(Triphenylphosphoranylidene)acetonitrile → (E)-Methyl 4,5-dichloro-2-(2-cyanovinyl)benzoate

HRID 84937

Reaction equation

HRID 84937 reaction equation
[Cl:1][C:2]1[C:11]([Cl:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH:13]=O)[CH:3]=1.C1(P(=[CH:34][C:35]#[N:36])(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1>[Cl:1][C:2]1[C:11]([Cl:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4](/[CH:13]=[CH:34]/[C:35]#[N:36])[CH:3]=1

Participants

4

Reactant 2

HCID 85524(Triphenylphosphoranylidene)acetonitrileHCID 86647797Methyl 4,5-dichloro-2-formylbenzoate

Product 1

HCID 86647796(E)-Methyl 4,5-dichloro-2-(2-cyanovinyl)benzoate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of the product from Example 56C (2.0 g, 8.6 mmol) and (triphenylphosphoranylidene)acetonitrile (2.87 g, 9.5 mmol) in toluene (30 mL) was refluxed for 24 hours. The reaction was cooled to room temperature and filtered through a short plug of silica gel eluting with diethyl ether to remove the triphenyl phosphine oxide. The filtrate was concentrated and the residue was purified via flash chromatography on a silica gel column (5:95 ethyl acetate:hexane) to afford the title compound and the corresponding Z isomer. 1H NMR (300 MHz, DMSO-d6) δ ppm 3.88 (s, 3H) 6.55 (d, J=16.27 Hz, 1H) 8.05 (d, J=16.95 Hz, 1H) 8.09 (s, 1H) 8.13 (s, 1H); MS (DCI+) m/z 273.0 [M+H]+.

Workup

  1. temperaturewas refluxed for 24 hours
  2. filtrationfiltered through a short plug of silica gel eluting with diethyl ether
  3. customto remove the triphenyl phosphine oxide
  4. concentrationThe filtrate was concentrated
  5. customthe residue was purified via flash chromatography on a silica gel column (5:95 ethyl acetate:hexane)

Sources & evidence

ORD record
ord-6fbeb336356947ea9aa4ad3a0f377ec9
Source dataset
uspto-grants-2014_09
Patent number
US08846951B2

Linked notes

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