Ethyl Thioglycolate → Ethyl 4-phenyl-5-(trifluoromethyl)thiophene-2-carboxylate

HRID 552267Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 552267
[SH:1][CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].Cl[C:9]([C:19]([F:22])([F:21])[F:20])=[C:10]([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[CH:11]=O>C1COCC1.O.[OH-].[Na+]>[CH2:6]([O:5][C:3]([C:2]1[S:1][C:9]([C:19]([F:20])([F:22])[F:21])=[C:10]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:11]=1)=[O:4])[CH3:7]

Komponenten

6

Edukt 2

HCID 12185Ethyl ThioglycolateHCID 533961223-Chloro-4,4,4-trifluoro-2-phenyl-but-2-enal

Produkt 1

HCID 2781475Ethyl 4-phenyl-5-(trifluoromethyl)thiophene-2-carboxylateAusbeute 56,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 14798Sodium HydroxideLösungsmittel2×

Versuchsvorschrift

To a solution of ethyl 2-mercaptoacetate (0.88 g, 6.75 mmol) in THF (45 mL) NaH (271 mg, 6.75 mmol, 60% in mineral oil) is added at −10° C. The mixture is stirred at 0° C. for 30 min before a solution of 3-chloro-4,4,4-trifluoro-2-phenyl-but-2-enal 1.32 g (4.5 mmol) in THF (5 mL) is added. The reaction mixture is stirred at it for 45 min, then treated with 2 N aq. NaOH (2 mL). Stirring is continued for 15 min and the mixture is diluted with water (100 mL) and 1 N aq. NaOH (15 mL). The mixture is extracted with diethyl ether (70 mL). The organic extract is dried over Na2SO4 and evaporated. The crude product is purified by prep. HPLC (Waters Xterra MS18, 75×30 mm, 10 μm, 10 to 95% acetonitrile in water containing 0.5% formic acid) to give 4-phenyl-5-trifluoromethyl-thiophene-2-carboxylic acid ethyl ester (760 mg) as a brownish oil, LC-MS: tR=1.12 min; 1H NMR (CDCl3): δ 7.75-7.72 (m, 1H), 7.42 (s, 5H), 4.39 (q, J=7.0 Hz, 2H), 1.40 (t, J=7.0 Hz, 3H).

Aufarbeitung

  1. additionis added
  2. stirringStirring
  3. waitis continued for 15 min
  4. extractionThe mixture is extracted with diethyl ether (70 mL)
  5. extractionThe organic extract
  6. dry with materialis dried over Na2SO4
  7. customevaporated
  8. customThe crude product is purified by prep

Quellen und Nachweise

ORD-Eintrag
ord-bd0bbe12910c41dcb25c780f3c68101c
Quelldatensatz
uspto-grants-2011_05
Patentnummer
US07951794B2

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