PHOSPHITE ADDITION TO DIMINES
1003
(2:1). Calcd. for C22H30N2O8P2: C, 51.57; H, 5.90; N, 5.47. Found: C, 51.33; H, 6.03; N,
5.30%.
Tetramethyl 2,6-Pyridine-bis(N-p-methoxyphenylaminomethane)-
bis(phosphonate) (4Aa)
Yield: 85% (0.24 g). 1H NMR (600 MHz, CDCl3): δ = 7.65 (t, 3JHH = 7.8 Hz, 1H,
H-pyridyl), 7.64 (t, 3JHH = 7.8 Hz, 1H, H-pyridyl), 7.26 (dd, 3JHH = 7.8 Hz, 4JPH = 4.2 Hz,
2H, H-pyridyl), 7.25 (dd, 3JHH = 7.8 Hz, 4JPH = 4.2 Hz, 2H, H-pyridyl), 6.71 (A-part of
AA’BB’, 2H, 4-MeOC6H4), 6.70 (A-part of AA’BB’, 2H, 4-MeOC6H4), 6.64 (B-part of
AA’BB’, 4H, 4-MeOC6H4), 4.98 (d, 2JPH = 22.8 Hz, 2H, CHP), 4.96 (d, 2JPH = 22.8 Hz,
2H, CHP), 3.72 (s, 6H, OCH3), 3.71 (s, 6H, OCH3), 3.83 (d, 3JPH = 10.2 Hz, 6H, POCH3),
3.81 (d, 3JPH = 10.2 Hz, 6H, POCH3), 3.61 (d, 3JPH = 10.2 Hz, 6H, POCH3), 3.56 (d, 3JPH
= 10.2 Hz, 6H, POCH3). 31P NMR (243 MHz, CDCl3): δ = 22.74, 22.68 (1:1). Calcd. for
C25H33N3O8P2: C, 53.10; H, 5.88; N, 7.47. Found: C, 53.84; H, 5.97; N, 7.18%.
Tetraethyl 2,6-Pyridine-bis(N-p-methylphenylaminomethane)-bis
(phosphonate) (4Bb)
Yield: 73% (0.22 g). 1H NMR (600 MHz, CDCl3): δ = 7.62 (t, 3JHH = 7.6 Hz, 1H,
3
H-pyridyl), 7.61 (t, JHH = 7.6 Hz, 1H, H-pyridyl), 7.16 (m, 2H, H-pyridyl), 6.93 (A-
part of AA’BB’, 4H, 4-MeC6H4), 6.61 (B-part of AA’BB’, 4H, 4-MeC6H4), 6.90 (A-Part
2
of AA’BB’, 4H, 4-MeC6H4), 6.59 (B-part of AA’BB’, 4H, 4MeC6H4), 5.00 (d, JPH
=
2
22.8 Hz, 2H, CHP), 4.98 (d, JPH = 22.8 Hz, 2H, CHP), 4.21–4.13 (m, 4H, OCH2CH3),
4.02–3.95 (m, 2H, OCH2CH3), 3.87–3.81 (m, 2H, OCH2CH3), 2.22 (s, 6H, CH3), 2.21 (s,
6H, CH3), 1.32 (t, 3JHH = 7.2 Hz, 6H, OCH2CH3), 1.31 (t, 3JHH = 7.2 Hz, 6H, OCH2CH3),
1.16 (t, 3JHH = 7.2 Hz, 6H, OCH2CH3), 1.12 (t, 3JHH = 7.2 Hz, 6H, OCH2CH3). 31P NMR
(81 MHz, NaOD/D2O): δ = 21.42, 21.33 (3:2). Calcd. for C29H41N3O6P2: C, 59.08; H,
7.01; N, 7.13. Found: C, 59.41; H, 7.14; N, 7.35%.
Tetramethyl 2,6-Pyridine-bis(N-benzylaminomethyl)-bis(phosphonate)
(4Ac)
1
3
Yield: 78% (0.21 g). H NMR (600 MHz, CDCl3): δ = 7.42 (ddd, JHH = 7.5 Hz,
4JPH = 2.4 Hz, 4JHH = 1.8 Hz, 2H, H-pyridyl), 7.39 (ddd, 3JHH = 7.5 Hz, 4JPH = 2.4 Hz,
4JHH = 1.8 Hz, 2H, H-pyridyl), 7.32–7.29 (m, 10H, C6H5), 7.26 (m, 1H, H-pyridyl), 4.31
(d, 2JPH = 21.9 Hz, 2H, CHP), 4.28 (d, 2JPH = 21.9 Hz, 2H, CHP), 3.86 (d, J = 13.2 Hz,
2H, CH2Ph), 3.84 (d, J = 13.2 Hz, 2H, CH2Ph), 3.79 (d, 3JPH = 10.2 Hz, 6H, OCH3), 3.77
3
3
3
(d, JPH = 10.2 Hz, 6H, OCH3), 3.67 (d, JPH = 10.2 Hz, 6H, OCH3), 3.65 (2d, JPH
=
10.2 Hz, 6H, OCH3). 31P NMR (243 MHz, CDCl3): δ = 24.35. Calcd. for C25H33N3O6P2:
C, 56.28; H, 6.23; N, 7.88. Found: C, 56.12; H, 6.37; N, 7.73%.
Tetrabenzyl 2,6-Pyridine-bis(N-benzylaminomethyl)-bis(phosphonate)
(4Cc)
1
Yield: 55% (0.23 g). H NMR (600 MHz, CDCl3): δ = 7.62 (m, 1H, H-pyridyl),
7.39–7.20 (m, 32H, C6H5, H-pyridyl), 5.13–5.11 (part of AMX spectrum, 3JPH = 8.4 Hz,