Sodium Carbonate → 4-Fluoro-2-nitro-1,1'-biphenyl

HRID 1776164

反応式

HRID 1776164 の反応式
Cl[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[C:12]1(B(O)O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].CCOCC>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

参加物

9

反応物 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 66827Phenylboronic AcidHCID 676591-Chloro-4-fluoro-2-nitrobenzene

生成物 1

HCID 113789504-Fluoro-2-nitro-1,1'-biphenyl収率 82.4%

試薬・触媒・溶媒 4

HCID 74236Tetrabutylammonium Bromide触媒HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒

反応条件

温度
165 °C

実験手順

A microwave reaction vessel was charged with 2-chloro-5-fluoronitrobenzene (0.175 g, 1 mmol), phenylboronic acid (0.134 g, 1.1 mmol), sodium carbonate (0.317 g, 3 mmol), palladium diacetate (0.009 g, 0.04 mmol), tetrabutylammonium bromide (0.322 g, 1 mmol) in water (2 mL). The mixture was heated to 165° C. in a microwave reactor for 7.5 minutes. The reaction was cooled and poured into ether and 0.1N aqueous sodium hydroxide. The ether layer was washed with saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated. The crude product was purified by silica gel column chromatography (5-30% methylene chloride in hexanes) to give the desired product as a pale yellow oil (0.179 g, 82%). 1H NMR (CDCl3, 300 MHz) δ 7.62-7.58 (dd, 1H, J=2.7, 8.1 Hz), 7.46-7.40 (m, 4H), 7.38-7.34 (m, 1H), 7.31-7.26 (m, 2H). HPLC analysis (C18, 5-95% acetonitrile in H2O+0.1% trifluoroacetic acid over 20 min: retention time, % area at 254 nm): 9.95 min, 96.3%.

後処理

  1. customA microwave reaction vessel
  2. temperatureThe reaction was cooled
  3. washThe ether layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried (anhydrous sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product was purified by silica gel column chromatography (5-30% methylene chloride in hexanes)

出典と根拠

ORDレコード
ord-44c15b57a1cb4f52be96b51a20434241
出典データセット
uspto-grants-2016_02
特許番号
US09265772B2

関連ノート

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