Sodium Hydroxide → 2-Carboxy-3-chloro-4-(hydroxymethyl)thiophene

HRID 2300916Notes

Reaction equation

HRID 2300916 reaction equation
C[O:2][C:3]([C:5]1[S:6][CH:7]=[C:8]([CH2:11][O:12]C(=O)C)[C:9]=1[Cl:10])=[O:4].[OH-].[Na+]>O1CCOCC1.O>[C:3]([C:5]1[S:6][CH:7]=[C:8]([CH2:11][OH:12])[C:9]=1[Cl:10])([OH:4])=[O:2]

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 183769232-Methoxycarbonyl-3-chloro4-(acetoxymethyl)thiophene

Product 1

HCID 183769972-Carboxy-3-chloro-4-(hydroxymethyl)thiopheneYield 99.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 2-methoxycarbonyl-3-chloro4-(acetoxymethyl)thiophene (83 g, 0.33 mol) in 1,4-dioxane (350 mL) was added a solution of sodium hydroxide (26.5 g, 0.66 mol) in water (200 mL) and the mixture stirred at ambient temperature. After 1 hour the dioxane was removed in vacuo and the aqueous solution washed with ethyl acetate (2×100 mL). The aqueous layer was brought to pH 2 by addition of concentrated HCl, then extracted with n-butanol (4×200 mL). The combined extracts were concentrated and the resulting solid dried in vacuo to afford 63 g (90% yield) of 2-carboxy-3-chloro-4-(hydroxymethyl)thiophene as a tan powder; NMR (DMSO-d6) 7.7 (s, 1), 4.4 (s, 2) ppm.

Workup

  1. customAfter 1 hour the dioxane was removed in vacuo
  2. washthe aqueous solution washed with ethyl acetate (2×100 mL)
  3. additionThe aqueous layer was brought to pH 2 by addition of concentrated HCl
  4. extractionextracted with n-butanol (4×200 mL)
  5. concentrationThe combined extracts were concentrated
  6. customthe resulting solid dried in vacuo

Sources & evidence

ORD record
ord-66f69eb269ad4ac6a56de78abd088b2a
Source dataset
uspto-grants-2002_12
Patent number
US06498185B1

Reaction notes

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