Dimethylformamide → 3-Amino-4-nitrobenzonitrile

HRID 252857Notes

Reaction equation

HRID 252857 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([NH2:8])[CH:7]=1.[CH3:12][N:13](C)C=O>[C-]#N.[Zn+2].[C-]#N.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[NH2:8][C:6]1[CH:7]=[C:2]([CH:3]=[CH:4][C:5]=1[N+:9]([O-:11])=[O:10])[C:12]#[N:13]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 53147665-Bromo-2-nitroaniline

Product 1

HCID 114919823-Amino-4-nitrobenzonitrileYield 63%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Procedure

A suspension of bromoarene 2 (801 mg; 3.7 mmol) and zinc cyanide (570 mg; 4.85 mmol; 1.3 eq.) in degassed dimethylformamide (15 mL) was stirred at room temperature under nitrogen in the dark for 45 min and then treated with tetrakis(triphenylphosphine) palladium(O) (310 mg, 1.6 mmol). The mixture was stirred at 90° C. for 18 h; filtered through a celite pad, concentrated under reduced pressure and purified by flash chromatography on silica gel, eluent EtOAc-hexane (1:1) to afford the title compound 274 (380 mg, 63% yield). 1H NMR: (400.2 MHz, CDCl3) δ (ppm): 8.22 (d, J=8.6 Hz; 1H); 7.19 (d, J=1.8 Hz; 1H); 6.95 (dd, J=1.8, 8.6 Hz; 1H); 6.27 (bs; 2H). MS: calc: 163.1; found: 164.1 (M+H)

Workup

  1. stirringThe mixture was stirred at 90° C. for 18 h
  2. filtrationfiltered through a celite pad
  3. concentrationconcentrated under reduced pressure
  4. custompurified by flash chromatography on silica gel, eluent EtOAc-hexane (1:1)

Sources & evidence

ORD record
ord-075ccffe71294255b648e9ce3ddc46d8
Source dataset
uspto-grants-2011_01
Patent number
US07868205B2

Reaction notes

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