Solketal → 1-O-Hexadecylglycerol

HRID 1692539Notes

Reaction equation

HRID 1692539 reaction equation
C[C:2]1([CH3:9])[O:6][CH: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>C1C=CC=CC=1.CCOCC>[CH2:2]([O:3][CH2:4][CH: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 3

HCID 7528SolketalHCID 82131-BromohexadecaneHCID 14797Potassium Hydroxide

Product 1

HCID 727331-O-HexadecylglycerolYield 77.2%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent

Procedure

D-Acetone glycerol (4 grams) for synthesis of L-ALLE or L-Acetone glycerol for synthesis of D-ALLE, powdered potassium hydroxide (approximately 10 grams) and hexadecyl bromide (9.3 grams) in benzene (100 ml) were stirred and refluxed for 5 hours, while removing the water formed by azeotropic distillation (compare W. J. Baumann and H. K. Mangold, J. Org. Chem. 29: 3055, 1964 and F. Paltauf, Monatsh. 99:1277, 1968). The volume of the solvent was gradually reduced to about 20 ml, and the resulting mixture was cooled to room temperature and dissolved in ether (100 ml). The resulting solution was washed with water (2×50 ml), and the solvent was removed under reduced pressure. A 100 ml mixture of 90:10:5 methanol:water:concentrated hydrochloric acid was added to the residue and the mixture was refluxed for 10 minutes. The product was extracted with ether (200 ml) and was washed consecutively with water (50 ml), 10% sodium hydroxide (20 ml) and again with water (volumes of 20 ml) until neutral. The solvent was removed under reduced pressure and the product (8.8 grams) was crystallized from hexane to give 7.4 grams of pure 1-hexadecyl-glyceryl ether (compound I, FIG. 1) for synthesis of D-ALLE or 3-hexadecyl-glyceryl ether for synthesis of L-ALLE.

Workup

  1. temperaturerefluxed for 5 hours
  2. customwhile removing the water
  3. customformed by azeotropic distillation (compare W. J. Baumann and H. K. Mangold, J. Org. Chem. 29: 3055, 1964 and F. Paltauf, Monatsh. 99:1277, 1968)
  4. washThe resulting solution was washed with water (2×50 ml)
  5. customthe solvent was removed under reduced pressure
  6. additionA 100 ml mixture of 90:10:5 methanol:water:concentrated hydrochloric acid was added to the residue
  7. temperaturethe mixture was refluxed for 10 minutes
  8. extractionThe product was extracted with ether (200 ml)
  9. washwas washed consecutively with water (50 ml), 10% sodium hydroxide (20 ml) and again with water (volumes of 20 ml) until neutral
  10. customThe solvent was removed under reduced pressure
  11. customthe product (8.8 grams) was crystallized from hexane

Sources & evidence

ORD record
ord-63ee0f8a27464c1598a4827c8daff0df
Source dataset
uspto-grants-2012_04
Patent number
US08158611B2

Reaction notes

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