Pyridine → Ethyl 2-(2,2,2-trichloroethoxycarbonyloxymethyl)thiazole-4-carboxylate

HRID 348241Notes

Reaction equation

HRID 348241 reaction equation
[OH:1][CH2:2][C:3]1[S:4][CH:5]=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[N:7]=1.N1C=CC=CC=1.Cl[C:20]([O:22][CH2:23][C:24]([Cl:27])([Cl:26])[Cl:25])=[O:21]>C(Cl)Cl>[Cl:25][C:24]([Cl:27])([Cl:26])[CH2:23][O:22][C:20]([O:1][CH2:2][C:3]1[S:4][CH:5]=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[N:7]=1)=[O:21]

Participants

5

Reactant 3

HCID 1049PyridineHCID 870632,2,2-Trichloroethyl chloroformateHCID 10655181Ethyl 2-(hydroxymethyl)-1,3-thiazole-4-carboxylate

Product 1

HCID 10594849Ethyl 2-(2,2,2-trichloroethoxycarbonyloxymethyl)thiazole-4-carboxylateYield 47.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of ethyl 2-(hydroxymethyl)-thiazole-4-carboxylate 33 (38.4 g) and pyridine (41 mL) in 100 mL of CH2Cl2 is slowly added 2,2,2-trichloroethyl chloroformate (32 mL, 0.23 mol) at 0° C. After the resulting mixture is stirred for 30 minutes, the reaction is quenched by the addition of 10% aq NaHCO3. The organic layer is separated, and the aqueous layer is extracted with CH2Cl2. The combined organic extracts are washed with 2 N HCl, 10% aq NaHCO3, and brine, dried (Na2SO4), and concentrated. The residue is then recrystallized in ethanol (50 mL) to yield a light yellow solid (35 g). The mother liquor is concentrated and chromatographed to afford an additional amount (35 g) of product.

Workup

  1. customat 0° C
  2. customthe reaction is quenched by the addition of 10% aq NaHCO3
  3. customThe organic layer is separated
  4. extractionthe aqueous layer is extracted with CH2Cl2
  5. washThe combined organic extracts are washed with 2 N HCl, 10% aq NaHCO3, and brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. customThe residue is then recrystallized in ethanol (50 mL)

Sources & evidence

ORD record
ord-d6e5a995fc2a4e63b15d0b2b63bc8f8a
Source dataset
uspto-grants-2007_02
Patent number
US07176235B2

Reaction notes

Loading…