Benzyl Bromide → Methyl 3-Benzyloxy-5-(methylsulfonyl)-2-thiophenecarboxylate

HRID 1953963Notes

Reaction equation

HRID 1953963 reaction equation
[H-].[Na+].[OH:3][C:4]1[CH:8]=[C:7]([S:9]([CH3:12])(=[O:11])=[O:10])[S:6][C:5]=1[C:13]([O:15][CH3:16])=[O:14].[CH2:17](Br)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>CN(C)C=O.O>[CH2:17]([O:3][C:4]1[CH:8]=[C:7]([S:9]([CH3:12])(=[O:11])=[O:10])[S:6][C:5]=1[C:13]([O:15][CH3:16])=[O:14])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

6

Reactant 3

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 54724750Methyl 3-hydroxy-5-(methylsulfonyl)thiophene-2-carboxylate

Product 1

HCID 15477099Methyl 3-Benzyloxy-5-(methylsulfonyl)-2-thiophenecarboxylateYield 84%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

A mixture of NaH (3.18 g, 79.5 mmol) in dimethylformamide (DMF) is treated dropwise with a solution of methyl 3-hydroxy-5-(methylsulfonyl)-2-thiophenecarboxylate (15.0 g, 63.6 mmol) in DMF at 0° C., stirred for 10 minutes, treated with benzylbromide (8.30 ml, 70 mmol) at ice bath temperatures, allowed to warm to room temperature overnight and diluted with water. The resultant reaction mixture is filtered. The filtercake is washed with water, dried, stirred in a mixture of ethyl acetate/hexane (20 ml/130 ml), and filtered. The filtercake is washed with hexanes and dried in a Kugelrohr at 40° C. to give the title product as a white solid, 17. 4 g (84% yield), mp 125-126° C. identified by 1HNMR, 13CNMR, IR and mass spectral analyses.

Workup

  1. customThe resultant reaction mixture
  2. filtrationis filtered
  3. washThe filtercake is washed with water
  4. customdried
  5. stirringstirred in a mixture of ethyl acetate/hexane (20 ml/130 ml)
  6. filtrationfiltered
  7. washThe filtercake is washed with hexanes
  8. customdried in a Kugelrohr at 40° C.

Sources & evidence

ORD record
ord-9681226c205345babd68f187519a3f51
Source dataset
uspto-grants-2000_09
Patent number
US06121202

Reaction notes

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