Water → 1-Bromo-5-fluoro-2-methyl-3-nitrobenzene

HRID 383254

反応式

HRID 383254 の反応式
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.S(=O)(=O)(O)O.C1C(=O)N([Br:24])C(=O)C1.O>FC(F)(F)C(O)=O>[Br:24][C:6]1[CH:7]=[C:2]([F:1])[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]=1[CH3:8]

参加物

6

反応物 4

HCID 962WaterHCID 1118Sulfuric AcidHCID 67184N-bromobutanimideHCID 679654-Fluoro-2-nitrotoluene

生成物 1

HCID 27733851-Bromo-5-fluoro-2-methyl-3-nitrobenzene収率 100%

試薬・触媒・溶媒 1

HCID 6422Trifluoroacetic acid溶媒

実験手順

To a solution of 4-fluoro-2-nitrotoluene (10.0 g, 64.4 mmol) in trifluoroacetic acid (40 mL) was added con. sulfuric acid (12.5 mL) followed by NBS (17.2 g, 96.6 mmol) and the reaction mixture was stirred at room temperature for 16 h. Then the reaction mixture was poured into ice and water and stirred for 15 min. Extracted with ethyl acetate and the organic layer was washed with brine, dried, concentrated to get compound 1-bromo-5-fluoro-2-methyl-3-nitrobenzene (15.0 g, 100%) as a yellow oil. 1H NMR (400 MHz, DMSO-d6) δ 2.41 (s, 3H), 7.96 (dd, J=8.0, 2.4 Hz, 1H), 8.02 (dd, J=8.0, 2.4 Hz, 1H). A mixture of above prepared compound (15.0 g, 64.4 mmol), Fe (18.0 g, 0.32 mol), con. HCl (2 mL) in MeOH (150 mL) and water (30 mL) was stirred at reflux for 4 h. Then the mixture was adjusted to pH 12 with aqueous NaOH solution and filtered. The solvent was removed and diluted with water. Extracted with ethyl acetate, dried, concentrated. The residue was purified by column chromatograph (ethyl acetate in petroleum ether, 7%) to get compound 0104-69 (5.8 g, 44%) as yellow oil. LCMS: 204 [M+1]+, 1H NMR (400 MHz, DMSO-d6) δ 2.12 (s, 3H), 5.57 (s, 2H), 6.45 (dd, J=11.2, 2.4 Hz, 1H), 6.60 (dd, J=8.0, 2.4 Hz, 1H).

後処理

  1. stirringstirred for 15 min
  2. extractionExtracted with ethyl acetate
  3. washthe organic layer was washed with brine
  4. customdried
  5. concentrationconcentrated

出典と根拠

ORDレコード
ord-75554ad10fdb4ce28f6470f3da4f36ea
出典データセット
uspto-grants-2013_02
特許番号
US08367663B2

関連ノート

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