Hydrochloric Acid → 2-(4-Vinyl-phenyl)-malononitrile

HRID 1169536Notes

Reaction equation

HRID 1169536 reaction equation
[H-].[Na+].[C:3](#[N:7])[CH2:4][C:5]#[N:6].I[C:9]1[CH:14]=[CH:13][C:12]([CH:15]=[CH2:16])=[CH:11][CH:10]=1.Cl>COCCOC.C1COCC1>[CH:15]([C:12]1[CH:13]=[CH:14][C:9]([CH:4]([C:3]#[N:7])[C:5]#[N:6])=[CH:10][CH:11]=1)=[CH2:16]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8010MalononitrileHCID 24758Sodium hydrideHCID 110097554-Iodostyrene

Product 1

HCID 585105282-(4-Vinyl-phenyl)-malononitrileYield 71.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 80711,2-DimethoxyethaneSolvent2×

Procedure

To an ice-cooled suspension of NaH (0.792 g, 33.0 mmol) in anhydrous 1,2-dimethoxyethane (20 mL) was added dropwise via syringe a solution of malononitrile (0.99 g, 15 mmol) in anhydrous 1,2-dimethoxyethane (5 mL) under N2. The mixture was stirred for 1 h at room temperature under N2. Next, 1-iodo-4-vinyl-benzene (1.15 g, 5.00 mmol), dry THF (15 mL), and tetrakis(triphenyphophine)palladium(0) (0.58g, 0.50 mmol) were added to the resulting pink suspension under an N2 flow, and the reaction mixture stirred at 85° C. for 2 h. After cooling to room temperature, the reaction mixture was poured into ice, neutralized with 10% HCl, and extracted with CH2Cl2 (100 mL). The organic layer was separated, dried over anhydrous Na2SO4, and concentrated in vacuo. The crude product was then purified by flash chromatography on silica gel eluting with 1:1 hexane: CH2Cl2, to give 0.603 g (71.8%) of the title compound as pale yellow solid: mp 40-42° C. ° C; 1H NMR (400 MHz, CDCl3): δ 7.526 (d, 2H, J=7.6 Hz), 7.462 (d, 2H, J=7.6 Hz), 6.738 (d×d, 1H, J1=17.6 Hz, J2=10.8 Hz), 5.846 (d, 1H, J=17.6 Hz), 5.398 (d, 1H, J=10.8 Hz), 5.075 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 139.840, 135.372, 127.766, 127.556, 125.245, 116.619, 111.897, 28.050; Anal. Calcd. for C11H8N2: C, 78.55; H, 4.79; N, 16.66. Found; C, 78.76; H, 4.75; N, 16.02.

Workup

  1. stirringthe reaction mixture stirred at 85° C. for 2 h
  2. temperatureAfter cooling to room temperature
  3. additionthe reaction mixture was poured into ice
  4. extractionextracted with CH2Cl2 (100 mL)
  5. customThe organic layer was separated
  6. dry with materialdried over anhydrous Na2SO4
  7. concentrationconcentrated in vacuo
  8. customThe crude product was then purified by flash chromatography on silica gel eluting with 1:1 hexane

Sources & evidence

ORD record
ord-e36bd9bb403c43e8a7f1c9d6529d877f
Source dataset
uspto-grants-2010_11
Patent number
US07824582B2

Reaction notes

Loading…