Tert-Butyl nitrite → 2-Methyl-6-nitrothioanisole

HRID 970165

Reaction equation

HRID 970165 reaction equation
N(OC(C)(C)C)=O.[CH3:8][C:9]1[CH:15]=[CH:14][CH:13]=[C:12]([N+:16]([O-:18])=[O:17])[C:10]=1N.[CH3:19][S:20]SC>[Cu]>[CH3:8][C:9]1[CH:15]=[CH:14][CH:13]=[C:12]([N+:16]([O-:18])=[O:17])[C:10]=1[S:20][CH3:19]

Participants

5

Reactant 3

HCID 10906Tert-Butyl nitriteHCID 112982-Methyl-6-nitroanilineHCID 12232Dimethyl Disulfide2×

Product 1

HCID 187572722-Methyl-6-nitrothioanisole

Reagents, catalysts & solvents 1

HCID 23978CopperCatalyst

Conditions

Temperature
75 °C

Procedure

226 g (1.97 mmol) of tert-butyl nitrite and 100 g of copper powder are initially-charged in 300 ml of dimethyl disulfide, and a solution of 200 g (1.32 mol) of 2-methyl-6-nitroaniline in 700 ml of dimethyl disulfide is added dropwise at 50-55° C. The mixture is then stirred at 75° C. for 8 hours. For work-up, the solid is filtered off with suction and the solution is diluted with methylene chloride and extracted with dilute hydrochloric acid. The organic phase is washed with saturated aqueous NaHCO3 solution, dried over sodium sulfate, filtered off and concentrated using a rotary evaporator. Excess dimethyl disulfide is removed under oil pump vacuum. This gives 271 g (99%) of a dark-red oil, purity according to HPLC 87%.

Workup

  1. filtrationFor work-up, the solid is filtered off with suction
  2. additionthe solution is diluted with methylene chloride
  3. extractionextracted with dilute hydrochloric acid
  4. washThe organic phase is washed with saturated aqueous NaHCO3 solution
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered off
  7. concentrationconcentrated
  8. customa rotary evaporator
  9. customExcess dimethyl disulfide is removed under oil pump vacuum

Sources & evidence

ORD record
ord-41db68b6154347438a447213ddb9b14a
Source dataset
uspto-grants-2007_12
Patent number
US07309802B2

Linked notes

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