Hydrochloric Acid → Isoxazole, 3-[3-bromo-2-methyl-6-(methylthio)phenyl]-4,5-dihydro-

HRID 1594433Notes

Reaction equation

HRID 1594433 reaction equation
[Br:1][C:2]1[CH:8]=[CH:7][C:5](N)=[C:4]([C:9]2[CH2:13][CH2:12][O:11][N:10]=2)[C:3]=1[CH3:14].[CH3:15][S:16]SC.N([O-])=O.[Na+].S(=O)(=O)(O)O.Cl>[Cu].O>[Br:1][C:2]1[C:3]([CH3:14])=[C:4]([C:9]2[CH2:13][CH2:12][O:11][N:10]=2)[C:5]([S:16][CH3:15])=[CH:7][CH:8]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 1118Sulfuric AcidHCID 12232Dimethyl DisulfideHCID 9813747Benzenamine, 4-bromo-2-(4,5-dihydro-3-isoxazolyl)-3-methyl-HCID 23668193Sodium Nitrite

Product 1

HCID 9860657Isoxazole, 3-[3-bromo-2-methyl-6-(methylthio)phenyl]-4,5-dihydro-Yield 58%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 962WaterSolvent

Procedure

10 g (35.3 mmol) of 4-bromo-2-(4,5-dihydroisoxazol-3-yl)-3-methylaniline, 67.3 mg of copper powder and 58.5 ml of dimethyl disulfide are initially charged, and the mixture is stirred for one hour. At 50° C., 9.05 g of a 40.4% strength aqueous sodium nitrite solution are added. At 63-65° C., 6.96 g of 25% strength sulfuric acid are then metered in, and the mixture is stirred at 65° C. for 3 hours. At 20-25° C., 15 ml of conc. hydrochloric acid are added, and the mixture is stirred for one hour. 15 ml of water are added, and the phases are then separated. Washing is repeated twice. The organic phase is concentrated, giving 6.7 g of a brown solid (yield: 58%).

Workup

  1. customAt 63-65° C.
  2. stirringis stirred at 65° C. for 3 hours
  3. stirringthe mixture is stirred for one hour
  4. customthe phases are then separated
  5. washWashing
  6. concentrationThe organic phase is concentrated

Sources & evidence

ORD record
ord-3e674bd8e7524b0eb17c8211b43b31b1
Source dataset
uspto-grants-2007_11
Patent number
US07301034B2

Reaction notes

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