Azobisisobutyronitrile → 2-Bromomethyl-3-fluoro-6-nitro-benzoic acid methyl ester

HRID 604263ノート

反応式

HRID 604263 の反応式
[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([F:13])[C:5]=1[CH3:14].[Br:16]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([F:13])[C:5]=1[CH2:14][Br:16]

参加物

5

反応物 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 59849164Methyl 3-fluoro-2-methyl-6-nitrobenzoate

生成物 1

HCID 598492172-Bromomethyl-3-fluoro-6-nitro-benzoic acid methyl ester収率 54%

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 suspension of 3-fluoro-2-methyl-6-nitro-benzoic acid methyl ester (6.1 g, 28.6 mmol) and N-bromosuccinimide in 70 mL of CCl4 is added 2,2′-azobisisobutyronitrile at room temperature under nitrogen atmosphere. The reaction mixture is stirred at 85° C. for 6 hours under N2, then cooled to room temperature and filtrated. The filtrate is extracted with CH2Cl2 and washed with aqueous NaHCO3 solution followed by brine, dried over Na2SO4, filtered and evaporated in vacuo. The residue is purified by silica gel column chromatography (n-hexane:ethyl acetate=4:1) to afford the 2-bromomethyl-3-fluoro-6-nitro-benzoic acid methyl ester (4.48 g, 15.3 mmol, 54%) as yellow oil. 1H-NMR (400 MHz, δ, ppm) CDCl3: 4.01 (s, 3H), 4.53 (d, 2H), 7.31 (dd, 1H), 8.17 (dd, 1H).

後処理

  1. temperaturecooled to room temperature
  2. filtrationfiltrated
  3. extractionThe filtrate is extracted with CH2Cl2
  4. washwashed with aqueous NaHCO3 solution
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customevaporated in vacuo
  8. customThe residue is purified by silica gel column chromatography (n-hexane:ethyl acetate=4:1)

出典と根拠

ORDレコード
ord-80d4feb0551e4a54aecb612d0f5cd661
出典データセット
uspto-grants-2011_03
特許番号
US07910585B2

反応ノート

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