1-Bromohexadecane → (R)-2-Phenyl-(S)-4-hexadecyloxymethyl-1,3dioxane

HRID 1166049Notes

Reaction equation

HRID 1166049 reaction equation
[H-].[Na+].[C:3]1([C@@H:9]2[O:14][C@@H:13]([CH2:15][OH:16])[CH2:12][CH2:11][O:10]2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[CH2:17](Br)[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32]>C1COCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[C:3]1([C@@H:9]2[O:14][C@@H:13]([CH2:15][O:16][CH2:32][CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][CH3:17])[CH2:12][CH2:11][O:10]2)[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1

Participants

6

Reactant 3

HCID 82131-BromohexadecaneHCID 24758Sodium hydrideHCID 69989668(R)-2-phenyl-(S)-4-hydroxymethyl-1,3-dioxane

Product 1

HCID 69989963(R)-2-Phenyl-(S)-4-hexadecyloxymethyl-1,3dioxaneYield 50%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of NaH (3 g, 60% in mineral oil) in 30 mL of dry THF was added a solution of (R)-2-phenyl-(S)-4-hydroxymethyl-1,3-dioxane (1.47 g, 7.6 mmol) in 10 mL of THF at 0° C. After 30 min, hexadecyl bromide (3 mL, 9.88 mmol) and tetrabutylammonium iodide (0.28 g, 0.76 mmol) were added. After the mixture was stirred overnight, the reaction was quenched by addition of 5 mL of MeOH. The solvent was removed under reduced pressure, and ether and water were added. The product was extracted with ether. The organic layer was dried over Na2SO4 and concentrated. The product was purified by column chromatography on silica gel, eluting with EtOAc-PE (5%) to afford 1.55 g (50%) of 6 as a white solid; mp 51-54° C. MS: m/z 441 (M++Na+), (calcd. for C27H45O3, 418.662). 1H NMR (300 MHz, CDCl3): δ7.51-7.31 (m, 5H, Ph), 5.54 (s, PhCH—), 4.32-4.27 (m, —CHO), 4.10-3.94 (m, 2H, —CH2O—), 3.65-3.59 (m, 4H, —CH2O), 1.89-1.83 (m, 2H, —CH2—), 1.62-1.54 (m, 2H), 1.25 (s, 26H), 0.88 (t, 3H, CH3). 13C-NMR (CDCl3, 75 MHz): δ139.28, 129.32, 128.77, 126.79, 101.88, 77.09, 74.44, 72.61, 67.61, 32.74, 30.51, 30.30, 30.18, 29.18, 26.93, 23.51, 14.94.

Workup

  1. customthe reaction was quenched by addition of 5 mL of MeOH
  2. customThe solvent was removed under reduced pressure, and ether and water
  3. additionwere added
  4. extractionThe product was extracted with ether
  5. dry with materialThe organic layer was dried over Na2SO4
  6. concentrationconcentrated
  7. customThe product was purified by column chromatography on silica gel
  8. washeluting with EtOAc-PE (5%)

Sources & evidence

ORD record
ord-1bef7e747c1646a6b4257aec5da93b78
Source dataset
uspto-grants-2003_09
Patent number
US06613748B2

Reaction notes

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