Cesium carbonate → ethyl 5-[(2'-oxospiro[furo[2,3-f][1,3]benzodioxole-7,3'-indol]-1'(2'H)-yl)methyl]-2-(trifluoromethyl)furan-3-carboxylate

HRID 2385050Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2385050
[NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]2([C:13]3=[CH:14][C:15]4[O:19][CH2:18][O:17][C:16]=4[CH:20]=[C:12]3[O:11][CH2:10]2)[C:2]1=[O:21].C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:29][C:30]1[O:34][C:33]([C:35]([F:38])([F:37])[F:36])=[C:32]([C:39]([O:41][CH2:42][CH3:43])=[O:40])[CH:31]=1>CC(=O)CC>[O:21]=[C:2]1[C:3]2([C:13]3=[CH:14][C:15]4[O:19][CH2:18][O:17][C:16]=4[CH:20]=[C:12]3[O:11][CH2:10]2)[C:4]2[C:9](=[CH:8][CH:7]=[CH:6][CH:5]=2)[N:1]1[CH2:29][C:30]1[O:34][C:33]([C:35]([F:38])([F:36])[F:37])=[C:32]([C:39]([O:41][CH2:42][CH3:43])=[O:40])[CH:31]=1

Komponenten

5

Edukt 3

HCID 10796Cesium carbonateHCID 13237850Ethyl 5-(bromomethyl)-2-(trifluoromethyl)furan-3-carboxylateHCID 53375495spiro[furo[2,3-f][1,3]benzodioxole-7,3'-indol]-2'(1'H)-one

Produkt 1

HCID 68598357ethyl 5-[(2'-oxospiro[furo[2,3-f][1,3]benzodioxole-7,3'-indol]-1'(2'H)-yl)methyl]-2-(trifluoromethyl)furan-3-carboxylateAusbeute 61,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6569Methyl Ethyl KetoneLösungsmittel

Versuchsvorschrift

To a solution of spiro[furo[2,3-f][1,3]benzodioxole-7,3′-indol]-2′(1′H)-one (4.26 g, 15.10 mmol) in 2-butanone (120 mL) was added cesium carbonate (14.76 g, 45.30 mmol) and ethyl 5-(bromomethyl)-2-(trifluoromethyl)furan-3-carboxylate (Lyalin, V. V.; et al., Zhurnal Organicheskoi Khimii (1984), 20(4):846) (4.80 g, 15.90 mmol). The reaction mixture was heated at 60° C. to 70° C. for 18 h, cooled to ambient temperature and filtered. The solid was washed with ethyl acetate. The filtrate was concentrated in vacuo, the residue was purified by column chromatography with ethyl acetate and hexanes to afford ethyl 5-[(2′-oxospiro[furo[2,3-f][1,3]benzodioxole-7,3′-indol]-1′(2′H)-yl)methyl]-2-(trifluoromethyl)furan-3-carboxylate (4.65 g, 61%): mp 162-164° C.; 1H NMR (300 MHz, CDCl3) δ 7.23-7.17 (m, 2H), 7.12-7.06 (m, 1H), 6.94 (d, J=7.8 Hz, 1H), 6.76 (s, 1H), 6.50 (s, 1H), 5.86-5.85 (m, 2H), 5.05-4.87 (m, 3H), 4.68-4.64 (m, 1H), 4.31 (q, J=7.2 Hz, 2H), 1.32 (t, J=7.2 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 177.2, 160.4, 155.9, 150.6, 149.1, 143.5, 142.5, 141.1, 132.0, 129.1, 124.2, 124.0, 120.7, 120.0, 119.0, 116.4, 111.1, 108.7, 103.0, 101.6, 93.7, 80.4, 61.7, 58.2, 36.7, 13.9; MS (ES+) m/z 502.1 (M+1).

Aufarbeitung

  1. temperatureThe reaction mixture was heated at 60° C. to 70° C. for 18 h
  2. filtrationfiltered
  3. washThe solid was washed with ethyl acetate
  4. concentrationThe filtrate was concentrated in vacuo
  5. customthe residue was purified by column chromatography with ethyl acetate and hexanes

Quellen und Nachweise

ORD-Eintrag
ord-fbc523ce64fe45028d462b139768aae4
Quelldatensatz
uspto-grants-2012_09
Patentnummer
US08263606B2

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