Tert-Butyl nitrite → 3-(2-Methyl-6-methylthiophenyl)-4,5-dihydroisoxazole

HRID 970152Notes

Reaction equation

HRID 970152 reaction equation
N(OC(C)(C)C)=O.[O:8]1[CH2:12][CH2:11][C:10]([C:13]2[C:19]([CH3:20])=[CH:18][CH:17]=[CH:16][C:14]=2N)=[N:9]1.[CH3:21][S:22]SC>[Cu]>[CH3:20][C:19]1[CH:18]=[CH:17][CH:16]=[C:14]([S:22][CH3:21])[C:13]=1[C:10]1[CH2:11][CH2:12][O:8][N:9]=1

Participants

5

Reactant 3

HCID 10906Tert-Butyl nitriteHCID 12232Dimethyl Disulfide2×HCID 97940062-(4,5-Dihydroisoxazol-3-yl)-3-methylaniline

Product 1

HCID 108783423-(2-Methyl-6-methylthiophenyl)-4,5-dihydroisoxazole

Reagents, catalysts & solvents 1

HCID 23978CopperCatalyst

Conditions

Temperature
60 °C

Procedure

19.5 g (170 mmol) of tert-butyl nitrite and 20 g of copper powder are initially charged in 30 ml of dimethyl disulfide, and a solution of 20 g (114 mmol) of 2-(4,5-dihydroisoxazol-3-yl)-3-methylaniline in 100 ml of dimethyl disulfide is added dropwise at from 50 to 55° C. The mixture is then stirred at 60° C. for 1.5 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. 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. customExcess dimethyl disulfide is removed under oil pump vacuum

Sources & evidence

ORD record
ord-9430145af0f8495588275b0913c1ff7d
Source dataset
uspto-grants-2007_12
Patent number
US07309802B2

Reaction notes

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