N-bromobutanimide → 1-(Bromomethyl)-4-methoxy-2-nitrobenzene

HRID 1914675ノート

反応式

HRID 1914675 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[Br:13]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl>[Br:13][CH2:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11]

参加物

4

反応物 2

HCID 67184N-bromobutanimideHCID 871374-Methyl-3-nitroanisole

生成物 1

HCID 37478301-(Bromomethyl)-4-methoxy-2-nitrobenzene収率 59.1%

試薬・触媒・溶媒 1

HCID 5943Carbon Tetrachloride溶媒

反応条件

温度
85 °C

実験手順

To a solution of 4-methyl-3-nitroanisole (16.53 mL; 119.64 mmol; 1 eq), in CCl4 (500 mL) is added N-bromosuccinimide (21.29 g; 119.64 mmol; 1 eq) and azoisobutyronitrile (392.9 mg; 2.39 mmol; 0.02 eq). The mixture is heated at 85° C. for 20 h. The solution is cooled down to room temperature and the precipitate of succinimide is removed by filtration. The filtrate is concentrated to afford a yellow oil. The oil crystallizes after one night at −25° C. It is redissolved in EtOAc (15 mL) and petroleum ether is added. After 2 h at −25° C., the compound recrystallizes. After filtration and washing with petroleum ether, the solid is dried under vacuum to afford 17.4 g (59%) of the title compound as a liquid. 1H NMR (DMSO-d6) δ 7.68 (d, J=8 Hz, 1H), 7.56 (d, J=3 Hz, 1H), 7.33 (dd, J=8.0, 3.0 Hz, 1H), 4.89 (s, 2H), 3.87 (s, 3H). HPLC (max plot) 99%; Rt 4.09 min.

後処理

  1. temperatureThe solution is cooled down to room temperature
  2. customthe precipitate of succinimide is removed by filtration
  3. concentrationThe filtrate is concentrated
  4. customto afford a yellow oil
  5. customThe oil crystallizes after one night at −25° C
  6. dissolutionIt is redissolved in EtOAc (15 mL)
  7. additionpetroleum ether is added
  8. customthe compound recrystallizes
  9. filtrationAfter filtration
  10. washwashing with petroleum ether
  11. customthe solid is dried under vacuum

出典と根拠

ORDレコード
ord-f239c2fc4bd14fdf83b92f423f9a9511
出典データセット
uspto-grants-2013_12
特許番号
US08614215B2

反応ノート

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