4-Fluoroaniline → alpha-Ethynyl-N-(p-fluorophenyl)-benzenemethanamine

HRID 14425

反応式

HRID 14425 の反応式
C(=O)([O-])O[CH2:3][CH:4]=[CH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[F:14][C:15]1[CH:21]=[CH:20][C:18]([NH2:19])=[CH:17][CH:16]=1>>[C:4]([CH:5]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[NH:19][C:18]1[CH:20]=[CH:21][C:15]([F:14])=[CH:16][CH:17]=1)#[CH:3]

参加物

3

反応物 2

HCID 97314-FluoroanilineHCID 71446589Cinnamyl carbonate

生成物 1

HCID 86607477alpha-Ethynyl-N-(p-fluorophenyl)-benzenemethanamine収率 97%

実験手順

The general procedure was followed with cinnamyl carbonate (0.188 g, 0.979 mmol) and p-fluoroaniline (0.130 g, 1.17 mmol). The reaction was conducted at room temperature for 12 h. 1H NMR analysis of the crude reaction mixture indicated the ratio of regioisomers to be 95/5. The mixture was purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes) to give the title compound (0.214 g, 96%). HPLC analysis indicated the enantiomeric excess of the product was 94% [Diacel CHIRALCEL OD-H (0.46 cm×25 cm); hexane/2-propanol=99.75/0.25; flow rate=0.6 mL/min; detection wavelength=254 nm; TR=22.5 (major), 29.4 (minor) min]: [α]DRT=(c, CHCl3). 1H NMR (400.13 MHz, CDCl3) δ 7.48-7.41 (m, 4H), 7.39-7.34 (m, 1H), 6.96-6.89 (m, 2H), 6.63-6.56 (m, 2H), 6.11 (ddd, J=16.8, 10.4, 6.0 Hz, 1H), 5.36 (dt, J=17.2, 1.2 Hz, 1H), 5.31 (dt, J=10.0, 1.2 Hz, 1H), 4.95 (d, J=5.6 Hz, 1H), 4.02 (br s, 1H). 13C NMR (100.59 MHz, CDCl3) δ 155.76 (d. J=234 Hz), 143.44 (d, J=2.3 Hz), 141.61, 128.71, 127.45, 127.03, 116.03, 115.44 (d, J=22.1 Hz), 114.30 (d, J=8.4 Hz), 61.36. Anal. Calcd for C15H14NF: C, 79.27; H, 6.21; N, 6.16; F, 8.36. Found: C, 79.16; H, 6.24; N, 6.24; F, 8.46.

後処理

  1. custom1H NMR analysis of the crude reaction mixture
  2. customThe mixture was purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-23c0e8f329fc43b0a996c074c7283b93
出典データセット
uspto-grants-2010_06
特許番号
US07732365B2

関連ノート

読み込み中…