Sodium hydride → 2-(4-methanesulfonylbenzyl)-3-oxothiobutyric acid S-tert-butyl Ester

HRID 2266499Notes

Reaction equation

HRID 2266499 reaction equation
[C:1]([S:5][C:6](=[O:11])[CH2:7][C:8](=[O:10])[CH3:9])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].Br[CH2:15][C:16]1[CH:21]=[CH:20][C:19]([S:22]([CH3:25])(=[O:24])=[O:23])=[CH:18][CH:17]=1>COCCOC.[Cl-].[NH4+]>[C:1]([S:5][C:6](=[O:11])[CH:7]([CH2:15][C:16]1[CH:17]=[CH:18][C:19]([S:22]([CH3:25])(=[O:24])=[O:23])=[CH:20][CH:21]=1)[C:8](=[O:10])[CH3:9])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 140007Butanethioic acid, 3-oxo-, S-(1,1-dimethylethyl) esterHCID 27335814-(Methylsulfonyl)benzyl Bromide

Product 1

HCID 866314382-(4-methanesulfonylbenzyl)-3-oxothiobutyric acid S-tert-butyl Ester

Reagents, catalysts & solvents 2

HCID 80711,2-DimethoxyethaneSolvent3×HCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 3-oxothiobutyric acid S-tert-butyl ester (7.5 g) in 1,2-dimethoxyethane (10 mL) was added to a stirred suspension of sodium hydride (60% in oil, 1.9 g) in 1,2-dimethoxyethane (100 mL) at −20° C. The mixture was warmed to 0° C. for 10 minutes and then a solution of 1-bromomethyl-4-methanesulfonylbenzene (12.9 g) in 1,2-dimethoxyethane (30 mL) was added dropwise over a period of 10 minutes. The resulting mixture was warmed to room temperature over 30 minutes and then stirred at this temperature for 17 hours. The mixture was diluted with saturated aqueous ammonium chloride solution (70 mL) and the phases separated. The aqueous phase was extracted with diethyl ether and the combined organic phases were dried over magnesium sulfate. The solvent was removed under reduced pressure and purification of the residue by column chromatography on silica gel, eluting with a mixture of dichloromethane and ethyl acetate (1:0 to 4:1 by volume) gave title compound, 7.1 g.

Workup

  1. temperatureThe resulting mixture was warmed to room temperature over 30 minutes
  2. customthe phases separated
  3. extractionThe aqueous phase was extracted with diethyl ether
  4. dry with materialthe combined organic phases were dried over magnesium sulfate
  5. customThe solvent was removed under reduced pressure and purification of the residue by column chromatography on silica gel
  6. washeluting with a mixture of dichloromethane and ethyl acetate (1:0 to 4:1 by volume)

Sources & evidence

ORD record
ord-559e7a9e997f4b87a5994f3c9ada7549
Source dataset
uspto-grants-2010_12
Patent number
US07858640B2

Reaction notes

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