Dimethylformamide → HCID 57470259, compound

HRID 401401Notes

Reaction equation

Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[C:11]([CH3:14])([CH3:13])[CH3:12].[CH3:15][N:16](C=O)C>O.[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:11]([C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[C:15]#[N:16])([CH3:14])([CH3:13])[CH3:12]

Participants

Conditions

Temperature: 205 °C

Procedure

To a solution of 2-bromo-1-tert-butyl-4-nitrobenzene (2.13 g, 8.2 mmol) and Zn(CN)2 (770 mg, 6.56 mmol) in DMF (10 mL) was added Pd(PPh3)4 (474 mg, 0.41 mmol) under a nitrogen atmosphere. The mixture was heated in a sealed vessel at 205° C. for 5 h. After cooling to room temperature, the mixture was diluted with water and extracted with EtOAc twice. The combined organic layers were washed with brine and dried over MgSO4. After removal of solvent, the residue was purified by column chromatography (0-10% EtOAc-Hexane) to give 2-tert-butyl-5-nitrobenzonitrile (1.33 g, 80%). 1H NMR (400 MHz, CDCl3) δ 8.55 (d, J=2.3 Hz, 1H), 8.36 (dd, J=8.8, 2.2 Hz, 1H), 7.73 (d, J=8.9 Hz, 1H), 1.60 (s, 9H); HPLC ret. time 3.42 min, 10-100% CH3CN, 5 min gradient.

Workup

temperatureAfter cooling to room temperature
extractionextracted with EtOAc twice
washThe combined organic layers were washed with brine
dry with materialdried over MgSO4
customAfter removal of solvent
customthe residue was purified by column chromatography (0-10% EtOAc-Hexane)

Sources & evidence

ORD record: ord-789c85781a1f404d81032780145b3928
Source dataset: uspto-grants-2014_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08741925B2

Reaction notes

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