M-Phenylenediamine → HCID 24709503, compound

HRID 968446Notes

Reaction equation

HRID 968446 reaction equation
[C:1]1([NH2:8])[CH:6]=[CH:5][CH:4]=[C:3]([NH2:7])[CH:2]=1.F[C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][N:11]=1>CS(C)=O>[N+:16]([C:13]1[CH:14]=[CH:15][C:10]([NH:7][C:3]2[CH:4]=[CH:5][CH:6]=[C:1]([NH2:8])[CH:2]=2)=[N:11][CH:12]=1)([O-:18])=[O:17]

Participants

4

Reactant 2

HCID 7935M-PhenylenediamineHCID 952642-Fluoro-5-nitropyridine

Product 1

HCID 24709503HCID 24709503, compound

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
80 °C

Procedure

m-Phenylenediamine (2.8 mmol, 0.30 g) and 2-fluoro-5-nitropyridine (0.92 mmol, 0.13 g) were dissolved in 6 mL of DMSO. The solution was heated to 80° C. for 18 hours. 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 N1-(5-nitropyridin-2-yl)benzene-1,3-diamine as a reddish crystalline compound (0.19 g, 89% yield): 1H NMR (500 MHz, CDCl3) δ 9.08 (d, 1H, J=2.5 Hz), 8.24 (dd, 1H, J1=2.5 Hz, J2=9.5 Hz), 7.281 (s, 1H), 7.19 (t, 1H, J=8.0 Hz), 6.82 (d, 1H, J=9.5 Hz), 6.74 (s, 1H), 6.70 (d, 1H, J=8.0 Hz), 6.56 (d, 1H, J=7.5 Hz), 3.80 (br, 2H); 13C NMR (125 MHz, CDCl3) δ 159.91, 148.05, 146.93, 139.09, 137.15, 133.59, 130.77, 112.80, 112.66, 109.13, 106.67. The nitro compound (0.43 mmol, 0.10 g) and 10% Pd/C (10 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 filtered through an Acrodisc syringe Filter into a 100 mL round bottom flask containing 37% aqueous HCl (3 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. B. Primary Intermediates of Formula (5)

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. custompurified directly by flash column chromatography (silica, EtOAc:Hexanes=1:3)

Sources & evidence

ORD record
ord-2d8d661cb7d94e8d97f21521ff89ad6f
Source dataset
uspto-grants-2007_12
Patent number
US07303592B2

Reaction notes

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