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

HRID 844155Notes

Reaction equation

HRID 844155 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-14e39ad2b34c465a93664b1f7bfab173
Source dataset
uspto-grants-2002_04
Patent number
US06380221B1

Reaction notes

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