2-Bromoaniline → alpha-Ethynyl-N-(o-bromophenyl)-benzenemethanamine

HRID 14422

Reaktionsgleichung

Reaktionsgleichung von HRID 14422
C(=O)([O-])O[CH2:3][CH:4]=[CH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[Br:14][C:15]1[CH:21]=[CH:20][CH:19]=[CH:18][C:16]=1[NH2:17]>>[C:4]([CH:5]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[NH:17][C:16]1[CH:18]=[CH:19][CH:20]=[CH:21][C:15]=1[Br:14])#[CH:3]

Komponenten

3

Edukt 2

HCID 119922-BromoanilineHCID 71446589Cinnamyl carbonate

Produkt 1

HCID 86607475alpha-Ethynyl-N-(o-bromophenyl)-benzenemethanamineAusbeute 66 %

Versuchsvorschrift

The general procedure was followed with cinnamyl carbonate (0.188 g, 0.979 mmol) and o-bromoaniline (0.215 g, 1.25 mmol). The reaction was conducted at room temperature for 16 h. 1H NMR analysis of the crude reaction mixture indicated the ratio of regioisomers to be 93/7. The mixture was purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes) to give the title compound (0.185 g, 66%). 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/1 min; detection wavelength=254 nm; TR=14.8 (minor), 23.9 (major) min]: [α]DRT=(c, CHCl3). 1H NMR (400.13 MHz, CDCl3) δ 7.46-7.25 (m, 6H), 7.07 (td, J=7.6, 0.8 Hz, 1H), 6.55 (t, J=7.6 Hz, 2 H), 6.07 (ddd, J=16.8, 10.4, 6.0 Hz, 1H), 5.27 (d, J=10.0 Hz, 1H), 5.24 (t, J=1.2 Hz, 1H), 4.98 (t, J=5.6 Hz, 1H), 4.75 (d, J=5.2 Hz, 1H). 13C NMR (100.59 MHz, CDCl3) δ 143.82, 141.13, 138.58, 132.26, 128.79, 128.26, 127.54, 126.94, 118.05, 116.25, 112.71, 109.91, 60.53. Anal. Calcd for C15H14NBr: C, 62.52; H, 4.90; N, 4.86; Br, 27.73. Found: C, 62.77; H, 4.92; N, 4.87; Br, 27.46.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-657f5b5be837443eb075762dc5f35ed2
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07732365B2

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