Morpholine → 4-(5-Bromo-2-(methylsulfonyl)phenyl)morpholine

HRID 40747Notes

Reaction equation

HRID 40747 reaction equation
Br[C:2]1[CH:7]=[C:6]([Br:8])[CH:5]=[CH:4][C:3]=1[S:9]([CH3:12])(=[O:11])=[O:10].[NH:13]1[CH2:18][CH2:17][O:16][CH2:15][CH2:14]1>COCCOC>[Br:8][C:6]1[CH:5]=[CH:4][C:3]([S:9]([CH3:12])(=[O:11])=[O:10])=[C:2]([N:13]2[CH2:18][CH2:17][O:16][CH2:15][CH2:14]2)[CH:7]=1

Participants

4

Reactant 2

HCID 8083MorpholineHCID 153547912,4-Dibromo-1-(methylsulfonyl)benzene

Product 1

HCID 595880684-(5-Bromo-2-(methylsulfonyl)phenyl)morpholine

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 2,4-dibromo-1-(methylsulfonyl)benzene (0.3 g, 0.96 mmol) and morpholine (0.25 g, 2.9 mmol) in DME was heated at 90° C. for 16 h, cooled, and concentrated in vacuo. The crude residue was dissolved in EtOAc and washed with brine (2×). The organic layer was dried (MgSO4), concentrated to give a near colorless solid which was ˜1:1 mixture of regioisomers by analytical HPLC and LC/MS analysis. This residue was purified by chromatography on silica gel (EtOAc/hexanes) to afford 4-(5-bromo-2-(methylsulfonyl)phenyl)morpholine as a near colorless solid. 1H NMR (DMSO-d6, 400 MHz) δ 8.2 (d, 1H), 7.8 (s, 1H), 7.7 (d, 1H), 3.8-3.6 (m, 4H), 3.4 (s, 3H), 3.1-2.9 (m, 4H). MS (ESI) 322.1, 320.1 (M+H).

Workup

  1. temperaturecooled
  2. concentrationconcentrated in vacuo
  3. dissolutionThe crude residue was dissolved in EtOAc
  4. washwashed with brine (2×)
  5. dry with materialThe organic layer was dried (MgSO4)
  6. concentrationconcentrated
  7. customto give a near colorless solid which
  8. addition˜1:1 mixture of regioisomers by analytical HPLC and LC/MS analysis
  9. customThis residue was purified by chromatography on silica gel (EtOAc/hexanes)

Sources & evidence

ORD record
ord-4a23ec7c9e1e4a178f647d7e0109d943
Source dataset
uspto-grants-2013_09
Patent number
US08530480B2

Reaction notes

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