Ethyl 4-chloroacetoacetate → Ethyl 2-(4-Bromophenyl)-thiazol-4-ylacetate

HRID 1154891Notes

Reaction equation

HRID 1154891 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([NH2:8])=[S:7])=[CH:4][CH:3]=1.Cl[CH2:12][C:13](=O)[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16]>CN(C)C=O>[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]2[S:7][CH:12]=[C:13]([CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16])[N:8]=2)=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 69484Ethyl 4-chloroacetoacetate2×HCID 15492894-Bromothiobenzamide

Product 1

HCID 13030832Ethyl 2-(4-Bromophenyl)-thiazol-4-ylacetate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 4-bromothiobenzamide (7.62 g), 35.2 mmole), ethyl 4-chloroacetoacetate (5.82 g, 35.2 mmole) and dimethylformamide (23 ml) was stirred under nitrogen and heated in an oil-bath at 115°-120° C. for 11/2 hours. Thin layer chromatography showed the presence of unreacted thioamide. More ethyl chloroacetoacetate (2.91 g, 17.6 mmole) was added and heating was continued for 11/2 hours, by which time no unreacted thioamide remained. The mixture was cooled and poured into ice-water (125 ml) and extracted with ether (2×100 ml). The extract was washed with water (2×100 ml), dried (MgSO4) and evaporated to a semi-solid which contained the desired ester and the corresponding acid. The mixture was dissolved in ethanol (100 ml) saturated with hydrogen chloride and the solution was allowed to stand at room temperature for 1 day. The solution was evaporated to dryness and the ester was used without further purification for preparing the amide.

Workup

  1. temperatureheated in an oil-bath at 115°-120° C. for 11/2 hours
  2. temperatureheating
  3. custom2 hours
  4. temperatureThe mixture was cooled
  5. extractionextracted with ether (2×100 ml)
  6. washThe extract was washed with water (2×100 ml)
  7. dry with materialdried (MgSO4)
  8. customevaporated to a semi-solid which
  9. dissolutionThe mixture was dissolved in ethanol (100 ml) saturated with hydrogen chloride
  10. customThe solution was evaporated to dryness
  11. customthe ester was used without further purification for preparing the amide

Sources & evidence

ORD record
ord-bf466aa2643a4f07b040744ee74c8b95
Source dataset
uspto-grants-1981_11
Patent number
US04298743

Reaction notes

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