Sulfuryl chloride → 4-Amino-3,6-dichloro-5-fluoropicolinonitrile

HRID 1913903Notes

Reaction equation

HRID 1913903 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6](NN)[N:5]=[C:4]([C:11]#[N:12])[C:3]=1[Cl:13].S(Cl)([Cl:17])(=O)=O>C(Cl)Cl>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([Cl:17])[N:5]=[C:4]([C:11]#[N:12])[C:3]=1[Cl:13]

Participants

4

Reactant 2

HCID 24648Sulfuryl chlorideHCID 704958804-Amino-3-chloro-5-fluoro-6-hydrazinopicolinonitrile

Product 1

HCID 715514574-Amino-3,6-dichloro-5-fluoropicolinonitrileYield 76%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of 4-amino-3-chloro-5-fluoro-6-hydrazinylpicolinonitrile (9.04 g, 44.8 mmol) in CH2Cl2 (150 mL) was added sulfuryl chloride (7.20 mL, 89 mmol). The mixture was stirred at room temperature for 40 h. The solvent was removed under reduced pressure, and the residue was partitioned with saturated aqueous sodium bicarbonate (NaHCO3) and EtOAc. The organic phase was separated, dried over Na2SO4, and filtered. The solution was concentrated and the residue was purified by silica gel chromatography to give the product (7.01 g, 76%) as an off-white solid: 1H NMR (300 MHz, DMSO-d6) δ 7.55 (s, 2H); 13C NMR (101 MHz, DMSO-d6) δ 143.26 (d, J=259.2 Hz, C5), 142.69 (d, J=14.0 Hz, C4), 135.53 (d, J=17.6 Hz. C6), 126.07 (d, J=4.4 Hz, C2), 120.14 (d, J=4.3 Hz, C3), 114.36 (s, CN); 19F NMR (376 MHz, DMSO-d6) δ −132.30 (s); ESIMS m/z 203 ([M+H]+), 206.

Workup

  1. customThe solvent was removed under reduced pressure
  2. customthe residue was partitioned with saturated aqueous sodium bicarbonate (NaHCO3) and EtOAc
  3. customThe organic phase was separated
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationThe solution was concentrated
  7. customthe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-73ee08f620ec43f696fb982897718618
Source dataset
uspto-grants-2013_12
Patent number
US08609853B2

Reaction notes

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