Hydrochloric Acid → Methyl 3-hydroxy-4,5-dimethylthiophene-2-carboxylate

HRID 1200097Notes

Reaction equation

HRID 1200097 reaction equation
Cl.[CH3:2][CH:3]([C:9](=O)[CH3:10])[C:4](OCC)=[O:5].[SH:12][CH2:13][C:14]([O:16][CH3:17])=[O:15]>ClCCl>[CH3:2][C:3]1[C:4]([OH:5])=[C:13]([C:14]([O:16][CH3:17])=[O:15])[S:12][C:9]=1[CH3:10]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 701Ethyl 2-methylacetoacetateHCID 16907Methyl Thioglycolate

Product 1

HCID 54691275Methyl 3-hydroxy-4,5-dimethylthiophene-2-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Dry hydrogen chloride gas was bubbled through a mixture of ethyl 2-methyl-3-oxobutanoate (7.6 g, 50 mmol) and methyl 2-mercaptoacetate (11.2 g, 100 mmol) at -10° C. until saturated. The oil was allowed to stand for 3 hours at room temperature, diluted with dichloromethane and washed with brine. After drying with sodium sulphate and evaporation of solvent the oil was dissolved in methanol (10 ml) and added dropwise to methanolic potassium hydroxide (2N; 75 ml), stirring at room temperature for 1 hour. The solution was diluted with iced water (125 ml) and acidified with 3N hydrochloric acid at -3° to 0° C. to pH1. The precipitate was filtered and washed with water (5.5 g, m.p. 50°-51° C., methanol).

Workup

  1. washwashed with brine
  2. dry with materialAfter drying with sodium sulphate and evaporation of solvent the oil
  3. dissolutionwas dissolved in methanol (10 ml)
  4. additionadded dropwise to methanolic potassium hydroxide (2N; 75 ml)
  5. additionThe solution was diluted with iced water (125 ml)
  6. customacidified with 3N hydrochloric acid at -3° to 0° C. to pH1
  7. filtrationThe precipitate was filtered
  8. washwashed with water (5.5 g, m.p. 50°-51° C., methanol)

Sources & evidence

ORD record
ord-0cef3aabf50f48c9aa9f8b0d1e17e4ed
Source dataset
uspto-grants-1990_02
Patent number
US04904686

Reaction notes

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