Linalool → (+/-)-Linalyl (2-naphthoyl)acetate

HRID 2301264Notes

Reaction equation

HRID 2301264 reaction equation
[H-].[Na+].[CH3:3][C:4]1(C)OC(=O)CC(=O)[O:5]1.[CH:13]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[CH:16]=[CH:15][C:14]=1[C:23](Cl)=[O:24].[CH3:26][C:27]([OH:36])([CH2:30][CH2:31][CH:32]=[C:33]([CH3:35])[CH3:34])[CH:28]=[CH2:29]>O1CCCC1.O>[CH:13]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[CH:16]=[CH:15][C:14]=1[C:23](=[O:24])[CH2:3][C:4]([O:36][C:27]([CH3:26])([CH2:30][CH2:31][CH:32]=[C:33]([CH3:35])[CH3:34])[CH:28]=[CH2:29])=[O:5]

Participants

7

Reactant 4

HCID 6549LinaloolHCID 162492,2-Dimethyl-1,3-dioxane-4,6-dioneHCID 24758Sodium hydrideHCID 752462-Naphthoyl chloride

Product 1

HCID 10991722(+/-)-Linalyl (2-naphthoyl)acetate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
0 °C

Procedure

Sodium hydride (1.26 g, 0.057 mol, 95%) is charged to a 250 mL three-necked round-bottomed flask fitted with a magnetic stirrer, ice bath, addition funnel, internal thermometer and argon inlet. The contents of the reaction vessel are slurried with 50 mL of tetrahydrofuran (THF) and subsequently cooled to 0° C. 2,2-dimethyl-1,3-dioxan-4,6-dione (Meldrum's acid) (3.78 g, 0.026 mol) is dissolved in 20 mL of THF and the solution is subsequently added over 15 min. The evolution of gas indicates the reaction is ensuing. After 30 min, 2-naphthoyl chloride (5.00 g, 0.026 mol) which is dissolved in 30 mL of THF is added over 15 min. The mixture is allowed to warm to room temperature and stirred for 72 h. A solution of 3,7-dimethyl-1,6-octadien-3-ol (linalool) (4.05 g, 0.026 mol) dissolved in 30 mL of THF is added over 30 min. The mixture is heated to reflux for 18 h. The cooled mixture is poured into 100 mL of water and extracted with ether (50 mL) three times. The organic layers are washed with saturated NaHCO3 solution, water, dried over MgSO4, filtered, concentrated by rotary evaporation and purified by flash chromatography to yield 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate.

Workup

  1. customfitted with a magnetic stirrer, ice bath, addition funnel
  2. additionthe solution is subsequently added over 15 min
  3. additionis added over 15 min
  4. temperatureto warm to room temperature
  5. additionis added over 30 min
  6. temperatureThe mixture is heated
  7. temperatureto reflux for 18 h
  8. extractionextracted with ether (50 mL) three times
  9. washThe organic layers are washed with saturated NaHCO3 solution, water
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated by rotary evaporation
  13. custompurified by flash chromatography

Sources & evidence

ORD record
ord-340e8c0cd91048f4983a43451dd576ad
Source dataset
uspto-grants-2002_12
Patent number
US06500797B1

Reaction notes

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