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

HRID 471944Notes

Reaction equation

HRID 471944 reaction equation
[C:1](=[O:13])([O:11][CH3:12])[O:2][C:3]1[CH:8]=[CH:7][C:6]([Br:9])=[CH:5][C:4]=1[CH3:10].OS(O)(=O)=O.[N+:19]([O-])([O-:21])=[O:20].[K+]>>[C:1](=[O:13])([O:11][CH3:12])[O:2][C:3]1[CH:8]=[C:7]([N+:19]([O-:21])=[O:20])[C:6]([Br:9])=[CH:5][C:4]=1[CH3:10]

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 24434Potassium NitrateHCID 593949854-Bromo-2-methylphenyl methyl carbonate

Product 1

HCID 593950554-Bromo-2-methyl-5-nitrophenyl methyl carbonateYield 71.8%

Procedure

4-Bromo-2-methylphenyl methyl carbonate (4.0 g, 16.32 mmol) was added portion-wise to H2SO4 (12.0 mL) to generate a homogeneous solution. This solution was then cooled to 0° C. internal temperature and KNO3 (2.0 g, 19.6 mmol) was added portion-wise maintaining the internal temperature below 5° C. The reaction was stirred for 2 h and then poured over ice. The aqueous layer was extracted with dichloromethane, washed with saturated NaHCO3 and water, dried over Na2SO4, and concentrated. Purification by silica gel chromatography (0-5% ethyl acetate/hexanes) provided 4-bromo-2-methyl-5-nitrophenyl methyl carbonate (3.4 g, 71% yield). 1H NMR (400.0 MHz, DMSO-d6) δ 8.11 (s, 1H), 7.95 (s, 1H), 3.88 (s, 3H), 2.25 (s, 3H).

Workup

  1. additionwas added portion-wise
  2. temperaturemaintaining the internal temperature below 5° C
  3. additionpoured over ice
  4. extractionThe aqueous layer was extracted with dichloromethane
  5. washwashed with saturated NaHCO3 and water
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customPurification by silica gel chromatography (0-5% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-ec1d57d5de964f6b8c9980c970cb77d9
Source dataset
uspto-grants-2014_01
Patent number
US08633189B2

Reaction notes

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