Reacción #833544

Ecuación de reacción

16-bromohexadecan-l-ol

HCl

sodium

NaOH

thioacetic acid

→

desired product

Rendimiento 70.3%

16-Mercaptohexadecan-l-ol

Rendimiento 70.3%

Disolventes

methanol

Condiciones de reacción

Tratamiento posterior

1. 1
   workup.ADDITIONAfter completion of addition the reaction mixture
2. 2
   workup.STIRRINGAfter additional 10 min of stirring 3 ml
3. 3
   workup.ADDITIONwere added
4. 4
   TemperaturaThe resulted mixture was refluxed for 15 hrs
5. 5
   Temperaturato cool to RT
6. 6
   TemperaturaThe reaction completion required additional 3 hr of reflux
7. 7
   OtroResulted
8. 8
   Otroreaction mixture
9. 9
   Temperaturawas cooled with ice bath
10. 10
    workup.ADDITIONpoured
11. 11
    workup.STIRRINGwith stirring, into a vessel
12. 12
    Extracciónextracted with 300 ml of ether
13. 13
    OtroThe organic layer was separated
14. 14
    Lavadowashed with 3×150 ml of water, 150 ml of saturated NaCl aqueous solution
15. 15
    Secadodried over sodium sulfate
16. 16
    OtroAfter ether removal material
17. 17
    workup.DISSOLUTIONwas dissolved in minimum amount of dichloromethane
18. 18
    Otropurified by silica gel chromatography (100% dichloromethane as eluent)

Procedimiento

Under inert atmosphere 365 mg of sodium metal suspension (40% in mineral oil) were added dropwise to 20 ml of dry methanol at 0° C. After completion of addition the reaction mixture was stirred for 10 min at RT followed by addition of 0.45 ml (6.30 mmole) of thioacetic acid. After additional 10 min of stirring 3 ml degassed methanolic solution of 1.0 gr (3.11 mmole) of 16-bromohexadecan-l-ol were added. The resulted mixture was refluxed for 15 hrs, allowed to cool to RT and 20 ml of degassed 1.0 M NaOH aqueous solution were injected. The reaction completion required additional 3 hr of reflux. Resulted reaction mixture was cooled with ice bath and poured, with stirring, into a vessel containing 200 ml of ice water. This mixture was titrated to pH=7 by 1.0 M HCl and extracted with 300 ml of ether. The organic layer was separated, washed with 3×150 ml of water, 150 ml of saturated NaCl aqueous solution and dried over sodium sulfate. After ether removal material was dissolved in minimum amount of dichloromethane and purified by silica gel chromatography (100% dichloromethane as eluent). 600 mg (70% yield) of the desired product were obtained.

Fuente