Tert-Butyl nitrite → 2-Methyl-3,4-dimethylthiobromobenzene

HRID 397157Notes

Reaction equation

HRID 397157 reaction equation
N(OC(C)(C)C)=O.[Br:8][C:9]1[CH:15]=[CH:14][C:12](N)=[C:11]([S:16][CH3:17])[C:10]=1[CH3:18].[CH3:19][S:20]SC>[Cu]>[CH3:18][C:10]1[C:11]([S:16][CH3:17])=[C:12]([S:20][CH3:19])[CH:14]=[CH:15][C:9]=1[Br:8]

Participants

5

Reactant 3

HCID 10906Tert-Butyl nitriteHCID 12232Dimethyl Disulfide2×HCID 18757264HCID 18757264, compound

Product 1

HCID 187572682-Methyl-3,4-dimethylthiobromobenzene

Reagents, catalysts & solvents 1

HCID 23978CopperCatalyst

Conditions

Temperature
50 °C

Procedure

14.8 g (129 mmol) of tert-butyl nitrite and 20 g of copper powder are initially charged in 50 ml of dimethyl disulfide, and a solution of 20 g (86 mol) of 4-bromo-3-methyl-2-methylthioaniline in 100 ml of dimethyl disulfide is added dropwise at 50-55° C. The mixture is then stirred at 50° C. for 4 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.

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-0a59003bacf84fbb9cd1b78fc7d710f4
Source dataset
uspto-grants-2003_08
Patent number
US06608209B2

Reaction notes

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