1-Naphthylamine → alpha-Ethynyl-N-1-napthyl-benzenemethanamine

HRID 14429

Reaction equation

HRID 14429 reaction equation
C(=O)([O-])O[CH2:3][CH:4]=[CH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[C:14]1([NH2:24])[C:23]2[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=2)[CH:17]=[CH:16][CH:15]=1>>[C:4]([CH:5]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[NH:24][C:14]1[C:23]2[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=2)[CH:17]=[CH:16][CH:15]=1)#[CH:3]

Participants

3

Reactant 2

HCID 86401-NaphthylamineHCID 71446589Cinnamyl carbonate

Product 1

HCID 86607481alpha-Ethynyl-N-1-napthyl-benzenemethanamineYield 83.4%

Procedure

The general procedure was followed with cinnamyl carbonate (0.188 g, 0.979 mmol) and 1-napthylamine (0.170 g, 1.18 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 98/2. The mixture was purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes) to give the title compound (0.210 g, 83%). HPLC analysis indicated the enantiomeric excess of the product was 95% [Diacel CHIRALCEL OD-H (0.46 cm×25 cm); hexane/2-propanol=99/1; flow rate=0.6 mL/min; detection wavelength=254 μm; TR=29.3 (minor), 40.3 (major) min]: [α]DRT=(c, CHCl3). 1H NMR (400.13 MHz, CDCl3) δ 7.68 (dd, J=8.4, 1.6 Hz, 1H), 7.62 (dd, J=7.6, 2.0 Hz, 1H), 7.30-7.03 (m, 9H), 6.39 (dd, J=6.6, 1.8 Hz, 1H), 5.97 (ddd, J=17.2, 10.4, 6.0 Hz, 1H), 5.18 (dt, J=16.8, 1.2 Hz, 1H), 5.10 (dt, J=10.0, 1.2 hz, 1H), 4.95 (d, J=6.0 Hz, 1H), 4.57 (br s, 1H). 13C NMR (100.59 MHz, CDCl3) δ 141.95, 141.57, 138.88, 134.17, 128.74, 128.67, 127.46, 127.08, 126.41, 125.61, 124.69, 123.37, 119.79, 117.59, 116.25, 106.20, 60.86. Anal. Calcd for C19H17N: C, 87.99; H, 6.61; N, 5.40. Found: C, 88.07; H, 6.53; N, 5.49.

Workup

  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)

Sources & evidence

ORD record
ord-f4c4d087666f48e0a99666e704ffb812
Source dataset
uspto-grants-2010_06
Patent number
US07732365B2

Linked notes

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