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Ethyl Acetate → (E)-(3-Fluoro-6H-dibenzo[b,e]oxepin-11-ylidene)-acetic acid ethyl ester

HRID 244343
ノート
印刷プレビュー

反応式

HRID 244343 の反応式
CN1C(=O)CCC1.C([O-])(=O)C.[Na+].[CH2:13]([O:15][C:16](=[O:35])[CH:17]=[CH:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1[CH2:25][O:26][C:27]1[CH:32]=[C:31]([F:33])[CH:30]=[CH:29][C:28]=1Br)[CH3:14].C(OCC)(=O)C>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[CH2:13]([O:15][C:16](=[O:35])/[CH:17]=[C:18]1/[C:28]2[CH:29]=[CH:30][C:31]([F:33])=[CH:32][C:27]=2[O:26][CH2:25][C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][C:19]/1=2)[CH3:14]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 8857Ethyl AcetateHCID 13387N-methyl-2-pyrrolidoneHCID 517045Sodium AcetateHCID 671334433-[2-(2-Bromo-5-fluoro-phenoxymethyl)-phenyl]-acrylic acid ethyl ester

生成物 1

HCID 67333776(E)-(3-Fluoro-6H-dibenzo[b,e]oxepin-11-ylidene)-acetic acid ethyl ester収率 64%

試薬・触媒・溶媒 2

HCID 74236
Tetrabutylammonium Bromide
触媒
HCID 962Water溶媒

反応条件

温度
55 °C

実験手順

To a clean, dry 100-gallon reactor with stirring under nitrogen add N-methyl pyrrolidinone (83.4 L), sodium acetate (2.706 kg, 32.98 mol), 3-[2-(2-bromo-5-fluoro-phenoxymethyl)-phenyl]-acrylic acid ethyl ester (9.256 kg, 21.99 mol) and tetrabutylammonium bromide (7.088 kg, 21.99). Initiate stirring and de-gas the reaction mixture under full vacuum for 30 min, purging with nitrogen. Allow the reactor to return to ambient pressure under nitrogen and repeat the degassing procedure. Add palladium (II) acetate (167 g, 2% weight) to the reaction mixture. Heat the reaction to between 100° C. and 125° C., stirring for a minimum of 3 to 5 h. Add ethyl acetate (100 L) and stir 30 min. Add water (100 L) and stir 30 min. Discontinue stirring and allow the layers to separate for a minimum of one hour. Collect the organic layer and extract the aqueous layer with ethyl acetate (50 L, then 25 L). Combine the organic portions and wash with water (40 L), a 20% aqueous sodium chloride solution (2×20 L), stirring for a minimum of 30 min each and allowing at least 30 min for layer separation. Dry the organic solution with magnesium sulfate (8.0 kg) and add activated carbon (2.0 kg) and silica gel 60 (2.0 kg), stirring for a minimum of one hour. Filter to remove the solids. Concentrate the filtrate to dryness under vacuum at <35° C. Add methanol (20 L) to the solid residue and heat the mixture to a clear solution at 50-60° C. Add heptane (40 L) and cool to between 20° C. and 25° C. Continue to further cool the reaction mixture to −10° C. over a minimum of 3 h. Stir at −10° C. for a minimum of 12 h. Filter to collect the resulting solid product, washing with a mixture of heptane:methanol, (75:25) (2×20 L). Dry the solids under vacuum at <40° C. to a constant weight to obtain the title compound (3.7 kg, 64%).

後処理

  1. customTo a clean, dry 100-gallon reactor
  2. stirringInitiate stirring
  3. customde-gas the reaction mixture under full vacuum for 30 min
  4. custompurging with nitrogen
  5. temperatureHeat
  6. customthe reaction to between 100° C. and 125° C.
  7. stirringstirring for a minimum of 3 to 5 h
  8. stirringDiscontinue stirring
  9. customto separate for a minimum of one hour
  10. customCollect the organic layer
  11. extractionextract the aqueous layer with ethyl acetate (50 L
  12. washCombine the organic portions and wash with water (40 L)
  13. stirringa 20% aqueous sodium chloride solution (2×20 L), stirring for a minimum of 30 min each and
  14. customallowing at least 30 min for layer separation
  15. dry with materialDry the organic solution with magnesium sulfate (8.0 kg)
  16. additionadd activated carbon (2.0 kg) and silica gel 60 (2.0 kg)
  17. stirringstirring for a minimum of one hour
  18. filtrationFilter
  19. customto remove the solids
  20. concentrationConcentrate the filtrate to dryness under vacuum at <35° C
  21. temperatureAdd heptane (40 L) and cool to between 20° C. and 25° C
  22. temperatureto further cool the reaction mixture to −10° C. over a minimum of 3 h
  23. stirringStir at −10° C. for a minimum of 12 h
  24. filtrationFilter
  25. customto collect the resulting solid product
  26. washwashing with a mixture of heptane
  27. customDry the solids under vacuum at <40° C. to a constant weight

出典と根拠

ORDレコード
ord-d04c2f999d804d408f6ceb65467ae1ca
出典データセット
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08658638B2

反応ノート

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