Water → (S)-3-(Hexadecyloxy)propane-1,2-diol

HRID 1501891Notes

Reaction equation

HRID 1501891 reaction equation
C[C:2]1([CH3:9])[O:6][C@H:5]([CH2:7][OH:8])[CH2:4][O:3]1.[OH-].[K+].[CH2:12](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]CC.O>C1(C)C=CC=CC=1>[CH2:2]([O:3][CH2:4][C@H:5]([CH2:7][OH:8])[OH:6])[CH2:9][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH3:12]

Participants

6

Reactant 4

HCID 962WaterHCID 82131-BromohexadecaneHCID 14797Potassium HydroxideHCID 736056(R)-Solketal

Product 1

HCID 10448487(S)-3-(Hexadecyloxy)propane-1,2-diolYield 82.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

11 grams of (R)-(−)-2,2-dimethyl-1,3-dioxolane-4-methanol, 20 grams of powdered potassium hydroxide and 27.96 grams of hexadecyl bromide were stirred in 150 ml toluene and refluxed for 6 hours, while removing the water formed by azeotropic distillation. The volume of the solvent was gradually reduced to about 40 ml. The reaction mixture was cooled to room temperature, 100 ml water was added, and the reaction mixture was extracted thrice with 75 ml dichloromethane. The combined organic phase was washed with 50 ml water and the solvent was removed under reduced pressure. The residue was dissolved in 200 ml of a mixture of 90:10:5 (volume/volume) methanol:water:concentrated hydrochloric acid, and the resulting solution was refluxed for 2 hours. After cooling to room temperature, 100 ml of water was added. The product was extracted thrice with 100 ml dichloromethane, washed consecutively with 100 ml water, 100 ml saturated aqueous solution of sodium carbonate and again with 100 ml water. The solvent was then removed under reduced pressure, and the product was crystallized from hexane (200 ml) to give 21.69 grams pure (S)-1-hexadecyl-glycerol, which was dried in a desiccator under reduced pressure. The yield was 82%.

Workup

  1. temperaturerefluxed for 6 hours
  2. customwhile removing the water
  3. customformed by azeotropic distillation
  4. extractionthe reaction mixture was extracted thrice with 75 ml dichloromethane
  5. washThe combined organic phase was washed with 50 ml water
  6. customthe solvent was removed under reduced pressure
  7. dissolutionThe residue was dissolved in 200 ml of a mixture of 90:10:5 (volume/volume) methanol
  8. temperaturewater:concentrated hydrochloric acid, and the resulting solution was refluxed for 2 hours
  9. temperatureAfter cooling to room temperature
  10. addition100 ml of water was added
  11. extractionThe product was extracted thrice with 100 ml dichloromethane
  12. washwashed consecutively with 100 ml water, 100 ml saturated aqueous solution of sodium carbonate and again with 100 ml water
  13. customThe solvent was then removed under reduced pressure
  14. customthe product was crystallized from hexane (200 ml)

Sources & evidence

ORD record
ord-407bef6ade1b40d8baa76ac0b5241160
Source dataset
uspto-grants-2015_12
Patent number
US09206206B2

Reaction notes

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