Quinoline → Ethyl 5-cyano-1-benzothiophene-7-carboxylate

HRID 749430Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 749430
Cl([O-])(=O)(=O)=O.[C:6]([C:8](=[CH:13]N(C)C)[CH:9]=[N+](C)C)#[N:7].[S:17]1[CH:21]=[CH:20][CH:19]=[C:18]1[CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24].N1C2C(=CC=CC=2)C=CC=1.[O-]CC.[Na+]>Cl>[C:6]([C:8]1[CH:13]=[C:22]([C:23]([O:25][CH2:26][CH3:27])=[O:24])[C:18]2[S:17][CH:21]=[CH:20][C:19]=2[CH:9]=1)#[N:7]

Komponenten

6

Edukt 4

HCID 7047QuinolineHCID 93657Ethyl 2-thienylacetateHCID 2723922Sodium ethoxideHCID 53444588N-[2-cyano-3-(dimethylamino)prop-2-en-1-ylidene]-N-methylmethanaminium perchlorate

Produkt 1

HCID 68979189Ethyl 5-cyano-1-benzothiophene-7-carboxylateAusbeute 43 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 313Hydrochloric AcidLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

N-[2-cyano-3-(dimethylamino)prop-2-en-1-ylidene]-N-methylmethanaminium perchlorate (see Collect. Czech. Chem. Commun.; 32; 5; 1967; 1704; 5.84 g, 23.2 mmol) and ethyl 2-thienylacetate (3.95 g, 23.2 mmol) were mixed with quinoline (117 mL) at 0° C. Sodium ethoxide (1.97 g, 27.9 mmol) was added and the mixture was stirred at 0° C. for 30 min and then at room temperature for 15 min. The reaction mixture was heated to 75° C. under nitrogen for 5 h and then cooled to 0° C. Hydrochloric acid (200 mL of 2 M aqueous solution) was added and the mixture extracted thrice with chloroform. The organic solution was washed with brine and then dried over Na2SO4. The solvent was removed by evaporation and the residue flash chromatographed on silica gel (hexane-ethyl acetate, 8:1). There was obtained 2.3 g (43%) of ethyl 5-cyano-1-benzothiophene-7-carboxylate as a pale yellow solid. 1H NMR (300 MHz, CDCl3): 1.5 (t, 3H), 4.5 (qt, 2H), 7.5 (d, 1H), 7.7 (d, 1H), 8.3 (m, 2H).

Aufarbeitung

  1. waitat room temperature for 15 min
  2. temperatureThe reaction mixture was heated to 75° C. under nitrogen for 5 h
  3. temperaturecooled to 0° C
  4. extractionthe mixture extracted thrice with chloroform
  5. washThe organic solution was washed with brine
  6. dry with materialdried over Na2SO4
  7. customThe solvent was removed by evaporation
  8. customthe residue flash chromatographed on silica gel (hexane-ethyl acetate, 8:1)

Quellen und Nachweise

ORD-Eintrag
ord-e1b6cdee38834a8092581837ea43ee41
Quelldatensatz
uspto-grants-2008_07
Patentnummer
US07402581B2

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