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

HRID 1531431Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1531431
[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

Komponenten

4

Edukt 2

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel

Reaktionsbedingungen

Temperatur
220 °C

Versuchsvorschrift

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).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-8f82ab5935d5453da652a1bfbadde460
Quelldatensatz
uspto-grants-2001_03
Patentnummer
US06197978B1

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