2,4,6-Trimethylaniline → alpha-Ethynyl-N-(2,4,6-trimethylphenyl)-benzenemethanamine

HRID 14423

Reaction equation

HRID 14423 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.[CH3:14][C:15]1[CH:21]=[C:20]([CH3:22])[CH:19]=[C:18]([CH3:23])[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[C:18]([CH3:23])=[CH:19][C:20]([CH3:22])=[CH:21][C:15]=1[CH3:14])#[CH:3]

Participants

3

Reactant 2

HCID 69132,4,6-TrimethylanilineHCID 71446589Cinnamyl carbonate

Product 1

HCID 86607476alpha-Ethynyl-N-(2,4,6-trimethylphenyl)-benzenemethanamineYield 85%

Procedure

The general procedure was followed with cinnamyl carbonate (0.188 g, 0.979 mmol) and 2,4,6-trimethylaniline (0.170 g, 1.25 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 97/3. The mixture was purified by flash column chromatography on silica gel (1% ethyl acetate in hexanes) to give the title compound (0.207 g, 85%). HPLC analysis indicated the enantiomeric excess of the product was 96% [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=17.0 (major), 19.5 (minor) min]: [α]DRT=(c, CHCl3). 1H NMR (400.13 MHz, CDCl3) δ 7.38-7.23 (m, 5H), 6.78 (s, 2H), 6.05 (ddd, J=17.2, 10.0, 6.4 Hz, 1H), 5.25 (dt, J=16.8, 1.6 Hz, 1H), 5.17 (dt, J=10.4, 1.3 Hz, 1H), 4.61 (t, J=6.4 Hz, 1H), 3.12 (br s, 1H), 2.22 (s, 3H), 2.11 (s, 6H). 13C NMR (100.59 MHz, CDCl3) δ 142.92, 141.89, 139.34, 130.89, 129.77, 129.34, 128.41, 127.10, 126.93, 115.51, 64.19, 20.56, 18.61. Anal. Calcd for C18H21N: C, 86.01; H, 8.42; N, 5.57. Found: C, 86.18; H, 8.49; N, 5.62.

Workup

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

Sources & evidence

ORD record
ord-5acc5f972aa7412daac73046d4b1f8af
Source dataset
uspto-grants-2010_06
Patent number
US07732365B2

Linked notes

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