Dimethylformamide → (2-Chloro-6-cyano-naphthalen-1-yl)-acetic acid ethyl ester

HRID 639200ノート

反応式

HRID 639200 の反応式
[CH2:1]([O:3][C:4](=[O:25])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][C:12](OS(C(F)(F)F)(=O)=O)=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:24])[CH3:2].[CH3:26][N:27](C=O)C>C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].[C-]#N.[Zn+2].[C-]#N>[CH2:1]([O:3][C:4](=[O:25])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][C:12]([C:26]#[N:27])=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:24])[CH3:2]

参加物

5

反応物 2

HCID 6228DimethylformamideHCID 86623398(2-Chloro-6-trifluoromethanesulfonyloxy-naphthalen-1-yl)-acetic acid ethyl ester

生成物 1

HCID 68704275(2-Chloro-6-cyano-naphthalen-1-yl)-acetic acid ethyl ester

試薬・触媒・溶媒 2

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 11979704Tetrakis(triphenylphosphine)palladium触媒

反応条件

温度
125 °C

実験手順

(2-Chloro-6-trifluoromethanesulfonyloxy-naphthalen-1-yl)-acetic acid ethyl ester (3.59 g, 9.04 mmol) is dissolved in DMF (30 ml) under an atmosphere of argon. After addition of palladium(0) tetrakis(triphenylphosphane) (418 mg, 0.36 mmol) and zinc(II) cyanide (2.12 g, 18.09 mmol), the reaction mixture is heated to 125° C. After 1 h, TLC analysis indicates complete consumption of starting material. The suspension is cooled to RT and poured onto water. Extraction with EtOAc is followed by washing the organic layer with 1 M aqueous HCl, sat. aqueous NaHCO3 solution and brine. After drying over Na2SO4 and removal of solvent, purification by FCC (hexane/EtOAc 3:1) affords the title compound. 1H NMR (d6-DMSO, 400 MHz): δ 1.06 (t, J=8 Hz, 3H), 3.98 (q, J=8 Hz, 2H), 4.24 (s, 2H), 7.66 (d, J=10 Hz, 1H), 7.79 (d, J=10 Hz, 1H), 7.96 (d, J=10 Hz, 1H), 8.13 (d, J=10 Hz, 1H), 8.54 (s, 1H).

後処理

  1. customconsumption of starting material
  2. temperatureThe suspension is cooled to RT
  3. additionpoured onto water
  4. extractionExtraction with EtOAc
  5. washby washing the organic layer with 1 M aqueous HCl, sat. aqueous NaHCO3 solution and brine
  6. dry with materialAfter drying over Na2SO4 and removal of solvent, purification by FCC (hexane/EtOAc 3:1)

出典と根拠

ORDレコード
ord-d0ee6f39e8a54df08c987918d63e38b7
出典データセット
uspto-grants-2010_04
特許番号
US07691861B2

反応ノート

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