Sodium Acetate → 2-Methoxycarbonyl-3-chloro4-(acetoxymethyl)thiophene

HRID 370086Notes

Reaction equation

HRID 370086 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][CH:7]=[C:8]([CH2:11]Cl)[C:9]=1[Cl:10])=[O:4].[C:13]([O-:16])(=[O:15])[CH3:14].[Na+]>C(O)(=O)C>[CH3:1][O:2][C:3]([C:5]1[S:6][CH:7]=[C:8]([CH2:11][O:16][C:13](=[O:15])[CH3:14])[C:9]=1[Cl:10])=[O:4]

Participants

4

Reactant 2

HCID 517045Sodium AcetateHCID 183767792-Methoxycarbonyl-3-chloro4-(chloromethyl)thiophene

Product 1

HCID 183769232-Methoxycarbonyl-3-chloro4-(acetoxymethyl)thiopheneYield 90%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To 2-methoxycarbonyl-3-chloro-4-(chloromethyl)thiophene (48 g, 0.21 mol) in glacial acetic acid (500 mL) was added sodium acetate (35 g, 0.42 mol). The reaction was heated at reflux for 24 hours, then cooled and concentrated in vacuo. The residual oil was made basic by addition of saturated aqueous sodium bicarbonate, and the resulting solution extracted with ethyl acetate (4×150 mL). The combined extracts were dried over sodium sulfate and concentrated to afford 47 g (90% yield) of 2-methoxycarbonyl-3-chloro-4-(acetoxymethyl)thiophene as a light brown oil; NMR (CDCl3) 7.6 (s, 1), 5.1 (s, 2), 3.9 (s, 3), 2.1 (s, 3) ppm.

Workup

  1. temperatureThe reaction was heated
  2. temperatureat reflux for 24 hours
  3. temperaturecooled
  4. concentrationconcentrated in vacuo
  5. additionThe residual oil was made basic by addition of saturated aqueous sodium bicarbonate
  6. extractionthe resulting solution extracted with ethyl acetate (4×150 mL)
  7. dry with materialThe combined extracts were dried over sodium sulfate
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-c30db98f444f4a31abd0822d23bf3cde
Source dataset
uspto-grants-2000_10
Patent number
US06140351

Reaction notes

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