Potassium Iodide → ethyl {3-[(2'-oxo-5,6-dihydrospiro[benzo[1,2-b:5,4-b']difuran-3,3'-indol]-1'(2'H)-yl)methyl]phenoxy}acetate

HRID 422866ノート

反応式

HRID 422866 の反応式
[OH:1][C:2]1[CH:3]=[C:4]([CH:27]=[CH:28][CH:29]=1)[CH2:5][N:6]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]2([CH2:18][O:17][C:16]3[CH:19]=[C:20]4[C:24](=[CH:25][C:15]2=3)[CH2:23][CH2:22][O:21]4)[C:7]1=[O:26].C(=O)([O-])[O-].[K+].[K+].Br[CH2:37][C:38]([O:40][CH2:41][CH3:42])=[O:39].[I-].[K+]>CN(C)C=O.C(OCC)(=O)C.O>[O:26]=[C:7]1[C:8]2([CH2:18][O:17][C:16]3[CH:19]=[C:20]4[C:24](=[CH:25][C:15]2=3)[CH2:23][CH2:22][O:21]4)[C:9]2[C:14](=[CH:13][CH:12]=[CH:11][CH:10]=2)[N:6]1[CH2:5][C:4]1[CH:3]=[C:2]([CH:29]=[CH:28][CH:27]=1)[O:1][CH2:37][C:38]([O:40][CH2:41][CH3:42])=[O:39]

参加物

8

反応物 4

HCID 4875Potassium IodideHCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 593525401'-(3-hydroxybenzyl)-5,6-dihydrospiro[benzo[1,2-b:5,4-b']difuran-3,3'-indol]-2'(1'H)-one

生成物 1

HCID 45280396ethyl {3-[(2'-oxo-5,6-dihydrospiro[benzo[1,2-b:5,4-b']difuran-3,3'-indol]-1'(2'H)-yl)methyl]phenoxy}acetate収率 93.5%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
40 °C

実験手順

To a stirred solution of 1′-(3-hydroxybenzyl)-5,6-dihydrospiro[benzo[1,2-b:5,4-b′]difuran-3,3′-indol]-2′(1′H)-one (0.46 g, 1.18 mmol) in N,N-dimethylformamide (4 mL) were added potassium carbonate (0.32 g, 2.36 mmol), ethyl bromoacetate (0.20 mL, 1.77 mmol), and potassium iodide (0.024 g, 0.14 mmol) at ambient temperature. The mixture was stirred at 40° C. for 16 h. Water (50 mL) and ethyl acetate (150 mL) were added to the mixture. The organic solution was separated and the aqueous layer was extracted with ethyl acetate (2×80 mL). The combined organic solution was washed with brine (100 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The residue was purified by column chromatography (hexanes/ethyl acetate from 2:1 to 1:1) to afford ethyl {3-[(2′-oxo-5,6-dihydrospiro[benzo[1,2-b:5,4-b′]difuran-3,3′-indol]-1′(2′H)-yl)methyl]phenoxy}acetate (0.52 g, 93%): mp 45-46° C.; 1H NMR (300 MHz, CDCl3) δ 7.30-7.15 (m, 3H), 7.06-6.96 (m, 2H), 6.90 (br s, 1H), 6.84-6.76 (m, 2H), 6.50 (s, 1H), 6.43 (s, 1H), 5.07-4.96 (m, 2H), 4.87-4.78 (m, 1H), 4.75-4.68 (m, 1H), 4.60-4.50 (m, 4H), 4.22 (q, J=7.1 Hz, 2H), 3.11-2.91 (m, 2H), 1.26 (t, J=7.1 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 177.9, 168.7, 161.8, 161.3, 158.2, 142.0, 137.6, 132.7, 130.0, 128.7, 123.8, 123.4, 120.7, 120.2, 119.9, 118.9, 114.0, 113.7, 109.2, 93.2, 80.6, 72.4, 65.4, 61.4, 57.7, 44.0, 29.0, 14.1; MS (ES+) m/z 471.9 (M+1).

後処理

  1. customThe organic solution was separated
  2. extractionthe aqueous layer was extracted with ethyl acetate (2×80 mL)
  3. washThe combined organic solution was washed with brine (100 mL)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by column chromatography (hexanes/ethyl acetate from 2:1 to 1:1)

出典と根拠

ORDレコード
ord-a0c53a2f00274e46bf54413300a28378
出典データセット
uspto-grants-2012_01
特許番号
US08101647B2

反応ノート

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