Formic Acid → [3-[4-Chloro-2-(2-fluorobenzoyl)-phenyl]-3-oxopropyl]-carbamic acid tert-butyl ester

HRID 513128

反応式

HRID 513128 の反応式
[C:1]([O:5][C:6](=[O:27])[NH:7][CH2:8][C:9]#[C:10][C:11]1[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][C:12]=1[C:18](=[O:26])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1[F:25])([CH3:4])([CH3:3])[CH3:2].C(O)=[O:29]>C(Cl)Cl.O.[NH4+].[OH-].S([O-])([O-])(=O)=O.[Hg+2]>[C:1]([O:5][C:6](=[O:27])[NH:7][CH2:8][CH2:9][C:10]([C:11]1[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][C:12]=1[C:18](=[O:26])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1[F:25])=[O:29])([CH3:4])([CH3:2])[CH3:3]

参加物

7

反応物 2

HCID 284Formic AcidHCID 67505268{3-[4-Chloro-2-(2-fluoro-benzoyl)-phenyl]-prop-2-ynyl}-carbamic acid tert-butyl ester

生成物 1

HCID 67505459[3-[4-Chloro-2-(2-fluorobenzoyl)-phenyl]-3-oxopropyl]-carbamic acid tert-butyl ester収率 95%

試薬・触媒・溶媒 4

HCID 24544Mercuric sulfate触媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 14923Ammonium Hydroxide溶媒

反応条件

温度
0 °C

実験手順

A solution of {3-[4-chloro-2-(2-fluoro-benzoyl)-phenyl]-prop-2-ynyl}-carbamic acid tert-butyl ester (9.2 g, 23 mmol) in CH2Cl2 (100 mL) containing formic acid (9.18 mL) was cooled to 0° C. Mercury(II) sulphate (2.1 g, 7.1 mmol) was added and the reaction stirred for 2 h at 0° C. The mixture was diluted with H2O (20 mL) and NH4OH (20 mL). The organic phase was collected and the aqueous phase was extracted with EtOAc (3×100 mL). The combined organic portions were washed with H2O, dried over MgSO4, filtered and the solvents evaporated in vacuo to afford [3-[4-chloro-2-(2-fluorobenzoyl)-phenyl]-3-oxopropyl]-carbamic acid tert-butyl ester 8.9 g (95%) as a brown solid. This material (8.9 g, 22 mmol) was dissolved in HCl (4N in dioxane, 185 mL) and stirred at room temperature for 30 min. The solution was then evaporated in vacuo. The residue was dissolved in CH2Cl2 (250 mL) and diisopropylethylamine amine (18 mL) was added. The solution was stirred at room temperature for 2 h. The solution was evaporated in vacuo and the residue purified by column chromatography (silica gel, 10 to 50% EtOAc/hexanes) to provide 4k (2.9 g, 46%) as a brown solid MS m/z=288 (M+H).

後処理

  1. customThe organic phase was collected
  2. extractionthe aqueous phase was extracted with EtOAc (3×100 mL)
  3. washThe combined organic portions were washed with H2O
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customthe solvents evaporated in vacuo

出典と根拠

ORDレコード
ord-ccd446c6f6fe4c64b373899017c3cb5e
出典データセット
uspto-grants-2015_08
特許番号
US09102678B2

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