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

HRID 1757236Notes

Reaction equation

HRID 1757236 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 min, 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 gel using hexane as eluant. This afforded the product 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 min
  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 gel

Sources & evidence

ORD record
ord-f017a6a8fa5d433c89cda4bbb1e35736
Source dataset
uspto-grants-1995_08
Patent number
US05444074

Reaction notes

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