Benzenemethanamine, 3,4-dichloro- → Methyl 6-(3,4-dichlorobenzylamino)nicotinate

HRID 77442

Reaction equation

[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9][NH2:10])[CH:5]=[CH:6][C:7]=1[Cl:8].Cl[C:12]1[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][N:13]=1>C(O)C>[Cl:1][C:2]1[CH:3]=[C:4]([CH:5]=[CH:6][C:7]=1[Cl:8])[CH2:9][NH:10][C:12]1[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][N:13]=1

Participants

Conditions

Temperature: 120 °C

Procedure

A mixture of (3,4-dichlorophenyl)methanamine (1.010 mL, 7.58 mmol), TEA (1.218 mL, 8.74 mmol), and methyl 6-chloronicotinate (1 g, 5.83 mmol) in ethanol (29 mL) was heated at 120° C. for 5 min in a microwave oven. The reaction mixture was further heated at 100° C. for 54 h, then concentrated. The residue was purified by flash chromatography on silica gel using 5-35% ethyl acetate in hexanes. The desired fractions were concentrated to give methyl 6-(3,4-dichlorobenzylamino)nicotinate as a pale yellow solid (0.55 g, 33%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 8.77 (1H, s), 8.01 (1H, dd, J=8.78, 2.01 Hz), 7.33-7.52 (2H, m), 7.19 (1H, d, J=8.03 Hz), 6.37 (1H, d, J=8.78 Hz), 5.37 (1H, br. s.), 4.58 (2H, d, J=6.02 Hz), 3.88 (3H, s). LCMS: R.T.=2.81; [M+H]+=311.18.

Workup

temperatureThe reaction mixture was further heated at 100° C. for 54 h
concentrationconcentrated
customThe residue was purified by flash chromatography on silica gel using 5-35% ethyl acetate in hexanes
concentrationThe desired fractions were concentrated

Sources & evidence

ORD record: ord-315f4008d95f4cddbbd565fc70894b6d
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08841301B2

Linked notes

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