Ethyl 2-(2,2,2-trichloroethoxycarbonyloxymethyl)thiazole-4-carboxylate → 2-(2,2,2-Trichloroethoxycarbonyloxymethyl)thiazole-4-carboxaldehyde

HRID 348242Notes

Reaction equation

HRID 348242 reaction equation
[Cl:1][C:2]([Cl:20])([Cl:19])[CH2:3][O:4][C:5]([O:7][CH2:8][C:9]1[S:10][CH:11]=[C:12]([C:14](OCC)=[O:15])[N:13]=1)=[O:6].[H-].C([Al+]CC(C)C)C(C)C>C(Cl)Cl>[Cl:20][C:2]([Cl:1])([Cl:19])[CH2:3][O:4][C:5]([O:7][CH2:8][C:9]1[S:10][CH:11]=[C:12]([CH:14]=[O:15])[N:13]=1)=[O:6]

Participants

4

Reactant 2

HCID 10594849Ethyl 2-(2,2,2-trichloroethoxycarbonyloxymethyl)thiazole-4-carboxylateHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 104958262-(2,2,2-Trichloroethoxycarbonyloxymethyl)thiazole-4-carboxaldehydeYield 79.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of ethyl 2-(2,2,2-trichloroethoxycarbonyloxymethyl)thiazole-4-carboxylate (23 g) in CH2Cl2 (200 mL) is added a solution of diisobutylaluminum hydride (1.0 M in CH2Cl2, 120 mL) at −78° C. over 30 minutes. The resulting mixture is kept at −78° C. for 10 hours. The excess hydride is quenched with acetic acid (5 mL) and the reaction is warmed to ambient temperature, and the mixture is stirred with sat. aq. Rochelle's salt (150 mL) until the suspension clears. The organic layer is washed with 10% aq NaHCO3 and brine, dried (Na2SO4), filtered, and concentrated. Purification by column chromatography on SiO2 (toluene/ethyl acetate, 6:1) affords the product as a light yellow syrup (16 g).

Workup

  1. customThe excess hydride is quenched with acetic acid (5 mL)
  2. washThe organic layer is washed with 10% aq NaHCO3 and brine
  3. dry with materialdried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by column chromatography on SiO2 (toluene/ethyl acetate, 6:1)

Sources & evidence

ORD record
ord-87c0cb1aa279430d85e4159b5e776e2d
Source dataset
uspto-grants-2007_02
Patent number
US07176235B2

Reaction notes

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