2-AMINO-4-CYANO-PHENOL

Preparation of 3-amino-4-hydroxybenzonitrile. 3-AMINO4-HYDROXYBENZONITRILE : To a mixture of 5 G (30.5 MMOT) of 4-hydroxy-3-nitrobenzonitrile, 18.1 G of powder tin metal (152.5 mmol, 325 mesh), and 45 mL of ethanol was added with stirring a solution of 10 mL of concentrated HCI in 30 mL of H2O. The suspension was heated at reflux for 45 min and the resulting hot solution was poured into 100 ML of H20. Saturated aqueous NAHCO3 solution was slowly added to bring the pH to ca. 7. The suspension was filtered, and the residue was washed with MeOH giving the title compound (3.15 G, 77percent) as a white powder. Rf (CH2CI2/MEOH 9: 1) O. 47 ;1H NMR (CD30D) U 6. 96 (d, 1H, J=1. 3 Hz, H-2), 6.92 (d, 1H, J=8.1 Hz, H-6), 6.75 (d, 1H, J=8.1 Hz, H-5) ; 13C NMR (CD30D) 8 151.1 (C-4), 138.6 (C-3), 124.7 (C-6), 121. 6 (CN), 119. 1 (C- 2), 115.9 (C-5), 103.6 (C-1).Step B: 3-Amino-4-hydroxybenzonitrile; A mixture of 4-hydroxy-3-nitrobenzonitrile (100 mg, 0.61 mmol), palladium on charcoal (10 mg, 10 percent), EtOH (0.67 mL) and ethyl acetate (0.33 mL) was hydrogenated at rt for 2 h.Then the mixture was filtered and concentrated to give 3-amino-4-hydroxybenzonitrile 60 mg(73 percent) as a solid.To a solution of 4-hydroxy-3-nitrobenzonitrile (5g, 30.4mmol) in EtOH (lOOmL) was added 10percent Pd/C (4g). The reaction mixture was stirred at rt under H2 balloon atmosphere for 4 h. The TLC showed reaction to be complete. The reaction mixture was passed through a pad of celite. The celite was washed with EtOH (lOOmL). The filtrate was concentrated under reduced pressure to afford 3-amino-4- hydroxybenzonitrile as a black solid. Yield: 2.5g (67percent); 1H NMR (400 MHz, DMSOd 6): 9.02 (bs, 1H), 6.81-6.86 (m, 1H), 6.73 (d, J= 7.8 Hz, 1H), 6.49 (d, J= 7.8 Hz, 1H), 6.38 (bs, 1H), 6.17 (d, J = 6.5 Hz, 1H); MS (ESl+) for CHNOS m/z 165.10 [M+H].4-Hydroxy-3-nitrobenzonitrile (0.5 g, 3.05 mmol) was dissolved in ethanol (20 ml_) and methanol (10 ml_), and Raney-Nickel (1 ml_, 10percent aqueous solution) was added at rt followed by hydrazine mono hydrate (0.296 ml_, 6.09 mmol). The mixture was stirred at rt overnight. The mixture was then filtered through celite and concentrated by rotary evaporation. The residue was purified via chromatography (silica, n-hexane to ethyl acetate) to give 3-amino-4-hydroxybenzonitrile (D19, 200 mg, 49 percent) as an orange solid.M+HDescription 1. 3-Amino-4-hydroxybenzonitrile. (D1)4-Hydroxy-3-nitrobenzonitrile (0.5 g, 3.05 mmol) was dissolved in ethanol (20 ml.) and methanol (10 ml_), and Raney-Nickel (1 ml_, 10percent aqueous solution) was added at rt followed by hydrazine mono hydrate (0.296 ml_, 6.09 mmol). The mixture was stirred at rt overnight. The mixture was then filtered through celite and concentrated by rotary evaporation. The residue was purified via chromatography (silica, n-hexane to ethyl acetate) to give 3-amino-4-hydroxybenzonitrile (D1 , 200 mg, 49 percent) as an orange solid.M+H15 g of 2-nitro-4-cyanophenol and 1 g of 10percent palladium on carbon were added to 120 ml of methanol, Access to hydrogen, Stirred at room temperature for 8 hours, filter, Collecting filtrate, concentrate, To give 13 g of 3-amino-4-hydroxybenzonitrile.

Molecular Weight:134.14
XLogP3:0.9
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:3
Exact Mass:134.048012819
Monoisotopic Mass:134.048012819
Topological Polar Surface Area:70
Heavy Atom Count:10
Complexity:160
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes