Reaktion #168698

Reaktionsgleichung

5-(3-bromo-phenyl)-5-methyl-morpholine-3-thione

t-BuOOH

NH4OH

→

title compound

5-(3-Bromo-phenyl)-5-methyl-5,6-dihydro-2H-[1,4]oxazin-3-ylamine

Lösungsmittel

MeOH NH3

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigequenched with aqueous Na2S2O3 solution
2. 2
   Einengenconcentrated in vacuo
3. 3
   Sonstigeto remove the methanol solution
4. 4
   Extraktionextracted with EtOAc (3×30 ml)
5. 5
   TrocknenThe organic phase was dried with Na2SO4
6. 6
   Einengenconcentrated in vacuo
7. 7
   Sonstigeto give the crude product, which
8. 8
   Sonstigewas purified by preparative HPLC [column
9. 9
   workup.WAITmobile phase: CH3CN/H2O=10 to 35% (0.1% formic acid) gradient for 15 min
10. 10
    Waschenwashed with 95% CH3CN for 4 min, back to 10% balance for 4 min]

Vorschrift

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).

Quelle