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

HRID 81559

Reaction equation

HRID 81559 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C@@:11]2([CH3:18])[NH:16][C:15](=S)[CH2:14][O:13][CH2:12]2)[CH:5]=[C:6]([N+]([O-])=O)[CH:7]=1.C([O:23]O)(C)(C)C.[OH-:25].[NH3:26].[O-]S([O-])(=S)=O.[Na+].[Na+].[NH3:34]>CO>[Br:1][C:2]1[CH:3]=[C:4]([C@:11]2([CH3:18])[CH2:12][O:13][CH2:14][C:15]([NH2:16])=[N:34]2)[C:5]([N+:26]([O-:23])=[O:25])=[CH:6][CH:7]=1

Participants

7

Reactant 5

HCID 222AmmoniaHCID 6410tert-Butyl hydroperoxideHCID 24477Sodium ThiosulfateHCID 21862953Ammonia hydroxideHCID 86667520HCID 86667520, compound

Product 1

HCID 86716531(R)-5-(3-Bromo-6-nitro-phenyl)-5-methyl-5,6-dihydro-2H-[1,4]oxazin-3-ylamine

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

(R)-5-(3-Bromo-5-nitro-phenyl)-5-methyl-morpholine-3-thione (2.86 g, 7.77 mmol) was dissolved in 7M NH3 in methanol (50 ml). Tert-Butylhydroperoxide (9.41 ml, 78 mmol) and ammonia hydroxide (25% sol., 21.2 ml, 136 mmol) were added and the reaction was stirred at r.t. for 2 hrs. Upon completion, 50 ml half-saturated Na2S2O3 solution was added to the reaction and the product was extracted with ethyl acetate. The organic phases were washed with water and brine, combined and dried over Na2SO4. Volatiles were removed under reduced pressure, yielding the title compound as yellowish solid. 1H-NMR (360 MHz, DMSO-d6): 8.34 (s, 1H), 8.25 (s, 1H), 8.12 (s, 1H), 5.85 (br, 2H), 4.01 (m, 1H), 3.80 (m, 1H), 3.55 (m, 1H), 1.38 (s, 3H); MS: 314 [(M+H)+].

Workup

  1. extractionthe product was extracted with ethyl acetate
  2. washThe organic phases were washed with water and brine
  3. dry with materialdried over Na2SO4
  4. customVolatiles were removed under reduced pressure

Sources & evidence

ORD record
ord-adb68345b7214d86b2eae8950c5ec4b1
Source dataset
uspto-grants-2014_09
Patent number
US08846658B2

Linked notes

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