2-Fluoroaniline → Bis(2-fluorophenyl)amine

HRID 916891ノート

反応式

HRID 916891 の反応式
[F:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].Br[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[F:16].C1C=CC(P(C2C(OC3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=CC=3)=CC=CC=2)C2C=CC=CC=2)=CC=1.CC([O-])(C)C.[Na+]>CC([O-])=O.CC([O-])=O.[Pd+2].C1(C)C=CC=CC=1>[F:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH:4][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[F:16]

参加物

7

反応物 4

HCID 95842-FluoroanilineHCID 612591-Bromo-2-fluorobenzeneHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 23676156Sodium t-butoxide

生成物 1

HCID 12160182Bis(2-fluorophenyl)amine

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 1140Toluene溶媒

実験手順

A Schlenk flask was charged with 2-fluoroaniline (5.55 g, 50 mmol), 1-bromo-2-fluorobenzene (8.75 g, 50 mmol), Pd(OAc)2 (0.020 g, 0.089 mmol, 0.5% equiv), DPEPhos (0.216 g, 0.401 mmol, 0.75% equiv), NaOtBu (7.185 g, 74.84 mmol, 1.4 equiv), and toluene (45 mL) under nitrogen. The reaction mixture was heated to reflux with stirring. The reaction was monitored by GC, which showed complete formation of the desired product in 1 d. After being cooled to room temperature, the reaction was quenched with deionized water (45 mL). The organic portion was separated from the aqueous layer, which was further extracted with toluene (10 mL×2). The combined organic solution was dried over MgSO4 and filtered. All volatiles were removed in vacuo to yield red oil, which was directly used for the subsequent reaction; yield 9.38 g (91.4%). 1H NMR (CDCl3, 500 MHz) δ 7.42 (m, 2, Ar), 7.25 (m, 2, Ar), 7.20 (m, 2, Ar), 7.04 (m, 2, Ar), 6.03 (br s, 1, NH). 19F NMR (CDCl3, 470.5 MHz) δ−133.07. 13C NMR (CDCl3, 125 MHz) δ 153.45 (JCF=241, CF), 130.45 (JCF=11.75, CN), 124.14 (JCF=3.63, CH), 121.38 (JCF=7.25, CH), 117.98 (CH), 115.45 (JCF=19.00, CH). LR-MS (EI): calcd. for C12H9F2N m/z 205, found m/z 205. Anal. Calcd. for C12H9F2N: C, 70.24; H, 4.42; N, 6.83. Found: C, 70.13; H, 4.52; N, 6.69.

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux

出典と根拠

ORDレコード
ord-76ce20ad569949b6bcd432a52e71a233
出典データセット
uspto-grants-2007_09
特許番号
US07271276B2

反応ノート

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