Sodium Carbonate → 2-Nitro-6-(2-methylprop-1-enyl)benzonitrile

HRID 471593Notes

Reaction equation

HRID 471593 reaction equation
FC(F)(F)S(O[C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([N+:13]([O-:15])=[O:14])[C:8]=1[C:16]#[N:17])(=O)=O.[CH3:20][C:21]([CH3:26])=[CH:22]B(O)O.C(=O)([O-])[O-].[Na+].[Na+]>C(COC)OC.O.CCOC(C)=O>[N+:13]([C:9]1[CH:10]=[CH:11][CH:12]=[C:7]([CH:20]=[C:21]([CH3:26])[CH3:22])[C:8]=1[C:16]#[N:17])([O-:15])=[O:14]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27632992,2-Dimethylethenylboronic acidHCID 866574732-Cyano-3-nitrophenyl trifluoromethanesulfonate

Product 1

HCID 674005172-Nitro-6-(2-methylprop-1-enyl)benzonitrileYield 61.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A suspension of 2-cyano-3-nitrophenyl trifluoromethanesulfonate (Example 129d) (4.80 g; 16.21 mmol), 2-methyl-1-propenylboronic acid (2.43 g; 24.32 mmol), tetrakis(tiphenylphosphine)palladium(0) (1.87 g; 1.62 mmol), sodium carbonate (1.89 g; 17.83 mmol) and water (33.0 mL) in dimethoxyethane (DME) (132.0 mL) was heated at reflux for 4 h, under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and diluted with water (100 mL) and EtOAc (250 mL). The organic phase was separated and the aqueous phase was extracted with EtOAc (3×100 mL). The combined extract was washed with brine and dried with anhydrous MgSO4. The filtrate was evaporated and the residue was purified by chromatography on silica gel using gradient hexanes to hexanes/EtOAc (7:3), to give 2.01 g (61%) of the title compound as a yellow solid. 1H-NMR (400 MHz, DMSO-d6) δ 8.19-8.23 (m, 1H), 7.83-7.93 (m, 2H), 6.45 (broad s, 1H), 1.95-1.98 (m, 3H), 1.75-1.79 (m, 3H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 4 h, under a nitrogen atmosphere
  3. customThe organic phase was separated
  4. extractionthe aqueous phase was extracted with EtOAc (3×100 mL)
  5. extractionThe combined extract
  6. washwas washed with brine
  7. dry with materialdried with anhydrous MgSO4
  8. customThe filtrate was evaporated
  9. customthe residue was purified by chromatography on silica gel using gradient hexanes to hexanes/EtOAc (7:3)

Sources & evidence

ORD record
ord-63a5975ff4174c44ba83cc3482ae3891
Source dataset
uspto-grants-2014_01
Patent number
US08633186B2

Reaction notes

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