Dimethyl Sulfoxide → Methyl 4-fluoro-1-benzothiophene-2-carboxylate

HRID 343880

Reaktionsgleichung

Reaktionsgleichung von HRID 343880
CS(C)=O.F[C:6]1[CH:13]=[CH:12][CH:11]=[C:10]([F:14])[C:7]=1[CH:8]=O.C(N(CC)CC)C.[C:22]([O:26][CH3:27])(=[O:25])[CH2:23][SH:24]>ClCCl.CCCCCC>[F:14][C:10]1[C:7]2[CH:8]=[C:23]([C:22]([O:26][CH3:27])=[O:25])[S:24][C:6]=2[CH:13]=[CH:12][CH:11]=1

Komponenten

6

Edukt 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 16907Methyl ThioglycolateHCID 1362842,6-Difluorobenzaldehyde

Produkt 1

HCID 2783209Methyl 4-fluoro-1-benzothiophene-2-carboxylateAusbeute 78 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 21226440Methylenechloride HexaneLösungsmittel

Versuchsvorschrift

A 100 ml 3-necked round-bottomed flask, reflux condenser, thermometer adapter, gas inlet, and Teflon stirrer were oven-dried for 12 hours at 160° C. The apparatus was rapidly assembled, fitted with a thermometer, flushed with dry nitrogen gas, sealed with rubber septa, and allowed to cool to room temperature. The cooled reaction flask was charged with anhydrous dimethyl sulfoxide (40 ml), 2, 6-difluorobenzaldehyde (5 g, 35.18 mmole), anhydrous triethylamine (2.5 equivalents, 87.95 mmole, 8,952 g, 12.33 ml) and methyl thioglycolate (1.1 equivalents, 4.10 g, 38.70 mmole). The mixture was heated to 75° C. with rapid stirring. The progress of the reaction was monitored by TLC (silica, 10% dichloromethane-hexane, UV visualization). After 19 hours the reaction mixture was cooled to room temperature and poured onto an ice/water mixture (250 ml). The resulting slurry was stirred for 20 minutes, filtered, washed with cold water (2×100 ml) and dried in vacuo to give 5.76 g (78%) of methyl 4-fluorobenzo[b]thiophene-2-carboxylate. See, A. J. Bridges, A. Lee, E. C. Madukor, and C. E. Schwartz, Tetrahedron Letters, 33:7499 (1992).

Aufarbeitung

  1. temperatureA 100 ml 3-necked round-bottomed flask, reflux condenser, thermometer adapter, gas inlet, and Teflon stirrer
  2. customwere oven-dried for 12 hours at 160° C
  3. customfitted with a thermometer
  4. customflushed with dry nitrogen gas
  5. customsealed with rubber septa
  6. customThe cooled reaction flask
  7. temperatureThe mixture was heated to 75° C. with rapid stirring
  8. temperatureAfter 19 hours the reaction mixture was cooled to room temperature
  9. filtrationfiltered
  10. washwashed with cold water (2×100 ml)
  11. customdried in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-a3bd888ae3aa4e15aa9811b59f9544d0
Quelldatensatz
uspto-grants-1999_01
Patentnummer
US05863936

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