Stannous Chloride → tert-Butyl 1-(3-amino-4-chlorobenzyl)-2,2-difluorocyclopropanecarboxylate

HRID 1475628ノート

反応式

HRID 1475628 の反応式
[Cl:1][C:2]1[CH:20]=[CH:19][C:5]([CH2:6][C:7]2([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:9][C:8]2([F:11])[F:10])=[CH:4][C:3]=1[N+:21]([O-])=O.[Sn](Cl)Cl.[F-].[K+]>O1CCOCC1.Cl>[NH2:21][C:3]1[CH:4]=[C:5]([CH:19]=[CH:20][C:2]=1[Cl:1])[CH2:6][C:7]1([C:12]([O:14][C:15]([CH3:18])([CH3:16])[CH3:17])=[O:13])[CH2:9][C:8]1([F:11])[F:10]

参加物

6

反応物 3

HCID 24479Stannous ChlorideHCID 522689Potassium FluorideHCID 68170286(+/-)-Tert-butyl 1-(4-chloro-3-nitrobenzyl)-2,2-difluorocyclopropane-carboxylate

生成物 1

HCID 68170287tert-Butyl 1-(3-amino-4-chlorobenzyl)-2,2-difluorocyclopropanecarboxylate

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
70 °C

実験手順

1.60 g (4.60 mmol) of (+/−)-tert-butyl 1-(4-chloro-3-nitrobenzyl)-2,2-difluorocyclopropanecarboxylate were dissolved in 20 ml of dioxane, and 4.36 g (23.0 mmol) of tin(II) chloride and a few drops of 1 N hydrochloric acid were added at RT. The reaction mixture was heated at 70° C. for 1 h. After cooling to RT, 10 ml of 10% strength aqueous potassium fluoride solution were added. The mixture was extracted three times with ethyl acetate, and the combined organic phases were dried over magnesium sulphate and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 50:1→10:1). This gave 1.16 g of the target product (79.3% of theory).

後処理

  1. temperatureAfter cooling to RT
  2. extractionThe mixture was extracted three times with ethyl acetate
  3. dry with materialthe combined organic phases were dried over magnesium sulphate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 50:1→10:1)

出典と根拠

ORDレコード
ord-1ffbbb596b87490384a5f5e0ee0c88eb
出典データセット
uspto-grants-2015_04
特許番号
US09018258B2

反応ノート

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