4-Bromoanisole → 1-(5-Bromo-2-hydroxyphenyl)-2-o-tolylethanone

HRID 239610

反応式

HRID 239610 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][C:9]([OH:11])=O.C(Cl)(=O)C(Cl)=O.[Br:18][C:19]1[CH:24]=[CH:23][C:22]([O:25]C)=[CH:21][CH:20]=1.[Al+3].[Cl-].[Cl-].[Cl-]>ClCCl.CN(C=O)C>[Br:18][C:19]1[CH:20]=[CH:21][C:22]([OH:25])=[C:23]([C:9](=[O:11])[CH2:8][C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[CH3:1])[CH:24]=1

参加物

7

反応物 4

HCID 77304-BromoanisoleHCID 65578Oxalyl chlorideHCID 69519o-Tolylacetic acidHCID 6451240Aluminum(III) Chloride

生成物 1

HCID 532343631-(5-Bromo-2-hydroxyphenyl)-2-o-tolylethanone収率 33%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

2-Methylphenylacetic acid (9.60 g, 64.15 mmoles) was dissolved in 10 ml dichloromethane. To this mixture, oxalylchloride (7 ml, 80.19 mmoles) and DMF (3 drops) were added at 0° C. and stirred for 30 min. The solvent was evaporated and dissolved in 100 ml dichloromethane. To this mixture, 4-bromoanisole (10 g, 53.47 mmoles) was added and cooled to 0° C. At 0° C. AlCl3 (10.6 g, 80.19 mmoles) was added and the reaction mixture was warmed to RT and stirred for 24 h. The reaction mixture was quenched by the addition of 2N HCl and extracted with ethyl acetate, dried over sodium sulphate and concentrated. The crude product was purified by column chromatography with ethyl acetate: petroleum ether to afford the title compound as white solid (5.5 g, 33% yield. 1H-NMR (δ ppm, DMSO-d6, 400 MHz): δ 11.52(s,1H), 8.02(d, J=2.4 Hz, 1H), 7.65(dd, J=8.8, 2.5 Hz, 1H), 7.16(m, 4H), 6.97(d, J=8.9 Hz, 1H), 4.47(s, 2H), 2.14(s, 3H).

後処理

  1. customThe solvent was evaporated
  2. dissolutiondissolved in 100 ml dichloromethane
  3. customAt 0° C
  4. temperaturethe reaction mixture was warmed to RT
  5. stirringstirred for 24 h
  6. customThe reaction mixture was quenched by the addition of 2N HCl
  7. extractionextracted with ethyl acetate
  8. dry with materialdried over sodium sulphate
  9. concentrationconcentrated
  10. customThe crude product was purified by column chromatography with ethyl acetate

出典と根拠

ORDレコード
ord-7584a19b4fdd4b498a1059ad21bb3e7e
出典データセット
uspto-grants-2014_02
特許番号
US08642607B2

関連ノート

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