Nitric Acid → 2-Tert-butyl-4-fluoro-5-nitrophenyl methyl carbonate

HRID 470015Notes

Reaction equation

HRID 470015 reaction equation
[C:1](=[O:16])([O:14][CH3:15])[O:2][C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][C:4]=1[C:10]([CH3:13])([CH3:12])[CH3:11].[N+:17]([O-:20])([OH:19])=[O:18]>OS(O)(=O)=O>[C:1](=[O:16])([O:14][CH3:15])[O:2][C:3]1[CH:8]=[C:7]([N+:17]([O-:19])=[O:18])[C:6]([F:9])=[CH:5][C:4]=1[C:10]([CH3:11])([CH3:12])[CH3:13].[C:1](=[O:16])([O:14][CH3:15])[O:2][C:3]1[C:8]([N+:17]([O-:20])=[O:18])=[CH:7][C:6]([F:9])=[CH:5][C:4]=1[C:10]([CH3:11])([CH3:12])[CH3:13]

Participants

5

Reactant 2

HCID 944Nitric AcidHCID 574702152-Tert-butyl-4-fluorophenyl methyl carbonate

Product 2

HCID 574702162-Tert-butyl-4-fluoro-5-nitrophenyl methyl carbonateYield 55%HCID 574702172-Tert-butyl-4-fluoro-6-nitrophenyl methyl carbonateYield 12%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Procedure

To a solution of 2-tert-butyl-4-fluorophenyl methyl carbonate (1.81 g, 8 mmol) in H2SO4 (98%, 1 mL) was added slowly a cooled mixture of H2SO4 (1 mL) and HNO3 (1 mL) at 0° C. The mixture was stirred for 2 h while warming to room temperature, poured into ice and extracted with diethyl ether. The ether extract was washed with brine, dried over MgSO4 and concentrated. The residue was purified by column chromatography (0-10% EtOAc—Hexane) to give 2-tert-butyl-4-fluoro-5-nitrophenyl methyl carbonate (C-7-a) (1.2 g, 55%) and 2-tert-butyl-4-fluoro-6-nitrophenyl methyl carbonate (C-6-a) (270 mg, 12%). 2-tert-Butyl-4-fluoro-5-nitrophenyl methyl carbonate (C-7-a): 1H NMR (400 MHz, DMSO-d6) δ 8.24 (d, J=7.1 Hz, 1H), 7.55 (d, J=13.4 Hz, 1H), 3.90 (s, 3H), 1.32 (s, 9H). 2-tert-butyl-4-fluoro-6-nitrophenyl methyl carbonate (C-6-a): 1H NMR (400 MHz, DMSO-d6) δ 8.04 (dd, J=7.6, 3.1 Hz, 1H), 7.69 (dd, J=10.1, 3.1 Hz, 1H), 3.91 (s, 3H), 1.35 (s, 9H).

Workup

  1. additionpoured into ice
  2. extractionextracted with diethyl ether
  3. extractionThe ether extract
  4. washwas washed with brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customThe residue was purified by column chromatography (0-10% EtOAc—Hexane)

Sources & evidence

ORD record
ord-e400d020856d46f39fedcfd23eab31d6
Source dataset
uspto-grants-2014_01
Patent number
US08629162B2

Reaction notes

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