Ammonium Hydroxide → HCID 70497940, compound

HRID 882004Notes

Reaction equation

HRID 882004 reaction equation
[OH-].[NH4+:2].F[C:4]1[C:9]([F:10])=[C:8]([F:11])[N:7]=[C:6]([C:12]#[N:13])[CH:5]=1>>[NH2:2][C:4]1[C:9]([F:10])=[C:8]([F:11])[N:7]=[C:6]([C:12]#[N:13])[CH:5]=1

Participants

3

Reactant 2

HCID 14923Ammonium HydroxideHCID 70498364HCID 70498364, compound

Product 1

HCID 70497940HCID 70497940, compoundYield 24.4%

Procedure

Ammonium hydroxide (NH4OH) was added to crude 4,5,6-trifluoropicolinonitrile (2.5 g, 15.8 mmol) and stirred at room temperature for 2 h. A brown solid formed which was filtered, washed with water and dried to give 0.72 g. Analysis by gas chromatography-mass spectroscopy (GC-MS) indicated the presence of two isomeric products. The aqueous filtrate was extracted with EtOAc. The combined organic extracts were washed with brine, dried over Na2SO4, and evaporated to give additional brown solid. The two crops were combined and purified by silica gel chromatography to give 4-amino-5,6-difluoro-picolinonitrile (0.60 g, 24.4%): 1H NMR (400 MHz, CDCl3) δ 7.13 (d, J=5.3 Hz, 1H, aromatic), 6.62 (s, 2H, NH2); 13C NMR (101 MHz, CDCl3) δ 157.0 (dd, J=235, 12 Hz), 151.7 (dd, J=10, 7 Hz), 139.5 (dd, J=254, 29 Hz), 128.8 (d, J=19 Hz), 121.2 (s), 121.0 (s); 19F NMR (376 MHz, CDCl3) δ −85.29 (d, J=24.5 Hz), −156.98 (dd, J=24.5, 5.2 Hz).

Workup

  1. customA brown solid formed which
  2. filtrationwas filtered
  3. washwashed with water
  4. customdried
  5. customto give 0.72 g
  6. extractionThe aqueous filtrate was extracted with EtOAc
  7. washThe combined organic extracts were washed with brine
  8. dry with materialdried over Na2SO4
  9. customevaporated
  10. customto give additional brown solid
  11. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-09eb5fbd3ea84bf89da56a6f62d80eca
Source dataset
uspto-grants-2015_03
Patent number
US08993772B2

Reaction notes

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