Trifluoroacetic acid → 4-Allyloxycarbonylamino-2-(formylamino)methylthiazole

HRID 1603465Notes

Reaction equation

HRID 1603465 reaction equation
FC(F)(F)C(O)=O.[CH2:8]([O:11][C:12]([NH:14][C:15]1[N:16]=[C:17]([CH2:20][NH:21][C:22](OC(C)(C)C)=[O:23])[S:18][CH:19]=1)=[O:13])[CH:9]=[CH2:10].C(=O)(O)[O-].[Na+]>ClCCl.O.C(O)=O.C(O)(=O)C>[CH2:8]([O:11][C:12]([NH:14][C:15]1[N:16]=[C:17]([CH2:20][NH:21][CH:22]=[O:23])[S:18][CH:19]=1)=[O:13])[CH:9]=[CH2:10]

Participants

8

Reactant 3

HCID 6422Trifluoroacetic acidHCID 516892Sodium Bicarbonate2×HCID 196052054-allyloxycarbonylamino-2-(N-t-butoxycarbonylamino)methylthiazole

Product 1

HCID 196051274-Allyloxycarbonylamino-2-(formylamino)methylthiazoleYield 92.4%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolvent2×HCID 284Formic AcidSolvent2×HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

A 24.0 ml portion of trifluoroacetic acid was added to 4.791 g of 4-allyloxycarbonylamino-2-(N-t-butoxycarbonylamino)methylthiazole, and the mixture was then stirred at room temperature for 50 minutes. The reagent was evaporated under reduced pressure to obtain a dark red oil, and this oil was then dissolved in 50 ml of dichloromethane and 50 ml of distilled water, followed by adjustment to pH 5 with sodium bicarbonate. A mixed solution of 7.2 ml of anhydrous acetic acid and 14.4 ml of formic acid was added dropwise to the solution at room temperature over 15 minutes under vigorous stirring. After the pH of the solution was adjusted to 5 again, it was stirred for 2.5 hours. Furthermore, a mixed solution of 2.9 ml of anhydrous acetic acid and 5.8 ml of formic acid was added dropwise to the solution over 25 minutes, and adjustment to pH 5 was carried out with sodium bicarbonate again, followed by stirring for 2.5 hours. After the addition of 250 ml of dichloromethane and sufficient shaking, the resulting precipitate was collected by filtration, and from the filtrate, the organic layer was separated, dried (magnesium sulfate), and then filtered. This filtrate was combined with a liquid eluted from the precipitate with a dichloromethane-methanol mixture solvent, and the solvent was then evaporated under reduced pressure to obtain 3.408 g of 4-allyloxycarbonylamino-2-(formylamino)methylthiazole as a light orange powder.

Workup

  1. customThe reagent was evaporated under reduced pressure
  2. customto obtain a dark red oil
  3. stirringit was stirred for 2.5 hours
  4. stirringby stirring for 2.5 hours
  5. filtrationthe resulting precipitate was collected by filtration
  6. customfrom the filtrate, the organic layer was separated
  7. dry with materialdried (magnesium sulfate)
  8. filtrationfiltered
  9. washeluted from the precipitate with a dichloromethane-methanol mixture solvent
  10. customthe solvent was then evaporated under reduced pressure

Sources & evidence

ORD record
ord-353bfb41eaf04826bfca82d32d4bf229
Source dataset
uspto-grants-1999_11
Patent number
US05990101

Reaction notes

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