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

HRID 460501

Reaction equation

HRID 460501 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

Procedure

160 g of copper powder and 500 ml of dimethyl disulfide were added to 357 g (3.12 mol) of tert-butyl nitrite. At 50–52° C., a solution of 316 g (2.08 mol) of 2-methyl-6-nitroaniline in 1600 ml of dimethyl disulfide was added dropwise, and the mixture was stirred at 50–55° C. for 4 hours. After cooling, the reaction mixture was filtered off with suction through kieselguhr, and dichloromethane was added to the filtrate. The organic phase was washed with dilute hydrochloric acid and then with water and subsequently dried over magnesium sulfate. Concentration under high vacuum gave 452 g of 2-methyl-6-nitrothioanisole as a red-black oil which was used for the next reaction step without further purification.

Workup

  1. temperatureAfter cooling
  2. filtrationthe reaction mixture was filtered off with suction through kieselguhr, and dichloromethane
  3. additionwas added to the filtrate
  4. washThe organic phase was washed with dilute hydrochloric acid
  5. dry with materialwith water and subsequently dried over magnesium sulfate
  6. concentrationConcentration under high vacuum

Sources & evidence

ORD record
ord-58ea4b3780c3416b8f4265eca50208fb
Source dataset
uspto-grants-2007_03
Patent number
US07196229B2

Linked notes

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