N,N-Diethylaniline → Methyl 8-fluoro-2H-1-benzopyran-5-carboxylate

HRID 1531431ノート

反応式

HRID 1531431 の反応式
[F:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[O:12][CH2:13][C:14]#[CH:15].C(N(CC)C1C=CC=CC=1)C>C(OCC)C>[F:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]2[C:3]=1[O:12][CH2:13][CH:14]=[CH:15]2

参加物

4

反応物 2

HCID 7061N,N-DiethylanilineHCID 11138296Methyl 4-fluoro-3-(prop-2-yn-1-yloxy)benzoate

生成物 1

HCID 12016893Methyl 8-fluoro-2H-1-benzopyran-5-carboxylate

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

反応条件

温度
220 °C

実験手順

Methyl 4-fluoro-3-propargyloxybenzoate (14.0 g, 67.2 mmol) was mixed with N,N-diethylaniline and the reaction was heated to 220° C. for 5 hours. The black reaction mixture was allowed to cool, dissolved in diethyl ether (600 mL) and washed with 2 M HCl in portions (1 L). The aqueous washings were re-extracted with diethyl ether, the combined ether phases were washed with H2O until neutral, treated with brine, dried with MgSO4, filtered, and the solvent was removed in vacuo to give a dark brown crude residue. The crude solid was chromatographed on silica (eluent: methylene chloride/carbon tetrachloride 1:1) to give 11.9 g (85% yield) of a tannish yellow solid as the title compound (mp 73.5-74.5° C.). EIMS (70 eV) m/z (relative intensity) 208 (65, M+), 207 (42), 194 (12), 193 (100), 177 (32), 149 (10), 148 (12).

後処理

  1. customThe black reaction mixture
  2. temperatureto cool
  3. washwashed with 2 M HCl in portions (1 L)
  4. extractionThe aqueous washings were re-extracted with diethyl ether
  5. washthe combined ether phases were washed with H2O until neutral,
  6. additiontreated with brine
  7. dry with materialdried with MgSO4
  8. filtrationfiltered
  9. customthe solvent was removed in vacuo
  10. customto give a dark brown crude residue
  11. customThe crude solid was chromatographed on silica (eluent: methylene chloride/carbon tetrachloride 1:1)

出典と根拠

ORDレコード
ord-8f82ab5935d5453da652a1bfbadde460
出典データセット
uspto-grants-2001_03
特許番号
US06197978B1

反応ノート

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