2-Naphthoyl chloride → (+/-)-Linalyl (2-naphthoyl)acetate

Temperature

-20 °C

Lithium diisopropylamnide (101.0 mL of a 2.0 M solution, 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 fiunel. The flask is placed in a dry ice-acetone bath. 3,7-Dimethyl-1,6-octadien-3-yl acetate (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 fumnel 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, 1H and 13C NMR.

1. customfitted with a magnetic stirrer
2. additioninternal thermometer, argon inlet, and addition fiunel
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 fumnel
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

ORD record

ord-568236dba6af44718b8b705e2ee23f3b

Source dataset

uspto-grants-2001_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06184188B2