Phenacyl bromide → Ethyl 4-phenyl-1,3-thiazole-2-carboxylate

HRID 625093Notes

Reaction equation

HRID 625093 reaction equation
Br[CH2:2][C:3]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=O.[NH2:11][C:12](=[S:18])[C:13]([O:15][CH2:16][CH3:17])=[O:14]>C1C=CC=CC=1.C(O)C>[C:5]1([C:3]2[N:11]=[C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[S:18][CH:2]=2)[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

5

Reactant 2

HCID 6259Phenacyl bromideHCID 2733398Ethyl thiooxamate

Product 1

HCID 24730326Ethyl 4-phenyl-1,3-thiazole-2-carboxylateYield 75.7%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 702EthanolSolvent

Procedure

A mixture of 2-bromo-1-phenylethanone (1.790 g, 8.99 mmol) and ethyl 2-amino-2-thioxoacetate (Example 4A, 1.20 g, 9.01 mmol) in benzene (80 mL) and ethanol (10 mL) was stirred at room temperature for 18 h. The mixture was heated at 80° C. for 1 h. The solvent was evaporated under reduced pressure and the residue was partitioned between ethyl acetate (300 mL) and saturated aqueous sodium bicarbonate (100 mL). The organic phase was washed with brine, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residual clear oil was chromatographed on silica gel (4×10 cm, elution toluene-ethyl acetate 0-2-4%) and gave a yellow oil (1.588 g). This was distilled in vacuo (bp: 105-115° C./0.1 torr, bulb to bulb distillation, air bath temperature) to provide the title material (1.409 g, 67%) as a pale yellow syrup which solidified to an almost colorless solid upon standing. LC (Method C): 2.009 min. HRMS (ESI) calcd for C12H12NO2S [M+H]+ m/z 234.0583, found 234.0597. 1H NMR (CDCl3, 400 MHz) δ ppm: 1.48 (t, J=7.2 Hz, 3H), 4.52 (q, J=17.2 Hz, 2H), 735-7.49 (m, 3H), 7.75 (s, 1H), 7.93-8.00 (m, 2H).

Workup

  1. temperatureThe mixture was heated at 80° C. for 1 h
  2. customThe solvent was evaporated under reduced pressure
  3. customthe residue was partitioned between ethyl acetate (300 mL) and saturated aqueous sodium bicarbonate (100 mL)
  4. washThe organic phase was washed with brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residual clear oil was chromatographed on silica gel (4×10 cm, elution toluene-ethyl acetate 0-2-4%)

Sources & evidence

ORD record
ord-82ce4b5a40d8436c97bf33a6f515d543
Source dataset
uspto-grants-2016_04
Patent number
US09303065B2

Reaction notes

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