2-Fluoroaniline → Bis(2-fluorophenyl)amine

HRID 1988069노트

반응식

HRID 1988069 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

HCID 12160182Bis(2-fluorophenyl)amine

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 1140Toluene용매

실험 절차

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.

후처리

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux

출처 및 근거

ORD 기록
ord-cc8db4e4f2ab4ab49336e75d0c8a9b3a
출처 데이터셋
uspto-grants-2009_06
특허 번호
US07553924B2

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