Benzoyl Peroxide → 2-(Bromomethyl)-4-fluorobenzonitrile

HRID 505695

反応式

HRID 505695 の反応式
[CH3:1][C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[Br:11]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[Br:11][CH2:1][C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5]

参加物

5

反応物 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 38260554-Fluoro-2-methylbenzonitrile

生成物 1

HCID 219849902-(Bromomethyl)-4-fluorobenzonitrile収率 25%

試薬・触媒・溶媒 1

HCID 5943Carbon Tetrachloride溶媒

実験手順

A solution of 2-methyl-4-fluoro-benzonitrile (3.5 g, 25.9 mmol) in 40 mL of carbon tetrachloride was treated with N-Bromosuccinimide (4.6 g, 25.9 mmol) and benzoylperoxide (157 mg, 0.65 mmol). The mixture was heated to reflux for 3 hours, cooled to room temperature and allowed to stir overnight. The solids were filtered off and washed with carbon tetrachloride. The filtrate was condensed and purified by normal phase flash column chromatography on a 50 g silica gel column (5-50% ethyl acetate/hexanes gradient). Two peaks separated. It was determined that the second eluting peak is the desired product. Pure fractions of this peak were pooled and concentrated in vacuo to yield 2-(bromomethyl)-4-fluorobenzonitrile (1.35 g, 0.63 mmol, 25% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 4.79 (s, 2H), 7.44 (dt, J=8.59, 2.69 Hz, 1H), 7.68 (dd, J=9.53, 2.55 Hz, 1H), 8.01 (dd, J=8.59, 5.64 Hz, 1H).

後処理

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 3 hours
  3. filtrationThe solids were filtered off
  4. washwashed with carbon tetrachloride
  5. customcondensed
  6. custompurified by normal phase flash column chromatography on a 50 g silica gel column (5-50% ethyl acetate/hexanes gradient)
  7. customTwo peaks separated
  8. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-15e7e22a8e164223882fa189072229dc
出典データセット
uspto-grants-2010_08
特許番号
US07781428B2

関連ノート

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