Glycerol → Methyl 3,4-dimethyl-3-hydroxy-6-heptenoate

HRID 551687Notes

Reaction equation

HRID 551687 reaction equation
[CH3:1][CH:2]([CH2:6][CH:7]=[CH2:8])[C:3](=[O:5])[CH3:4].Br[CH2:10][C:11]([O:13][CH3:14])=[O:12].OCC(CO)O.[Cl-].N>O1CCCC1>[CH3:4][C:3]([OH:5])([CH:2]([CH3:1])[CH2:6][CH:7]=[CH2:8])[CH2:10][C:11]([O:13][CH3:14])=[O:12]

Participants

6

Reactant 4

HCID 753GlycerolHCID 60984Methyl bromoacetateHCID 124223183-Methylhex-5-en-2-oneHCID 20976574Ammonia chloride

Product 1

HCID 86646146Methyl 3,4-dimethyl-3-hydroxy-6-heptenoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

3-Methyl-5-hexen-2-one (J. Chem. Soc., Chem. Comm. 19, 1991, 1399) (17 g, 106 mmol) and methyl bromoacetate (24.4 g, 159 mmol) were dissolved in tetrahydrofuran (100 mL), and the solution was added dropwise to a tetrahydrofuran (50 mL) (zinc (10.4 g, 159 mmol) and trimethyl borate (30 mL)) solution under reflux. After reflux for 3 hours, the mixture was cooled to room temperature, and glycerin (30 mL) and a saturated aqueous solution of ammonia chloride (100 mL) were added thereto, followed by two extractions with ethyl acetate. The ethyl acetate layer was washed with saturated saline, then dried, and then concentrated. The residue was purified by silica gel column chromatography (200 g) to obtain the compound of interest as an oil substance (11.7 g, 60%).

Workup

  1. temperatureunder reflux
  2. temperatureAfter reflux for 3 hours
  3. extractionfollowed by two extractions with ethyl acetate
  4. washThe ethyl acetate layer was washed with saturated saline
  5. customdried
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel column chromatography (200 g)
  8. customto obtain the compound of interest as an oil substance (11.7 g, 60%)

Sources & evidence

ORD record
ord-915e8305ead74a959ddda63652cb621c
Source dataset
uspto-grants-2011_05
Patent number
US07947738B2

Reaction notes

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