Tert-Butylamine → 6-Bromo-N-(tert-butyl)-3-methylpyridin-2-amine

HRID 1922740Notes

Reaction equation

HRID 1922740 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][N+:3]=1[O-].[C:10]([NH2:14])([CH3:13])([CH3:12])[CH3:11].C1(C)C=CC(S(OS(C2C=CC(C)=CC=2)(=O)=O)(=O)=O)=CC=1>C(Cl)Cl.FC1C(F)=C(F)C=CC=1>[Br:1][C:2]1[N:3]=[C:4]([NH:14][C:10]([CH3:13])([CH3:12])[CH3:11])[C:5]([CH3:8])=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 6385Tert-ButylamineHCID 77773Toluene-p-sulphonic anhydrideHCID 131787372-Bromo-5-methylpyridine 1-oxide

Product 1

HCID 596061846-Bromo-N-(tert-butyl)-3-methylpyridin-2-amineYield 19.4%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 151471,2,3-TrifluorobenzeneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 2-bromo-5-methylpyridine 1-oxide (2.0 g, 10.6 mmol) in DCM (40 mL) and trifluorobenzene (17 mL) at 0° C. were added tert-butylamine (8.0 mL, 76.7 mmol) and p-toluenesulfonic anhydride (11.4 g, 35.0 mmol) portion-wise. The reaction mixture was stirred at 0° C. for 1.5 hours and then filtered. The filtrate was concentrated to give a residue that was purified by flash chromatography (Si—PPC, Et2O:pentane, gradient 0:100 to 100:0) to give (6-Bromo-3-methylpyridin-2-yl)-tert-butylamine as a colourless oil (500 mg, 19%). 1H NMR (400 MHz, CHCl3-d): δ 6.98 (d, J=7.5 Hz, 1 H); 6.59 (d, J=7.5 Hz, 1 H); 4.05 (s, 1 H); 1.96 (s, 3 H); 1.47 (s, 9 H).

Workup

  1. filtrationfiltered
  2. concentrationThe filtrate was concentrated
  3. customto give a residue that
  4. customwas purified by flash chromatography (Si—PPC, Et2O:pentane, gradient 0:100 to 100:0)

Sources & evidence

ORD record
ord-fb247722bcce4aaeb924a700dcba3993
Source dataset
uspto-grants-2012_05
Patent number
US08173650B2

Reaction notes

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