1-Bromo-4-isopropyl-2-nitrobenzene → 4-Isopropyl-2-nitrobenzonitrile

HRID 883999Notes

Reaction equation

HRID 883999 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH3:10])[CH3:9])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].[Cu][C:15]#[N:16]>CN(C)C=O.O.Cl.O.O.O.O.O.O.[Fe](Cl)(Cl)Cl>[CH:8]([C:5]1[CH:6]=[CH:7][C:2]([C:15]#[N:16])=[C:3]([N+:11]([O-:13])=[O:12])[CH:4]=1)([CH3:10])[CH3:9]

Participants

7

Reactant 2

HCID 215318151-Bromo-4-isopropyl-2-nitrobenzeneHCID 178418546HCID 178418546, compound

Product 1

HCID 249719534-Isopropyl-2-nitrobenzonitrileYield 77.5%

Reagents, catalysts & solvents 4

HCID 16211236Trichloroiron;hexahydrateCatalystHCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

The product of Example 91A (0.581 g, 2.380 mmol) and copper (I) cyanide (0.426 g, 4.760 mmol) in N,N-dimethylformamide (5 mL) under a nitrogen atmosphere were heated in 160° oil bath for 1.5 hour. The reaction was cooled, treated with a solution of iron (III) chloride hexahydrate (2.48 g) in water (3.72 mL) and concentrated hydrochloric acid (0.62 mL), and then heated at 65° for 20 minutes. The cooled reaction mixture was extracted with ethyl ether (2×50 mL). The combined ethereal extracts were washed sequentially with 1N aqueous HCl (25 mL), 3N aqueous sodium hydroxide (25 mL), water (25 mL), and brine (25 mL) then dried over magnesium sulfate, filtered, and concentrated by rotary evaporation. Purification of the residue by silica gel flash chromatography eluting with 20:80 ethyl acetate/hexanes afforded the title compound as a yellow liquid (0.351 g, 1.845 mmol, 58%). 1H NMR (300 MHz, CHLOROFORM-D) □ppm 1.33 (d, J=6.99 Hz, 6 H) 2.82-3.47 (m, 1 H) 7.66 (dd, J=7.91, 1.29 Hz, 1 H) 7.83 (d, J=7.72 Hz, 1 H) 8.18 (d, J=1.47 Hz, 1 H); MS (DCI) m/z 208 (M+NH4)+.

Workup

  1. temperatureThe reaction was cooled
  2. temperatureheated at 65° for 20 minutes
  3. customThe cooled reaction mixture
  4. extractionwas extracted with ethyl ether (2×50 mL)
  5. washThe combined ethereal extracts were washed sequentially with 1N aqueous HCl (25 mL), 3N aqueous sodium hydroxide (25 mL), water (25 mL), and brine (25 mL)
  6. dry with materialthen dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated by rotary evaporation
  9. customPurification of the residue by silica gel flash chromatography
  10. washeluting with 20:80 ethyl acetate/hexanes

Sources & evidence

ORD record
ord-a444221385084946a13396bc967deafc
Source dataset
uspto-grants-2012_08
Patent number
US08236950B2

Reaction notes

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