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

HRID 659149Notes

Reaction equation

HRID 659149 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

5

Reactant 4

HCID 6115AnilineHCID 707376-Methyl-2-pyridinecarboxaldehydeHCID 18958553Chloride octahydrateHCID 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).

Workup

  1. extractionThe reaction mixture was extracted with CH2Cl2 (3×50 mL)
  2. washthe CH2Cl2 solution was washed with water (2×20 mL)
  3. dry with materialdried over anhydrous Na2SO4
  4. filtrationfiltered
  5. customevaporated to dryness under reduced pressure
  6. customThe residue was purified by MPLC on silica gel using
  7. additiona mixture of EtOAc and hexane as eluent

Sources & evidence

ORD record
ord-8c9ce0023d564e10a0fbcc878406b79b
Source dataset
uspto-grants-2011_12
Patent number
US08080568B1

Reaction notes

Loading…