Solketal → 4-[(Hexadecyloxy)methyl]-2,2-dimethyl-1,3-dioxolane

HRID 881581Notes

Reaction equation

HRID 881581 reaction equation
[H-].[Na+].[CH3:3][C:4]1([CH3:11])[O:8][CH:7]([CH2:9][OH:10])[CH2:6][O:5]1.Br[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]>CN(C)C=O>[CH3:3][C:4]1([CH3:11])[O:8][CH:7]([CH2:9][O:10][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH3:13])[CH2:6][O:5]1

Participants

5

Reactant 3

HCID 7528SolketalHCID 82131-BromohexadecaneHCID 24758Sodium hydride

Product 1

HCID 139162514-[(Hexadecyloxy)methyl]-2,2-dimethyl-1,3-dioxolaneYield 57%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

To NaH (1.85 g, 60% dispersed in mineral oil) under argon was added anhydrous N,N-dimethylformamide (DMF, 30 mL) at RT. Solketal (2.20 g, 16.7 mmol) in 10 mL anhydrous DMF was then added dropwise with constant stirring. 1-Bromohexadecane (5.10 g, 16.7 mmol), dissolved in anhydrous DMF (20 mL) was then added to the reaction mixture dropwise and stirred for 72 hours. The reaction was quenched by adding about 5 mL of methanol. It was then poured into cold ice water (100 mL) and extracted with hexane (100 mL, 3×). The solvent was removed under reduced pressure and the residue chromatographed on silica gel using hexane-dichloromethane to obtain 1a (3.363 g, 57% yield); 1H NMR (in CDCl3): δ in ppm 0.83-0.86 (3H, t, J=6.5 Hz), 1.22 (26H, m), 1.33 (3H, s), 1.39 (3H, s), 1.52-1.55 (2H, m), 3.37-3.48 (4H, m), 3.68-3.71 (1H, t, J=6.5 Hz), 4.01-4.03 (1H, t, J=6.5 Hz), 4.20-4.25 (1H, quintet, J=6.0 Hz); 13C NMR (in CDCl3): δ in ppm 14.3, 22.9, 25.6, 26.2, 27.0, 29.6, 29.7, 29.8, 29.9, 32.1, 67.1, 72.0, 72.1, 74.9, 109.5.

Workup

  1. additionwas then added to the reaction mixture dropwise
  2. customThe reaction was quenched
  3. additionby adding about 5 mL of methanol
  4. additionIt was then poured into cold ice water (100 mL)
  5. extractionextracted with hexane (100 mL, 3×)
  6. customThe solvent was removed under reduced pressure
  7. customthe residue chromatographed on silica gel

Sources & evidence

ORD record
ord-6d3388d808dc4316aa43f8dd73e29865
Source dataset
uspto-grants-2015_03
Patent number
US08993623B2

Reaction notes

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