Ethyl bromoacetate → (9-Cyano-9H-xanthen-9-yl)-acetic acid ethyl ester

HRID 393258

反応式

HRID 393258 の反応式
[CH:1]1[C:14]2[CH:13]([C:15]#[N:16])[C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[O:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.C([Li])CCC.[CH3:22][CH2:23][O:24][C:25]([CH2:27]Br)=[O:26]>CCOCC>[CH2:23]([O:24][C:25](=[O:26])[CH2:27][C:13]1([C:15]#[N:16])[C:14]2[CH:1]=[CH:2][CH:3]=[CH:4][C:5]=2[O:6][C:7]2[C:12]1=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH3:22]

参加物

5

反応物 3

HCID 7748Ethyl bromoacetateHCID 133395799H-xanthene-9-carbonitrileHCID 178418339Butyllithium

生成物 1

HCID 12132644(9-Cyano-9H-xanthen-9-yl)-acetic acid ethyl ester収率 64%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

実験手順

9H-Xanthene-9-carbonitrile [27] (1.0 g, 4.825 mmol) was dissolved in anhydrous Et2O and cooled in an icebath. n-Butyl lithium (1.93 mL, 6.75 mmol. 2.5M soln. in hexanes) was added dropwise over 10 min. with continuos stirring. Stirring was continued for 30 min. at the same temperature and then brought to room temperature. The reaction mixture was heated at reflux (1 hr), cooled in an icebath and ethyl bromo acetate (0.75 mL, 6.755 mmol) was added dropwise via syringe. The resulting mixture was heated at reflux (4 h) cooled and filtered. The residue was washed with ether (25 mL). Water (25 mL) was added to the filterate and the organic layer was separated. The aqueous layer was once again extracted with ether (25 mL). The combined ether extracts were washed with water and brine, dried (MgSO4) and evaporated under reduced pressure to give an oil which was purified by mplc using pet. ether: EtOAc (9:1) as eluent to give 0.9 g (64%) of the product as a colorless oil. 1H NMR (CDCl3)d: 1.04-1.08 (t, J=7.5 Hz, CH3), 3.01 (s, 2H, CH2), 3.90-3.99 (q, 2H, CH2), 7.14-7.69 (m, 8H, Ar—H). 13C NMR (CDCl3)d: 13.54, 39.06, 48.47, 60.85, 116.88, 118.90, 119.75, 123.81, 127.34, 129.83, 150.30, 166.98.

後処理

  1. temperaturecooled in an icebath
  2. stirringStirring
  3. custombrought to room temperature
  4. temperatureThe reaction mixture was heated
  5. temperatureat reflux (1 hr)
  6. additionwas added dropwise via syringe
  7. temperatureThe resulting mixture was heated
  8. temperatureat reflux (4 h)
  9. temperaturecooled
  10. filtrationfiltered
  11. washThe residue was washed with ether (25 mL)
  12. additionWater (25 mL) was added to the filterate
  13. customthe organic layer was separated
  14. extractionThe aqueous layer was once again extracted with ether (25 mL)
  15. washThe combined ether extracts were washed with water and brine
  16. dry with materialdried (MgSO4)
  17. customevaporated under reduced pressure
  18. customto give an oil which
  19. customwas purified by mplc

出典と根拠

ORDレコード
ord-cae741d50de44b61b2303b339992ea17
出典データセット
uspto-grants-2004_10
特許番号
US06806283B2

関連ノート

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