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

HRID 84937

反応式

HRID 84937 の反応式
[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

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

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]+.

後処理

  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)

出典と根拠

ORDレコード
ord-6fbeb336356947ea9aa4ad3a0f377ec9
出典データセット
uspto-grants-2014_09
特許番号
US08846951B2

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