Methyl 9-dodecenoate → 9-Dodecen-1-ol

To a dry 2 L 3-neck round bottom flask fitted with a nitrogen inlet and outlet, thermocouple, condenser, mechanical stirrer and pressure-equalizing dropping funnel was added lithium aluminum hydride (30.10 g, 0.754 mol, 95% technical grade solid) in one portion, under a positive pressure of nitrogen. The metal hydride was suspended in anhydrous tetrahydrofuran (500 mL) and the mixture cooled on an ice bath. Methyl 9-dodecenoate (200 g, 0.942 mol) was added dropwise via addition funnel to the stirred lithium aluminum hydride suspension over 1 h at such a rate as to maintain the internal temperature below 50° C. When the reaction exotherm subsided, the external cooling bath was removed and the resulting viscous mixture was stirred for a further 8 h at ambient temperature. Complete consumption of starting material was confirmed by thin layer chromatography and by FTIR. The reaction was quenched by the careful addition of the reactor contents to a 4 L Erlenmeyer flask containing chilled concentrated aqueous sodium chloride (300 mL). The reactor was rinsed with ethyl acetate (100 mL) then 10% (v/v) aqueous sulfuric acid (100 mL); both rinse aliquots were combined with the reaction neutralization mixture. An additional aliquot of 10% (v/v) aqueous sulfuric acid was added to neutralize the aqueous phase then the biphasic neutralization mixture was transferred to a separatory funnel. The aqueous phase was partitioned and washed with ethyl acetate (100 mL×2). The combined organic phases were successively washed with concentrated aqueous sodium bicarbonate (100 mL), brine (100 mL), dried (MgSO4) then filtered. The organic phase was concentrated in vacuo, giving 9-dodecen-1-ol (165 g, 95%) as clear, colorless oil.

1. customTo a dry 2 L 3-neck round bottom flask fitted with a nitrogen inlet and outlet
2. customthermocouple, condenser, mechanical stirrer and pressure-equalizing dropping
3. temperaturethe mixture cooled on an ice bath
4. temperatureto maintain the internal temperature below 50° C
5. customthe external cooling bath was removed
6. customconsumption of starting material
7. customThe reaction was quenched by the careful addition of the reactor contents to a 4 L Erlenmeyer flask
8. additioncontaining
9. temperaturechilled concentrated aqueous sodium chloride (300 mL)
10. washThe reactor was rinsed with ethyl acetate (100 mL)
11. additionAn additional aliquot of 10% (v/v) aqueous sulfuric acid was added
12. customthe biphasic neutralization mixture was transferred to a separatory funnel
13. customThe aqueous phase was partitioned
14. washwashed with ethyl acetate (100 mL×2)
15. washThe combined organic phases were successively washed with concentrated aqueous sodium bicarbonate (100 mL), brine (100 mL)
16. dry with materialdried (MgSO4)
17. filtrationthen filtered
18. concentrationThe organic phase was concentrated in vacuo

ORD record

ord-00d8610c747240d1a3eb61ce529cf5b8

Source dataset

uspto-grants-2016_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09266918B2