Reaction #1914826

Reaction equation

16-bromohexadecan-1-ol

HCl

sodium

NaOH

thiolacetic acid

→

desired product

Yield 70.3%

16-Mercaptohexadecan-1-ol

Yield 70.3%

Solvents

methanol

Conditions

Workup

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
   TemperatureThe resulted mixture was refluxed for 15 hrs
5. 5
   Temperatureto cool to RT
6. 6
   TemperatureThe reaction completion required additional 3 hr of reflux
7. 7
   OtherResulted
8. 8
   Otherreaction mixture
9. 9
   Temperaturewas cooled with ice bath
10. 10
    workup.ADDITIONpoured
11. 11
    workup.STIRRINGwith stirring, into a vessel
12. 12
    Extractionextracted with 300 ml of ether
13. 13
    OtherThe organic layer was separated
14. 14
    Washwashed with 3×150 ml of water, 150 ml of saturated NaCl aqueous solution
15. 15
    Dryingdried over sodium sulfate
16. 16
    OtherAfter ether removal material
17. 17
    workup.DISSOLUTIONwas dissolved in minimum amount of dicloromethane
18. 18
    Otherpurified by silica gel chromatography (100% dicloromethane as eluent)

Procedure

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 thiolacetic acid. After additional 10 min of stirring 3 ml degassed methanolic solution of 1.0 gr (3.11 mmole) of 16-bromohexadecan-1-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 dicloromethane and purified by silica gel chromatography (100% dicloromethane as eluent). 600 mg (70% yield) of the desired product were obtained.

Source