Selectfluor → N'-(3-Cyano-5-fluoro-6-isopropylpyridin-2-yl)-N,N-dimethylformimidamide

HRID 605430Notes

Reaction equation

HRID 605430 reaction equation
[C:1]([C:3]1[C:4]([N:12]=[CH:13][N:14]([CH3:16])[CH3:15])=[N:5][C:6]([CH:9]([CH3:11])[CH3:10])=[CH:7][CH:8]=1)#[N:2].[F:17][B-](F)(F)F.F[B-](F)(F)F.ClC[N+]12CC[N+](F)(CC1)CC2>CC#N>[C:1]([C:3]1[C:4]([N:12]=[CH:13][N:14]([CH3:16])[CH3:15])=[N:5][C:6]([CH:9]([CH3:11])[CH3:10])=[C:7]([F:17])[CH:8]=1)#[N:2]

Participants

4

Reactant 2

HCID 2724933SelectfluorHCID 66808369(E)-N'-(3-cyano-6-isopropylpyridin-2-yl)-N,N-dimethylformimidamide

Product 1

HCID 67040814N'-(3-Cyano-5-fluoro-6-isopropylpyridin-2-yl)-N,N-dimethylformimidamideYield 19.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of N′-(3-cyano-6-isopropyl-pyridin-2-yl)-N,N-dimethyl-formamidine (3.0 g, 14 mmol) in dry CH3CN (139 mL) was added 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) [SELECTFLUOR™] (5.4 g, 15 mmol) at room temperature. The mixture was stirred at room temperature for 18 hours under N2, then concentrated. The residue was diluted with ethyl acetate (100 mL), washed with water (5×40 mL) and brine, dried over MgSO4, and concentrated. The oily residue was purified by column chromatography (SiO2, n-hexane/ethyl acetate=3/1) to give the title compound as colorless crystals (0.63 g, 19%). 1H-NMR (300 MHz, CDCl3) δ ppm: 1.26 (d, J=7.0 Hz, 6H), 3.15 (s, 3H), 3.16 (s, 3H), 3.29 (septet-d, J=7.0, 1.9 Hz, 1H), 7.41 (d, J=8.8 Hz, 1H), 8.55 (s, 1H). MS ESI+ m/z: 235 (M+H).

Workup

  1. concentrationconcentrated
  2. additionThe residue was diluted with ethyl acetate (100 mL)
  3. washwashed with water (5×40 mL) and brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customThe oily residue was purified by column chromatography (SiO2, n-hexane/ethyl acetate=3/1)

Sources & evidence

ORD record
ord-6dae3dd13fc14000990d730a45b78892
Source dataset
uspto-grants-2011_03
Patent number
US07910595B2

Reaction notes

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