Methyl iodide → tert-Butyl 4-(2-(6-bromopyridin-2-yl)-2-methylhydrazono)piperidine-1-carboxylate

HRID 882014Notes

Reaction equation

HRID 882014 reaction equation
[H-].[Na+].[Br:3][C:4]1[N:9]=[C:8]([NH:10][N:11]=[C:12]2[CH2:17][CH2:16][N:15]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:14][CH2:13]2)[CH:7]=[CH:6][CH:5]=1.[CH3:25]I>CN(C=O)C>[Br:3][C:4]1[N:9]=[C:8]([N:10]([CH3:25])[N:11]=[C:12]2[CH2:17][CH2:16][N:15]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:14][CH2:13]2)[CH:7]=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 57514756tert-Butyl 4-(2-(6-bromopyridin-2-yl)hydrazono)piperidine-1-carboxylate

Product 1

HCID 71551309tert-Butyl 4-(2-(6-bromopyridin-2-yl)-2-methylhydrazono)piperidine-1-carboxylateYield 99.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Sodium hydride (60% dispersion in oil, 0.72 g, 18 mmol) was added to a solution of tert-butyl 4-(2-(6-bromopyridin-2-yl)hydrazono)piperidine-1-carboxylate (5.5 g, 15 mmol) in DMF (50 mL) at room temperature under N2, and the resulting solution was stirred for 20 min. Methyl iodide (1.0 mL, 17 mmol) was added to the solution, and the resulting solution was stirred for 2 h at ambient temperature. The mixture was quenched with H2O (100 mL) and extracted with EtOAc (4×50 mL). The combined organic extracts were concentrated to an orange oil under reduced pressure. The oil was diluted with EtOAc (100 mL) and washed with brine (7×50 mL). The organics were dried over Na2SO4, filtered, and concentrated to dryness under reduced pressure to provide the title compound (5.7 g, 99%) as an orange oil: 1H NMR (300 MHz, DMSO-d6) δ 7.45 (dd, J=8.1, 7.5 Hz, 1H), 6.91 (d, J=7.5 Hz, 1H), 6.67 (d, J=8.4 Hz, 1H), 3.56 (t, J=6.0 Hz, 2H), 3.44 (t, J=6.0 Hz, 2H), 3.09 (s, 3H), 2.53-2.46 (m, 4H, overlap with solvent), 1.42 (s, 9H).

Workup

  1. stirringthe resulting solution was stirred for 2 h at ambient temperature
  2. customThe mixture was quenched with H2O (100 mL)
  3. extractionextracted with EtOAc (4×50 mL)
  4. concentrationThe combined organic extracts were concentrated to an orange oil under reduced pressure
  5. additionThe oil was diluted with EtOAc (100 mL)
  6. washwashed with brine (7×50 mL)
  7. dry with materialThe organics were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated to dryness under reduced pressure

Sources & evidence

ORD record
ord-b0bcb231788b45c38eecf5315e990545
Source dataset
uspto-grants-2015_03
Patent number
US08993765B2

Reaction notes

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