Sodium Carbonate → (E)-2-nitro-6-(prop-1-enyl)benzonitrile

HRID 711735Notes

Reaction equation

HRID 711735 reaction equation
I[C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[C:3]=1[C:4]#[N:5].[CH:13](/B(O)O)=[CH:14]\[CH3:15].C(=O)([O-])[O-].[Na+].[Na+]>C(COC)OC.O.CCOC(C)=O>[N+:10]([C:6]1[CH:7]=[CH:8][CH:9]=[C:2](/[CH:13]=[CH:14]/[CH3:15])[C:3]=1[C:4]#[N:5])([O-:12])=[O:11]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 6157276((1E)-prop-1-en-1-yl)boronic acidHCID 249719892-Iodo-6-nitrobenzonitrile

Product 1

HCID 67399195(E)-2-nitro-6-(prop-1-enyl)benzonitrileYield 94.2%

Reagents, catalysts & solvents 3

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

Procedure

A suspension of 2-iodo-6-nitrobenzonitrile (Example 130d) (1.52 g, 5.53 mmol), tetrakis(tiphenylphosphine)palladium(0) (0.64 g, 0.55 mmol), trans-1-propen-1-ylboronic acid (0.95 g, 11.06 mmol), sodium carbonate (0.65 g, 6.08 mmol) and water (10.0 mL) in dimethoxyethane (DME) (40.0 mL) was heated at reflux for 15 h, under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and diluted with water (20 mL) and EtOAc (100 mL). The organic phase was separated and the aqueous phase was extracted with EtOAc (3×50 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 0.98 g (94%) of the title compound as a white solid. 1H-NMR (400 MHz, DMSO-d6) δ 8.16-8.24 (m, 2H), 7.83-7.89 (m, 1H), 6.71-6.84 (m, 2H), 1.90-2.02 (m, 3H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 15 h, under a nitrogen atmosphere
  3. customThe organic phase was separated
  4. extractionthe aqueous phase was extracted with EtOAc (3×50 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-ade5cbbecf8a4ee0a876e8eb077cf055
Source dataset
uspto-grants-2015_11
Patent number
US09181276B2

Reaction notes

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