Triethyl phosphite → Tetraethyl [[2,2'-bipyridine]-4,4'-diylbis(methylene)]bis(phosphonate)

HRID 2301251Notes

Reaction equation

HRID 2301251 reaction equation
Br[CH2:2][C:3]1[CH:8]=[CH:7][N:6]=[C:5]([C:9]2[CH:14]=[C:13]([CH2:15]Br)[CH:12]=[CH:11][N:10]=2)[CH:4]=1.C([O:19][P:20]([O:24][CH2:25][CH3:26])[O:21][CH2:22][CH3:23])C>C(Cl)(Cl)Cl>[CH3:23][CH2:22][O:21][P:20]([O:24][CH2:25][CH3:26])([CH2:2][C:3]1[CH:8]=[CH:7][N:6]=[C:5]([C:9]2[CH:14]=[C:13]([CH2:15][P:20]([O:21][CH2:22][CH3:23])([O:24][CH2:25][CH3:26])=[O:19])[CH:12]=[CH:11][N:10]=2)[CH:4]=1)=[O:19]

Participants

4

Reactant 2

HCID 31215Triethyl phosphiteHCID 10893230HCID 10893230, compound

Product 1

HCID 46911978Tetraethyl [[2,2'-bipyridine]-4,4'-diylbis(methylene)]bis(phosphonate)Yield 80%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A chloroform (10 mL) solution of (3) (1.5 g, 4.4 mmol) and 15 mL of triethylphosphite was refluxed for 3 hours under nitrogen. The excess phosphite was removed under high vacuum, then the crude product was purified by column chromatography on silica gel (eluent ethyl acetate/methanol 80/20) yielding 1.6 g (80%) of (4). 1H NMR (300 MHz, CDCl3) δ ppm: 1.29(12H, t, 3JHH=7 Hz, 4 POCH2CH3), 3.23 (4H, d, 2JPCH=22 Hz, 2CH2P), 4.09 (8H, dq, 3JPOCH=7 Hz, 3JHH=7 Hz, 4 POCH2CH3), 7.35-7.38 (2H, m, aryl H on C5 and C5′), 8.34-8.37 (2H, m, aryl H on C3 and C3′), 8.62 (2H, d, 3JHH=5 Hz, aryl H on C6 and C6′). 31P NMR (CDCl3) δ ppm: 25.37. Elemental analysis C20H30N2O6P2: calcd. C 52.63, H 6.63, N 6.14%, found C 52.83, H 6.59, N 6.01%.

Workup

  1. customThe excess phosphite was removed under high vacuum
  2. customthe crude product was purified by column chromatography on silica gel (eluent ethyl acetate/methanol 80/20)

Sources & evidence

ORD record
ord-13eaf13a200b4ac689c2bd4ecf109247
Source dataset
uspto-grants-2002_12
Patent number
US06500510B1

Reaction notes

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