Hydrochloric Acid → Di-tert-butyl (3-fluoro-4-nitrophenyl)malonate

HRID 1372606ノート

反応式

HRID 1372606 の反応式
[F:1][C:2]1[CH:7]=[C:6](F)[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[C:12]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])(=[O:21])[CH2:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15].[H-].[Na+].Cl>C1COCC1>[F:1][C:2]1[CH:7]=[C:6]([CH:13]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[C:12]([O:22][C:23]([CH3:26])([CH3:24])[CH3:25])=[O:21])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10]

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 679672,4-DifluoronitrobenzeneHCID 68324Di-tert-butyl malonate

生成物 1

HCID 67407431Di-tert-butyl (3-fluoro-4-nitrophenyl)malonate収率 13.3%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

In THF (400 ml) were dissolved 2,4-difluoronitrobenzene (17.4 g, 109 mmol) and di-tert-butyl malonate (27.0 ml, 120 mmol). Under stirring at 0° C., sodium hydride (60% in oil, 4.82 g, 120 mmol) was added in portions. The reaction mixture was then stirred overnight at room temperature. The reaction mixture was poured in 1.0N-HCl (300 ml), followed by extraction with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent. The residue was purified by chromatography on a silica gel column, whereby from hexane-ethyl acetate (20:1 to 10:1) eluate fractions, di-tert-butyl (3-fluoro-4-nitrophenyl)malonate (5.17 g, 13%) was obtained as a pale yellow oil.

後処理

  1. stirringThe reaction mixture was then stirred overnight at room temperature
  2. extractionfollowed by extraction with ethyl acetate
  3. washThe extract was washed with saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. distillationdistilled under reduced pressure
  6. customto remove the solvent
  7. customThe residue was purified by chromatography on a silica gel column, whereby from hexane-ethyl acetate (20:1 to 10:1) eluate fractions

出典と根拠

ORDレコード
ord-3c7d02f449d74491a5c4769793bb2997
出典データセット
uspto-grants-2007_01
特許番号
US07157487B2

反応ノート

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