxymethyl-2,2-dimethyl-[1,3]dioxane (5.28 g, 80%) as a clear oil: 1H NMR (300 MHz, CDCl3) δ ppm 1.40 (s, 3H, CH3), 1.43 (s, 3H, CH3), 1.97-2.09 (m, 1H, CH), 3.53 (d, J=6.8 Hz, 2H, OCH2), 3.79 (dd, Jgem=11.9 Hz, J=6.4 Hz, 2H, 2×OCH of 2×OCH2), 3.98 (dd, Jgem=11.9 Hz, J=4.3 Hz, 2H, 2×OCH of 2×OCH2), 4.52 (s, 2H, OCH2Ar), 7.27-7.39 (m, 5H, Ar).

Workup

  1. temperatureAfter that time, the reaction was cooled back to 0° C.
  2. stirringThe reaction was stirred overnight at 25° C
  3. washwashed with water
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification on an AnaLogix Intelliflash system (120 g column, 15% ethyl acetate/hexanes to 25% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-4f7d88a9ed884751ba63f65dbb3dc0c4
Source dataset
uspto-grants-2011_05
Patent number
US07935699B2

Reaction notes

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