Malononitrile → 2-(1-(4-(Benzyloxy)phenyl)ethylidene)malononitrile

HRID 1518320Notes

Reaction equation

HRID 1518320 reaction equation
C[Si](C)(C)N[Si](C)(C)C.[CH2:10]([O:17][C:18]1[CH:23]=[CH:22][C:21]([C:24](=O)[CH3:25])=[CH:20][CH:19]=1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[C:27](#[N:31])[CH2:28][C:29]#[N:30]>C(O)(=O)C>[CH2:10]([O:17][C:18]1[CH:19]=[CH:20][C:21]([C:24](=[C:28]([C:27]#[N:31])[C:29]#[N:30])[CH3:25])=[CH:22][CH:23]=1)[C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

Participants

5

Reactant 3

HCID 8010MalononitrileHCID 13838HexamethyldisilazaneHCID 2452261-[4-(Benzyloxy)phenyl]ethan-1-one

Product 1

HCID 866443242-(1-(4-(Benzyloxy)phenyl)ethylidene)malononitrileYield 99.9%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

Hexamethyldisilazane (2.50 mL, 1.937 g, 12.0 mmol) was added to 1-(4-(benzyloxy)phenyl)ethanone (2.263 g, 10 mmol) in acetic acid (6 mL) at a rate to maintain the internal temperature below 74° C. After the addition was over, malononitrile (1.32 g, 20 mmol) in acetic acid (6 mL) was added to the solution. The reaction was heated at 90 C.° for 12 hours. After cooling, the reaction was poured into ice/water, extracted with EtOAc, dried, and concentrated under reduced pressure to give the crude product. The solid was triturated with 1:9 EtOAc/hexanes to provide 2.74 g of the desired product. 1H NMR (DMSO-d6): δ 7.72-7.75 (m, 2H), 7.35-7.49 (m, 5H), 7.18-7.21 (d, 2H), 5.22 (s, 2H), 2.61 (s, 3H). MS (ESI(+)): m/z 291 (M+NH4).

Workup

  1. temperatureto maintain the internal temperature below 74° C
  2. additionAfter the addition
  3. additionwas added to the solution
  4. temperatureThe reaction was heated at 90 C.° for 12 hours
  5. temperatureAfter cooling
  6. extractionextracted with EtOAc
  7. customdried
  8. concentrationconcentrated under reduced pressure
  9. customto give the crude product
  10. customThe solid was triturated with 1:9 EtOAc/hexanes

Sources & evidence

ORD record
ord-410f0f3d71a14f679a327acb0d7764d0
Source dataset
uspto-grants-2012_07
Patent number
US08232273B2

Reaction notes

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