Nitric Acid → 3-bromo-4-tert-butylbenzoic acid

HRID 2201723Notes

Reaction equation

HRID 2201723 reaction equation
[C:1]([C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[N+]([O-])(O)=O.[Br:18]Br>C(O)(=O)C.O.[N+]([O-])([O-])=O.[Ag+]>[Br:18][C:13]1[CH:12]=[C:8]([CH:7]=[CH:6][C:5]=1[C:1]([CH3:4])([CH3:2])[CH3:3])[C:9]([OH:11])=[O:10]

Participants

7

Reactant 3

HCID 944Nitric AcidHCID 74034-tert-Butylbenzoic acidHCID 24408Bromine

Product 1

HCID 2829923-bromo-4-tert-butylbenzoic acidYield 36.5%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

4-tert-butyl benzoic acid (500 mg, 2.8 mmol) was stirred rapidly in acetic acid (11 mL), nitric acid (1.7 mL) and bromine (114 μL, 5.9 mmol). To this was added a solution of silver nitrate (1.01 g, 5.9 mmol) in water (5 mL). A thick yellow precipitate resulted and further acetic acid was added (2 mL) before heating at reflux for 1 h. The hot solution was filtered and water added to the filtrate until a white solid precipitated. The solid was filtered, air dried and recrystallised from acetic acid to give 3-bromo-4-tert-butyl-benzoic acid as a white solid (263 mg, 36%). 1H NMR (CDCl3, 300 MHz) δ 1.85 (s, 9H, (CH3)3), 7.86 (d, 1H, J=8.5 Hz, ArH), 8.26 (dd, 1H, J=2.0, 8.5 Hz, ArH), 8.62 (d, 1H, J=2.0 Hz).

Workup

  1. customA thick yellow precipitate resulted
  2. temperaturebefore heating
  3. temperatureat reflux for 1 h
  4. filtrationThe hot solution was filtered
  5. additionwater added to the filtrate until a white solid
  6. customprecipitated
  7. filtrationThe solid was filtered
  8. customair dried
  9. customrecrystallised from acetic acid

Sources & evidence

ORD record
ord-4659657179bc4681be872f359e59bc6f
Source dataset
uspto-grants-2016_06
Patent number
US09365508B2

Reaction notes

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