Aniline → Diphenyl ((6-methylpyridin-2-yl)(phenylamino)methyl)phosphonate

Reaction equation

[CH3:1][C:2]1[N:7]=[C:6]([CH:8]=O)[CH:5]=[CH:4][CH:3]=1.[NH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[P:17]([O-:32])([O:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[O:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.O.O.O.O.O.O.O.O.[Cl-]>>[CH3:1][C:2]1[N:7]=[C:6]([CH:8]([P:17](=[O:32])([O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:18][C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:5]=[CH:4][CH:3]=1

Participants

Reactant 4

HCID 6115Aniline

HCID 707376-Methyl-2-pyridinecarboxaldehyde

HCID 18958553Chloride octahydrate

HCID 23418553Diphenoxyphosphanolate

Product 1

HCID 58748142Diphenyl ((6-methylpyridin-2-yl)(phenylamino)methyl)phosphonateYield 92.4%

Procedure

A mixture of 6-methylpyridine-2-carboxaldehyde (2.12 g, 17.50 mmol), aniline (1.63 g, 17.50 mmol), diphenyl phosphite (4.92 g, 21.00 mmol), and zirconyl chloride octahydrate (0.56 g, 1.75 mmol) was stirred at room temperature 1 h. The reaction mixture was extracted with CH2Cl2 (3×50 mL), and the CH2Cl2 solution was washed with water (2×20 mL), dried over anhydrous Na2SO4, filtered, and evaporated to dryness under reduced pressure. The residue was purified by MPLC on silica gel using a mixture of EtOAc and hexane as eluent to give the titled compound (6.96 g, 92%) as a white solid. 1H NMR (400 MHz, CDCl3): δ 7.51 (t, 1H, J=7.8 Hz), 7.38 (dd, 1H, J=7.6, 2.0 Hz), 7.27-7.22 (m, 4H), 7.19-7.15 (m, 2H), 7.14-7.07 (m, 4H), 7.05-7.02 (m, 3H), 6.80-6.74 (m, 3H), 5.53 (pseudo t, 1H, J=7.4 Hz), 5.36 (dd, 1H, J=21.0, 8.2 Hz), 2.54 (s, 3H).