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 1965321노트

반응식

HRID 1965321 반응식
[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

참가 물질

5

반응물 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

생성물 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-carboxylate수율 61.4%

시약·촉매·용매 1

HCID 6569Methyl Ethyl Ketone용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-443256da51ea4b9dac2ff02129ba68e1
출처 데이터셋
uspto-grants-2013_04
특허 번호
US08415370B2

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