Tert-Butylamine → (6-Bromo-5-fluoropyridin-2-yl)-tert-butylamine

HRID 1922744Notes

Reaction equation

HRID 1922744 reaction equation
[Br:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[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])[CH:5]=[CH:6][C:7]=1[F:8]

Participants

6

Reactant 3

HCID 6385Tert-ButylamineHCID 77773Toluene-p-sulphonic anhydrideHCID 596053452-Bromo-3-fluoropyridine 1-oxide

Product 1

HCID 59605446(6-Bromo-5-fluoropyridin-2-yl)-tert-butylamineYield 5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 151471,2,3-TrifluorobenzeneSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 2-bromo-3-fluoropyridine 1-oxide (511 mg, 2.7 mmol) in DCM (10 mL) and trifluorobenzene (4 mL) at 50° C. were added tert-butylamine (2.5 mL, 23.9 mmol) and p-toluenesulfonic anhydride (3.7 g, 11.4 mmol) portion-wise. The reaction mixture was stirred at 50° C. for 2 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 5:95) to give (6-Bromo-5-fluoropyridin-2-yl)-tert-butylamine as a colourless oil (30 mg, 5%). 1H NMR (400 MHz, CHCl3-d): δ 7.13 (dd, J=8.8, 7.3 Hz, 1 H); 6.29 (dd, J=8.8, 2.5 Hz, 1 H); 4.49 (s, 1 H); 1.40 (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 5:95)

Sources & evidence

ORD record
ord-12162d0ee89e45c98cd86984643fed63
Source dataset
uspto-grants-2012_05
Patent number
US08173650B2

Reaction notes

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