2,2,2-Trifluoroethyl formate → benzyl-(N-hydroxy)formamide

HRID 1700840Notes

Reaction equation

HRID 1700840 reaction equation
Cl.[CH2:2]([NH:9][OH:10])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[C:11](=O)(O)[O-:12].[K+].C(OCC(F)(F)F)=O>C(OC)(C)(C)C>[CH2:2]([N:9]([OH:10])[CH:11]=[O:12])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 1416812,2,2-Trifluoroethyl formateHCID 516893Potassium BicarbonateHCID 11332622N-benzylhydroxylamine hydrochloride

Product 1

HCID 11275113benzyl-(N-hydroxy)formamideYield 96%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Procedure

A suspension of N-benzyl-N-hydroxylamine hydrochloride (1.0 g, 6.26 mmol; Aldrich Chemical Company, Milwaukee, Wis.) in methyl tert-butyl ether (10 mL) was vigorously stirred 10% potassium bicarbonate solution and separated into an aqueous fraction and an organic fraction. The organic fraction was treated with the 2,2,2-trifluoroethyl formate reagent (92% (w/w), 4.35 g, 31.3 mmol, 5 equiv), and heated at reflux for 6 hours. The mixture was washed sequentially with water, 15% potassium bicarbonate, and 15% brine, then concentrated to provide 0.90 g (96%) of the desired product as a mixture of rotamers. 1H NMR (300 MHz, CDCl3) δ 8.28, 7.86 (2s, 1H total), 7.35-7.15 (m, 5H total), 7.10, 6.90 (2 br s, 1H total), 4.64, 4.56 (2s, 2H total).

Workup

  1. customseparated into an aqueous fraction
  2. temperatureheated
  3. temperatureat reflux for 6 hours
  4. washThe mixture was washed sequentially with water, 15% potassium bicarbonate, and 15% brine
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-054ecea003dd40daaba4fd464c6a4f05
Source dataset
uspto-grants-2002_02
Patent number
US06350902B2

Reaction notes

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