Carbon Dioxide → 3-Bromo-6-chloro-2-fluorobenzoic acid

HRID 1270735ノート

反応式

HRID 1270735 の反応式
[Li].[Li]CCCC.C(NC(C)C)(C)C.[Br:14][C:15]1[CH:20]=[CH:19][C:18]([Cl:21])=[CH:17][C:16]=1[F:22].[C:23](=[O:25])=[O:24]>C1COCC1.C(=O)=O.CC(C)=O.CCOCC.Cl>[Cl:21][C:18]1[CH:19]=[CH:20][C:15]([Br:14])=[C:16]([F:22])[C:17]=1[C:23]([OH:25])=[O:24]

参加物

10

反応物 5

HCID 280Carbon DioxideHCID 7912DiisopropylamineHCID 1372751-Bromo-4-chloro-2-fluorobenzeneHCID 3028194LithiumHCID 178418339Butyllithium

生成物 1

HCID 217423273-Bromo-6-chloro-2-fluorobenzoic acid

試薬・触媒・溶媒 4

HCID 313Hydrochloric Acid溶媒HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒HCID 18522661Acetone cardice溶媒

反応条件

温度
-70 °C

実験手順

A solution of lithium diiosopropyl amide is generated by adding n-BuLi (360 mL of 2 M solution in THF) to diisopropylamine (73 g, 0.722 mol) in 500 mL of anhydrous THF while a reaction temperature of −60° C. is maintained by cooling in dry-ice acetone bath. After stirring for 30 minutes, 1-bromo-4-chloro-2-fluorobenzene (75 g, 0.36 mol) is added and stirring maintained at −70° C. for 2 hours. The cold solution is then transferred, via a cannula, under an inert atmosphere to a suspension of solid CO2 (100 g, excess) in anhydrous Et2O. The mixture is allowed to warm to room temperature with stirring and then the solvent removed by rotary evaporator. The residual solid is treated with 1 N HCl solution until pH=3.0 and the mixture is filtered. The white solid that is obtained is suspended in 1000 mL of 2 N HCl solution and stirred for an additional 1 hour. The suspension is filtered to collect a white solid which is air dried, suspended in 100 mL of hexanes and collected to give 2-chloro-5-bromo-6-fluorobenzoic acid.

後処理

  1. temperatureis maintained
  2. stirringstirring
  3. temperatureto warm to room temperature
  4. stirringwith stirring
  5. customthe solvent removed by rotary evaporator
  6. additionThe residual solid is treated with 1 N HCl solution until pH=3.0
  7. filtrationthe mixture is filtered
  8. customThe white solid that is obtained
  9. stirringstirred for an additional 1 hour
  10. filtrationThe suspension is filtered
  11. customto collect a white solid which
  12. customdried
  13. customcollected

出典と根拠

ORDレコード
ord-6c9ea5fcd81343a7acbd50557642ace7
出典データセット
uspto-grants-2007_04
特許番号
US07202364B2

反応ノート

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