Potassium Nitrate → Methyl 4-nitro-2-(trifluoromethoxy)phenyl carbonate

HRID 1465091Notes

Reaction equation

HRID 1465091 reaction equation
[C:1](=[O:16])([O:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[O:11][C:12]([F:15])([F:14])[F:13])[O:2][CH3:3].[N+:17]([O-:20])([O-:19])=[O:18].[K+]>OS(O)(=O)=O>[C:1](=[O:16])([O:4][C:5]1[CH:10]=[C:9]([N+:17]([O-:19])=[O:18])[CH:8]=[CH:7][C:6]=1[O:11][C:12]([F:15])([F:13])[F:14])[O:2][CH3:3].[C:1](=[O:16])([O:4][C:5]1[CH:10]=[CH:9][C:8]([N+:17]([O-:20])=[O:18])=[CH:7][C:6]=1[O:11][C:12]([F:15])([F:13])[F:14])[O:2][CH3:3]

Participants

5

Reactant 2

HCID 24434Potassium NitrateHCID 59395054Methyl 2-(trifluoromethoxy)phenyl carbonate

Product 2

HCID 59394967Methyl 4-nitro-2-(trifluoromethoxy)phenyl carbonateHCID 59395076Methyl 5-nitro-2-(trifluoromethoxy)phenyl carbonate

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

Methyl 2-(trifluoromethoxy)phenyl carbonate (200 mg, 0.85 mmol) was added portion-wise to H2SO4 (600 μL) at 0° C. to generate a colorless homogeneous solution. KNO3 (103 mg, 1.02 mmol) was added portion-wise maintaining the internal temperature below 5° C. The reaction was stirred for 2 h and then poured on ice water. The aqueous layer was extracted with dichloromethane (3×10 mL). The combined organic extracts were dried over Na2SO4, filtered and concentrated. Purification by silica gel chromatography (0-10% ethyl acetate/hexanes) provided the two regioisomers methyl 5-nitro-2-(trifluoromethoxy)phenyl carbonate (Isomer A, 120 mg) and methyl 4-nitro-2-(trifluoromethoxy)phenyl carbonate (Isomer B, 75 mg).

Workup

  1. temperaturemaintaining the internal temperature below 5° C
  2. additionpoured on ice water
  3. extractionThe aqueous layer was extracted with dichloromethane (3×10 mL)
  4. dry with materialThe combined organic extracts were dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification by silica gel chromatography (0-10% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-567f34bd417a4ff592ac3c23eb4bc14c
Source dataset
uspto-grants-2015_04
Patent number
US08999976B2

Reaction notes

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