Sulfuric Acid → 1-tert-Butyl-3-chloro-5-methylbenzene

HRID 1781959Notes

Reaction equation

HRID 1781959 reaction equation
[C:1]([C:5]1[CH:11]=[C:10]([CH3:12])[C:8](N)=[C:7]([Cl:13])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].S(=O)(=O)(O)O.N([O-])=O.[Na+]>C(O)C>[C:1]([C:5]1[CH:11]=[C:10]([CH3:12])[CH:8]=[C:7]([Cl:13])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 19046432HCID 19046432, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 190464341-tert-Butyl-3-chloro-5-methylbenzene

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

4-t-Butyl-2-chloro-6-methylaniline (1.97 g) was dissolved in ethanol (50 ml), sulphuric acid (1.88 ml, conc.) was added dropwise and the resulting blue solution was heated at reflux. Sodium nitrite (1.72 g) was added portionwise over 30 min. The resulting mixture was heated at reflux for a further 30 rain, then cooled and was poured onto ice water and extracted with ether (2×50 ml). The ethereal extract was dried (MgSO4) and evaporated and the residue was purified on silica using hexane as eluent to afford 3-t-butyl-5-chlorotoluene as a colourless oil. 1H NMR (360 MHz, CDCl3) δ1.29 (9H, s, (CH3)3), 2.31 (3H, s, CH3), 6.98 (1H, brs, ArH), 7.05 (1H, brs, ArH), 7.15 (1H, brs, ARH). MS (CI-) m/z 181 (M+ -H, 100%).

Workup

  1. temperaturethe resulting blue solution was heated
  2. temperatureat reflux
  3. temperatureThe resulting mixture was heated
  4. temperatureat reflux for a further 30 rain
  5. temperaturecooled
  6. additionwas poured onto ice water
  7. extractionextracted with ether (2×50 ml)
  8. extractionThe ethereal extract
  9. dry with materialwas dried (MgSO4)
  10. customevaporated
  11. customthe residue was purified on silica

Sources & evidence

ORD record
ord-4135a6eeef0c445ba7a7b80232208f57
Source dataset
uspto-grants-1997_05
Patent number
US05633281

Reaction notes

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