Sodium Cyanide → 2-Amino-5-cyanopyridine

HRID 1355178Notes

Reaction equation

HRID 1355178 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C-:20]#[N:21].[Na+].[NH2:23][C:24]1[CH:29]=[CH:28][C:27](Br)=[CH:26][N:25]=1>C(#N)C.C(OCC)(=O)C.[Ni](Br)Br.[Zn]>[NH2:23][C:24]1[CH:29]=[CH:28][C:27]([C:20]#[N:21])=[CH:26][N:25]=1

Participants

8

Reactant 3

HCID 8929Sodium CyanideHCID 11776TriphenylphosphineHCID 706222-Amino-5-bromopyridine

Product 1

HCID 8182602-Amino-5-cyanopyridineYield 42%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 278492Nickel(II) bromideCatalystHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

A solution of nickel(II) bromide (253 mg, 1.16 mmol), triphenylphosphine (1.15 g, 4.39 mmol), and zinc powder (113 mg, 1.73 mmol) in acetonitrile (11 mL) was stirred under argon at 60° C. for 1 h. The reaction turned dark brown in color. After such time, the reaction mixture was treated with sodium cyanide (578 mg, 11.8 mmol) and 2-amino-5-bromopyridine (2.00 g, 11.6 mmol), and the reaction mixture was stirred at 60° C. for 16 h. The reaction mixture was then cooled to 25° C., diluted with ethyl acetate (50 mL), and then filtered through celite. The filtrate was concentrated in vacuo. Flash chromatography (Merck Silica gel 60, 230–400 mesh, 100% ethyl acetate) afforded 6-amino-nicotinonitrile (577 mg, 42%) as a white solid: mp 156.8–158.5° C.; EI-HRMS m/e calcd for C6H5N3 (M+) 119.0483, found 119.0480.

Workup

  1. temperatureThe reaction mixture was then cooled to 25° C.
  2. filtrationfiltered through celite
  3. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-8f3d11e5628c41c6a4750c0182dfaa29
Source dataset
uspto-grants-2007_05
Patent number
US07223868B2

Reaction notes

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