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

HRID 1276063Notes

Reaction equation

HRID 1276063 reaction equation
C([N-]C(C)C)(C)C.[Li+].[C:9]([O:12][C:13]([CH2:17][CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])([CH:15]=[CH2:16])[CH3:14])(=[O:11])[CH3:10].[CH:23]1[C:32]2[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=2)[CH:26]=[CH:25][C:24]=1[C:33](Cl)=[O:34]>C1COCC1>[CH:23]1[C:32]2[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=2)[CH:26]=[CH:25][C:24]=1[C:33]([CH2:10][C:9]([O:12][C:13]([CH2:17][CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])([CH:15]=[CH2:16])[CH3:14])=[O:11])=[O:34]

Participants

5

Reactant 3

HCID 8294Linalyl AcetateHCID 752462-Naphthoyl chlorideHCID 2724682Lithium diisopropylamide

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-20 °C

Procedure

Lithium diisopropylamide in the amount of 101.0 mL (2.0 M, 0.202 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a dry ice-acetone bath. Linalyl acetate in the amount of 18.66 g (0.095 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of 17.43 g (0.090 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (53 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO3 solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO4 and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and GC analysis and the structure confirmed by mass spectrometry, 1 and 13C NMR.

Workup

  1. customfitted with a magnetic stirrer
  2. additioninternal thermometer, argon inlet, and addition funnel
  3. customThe flask is placed in a dry ice-acetone bath
  4. additionthe resulting solution added to the flask over 45 min
  5. additionOnce addition
  6. stirringstirred at that temperature for 18 h
  7. temperatureAfter warming to 0° C.
  8. customthe mixture is quenched with 20% HCl (53 mL)
  9. additionThe mixture is poured into a separatory funnel
  10. additioncontaining ether (150 mL) and water (250 mL)
  11. extractionThe aqueous layer is extracted with ether (150 mL)
  12. washThe combined organic layers are washed with saturated NaHCO3 solution (2×100 mL), water (2×150 mL) and brine (150 mL)
  13. dry with materialdried over MgSO4
  14. filtrationfiltered
  15. customThe solvent is removed by rotary evaporation
  16. customto give an orange/red oil
  17. customThe oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether)
  18. customto give an oil

Sources & evidence

ORD record
ord-059f5ae7f4f64d8781b34c55e7b0119c
Source dataset
uspto-grants-2000_12
Patent number
US06165953

Reaction notes

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