Carbon tetrabromide → 2-Bromomethyl-4'-fluorobiphenyl

HRID 76857ノート

反応式

HRID 76857 の反応式
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[CH2:14]O)=[CH:4][CH:3]=1.C(Br)(Br)(Br)[Br:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[Br:17][CH2:14][C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=1[C:5]1[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=1

参加物

5

反応物 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 1392777(4'-Fluorobiphenyl-2-yl)methanol

生成物 1

HCID 114484672-Bromomethyl-4'-fluorobiphenyl

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

To a solution of (4′-fluorobiphenyl-2-yl)-methanol (2.58 g, 12.8 mmol) in CH2Cl2 (100 mL), carbon tetrabromide (7.40 g, 22.3 mmol) is added. The solution is cooled to 0° C. and then triphenylphosphine (7.53 g, 28.7 mmol) is added portionwise. The reaction is stirred at 0° C. for 1.5 h and then at room temperature for 90 h before the solvent is removed. The resulting residue is partitioned between Et2O and water and then filtered. The layers are separated and the aqueous layer is extracted with Et2O. The combined organic layers are washed with water, brine and dried over Na2SO4. After concentration, the residue is purified by flash chromatography (hexane) to give 2-bromomethyl-4′-fluorobiphenyl as an oil. (an alternative preparation appears in J. Med. Chem. 2004, 47(22), 5441) 1H NMR (400 MHz, CDCl3) δ 7.53-7.50 (m, 1H), 7.43-7.31 (m, 4H), 7.24-7.21 (m, 1H), 7.15-6.80 (m, 2H), 4.42 (s, 2H).

後処理

  1. customat room temperature for 90 h before the solvent is removed
  2. customThe resulting residue is partitioned between Et2O and water
  3. filtrationfiltered
  4. customThe layers are separated
  5. extractionthe aqueous layer is extracted with Et2O
  6. washThe combined organic layers are washed with water, brine
  7. dry with materialdried over Na2SO4
  8. concentrationAfter concentration
  9. customthe residue is purified by flash chromatography (hexane)

出典と根拠

ORDレコード
ord-87f8d6b1ac3c47f7b8541868052ab516
出典データセット
uspto-grants-2014_09
特許番号
US08835646B2

反応ノート

読み込み中…