Ammonia → HCID 68153470, compound

HRID 1946908Notes

Reaction equation

HRID 1946908 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:9]2([CH3:16])[NH:14][C:13](=S)[CH2:12][O:11][CH2:10]2)[CH:5]=[CH:6][C:7]=1[F:8].[NH3:17].C(OO)(C)(C)C>CO.O>[Br:1][C:2]1[CH:3]=[C:4]([C:9]2([CH3:16])[CH2:10][O:11][CH2:12][C:13]([NH2:17])=[N:14]2)[CH:5]=[CH:6][C:7]=1[F:8]

Participants

6

Reactant 3

HCID 222AmmoniaHCID 6410tert-Butyl hydroperoxideHCID 86668498HCID 86668498, compound

Product 1

HCID 68153470HCID 68153470, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 962WaterSolvent

Procedure

A solution of (RS)-5-(3-bromo-4-fluoro-phenyl)-5-methyl-morpholin-3-thione (intermediate XVIII-1) (202 mg, 0.7 mmol) in methanol (15 ml) was treated with a solution of ammonia in methanol (7M, 5.7 ml, 39.8 mmol) and an aqueous solution of tert-butyl hydroperoxide (70% in water, 0.91 ml, 6.6 mmol). After stiffing at room temperature overnight, the reaction mixture was diluted with water and extracted three times with dichloromethane. The combined organic layers were washed with water, then dried over sodium sulphate and evaporated. The crude product was purified by chromatography on silica gel using a gradient of heptane/ethyl acetate=100/0 to 0/100 as the eluent. The (RS)-5-(3-bromo-4-fluoro-phenyl)-5-methyl-5,6-dihydro-2H-[1,4]oxazin-3-ylamine was obtained as a colorless gum (109 mg, 57% of theory). MS (ISP): m/z=287.2 [M+H]+, 289.1 [M+2+H]+.

Workup

  1. extractionextracted three times with dichloromethane
  2. washThe combined organic layers were washed with water
  3. dry with materialdried over sodium sulphate
  4. customevaporated
  5. customThe crude product was purified by chromatography on silica gel using a gradient of heptane/ethyl acetate=100/0 to 0/100 as the eluent

Sources & evidence

ORD record
ord-9e478715fc6c49dcaf1152462848b6f7
Source dataset
uspto-grants-2013_03
Patent number
US08399459B2

Reaction notes

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