Carbon Dioxide → HCID 69135640, compound

HRID 968445Notes

Reaction equation

HRID 968445 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([NH2:17])[N:12]=2)=[N:8][CH:9]=1)([O-])=O.C(=O)=O>[Pd].CO>[NH2:1][C:4]1[CH:5]=[CH:6][C:7]([NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([NH2:17])[N:12]=2)=[N:8][CH:9]=1

Participants

5

Reactant 2

HCID 280Carbon DioxideHCID 86066180HCID 86066180, compound

Product 1

HCID 69135640HCID 69135640, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

2,6-Diaminopyridine (9.2 mmol, 1.0 g) and 2-fluoro-5-nitropyridine (4.6 mmol, 0.65 g) were dissolved in 6 mL of DMSO. The solution was heated to 80° C. for 18 h. The solution eventually turned dark red. The reaction mixture was cooled to room temperature and purified directly by flash column chromatography (silica, EtOAc:Hexanes=1:3) to give N2-(5-nitropyridin-2-yl)pyridine-2,6-diamine as a reddish crystalline solid (0.21 g, 20% yield): 1H NMR (500 MHz, CDCl3) δ 9.13 (d, 1H, J=3.0 Hz), 8.36 (dd, 1H, J=3.0 Hz, J2=9.5 Hz), 7.94 (d, 1H, J=9.5 Hz), 7.66 (s, 1H), 7.46 (t, 1H, J=8.0 Hz), 6.68 (d, 1H, J=8.0 Hz), 6.23 (d, 1H, J=8.0 Hz), 4.46 (s, 2H); Ms m/z (relative intensity) 232 (M+1, 100), 186 (57). The nitro compound (0.78 mmol, 0.18 g) and 10% Pd/C (20 mg) were added to a 20 mL test tube equipped with a stir bar, dry ice (0.5 g) was added to the mixture just before MeOH (7 mL) was added. The suspension was then put into a pressure vessel under 80 psi of H2. The reaction mixture was stirred for 2 hours. The solution turned from yellow to colorless. The reaction mixture was transferred into a 10 mL syringe and was then filtered through an Acrodisc syringe Filter into a 100 mL round bottom flask containing 37% aqueous HCl (4 mL). The solvent was then evaporated and azeotroped to dryness with toluene and absolute ethanol (3×30 mL of 1:1 mixture). The product was obtained as a grayish yellow powder in quantitative yield.

Workup

  1. customequipped with a stir bar
  2. additionwas added
  3. customThe suspension was then put into a pressure vessel under 80 psi of H2
  4. customThe reaction mixture was transferred into a 10 mL syringe
  5. filtrationwas then filtered through an Acrodisc syringe
  6. filtrationFilter into a 100 mL round bottom flask
  7. additioncontaining 37% aqueous HCl (4 mL)
  8. customThe solvent was then evaporated
  9. customazeotroped to dryness with toluene and absolute ethanol (3×30 mL of 1:1 mixture)
  10. customThe product was obtained as a grayish yellow powder in quantitative yield

Sources & evidence

ORD record
ord-39029264db9946c4938170f37f256a34
Source dataset
uspto-grants-2007_12
Patent number
US07303592B2

Reaction notes

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