Reaction #1265377

Reaction equation

methyl methanethiolsulfonate

sodium carbonate

mercaptopentanoic acid

4-Mercapto-4-methylpentanoic acid

methyl methanethiolsulfonate

→

product 8

Yield 70.0%

4-Methyl-4-(methyldithio)pentanoic acid

Yield 70.0%

Solvents

ethanol

water

Conditions

Workup

1. 1
   workup.ADDITIONwas added to the acid at a rate that would not
2. 2
   OtherThe flask was equipped with a 100 mL addition funnel
3. 3
   TemperatureThe flask was cooled in an ice/water bath
4. 4
   Temperaturethe system was maintained under an argon atmosphere
5. 5
   OtherThe cooling bath was removed
6. 6
   OtherSolvent was removed by rotary evaporation under vacuum, until approximately 20 mL
7. 7
   workup.ADDITIONAfter which 10 mL of saturated sodium bicarbonate and 30 mL of deionized water were added
8. 8
   WashThe mixture was washed three times with 25 mL portions of ethyl acetate in a separatory funnel
9. 9
   Extractionwas extracted twice with 120 mL portions of ethyl acetate
10. 10
    Washwashed with 20 mL of a solution
11. 11
    DryingThe organic layer was then dried over 14 g of anhydrous sodium sulfate and solvent
12. 12
    Otherwas removed by rotary evaporation under vacuum

Procedure

A solution of mercaptopentanoic acid 7 (6.0 mL, 40 mmol) was dissolved in 50 mL of deionized water in a 250 mL flask. The solution was magnetically stirred as sodium carbonate (6.4 g, 60 mmol) was added to the acid at a rate that would not cause excessive frothing. The flask was equipped with a 100 mL addition funnel, which was charged with a solution of methyl methanethiolsulfonate (7.5 g, 60 mmol) dissolved in 30 mL of glass-distilled 100% ethanol. The flask was cooled in an ice/water bath and the system was maintained under an argon atmosphere. The methyl methanethiolsulfonate solution was added drop-wise to the flask as rapidly as possible but without causing excessive frothing. The cooling bath was removed and the reaction mixture was allowed to stir for an additional 3 hours. Solvent was removed by rotary evaporation under vacuum, until approximately 20 mL remained. After which 10 mL of saturated sodium bicarbonate and 30 mL of deionized water were added. The mixture was washed three times with 25 mL portions of ethyl acetate in a separatory funnel. The aqueous layer was adjusted to approximately pH 2 with 5 M HCl and was extracted twice with 120 mL portions of ethyl acetate. The organic layers were combined and washed with 20 mL of a solution composed of saturated NaCl and 1M HCl at a ratio of 4:1. The organic layer was then dried over 14 g of anhydrous sodium sulfate and solvent was removed by rotary evaporation under vacuum to give 5.4 g of product 8 (70% yield). The material can be taken to the next step without further purification. 1H NMR (CDCl3): δ1.54 (6H, s), 2.15-2.21 (2H, m), 2.64 (3H, s), 2.69-2.72 (2H, m). MS (M+Na+) calc.: 217.0, found: 217.1

Source