tert-Butyl hydroperoxide → HCID 58155185, compound

HRID 221665Notes

Reaction equation

HRID 221665 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:8]2([CH3:15])[NH:13][C:12](=S)[CH2:11][O:10][CH2:9]2)[CH:5]=[CH:6][CH:7]=1.C(OO)(C)(C)C.[NH4+:22].[OH-]>CO.N>[Br:1][C:2]1[CH:3]=[C:4]([C:8]2([CH3:15])[CH2:9][O:10][CH2:11][C:12]([NH2:22])=[N:13]2)[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 6410tert-Butyl hydroperoxideHCID 14923Ammonium HydroxideHCID 726812675-(3-Bromophenyl)-5-methyl-3-morpholinethione

Product 1

HCID 58155185HCID 58155185, compound

Reagents, catalysts & solvents 1

HCID 21705897Ammonia methanolSolvent

Procedure

To a solution of 5-(3-bromo-phenyl)-5-methyl-morpholine-3-thione (5 g, 17.5 mmol) in MeOH/NH3 (110 ml) were added at room temperature t-BuOOH (28 ml, 65%) and NH4OH (47 ml, 25%). The mixture was stirred overnight, quenched with aqueous Na2S2O3 solution, concentrated in vacuo to remove the methanol solution and extracted with EtOAc (3×30 ml). The organic phase was dried with Na2SO4 and concentrated in vacuo to give the crude product, which was purified by preparative HPLC [column: Venusil XBP-C18, 250×21.2 mm, 10 μm; injection volume: 10 ml/injection; mobile phase: CH3CN/H2O=10 to 35% (0.1% formic acid) gradient for 15 min, washed with 95% CH3CN for 4 min, back to 10% balance for 4 min] to give the title compound in the form of a formic acid salt. 1H-NMR (300 MHz, DMSO-d6): 9.99 (s, 1H), 8.39 (s, 1H), 7.65 (s, 1H), 7.55 (d, 1H), 7.47 (d, 1H), 7.39 (t, 1H), 4.46 (s, 2H), 4.05 (d, 1H), 3.85 (d, 1H), 1.55 (s, 3H).

Workup

  1. customquenched with aqueous Na2S2O3 solution
  2. concentrationconcentrated in vacuo
  3. customto remove the methanol solution
  4. extractionextracted with EtOAc (3×30 ml)
  5. dry with materialThe organic phase was dried with Na2SO4
  6. concentrationconcentrated in vacuo
  7. customto give the crude product, which
  8. customwas purified by preparative HPLC [column
  9. waitmobile phase: CH3CN/H2O=10 to 35% (0.1% formic acid) gradient for 15 min
  10. washwashed with 95% CH3CN for 4 min, back to 10% balance for 4 min]

Sources & evidence

ORD record
ord-977030ec39e04a8a8e33949ad5a29345
Source dataset
uspto-grants-2012_06
Patent number
US08207164B2

Reaction notes

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