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

HRID 992822

Reaction equation

HRID 992822 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 mol) 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 from 50 to 55° C. The mixture is subsequently stirred at 75° C. for 8 hours. For work-up, the solid is filtered off with suction and the filtrate 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. 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 filtrate 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. customExcess dimethyl disulfide is removed under oil pump vacuum

Sources & evidence

ORD record
ord-9a681ff52a35465cbae44ea815a9090f
Source dataset
uspto-grants-2002_10
Patent number
US06469176B1

Linked notes

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