Tert-Butylamine → 2-Pyridinecarboxamide, 5-bromo-N-(1,1-dimethylethyl)-

HRID 520733Notes

Reaction equation

HRID 520733 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]([OH:10])=O)=[N:6][CH:7]=1.CCN(C(C)C)C(C)C.CN(C(ON1N=NC2C=CC=CC1=2)=[N+](C)C)C.[B-](F)(F)(F)F.[C:42]([NH2:46])([CH3:45])([CH3:44])[CH3:43]>O1CCOCC1>[C:42]([NH:46][C:8]([C:5]1[CH:4]=[CH:3][C:2]([Br:1])=[CH:7][N:6]=1)=[O:10])([CH3:45])([CH3:44])[CH3:43]

Participants

6

Reactant 4

HCID 6385Tert-ButylamineHCID 81531DiisopropylethylamineHCID 6085445-Bromopyridine-2-carboxylic acidHCID 2733207O-(Benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate

Product 1

HCID 109996962-Pyridinecarboxamide, 5-bromo-N-(1,1-dimethylethyl)-Yield 92.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

5-Bromopicolinic acid (200 mg, 0.99 mmol) was dissolved in dioxane (2 ml) and Hunig's Base (520 μl, 2.97 mmol, 3 equiv.), TBTU (350 mg, 1.09 mmol, 1.1 equiv.) and tert-butyl amine (124 μl, 1.19 mmol, 1.2 equiv.) were added at room temperature. The mixture was stirred for 16 hours at room temperature. The reaction mixture was evaporated and extracted saturated NaHCO3 solution and two times with a small volume of dichloromethane. The crude product was purified by flash chromatography by directly loading the dichloromethane layers onto a silica gel column and eluting with an ethyl acetate:heptane gradient 0:100 to 50:50. The desired 5-bromo-pyridine-2-carboxylic acid tert-butylamide (235 mg, 92% yield) was obtained as a colorless oil, MS: m/e=257.0/259.0 (M+H+).

Workup

  1. customThe reaction mixture was evaporated
  2. extractionextracted saturated NaHCO3 solution and two times with a small volume of dichloromethane
  3. customThe crude product was purified by flash chromatography
  4. washeluting with an ethyl acetate

Sources & evidence

ORD record
ord-73af5e4c2f7945d5ade73abfad7d2108
Source dataset
uspto-grants-2016_05
Patent number
US09328070B2

Reaction notes

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