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

HRID 383374Notes

Reaction equation

HRID 383374 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-6b463a950a9c488b8fe064d088814f3e
Source dataset
uspto-grants-2013_02
Patent number
US08367660B2

Reaction notes

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