Sodium Carbonate → 2-Bromo-6-(2,2,6,6-tetramethyltetrahydro-2H-pyran-4-yl)pyridin-3-amine

HRID 456005Notes

Reaction equation

HRID 456005 reaction equation
[CH3:1][C:2]1([CH3:17])[CH2:7][CH:6]([C:8]2[N:13]=[CH:12][C:11]([NH2:14])=[CH:10][CH:9]=2)[CH2:5][C:4]([CH3:16])([CH3:15])[O:3]1.C1C(=O)N([Br:25])C(=O)C1.C([O-])([O-])=O.[Na+].[Na+]>C(Cl)Cl>[Br:25][C:12]1[C:11]([NH2:14])=[CH:10][CH:9]=[C:8]([CH:6]2[CH2:7][C:2]([CH3:17])([CH3:1])[O:3][C:4]([CH3:16])([CH3:15])[CH2:5]2)[N:13]=1

Participants

5

Reactant 3

HCID 10340Sodium CarbonateHCID 67184N-bromobutanimideHCID 576665556-(2,2,6,6-Tetramethyl-tetrahydro-pyran-4-yl)-pyridin-3-ylamine

Product 1

HCID 576664472-Bromo-6-(2,2,6,6-tetramethyltetrahydro-2H-pyran-4-yl)pyridin-3-amineYield 95%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 6-(2,2,6,6-tetramethyl-tetrahydro-pyran-4-yl)-pyridin-3-ylamine (as prepared in the previous step, 13.5 g, 0.057 mol) in DCM (100 mL) was added a solution of freshly recrystallized NBS (10.2 g, 0.0570 mol) in DCM (300 mL) dropwise at 0° C. for 1 h. The reaction mixture was allowed to warm to RT, stirred for 30 min and then treated with satd aq Na2CO3 (300 mL). The organic phase was washed with 10% Na2S2O3 (300 mL) and water (300 mL), dried (Na2SO4) and concentrated to obtain the title compound as red solid (17.1 g, 95%) which was directly used in the next step without further purification. 1H-NMR (CDCl3; 400 MHz): δ 6.95 (d, 1H, J=8.1 Hz), 6.91 (d, 1H, j=8.1 Hz), 4.03 (br s, 2H), 3.08 (m, 1H), 1.73 (m, 2H), 1.44 (m, 2H), 1.28 (s, 6H), 1.26 (s, 6H). Mass spectrum (ESI, m/z): Calcd. for C14H21BrN2O, 313.2 and 315.2 (M+H), found 313.2 and 315.1.

Workup

  1. washThe organic phase was washed with 10% Na2S2O3 (300 mL) and water (300 mL)
  2. dry with materialdried (Na2SO4)
  3. concentrationconcentrated

Sources & evidence

ORD record
ord-fa99efac23e143d8b62630d56042ff27
Source dataset
uspto-grants-2013_07
Patent number
US08497376B2

Reaction notes

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