Sulfuric Acid → 2-Bromo-4-tert-butyl-5-nitrophenyl methyl carbonate

HRID 471916Notes

Reaction equation

HRID 471916 reaction equation
[C:1](=[O:16])([O:14][CH3:15])[O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]([CH3:12])([CH3:11])[CH3:10])=[CH:5][C:4]=1[Br:13].OS(O)(=O)=O.[N+:22]([O-])([O-:24])=[O:23].[K+]>>[C:1](=[O:16])([O:14][CH3:15])[O:2][C:3]1[CH:8]=[C:7]([N+:22]([O-:24])=[O:23])[C:6]([C:9]([CH3:11])([CH3:12])[CH3:10])=[CH:5][C:4]=1[Br:13]

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 24434Potassium NitrateHCID 593949442-Bromo-4-tert-butylphenyl methyl carbonate

Product 1

HCID 593950502-Bromo-4-tert-butyl-5-nitrophenyl methyl carbonateYield 76.1%

Conditions

Temperature
0 °C

Procedure

2-Bromo-4-tert-butylphenyl methyl carbonate (5.0 g, 17.4 mmol) was added portion-wise to H2SO4 (9.3 mL, 174.1 mmol) to generate a colorless homogeneous solution. This solution was then cooled to 0° C. and treated with KNO3 (2.1 g, 20.9 mmol) 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 was dried over Na2SO4, filtered and concentrated. Purification by silica gel chromatography (10% ethyl acetate/hexane) provided 2-bromo-4-tert-butyl-5-nitrophenyl methyl carbonate (4.4 g, 76% yield). 1H NMR (400.0 MHz, DMSO-d6) δ 7.97 (s, 1H), 7.92 (s, 1H), 3.90 (s, 3H), 1.34 (d, J=5.4 Hz, 9H).

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 was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification by silica gel chromatography (10% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-3e2fdf4e1ad541c8a7d2d13fc80e101e
Source dataset
uspto-grants-2014_01
Patent number
US08633189B2

Reaction notes

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